CN113060726B - Viscose-based nitrogen-containing activated carbon fiber material and preparation method and application thereof - Google Patents

Viscose-based nitrogen-containing activated carbon fiber material and preparation method and application thereof Download PDF

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CN113060726B
CN113060726B CN202110321183.7A CN202110321183A CN113060726B CN 113060726 B CN113060726 B CN 113060726B CN 202110321183 A CN202110321183 A CN 202110321183A CN 113060726 B CN113060726 B CN 113060726B
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carbon fiber
viscose
fiber material
activated carbon
nitrogen
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CN113060726A (en
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李瑶
高雅茹
王彬彬
王燕
王娅鸽
张涛
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Henan University of Technology
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
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    • C01B32/318—Preparation characterised by the starting materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention belongs to the technical field of preparation and application of activated carbon fiber materials, and particularly relates to an adhesive-based nitrogen-containing activated carbon fiber material and a preparation method and application thereof. The material has the mass content of nitrogen of 4.27-7.43% and the specific surface area of 609-1159 cm2(ii) a total pore volume of 0.31 to 0.54cm3(ii) in terms of/g. The viscose-based nitrogen-containing activated carbon fiber material has the advantages of large specific surface area, high microporosity, easily obtained raw materials, economy, environmental friendliness, realization of one-step carbonization-activation for preparation of the viscose-based nitrogen-containing activated carbon fiber material, simple operation, and reduction of time consumption and energy consumption. The viscose-based nitrogen-containing activated carbon fiber material has good adsorbability on carbon dioxide and excellent CO2/CH4Selectivity and wide application prospect in the field of gas adsorption and separation.

Description

Viscose-based nitrogen-containing activated carbon fiber material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation and application of activated carbon fiber materials, and particularly relates to an adhesive-based nitrogen-containing activated carbon fiber material and a preparation method and application thereof.
Background
The active porous carbon has high specific surface area and porosity; the preparation process is simple, the yield is high, the raw materials are easy to obtain, and the cost is low; the pore channel structure is easy to regulate and control by changing preparation parameters and optimizing a combination mode; the pore-forming agent used has been widely studied as an adsorbent because of its many advantages such as the ability to form pores by self-sublimation.
In recent years, activated carbon fiber cloth (i.e., activated porous carbon fiber material) has been studied and found to be a highly efficient gas adsorbent, and compared with conventional powdered and granular activated carbon, activated carbon fiber cloth has the following advantages: (1) most of the pores of the activated carbon fiber cloth are on the surface, so that the mass transfer diffusion resistance is small, and the adsorption and desorption rate is high; (2) the activated carbon fiber cloth has a large specific surface area, which provides a fast adsorption rate and mass transfer rate for the activated carbon fiber cloth; (3) also has low density, high microporosity, excellent chemical stability and excellent conductivity; (4) low production cost, rich manufacturing process and the like, and is used in the fields of energy storage, adsorption, environmental protection, catalyst carriers, electrochemical materials and the like.
The preparation method of the active porous carbon fiber material mainly comprises a physical activation method and a chemical activation method.
The chemical activation method is to select a proper chemical reagent as an activating agent, mix the activating agent with raw materials and then perform a series of crosslinking polycondensation reactions, and then the chemical reagent is embedded into the carbon fiber to form micropores. The chemical activation and the carbonization can be carried out simultaneously, namely, the carbonization and the activation are carried out by directly raising the temperature to the activation temperature.
The physical activation method is to react the raw material with oxidizing gas such as water vapor, carbon dioxide or air at high temperature, and disordered carbon is oxidized and etched to form pores in the activation process, so that a developed microporous structure is formed in the material. The physical activation generally needs to be carried out after carbonization, the carbonization temperature is generally 600 ℃, and the activation temperature is generally 800-900 ℃.
Chemical activation requires lower temperature than physical activation, and the reaction conditions are controlled by selecting a proper activating agent to prepare the activated carbon with high specific surface area. However, chemical activation is highly corrosive to equipment and pollutes the environment, and the prepared activated carbon has residual chemical activating agent and is limited in application.
