CN117757267A - Fe-BTC/PDMS recyclable composite material for reducing ammonia emission and preparation method thereof - Google Patents

Fe-BTC/PDMS recyclable composite material for reducing ammonia emission and preparation method thereof Download PDF

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Publication number
CN117757267A
CN117757267A CN202311770610.5A CN202311770610A CN117757267A CN 117757267 A CN117757267 A CN 117757267A CN 202311770610 A CN202311770610 A CN 202311770610A CN 117757267 A CN117757267 A CN 117757267A
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pdms
btc
polymer matrix
composite material
composting
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沈玉君
张冬丽
周海宾
丁京涛
张阳
徐鹏翔
王健
程琼仪
张朋月
张芸
马双双
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Academy of Agricultural Planning and Engineering MARA
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Academy of Agricultural Planning and Engineering MARA
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Abstract

The invention discloses a Fe-BTC/PDMS recyclable composite material for reducing ammonia gas emission and a preparation method thereof. Consists of a PDMS polymer matrix and Fe-BTC materials which grow in situ and are loaded on the surface and in pore channels of the PDMS polymer matrix. The Fe-BTC/PDMS recyclable composite material is prepared by a preparation process with low price and simple operation, and the Fe-BTC/PDMS recyclable composite material is added into excrement to perform electric field composting, so that the problem of low efficiency of materials applied in the fields of electric field composting odor adsorption, nitrogen protection and the like is effectively solved. The invention solves the problems of accumulated influence damage to soil and high cost caused by difficult recycling of the traditional materials, and has great advantages and practical value compared with the traditional materials.

