CN115090276B - In-situ loaded X-zeolite porous geopolymer, preparation method and application - Google Patents

In-situ loaded X-zeolite porous geopolymer, preparation method and application Download PDF

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CN115090276B
CN115090276B CN202210692412.0A CN202210692412A CN115090276B CN 115090276 B CN115090276 B CN 115090276B CN 202210692412 A CN202210692412 A CN 202210692412A CN 115090276 B CN115090276 B CN 115090276B
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type zeolite
porous geopolymer
situ
fly ash
mass
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CN115090276A (en
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韩乐
王晓东
许刚刚
朱世彬
武博强
王强民
王海
张跃宏
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Xian Research Institute Co Ltd of CCTEG
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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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—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 surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The invention provides an in-situ loaded X-type zeolite porous geopolymer, a preparation method and application thereof, wherein the method adopts a saturated steam curing method to load X-type zeolite on the pore wall of the porous geopolymer in situ to obtain the in-situ loaded X-type zeolite porous geopolymer; is prepared by mixing the slurry; the raw material components of the mixed slurry of (1) comprise fly ash, sodium hydroxide, water glass, water and foaming agent; the foaming agent is prepared by compounding 20-30% of sodium dodecyl benzene sulfonate and 70-80% of hydrogen peroxide by mass percent. The in-situ loaded X-type zeolite porous geopolymer material shows micro-to-macroscopic multi-gradient pore and multi-crack distribution, so that the mass transfer coefficient of the material is greatly improved, the material can be applied to a fixed bed to capture carbon dioxide in flue gas, and the polymer material has quite excellent stability and repeatability and can be directly recycled after being used, thereby realizing the concept of treating waste with waste.

Description

In-situ loaded X-zeolite porous geopolymer, preparation method and application
Technical Field
The invention belongs to the field of environmental materials, relates to a composite material, and in particular relates to an in-situ loaded X-type zeolite porous geopolymer, a preparation method and application.
Background
The coal reserves in China are huge, the thermal power generation is a main power source, along with the increase of power demand, carbon dioxide and fly ash generated by the thermal power generation become main factors restricting sustainable development of the coal-fired thermal power plant, in recent years, the development of technologies such as carbon capture, utilization and sealing up provides possibility for reducing carbon dioxide greenhouse gases, and the capture of carbon dioxide is a more effective way for reducing carbon dioxide in the flue gas of the coal-fired thermal power plant, because the existing facilities and processes of the thermal power plant are not required to be changed in the capture process, and the carbon dioxide can be effectively separated and concentrated. In recent years, along with the continuous progress of preparing zeolite from fly ash, zeolite with a unique molecular sieve structure has been synthesized, so that carbon dioxide in flue gas can be effectively trapped, and a trigger is provided for combining fly ash disposal with carbon dioxide trapping.
However, existing processes for capturing carbon dioxide from flue gases still use large amounts of powdered zeolite materials which are not easily shaped and still need to be composited with other inert supports such as steel, ceramics, membranes, etc. in practical use. Although some studies have proposed mixing zeolite and clay together to prepare composite materials for capturing carbon dioxide while reducing production costs, these materials still suffer from high density, low porosity, low capture efficiency, and the like.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide an in-situ loaded X-type zeolite porous geopolymer, a preparation method and application thereof, and solves the technical problems that materials for adsorbing carbon dioxide in flue gas in the prior art are difficult to form and have poor adsorption effect.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the in-situ loaded X-type zeolite porous geopolymer comprises the steps of adopting a saturated steam curing method to load X-type zeolite on the pore wall of the porous geopolymer in situ to obtain the in-situ loaded X-type zeolite porous geopolymer;
the porous geopolymer is prepared by mixing slurry;
the raw material components of the mixed slurry comprise fly ash, sodium hydroxide, sodium silicate, water and a foaming agent; the foaming agent is prepared by compounding 20-30% of sodium dodecyl benzene sulfonate and 70-80% of hydrogen peroxide in percentage by mass.
