CN117125709A - Carbon-fixing material, preparation method thereof, composite carbon-fixing material and carbon-fixing cement-based material - Google Patents
Carbon-fixing material, preparation method thereof, composite carbon-fixing material and carbon-fixing cement-based material Download PDFInfo
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Classifications
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- 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
- C01B32/318—Preparation characterised by the starting materials
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- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
Abstract
The application relates to the technical field of environment-friendly materials, in particular to a carbon-fixing material, a preparation method thereof, a composite carbon-fixing material and a carbon-fixing cement-based material. The preparation method of the carbon-fixing material comprises the steps of carrying out spray drying treatment on a solution containing particles of plant substances to obtain carbon precursor particles; carbonizing the carbon precursor particles to obtain biochar particles; mixing an activating agent and/or a template agent with biochar particles, and sintering in a protective atmosphere to obtain the porous carbon-fixing material containing polycyclic aromatic hydrocarbon. The prepared carbon-fixing material has various shapes such as concave carbon spheres, rings and the like on microcosmic scale, and the whole carbon-fixing material has rich pore structures and higher specific surface areas, and has far better trapping and sealing effects on carbon dioxide than the existing biochar. The composite carbon-fixing material comprises a carbon-fixing material and graphene oxide, and can be synergistic. The carbon-fixing cement-based material comprises cement and a carbon-fixing material or a composite carbon-fixing material.
Description
Technical Field
The application relates to the technical field of environment-friendly materials, in particular to a carbon-fixing material, a preparation method thereof, a composite carbon-fixing material and a carbon-fixing cement-based material.
Background
Research on carbon-fixing materials has been a very popular direction. The method for preparing the biochar from the biomass is an effective method, firstly, the biochar prepared from the biomass is a carbon-fixing form, and the prepared biochar can be deeply buried underground or used in the existing materials; in addition, there are applications for carbon dioxide capture and sequestration using the porous structure of biochar. In order to improve the effect of capturing and sealing carbon dioxide by the porous biochar, most of preparation methods are carried out by sintering biomass, and researches show that an activating agent can be added for further activation during sintering, so that the porosity, specific surface area and the like of the prepared biochar can be improved, but the carbon fixing effect on carbon dioxide still needs to be further enhanced.
In the prior art, there is also a method for carbon fixation by using a cement-based material, which comprises the following steps of (1) direct solidification: the cement-based material is directly contacted with carbon dioxide to cause carbonization reaction to form carbonized concrete. (2) admixture: additives such as biomass charcoal and the like are added to cement raw materials to improve the effect of capturing and sequestering carbon dioxide, and to enhance the stability and durability of cement-based materials. However, there are still many problems with cement-based carbon fixation, such as (1) low carbon sequestration efficiency of directly carbonized concrete and reduced properties (strength, corrosion resistance) of the carbonized concrete; (2) The preparation of biochar for cement-based materials is limited by the specific surface area, pore volume, dispersibility in cement and other properties, and proper processes are needed for improvement, so that the carbon fixation efficiency in cement materials is improved.
Disclosure of Invention
The application aims to provide a carbon-fixing material, a preparation method thereof and a composite carbon-fixing material, and aims to solve the technical problem that the carbon-fixing material has poor effect of capturing and sealing carbon dioxide in the prior art.
The application further aims to provide a carbon-fixing cement-based material, which aims to solve the technical problems that the carbon dioxide trapping and sealing rate is low, the final performance is affected, the combination effect of cement and biochar is not ideal, and the carbon-fixing effect is not high when the existing cement-based material is used for carbon fixing.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a carbon-fixing material. The preparation method comprises the following steps:
spray drying the solution containing the particles of plant matter to obtain carbon precursor particles;
carbonizing the carbon precursor particles to obtain biochar particles;
mixing at least one of an activating agent and a template agent with biochar particles, and sintering in a protective atmosphere to obtain the porous carbon-fixing material containing polycyclic aromatic hydrocarbon.
According to the preparation method of the carbon-fixing material, the carbon precursor particles which are spherical in microcosmic are prepared through spray drying treatment, and the dispersion is good, so that the biochar particles obtained through carbonization treatment are spherical in microcosmic and good in dispersion. The obtained biochar particles are modified through sintering treatment by at least one of an activating agent or a template agent, so that the generated carbon-fixing material microscopically presents various shapes such as concave carbon spheres, circular rings and the like, and the whole has rich pore structures, thereby having higher specific surface area. And the polycyclic aromatic hydrocarbon contained in the carbon-fixing material further improves the trapping and sealing effects on carbon dioxide. The preparation method improves the sealing effect of the prepared carbon-fixing material on carbon dioxide, and the effect is far better than that of the existing biochar material. The preparation method has controllable process, and the prepared carbon-fixing material has stable property.
In a second aspect, the present application provides a carbon-fixing material. The carbon-fixing material is prepared by the preparation method.
The carbon-fixing material provided by the embodiment of the application is prepared by the preparation method of the embodiment of the application, so that the carbon-fixing material has various shapes such as concave carbon spheres, circular rings and the like on microcosmic scale, and has a rich pore structure as a whole, so that the carbon-fixing material has a higher specific surface area, and the capturing and sealing effects on carbon dioxide are better than those of the existing biochar material.
