CN115254027B

CN115254027B - Fibrous clay/lignin carbon porous composite material, preparation method and adsorption application

Info

Publication number: CN115254027B
Application number: CN202211033239.XA
Authority: CN
Inventors: 邵礼书; 万欢爱; 詹鹏; 张�林; 吴志平
Original assignee: Central South University of Forestry and Technology
Current assignee: Central South University of Forestry and Technology
Priority date: 2022-08-26
Filing date: 2022-08-26
Publication date: 2023-09-15
Anticipated expiration: 2042-08-26
Also published as: CN115254027A

Abstract

The invention belongs to the field of carbon material preparation, and particularly relates to a preparation method of a fiber clay/lignin carbon porous composite material, which comprises the following steps: step (1): mixing the enzymatic lignin and the fiber clay in a liquid phase, and then performing vacuum freeze drying treatment to obtain a precursor; the fiber type clay mineral is at least one of palygorskite and sepiolite; step (2): the precursor is subjected to first-stage roasting, then the roasting material and the modifier are mixed, second-stage roasting is carried out, and then the fiber clay/lignin carbon porous composite material is obtained after washing and drying; the modifier is at least one of Lewis acid and alkaline substances; the roasting temperature of the first section is 700-900 ℃; the second stage roasting temperature is 600-900 ℃. The invention also provides the material prepared by the preparation method and the application of the material as an adsorbent. The material prepared by the preparation method disclosed by the invention has excellent adsorption performance.

Description

Fibrous clay/lignin carbon porous composite material, preparation method and adsorption application

Technical Field

The invention belongs to the technical field of biomass resource utilization and biomass materials, and particularly relates to the field of pollutant adsorption materials.

Background

Clay minerals are silicate minerals mainly containing aluminum, magnesium and other elements, widely exist in natural environment, are rich in resources and low in cost, have certain special structural properties such as surface adsorption, ion exchange, chemical activity and the like, and are widely applied to various fields such as environmental pollution control and the like, but the adsorption property of the independent mineral materials is limited, so that the preparation of composite materials by taking clay minerals as raw materials becomes a research focus, for example, the preparation of sulfur-doped clay mineral composite materials by taking clay minerals and sulfur-containing compounds as raw materials (patent: CN 109453737A); preparing an attapulgite/carbon nanocomposite (patent: CN 105289495A) and the like by taking attapulgite palm oil decolorized waste soil as a raw material; chinese patent CN103055806A discloses a carbon-coated attapulgite composite material and Chinese patent CN113083228A discloses a preparation method of a carbon-doped sepiolite composite porous adsorption material, and although the clay mineral carbon-containing composite material can be obtained, the carbon source is expensive micromolecular glucose, the cost is high, and the preparation process of the clay composite material still has the problems of not abundant pore structure, uncontrollable morphology, content and distribution of carbon phases, poor combination stability and the like, so that the material has high preparation cost and poor structural controllability.

Lignin is the second largest biomass resource next to cellulose, with carbon content up to 60%, widely available and in huge yields, but more than 90% of industrial lignin is utilized at low values. Lignin can be classified into alkali lignin, lignosulfonate, enzymatic hydrolysis lignin and the like, wherein the enzymatic hydrolysis lignin is not subjected to the separation process of high temperature, high pressure, strong acid, strong alkali and the like, the original chemical activity of the lignin is well reserved, and the ratio of the enzymatic hydrolysis lignin is increased year by year along with the maturation of the biorefinery process. In addition, lignin is a natural organic polymer compound composed of phenylpropane units, contains a large number of active functional groups such as phenyl groups, methoxy groups, conjugated double bonds, and oxygen-containing groups such as hydroxyl groups, carboxyl groups, carbonyl groups and the like, can form a large number of intramolecular and intermolecular hydrogen bonds, and can perform a plurality of chemical reactions such as oxidation, reduction, hydrolysis, polycondensation, graft copolymerization and the like. The lignin is rich and has excellent chemical properties, so that the lignin is used as a carbon source to prepare carbon materials, such as lignin-based trimetallic nitrogen-doped carbon materials (patent: CN 114196989A), lignin-doped metal-organic framework-derived carbon-iron composite materials (patent: CN 113546606A), ordered lignin carbon-carbon nanotube composite materials (patent: CN 113307250A) and the like, become a research hot spot.