The invention also has the following technical characteristics:
step one, preparing an alkaline excitant;
step two, preparing mixed slurry;
mixing and stirring the alkaline excitant prepared in the first step with the fly ash to obtain a mixture A, adding a foaming agent into the mixture A, and stirring to prepare mixed slurry;
wherein the mass of the sodium hydroxide is 18-25% of the mass of the fly ash, the mass of the water glass is 40-70% of the mass of the fly ash, the mass of the water is 21-38% of the mass of the fly ash, and the mass of the foaming agent is 1-2% of the mass of the fly ash
Step three, preparing an in-situ loaded X-type zeolite porous geopolymer;
pouring the mixed slurry prepared in the second step into a mould, coating a layer of film on the surface of the mould to seal the mixed slurry, and finally placing the mould in a saturated steam generator for curing, thereby preparing the in-situ loaded X-type zeolite porous geopolymer after curing is finished;
wherein the autoclaved pressure of the curing is 0.05 MPa-0.1 MPa, the autoclaved temperature is 80-100 ℃, and the curing time is 12-24 h.
Preferably, in the fourth step, the autoclaved pressure is 0.1MPa, the autoclaved temperature is 80 ℃, and the autoclaved curing time is 24 hours.
Specifically, in the second step, the mixed slurry comprises the following raw material components in percentage by mass: 46.4 to 49.8 percent of fly ash, 8.6 to 12.4 percent of sodium hydroxide, 18.3 to 34.2 percent of sodium silicate, 9.6 to 18.3 percent of water, 0.5 to 1 percent of foaming agent and 100 percent of total mass percent of all components.
Preferably, in the second step, the mixed slurry comprises the following raw material components in percentage by mass: 46.5% of fly ash, 8.6% of sodium hydroxide, 34.2% of water glass, 9.7% of water, 0.2% of sodium dodecyl benzene sulfonate and 0.8% of hydrogen peroxide.
Specifically, the alkaline activator is Na 2 O·nSiO 2 Where n=2.42.
Specifically, the specific process of the second step is as follows: and (3) mixing and stirring the alkaline excitant prepared in the step (I) with the fly ash for 2min to obtain a mixture A, adding the foaming agent into the mixture A, and stirring for 1min to obtain mixed slurry.
Specifically, the specific process of the first step is as follows:
uniformly mixing water glass, water and sodium hydroxide to prepare an alkaline excitant;
or mixing water and sodium hydroxide uniformly to obtain the alkaline activator.
The invention also protects the in-situ loaded X-type zeolite porous geopolymer, and the composite material is prepared by adopting the preparation method of the in-situ loaded X-type zeolite porous geopolymer; the apparent density of the in-situ loaded X-type zeolite porous geopolymer is 300-400 kg/m 3 The compressive strength is 2-3 MPa, and the mass percentage content of the X-type zeolite in the in-situ loaded X-type zeolite porous geopolymer is 30-55%.
The invention also protects the application of the in-situ loaded X-zeolite porous geopolymer prepared by the preparation method of the in-situ loaded X-zeolite porous geopolymer in capturing carbon dioxide in flue gas; or the use of an in situ loaded X-zeolite porous geopolymer as described above for capturing carbon dioxide in flue gas.
Compared with the prior art, the invention has the following beneficial technical effects:
the in-situ loaded X-type zeolite porous geopolymer prepared by the method is a massive solid adsorbent, has the characteristics of low density, high strength and high carbon dioxide trapping capacity, can be directly used as a filler for trapping carbon dioxide from flue gas in a fixed bed, can be recycled for multiple times, and can effectively trap carbon dioxide from the flue gas and realize the reutilization of fly ash.
The preparation method of the invention adopts the saturated steam curing method to load the X zeolite on the porous geopolymer pore wall for the first time, the saturated steam curing process has lower temperature and pressure, can fully utilize the waste heat steam of a power plant, has simple preparation process and easy operation, and can adjust the content of the X zeolite according to the on-site requirement at any time.
The generation of (III) X-type zeolite can obviously improve the pore structure of the material, and is beneficial to capturing carbon dioxide from flue gas in a fixed bed by in-situ loading of X-type zeolite porous geopolymer.
Drawings
FIG. 1 is a process diagram of the preparation of an in situ supported X-zeolite porous geopolymer.