In a third aspect, the present application provides a composite carbon-fixing material. The composite carbon-fixing material comprises a carbon-fixing material and graphene oxide which is mixed with the carbon-fixing material.
The composite carbon-fixing material has a synergistic effect due to the fact that the composite carbon-fixing material comprises the carbon-fixing material and graphene oxide (namely GO). After the carbon-fixing material and the GO are mixed, the GO is adhered to the carbon-fixing material, which is beneficial to improving the CO 2 The adsorption of the composite carbon-fixing material is good in dispersibility, and compared with the prior art, the composite carbon-fixing material has stronger CO when being mixed with the biochar and the GO 2 Trapping and sealing effects.
In a fourth aspect, the present application provides a carbon-fixed cement-based material. The carbon-fixing cement-based material comprises the following components in parts by weight:
and (3) cement: 800-1200 parts;
carbon fixing agent: 5-15 parts;
sand: 2400-3600 parts;
water: 400-600 parts;
water reducing agent: 0.05 to 0.15 part;
the carbon fixing agent comprises the carbon fixing material prepared by the preparation method, or comprises the carbon fixing material or comprises the composite carbon fixing material.
The carbon-fixing cement-based material comprises cement and a carbon-fixing agent, namely the carbon-fixing agent is added into the cement-based material, and the carbon-fixing agent is coatedThe carbon-fixing material or the composite carbon-fixing material of the application endows the carbon-fixing cement-based material with CO trapping and sealing 2 Ca in the pore liquid of the carbon-fixed cement-based material 2+ With CO 2 Reacting to generate CaCO 3 Thereby promoting the capture and the sequestration of CO 2 Is to simultaneously generate CaCO 3 The pores are thinned, and the carbon fixing agent also promotes the hydration of cement and improves the strength of the carbon fixing cement-based material. In addition, the carbon-fixing material and the composite carbon-fixing material have good dispersibility, so that the composite carbon-fixing material has good dispersibility in cement. Compared with the prior art, the cement-based carbon-fixing material seals CO 2 The effect of the carbon-fixing cement-based material is greatly improved, and the problem that the strength of cement is reduced as the prior art biochar is added into cement is solved, so that the strength of the carbon-fixing cement-based material is not negatively influenced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of biochar particles obtained by spray drying and carbonization according to example A1 of the present application;
FIG. 2 is an SEM image of a carbon-fixing material of example A1 of the present application;
FIG. 3 is an SEM image of a composite carbon-fixing material of example B1 of the present application;
FIG. 4 is a partial sample of CO in example C1 of the present application 2 Adsorption test result diagram;
FIG. 5 shows the CO of the samples prepared in examples C1, C4, comparative examples C3, C4 according to the application 2 Adsorption test result diagram.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass in the specification of the embodiment of the application can be a mass unit which is known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a preparation method of a carbon-fixing material. The preparation method of the embodiment of the application comprises the following steps:
s10: spray drying the solution containing the particles of plant matter to obtain carbon precursor particles;
s20: carbonizing the carbon precursor particles to obtain biochar particles;
s30: mixing at least one of an activating agent and a template agent with biochar particles, and sintering in a protective atmosphere to obtain the porous carbon-fixing material containing polycyclic aromatic hydrocarbon.
The preparation method of the carbon-fixing material improves the existing preparation method of the biochar, and carbon precursor particles which are spherical in microcosmic and good in dispersibility are prepared through spray drying treatment, so that the biochar particles obtained through carbonization treatment are spherical in microcosmic and good in dispersibility, as shown in figure 1. Firstly, the obtained biochar particles are modified through sintering treatment by at least one of an activating agent or a template agent, so that the prepared carbon-fixing material microscopically presents various morphologies such as concave carbon spheres, circular rings and the like (as shown in figure 2), and the whole carbon-fixing material has a rich pore structure, so that the carbon-fixing material has a higher specific surface area and is beneficial to capturing and sealing carbon dioxide gas. Secondly, the prepared carbon-fixing material is used for CO 2 The nonpolar material has strong affinity, and oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, etc. contained in plant material can generate a large number of polar bonds during pyrolysis and rearrangement reactionPolar bond at sexual terminal can adsorb CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Finally, after carbonization and sintering treatment, organic compounds such as cellulose, hemicellulose, lignin and the like in the plant materials are cracked, saccharides and phenolic compounds in the plant materials are released, and the micromolecular organic compounds are pyrolyzed, dehydrated and carbonized to form polycyclic aromatic hydrocarbons with aromatic structures, particularly the polycyclic aromatic hydrocarbons on the surface of the carbon-fixing material are electronegative, and have stronger electron-withdrawing capability, when CO 2 The molecules move parallel to the surface of the carbon-fixing material, and due to electrostatic effect, the CO 2 Can be adsorbed on the surface of the carbon-fixing material. Therefore, the preparation method of the embodiment of the application improves the capturing and sealing effect of the carbon dioxide of the prepared carbon-fixing material, and the effect is far better than that of the existing biochar material. The preparation method has controllable process, and the prepared carbon-fixing material has stable property.
Step S10:
compared with common grinding and other modes in the prior art, the preparation method provided by the embodiment of the application is changed into a spray drying treatment mode, so that the prepared carbon precursor particles are microscopically spherical and have good dispersibility, the biochar particles obtained by subsequent further carbonization treatment are spherical and have good dispersibility, as shown in figure 1, the preparation method is favorable for finally preparing the carbon-fixing material with good dispersibility and large specific surface area, and the effect of carbon dioxide sealing is improved.