In the prior art, a carbon layer of the lignin-based carbon composite material is easy to self-polymerize into balls or irregular particles, coating uniformity is not ideal, and the carbon layer is thicker and not ideal in uniformity, so that the structural stability and the adsorption performance of the composite material can be affected to a certain extent.

Disclosure of Invention

Aiming at the defects of the prior art scheme, the first aim of the invention is to provide a preparation method of a fibrous clay/lignin carbon porous composite material, which aims to prepare a fibrous clay composite new material completely coated by a uniform thin carbon film and further improve the adsorption performance of the prepared material.

The second aim of the invention is to provide the fiber clay/lignin carbon porous composite material prepared by the preparation method.

The third object of the invention is to provide the application of the fiber clay/lignin carbon porous composite material as an adsorption material.

The uniformity of the carbon coating layer of the existing carbon-fiber clay composite material is not ideal, carbon aggregates are easy to form, and the thickness of the coating layer of the carbon layer is large, so that the effect of the carbon-fiber clay composite material in adsorption application is affected. Aiming at the problems existing in the prior art, the invention provides the following scheme:

a preparation method of a fibrous clay/lignin carbon porous composite material comprises the following steps:

step (1): mixing the enzymatic hydrolysis lignin and the fiber clay mineral liquid phase, and then carrying out vacuum freeze drying treatment to obtain a precursor;

step (2): the precursor is subjected to first-stage roasting, then the roasting material and the modifier are mixed, second-stage roasting is carried out, and then the fiber clay/lignin carbon porous composite material is obtained after washing and drying;

the modifier is at least one of Lewis acid and alkaline substances;

the roasting temperature of the first section is 700-900 ℃;

the second stage roasting temperature is 600-900 ℃.

According to the invention, the research discovers that the combination of the special enzymolysis lignin and the raw materials of the fibrous clay mineral is innovatively adopted, and the liquid phase mixing, the vacuum drying and the special two-stage roasting process are further matched, so that the synergy can be realized, the uniform compounding of the carbon material on the clay surface can be unexpectedly induced, the novel composite material with the hierarchical pore structure, which is uniformly coated by the thin carbon film, is formed, and the special new material prepared by the preparation method disclosed by the invention has excellent adsorption capacity and excellent acid resistance and alkali resistance stability.

In the invention, the combination of the enzymolysis lignin, the fibrous clay mineral raw material, the liquid phase compounding, the freeze drying and the first-stage roasting and second-stage roasting processes and parameters is the key of synergistically inducing the uniform compounding of the thin-layer carbon film, constructing the brand new structural material and improving the adsorption performance of the prepared material.

According to the research of the invention, the enzymolysis lignin and the special fiber clay mineral are key to synergistically improve the uniform coating of the thin carbon film and the adsorption capacity and the acid and alkali resistance stability.

Preferably, the fiber clay mineral is at least one of palygorskite and sepiolite; palygorskite is preferred. According to the research of the invention, the palygorskite can be used for unexpectedly obtaining better synergism, and can show better comprehensive adsorption performance.

According to the invention, under the cooperation of the special raw materials, the liquid phase compounding and freeze drying treatment are further matched, so that the novel material with excellent adsorption performance, wherein the thin carbon film is uniformly compounded, can be synergistically improved.

Preferably, in the step (1), the weight ratio of the enzymatic hydrolysis lignin to the fiber clay mineral is 1: 3-3: 1.

preferably, the solvent in the liquid phase mixing stage is at least one of water and alcohol;

preferably, the liquid phase mixing stage is carried out under mechanical stirring and ultrasound; it is further preferred that the liquid phase mixing stage comprises a mechanical agitation performed in advance and a subsequent sonication process. For example, the enzymatic lignin is put in a solvent in advance, and then is mixed with the fiber clay mineral, fully stirred and sonicated, and the obtained mixture is then subjected to vacuum freeze-drying to obtain a precursor. Stirring time is 1-6 h, and ultrasonic is 0.5-1 h.

Preferably, the solid content of the fibrous clay mineral in the solution after liquid phase mixing is 0.01 to 0.5g/mL.

In the invention, the prepared precursor is subjected to first-stage roasting treatment and then is compounded with the modifier to carry out second-stage modification treatment, so that a brand new material which is favorable for uniformly coating the thin carbon film and has excellent adsorption capacity and acid and alkali resistance stability is cooperatively constructed.