Description

Fe-BTC/PDMS recyclable composite material for reducing ammonia emission and preparation method thereof
Technical Field
The invention belongs to the technical field of ammonia gas emission reduction, and particularly relates to a Fe-BTC/PDMS recyclable composite material for reducing ammonia gas emission and a preparation method thereof.
Background
Controlling ammonia emissions is critical to reducing the atmospheric secondary inorganic salt and PM2.5 concentrations, improving air quality. Livestock and poultry cultivation is the main emission source of ammonia, and the ammonia emission amount of livestock and poultry cultivation in China accounts for 54.06% of the total emission amount. Therefore, the control of the ammonia emission of livestock and poultry breeding plays a vital role in reducing the ammonia emission, and has important significance in improving the air quality. In order to control the emission of ammonia, the introduction of materials with high ammonia adsorption capacity is an effective measure, and common materials include biochar, zeolite, acid substances and the like. However, these materials are difficult to recycle, often with the compost product accumulating directly in the soil, which not only increases the cost of the compost, but may also cause irreversible damage to the soil. Therefore, while these materials are used to control ammonia emissions, effective measures need to be taken to address their recycling issues to reduce the negative impact on the environment and soil.
Fe-BTC is formed by self-assembly of iron ions and trimesic acid, is a novel multifunctional crystallization adsorption MOFs material, and has remarkable adsorption effect on ammonia gas due to a special topological structure and a metal center. However, fe-BTC itself is expensive and difficult to recycle, and addition alone is not practical in composting.
Aiming at the problem that the ammonia gas emission adsorption material is difficult to recover in the composting process, a novel composite material with high adsorption performance and recoverability is developed to become a current break.
Disclosure of Invention
The invention aims to provide a Fe-BTC/PDMS recyclable composite material capable of reducing ammonia gas emission and a preparation method thereof. The preparation method disclosed by the invention is simple in preparation process, reasonable in raw material formula and strong in practicability, and the prepared composite material has the advantages of recycling, high porosity, adjustable pore channels and the like, can effectively reduce the emission of ammonia in the compost, can be recycled, and overcomes the defects of the prior art.
The Fe-BTC/PDMS recyclable composite material provided by the invention consists of a PDMS polymer matrix and Fe-BTC materials which grow in situ and are loaded on the surface and in pore channels of the PDMS polymer matrix;
wherein BTC represents trimesic acid;
the PDMS polymer matrix has a compressible porous structure, also known as a PDMS sponge;
the proportion of the iron ion salt in the PDMS polymer matrix and the Fe-BTC material can be as follows: 40g:0.001mol to 0.007mol; specifically, 40g:0.003mol.
The Fe-BTC material is formed by self-assembly connection of iron ions and organic ligand trimesic acid, wherein the molar ratio of the iron ions to the organic ligand trimesic acid is 1:1.
The PDMS polymer matrix is prepared from polydimethylsiloxane and a curing agent thereof through a sucrose template technology.
The PDMS gauge may be 20 x 10mm.
The invention also provides a preparation method of the Fe-BTC/PDMS recyclable composite material.
The preparation method of the Fe-BTC/PDMS recyclable composite material provided by the invention comprises the following steps:
1) Preparing a PDMS polymer matrix (PDMS sponge) with a compressible porous structure by a sucrose template method;
2) In-situ growing Fe-BTC to obtain Fe-BTC/PDMS recyclable composite material:
adding a PDMS polymer matrix with a compressible porous structure into an iron ion salt solution for full immersion, mixing the obtained mixture with an aqueous solution of organic ligand trimesic acid, and carrying out hydrothermal reaction, wherein Fe-BTC is loaded into the surface and pore canal of the PDMS polymer matrix through in-situ growth.
In the step 1), square sugar blocks are placed in a polydimethylsiloxane solution containing a curing agent for full immersion, and vacuum treatment is carried out so that the polydimethylsiloxane fully enters into pores of the square sugar, the square sugar blocks are cured, deionized water is repeatedly washed to remove the square sugar blocks, and a PDMS polymer matrix with a compressible porous structure is obtained;
in the step 2), the ratio of the PDMS polymer matrix to the iron salt may be: 40g:0.001mol to 0.007mol, specifically 40g:0.003mol;
the iron ion salt can be ferric chloride;
in the iron ion salt solution, the mass concentration of the iron ion substances is 0.01mol/L-0.07mol/L;
in the aqueous solution of the organic ligand trimesic acid, the mass concentration of the organic ligand trimesic acid is 0.01mol/L-0.07mol/L, and can be specifically 0.03mol/L;
the molar ratio of the iron ions to the organic ligand trimesic acid is 1:1;
the temperature of the hydrothermal reaction is 60-80 ℃ and the time is 1-2 h.
After the hydrothermal reaction is finished, the method further comprises the steps of centrifugally separating the composite material and drying in vacuum.
The prepared Fe-BTC/PDMS composite material is dried in vacuum to remove coordinated water molecules and ethanol molecules.
The invention also provides application of the Fe-BTC/PDMS recyclable composite material in composting.
In particular, the Fe-BTC/PDMS recyclable composite is used to reduce ammonia emissions during composting, which may be electric field composting in particular.
The invention also provides a method for reducing the ammonia gas emission in the composting process.
The method for reducing the ammonia emission in the composting process provided by the invention comprises the following steps: and fully mixing the Fe-BTC/PDMS recyclable composite material with a composting material, and composting.
The composting materials comprise fresh pig manure and corn straw, wherein the fresh pig manure accounts for 80 percent,
the carbon-nitrogen ratio and the water content of the compost materials are respectively 20:1 and 60%, and the ventilation rate is adjusted to be 0.5 L.Kg -1 ·DM -1 ·min -1 The ventilation condition is set to be ventilation for 30min and stop for 30min;
the composting can be electric field composting, and more specifically, composting can be performed by applying a 2V direct current annular electric field.
In the method, the mass ratio of the Fe-BTC/PDMS recoverable composite material to the compost material is 0.8-1.5kg:30kg.
The method further comprises the following steps: and (3) recovering the Fe-BTC/PDMS recyclable composite material from the decomposed material after composting.