In some embodiments, the plant matter may include pine needles or broadleaf plant leaves. Compared with the preparation of biochar by using biomass raw materials such as straw and the like, the embodiment of the application selects needle leaves and broadleaf plant leaves with high lignin and cellulose content, has higher char yield, and simultaneously increases the porosity and specific surface area of the prepared carbon-fixing material. The particles of the plant material can be prepared by grinding after drying, and can be specifically prepared into 50-80 mesh powder.
During spray drying treatment, the mass volume ratio of the particles of the plant matter to the water in the solution can be 75-200 g: 500-1000 mL, which may include, but is not limited to (75, 100, 130, 170, 200) g: (500, 600, 700, 800, 900, 1000) mL, which are advantageous for improving the spray drying treatment effect and improving the dispersibility of the produced carbon precursor particles. In some embodiments, the spray drying process may be performed with a spray dryer, and may include at least one of the following conditions (1) to (5):
(1) The atomizing air threshold temperature is 250-300 ℃, which may include, but is not limited to, 250 ℃, 270 ℃, 290 ℃, 300 ℃ in an exemplary example;
(2) The atomization pressure is 0.1-0.2 MPa, and in the exemplary examples, the atomization pressure can comprise, but is not limited to, 0.1MPa, 0.15MPa and 0.2MPa;
(3) The atomization rate is 1200-1500 mL/h, and in an exemplary example, the atomization rate can comprise, but is not limited to, 1200mL/h, 1300mL/h, 1400mL/h and 1500mL/h;
(4) The flow rate of the atomized air is 25-35 m 3 /h, exemplary examples may include, but are not limited to, 25m 3 /h、30m 3 /h、35m 3 /h；
(5) The temperature of the spray-dried outlet gas-powder mixture is 120-150 ℃, which may include, but is not limited to, 120 ℃, 130 ℃, 140 ℃, 150 ℃ in an exemplary example.
These conditions are advantageous for improving the spray drying treatment effect and improving the dispersibility of the prepared carbon precursor particles.
Step S20:
the step is a step of carbonizing to obtain biochar particles, wherein the carbonizing can be heating the carbon precursor particles to 300-400 ℃ in an oxygen-isolated protective atmosphere to carry out pyrolysis reaction to obtain the biochar particles, the carbonizing time can be 1-3 h, and in the example, the carbonizing can include but is not limited to 1h, 2h and 3h, and the carbonizing can be heating in a muffle furnace. The carbon precursor particles are obtained through spray drying treatment, are microscopically spherical and have good dispersibility, so that the prepared biochar particles are microscopically spherical and have good dispersibility, and have large specific surface area, as shown in figure 1, so that the carbon-fixing material with good carbon dioxide capturing and sealing effects can be further prepared.
Step S30:
the step is a step of further processing the biochar particles to generate the porous structure carbon-fixing material. The mixing treatment can be to sufficiently mix and disperse at least one of the activator and the template agent and the biochar particles in a grinding way, so that the activator, the template agent and the biochar particles are sufficiently combined, and the template effect is activated and exerted. Water may also be added to the mixing process.
In some embodiments, the activator comprises KOH, KHCO 3 、NaOH、HF、H 3 PO 4 At least one of them. The activator is used for reacting with carbon in the biochar to generate various gas byproducts in the sintering treatment process, and a large amount of gas is released to raise the internal pressure in the biochar particles, so that a plurality of tiny holes are formed in the biochar particles, a highly distributed dense porous structure is formed, the porosity of the biochar particles can be further increased, and the total micropore volume and the total specific surface area of the carbon-fixing material obtained after the biochar particles are activated by the activators can be obviously increased. The mass ratio of the biochar particles to the activating agent is 1:5 to 1:10, in an exemplary embodiment, the mass ratio may include, but is not limited to, 1: 5. 1: 7. 1:8. 1:10, the ratio ensures the activation effect, and the activator may include water when used, so as to improve the dispersion effect of the activator and the biochar particles, and the activation effect may be, for example, a KOH solution.
In some embodiments, the templating agent comprises CaO, mgO, znO, al 2 O 3 At least one of them. The main function of the template is to make pores through the hard template and finally remove to make a rich pore structure on the biochar particles. In addition, a part of the template agent can also play a small amount of role in activation. Taking CaO as an example, caO can be introduced into a hard template pore canal during mixing treatment, and then water is added to convert the CaO into slightly soluble Ca (OH) 2 CaCO can be firstly generated in the nano pore canal through sintering treatment 3 Crystals, followed by CaCO 3 And converting the CaO into CaO, filling the CaO obtained by conversion into a pore canal, washing the pore canal with acid or deionized water, and drying to remove the hard template, thereby creating corresponding mesopores in the biochar particles, and obtaining the carbon-fixing material with a porous structure, wherein the prepared carbon-fixing material can keep the pore canal morphology of the original template. Thereby improving the capturing and sealing effect of the carbon dioxide of the prepared carbon-fixing material. Some of the followingIn an embodiment, the mass ratio of the biochar particles to the template agent may be 1: 3-1: 5, in an exemplary embodiment, the mass ratio may include, but is not limited to, 1: 3. 1: 4. 1: and 5, the mass ratios can improve the pore-forming effect of the template agent.