In the invention, the first stage roasting and the second stage roasting are carried out under a protective atmosphere, wherein the protective atmosphere is at least one of nitrogen and inert gas;

preferably, the flow rate of the protective atmosphere in the first-stage roasting and the second-stage roasting stages is 40-120 mL/min; preferably 60 to 80mL/min.

Preferably, the temperature rising rate of the first stage roasting and the second stage roasting is 2-6 ℃/min.

In the invention, the precursor is presintered in advance before the first stage of calcination, wherein the presintering temperature is 300-450 ℃, preferably 350-400 ℃;

preferably, the pre-sintering time is 1 to 3 hours.

Preferably, the temperature of the first stage calcination is 700 to 800 ℃, and more preferably 750 to 800 ℃;

preferably, the first stage calcination is carried out for a period of 1 to 3 hours.

In the invention, the combined control of the type and the temperature of the modifier of the second stage roasting is the key for preparing the material in a synergic mode and improving the adsorption capacity and the acid and alkali resistance stability of the material.

In the present invention, the alkaline substance in the modifier is, for example, at least one of hydroxide, carbonate and bicarbonate of an alkali metal.

Preferably, the modifier is AlCl ₃ 、FeCl ₃ 、MgCl ₂ 、ZnCl ₂ 、KOH、NaOH、Na ₂ CO ₃ 、K ₂ CO ₃ At least one of them.

Preferably, the weight ratio of the modifier to the roasting material is 0.5-4:1; preferably 1 to 2:1.

The second stage calcination temperature is preferably 800 to 900 ℃, more preferably 800 to 850 ℃.

Preferably, the second stage calcination is carried out for a period of 1 to 5 hours.

In the invention, after the second stage roasting treatment, washing and drying treatment are carried out to obtain the target product.

Preferably, the washing process includes an acid treatment stage performed in advance and a water washing stage performed later;

preferably, the acid liquor adopted in the acid washing stage is an inorganic strong acid aqueous solution, and the mass percentage concentration of the acid liquor is preferably 2-5%;

preferably, the pickling treatment is carried out for 1.0-12.0 h;

preferably, the filtrate is washed with water to a pH of 6.8 to 7.2.

The invention also provides a fiber type clay/lignin carbon porous composite material prepared by the preparation method, which comprises a one-dimensional clay skeleton and a thin carbon film uniformly coated on the surface of the fiber type clay skeleton;

preferably, the thin carbon film is an amorphous carbon material film;

preferably, the thin carbon layer is an oxygen hybrid carbon, preferably having an oxygen content: 22-31 atm.%;

preferably, the thickness of the thin-layer carbon film is 4.0-20.0 nm;

preferably, the fibrous clay/lignin carbon porous composite material has a hierarchical pore structure comprising micropores, mesopores and macropores; wherein the micropore content is 49.9-71.8%; the mesoporous content is 3.46-20.6%; the specific surface area is 202.3-251.7 m ² /g。

The invention also provides application of the fiber clay/lignin carbon porous composite material, which is used as an adsorption material for adsorbing pollutants;

preferably, it is used as an adsorption material for adsorbing contaminants in gases, liquids;

preferably, the contaminants include gaseous contaminants, preferably at least one of carbon dioxide, iodine vapor, formaldehyde;

preferably, the contaminants include water-soluble, fat-soluble contaminants, preferably at least one of nitrogen and phosphorus, organic dyes, heavy metals.

The application of the invention, for example, the adsorption material is used for adsorbing the soluble harmful components in the water body or the volatile harmful components in the gas. The harmful substances are preferably at least one of radioactive iodine and organic dye; more preferred are iodine vapor and organic solutions of iodine and iodide ions.

Advantageous effects

(1) According to the invention, the research discovers that the combination of the special enzymolysis lignin and the raw materials of the fibrous clay mineral is innovatively adopted, and the liquid phase mixing, the vacuum drying and the special two-stage roasting process are further matched, so that the synergy can be realized, the uniform compounding of the carbon material on the clay surface can be unexpectedly induced, the novel composite material with the hierarchical pore structure, which is uniformly coated by the thin carbon film, is formed, and the special new material prepared by the preparation method disclosed by the invention has excellent adsorption capacity and excellent acid resistance and alkali resistance stability.

