CN113769716A - Preparation method and application of novel rubber seed shell-based composite material - Google Patents
Preparation method and application of novel rubber seed shell-based composite material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a novel rubber seed shell-based composite material, wherein rubber seed shells are crushed and mixed with KOH, and then temperature programming-heat preservation heat treatment is carried out in nitrogen atmosphere; mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water to prepare a dispersion liquid; immersing a rubber seed shell material into the dispersion liquid, stirring for reaction, filtering, cleaning and airing, and immobilizing MXene-graphene oxide on the surface of the rubber seed shell by a thermosetting method through the action of a coupling agent to obtain a novel rubber seed shell-based composite material; the prepared composite material is used as a scavenger for removing toxin creatinine and uric acid, the composite material can remove creatinine and uric acid respectively up to 431mg/g and 504mg/g, and the creatinine and uric acid scavenger has excellent performance.
Description
Technical Field
The invention relates to the field of pharmacy, in particular to a preparation method and application of a novel rubber seed shell-based composite material.
Background
Creatinine belongs to nitrogen-containing organic non-protein compounds and is a metabolic end product of energy storage substance creatine in muscle tissues of organisms; uric acid is the final product of purine nucleotide catabolic process in human body, and the generation of creatinine and uric acid in normal human body is relatively stable. Renal patients have renal hypofunction or failure, and a large amount of toxic components including creatinine and uric acid are accumulated in blood, and excessive creatinine and uric acid not only cause a series of toxic symptoms of the patients, but also further accelerate the renal failure process.
For chronic renal failure patients, hemodialysis, which is a very expensive medical procedure, is an unacceptable technique for adsorbing muscle complex by using oral adsorbent or blood perfusion, and has recently been attracting attention in clinical treatment. The oral adsorbent such as activated carbon scavenger has high affinity adsorption property for toxic substances, and has biocompatibility with blood. Therefore, in the face of increasing patients with kidney diseases, the design and preparation of a material with good creatinine and uric acid removal effects have great significance for treating kidney diseases and prolonging the lives of patients.
The rubber tree, also known as hevea rubber, is a plant of the family euphorbiaceae, a native brazil, a typical tropical rainforest plant, and belongs to perennial tropical trees. The planting area of the natural rubber tree in the southeast Asia area accounts for 90 percent of the world, the natural rubber is mainly produced, besides the rubber which is a main economic product, the rubber tree can produce about 0.8 to 1.2t of rubber seeds per hectare every year, the rubber tree which can bear fruits (more than 3 years old) in China is close to 100 ten thousand mu, and the rubber seeds can be produced 30 to 45kg/667m per year2. At present, over 90 percent of rubber seeds are rotted in the ground except a small amount of rubber seed oil obtained by breeding and sporadic primary processing, which causes huge resource waste.
The main components of the rubber seed shell are cellulose, hemicellulose and lignin, and the rubber seed shell is hard in texture, low in ash content and high in volatile content and is a high-quality precursor for producing aromatic cyclization materials. Graphene oxide is an oxide of graphene, MXene is composed of transition metal carbide, nitride or carbonitride with the thickness of a plurality of atomic layers, the transition metal carbide, nitride or carbonitride exists in the form of agglomerated loose micron powder in a normal state, the surface of the graphene oxide has a plurality of epoxy groups, hydroxyl groups and carboxyl groups, the graphene oxide has strong scavenging capacity, and can scavenge a large amount of organic matters, heavy metal ions and other micro pollutants, but the powdered graphene oxide and MXene cannot be produced and effectively used in the application of human toxin scavenging.
Disclosure of Invention
The invention provides a preparation method and application of an MXene-graphene oxide modified rubber seed shell-based composite material, aiming at the problems in the prior art, wherein MXene and graphene oxide powder materials and a coupling agent are pre-dispersed to prepare a water dispersion liquid, MXene-graphene oxide is loaded on the surface of a rubber seed shell in a stirring and heating mode, and MXene and graphene oxide are fixedly loaded on the surface of the rubber seed shell under the action of the coupling agent under the heating condition to obtain the composite material.