The Chinese patent application with the application publication number of CN106435841A discloses a method for preparing porous polyacrylonitrile fiber by electrostatic spinning and air flow drafting, wherein the method comprises the steps of pre-oxidizing raw materials, and carbonizing the raw materials at a high temperature to obtain the porous carbon fiber with honeycomb pore channels inside. The application publication number CN107221454A of the chinese invention discloses a porous carbon fiber cloth made of cotton fiber fabric as raw material, which retains the original hollow tubular structure of cotton fiber and the original tightly woven characteristics of fabric, and can be used as the flexible electrode of super capacitor.
At present, the research on porous carbon fiber cloth is mostly focused on two fibers, namely polyacrylonitrile fiber and cotton fiber, and reports on viscose-based fiber cloth for preparing activated carbon fiber cloth are rare. Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a viscose-based nitrogen-containing activated carbon fiber material with large specific surface area and high porosity, a preparation method and application thereof, and aims to solve the problem that the adsorption performance of the existing viscose-based nitrogen-containing activated carbon fiber material cannot meet the use requirement.
In order to achieve the purpose, the invention provides the following technical scheme:
the specific surface area of the viscose-based nitrogen-containing activated carbon fiber material is 609-1159 cm2(ii) a total pore volume of 0.31 to 0.54cm3The mass content of nitrogen is 4.27-7.43 percent.
Preferably, in the viscose-based nitrogen-containing activated carbon fiber material, the volume of ultramicropore pores with the pore diameter of less than 1nm accounts for 50-65% of the total pore volume, and the volume of micropore pores with the pore diameter of less than 2nm accounts for 67-80% of the total pore volume.
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material comprises the following steps:
(1) pretreatment
Soaking and drying the clean and dry viscose fabric in a chloride solution;
(2) activation-carbonization treatment
Heating the viscose fabric obtained in the step (1) in a tubular furnace, wherein the heating is carried out in a nitrogen atmosphere;
after the temperature is raised to the target temperature, converting nitrogen into carbon dioxide gas, and performing constant-temperature carbonization-activation treatment to obtain a semi-finished product of the nitrogen-containing activated carbon fiber material, wherein the target temperature is 700-900 ℃;
(3) post-treatment
And (3) soaking and washing the semi-finished product of the nitrogen-containing activated carbon fiber material obtained in the step (2) by using an acid solution until the washing liquid becomes neutral, and then drying to obtain the viscose-based nitrogen-containing activated carbon fiber material.
For the above preparation method, preferably, in the step (1), the chlorine salt solution is 5 wt% NH in mass fraction4Cl and ZnCl with the mass fraction of 5 wt%2A mixed salt solution of the components;
for the above preparation method, preferably, the soaking time is 60 min.
For the above preparation method, preferably, the drying is drying at a temperature of 60 ℃ for 240 min.
For the preparation method, preferably, in the step (1), the clean and dry viscose fabric is obtained by sequentially ultrasonically cleaning the waste viscose fabric in ethanol and deionized water and then drying.
For the above production method, preferably, in the step (2), the temperature increase rate of the temperature increase treatment is 3 ℃/min.
For the above production method, it is preferable that the flow rate of nitrogen gas in the tube furnace is 40mL/min at the time of the temperature-raising treatment.
For the above production method, preferably, in the step (2), the flow rate of carbon dioxide in the tube furnace at the time of the carbonization-activation treatment is 40 mL/min.
For the above production method, preferably, the time of the carbonization-activation treatment is 60 min.
For the above production method, preferably, in the step (3), the acid solution is an HCl solution having a concentration of 0.1 mol/L.
For the above preparation method, the soaking time of the acid solution is preferably 30 min.
For the above production method, preferably, in the step (3), the drying is drying at a temperature of 60 ℃ for 240 min.
The invention also provides application of the viscose-based nitrogen-containing activated carbon fiber material, and specifically relates to application of the viscose-based nitrogen-containing activated carbon fiber materialUse of carbon fiber materials for CO2Adsorption and CO2/CH4Separation of (4).