FIG. 2 is a graphical representation of in situ loaded X-zeolite porous geopolymer.
FIG. 3 is a microstructure of an in situ loaded X-zeolite porous geopolymer.
FIG. 4 (a) is an XRD pattern of the in-situ supported X-zeolite porous geopolymer of example 1.
Fig. 4 (b) is an XRD pattern of the in-situ supported X zeolite porous geopolymer of example 2.
FIG. 4 (c) is an XRD pattern of the in-situ supported X-zeolite porous geopolymer of example 3.
Fig. 4 (d) is the XRD patterns of the materials in example 1 and comparative examples 1, 2.
FIG. 5 (a) is a graph of carbon dioxide capture by in situ loaded X-zeolite porous geopolymer cycle.
FIG. 5 (b) is a carbon dioxide breakthrough curve captured by the in-situ loaded X-zeolite porous geopolymer of example 1.
FIG. 5 (c) is a carbon dioxide breakthrough curve captured by the in situ loaded X zeolite porous geopolymer of example 2.
FIG. 5 (d) is a carbon dioxide breakthrough capture curve for the in-situ loaded X-zeolite porous geopolymer of example 3.
Fig. 5 (e) is a breakthrough plot of the capture of carbon dioxide for the materials of example 1 and comparative examples 1 and 2.
Meaning of symbols in the drawings:
diff: analog calculation error curveA wire; obs: an actual XRD pattern; calc: XRD simulation calculation map; bckgr-: a back ground curve; integrity (a.u.): XRD pattern intensity; c (C) t /C 0 : concentration of oral gas (C) t ) A ratio to the outlet gas concentration at equilibrium; time(s): time.
The technical scheme of the invention is further described below by referring to examples.
Detailed Description
The invention takes fly ash, sodium hydroxide, water, foaming agent and foam stabilizer as raw materials to prepare an in-situ loaded X-type zeolite porous geopolymer, which is characterized in that: na-X zeolite is the predominant zeolite phase present, ranging from microporous to macroporous.
The preparation method of the invention is shown in figure 1, the coal ash is subjected to a polymerization reaction under the chemical excitation of sodium hydroxide and sodium silicate to generate a geopolymer, the obtained geopolymer is cast and molded, and is covered with a sealing film, and then the geopolymer is placed in a saturated steam generator for curing, wherein hydrogen peroxide in a foaming agent is heated and decomposed into generated gas in the curing process, and the geopolymer gradually forms a porous structure under the guidance of sodium dodecyl benzene sulfonate.
The saturated steam curing method in the invention is to utilize a saturated steam generator to generate saturated steam, so that the saturated steam is filled around a sealed mould, and a continuous and stable hydrothermal environment is provided for a sample in the mould.
Compared with the common hydrothermal method or autoclaved curing method, the saturated steam curing method adopted by the invention has the advantages that: the saturated steam curing has small steaming pressure and low steaming temperature, and is easy to realize industrialization; in the process of curing by using saturated steam, the mixed slurry does not need to be contacted with alkaline solution or high-temperature and high-pressure steam, so that the structure of the geopolymer is prevented from collapsing, the geopolymer can be effectively prevented from continuously absorbing water from the saturated steam, the alkali concentration in the geopolymer can be ensured to be kept for a longer time, and the yield of the X-type zeolite porous geopolymer is greatly improved. In the preparation method, the temperature and pressure of the saturated steam curing process are lower, and the sealing film is used for blocking, so that the novel process can effectively prevent the geopolymer from continuously absorbing water from the saturated steam, thereby ensuring that the alkali concentration in the geopolymer can be kept for a longer time until the reaction is finished, and greatly improving the yield of the X-type zeolite porous geopolymer; meanwhile, the airtight maintenance environment can prevent unreacted intermediate products (N-A-S-H gel) from being continuously washed and lost by steam, and the unreacted N-A-S-H gel is kept stable in the material, so that strong support is provided for the in-situ loaded X-zeolite porous geopolymer.
