CN111203196A - Carboxymethyl magnetic lignin-based biochar and preparation method thereof - Google Patents
Carboxymethyl magnetic lignin-based biochar and preparation method thereof Download PDFInfo
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- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 76
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- 238000000034 method Methods 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 230000005415 magnetization Effects 0.000 claims abstract description 20
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- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims abstract description 8
- 238000007885 magnetic separation Methods 0.000 claims abstract description 5
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- 239000000243 solution Substances 0.000 claims description 40
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
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- 241001330002 Bambuseae Species 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
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- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- 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
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a carboxymethyl magnetic lignin-based biochar and a preparation method thereof2Under the medium protection, the magnetic lignin-based biochar is formed after being micro-carbonized for 2h at the temperature of 350-450 ℃, and then the carboxymethyl magnetic lignin-based biochar is prepared by alkalization and etherification in a medium solution. The carboxymethyl content of the product of the invention is 0.3 mmol.g‑1‑1.2 mmol·g‑1The adsorption value to methylene blue was 294.9 mg g‑1‑432.0 mg·g‑1Is obviously higher than the commercial active carbon, andthe specific surface area can reach 302.0 m2·g‑1. In addition, the product has stable magnetic performance, and the specific saturation magnetization is up to 11.7 emu.g‑1They can be separated by magnetic separation. In addition, the invention has simple process and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of composite material synthesis and the field of environment-friendly adsorbent materials, and relates to carboxymethyl magnetic lignin-based biochar and a preparation method thereof.
Background
Lignin is one of the main components of lignocellulose, mainly comes from agricultural wastes and agricultural industrial byproducts, is a renewable resource with abundant sources and low price, has great application potential from the aspects of economy and environment, and nowadays, the recovery and resource utilization of lignin are spotlighted.
As an adsorbent, the lignin-based biochar has the advantages of low preparation raw material cost, rich pore structure, large specific surface area, highly developed pore structure and strong adsorption capacity, so that the lignin-based biochar is widely applied to the fields of industry, environmental pollution treatment and the like, and is gradually used for replacing other adsorbents with higher cost. However, since unmodified biochar tends to have limitation on selective adsorption, it is one of the means for realizing efficient utilization of biochar adsorbent to explore a modification method for biochar, such as carboxymethyl modification, to increase the surface functional groups of biochar and improve the selective adsorption capacity of biochar to adsorbates. At present, methods for modifying carbon materials such as biochar, activated carbon and the like mainly comprise methods such as organic material graft polymerization such as chitosan, glucose and the like, acid-base modification and the like, wherein the former method is easy to cause pore blockage and reduce the adsorption performance of the organic material graft polymerization, and the latter method is weaker in selective adsorption due to lack of a certain functional group on the surface of the carbon material. However, by performing functional modification such as carboxymethyl modification on the lignin-based carbonaceous material, the lignin-based carbonaceous material is green and environment-friendly, has low cost, and has increased molecular weight and increased carboxyl content, thereby improving the adsorption performance on cationic dyes such as methylene blue and malachite green. In summary, the lignin is used as the base material, and is subjected to carboxymethyl modification after micro-carbonization, so that the porous structure of the carbon material is retained, the functional groups on the surface of the carbon material are greatly increased, and the adsorption performance of the carbon material is effectively improved.
In addition, the powdered carbon has the problems of difficult recovery and regeneration and the like in practical application, so that the application of the powdered carbon in the field of environmental control and other aspects is greatly limited. Compared with the traditional filtration separation method, the magnetic separation is a simple and efficient separation method, can separate substances such as magnetic or magnetizable adsorbents, carriers and the like, and is low in price and simple to operate. Therefore, in recent years, the preparation method and the application of the magnetic carbon become hot spots of domestic and foreign research. At present, the preparation method of the magnetic carbon mainly comprises a one-step method and a two-step method. The two-step method is to prepare the biological carbon or the activated carbon firstly and then load the magnetic iron on the carbon, and the magnetic carbon prepared by the method generally has the defects of small magnetization intensity, poor magnetic performance, pore blockage, small specific surface area and the like. In addition, the one-step method is to add Fe into the base material such as coal, sludge and lignin under alkaline condition3+And Fe2+The magnetic carbon is prepared by compounding the solution at high temperature, and compared with a two-step method, the magnetic carbon prepared by the one-step method has relatively high specific surface area and stable magnetic performance, but the method needs additional alkaline solution, and has high cost and complex process. Therefore, the preparation method of the magnetic biochar, which can realize the magnetization of the biochar and overcome the defects of the prior art, is more and more emphasized by scientific researchers.