Preferably, the viscose-based nitrogen-containing activated carbon fiber material is used for CO2/CH4In the separation of (2), CO2/CH4The selectivity coefficient of (A) is 3.29-5.48.
Has the advantages that:
the viscose-based nitrogen-containing activated carbon fiber material has a specific surface area of 609-1159 cm2(ii) a total pore volume of 0.31 to 0.54cm3The volume of the ultramicropore volume with the pore diameter of less than 1nm accounts for 50-59% of the total pore volume, the volume of the micropore volume with the pore diameter of less than 2nm accounts for 74-76% of the total pore volume, and the mass content of nitrogen is 4.27-7.42%.
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material has the following advantages:
(1) with CO2The pore-forming agent is an activating agent, has higher pore-forming rate, does not need other chemical activating reagents, and reduces the consumption of the reagents and the pollution to equipment and environment;
(2) the prepared viscose-based nitrogen-containing activated carbon fiber material has the advantages of large specific surface area, high microporosity and excellent flexibility.
(3) The carbonization and the activation are completed in one step, the operation is simple, the preparation process is simplified, the preparation time is shortened, the energy consumption and the cost are reduced, and the industrial production is facilitated.
(4) The used raw materials are waste viscose fabrics, the raw materials are widely and easily obtained, the effective recycling of wastes is realized, the production cost of the viscose-based nitrogen-containing activated carbon fiber material is effectively reduced, and the method has obvious economic benefit.
(5) Prepared viscose-based nitrogen-containing activated carbon fiber material is used for CO2Has good adsorptivity and excellent CO2/CH4Selectivity, can be applied to the field of separation of carbon dioxide and methane.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Wherein:
fig. 1 is a scanning electron micrograph of the viscose-based nitrogen-containing activated carbon fiber material of example 1 of the present invention, which is 177 times, 2230 times, and 3000 times magnified in sequence from left to right;
fig. 2 is an energy dispersion X-ray energy spectrum of the viscose-based nitrogen-containing activated carbon fiber material of example 1 of the present invention;
fig. 3 is a nitrogen isothermal adsorption and desorption curve diagram of the viscose-based nitrogen-containing activated carbon fiber material of example 1 of the present invention, which is measured at-196 ℃;
FIG. 4 shows CO at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 1 of the present invention2Adsorption isotherm plot;
FIG. 5 shows CH of the viscose-based nitrogen-containing activated carbon fiber material of example 1 at 25 ℃4Adsorption isotherm plot;
FIG. 6 shows a binary mixed gas (CO) at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 1 of the present invention2/CH4) Selectivity profiles at different mixing ratios;
fig. 7 is a nitrogen isothermal adsorption and desorption curve diagram of the viscose-based nitrogen-containing activated carbon fiber material of example 2 of the present invention, which is measured at-196 ℃;
FIG. 8 shows CO at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 2 of the present invention2Adsorption isotherm plot;
fig. 9 is a nitrogen isothermal adsorption and desorption curve diagram of the viscose-based nitrogen-containing activated carbon fiber material of example 3 of the present invention, which is measured at-196 ℃;
FIG. 10 shows CO at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 3 of the present invention2Adsorption isotherm plot;
fig. 11 is a nitrogen isothermal adsorption and desorption curve diagram of the viscose-based nitrogen-containing activated carbon fiber material of example 4 of the present invention, which is measured at-196 ℃;
FIG. 12 shows CO at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 4 of the present invention2Adsorption isotherm plot；
Fig. 13 is a nitrogen isothermal adsorption and desorption curve diagram of the viscose-based nitrogen-containing activated carbon fiber material of example 5 of the present invention, which is measured at-196 ℃;
FIG. 14 shows CO at 25 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of example 5 of the present invention2Adsorption isotherm plot;