In some embodiments, the protective atmosphere of the sintering process includes at least one of nitrogen, argon, helium, hydrogen. The gases can isolate oxygen, which is beneficial to the full action of the activating agent or the template agent on the biochar particles and is also beneficial to the further carbonization of the biochar particles.
In some embodiments, the sintering process may be performed at a temperature of 700-900 ℃, and in an exemplary embodiment, the sintering process may include, but is not limited to, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ for a period of 1-3 hours, and may include, but is not limited to, 1 hour, 2 hours, and 3 hours. The sintering temperature and the sintering time are favorable for the full action of the activating agent or the template agent on the biochar particles, further carbonization of the biochar particles, and finally the prepared carbon-fixing material microscopically presents various shapes such as concave carbon spheres, circular rings and the like, has rich pore structures, has higher specific surface area, contains polycyclic aromatic hydrocarbon and is favorable for improving the capturing and sealing effects of the prepared carbon-fixing material on carbon dioxide. In some embodiments, the polycyclic aromatic hydrocarbon comprises at least one of naphthalene, acenaphthene, and philosophy. The electronegativity provided by the polycyclic aromatic hydrocarbon can further endow the carbon fixing material of the embodiment of the application with better capturing and sealing effects on carbon dioxide.
In some embodiments, after the sintering process, the method further comprises the steps of:
s40: and (3) grafting basic functional groups on the surface of the carbon-fixing material, wherein the basic functional groups comprise at least one of amide, imide and pyridyl.
The basic functional groups grafted on the surface of the carbon-fixing material can provide active sites and acidic CO 2 Molecules can be connected to active sites on the surface of the carbon-fixing material through covalent bonds, so that the carbon-fixing material provided by the embodiment of the application has better carbon dioxide capturing and sealing effects. In an exemplary embodiment, step S40 may be to first mix the carbon-fixing material with the nitric acid solution at a ratio of 1:10 solid/liquid ratio, and stirring at room temperature for 1 hr to obtain solidThe surface of the carbon material was bound with nitrogen-containing active groups, and then the solids were separated from the aqueous phase by centrifugation and washed with 0.1mol/L NaOH solution until the pH of the washing solution reached 6 (neutral) to wash away the residual nitric acid solution. Finally, the carbon-fixing material with the surface combined with the nitrogen-containing active group and anhydrous ammonia gas (purity>99.99%) and continuously reacting for 1 hour at 450 ℃ to obtain the carbon-fixing material with grafted basic functional groups on the surface.
The second aspect of the embodiment of the application provides a carbon-fixing material. The carbon-fixing material is prepared by the preparation method of the embodiment of the application.
The carbon-fixing material provided by the embodiment of the application is prepared by the preparation method of the embodiment of the application, so that the carbon-fixing material has various shapes such as concave carbon spheres, circular rings and the like (shown in figure 2) on microcosmic scale, and has a relatively high abundant pore structure as a whole, so that the carbon-fixing material has a relatively high specific surface area, and is beneficial to capturing and sealing carbon dioxide gas. And to CO 2 The nonpolar substance has strong affinity, and can adsorb CO via polar bond at linear terminal 2 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, polycyclic aromatic hydrocarbon on the surface of the carbon-fixing material is electronegative, has stronger electron-withdrawing capability and is used as CO 2 The molecules move parallel to the surface of the carbon-fixing material, and due to electrostatic effect, the CO 2 Can be adsorbed on the surface of the carbon-fixing material. Thereby improving the capturing and sealing effect of the carbon fixing material on carbon dioxide.
According to detection, the carbon-fixing material provided by the embodiment of the application comprises at least one of the following characteristics (1) - (6):
(1) The specific surface area is 1400-1600 m 2 /g；
(2) Pore volume of 1.5-1.7 cm 3 /g；
(3) The volume of the mesoporous is 1.4-1.6 cm 3 /g；
(4) The micropore volume is 0.05-0.2 cm 3 /g；
(5) Average pore diameter of 3-5 cm 3 /g。
(6) The particle diameter Dv50 is 2 to 7 μm.
The carbon-fixing material with the parameters has the advantage of strong carbon dioxide capturing and sealing effect.
A third aspect of the embodiments of the present application provides a composite carbon-fixing material. The composite carbon-fixing material comprises a carbon-fixing material and graphene oxide (namely GO) which is mixed with the carbon-fixing material, wherein the carbon-fixing material comprises the carbon-fixing material prepared by the preparation method of the embodiment of the application or comprises the carbon-fixing material of the embodiment of the application.