The composite adsorption material provided by the invention can be added to effectively reduce the emission of odor such as ammonia gas in the composting process, and can also be used for recycling the composite adsorption material in the decomposed fertilizer.
The invention has the following beneficial technical effects:
1) The Fe-BTC/PDMS recyclable composite material is prepared by a preparation process with low price and simple operation, and the Fe-BTC/PDMS recyclable composite material is added into excrement to perform electric field composting, so that the problem of low efficiency of materials applied in the fields of electric field composting odor adsorption, nitrogen protection and the like is effectively solved.
2) The invention solves the problems of accumulated influence damage to soil and high cost caused by difficult recycling of the traditional materials, and has great advantages and practical value compared with the traditional materials.
Drawings
Fig. 1 is a flow chart of the preparation of a PDMS polymer block having a compressible porous structure according to the present invention.
FIG. 2 is a flow chart of the preparation of the Fe-BTC/PDMS recyclable composite material according to the present invention.
Fig. 3 a is a photograph of a PDMS polymer block prepared in example 1 of the present invention, and b is a physical image of a preferable supported Fe-BTC/PDMS recyclable composite (iron ion salt: PDMS sponge=0.003mol: 40 g).
FIG. 4 is a schematic diagram of a field composting reactor according to the invention for use in example 3.
Fig. 5 is a graph showing the effect of reducing ammonia gas emission during electric field composting of the materials prepared in examples 1 and 2 of the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of PDMS Polymer matrix with compressible porous Structure
The preparation flow is shown in figure 1.
The first step: weigh 5g of curing agent (SYLGARD) TM 184, dow Corning) to 50g of polydimethylsiloxane prepolymer (SYLGARD) TM 184, usa, dakangning) and mechanically stirring for 10min until the solution is mixed uniformly to obtain a polymer solution.
And a second step of: taking 20 square sugar blocks (the right north, the specification is 20 x 10 mm), fully immersing the square sugar blocks in the polymer solution prepared in the first step, placing the polymer solution in a vacuum oven, and carrying out vacuum treatment for 30min to remove air in the square sugar blocks so that the polymer solution is fully filled in a square pond.
And a third step of: the cube sugar in the polymer solution in the second step was taken out, placed in a vacuum oven, and vacuum cured for 4 hours at 105 ℃.
Fourth step: and (3) soaking and washing the cured material obtained in the third step in deionized water for 5 times until the square sugar is completely removed, and drying at 55 ℃ to obtain the PDMS polymer block with the compressible porous structure.
EXAMPLE 2 preparation of Fe-BTC/PDMS recoverable composite
The preparation flow is shown in figure 2.
The first step: 0g, 0.27g, 0.54g, 0.81g and 1.08g FeCl are respectively weighed 3 ·6H 2 O was dissolved in 100ml of pure water, and the solution A was obtained by mechanically stirring at room temperature for 30 minutes to completely dissolve O.
And a second step of: 0g, 0.21g, 0.42g, 0.63g and 0.84g of trimesic acid are weighed and dissolved in 100ml of pure water, and the solution B is obtained by mechanically stirring for 1 h.
And a third step of: the PDMS polymer block having a compressible porous structure prepared in example 1 was taken, fully immersed in the solution a, and air in the polymer block was discharged to obtain a mixed solution C. And adding the solution B prepared in the second step into the mixed solution C, carrying out hydrothermal reaction for 2 hours at 70 ℃ on the iron ion salt and the organic ligand (the mass ratio of the iron ion salt to the organic ligand is 1:1), carrying out in-situ growth on the iron ion salt to be loaded on the surface and the pore canal of the PDMS polymer block, and finally carrying out centrifugal washing and vacuum drying at 65 ℃ to obtain the Fe-BTC/PDMS recyclable composite material with different loadings. Table 1 is a statistical table of the specific surface area of the composite material produced.
Table 1 statistical table of specific surface area of composite material
Table 1 shows specific surface area characterization of Fe-BTC/PDMS recoverable composite materials with different loadings.
In fig. 3, a is a schematic representation of a PDMS sponge and b is a preferred loading of Fe-BTC/PDMS recoverable composite (iron ion salt: PDMS sponge = 0.003mol:40 g).
As can be seen from table 1, the iron ion salts: the proportion of the PDMS sponge is 0.003mol:40g, the specific surface area of the obtained composite material is maximum, which is more beneficial to the adsorption of ammonia.
Example 3 electric field composting experiments
The electric field assisted aerobic composting test is carried out by taking fresh pig manure as a main material and corn straw as an auxiliary material, and the composting period is 27 days. The experimental design is shown in table 2: altogether 3 treatments, blank, material addition prepared in examples 1,2 (iron ion salt: PDMS sponge = 0.003mol:40g prepared Fe-BTC/PDMS in example 2), adjusting the addition ratio to 1kg (500 pieces) of Fe-BTC/PDMS:30kg of composting materials, adjusting the proportion of fresh pig manure to corn straw, adding a proper amount of deionized water, and adjusting the carbon nitrogen ratio and the water content of the composting materials to be 20:1 and 60%, and the ventilation rate is adjusted to be 0.5 L.Kg -1 ·DM -1 ·min -1 The ventilation conditions were set to be 30min and stopped for 30min, and a 2V DC annular electric field was added to each treatment (electric field composting reactor is shown in FIG. 4), and composting experiments were performed. 09 am every day: 00 and 15 pm: 00 compost and ambient temperature were measured and the average value recorded. Determination of NH daily before device blast aeration 3 Concentration. Physical and chemical properties and ammonia gas discharge amount of each stage of compost are tested, the ammonia gas discharge amount is shown in figure 5, and the accumulated ammonia gas discharge amount of a blank control is 4.89g/kg -1 DM, the accumulated discharge of ammonia gas after adding the recoverable composite material of the invention is 2.62g/kg -1 DM, the emission reduction can reach 46%, and the emission reduction of the PDMS sponge prepared in the embodiment 1 to the ammonia of the compost is 20%.
The recovery effect of the additive in the decomposed material obtained in the example 3 is shown in the table 3, and the recovery rate of the composite material is above 95%.
TABLE 2 electric field compost experimental design table
Table 3 statistical table of recovery efficiency of composite materials
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.