The invention is realized by the following technical scheme:
a preparation method of a novel rubber seed shell-based composite material comprises the following steps:
(1) preparing a rubber seed shell material with aromatic cyclization on the surface: crushing the rubber seed shells to 20-200 meshes, mixing with KOH, and performing temperature programming-heat preservation treatment in a nitrogen atmosphere;
(2) preparing an aqueous dispersion liquid of MXene-graphene oxide: mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water to prepare a dispersion liquid;
(3) preparing MXene-graphene oxide modified rubber seed shells: soaking the rubber seed shell material treated in the step (1) into the dispersion liquid in the step (2), and carrying out high-speed stirring reaction at the temperature of 30-300 ℃ for 2-48 hours;
(4) preparing an MXene-graphene oxide modified rubber seed shell base composite material: and (3) filtering, cleaning and airing the product obtained in the step (3), and immobilizing MXene-graphene oxide on the surface of the rubber seed shells by using a thermosetting method through the action of a coupling agent to obtain the novel rubber seed shell-based composite material.
In the step (1), the mixing mass ratio of the rubber seed shell powder to the KOH is 1: 1-3.
The temperature rise rate of the temperature rise-heat preservation heat treatment in the step (1) is 10 ℃/min, the heat preservation temperature is 1000-.
In the step (2), the auxiliary agent is at least one of a surfactant, a defoaming agent, a dispersing agent, a chelating agent and a thickening agent, and the surfactant is at least one of sodium dodecyl sulfate, stearic acid and fatty glyceride; the defoaming agent is at least one of glycerol trihydroxy polyether, polydimethylsiloxane, myrcene and pinene; the dispersant is at least one of sodium hexametaphosphate, sodium polyphosphate, white oil and sodium methylene naphthalene sulfonate; the chelating agent is at least one of citric acid, tartaric acid, fumaric acid, polymethacrylic acid and polyacrylic acid; the thickener is at least one of sodium carboxymethylcellulose, sodium alginate and hydroxyethyl cellulose; the coupling agent is at least one of silane coupling agent, titanate coupling agent, aluminate coupling agent, bimetallic coupling agent, lignin coupling agent and tin coupling agent.
The mol concentration ratio of MXene, graphene oxide, the auxiliary agent and the coupling agent in the dispersion liquid in the step (2) is 3-4:5-7:1: 10-15.
And (3) the solid-to-liquid ratio (mg: mL) of the rubber seed shell material treated in the step (1) to the dispersion liquid in the step (2) is 0.5: 1-4.
The rotation speed of the high-speed stirring in the step (3) is 300-500 rpm.
The temperature of the thermosetting method in the step (4) is 100-350 ℃, and the time is 1-24 h.
The invention also provides the application of the novel rubber seed shell-based composite material as a creatinine and uric acid scavenger.
According to the invention, as the MXene-graphene oxide powder material is fully dispersed in advance, and MXene-graphene oxide is loaded on the surface of the rubber seed shell in a high-speed stirring and heating mode, and MXene and graphene oxide are immobilized on the surface of the rubber seed shell under the action of the coupling agent, the immobilized MXene and graphene oxide are not easy to fall off from the surface of the rubber seed shell, and the safety performance of the modified scavenging agent is ensured. In addition, MXene and graphene oxide are embedded, so that the scavenging capacity of the scavenging agent on creatinine and uric acid can be greatly improved.