(2) The carbon source, namely the enzymolysis lignin, has wide source and low cost, and can realize the resource utilization of waste materials. The invention selects one-dimensional fiber clay as raw material, wherein sepiolite and palygorskite belong to fiber clay, and the fiber clay has a 2:1 fiber rod-shaped structure formed by two layers of silicon oxygen tetrahedrons and one layer of magnesium oxygen octahedron, and the fiber clay is tubular 1:1 dioctahedral structure halloysite, the obtained composite material has more stable chemical property and better adsorption property, and the description of 2: the fiber clay mineral with the 1-type fiber rod-shaped structure is more beneficial to preparing materials with better adsorption effect.

Drawings

FIG. 1 is an SEM image of the enzymatically hydrolyzed lignin of example 1;

FIG. 2 is an SEM image of sepiolite of example 1;

FIG. 3 is an SEM image of palygorskite of example 2;

FIG. 4 is an SEM image of halloysite of comparative example 3;

FIG. 5 is a TEM image of the product of example 1;

FIG. 6 is a TEM image of the product of example 2;

FIG. 7 is a pore size distribution plot of the product of example 1;

FIG. 8 is N of the product of example 1 ₂ Adsorption and desorption curves;

Detailed Description

The following is a specific embodiment of the present invention, and the technical solution of the present invention is further described with reference to the accompanying drawings, but the scope of the present invention is not limited thereto.

The lignin used in the following examples was enzymatically hydrolyzed lignin available from Shandong Dragon technology Co., ltd, was tan powder, and was spherical particles. The used natural nano-scale fiber clay mineral, palygorskite is purchased from Ding Pont mineral products Limited company in Changzhou, jiangsu province, sepiolite is purchased from Hunan Tan source far sepiolite new material stock Limited company, and is in a fiber shape; halloysite is purchased from the company of the biological technology of saminida, western medicine, in the form of blocks and short tubes, all of which belong to one-dimensional nanomaterials. Other lignin such as alkali lignin, lignin sulfonate. Other such reagents and materials are commercially available or may be formulated by conventional methods.

Example 1

Step (1):

weighing 3g of enzymolysis lignin (SEM is shown in figure 1), placing in 75mL of ethanol water solution (v: v=4:1), standing for a period of time, fully stirring for dissolution, adding 1g of sepiolite (SEM is shown in figure 2), stirring at room temperature for 1h, performing ultrasonic treatment for 30min, placing the mixture in a low-temperature refrigerator, freezing, and drying in a freeze dryer to obtain a precursor of the composite material.

Step (2):

and (3) weighing a certain amount of precursors, placing the precursors into a porcelain boat, firstly raising the temperature from room temperature to 400 ℃ (presintering temperature) and preserving the heat for 2 hours under the condition that the flow rate of nitrogen gas is 75mL/min and the heating rate is 5 ℃/min, then raising the temperature to 800 ℃ (first-stage roasting) under the same condition and preserving the heat for 2 hours, and obtaining a roasting material after natural cooling.

Step (3):

taking 1 roasting material, 2g zinc chloride, fully and uniformly mixing, placing the mixture into a porcelain boat, heating to 800 ℃ (the second-stage roasting temperature) at a nitrogen gas flow rate of 75mL/min and a heating rate of 5 ℃/min, preserving heat for 2 hours, naturally cooling, soaking the mixture for 1 hour by using 5wt% HCl, washing the mixture to be neutral by using water, filtering, and drying the obtained solid to obtain the fiber clay/lignin carbon composite material.

TEM of the prepared material is shown in figure 5, and the TEM is a fiber type clay composite new material coated by a uniform thin (4.0-20.0 nm) carbon film, has rich pore diameter and is a multi-layer hole with micropores, mesopores and macropores.

Example 2

The only difference compared to example 1 is that palygorskite is used instead of sepiolite. Other operations and parameters were the same as in example 1. The TEM of the resulting material is shown in fig. 6, which shows that a hierarchical pore material with an ultra-thin carbon layer uniformly coated is obtained.

Example 3

The difference compared to example 1 is only that sepiolite is used in an amount of 3g. Other operations and parameters were the same as in example 1.

Example 4

The only difference compared to example 1 is that the zinc chloride in step (3) is changed to potassium hydroxide. Other operations and parameters were the same as in example 1.

Example 5

The only difference compared to example 1 is that the zinc chloride in step (3) is changed to ferric chloride. Other operations and parameters were the same as in example 1.

Example 6

The difference compared to example 1 is only that the zinc chloride in step (3) is used in an amount of 1g. Other operations and parameters were the same as in example 1.

Example 7

The difference compared with example 1 is that in the step (2), the pre-sintering temperature is 300 ℃ and the first stage roasting temperature is 700 ℃; in the step (3), the second-stage roasting temperature is 900 ℃. Other operations and parameters were the same as in example 1.