Compared with a hydrothermal method or an autoclaved curing method, the preparation method has the advantages that: the prepared massive solid material has low density, high compressive strength and high carbon dioxide trapping capacity, can be directly used as a filler for trapping carbon dioxide from flue gas of a fixed bed, can be recycled for multiple times, and can be used for effectively trapping carbon dioxide from flue gas and simultaneously treating part of fly ash.
In the invention, the following components are added:
the mold used to prepare the in situ supported X-zeolite porous geopolymer is a mold known in the art.
The steam generator used in the saturated steam curing method meets the industry standard JB/T8959-1999.
The fly ash comprises the following components in percentage by mass: siO (SiO) 2 40.5 to 55.6 percent of Al 2 O 3 36.7 to 48.9 percent, 2.5 to 6.5 percent of CaO and Fe 2 O 3 1.8 to 3.5 percent, the other components are 5.2 to 9.8 percent, the mass percent of each component is 100 percent, and the granularity is less than or equal to 200 meshes.
The following specific embodiments of the present invention are given according to the above technical solutions, and it should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
Example 1:
as shown in fig. 1, the present embodiment provides a method for preparing an in-situ supported X-zeolite porous geopolymer, which includes the following steps:
step one, preparing an alkaline excitant;
uniformly mixing 74g of sodium hydroxide, 295g of sodium silicate and 83g of water to prepare an alkaline activator; in this embodiment, the alkali-activator is Na 2 O·nSiO 2 Wherein n is 2.42;
step two, preparing mixed slurry;
mixing and stirring the alkaline excitant prepared in the first step with 400g of fly ash for 2 minutes to obtain a mixture A, and then adding 10g of foaming agent into the mixture A and stirring for 1 minute to prepare mixed slurry; in this example, the foaming agent consisted of 8g of hydrogen peroxide solution (mass concentration 35%) and 2g of sodium dodecylbenzenesulfonate.
Step three, preparing an in-situ loaded X-type zeolite porous geopolymer;
pouring the mixed slurry prepared in the second step into a mould, coating a layer of film on the surface of the mould to seal the mixed slurry, and finally placing the mould in a saturated steam generator for curing, thereby preparing the in-situ loaded X-type zeolite porous geopolymer after curing is finished;
wherein the autoclaved pressure of the curing is 0.1MPa, the autoclaved temperature is 80 ℃, and the autoclaved curing time is 24 hours.
In this example, after curing, the prepared sample was cooled and demolded and designated FGX1, and its XRD crystal phase analysis was as shown in FIG. 4 (a); the zeolite microstructure is shown in fig. 3, and the results of the X-type zeolite content, mechanical properties and material density tests are shown in table 1.
In this embodiment, the prepared in-situ loaded X-zeolite porous geopolymer is used for capturing carbon dioxide from flue gas after cooling and demolding, and the process of capturing carbon dioxide from industrial flue gas is simulated, and the specific simulation method is as follows:
dynamic carbon dioxide trapping experiments were performed on a gas chromatograph (GC-TCD analyzer) and a 3P instrument (mixSorbSHP) with a thermal conductivity detector, samples of different masses (50 mg, 75mg, and 100 mg) were previously degassed under vacuum at 300 ℃ for 6 hours, then the samples were cooled to 25 ℃ under nitrogen atmosphere, and then a mixture of 10% carbon dioxide and 90% nitrogen was introduced into the reactor at a flow rate of 20mL/min to begin the carbon dioxide trapping process.
The air pressure was maintained at 101.325kPa throughout the test. At the outlet gas concentration (C t ) With the outlet gas concentration at equilibrium (C 0 ) The ratio between the two builds a breakthrough curve, and the total trapping capacity of the sample is determined by carbon dioxide trapping accumulation in the dynamic trapping process. The method of calculation of the cumulative trapping capacity follows the differential loading, assuming very low concentrations, the volumetric flow rate is unchanged during trapping.
The simulation results obtained in this example are as follows:
the carbon dioxide capture capacity breakthrough curves of the in-situ loaded X-zeolite porous geopolymer with different masses are shown in FIG. 5 (a), and the carbon dioxide capture capacity values are shown in Table 2.