In conclusion, the carboxymethyl magnetic lignin-based biochar which is low in cost, high in specific surface area, strong in magnetic property, easy to separate and recover, strong in selective adsorption capacity and capable of efficiently removing pollutants in water has very important economic benefits and environmental significance.
Disclosure of Invention
The invention aims to provide a preparation method of carboxymethyl magnetic lignin-based biochar which has selective adsorption characteristics, strong adsorption capacity on target pollutants, particularly cationic pollutants, easy separation and recovery and low cost, so as to solve the problems of difficult separation, complicated preparation and recovery steps, poor selective adsorption, high cost and the like of the existing activated carbon in a solution, realize the recycling of biomass resources and greatly promote the development of environment-friendly materials.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of carboxymethyl magnetic lignin-based biochar comprises the following steps:
mixing alkali lignin and magnetic agent at a certain ratio, adding a certain amount of surfactant and water, stirring at room temperature, freeze drying to obtain mixture, grinding until particle diameter d is not less than 100 meshes, and flow rate is 80-100 mL/min-1Under the nitrogen atmosphere, the heating rate is 5 ℃ per minute-1Heating to 350-450 ℃, micro-carbonizing for 2h, cooling to room temperature to obtain magnetic lignin-based biochar, mechanically stirring the prepared magnetic biochar in a medium solution at the system temperature of 60 ℃ for 30-50min, adding a certain amount of alkaline solution after uniform mixing, carrying out alkalization reaction for 2-4h at the temperature of 50-70 ℃, then adding a mixed solution consisting of monochloroacetic acid and the medium solution, wherein the concentration of the monochloroacetic acid in the mixed solution is 15-40 wt%, carrying out etherification reaction for 1-5h at the temperature of 70-90 ℃, carrying out magnetic separation after the reaction is finished, collecting a product, repeatedly centrifuging and washing the collected solid with absolute ethyl alcohol and deionized water until the pH value is =6.5-7.5, and obtaining the carboxymethyl magnetic lignin-based biochar.
The carboxymethyl magnetic lignin-based biochar comprises the following raw materials in parts by weight: 87-104 parts of alkali lignin, 87-104 parts of a magnetizing agent, 1-2 parts of a surfactant, 35-62 parts of monochloroacetic acid, 88-103 parts of an alkaline solution and 701 parts of a medium solution.
The alkaline solution is NaOH solution, KOH solution or NH3·H2One or a mixture of more than two of O solution, wherein the concentration of the alkaline solution is 35.0wt% -45.0 wt%.
The alkali lignin is derived from pulping black liquor, the pulping black liquor is prepared from one or more of birch, bagasse, pennisetum hydridum, straw, oak, splendid achnatherum, bamboo, wheat straw, willow, reed, poplar, masson pine and eucalyptus through an alkaline method or a sulfate method, the solid content of the pulping black liquor is 20.0-75.0 wt%, the lignin content is 9.5-35.0 wt%, the density is 1.02-1.38 g/mL, and the required alkali lignin is obtained after separation and purification.
The magnetism-imparting agent is FeCl3·6H2O、Fe（NO3）3·9H2O、Fe2（SO4）3·9H2O or a mixture of two or more of them.
The surfactant is one or a mixture of more than two of sodium dodecyl sulfate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate.
The medium solution is a mixture of one or more of isopropanol, ethanol and water.