Comparative example 1

The only difference compared to example 1 is that alkali lignin is used instead of the enzymatic lignin, and other operations and parameters are the same as in example 1.

Comparative example 2

The only difference compared to example 1 is that sodium lignosulfonate is used instead of the enzymatic lignin, and other operations and parameters are the same as in example 1.

Comparative example 3

The only difference compared to example 1 is that halloysite (SEM see fig. 4) was used instead of sepiolite. Other operations and parameters were the same as in example 1.

Comparative example 4

Compared with the embodiment 1, the difference is that in the step (1), the precursor is obtained by adopting a solid-solid mixing mode, and the step (1) is as follows: weighing 3g of enzymolysis lignin and 1g of sepiolite, placing in a mortar, fully grinding and mixing to obtain a precursor, weighing a certain amount of the precursor, placing in a porcelain boat, and mixing to obtain the precursor.

Comparative example 5

The procedure (1) is different from example 1 only in that the conventional vacuum drying method (drying temperature 50 to 60 ℃ C.) is used instead of the freeze drying method to prepare a precursor, and other operations and parameters are the same as those of example 1.

Comparative example 6

The only difference compared to example 1 is that the second stage firing temperature in step (3) was 500℃and the other operations and parameters were the same as in example 1.

Comparative example 7

The difference from example 1 is that in step 3, no zinc chloride was added and other operations and parameters were the same as in example 1.

Application example 1

20mg of the products of examples 1 to 7 and comparative examples 1 to 7 were weighed, placed in an open glass vial, placed in a 250mL iodometric flask containing excess elemental iodine particles and fitted with a stopper for grinding, placed in a conventional drying oven heated to 78℃at regular intervals, and the weight change of the vial was measured until the weight was substantially unchanged, and the amount of iodine adsorbed by the product was calculated.

Application example 2

10mg of the products in examples 1 to 7 and comparative examples 1 to 7 are weighed, placed in 10ml of 500mg/L iodine-n-hexane solution, and vibrated at a constant temperature of 180rpm/min for 10 hours at 25 ℃, the iodine content in the solution after reaching the adsorption equilibrium is measured, and the adsorption quantity of the products on the iodine-n-hexane is calculated.

Application example 3

10mg of the product in examples 1 to 7 and comparative examples 1 to 7 are weighed, placed in 10ml of 500mg/L iodine ion solution, and vibrated at a constant temperature of 180rpm/min for 10 hours at 25 ℃, the iodine ion content in the solution after adsorption equilibrium is measured, and the adsorption amount of the product to the iodine ions is calculated.

Application example 4

10mg of the products in examples 1 to 7 and comparative examples 1 to 7 are weighed, placed in 10ml of a 500mg/L rhodamine B solution, vibrated for 10 hours at a constant temperature of 180rpm/min at 25 ℃, the rhodamine B content in the solution after reaching adsorption equilibrium is measured, and the adsorption quantity of the product to the rhodamine B is calculated.

Adsorption performance data (Table 1)

Stability of materials

And (3) carrying out stability analysis on the iodine-n-hexane adsorbed by the material, respectively soaking the materials obtained in examples 1-2 in aqueous solution with pH value of 2-12 for 24 hours, filtering, washing to neutrality, drying at 60 ℃, weighing 10mg of sample, placing in 10ml of 500mg/L iodine-n-hexane solution, vibrating at constant temperature of 180rpm/min for 10 hours at 25 ℃, measuring the iodine content in the solution after the adsorption balance is achieved, and calculating the adsorption quantity of the product on the iodine-n-hexane.

Adsorption stability (Table 2)

As can be seen from Table 2, the materials prepared by the present invention have excellent acid and alkali resistance, and can show adsorption performance close to Table 1 when immersed under different pH conditions.

Claims

1. The preparation method of the fibrous clay mineral/lignin carbon porous composite material is characterized by comprising the following steps:

step (1): mixing the enzymatic hydrolysis lignin and the fiber clay mineral liquid phase, and then carrying out vacuum freeze drying treatment to obtain a precursor; the fiber type clay mineral is at least one of palygorskite and sepiolite;

step (2): the precursor is subjected to first-stage roasting, then the roasting material and the modifier are mixed, second-stage roasting is carried out, and then the fiber clay mineral/lignin carbon porous composite material is obtained after washing and drying; the modifier is AlCl ₃ 、FeCl ₃ 、MgCl ₂ 、ZnCl ₂ 、KOH、NaOH、Na ₂ CO ₃ 、K ₂ CO ₃ At least one of (a) and (b);

the roasting temperature of the first section is 700-900 ℃;

the temperature of the second stage roasting is 600-900 ℃.