FIG. 15 is a nitrogen isothermal adsorption-desorption curve measured at-196 ℃ for the carbon fiber material of comparative example 1 of the present invention;
FIG. 16 shows CO at 25 ℃ of the carbon fiber material of comparative example 1 of the present invention2Adsorption isotherm plot.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material is 609-1159 cm2G (e.g. 609 cm)2/g、700cm2/g、850cm2/g、904cm2/g、1159cm2(g) total pore volume of 0.31-0.54 cm3In g (e.g. 0.31 cm)3/g、0.38cm3/g、0.40cm3/g、0.45cm3/g、0.54cm3(g), the nitrogen content is 4.27 to 7.43% by mass (for example, 4.27%, 4.50%, 5.00%, 6.00%, 7.42%). In the material, the volume of ultramicropore volume with the pore diameter less than 1nm accounts for 50-65% (such as 50%, 52%, 54%, 56%, 59%, 60%, 61%, 62%, 63%, 64%, 65%) of the total pore volume, and the volume of micropore pore volume with the pore diameter less than 2nm accounts for 67-80% (such as 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%) of the total pore volume.5％、75％、75.5％、76％、77％、78％、79％、80％)。
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material provided by the invention comprises the step of using NH4Cl and ZnCl2The waste viscose fiber fabric soaked and dried by the mixed solution is taken as a precursor, and is subjected to N2Raising the temperature to the target temperature under the atmosphere protection, and changing CO2And (3) carrying out constant-temperature treatment on the gas for 60min, simultaneously completing carbonization and activation of the viscose-based fibers, and carrying out post-treatment to prepare the viscose-based nitrogen-containing activated carbon fiber material.
Specifically, the preparation method of the viscose-based nitrogen-containing activated carbon fiber comprises the following steps:
(1) pretreatment
Firstly, ultrasonically cleaning waste viscose fiber fabrics in ethanol and deionized water in sequence to remove dust and impurities on the surfaces of the fibers, and then drying;
then, with NH4Cl and ZnCl2The dried viscose fiber fabric is soaked in the mixed salt solution for 60min, and the mixed salt solution can increase the output after calcination and reduce ash content; then drying is carried out; wherein NH4Cl and ZnCl2The concentration of the mixed salt solution of (a) is: 5 wt% NH4Cl and 5 wt% ZnCl2Soaking, and drying in a drying oven at 60 deg.C for 240 min;
(2) activation-carbonization treatment
Placing the viscose fiber fabric obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a tube furnace, and putting the porcelain boat in a furnace in N2Heating treatment is carried out in the atmosphere; wherein the heating rate is 3 ℃/min (carbonization is not thorough in the heating process), the target temperature is 700-900 ℃, and N in the tube furnace2The flow rate of (3) is 40 mL/min;
after the target temperature is reached, the protective gas N is introduced2Conversion to CO2Carbonizing and activating the gas at constant temperature, cooling to room temperature to obtain semi-finished product of nitrogen-containing active carbon fiber material, and treating with CO2During the thermal treatment of gases, semi-synthetic or regenerated viscose fibres, preferably used for carbonization and activation purposes, are converted into high nanometresPores and large surface area structures; wherein, CO2The speed of the airflow is 40mL/min, and the time of carbonization-activation treatment is 60 min;
(3) post-treatment
Soaking the semi-finished product of the nitrogenous active carbon fiber material obtained in the step (2) in HCl solution for 30min, washing the semi-finished product with deionized water for multiple times until the semi-finished product is neutral (namely the washing liquid is neutral), and finally drying the semi-finished product to obtain the viscose-based nitrogenous active carbon fiber material; wherein, the concentration of the HCl solution is 0.1mol/L, and the drying conditions are as follows: drying in a drying oven at 60 deg.C for 240 min. The reason for using HCl solution soaking is: ZnCl is used in the pretreatment2The acid washing is to remove the Zn oxide that may remain, and it is not desirable to introduce other ions.
The viscose-based nitrogen-containing activated carbon fiber material prepared by the invention can be used for treating CO2Has good adsorption performance on CO2/CH4Has good selectivity and can be applied to CO2Adsorption and CO2/CH4The field of separation of (1).