The carboxymethyl magnetic lignin-based biochar prepared by the method has the carboxymethyl content of 0.3 mmol-g-1-1.2 mmol·g-1The adsorption value to methylene blue was 294.9 mg g-1-432.0 mg·g-1And the specific surface area can reach 302.0 m2g-1Specific saturation magnetization (Ms) of 11.7 emu g-1。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention takes the alkali lignin as the base material and is a renewable resource with rich source and low price, and the utilization of the alkali lignin responds to the call for circular economy and sustainable development. And the alkaline property of the raw material provides favorable conditions for the excitation of the biochar, and an alkaline solution is not required to be added to meet the preparation conditions, so that the production cost is greatly reduced.
(2) Fe of the invention3+The solution not only serves as a magnetizing agent of the biochar, but also has a catalytic effect and a certain pore regulating effect, can promote the development of mesopores and macropores of the biochar, and improves the adsorption capacity of the biochar on pollutants.
(3) The drying of the invention adopts freeze drying, and the freeze drying leads alkali lignin and Fe3+The solution mixture is in a loose and expanded state after being dried, so that the problems of biochar pore blockage and the like caused by agglomeration, caking and the like in the magnetizing process can be relieved, and the adsorption performance of the solution mixture is improved.
(4) The introduction of carboxymethyl group in the invention enhances the selective adsorption performance of the biochar and greatly improves the adsorption capacity of cationic pollutants.
Drawings
FIG. 1 is an XRD diffraction pattern of carboxymethyl magnetic lignin-based biochar prepared in example 1;
FIG. 2 is an infrared spectrum of the magnetic lignin-based biochar (MB) prepared in example 1 and the carboxymethyl magnetic lignin-based biochar (CMB) prepared in example 1;
FIG. 3 is a VSM hysteresis regression line of carboxymethyl magnetic lignin-based biochar prepared in example 1;
fig. 4 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of the carboxymethyl magnetic lignin-based biochar prepared in example 1.
Detailed Description
The preparation process of the invention comprises the following steps: mixing alkali lignin and magnetic agent at a certain ratio, adding a certain amount of surfactant and water, stirring at room temperature, freeze drying to obtain mixture, grinding until particle diameter d is not less than 100 meshes, and flow rate is 80-100 mL/min-1Under the nitrogen atmosphere, the heating rate is 5 ℃ per minute-1Heating to 350-450 ℃, micro-carbonizing for 2h, cooling to room temperature to obtain magnetic lignin-based biochar, mechanically stirring the prepared magnetic biochar in a medium solution at the system temperature of 60 ℃ for 30-50min, adding a certain amount of alkaline solution after uniform mixing, carrying out alkalization reaction for 2-4h at the temperature of 50-70 ℃, then adding a mixed solution consisting of monochloroacetic acid and the medium solution, wherein the concentration of the monochloroacetic acid in the mixed solution is 15-40 wt%, carrying out etherification reaction for 1-5h at the temperature of 70-90 ℃, carrying out magnetic separation after the reaction is finished, collecting a product, repeatedly centrifuging and washing the collected solid with absolute ethyl alcohol and deionized water until the pH value is =6.5-7.5, and obtaining the carboxymethyl magnetic lignin-based biochar.
The carboxymethyl magnetic lignin-based biochar comprises the following raw materials in parts by weight: 87-104 parts of alkali lignin, 87-104 parts of magnetic agent, 1-2 parts of surfactant, 35-62 parts of monochloroacetic acid, 88-103 parts of alkaline solution and mesoporous material624 portions and 701 portions of the solution. The alkaline solution is NaOH solution, KOH solution or NH3·H2One or a mixture of more than two of O solution, wherein the concentration of the alkaline solution is 35.0-45.0 wt%. The alkali lignin is derived from pulping black liquor, the pulping black liquor is prepared from one or more of birch, bagasse, pennisetum hydridum, straw, oak, splendid achnatherum, bamboo, wheat straw, willow, reed, poplar, masson pine and eucalyptus through an alkaline method or a sulfate method, the solid content of the pulping black liquor is 20.0-75.0 wt%, the lignin content is 9.5-35.0 wt%, the density is 1.02-1.38 g/mL, and the required alkali lignin is obtained after separation and purification. The magnetism-imparting agent is FeCl3·6H2O、Fe（NO3）3·9H2O、Fe2（SO4）3·9H2O or a mixture of two or more of them. The surfactant is one or a mixture of more than two of sodium dodecyl sulfate, sodium lauryl sulfate and sodium dodecyl benzene sulfonate. The medium solution is a mixture of one or more of isopropanol, ethanol and water.