2. The method of claim 1, wherein in step (1), the weight ratio of the enzymatic lignin to the fiber clay mineral is 1:3~3:1.

3. the process according to claim 1, wherein in the step (1), the solvent in the liquid phase mixing stage is at least one of water and alcohol.

4. The process according to claim 1, wherein in step (1), the liquid phase mixing stage is carried out under mechanical stirring and ultrasound.

5. The process according to claim 4, wherein in step (1), the liquid phase mixing stage comprises mechanical agitation performed in advance and a subsequent ultrasonic treatment process.

6. The method according to claim 1, wherein the solid content of the fiber clay mineral in the solution after liquid phase mixing is 0.01 to 0.5g/mL.

7. The method of claim 1, wherein the first stage calcination and the second stage calcination are performed in a protective atmosphere, and the protective atmosphere is at least one of nitrogen and inert gas.

8. The preparation method of claim 7, wherein the flow rate of the protective atmosphere in the first-stage roasting and the second-stage roasting is 40-120 mL/min.

9. The preparation method of claim 1, wherein the heating rate of the first stage roasting and the second stage roasting is 2-6 ℃/min.

10. The method of claim 1, wherein the precursor is pre-sintered prior to the first stage firing, wherein the pre-sintering temperature is 300-450 ℃.

11. The method of claim 10, wherein the pre-sintering time is 1 to 3 hours.

12. The method of claim 1, wherein the first stage firing temperature is 700-800 ℃.

13. The method of claim 1, wherein the first firing time is 1 to 3 hours.

14. The method of claim 1, wherein the weight ratio of modifier to calcined material is 0.5-4:1.

15. The method of claim 14, wherein the weight ratio of modifier to calcined material is 1-2:1.

16. The method of claim 1, wherein the washing process comprises a pre-performed acid treatment stage and a subsequent water washing stage.

17. The preparation method of claim 16, wherein the acid solution adopted in the acid treatment stage is an inorganic strong acid aqueous solution, and the mass percentage concentration of the acid solution is 2-5%.

18. The method of claim 16, wherein the acid treatment stage is performed for a period of 1.0 to 12.0 hours.

19. The method of claim 16, wherein the filtrate is washed with water to a pH of 6.8 to 7.2.

20. A fibrous clay mineral/lignin carbon porous composite material prepared according to any one of claims 1 to 19, comprising a one-dimensional clay mineral framework and a thin carbon film uniformly encapsulated on the surface of the fibrous clay mineral framework.

21. The fibrous clay mineral/lignin carbon porous composite material according to claim 20 wherein said thin carbon film is an amorphous carbon material film.

22. The fibrous clay mineral/lignin carbon porous composite according to claim 21 wherein said thin layer carbon film is oxygen hybridized carbon.

23. The fibrous clay mineral/lignin carbon porous composite material according to claim 22 wherein the oxygen content of the oxygen hybrid carbon is 22-31 atm.%.

24. The fibrous clay mineral/lignin carbon porous composite material according to claim 20, wherein the thin carbon film has a thickness of 4.0-20.0 nm.

25. The fibrous clay mineral/lignin carbon porous composite material according to claim 20 wherein said fibrous clay mineral/lignin carbon porous composite material has a hierarchical pore structure comprising micropores, mesopores, and macropores; wherein the micropore content is 49.9-71.8%; the mesoporous content is 3.46-20.6%; the specific surface area is 202.3-251.7 m ² /g。

26. Use of a fibrous clay mineral/lignin carbon porous composite material according to any one of claims 20 to 25 as an adsorbent material for adsorbing contaminants.

27. Use according to claim 26 as an adsorbent material for adsorbing contaminants in gases and liquids.

28. The use of claim 27, wherein the contaminants comprise gaseous contaminants.

29. The use of claim 28, wherein the contaminant is at least one of carbon dioxide, iodine vapor, formaldehyde.

30. The use of claim 26, wherein the contaminant comprises a water-soluble, fat-soluble contaminant.

31. The use of claim 30, wherein the contaminant is at least one of nitrogen and phosphorus, an organic dye, and a heavy metal.