Example 2:
the embodiment provides a preparation method of an in-situ loaded X-type zeolite porous geopolymer, which comprises the following steps:
step one, preparing an alkaline excitant;
uniformly mixing 87g of sodium hydroxide, 221g of water glass and 115g of water to prepare an alkaline activator; in this embodiment, the alkali-activator is Na 2 O·nSiO 2 Wherein n is 2.42;
in this embodiment, the second step is the same as the second step in embodiment 1.
In this embodiment, step three is the same as step three in embodiment 1.
In this example, after curing, the prepared sample was cooled and demolded and designated FGX2, and its XRD crystal phase analysis was as shown in FIG. 4 (b); the zeolite microstructure is shown in fig. 3, and the results of the X-type zeolite content, mechanical properties and material density tests are shown in table 1.
In this example, the specific method for simulating in-situ loading of the X-zeolite porous geopolymer to capture carbon dioxide from industrial flue gas is the same as in example 1; the carbon dioxide capture capacity penetration curves of the geopolymers at different masses are shown in fig. 5 (b), and the carbon dioxide capture capacity values are shown in table 2.
Example 3:
the embodiment provides a preparation method of an in-situ loaded X-type zeolite porous geopolymer, which comprises the following steps:
step one, preparing an alkaline excitant;
uniformly mixing 100g of sodium hydroxide, 147g of sodium silicate and 146g of water to prepare an alkaline activator; in this embodiment, the alkali-activator is Na 2 O·nSiO 2 Wherein n is 2.42;
in this embodiment, the second step is the same as the second step in embodiment 1.
In this embodiment, step three is the same as step three in embodiment 1.
In this example, after curing, the prepared sample was cooled and demolded and designated FGX3, and its XRD crystal phase analysis was as shown in FIG. 4 (c); the zeolite microstructure is shown in fig. 3, and the results of the X-type zeolite content, mechanical properties and material density tests are shown in table 1.
In this example, the specific method for simulating in-situ loading of the X-zeolite porous geopolymer to capture carbon dioxide from industrial flue gas is the same as in example 1; the carbon dioxide capture capacity penetration curves of the geopolymers at different masses are shown in fig. 5 (b), and the carbon dioxide capture capacity values are shown in table 2.
Comparative example 1:
in this comparative example, step one was the same as step one in example 1;
step two is the same as step two in example 1;
step three, preparing an in-situ loaded X-type zeolite porous geopolymer
Pouring the mixed slurry prepared in the second step into a mould, and then directly placing the mould into a saturated steam generator for curing, and after curing, preparing the in-situ loaded X-type zeolite porous geopolymer;
wherein the autoclaved pressure of curing is 0.1MPa, the autoclaved temperature is 80 ℃, and the autoclaved curing time is 24h.
In this comparative example, after curing was completed, the prepared sample was cooled and demolded and designated as BC1, and the XRD crystalline phase analysis thereof was as shown in fig. 4 (d); the results of the X-type zeolite content, mechanical properties and material density tests are shown in Table 1.
In this comparative example 1, a specific method for simulating in-situ loading of an X-zeolite porous geopolymer to capture carbon dioxide from industrial flue gas is the same as in example 1; the carbon dioxide capture capacity penetration curves of different mass geopolymers are shown in fig. 5 (b), and the carbon dioxide capture capacity values are shown in table 2.
Comparative example 2:
the present embodiment provides a porous geopolymer without zeolite loading, comprising the steps of:
step one is the same as step one in example 1;
step two is the same as step two in example 1;
in this example, after curing, the prepared sample was cooled and demolded and named BC2, and the XRD crystalline phase analysis thereof was as shown in fig. 4 (d); the results of the X-type zeolite content, mechanical properties and material density tests are shown in Table 1.
In this comparative example, the specific method for simulating in-situ loading of an X-zeolite porous geopolymer to capture carbon dioxide from industrial flue gas is the same as in example 1; the carbon dioxide capture capacity penetration curves of the materials at different masses are shown in fig. 5 (b), and the carbon dioxide capture capacity values are shown in table 2.
