CN110548487B - Hydrothermal carbon-based composite material, and preparation and application thereof - Google Patents
Hydrothermal carbon-based composite material, and preparation and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical field of composite materials, and particularly relates to a hydrothermal carbon-based composite material, and preparation and application thereof. Mixing biomass with a metal organic framework material precursor solution to obtain a raw material mixed solution; carrying out hydrothermal reaction on the raw material mixed solution in a closed reactor, wherein carbonization of biomass and crystallization reaction of the metal organic framework material occur in the hydrothermal reaction process; and after the hydrothermal reaction is finished, carrying out solid-liquid separation, and cleaning and drying the obtained solid material to obtain the hydrothermal carbon-based composite material. By adding the metal organic framework precursor in the hydrothermal carbon preparation process, the hydrothermal carbon and the metal organic framework are organically combined to obtain the hydrothermal carbon-based composite material, so that the adsorption capacity of the hydrothermal carbon-based composite material on heavy metals is improved, and the technical problems that the raw materials for adsorbing the heavy metals by the hydrothermal carbon-based composite material in the prior art are not easy to obtain and the adsorption effect is poor are solved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a hydrothermal carbon-based composite material, and preparation and application thereof.
Background
Water pollution and its management have received wide attention in recent years. Among them, heavy metals are classified as key treatment objects due to their characteristics of high toxicity, easy enrichment and difficult degradation. The adsorption method is a convenient, effective and simple method for treating heavy metal in liquid phase, and the key point is selection and improvement of an adsorbent. The hydrothermal carbon is prepared from biomass or other carbon-containing raw materials in a hydrothermal mode, and has the potential of serving as a green adsorbent for liquid-phase pollutants due to the fact that the hydrothermal carbon is rich in surface functional groups, low in energy consumption in the preparation process and green. In order to improve the adsorption performance, many researches are based on modification treatment of hydrothermal carbon or material compounding.
Patent CN106904625 discloses a preparation method of a hydrothermal carbon/montmorillonite composite material, wherein the hydrothermal carbon is cellulose which is not easily available, so that the hydrothermal carbon is limited by the raw materials, and the process is difficult to be applied in large scale. Patent CN201910110705 discloses a preparation method of surface functional group functionalized hydrothermal carbon and a good adsorption effect on cr (vi), but for industrial wastewater, not only cr (vi) but also a plurality of heavy metal pollutants are contained, so that the process has a limitation in application. Furthermore, the existing reports on the improvement of the physicochemical properties of the hydrothermal carbon are mostly limited to one of surface functionalization and pore structure, while the adsorption process is a physicochemical process and involves both aspects, so that the simultaneous consideration is needed. CN106732374 discloses a method for simultaneously improving the surface functionalization and specific surface area of hydrothermal carbon, but the greenness of the preparation process is greatly reduced due to the addition of beta-FeOOH and KOH, the KOH toxicity is high, and the large-scale application is difficult.
The metal organic framework is a new material in recent years, has the characteristics of large specific surface area, adjustable pore size structure, rich surface functional groups and open metal center, and is widely applied to various fields, particularly the adsorption field. But the water stability is not very good, and the problem of poor cyclic adsorption stability is caused by the fact that the adsorbent is used for adsorbing liquid-phase pollutants alone, so that the application of the adsorbent in the aspect of liquid-phase pollutant adsorption is limited.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a hydrothermal carbon-based composite material, and preparation and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a hydrothermal carbon-based composite material, comprising the steps of:
(1) mixing biomass with a metal organic framework material precursor solution to obtain a raw material mixed solution;
(2) carrying out hydrothermal reaction on the raw material mixed solution in a closed reactor, wherein carbonization of biomass and crystallization reaction of the metal organic framework material occur in the hydrothermal reaction process; and after the hydrothermal reaction is finished, carrying out solid-liquid separation, and cleaning and drying the obtained solid material to obtain the hydrothermal carbon-based composite material.
Preferably, the biomass is granular biomass with the particle size of 1 mm-10 mm.
Preferably, the biomass is one or more of straw, wood chips and bamboo chips.
Preferably, the metal-organic framework material precursor solution comprises a metal salt solution obtained by dissolving a metal salt in a solvent and an organic framework ligand solution obtained by dissolving an organic framework ligand in a solvent; the metal salt is copper nitrate trihydrate, cobalt nitrate hexahydrate, ferric chloride hexahydrate or aluminum nitrate nonahydrate; the organic framework ligand is trimesic acid, terephthalic acid or 2-amino terephthalic acid.
Preferably, the solvent is water and/or ethanol.
Preferably, the mass ratio of the metal salt to the organic framework ligand is 1: 5-5: 1, and the mass ratio of the solvent to the metal salt is 1: 1-10: 1.
Preferably, the mass ratio of the biomass to the metal organic framework material precursor solution is 1: 1-1: 10.