The viscose-based nitrogen-containing activated carbon fiber material of the present invention, its preparation method and application are further described in the following with reference to specific examples, wherein the length of the tube furnace is 1000mm, the inner diameter is 60mm, and the volume is 2826cm3。
The specific test instruments and analysis methods involved in the following examples are as follows:
the element analyzer is used for measuring the nitrogen content of the viscose-based nitrogen-containing activated carbon fiber material;
intelligent gravimetric analyzer (IGA002) for CO measurement2And CH4Isothermal adsorption curve of (a);
calculating the specific surface area by a multipoint Brunauer-Emmett-Teller (BET) method;
according to P/P0Calculating the total pore volume of the viscose-based nitrogen-containing activated carbon fiber material according to the adsorbed liquid nitrogen amount when the liquid nitrogen amount is 0.99;
calculating ultra-microporous (less than 1nm) pore volume and microporous (less than 2nm) pore volume by non-localized density functional theory (NDFT);
scanning an electron microscope to represent the surface appearance of the viscose-based nitrogen-containing activated carbon fiber material;
energy is dispersed in X-ray to represent the distribution of surface elements of the viscose-based nitrogen-containing activated carbon fiber material.
Example 1
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material comprises the following steps:
(1) pretreatment
Placing the waste viscose fiber fabric of 5cm multiplied by 5cm in ethanol and deionized water for ultrasonic cleaning, removing dust and impurities on the surface of the fiber, and drying in an oven at 60 ℃ for 240min after cleaning;
2.78g of NH were weighed4Cl and 2.78g ZnCl2Dissolving the mixed solution in 50mL of deionized water to prepare 5 wt% NH4Cl and 5 wt% ZnCl2Soaking the cleaned waste viscose fiber fabric for 60min, and drying in a 60 ℃ oven for 240min after soaking to finish the pretreatment of the waste viscose fiber fabric;
(2) activation-carbonization treatment
Placing the treated viscose fabric into a porcelain boat, placing the porcelain boat into a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min under the protection of nitrogen atmosphere (the flow rate of nitrogen is 40mL/min), converting the nitrogen into carbon dioxide gas with the flow rate of 40mL/min after reaching 800 ℃, activating at constant temperature, carbonizing for 60min, naturally cooling to room temperature, and taking out to obtain a semi-finished product of the nitrogenous active carbon fiber material;
(3) post-treatment
And (3) soaking the nitrogen-containing activated carbon fiber material obtained in the step (2) in HCl solution with the concentration of 0.1mol/L for 30min, washing a sample with deionized water to be neutral, and drying in an oven at 60 ℃ for 240min to obtain the viscose-based nitrogen-containing activated carbon fiber material.
The layered scanning electron microscope image of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is shown in fig. 1, as seen from the low magnification (left image in fig. 1), the viscose-based nitrogen-containing activated carbon fiber material still maintains the yarn knitting chain shape after carbonization and activation, each yarn knitting chain is composed of tens of yarns, as seen from the high magnification (middle image and right image in fig. 1), each yarn diameter is about 10-15 μm (for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm), the broken surface is seen that the internal structure is compact, which indicates that the pores should have smaller dimension, most probably at nanometer level, but cannot be distinguished by SEM.
The distribution of surface elements of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is shown in fig. 2, and it can be seen from the figure that C, N and O elements are uniformly distributed on the surface of the fiber material.
The mass content of nitrogen in the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 5.87%.
The isothermal adsorption-desorption curve of nitrogen measured by the viscose-based nitrogen-containing activated carbon fiber material of the embodiment at-196 ℃ is shown in fig. 3, and according to the classification of international union of pure and applied chemistry, the isothermal adsorption-desorption curve of nitrogen is known to conform to type I, which indicates that the viscose-based nitrogen-containing activated carbon fiber material contains a large number of micropores.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 904m2In terms of/g, total pore volume of 0.41cm3Per g, micropore (less than 2nm) pore volume of 0.31cm3The volume ratio of the polymer to the total pore volume is 76%, and the volume of ultra-microporous (less than 1nm) pores is 0.24cm3The proportion of the total pore volume is 59 percent.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at 25 DEG C2The adsorption isotherm curve is shown in fig. 4, and it can be seen from the graph that the viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at a pressure of 1bar2The adsorption amount was 3.13 mmol/g.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CH at 25 DEG C4The adsorption isotherm curve is shown in fig. 5, and it can be seen from the graph that the CH of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is at 1bar pressure4The adsorption amount was 1.45 mmol/g.