From examples 1 to 3 and comparative examples 1 and 2, it can be seen that:
TABLE 1X zeolite content, mechanical Properties and Material Density
Examples 1 to 3 the in situ supported X zeolite porous geopolymer material obtained is shown in figure 2 and the material shows a grey black block porous structure. FGX exhibits excellent compressive strength (about 2.5 MPa) at lower densities (less than 400kg/m 3), demonstrating excellent mechanical properties that can ensure that it can withstand mechanical shock during repeated use and transportation without damaging the porous structure of the material.
The 1 μm and 100nm scale scanning electron microscope images of the in-situ loaded X-type zeolite porous geopolymer are shown in figure 3, the pore wall is covered with regular cube-shaped micron-sized X-type zeolite, excessive moisture in the material is converted into saturated steam in the curing process of A sample, A liquid-solid interface on the gas-pore wall is formed, and due to the continuous dissolution of sodium hydroxide on N-A-S-H gel, various substances such as Si-OH, al-OH, si-O-Na+ and the like are formed, and the monomer substances freely migrate and nucleate and crystallize into the X-type zeolite at A proper position. The porous structure of the material is favorable for the uniform distribution of saturated steam, so that each pore wall in the material can form a crystallization environment, thereby greatly improving the yield of the X-type zeolite.
Comparative example 1 a film was not coated on the surface of the mold to seal the mixed slurry during the saturated steam curing, so that the mixed slurry was exposed to the steam atmosphere, and comparative example 2 was not subjected to the saturated steam curing, and the results showed.
As shown in fig. 4 (d), the sample of example 1 showed a distinct X zeolite crystal phase peak, whereas the X zeolite crystal phase peak of comparative example 1 was significantly weaker, the crystal phase peak of X zeolite was not found in comparative example 2, and the zeolite content of the samples of both comparative examples was much lower than that of examples 1 to 3.Rietveld quantitative analysis results show that: in example 1, example 2 and example 3, the content of zeolite X in FGX was more than 40%.
As can be seen from fig. 4: the predominant crystalline phase of the FGX material was zeolite X (PDF # 38-0237), indicating that zeolite X was successfully loaded in situ into the pore walls of the porous geopolymer. Since the main synthetic raw material of FGX is fly ash, some impurities are inevitably contained, and thus, a weak impurity crystal phase peak can be observed in the XRD pattern.
(2) Carbon dioxide capture performance study of in situ supported X zeolite porous geopolymer:
TABLE 2 Capacity for capturing carbon dioxide
Breakthrough curves and breakthrough data for carbon dioxide capture of in-situ loaded X-zeolite porous geopolymers of different masses prepared in examples 1 to 3 are shown in FIGS. 5 (b), 5 (c), 5 (d) and Table 2.
The breakthrough curves and breakthrough data for FGX1 of different masses are shown in fig. 5 (b), where the carbon dioxide adsorption breakthrough curve increases dramatically in less than 200 seconds and continues to saturate after 1600 seconds. As FGX1 mass increases, the breakthrough front is significantly retarded, and FGX1 mass increases significantly the contact area between carbon dioxide and the sample, providing more adsorption sites for capturing carbon dioxide from the mixed gas. As the adsorption sites increase, more time is required to explore the adsorption potential of the sample, and therefore the second breakthrough time (reaching adsorption equilibrium) increases.
As shown in fig. 5 (c), as the mass of FGX2 increases, the number of carbon dioxide molecules that can be captured per unit time increases, and the breakthrough front moves forward; as a result, the adsorption process of FGX was significantly faster, and the time required to reach the second breakthrough front (to reach adsorption equilibrium) was significantly shortened. In general, the diffusion process is mainly controlled by concentration, and increasing the carbon dioxide concentration per unit volume can enhance the molecular diffusion driving force, so that the higher CO2 concentration can maximally improve the carbon dioxide capture potential of the material.
As shown in fig. 5 (d), as the mass of FGX3 increases, the dynamic adsorption rate of carbon dioxide increases significantly, and the breakthrough curves are similar to those of examples 1 and 2.
The geopolymers prepared in the three examples have different zeolite contents and therefore exhibit different breakthrough curves after the first breakthrough, but after the second breakthrough the total amount adsorbed per unit is almost the same, since the zeolite contents in the three geopolymers are not very different, the second breakthrough may fully reveal the adsorption potential of the zeolite, resulting in the final curve exhibiting the same trend.