The composite carbon-fixing material provided by the embodiment of the application has a synergistic effect due to the fact that the composite carbon-fixing material comprises the carbon-fixing material and graphene oxide which are mixed with each other, and has high specific surface area and good dispersibility. GO is a hydrophilic material, and CO 2 Is hydrophilic gas. Since GO has interconnected layers, CO is allowed 2 Enters, has good CO between layers 2 Adsorption performance. After the carbon-fixing material and the GO are mixed, the GO is attached to the carbon-fixing material (as shown in fig. 3), and the attached GO films block micropores of the carbon-fixing material and increase disorder degree, so that the order of the pore structure is damaged. Therefore, compared with the carbon-fixing material which is not mixed with GO, the specific surface area and the pore volume of the composite carbon-fixing material are slightly reduced, the pore diameter is increased, and the composite carbon-fixing material is beneficial to improving CO after synthesis 2 Is used for capturing and sealing. And the polycyclic aromatic hydrocarbon on the surface of the carbon-fixing material is electronegative, so that the carbon-fixing material has stronger electron-withdrawing capability and can be used as CO 2 The molecules move parallel to the surface of the carbon-fixing material and CO is acted by static electricity 2 Can be adsorbed on the surface of the carbon-fixing material; however, when CO 2 When molecules move towards the surface of the carbon-fixing material perpendicularly, CO is generated due to electrostatic repulsive force 2 Molecules are difficult to approach the surface of the carbon-fixing material, and can not form stable interaction force with the surface of the carbon-fixing material, so that CO 2 It is difficult to stably adsorb on the surface of the carbon-fixing material. In contrast, the surface of the composite carbon-fixing material obtained after GO coating is rich in oxygen-containing functional groups such as carboxyl, hydroxyl and other groups, and can form hydrogen bonds and react with CO 2 O atoms with negative potential interact to promote CO 2 Is adsorbed by the adsorbent. At the same time, H contained in the air 2 H atoms in O can form stronger interaction with the surface of the composite carbon-fixing material, and compared with the composite carbon-fixing material, the H atoms are easier to adsorb on the surface, and CO 2 And H is 2 O intermolecular also existThe action of weak static electricity, in particular the induction force between polar molecules and nonpolar molecules, also helps to promote CO 2 Is adsorbed by the adsorbent. Therefore, compared with the biochar and GO mixed in the prior art, the composite carbon-fixing material provided by the embodiment of the application has stronger CO 2 Trapping and sealing effects.
The mode of mixing the carbon-fixing material and the GO can be that the GO is pre-dispersed firstly, for example, the GO can be added into methanol (for example, 300mg of GO is added into 80-120 mL of methanol), the mixture is obtained by ultrasonic dispersion treatment (for example, 6000W power treatment for 30min at 25-30 ℃), then the GO methanol solution and the carbon-fixing material are mixed and stirred for 2-4 hours until the mixture is uniformly dispersed, part of the GO still remains on the carbon-fixing material and is not adhered to the surface of the carbon-fixing material, the non-adhered GO can be separated by washing with methanol, and finally, the composite carbon-fixing material is obtained by drying treatment, for example, the composite carbon-fixing material can be dried in vacuum for 10-12 hours at 80 ℃.
In some embodiments, the mass ratio of GO to carbon-fixing material in the composite carbon-fixing material is 1: 100-1: 200. the mass ratios are favorable for further improving the effect of the GO attached to the carbon-fixing material and further improving the CO of the composite carbon-fixing material 2 Trapping and sealing effects. In an example, the mass ratio may include, but is not limited to, 1: 100. 1: 130. 1: 170. 1:200.
according to a fourth aspect of the embodiment of the application, a carbon-fixing cement-based material is provided. The carbon-fixing cement-based material comprises the following components in parts by weight:
and (3) cement: 800-1200 parts;
carbon fixing agent: 5-15 parts;
sand: 2400-3600 parts;
water: 400-600 parts;
water reducing agent: 0.05 to 0.15 part;
the carbon fixing agent comprises the carbon fixing material prepared by the preparation method of the embodiment of the application, or comprises the carbon fixing material of the embodiment of the application, or comprises the composite carbon fixing material of the embodiment of the application.
The carbon-fixing cement-based material comprises cement and a carbon-fixing agent, namely, the carbon-fixing agent is added into the cement-based materialThe carbon fixing agent comprises the carbon fixing material or the composite carbon fixing material provided by the embodiment of the application, and has a synergistic effect with cement, thereby enhancing the capture and the sealing of CO of cement-based materials 2 Ca in the pore liquid of the carbon-fixed cement-based material 2+ With CO 2 Reacting to generate CaCO 3 Thereby improving the solidification of CO 2 Is to simultaneously generate CaCO 3 The pores are thinned, and the carbon fixing agent also promotes the hydration of cement and improves the strength of the carbon fixing cement-based material. In addition, the carbon-fixing materials in the carbon-fixing materials and the composite carbon-fixing materials are in various shapes such as concave carbon spheres, circular rings and the like, so that the carbon-fixing materials have high specific surface area, good dispersibility and good dispersibility in cement; besides the dispersing and cement hydration functions, the H atoms in the water can also perform the interaction with the surface of the composite carbon-fixing material to improve CO 2 Capturing and sealing; the water reducer can be added to improve the dispersibility of GO in the cement alkaline environment, further improve the effect of capturing and sealing carbon dioxide, and compared with the prior art, the method for capturing and sealing CO by cement-based materials 2 The effect of (3) is greatly improved. And the problem that the strength of cement is reduced as the biochar in the prior art is added into the cement is solved, and the carbon-fixing cement-based material has no negative influence on the strength. Examples may include, but are not limited to, the following: and (3) cement: 1000 parts; carbon fixing agent: 10 parts; sand: 3000 parts; water: 500 parts; water reducing agent: 0.1 part; or cement: 1200 parts; carbon fixing agent: 12 parts; sand: 3600 parts; water: 500 parts; water reducing agent: 0.15 parts; or cement: 800 parts; carbon fixing agent: 5 parts; sand: 2400 parts; water: 400 parts; 3, water reducing agent: 0.05 parts; or cement: 1000 parts; carbon fixing agent: 15 parts; sand: 3000 parts; water: 400 parts; water reducing agent: 0.15 parts. In some embodiments, the water reducer may include a polycarboxylate water reducer, which may further enhance the dispersion effect of the GO with the cement.