FIG. 6 is a calculation of binary mixed gas CO by ideal gas adsorption solution theory (IAST)2/CH4Selectivity profile at different mixing ratios, CO at 25 ℃ and 1bar pressure2/CH4CO at a mixing ratio (volume ratio, i.e., the ratio of the amounts of the substances) of 10/90 and 30/702/CH4Are 5.48 and 3.29, respectively, above or similar to the IAST selectivity of currently known nitrogen-containing activated carbon fiber materials. The selectivity coefficient in the present invention refers to the adsorption preference of the adsorbent for gas. The invention is the adsorption material to CO2Is superior to CH4Preference (c) of (c).
Example 2
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is different from that of the embodiment 1 only in that: in the step (2), the temperature is raised to 700 ℃ in the nitrogen atmosphere, and after the temperature reaches 700 ℃, nitrogen is converted into carbon dioxide gas with the flow rate of 40mL/min, and the carbon dioxide gas is activated at constant temperature and carbonized for 60 min. Other preparation steps are the same as those in example 1 and are not described again.
The isothermal adsorption-desorption curve of nitrogen measured at-196 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is shown in fig. 7, and according to the international union of pure and applied chemistry, it can be known that the isothermal adsorption-desorption curve of nitrogen conforms to type I, which indicates that the pores of the viscose-based nitrogen-containing activated carbon fiber material are micropores.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 645m2In terms of/g, total pore volume of 0.33cm3Per g, micropore (less than 2nm) pore volume of 0.22cm3The volume ratio of the polymer to the total pore volume is 67%, and the volume of ultra-microporous (less than 1nm) pores is 0.19cm3The proportion of the total pore volume is 58 percent.
The mass content of nitrogen in the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 7.43%.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at 25 DEG C2The adsorption isotherm curve is shown in fig. 8, and it can be seen from the graph that the adhesive-based nitrogen-containing activated carbon fiber material of the embodiment has CO at a pressure of 1bar2The adsorption capacity is 2.52mmol/g, and the CO content is lower than that of the viscose-based nitrogen-containing activated carbon fiber material in the example 1 under the same conditions2The amount of adsorption.
Example 3
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is different from that of the embodiment 1 only in that: in the step (2), the temperature is increased to 900 ℃ in the nitrogen atmosphere, and after the temperature reaches 900 ℃, nitrogen is converted into carbon dioxide gas with the flow rate of 40mL/min, and the carbon dioxide gas is activated at constant temperature and carbonized for 60 min. Other preparation steps are the same as those in example 1 and are not described again.
The isothermal adsorption-desorption curve of nitrogen measured at-196 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is shown in fig. 9, and according to the international union of pure and applied chemistry, it can be known that the isothermal adsorption-desorption curve of nitrogen conforms to type I, which indicates that the pores of the viscose-based nitrogen-containing activated carbon fiber material are micropores.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is 1159m2(ii)/g, total pore volume 0.54cm3Per g, micropore (less than 2nm) pore volume of 0.40cm3(ii)/g, accounting for 74% of the total pore volume, and the ultra-microporous (less than 21nm) pore volume of 0.27cm3The ratio of the total pore volume is 50%.
The mass content of nitrogen in the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 4.28%.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at 25 DEG C2The adsorption isotherm curve is shown in FIG. 10, from which it can be seen that the CO of the viscose-based nitrogen-containing activated carbon fiber material of example 3 is present at a pressure of 1bar2The adsorption capacity is 2.93mmol/g, and the CO content is lower than that of the viscose-based nitrogen-containing activated carbon fiber material in the example 1 under the same conditions2The amount of adsorption.
Example 4
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is different from that of the embodiment 1 only in that: in the step (2), the temperature is raised to 800 ℃ in the nitrogen atmosphere, and after the temperature reaches 800 ℃, nitrogen is converted into carbon dioxide gas with the flow rate of 40mL/min, and the carbon dioxide gas is activated at constant temperature and carbonized for 30 min. Other preparation steps are the same as those in example 1 and are not described again.