Claims (10)

1. The Fe-BTC/PDMS recyclable composite material for reducing ammonia emission comprises a PDMS polymer matrix and Fe-BTC materials which grow in situ and are loaded on the surface and in pore channels of the PDMS polymer matrix; the composite material can reduce the emission of ammonia in compost;
wherein BTC represents trimesic acid;
the Fe-BTC material is formed by self-assembly connection of iron ions and organic ligand trimesic acid, wherein the molar ratio of the iron ions to the organic ligand trimesic acid is 1:1;
the PDMS polymer matrix has a compressible porous structure;
the proportion of the iron ion salt in the PDMS polymer matrix and the Fe-BTC material is as follows: 40g:0.001mol to 0.007mol.
2. The Fe-BTC/PDMS recyclable composite according to claim 1, wherein the PDMS polymer matrix is made from polydimethylsiloxane and its curing agent by sucrose templating technique.
3. A method of preparing the Fe-BTC/PDMS recyclable composite according to claim 1 or 2, comprising the steps of:
1) Preparing a PDMS polymer matrix with a compressible porous structure by a sucrose template method;
2) In-situ growth of Fe-BTC to obtain Fe-BTC/PDMS recyclable composite material
Adding a PDMS polymer matrix with a compressible porous structure into an iron ion salt solution for immersing, mixing the obtained mixture with an aqueous solution of organic ligand trimesic acid, and carrying out hydrothermal reaction, wherein Fe-BTC is loaded into the surface and pore canal of the PDMS polymer matrix through in-situ growth.
4. A method according to claim 3, wherein the operation of step 1) is: immersing the square sugar block in a polydimethylsiloxane solution containing a curing agent, carrying out vacuum treatment, curing, and repeatedly washing with deionized water to remove the square sugar block, thereby obtaining the PDMS polymer matrix with a compressible porous structure.
5. A method according to claim 3, wherein in step 2), the ratio of PDMS polymer matrix to iron ion salt is: 40g:0.001mol to 0.007mol;
the iron ion salt is ferric chloride;
in the iron ion salt solution, the mass concentration of the iron ion substances is 0.01mol/L-0.07mol/L;
in the aqueous solution of the organic ligand trimesic acid, the mass concentration of the organic ligand trimesic acid is 0.01mol/L-0.07mol/L;
the molar ratio of the iron ions to the organic ligand trimesic acid is 1:1;
the temperature of the hydrothermal reaction is 60-80 ℃ and the time is 1-2 h.
6. Use of the Fe-BTC/PDMS recoverable composite material according to claim 1 or 2 in composting.
7. The use according to claim 6, wherein the Fe-BTC/PDMS recoverable composite is used to reduce ammonia emissions during composting.
8. A method for reducing ammonia emissions during composting comprising the steps of: the Fe-BTC/PDMS recyclable composite according to claim 1 or 2 is fully mixed with composting materials and composted.
9. The method of claim 8, wherein the composting material comprises fresh swine waste and corn stover, wherein the fresh swine waste comprises 80% of the composting material;
the carbon-nitrogen ratio and the water content of the compost materials are respectively 20:1 and 60%, and the ventilation rate is adjusted to be 0.5 L.Kg -1 ·DM -1 ·min -1 The ventilation condition is set to be ventilation for 30min and stop for 30min;
the mass ratio of the Fe-BTC/PDMS recoverable composite material to the compost material is 0.8-1.5kg:30kg.
10. The method according to claim 8 or 9, characterized in that the method further comprises: and (3) recovering the Fe-BTC/PDMS recyclable composite material from the decomposed material after composting.
CN202311770610.5A 2023-12-21 2023-12-21 Fe-BTC/PDMS recyclable composite material for reducing ammonia emission and preparation method thereof Pending CN117757267A (en)

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