The following description is made with reference to specific embodiments.
Example A1
Carbon-fixing material and preparation method thereof
The preparation method of the carbon-fixing material comprises the following steps:
s1: drying and grinding pine needles into 50-80 mesh powder, and then mixing the powder with water according to the mass volume ratio of 100g:1L of mixing, and generating carbon precursor particles from a precursor solution through spray drying treatment, wherein the threshold temperature of atomization air of a spray dryer is set to be 250-300 ℃; the atomization pressure is 0.2MPa; the atomization rate is 1200-1500 mL/h; the flow rate of the atomized air is 25-35 m 3 /h; the temperature of the outlet gas-powder mixture of the spray drying treatment is 120-150 ℃. Then the carbon precursor particles are subjected to carbonization treatment by low-temperature calcination at 350 ℃ in nitrogen atmosphere through a muffle furnace, and the calcination time is 2 hours, so as to obtain biochar particles;
s2: grinding and mixing biochar particles, KOH solution and CaO, wherein the mass ratio of the biochar particles to calcium oxide is 1:4, the mass ratio of the biochar particles to the potassium hydroxide in the KOH solution is 1:8. and then the ground mixture is calcined at a high temperature in a nitrogen atmosphere through a muffle furnace for 2 hours at 800 ℃, and is further cleaned by an acid solution or deionized water and then dried after being calcined at the high temperature, so that the carbon-fixing material with a porous structure and containing polycyclic aromatic hydrocarbon is prepared.
Example A2
Carbon-fixing material and preparation method thereof
The preparation method of the carbon-fixing material of this embodiment is different from the preparation method of embodiment A1 only in that: in the step S2, caO is not added during grinding and mixing.
Example A3
Carbon-fixing material and preparation method thereof
The preparation method of the carbon-fixing material of this embodiment is different from the preparation method of embodiment A1 only in that: the low-temperature calcination temperature in the step S1 is changed to 40 ℃;
in the step S2, the mass ratio of the biochar particles to the calcium oxide is changed to 1:3, changing the mass ratio of the biochar particles to the potassium hydroxide in the KOH solution into 1:5, the high-temperature calcination temperature is changed to 700 ℃.
Comparative example A1
Biochar and preparation method thereof
The biochar preparation method of this comparative example differs from that of example A1 only in that: in step S1, the pine needle powder is directly subjected to carbonization treatment by low-temperature calcination, excluding spray drying treatment.
Comparative example A2
Biochar and preparation method thereof
The biochar preparation method of this comparative example differs from that of example A1 only in that: in the step S2, the high-temperature calcination treatment is directly carried out on the biochar particles, and the grinding and mixing of the biochar particles with KOH solution and CaO are not included.
Example B1
Composite carbon-fixing material and preparation method thereof
The composite carbon-fixing material of this embodiment includes the carbon-fixing material provided in embodiment A1 and GO attached to the surface of the carbon-fixing material.
The preparation method comprises the following steps:
s3: 300mg of GO was added to 100mL of methanol and sonicated at 600W power for 30min at 30℃to give a GO methanol solution, which was mixed with 10g of carbon-fixed material as provided in example A1 and stirred for 4h. And finally, washing with methanol to separate the non-attached GO from the surface of the carbon-fixing material, and finally, drying in vacuum at 80 ℃ for 10 hours to obtain the composite carbon-fixing material.
Example B2
Composite carbon-fixing material and preparation method thereof
The composite carbon-fixing material and the preparation method thereof in this example are different from those in example B1 only in that: the carbon fixing material was changed to the carbon fixing material provided in example A2.
Example B3
Composite carbon-fixing material and preparation method thereof
The composite carbon-fixing material and the preparation method thereof in this example are different from those in example B1 only in that: the carbon fixing material was changed to the carbon fixing material provided in example A3.
Comparative example B1
Composite biochar and preparation method thereof
The comparative example composite biochar and the preparation method are different from example B1 only in that: the carbon fixing material was changed to biochar provided in comparative example A1.
Comparative example B2
Composite biochar and preparation method thereof
The comparative example composite biochar and the preparation method are different from example B2 only in that: the carbon fixing material was changed to biochar provided in comparative example A2.
Example C1
Carbon-fixing cement-based material
The carbon-fixing cement-based material of the embodiment comprises the following components in parts by weight: P-II type Portland cement (OPC) 52.5R:1000g of the composite carbon-fixing material provided in example B1: 10g, standard sand: 3000g, water: 500g, polycarboxylate water reducer: 0.1g.
Example C2
Carbon-fixing cement-based material
The difference between the carbon-fixed cement-based material of this example and example C1 is only that: the composite carbon fixation material was changed to the composite carbon fixation material provided in example B2.
Example C3
Carbon-fixing cement-based material
The difference between the carbon-fixed cement-based material of this example and example C1 is only that: the composite carbon fixing material was changed to the carbon fixing material provided in example B3.
Example C4
Carbon-fixing cement-based material
The difference between the carbon-fixed cement-based material of this example and example C1 is only that: the composite carbon fixing material was changed to the carbon fixing material provided in example A1.