The isothermal adsorption-desorption curve of nitrogen measured at-196 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of this embodiment is shown in fig. 11, and according to the international union of pure and applied chemistry, it can be known that the isothermal adsorption-desorption curve of nitrogen conforms to type I, which indicates that the pores of the viscose-based nitrogen-containing activated carbon fiber material are micropores.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is 667m2(ii)/g, total pore volume 0.30cm3Per g, micropore (less than 2nm) pore volume of 0.23cm3(77%) in total pore volume, and ultramicropore (less than 1nm) pore volume of 0.19cm3The proportion of the total pore volume is 63 percent.
The mass content of nitrogen in the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 5.84%.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at 25 DEG C2The adsorption isotherm curve is shown in fig. 12, and it can be seen from the graph that the adhesive-based nitrogen-containing activated carbon fiber material of the embodiment has CO at a pressure of 1bar2The adsorption capacity is 2.71mmol/g, and the CO content is lower than that of the viscose-based nitrogen-containing activated carbon fiber material in the example 1 under the same conditions2The amount of adsorption.
Example 5
The preparation method of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is different from that of the embodiment 1 only in that: in the step (2), the temperature is raised to 800 ℃ in the nitrogen atmosphere, and after the temperature reaches 800 ℃, nitrogen is converted into carbon dioxide gas with the flow rate of 40mL/min, and the carbon dioxide gas is activated at constant temperature and carbonized for 90 min. Other preparation steps are the same as those in example 1 and are not described again.
The isothermal adsorption-desorption curve of nitrogen measured at-196 ℃ of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is shown in fig. 13, and according to the international union of pure and applied chemistry, it can be known that the isothermal adsorption-desorption curve of nitrogen conforms to type I, which indicates that the pores of the viscose-based nitrogen-containing activated carbon fiber material are micropores.
The specific surface area of the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 1077m2In terms of/g, total pore volume of 0.46cm3Per g, muPore (less than 2nm) volume of 0.37cm3(g) 80% of total pore volume, and ultramicropore (less than 1nm) pore volume of 0.30cm3The proportion of the total pore volume is 65 percent per gram.
The mass content of nitrogen in the viscose-based nitrogen-containing activated carbon fiber material of the embodiment is determined to be 5.52%.
The viscose-based nitrogen-containing activated carbon fiber material of the embodiment has CO at 25 DEG C2The adsorption isotherm curve is shown in fig. 14, and it can be seen from the graph that the adhesive-based nitrogen-containing activated carbon fiber material of the embodiment has CO at a pressure of 1bar2The adsorption capacity is 2.90mmol/g, and the CO content is lower than that of the viscose-based nitrogen-containing activated carbon fiber material in the example 1 under the same conditions2The amount of adsorption.
Comparative example 1
Comparative example 1 differs from example 1 in that: in the step (2), under the protection of nitrogen atmosphere, heating to 800 ℃ at the speed of 3 ℃/min, carbonizing for 60min at constant temperature after reaching 800 ℃, and then naturally cooling to room temperature to obtain the carbon fiber material. Other preparation steps are the same as those in example 1 and are not described again.
The isothermal adsorption and desorption curve of nitrogen measured by the carbon fiber material of the comparative example at-196 ℃ is shown in fig. 15, and according to the classification of international union of pure and applied chemistry, the isothermal adsorption and desorption curve of nitrogen is known to conform to type I, which indicates that the pores of the carbon fiber material are micropores.
The carbon fiber material of this comparative example was determined to have a specific surface area of 609m2(ii)/g, total pore volume 0.31cm3Per g, micropore (less than 2nm) pore volume of 0.23cm3(ii)/g, accounting for 74% of the total pore volume, and the ultra-microporous (less than 1nm) pore volume of 0.18cm3The proportion of the total pore volume is 58 percent.
The carbon fiber material of the comparative example was determined to have a nitrogen content of 6.45% by mass.
The carbon fiber material of the present comparative example had CO at 25 deg.C2The adsorption isotherm curve is shown in FIG. 16, from which it can be seen that the carbon fiber material of the present comparative example has CO at a pressure of 1bar2The adsorption capacity is 2.49mmol/g, which is lower than that of example 1 under the same conditionsCO of gum base nitrogen-containing activated carbon fiber material2The amount of adsorption.