Example 1
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
(1) Weighing 104.0kg of alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2) and 104.0kg of FeCl3·6H2Mixing O and 1.0kg distilled water, adding 2.0kg sodium dodecyl sulfate, stirring at room temperature for 24 hr, freezing in an ultra-low temperature refrigerator at-70 deg.C,freeze drying, grinding the mixture to particle size d =100 mesh, and then flowing at 100mL min-1Under nitrogen atmosphere, at 5 ℃ for min-1Heating to 350 ℃ at a heating rate, slightly carbonizing for 2h, and cooling to room temperature after carbonization to obtain magnetic lignin-based biochar;
(2) mechanically stirring the prepared magnetic lignin-based biochar in 312.0kg of isopropanol solution at the temperature of 60 ℃ for 30min, after the magnetic lignin-based biochar is uniformly mixed, adding 42.0kg of NaOH solution uniformly mixed with 61.0kg of distilled water, carrying out alkalization reaction for 3h at the temperature of 60 ℃, then adding 62.0kg of monochloroacetic acid and 312.0kg of isopropanol mixed solution, and raising the temperature to 80 ℃ for etherification reaction for 5 h. And after the reaction is finished, collecting a product by using a magnet, repeatedly centrifuging and washing the collected solid by using absolute ethyl alcohol and deionized water until the pH is =6.5-7.5, and freeze-drying to obtain the carboxymethyl magnetic lignin-based biochar.
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 1 is 302.0 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 3.4 nm and a specific saturation magnetization of 11.7 emu g-1。
Example 2
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: in example 2, the temperature was controlled at 5 ℃ C. min-1The temperature rises to 400 ℃ at the temperature rising rate for constant-temperature carbonization.
Carboxymethyl magnetic wood prepared in example 2The specific surface area of the cellulose-based biochar is 282.0m2·g-1Pore volume of 0.2cm3·g-1And an average pore diameter of 3.1 nm and a specific saturation magnetization of 11.1emu g-1。
Example 3
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: in example 3, the temperature was controlled at 5 ℃ C. min-1The temperature rises to 450 ℃ at the temperature rising rate for constant-temperature carbonization.
The carboxymethyl magnetic lignin-based biochar prepared in example 3 has a specific surface area of 279.0 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 4.2 nm and a specific saturation magnetization of 11.0 emu g-1。
Example 4
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of bamboo and bagasse alkali lignin, the mass ratio is 1: 2): 87.0kg
FeCl3·6H2O：87.0kg
Sodium lauryl sulfate: 1.0kg
Monochloroacetic acid: 35.0kg
Isopropyl alcohol: 701.0kg
NaOH：35.0kg
Distilled water: 54.0kg
2. Preparation process steps and parameters
(1) Weighing 87.0kg of alkali lignin (mixture of bamboo and bagasse alkali lignin, the mass ratio is 1: 2) and 87.0kg of FeCl3·6H2Mixing O and 1.0kg distilled water, adding 1.0kg sodium dodecyl sulfate, stirring at room temperature for 24 hr, freezing in an ultra-low temperature refrigerator at-70 deg.C, freeze drying, grinding to particle size d =100 mesh, and flowing at 100 mL/min-1Under nitrogen atmosphere, at 5 ℃ for min-1Heating to 350 ℃ at a heating rate, slightly carbonizing for 2h, and cooling to room temperature after carbonization to obtain magnetic lignin-based biochar;
(2) mechanically stirring the prepared magnetic lignin-based biochar in 525.7kg of isopropanol solution at the temperature of 60 ℃ for 30min, after the magnetic lignin-based biochar is uniformly mixed, adding 35.0kg of NaOH solution uniformly mixed with 53.0kg of distilled water, carrying out alkalization reaction for 2h at the temperature of 60 ℃, then adding 35.0kg of monochloroacetic acid and 175.3kg of isopropanol mixed solution, and raising the temperature to 70 ℃ for etherification reaction for 1 h. And after the reaction is finished, collecting a product by using a magnet, repeatedly centrifuging and washing the collected solid by using absolute ethyl alcohol and deionized water until the pH is =6.5-7.5, and freeze-drying to obtain the carboxymethyl magnetic lignin-based biochar.