Example C5
Carbon-fixing cement-based material
The difference between the carbon-fixed cement-based material of this example and example C1 is only that: the composite carbon fixing material was changed to the carbon fixing material provided in example A2.
Example C6
Carbon-fixing cement-based material
The difference between the carbon-fixed cement-based material of this example and example C1 is only that: the composite carbon fixing material was changed to the carbon fixing material provided in example A3.
Comparative example C1
Carbon-fixing cement-based material
The comparative carbon-fixed cement-based material differs from example C1 only in that: the composite carbon-fixing material was changed to the composite carbon-fixing material provided in comparative example B1.
Comparative example C2
Carbon-fixing cement-based material
The comparative carbon-fixed cement-based material differs from example C1 only in that: the composite carbon-fixing material was changed to the composite carbon-fixing material provided in comparative example B2.
Comparative example C3
Carbon-fixing cement-based material
The comparative carbon-fixed cement-based material differs from example C1 only in that: the composite carbon-fixing material is changed into GO, and the GO has very low density and very large volume, so that the dispersion effect in cement is improved, and the mass is 0.5 g.
Comparative example C4
Carbon-fixing cement-based material
The comparative carbon-fixed cement-based material differs from example C1 only in that: the components do not contain composite carbon-fixing materials.
Correlation performance test and result analysis
1. Topography analysis
The morphology of the biochar particles (sample (1)) obtained by spray drying and carbonization treatment in step S1 of example A1, and the biochar particles (sample (2)) obtained by low-temperature calcination, and the morphology of the carbon-fixing material (sample (3)) obtained in step S2 were observed by SEM electron microscopy, and the images are shown in fig. 1, 2 and 3 in sequence.
In fig. 1, it can be seen that the biochar particles after spray drying and carbonization are spherical and uniformly dispersed.
In fig. 2, it can be seen that the carbon precursor particles, the activator and the template agent are sintered to obtain a carbon-fixing material which is in various spheres such as concave carbon spheres and rings and uniformly dispersed.
In fig. 3, it can be seen that the composite carbon-fixing material has various shapes such as concave carbon spheres, and is uniformly dispersed, wherein GO is attached to the surface of the carbon-fixing material, and is a nano-scale material, and the electron microscope shooting effect is not obvious.
BET test
10g of each of the above samples (1), (2) and (3) was subjected to BET test using ASAP 2460.01, and the results are shown in Table 1.
TABLE 1
The porous structure of the carbon-fixing material prepared by the biochar particles is richer and the specific surface area is larger after the biochar particles are modified by sintering treatment by the activating agent and the template agent. Further, the composite carbon-fixing material is prepared with GO, and the pore structure can be changed.
3. Carbon dioxide adsorption test:
and (3) respectively carrying out adsorption performance test on the samples (1), (2) and (3) by using a thermogravimetric analyzer. About 10mg of sample is taken and placed in a crucible, and 80mL/min of N is added 2 Raising the temperature from room temperature to 150 ℃ under the atmosphere, preserving the heat for 1h, naturally cooling to 30 ℃ and switching to pure CO 2 The atmosphere air flow is 80mL/min, the pressure is 101.325kPa, the temperature is kept at 25 ℃ for 180min, and the mass increase of the observed sample is the carbon dioxide adsorption amount. The results are shown in FIG. 4.
In fig. 4, it can be seen that the capturing and sealing effect of the carbon dioxide of the prepared carbon-fixing material is obviously enhanced after the biochar particles are subjected to high-temperature sintering treatment by the activating agent and the template agent. Further, the carbon dioxide capturing and sealing effect of the composite carbon-fixing material prepared by the composite carbon-fixing material and the GO can be further obviously enhanced.
4. Carbon dioxide capture and sequestration Effect test
The carbon-fixed cement-based materials provided in examples C1 to C6 and comparative examples C1 to C4 were prepared into test pieces, and the carbon dioxide trapping and sequestering effects were tested.
The carbon-fixing cement-based material provided in example C1 was operated as follows: cement and the composite carbon-fixing material provided in example B1 were placed in a stirring pot and stirred at 140rpm for 30s. Then, all the standard sand was added after stirring at 140r/min for 30s. Finally, water was added to the mortar mixture and stirred at 285rpm for 90s. The mixture was cast at 4X 16cm 3 A three-point bending test was performed in the mold of (c). After 24 hours, will take offThe molded samples were cured in a humidity chamber at a controlled temperature and humidity of 23 ℃ and 95%, respectively. After 3d of wet curing, a sample was obtained.
A small portion of the sample was moved to a CO gas concentration of 12% at the set conditions 2 Curing in a carbonization oven at 15psi, 23+ -5deg.C, 65+ -3% relative humidity for 7d to evaluate the carbon trapping and sequestering effect. Adopting thermogravimetric analysis, taking 50-60 mg of cured sample, placing the sample into a crucible, heating to 1000 ℃ to measure the residual mass at a specific temperature, and obtaining the residual mass according to the following formula
CO 2 Sealing rate= (M 525 -M 900 )÷M 1000 ×100％
M 525 And M 900 Represents the mass (g), M of the sample at the respective heating temperature 1000 Mass (g) of no sample heated to 1000 °c
Samples of the carbon-fixed cement-based materials provided by C2 to C6 and comparative examples C1 to C4 were prepared in this order in combination with the above method, and tested for carbon dioxide trapping and sequestering effects, comparative example C4 was actually a blank cement-based material, based on which the relative lifting effects of the results of the samples of each case were recorded as shown in table 2, and the partial results were recorded as shown in fig. 5.