Drawings
FIG. 1 is an SEM image of a composite material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a novel rubber seed shell-based composite material comprises the following steps:
(1) preparing a rubber seed shell material with aromatic cyclization on the surface: crushing rubber seed shells, sieving the crushed rubber seed shells with a 20-mesh sieve, mixing the crushed rubber seed shells with KOH, heating the mixture to 1000 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and keeping the temperature for 1h, wherein the mixing mass ratio of the rubber seed shell powder to the KOH is 1: 1;
(2) preparing an aqueous dispersion liquid of MXene-graphene oxide: mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water, and performing strong ultrasound (500W) and high-speed stirring (300rpm) for 2 hours at 80 ℃ to obtain 100mL of aqueous dispersion liquid, wherein the auxiliary agent is sodium dodecyl sulfate, and the coupling agent is (3-aminopropyl) dimethylethoxysilane; the concentration of MXene in the dispersion liquid is 3.0mM, the concentration of graphene oxide is 5.0mM, the concentration of sodium dodecyl sulfate is 1.0mM, the concentration of (3-aminopropyl) dimethyl ethoxy silane is 10.0mM, and the prepared MXene-graphene oxide aqueous dispersion liquid does not precipitate after standing for 72 hours;
(3) preparing an MXene-graphene oxide modified composite material: immersing the rubber seed shells subjected to the heat treatment in the step (1) into the aqueous dispersion prepared in the step (2), wherein the solid-to-liquid ratio (mg: mL) of the rubber seed shell material to the dispersion is 0.5:1, and stirring at a high speed (300rpm) at 100 ℃ for reaction for 2 hours;
(4) and (4) standing and cooling the product obtained in the step (3), filtering, cleaning, airing, and curing at a high temperature of 180 ℃ in an oven for 1 hour to obtain the MXene-graphene oxide modified rubber seed shell-based composite material with the core-shell structure.
The adsorption performance of the MXene-graphene oxide modified rubber seed shell-based composite material prepared in the example on creatinine and uric acid was studied by intermittent experiments, the adsorption experiments were all performed in a 100mL brown sample bottle with a polytetrafluoroethylene liner cover, the sample bottle was filled with 10mg of MXene-graphene oxide modified rubber seed shell-based composite material and 25mL of adsorption solution, the sample bottle was placed in a constant temperature shaker at a set temperature, after shaking for 12 hours, the sample bottle was filtered by a 0.22 μm nylon membrane, the contents of creatinine and uric acid in the remaining solution were determined by measuring the absorbance at wavelengths of 234 and 295nm using a UV/vis spectrophotometer (Agilent 8453 UV-Visible System, USA), and the removal efficiency and the adsorption capacity of creatinine and uric acid were calculated using equations (1) and (2).
η＝(C0-Ce)/C0×100％ (1)
qe＝(C0-Ce)/m×V (2)
In the formula, C0、CeThe initial and equilibrium concentrations (mg/L) of creatinine and uric acid solution, m is the mass (g) of RAC added, and V is the volume (L) of the adsorption solution, and the adsorption amounts of creatinine and uric acid of the composite material prepared in the embodiment as a scavenger are respectively 431mg/g and 504mg/g through calculation.
Fig. 1 is an SEM image of the composite material prepared in this example, and it can be seen from the SEM image that MXene and graphene oxide are immobilized on the surface of rubber seed shell and have a core-shell-like structure.
Example 2
A preparation method of a novel rubber seed shell-based composite material comprises the following steps:
(1) preparing a rubber seed shell material with aromatic cyclization on the surface: crushing rubber seed shells, sieving the crushed rubber seed shells with a 100-mesh sieve, mixing the crushed rubber seed shells with KOH, heating the mixture to 1200 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and keeping the temperature for 1.5h, wherein the mixing mass ratio of the rubber seed shell powder to the KOH is 1: 2;
(2) preparing an aqueous dispersion liquid of MXene-graphene oxide: mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water, and performing strong ultrasound (500W) and high-speed stirring (300rpm) at 80 ℃ for 12 hours to obtain 100mL of aqueous dispersion liquid, wherein the auxiliary agent is polydimethylsiloxane and the coupling agent is a titanate coupling agent; the concentration of MXene in the dispersion liquid is 3.5mM, the concentration of graphene oxide is 6.0mM, the concentration of polydimethylsiloxane is 1.0mM, the concentration of titanate coupling agent is 12.0mM, and the prepared MXene-graphene oxide aqueous dispersion liquid does not precipitate after standing for 72 hours;
(3) preparing an MXene-graphene oxide modified scavenging agent: immersing the rubber seed shells subjected to the heat treatment in the step (1) into the aqueous dispersion prepared in the step (2), wherein the solid-to-liquid ratio (mg: mL) of the rubber seed shell material to the dispersion is 0.5:2, and stirring at a high speed (400rpm) at 150 ℃ for reaction for 6 hours;
(4) and (4) standing and cooling the product obtained in the step (3), filtering, cleaning, airing, and curing at a high temperature of 200 ℃ in an oven for 6 hours to obtain the MXene-graphene oxide modified rubber seed shell-based composite material.