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 4 is 262.0 m2·g-1Pore volume of 0.5cm3·g-1And an average pore diameter of 2.8 nm and a specific saturation magnetization of 9.8 emu g-1。
Example 5
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of reed and bamboo alkali lignin, mass ratio is 1: 5): 87.0kg
FeCl3·6H2O：87.0kg
Sodium lauryl sulfate: 1.0kg
Monochloroacetic acid: 35.0kg
Isopropyl alcohol: 701.0kg
NaOH：35.0kg
Distilled water: 54.0kg
2. Preparation process steps and parameters
(1) Weighing 87.0kg of alkali lignin (mixture of reed and bamboo alkali lignin, mass ratio is 1: 5) and 87.0kg of FeCl3·6H2Mixing O and 1.0kg distilled water, adding 1.0kg sodium dodecyl sulfate, stirring at room temperature for 24 hr, freezing in an ultra-low temperature refrigerator at-70 deg.C, freeze drying, grinding to particle size d =100 mesh, and flowing at 100 mL/min-1Under nitrogen atmosphere, at 5 ℃ for min-1Heating to 350 ℃ at a heating rate, slightly carbonizing for 2h, and cooling to room temperature after carbonization to obtain magnetic lignin-based biochar;
(2) mechanically stirring the prepared magnetic lignin-based biochar in 525.7kg of isopropanol solution at the temperature of 60 ℃ for 30min, after the magnetic lignin-based biochar is uniformly mixed, adding 35.0kg of NaOH solution uniformly mixed with 53.0kg of distilled water, carrying out alkalization reaction for 3h at the temperature of 60 ℃, then adding 35.0kg of monochloroacetic acid and 175.3kg of isopropanol mixed solution, and raising the temperature to 80 ℃ for etherification reaction for 5 h. And after the reaction is finished, collecting a product by using a magnet, repeatedly centrifuging and washing the collected solid by using absolute ethyl alcohol and deionized water until the pH is =6.5-7.5, and freeze-drying to obtain the carboxymethyl magnetic lignin-based biochar.
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 5 is 280.0 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 2.8 nm and a specific saturation magnetization of 11.6 emu g-1。
Example 6
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (masson pine alkali lignin): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 1.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
(1) 104.0kg of alkali lignin (masson pine alkali lignin) and 104.0kg of FeCl were weighed3·6H2Mixing O and 1.0kg distilled water, adding 2.0kg sodium dodecyl sulfate, stirring at room temperature for 24 hr, freezing in an ultra-low temperature refrigerator at-70 deg.C, freeze drying, grinding to particle size d =100 mesh, and flowing at 100 mL/min-1Under nitrogen atmosphere, at 5 ℃ for min-1Heating to 350 ℃ at a heating rate, slightly carbonizing for 2h, and cooling to room temperature after carbonization to obtain magnetic lignin-based biochar;
(2) mechanically stirring the prepared magnetic lignin-based biochar in 312.0kg of isopropanol solution at the system temperature of 60 ℃ for 30min, after the magnetic lignin-based biochar is uniformly mixed, adding 42.0kg of NaOH solution uniformly mixed with 61.0kg of distilled water, carrying out alkalization reaction for 4h at 70 ℃, then adding 62.0kg of monochloroacetic acid and 312.0kg of isopropanol mixed solution, and raising the temperature to 90 ℃ for etherification reaction for 1 h. And after the reaction is finished, collecting a product by using a magnet, repeatedly centrifuging and washing the collected solid by using absolute ethyl alcohol and deionized water until the pH is =6.5-7.5, and freeze-drying to obtain the carboxymethyl magnetic lignin-based biochar.