In summary, comparing the data in examples 1 to 5 and comparative example 1, it can be seen that the CO content of the viscose-based nitrogen-containing activated carbon fiber material obtained in example 1 is the same under the same conditions2CO having an adsorption amount higher than that of examples 2, 3, 4, 5 and comparative example 12The adsorption capacity indicates that the temperature is raised to 800 ℃ under nitrogen, and carbon dioxide is activated and carbonized for 60min at 800 ℃, and CO is generated2The adsorption capacity is optimal.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. The preparation method of the viscose-based nitrogen-containing activated carbon fiber material is characterized by comprising the following steps:
(1) pretreatment
Soaking and drying the clean and dry viscose fabric in a chloride solution;
(2) activation-carbonization treatment
Heating the viscose fabric obtained in the step (1) in a tubular furnace, wherein the heating is carried out in a nitrogen atmosphere;
after the temperature is raised to a target temperature, converting nitrogen into carbon dioxide gas, and performing constant-temperature carbonization-activation treatment to obtain a semi-finished product of the nitrogen-containing activated carbon fiber material, wherein the target temperature is 700-900 ℃;
(3) post-treatment
Soaking and washing the semi-finished product of the nitrogenous active carbon fiber material obtained in the step (2) with an acid solution until the washing liquor is neutral, and then drying to obtain the viscose-based nitrogenous active carbon fiber material;
in the step (2), the time of the carbonization-activation treatment is 60 min.
2. The method according to claim 1, wherein the reaction mixture is heated to a temperature in the reaction mixtureIn the step (1), the chlorine salt solution is 5 wt% of NH4Cl and ZnCl with the mass fraction of 5 wt%2Mixed salt solution of the components.
3. The method of claim 2, wherein the soaking time is 60 min.
4. The method according to claim 2, wherein the drying is performed at a temperature of 60 ℃ for 240 min.
5. The preparation method according to claim 1, wherein in the step (1), the clean and dry viscose fiber fabric is obtained by sequentially ultrasonically cleaning waste viscose fiber fabric in ethanol and deionized water and then drying.
6. The production method according to claim 1, wherein in the step (2), the temperature increase rate of the temperature increase treatment is 3 ℃/min.
7. The production method according to claim 6, wherein the flow rate of nitrogen gas in the tube furnace at the time of the temperature-raising treatment is 40 mL/min.
8. The production method according to claim 1, wherein in the step (2), the flow rate of carbon dioxide in the tube furnace at the time of the carbonization-activation treatment is 40 mL/min.
9. The method according to claim 1, wherein in the step (3), the acid solution is an HCl solution having a concentration of 0.1 mol/L.
10. The method as claimed in claim 9, wherein the soaking time of the acid solution is 30 min.
11. The method according to claim 1, wherein in the step (3), the drying is performed at a temperature of 60 ℃ for 240 min.
12. The preparation method of any one of claims 1 to 11, wherein the specific surface area of the viscose-based nitrogen-containing activated carbon fiber material is 609-1159 m2(ii) a total pore volume of 0.31 to 0.54cm3The mass content of nitrogen is 4.27-7.43 percent.
13. The adhesive-based nitrogen-containing activated carbon fiber material according to claim 12, wherein the volume of the ultramicropore pores with a pore diameter of less than 1nm accounts for 50 to 65% of the total pore volume, and the volume of the micropore pores with a pore diameter of less than 2nm accounts for 67 to 80% of the total pore volume.
14. Use of the viscose-based nitrogen-containing activated carbon fiber material as claimed in claim 12 or 13, wherein the viscose-based nitrogen-containing activated carbon fiber material is used for CO2Adsorption and CO2/CH4Separation of (4).
15. Use of the viscose-based nitrogen-containing activated carbon fiber material as claimed in claim 14, wherein the viscose-based nitrogen-containing activated carbon fiber material is used for CO2/CH4In the separation of (2), CO2/CH4The selectivity coefficient of (A) is 3.29-5.48.
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