The adsorption performance of the MXene-graphene oxide modified rubber seed shell-based composite material on creatinine and uric acid prepared in the embodiment is researched according to the method in the embodiment 1, and the adsorption amounts of the composite material as a scavenger on creatinine and uric acid are 331mg/g and 401mg/g respectively.
Example 3
A preparation method of a novel rubber seed shell-based composite material comprises the following steps:
(1) preparing a rubber seed shell material with aromatic cyclization on the surface: crushing the rubber seed shells, sieving the crushed rubber seed shells with a 150-mesh sieve, mixing the crushed rubber seed shells with KOH, heating the mixture to 1300 ℃ at the speed of 10 ℃/min in a nitrogen atmosphere, and keeping the temperature for 1.4h, wherein the mixing mass ratio of the rubber seed shell powder to the KOH is 1: 3;
(2) preparing an aqueous dispersion liquid of MXene-graphene oxide: mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water, and performing strong ultrasound (500W) and high-speed stirring (300rpm) at 80 ℃ for 24 hours to obtain 100mL of aqueous dispersion liquid, wherein the auxiliary agent is sodium carboxymethylcellulose and the coupling agent is a lignin coupling agent; the concentration of MXene in the dispersion liquid is 4.0mM, the concentration of graphene oxide is 7.0mM, the concentration of sodium carboxymethylcellulose is 1.0mM, the concentration of lignin coupling agent alkane is 15.0mM, and the prepared MXene-graphene oxide aqueous dispersion liquid does not precipitate after standing for 72 hours;
(3) preparing an MXene-graphene oxide modified scavenging agent: soaking the rubber seed shells subjected to the heat treatment in the step (1) into the aqueous dispersion prepared in the step (2), wherein the solid-to-liquid ratio (mg: mL) of the rubber seed shell material to the dispersion is 0.5:3, and stirring at a high speed (500rpm) at 80 ℃ for reaction for 24 hours;
(4) and (4) standing and cooling the product obtained in the step (3), filtering, cleaning, airing, and then placing the product in an oven at the temperature of 100 ℃ for high-temperature curing for 24 hours to obtain the MXene-graphene oxide modified rubber seed shell-based composite material.
The adsorption performance of the MXene-graphene oxide modified rubber seed shell-based composite material prepared in the embodiment on creatinine and uric acid is studied according to the method in the embodiment 1, and the adsorption amounts of the composite material prepared in the embodiment as a scavenger on creatinine and uric acid are 301mg/g and 378mg/g respectively.
Example 4
A preparation method of a novel rubber seed shell-based composite material comprises the following steps:
(1) preparing a rubber seed shell material with aromatic cyclization on the surface: crushing rubber seed shells, sieving the crushed rubber seed shells with a 200-mesh sieve, mixing the crushed rubber seed shells with KOH, heating the mixture to 1500 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere, and keeping the temperature for 1h, wherein the mixing mass ratio of the rubber seed shell powder to the KOH is 1: 3;
(2) preparing an aqueous dispersion liquid of MXene-graphene oxide: mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water, and performing strong ultrasound (500W) and high-speed stirring (300rpm) for 48 hours at 80 ℃ to obtain 100mL of aqueous dispersion liquid, wherein the auxiliary agent is citric acid, and the coupling agent is a silane coupling agent; the concentration of MXene in the dispersion liquid is 3.0mM, the concentration of graphene oxide is 5.0mM, the concentration of citric acid is 1.0mM, the concentration of a silane coupling agent is 10.0mM, and the prepared MXene-graphene oxide aqueous dispersion liquid does not precipitate after standing for 72 hours;
(3) preparing an MXene-graphene oxide modified composite material: immersing the rubber seed shells subjected to the heat treatment in the step (1) into the aqueous dispersion prepared in the step (2), wherein the solid-to-liquid ratio (mg: mL) of the rubber seed shell material to the dispersion is 0.5:4, and stirring at a high speed (300rpm) at the temperature of 30 ℃ for reaction for 48 hours;
(4) and (4) standing and cooling the product obtained in the step (3), filtering, cleaning, airing, and curing in an oven at 350 ℃ for 1 hour at high temperature to obtain the MXene-graphene oxide modified rubber seed shell-based composite material.