The carboxymethyl magnetic lignin-based biochar prepared in example 6 has a specific surface area of 255.0 m2·g-1Pore volume of 0.5cm3·g-1And an average pore diameter of 4.9 nm and a specific saturation magnetization of 10.0 emu g-1。
Example 7
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the surfactant described in example 7 was sodium lauryl sulfate.
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 7 is 290.1 m2·g-1Pore volume of 0.6cm3·g-1And an average pore diameter of 2.7 nm and a specific saturation magnetization of 11.2 emu g-1。
Example 8
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
A mixture of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate (mass ratio is 1: 1): 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the surfactant described in example 8 is a mixture of sodium dodecylbenzenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 1.
The carboxymethyl magnetic lignin-based biochar prepared in example 8 has a specific surface area of 299.3 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 2.2 nm and a specific saturation magnetization of 11.3 emu g-1。
Example 9
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
Fe（NO3）3·9H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the magnetic-imparting agent described in example 9 was Fe (NO)3）3·9H2O。
The carboxymethyl magnetic lignin-based biochar prepared in example 9 has a specific surface area of 289.9 m2·g-1Pore volume of 0.4cm3·g-1And an average pore diameter of 2.6 nm and a specific saturation magnetization of 10.9 emu g-1。
Example 10
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
Fe2（SO4）3·9H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the magnetic-imparting agent described in example 10 was Fe2(SO4)3·9H2O。
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 10 is 302.0 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 3.4 nm and a specific saturation magnetization of 11.7 emu g-1。
Example 11
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
KOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the basic solution described in example 11 is a KOH solution.
The carboxymethyl magnetic lignin-based biochar prepared in example 11 has a specific surface area of 281.9 m2·g-1Pore volume of 0.4cm3·g-1And an average pore diameter of 2.7 nm and a specific saturation magnetization of 9.9 emu g-1。
Example 12
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Isopropyl alcohol: 624.0kg
NH3·H2O：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the alkaline solution described in example 12 is NH3·H2And (4) O solution.
Carboxymethyl magnetic lignin-based biochar prepared in example 12Has a specific surface area of 259.1 m2·g-1Pore volume of 0.2cm3·g-1And an average pore diameter of 4.6 nm and a specific saturation magnetization of 10.6 emu g-1。
Example 13
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Ethanol: 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: the reaction medium solution described in example 13 is ethanol.
The specific surface area of the carboxymethyl magnetic lignin-based biochar prepared in example 13 is 302.0 m2·g-1Pore volume of 0.2cm3·g-1And an average pore diameter of 1.9 nm and a specific saturation magnetization of 9.7 emu g-1。
Example 14
1. The raw material components used in this example were as follows (unit-kg):
alkali lignin (mixture of rice straw and masson pine alkali lignin, the mass ratio is 3: 2): 104.0kg
FeCl3·6H2O：104.0kg
Sodium lauryl sulfate: 2.0kg
Monochloroacetic acid: 62.0kg
Mixed liquor of distilled water and ethanol (mass ratio is 1: 2): 624.0kg
NaOH：42.0kg
Distilled water: 62.0kg
2. Preparation process steps and parameters
This example is prepared in essentially the same manner as example 1, except that: in example 14, the reaction medium solution was a mixture of water and ethanol at a mass ratio of 1: 2.
The carboxymethyl magnetic lignin-based biochar prepared in example 14 has a specific surface area of 257.0 m2·g-1Pore volume of 0.2cm3·g-1And an average pore diameter of 3.5 nm and a specific saturation magnetization of 9.3 emu g-1。
Performance testing
1. Characterization analysis of carboxymethyl magnetic lignin-based biochar and magnetic lignin-based biochar
The carboxymethyl magnetic lignin-based biochar and the magnetic lignin-based biochar obtained by the experiment are subjected to structural analysis through XRD, FT-IR, VSM and BET characterization and determination.