TABLE 2
It can be seen from table 2 that the preparation method of the embodiment of the application prepares the carbon-fixing material through spray drying treatment and carbonization treatment, and further sintering treatment by using the template agent and/or the activating agent, and the carbon-fixing effect (58% improvement) of the carbon-fixing cement material prepared by using the carbon-fixing material for cement and the carbon-fixing effect (95% improvement) of the cement carbon-fixing material prepared by using the prepared composite carbon-fixing material are far better than those of the cement material, and are far better than those of the biochar material prepared by other preparation methods and the carbon-fixing effect of GO for cement. And in combination with fig. 5, it can be seen that the carbon-fixing material and the composite carbon-fixing material obtained by mixing the carbon-fixing material and the GO have a synergistic effect, and the carbon-fixing effect applied to cement is higher than the sum of the carbon-fixing effects of the carbon-fixing material and the carbon-fixing effect of the GO applied to cement respectively (the sum of 95% is greater than 58% and 33%).
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The preparation method of the carbon-fixing material is characterized by comprising the following steps:
spray drying the solution containing the particles of plant matter to obtain carbon precursor particles;
carbonizing the carbon precursor particles to obtain biochar particles;
mixing at least one of an activating agent and a template agent with the biochar particles, and sintering in a protective atmosphere to obtain the porous carbon-fixing material, wherein the carbon-fixing material contains polycyclic aromatic hydrocarbon.
2. The method of manufacturing according to claim 1, characterized in that: the mass volume ratio of the particles of the plant substances to the water in the solution is 75-200 g: 500-1000 mL;
and/or
The spray-drying treatment includes at least one of the following conditions (1) to (5):
(1) The threshold temperature of the atomized air is 250-300 ℃;
(2) The atomization pressure is 0.1-0.2 MPa;
(3) The atomization rate is 1200-1500 mL/h;
(4) The flow rate of the atomized air is 25-35 m 3 /h；
(5) The temperature of the outlet gas-powder mixture of the spray drying treatment is 120-150 ℃; and/or
After the sintering treatment, the method further comprises the following steps:
and (3) grafting a basic functional group on the surface of the carbon-fixing material, wherein the basic functional group comprises at least one of amide, imide and pyridyl.
3. The preparation method according to claim 1 or 2, characterized in that: the mass ratio of the biochar particles to the activator is 1:5 to 1:10; and/or
The mass ratio of the biochar particles to the template agent is 1: 3-1: 5, a step of; and/or
The activator comprises KOH, K 2 CO 3 、KHCO 3 、NaOH、HF、H 3 PO 4 At least one of (a) and (b); and/or
The template agent comprises CaO, mgO, znO, al 2 O 3 At least one of (a) and (b); and/or
The polycyclic aromatic hydrocarbon comprises at least one of naphthalene, acenaphthene and Philippine.
4. The preparation method according to claim 1 or 2, characterized in that: the plant material comprises pine needles or broadleaf plant leaves; and/or
The particles of the plant material are 50-80 meshes; and/or
The carbonization temperature is 300-400 ℃; and/or
The temperature of the sintering treatment is 700-900 ℃; and/or
The protective atmosphere comprises at least one of nitrogen, argon, helium and hydrogen.
5. A carbon-fixing material, characterized in that the carbon-fixing material is obtained by the preparation method of the carbon-fixing material according to any one of claims 1 to 4.
6. The carbon-fixing material according to claim 5, characterized in that the carbon-fixing material comprises at least one of the following features (1) to (6):
(1) The specific surface area is 1400-1600 m 2 /g；
(2) Pore volume of 1.5-1.7 cm 3 /g；
(3) The volume of the mesoporous is 1.4-1.6 cm 3 /g；
(4) The micropore volume is 0.05-0.2 cm 3 /g；
(5) Average pore diameter of 3-5 cm 3 /g；
(6) The particle diameter Dv50 is 2 to 7 μm.
7. A composite carbon fixing material is characterized in that: comprising a carbon-fixing material and graphene oxide intermixed with the carbon-fixing material, the carbon-fixing material comprising the carbon-fixing material produced by the production method according to any one of claims 1 to 4, or comprising the carbon-fixing material according to claim 5 or 6.
8. The composite carbon-fixing material according to claim 7, wherein: the mass ratio of the graphene oxide to the carbon-fixing material is 1: 100-1: 200.
9. the carbon-fixing cement-based material is characterized by comprising the following components in parts by weight:
and (3) cement: 800-1200 parts;
carbon fixing agent: 5-15 parts;
sand: 2400-3600 parts;
water: 400-600 parts;
water reducing agent: 0.05 to 0.15 part;
wherein the carbon fixing agent comprises the carbon fixing material prepared by the preparation method of any one of claims 1 to 4 or comprises the carbon fixing material of claim 5 or 6 or comprises the composite carbon fixing material of claim 7 or 8.
10. The carbon-fixed cement-based material of claim 9, wherein: the water reducing agent comprises a polycarboxylate water reducing agent.
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