The adsorption performance of the MXene-graphene oxide modified rubber seed shell-based composite material prepared in the embodiment on creatinine and uric acid is studied according to the method in the embodiment 1, and the adsorption amounts of the composite material prepared in the embodiment as a scavenger on creatinine and uric acid are 211mg/g and 326mg/g respectively.
Example 5
Crushing the rubber seed shells, sieving the crushed rubber seed shells with a 60-mesh sieve, mixing the crushed rubber seed shells with KOH, heating the mixture to 1000 ℃ at a speed of 10 ℃/min in a nitrogen atmosphere at a mass ratio of 1:4, and keeping the temperature for 1h to prepare the surface aromatic cyclized rubber seed shell material.
The material prepared in this example was used for clearance of uremic toxins according to the method of example 1, with creatinine and uric acid adsorbed in amounts of 204mg/g and 290mg/g, respectively.
The MXene-graphene oxide modified scavenging agent prepared in each embodiment of the invention is subjected to quality inspection, the detection result is detailed in the following table 1, and the reference standard is ' pharmacopoeia of the people's republic of China ' 718 page.
The present invention is not limited to the above-described embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
TABLE 1
Claims (10)
1. The preparation method of the novel rubber seed shell-based composite material is characterized by comprising the following steps of:
(1) crushing the rubber seed shells to 20-200 meshes, mixing with KOH, and performing temperature programming-heat preservation treatment in a nitrogen atmosphere;
(2) mixing MXene, graphene oxide, an auxiliary agent, a coupling agent and water to prepare a dispersion liquid;
(3) immersing the rubber seed shells treated in the step (1) into the dispersion liquid in the step (2), and reacting for 2-48 hours at a high speed under stirring at the temperature of 30-300 ℃;
(4) and (3) filtering, cleaning and airing the product obtained in the step (3), and immobilizing MXene-graphene oxide on the surface of the rubber seed shells by using a thermosetting method through the action of a coupling agent to obtain the novel rubber seed shell-based composite material.
2. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the mixing mass ratio of the rubber seed shell to KOH in the step (1) is 1: 1-3.
3. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the temperature rise rate of the temperature rise-heat preservation heat treatment in the step (1) is 10 ℃/min, the heat preservation temperature is 1000-.
4. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the auxiliary agent in the step (2) is at least one of a surfactant, a defoaming agent, a dispersing agent, a chelating agent and a thickening agent, and the surfactant is at least one of sodium dodecyl sulfate, stearic acid and fatty glyceride; the defoaming agent is at least one of glycerol trihydroxy polyether, polydimethylsiloxane, myrcene and pinene; the dispersant is at least one of sodium hexametaphosphate, sodium polyphosphate, white oil and sodium methylene naphthalene sulfonate; the chelating agent is at least one of citric acid, tartaric acid, fumaric acid, polymethacrylic acid and polyacrylic acid; the thickener is at least one of sodium carboxymethylcellulose, sodium alginate and hydroxyethyl cellulose.
5. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the coupling agent in the step (2) is at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a bimetallic coupling agent, a lignin coupling agent and a tin coupling agent.
6. The preparation method of the novel rubber seed shell-based composite material as claimed in claim 1, wherein the molar concentration ratio of MXene, graphene oxide, auxiliary agent and coupling agent in the dispersion liquid in the step (2) is 3-4:5-7:1: 10-15.
7. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the solid-to-liquid ratio mg: mL of the rubber seed shell material treated in the step (1) to the dispersion liquid in the step (2) in the step (3) is 0.5: 1-4.
8. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the high-speed stirring speed in the step (3) is 300-500 rpm.
9. The method for preparing the novel rubber seed shell-based composite material as claimed in claim 1, wherein the temperature of the thermosetting method in the step (4) is 100-350 ℃ and the time is 1-24 h.
10. Use of the novel rubber seed shell based composite of claim 1 as a creatinine and uric acid scavenger.
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