FIG. 1 shows that the carboxymethyl magnetic lignin-based biochar prepared in example 1 has diffraction spectrum peaks at 2 theta of 30.4 degrees, 35.2 degrees, 43.6 degrees, 57.7 degrees and 62.9 degrees, and compared with standard PDF cards (JCPDS No. 65-3107) in report databases, the characteristic peaks belong to Fe3O4The crystal in the sample is stated to be Fe3O4The magnetism of which is made of Fe3O4And (4) causing.
FIG. 2 shows the spectrum of the magnetic lignin-based biochar at 1590.0cm after carboxymethyl modification compared to that before carboxymethyl modification in example 1-1At a sum of 1401.5 cm-1Obvious absorption characteristic peaks appear at the position, respectively-COO appears-And the antisymmetric stretching vibration absorption peak and the symmetric stretching vibration absorption peak of the optical fiber. The carboxyl group in the carboxylate is 1616.0 cm-1-1540.0 cm-1And 1450.0 cm-1-1400.0 cm-1Two characteristic absorption bands appear in between. And then the magnetic lignin-based biochar modified by carboxymethyl is 2927.6 cm-1Stretching vibration peaks of methyl, methylene and methine appear nearby. By comparison, the experiment proves that the carboxymethyl is successfully grafted to the magnetic lignin-based biochar. Before and after the carboxymethyl modification, the concentration was 570.8 cm-1And 548.2 cm-1An absorption characteristic peak appears due to the presence of Fe-O bonds.
FIG. 3 shows that the specific saturation magnetization (Ms) of the carboxymethyl magnetic lignin-based biochar prepared in example 1 is 11.7 emu g-1The remanence (Mr) is 0.2 emu g-1The coercivity (Hc) was 50.2 Oe, indicating that this biochar can be separated from solution using a permanent magnet.
Fig. 4 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of the carboxymethyl magnetic lignin-based biochar prepared in example 1. Wherein the carboxymethyl magnetic lignin-based biochar prepared in example 1 has a specific surface area of 302.0 m2·g-1Pore volume of 0.3cm3·g-1And an average pore diameter of 3.4 nm.
2. Carboxymethyl content determination result in carboxymethyl magnetic lignin-based biochar
The method for measuring the content of carboxymethyl in the carboxymethyl magnetic lignin-based biochar specifically comprises the step of measuring the content of carboxymethyl in the carboxymethyl magnetic lignin-based biochar prepared in examples 1 to 14 by using a potentiometric titrator (916 Ti-Touch). 0.1g of the carboxymethyl magnetic lignin-based biochar prepared in examples 1 to 14 was respectively weighed and dispersed in 100mL of 1 mmol. multidot.L-1In NaCl solution, ultrasonic treatment is carried out for 30min at room temperature to uniformly disperse the sample, and NaOH (1 mmol. L) is used-1) The sample was titrated until an equivalence point was observed, which is the volume used by NaOH to neutralize the carboxyl groups in the sample. Each sample was subjected to three parallel experiments, and the carboxymethyl group content (mmol. g) was calculated according to the formula (1)-1）：
Carboxymethyl content (mmol. g)-1）= Cn*Vn /m （1）
In the formula (1), the reaction mixture is,
cn is the concentration of NaOH, mmol. L-1；
Vn is the volume, mL, used by NaOH to neutralize the carboxymethyl groups in the sample;
m is the mass of the carboxymethyl lignin-based biochar in an absolute dry state, g.
The carboxymethyl group content in the carboxymethyl magnetic lignin-based biochar prepared in examples 1-14 is shown in the following table:
TABLE 1 carboxymethyl magnetic lignin-based biochar carboxymethyl content
3. Application of carboxymethyl magnetic lignin-based biochar in removal of methylene blue printing wastewater
The application of carboxymethyl magnetic lignin-based biochar in removing methylene blue dye wastewater is characterized in that methylene blue adsorption values of carboxymethyl magnetic lignin-based biochar prepared in examples 1-14 and magnetic lignin-based biochar prepared in step (1) of examples 1-3 are measured by a methylene blue adsorption value measuring method specified in GB/T12496.10-1999, and the results are shown in the following table:
TABLE 2 simulated wastewater adsorption values of magnetic lignin-based biochar on methylene blue before and after carboxymethyl modification
Remarking: the products in table 2, example 1 (1), example 2 (1), example 3 (1) represent the magnetic lignin-based biochar prepared in step (1) of examples 1-3, respectively.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention.