The breakthrough curves and breakthrough data for carbon dioxide of example 1 and comparative examples 1 and 2 are shown in fig. 5 (e) and table 2, and it is apparent that FGX1 exhibits higher carbon dioxide adsorption capacity.
All FGX1 samples had higher capture of CO, whether it occurred before the breakthrough front or after the second breakthrough 2 Is provided). Under the same adsorption condition, the breakthrough front of FGX1 lags behind BC1, and BC1 is more likely to be broken through by carbon dioxide due to the insufficient number of carbon dioxide adsorption sites, namely the curve starts to rise before the FGX1 curve. FGX1 after reaching the first breakthrough front, the adsorption potential is gradually excited, the breakthrough curve is decreased and then increased until the second breakthrough front is stabilized, and after the first breakthrough, the BC1 sample is stabilized while the curve is approximately 1.
Comparative example 2 does not contain zeolite X and therefore does not have the ability to capture carbon dioxide, and its breakthrough curve is straight in appearance, i.e., broken through at the beginning of adsorption, the curve rises directly to 1 and then continues straight.
In summary, the X-type zeolite is loaded on the pore wall of the porous geopolymer in situ, so that the carbon dioxide capturing capacity is greatly improved, and meanwhile, the massive structure is beneficial to recycling after the material is used.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims (3)

1. The application of the in-situ loaded X-type zeolite porous geopolymer for capturing carbon dioxide in flue gas is characterized in that the in-situ loaded X-type zeolite porous geopolymer adopts a saturated steam curing method, and X-type zeolite is loaded on the pore wall of the porous geopolymer in situ to obtain the in-situ loaded X-type zeolite porous geopolymer;
the porous geopolymer is prepared by mixing slurry;
the raw material components of the mixed slurry comprise fly ash, sodium hydroxide, sodium silicate, water and a foaming agent; the foaming agent is prepared by compounding 20-30% of sodium dodecyl benzene sulfonate and 70-80% of hydrogen peroxide in percentage by mass;
the method comprises the following steps:
step one, preparing an alkaline excitant;
the specific process is as follows: uniformly mixing water glass, water and sodium hydroxide to prepare an alkaline excitant;
step two, preparing mixed slurry;
mixing and stirring the alkaline excitant prepared in the first step with the fly ash to obtain a mixture A, adding a foaming agent into the mixture A, and stirring to prepare mixed slurry;
the sodium hydroxide accounts for 18-25% of the mass of the fly ash, the water glass accounts for 40-70% of the mass of the fly ash, the water accounts for 21-38% of the mass of the fly ash, and the foaming agent accounts for 1-2% of the mass of the fly ash;
step three, preparing an in-situ loaded X-type zeolite porous geopolymer;
pouring the mixed slurry prepared in the second step into a mould, coating a layer of film on the surface of the mould to seal the mixed slurry, and finally placing the mould in a saturated steam generator for curing, thereby preparing the in-situ loaded X-type zeolite porous geopolymer after curing is finished;
wherein the autoclaved pressure of the curing is 0.1MPa, the autoclaved temperature is 80 ℃, and the autoclaved curing time is 24 hours;
in the second step, the mixed slurry comprises the following raw material components in percentage by mass: 46.4-49.8% of fly ash, 8.6-12.4% of sodium hydroxide, 18.3-34.2% of sodium silicate, 9.6-18.3% of water, 0.5-1% of foaming agent and 100% of total mass percentage of each component;
the alkaline excitant is Na 2 O·nSiO 2 Where n=2.42.
2. The use according to claim 1, wherein in the second step, the mixed slurry comprises the following raw material components in mass percent: 46.5% of fly ash, 8.6% of sodium hydroxide, 34.2% of water glass, 9.7% of water, 0.2% of sodium dodecyl benzene sulfonate and 0.8% of hydrogen peroxide.
3. The application of claim 1, wherein the specific process of the second step is: and (3) mixing and stirring the alkaline excitant prepared in the step (I) with the fly ash for 2min to obtain a mixture A, adding the foaming agent into the mixture A, and stirring for 1min to obtain mixed slurry.
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