Claims (9)
1. The preparation method of the carboxymethyl magnetic lignin-based biochar is characterized by comprising the following steps:
mixing alkali lignin and magnetic agent at a certain ratio, adding a certain amount of surfactant and water, stirring at room temperature, freeze drying to obtain mixture, grinding until particle diameter d is not less than 100 meshes, and flow rate is 80-100 mL/min-1Under the nitrogen atmosphere, the heating rate is 5 ℃ per minute-1Heating to 350-450 deg.C, micro-carbonizing for 2h, cooling to room temperature to obtain magnetic biochar, and making into magnetic biocharMechanically stirring the mixture for 30-50min in a medium solution at the temperature of 60 ℃, adding a certain amount of alkaline solution after the mixture is uniformly mixed, carrying out alkalization reaction for 2-4h at the temperature of 50-70 ℃, then adding a mixed solution consisting of monochloroacetic acid and the medium solution, wherein the concentration of monochloroacetic acid in the mixed solution is 15-40 wt%, carrying out etherification reaction for 1-5h at the temperature of 70-90 ℃, collecting a product by a magnetic separation method after the reaction is finished, and repeatedly centrifuging and washing the collected solid by absolute ethyl alcohol and deionized water until the pH is =6.5-7.5 to obtain the carboxymethyl magnetic lignin-based biochar.
2. The method of claim 1, wherein: the carboxymethyl magnetic lignin-based biochar comprises the following raw materials in parts by weight: 87-104 parts of alkali lignin, 87-104 parts of a magnetizing agent, 1-2 parts of a surfactant, 35-62 parts of monochloroacetic acid, 88-103 parts of an alkaline solution and 701 parts of a medium solution.
3. The method of claim 2, wherein the alkaline solution is NaOH solution, KOH solution, or NH3·H2One or a mixture of more than two of O solution, wherein the concentration of the alkaline solution is 35.0wt% -45.0 wt%.
4. The production method according to claim 1 or 2, characterized in that: the alkali lignin is derived from pulping black liquor, the pulping black liquor is prepared from one or more of birch, bagasse, pennisetum hydridum, straw, oak, splendid achnatherum, bamboo, wheat straw, willow, reed, poplar, masson pine and eucalyptus through an alkaline method or a sulfate method, the solid content of the pulping black liquor is 20.0-75.0 wt%, the lignin content is 9.5-35.0 wt%, the density is 1.02-1.38 g/mL, and the required alkali lignin is obtained after separation and purification.
5. The method according to claim 1 or 2, wherein the magnetism-imparting agent is FeCl3·6H2O、Fe（NO3）3·9H2O、Fe2（SO4）3·9H2O or a mixture of two or more of them.
6. The method according to claim 1 or 2, wherein the surfactant is one or a mixture of two or more of sodium dodecyl sulfate, sodium lauryl sulfate, and sodium dodecyl benzene sulfonate.
7. The method according to claim 1 or 2, wherein the medium solution is a mixture of one or more of isopropyl alcohol, ethanol and water.
8. The method according to claim 1, wherein the carboxymethyl-magnetic lignin-based biochar has a carboxymethyl group content of 0.3 mmol-g-1-1.2 mmol·g-1The adsorption value to methylene blue was 294.9 mg g-1-432.0 mg·g-1And the specific surface area is as high as 302.0 m2·g-1The specific saturation magnetization is up to 11.7 emu g-1。
9. The carboxymethyl magnetic lignin-based biochar prepared by the preparation method of claim 1.
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| CN113019334A (en) * | 2021-03-11 | 2021-06-25 | 东北林业大学 | Preparation of modified lignin magnetic composite material and method for removing dye in wastewater by using modified lignin magnetic composite material |
| CN113332955A (en) * | 2021-06-04 | 2021-09-03 | 国际竹藤中心 | Magnetic activated carbon and preparation method, regeneration method and application thereof |
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