Preferably, the reaction temperature in the hydrothermal reaction is 150-300 ℃, and the reaction time is 8-48 h.
According to another aspect of the invention, the hydrothermal carbon-based composite material prepared by the preparation method is provided.
According to another aspect of the invention, the application of the hydrothermal carbon-based composite material as a heavy metal adsorbent is provided.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the invention, biomass and a precursor solution of a metal organic framework material are mixed, and the hydrothermal carbon-based composite material is prepared by a one-pot method. The method fully combines the characteristics of green, low energy consumption, rich oxygen-containing functional groups, high specific surface area of the metal organic framework material and adjustable pore diameter of the hydrothermal carbon, organically combines the two by adopting a one-pot method, and is simple and easy compared with other composite methods.
(2) Compared with hydrothermal carbon, the hydrothermal carbon-based composite material prepared by the invention has the advantages that the specific surface area is obviously improved, the aperture controllability is improved, and the physical adsorption capacity is greatly improved by optimizing the pore structure, so that the heavy metal adsorption capacity is effectively improved, and the requirement of sewage treatment can be met.
(3) According to the invention, the hydrothermal carbon is used as a composite substrate, so that on one hand, the water stability of the metal organic framework can be effectively improved, and therefore, the composite material can be suitable for adsorbing pollutants in a liquid phase, and the application range of the composite material is widened; on the other hand, the preparation method of the one-pot method can also increase the dispersion degree of the metal organic framework and avoid the reduction effect of the adsorption sites due to mutual coverage, thereby effectively improving the adsorption effect of the heavy metal and having wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of the hydrothermal carbon-based composite material and its immersion in water for 24 hours in example 1.
FIG. 2 is a Fourier infrared spectrum of the hydrothermal carbon-based composite material of example 1 and its immersion in water for 24 hours.
FIG. 3 is a scanning electron microscope image of the hydrothermal carbon-based composite material in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a hydrothermal carbon-based composite material, which comprises the following steps:
(1) mixing biomass with a metal organic framework material precursor solution to obtain a raw material mixed solution;
(2) carrying out hydrothermal reaction on the raw material mixed solution in a closed reactor, wherein carbonization of biomass and crystallization reaction of the metal organic framework material occur in the hydrothermal reaction process; and after the hydrothermal reaction is finished, carrying out solid-liquid separation, and cleaning and drying the obtained solid material to obtain the hydrothermal carbon-based composite material.
The particle size of the biomass raw material influences the physical characteristics of the formed hydrothermal carbon, so that the compounding condition of the hydrothermal carbon and a metal organic framework is influenced, the particle size is controlled within the range, the growth process of the metal organic framework and the carbonization process of the hydrothermal carbon can be effectively combined tightly, the dispersibility is better, and the composite material has more adsorption sites to adsorb heavy metals in a liquid phase. In some embodiments, the biomass is a granular biomass having a particle size of 1mm to 10 mm.
In some embodiments, the biomass agricultural waste is, for example, one or more of straw, wood chips, and bamboo shavings.
In some embodiments, the metal-organic framework material precursor solution comprises a metal salt solution obtained by dissolving a metal salt in a solvent and an organic framework ligand solution obtained by dissolving an organic framework ligand in a solvent; the metal salt is copper nitrate trihydrate, cobalt nitrate hexahydrate, ferric chloride hexahydrate or aluminum nitrate nonahydrate; the organic framework ligand is trimesic acid, terephthalic acid or 2-amino terephthalic acid.
In some embodiments, the solvent is water and/or ethanol.
In some embodiments, the mass ratio of the metal salt to the organic framework ligand is 1:5 to 5:1, and the mass ratio of the solvent to the metal salt is 1:1 to 10: 1.
In some embodiments, the mass ratio of the biomass to the metal organic framework material precursor solution is 1: 1-1: 10.
The reaction temperature and the reaction time in the reaction parameters greatly influence the carbon formation condition of the hydrothermal carbon, the crystallization effect and the particle size of the metal organic framework, the reaction time and the stirring rate influence the dispersion degree and the combination degree when the metal organic framework is combined with the hydrothermal carbon, and the control of the relevant parameters in the range can ensure that the finally generated composite material has an excellent pore structure and sufficient adsorption sites, so that the adsorption performance of the composite material on heavy metals is better.
In some embodiments, the heating rate in the hydrothermal reaction is 5 ℃/min to 20 ℃/min, the reaction temperature is 150 ℃ to 300 ℃, the reaction time is 8h to 24h, and the stirring rate is not higher than 1000 rpm. Too high a stirring rate may make the crystals less susceptible to nucleation.
In some embodiments, the solid obtained by solid-liquid separation in step (2) is washed with solvent water and/or ethanol, and the drying is performed in a vacuum drying manner at a temperature of 50 ℃ to 120 ℃.
The invention also provides the hydrothermal carbon-based composite material prepared by the preparation method. The composite material comprises a hydrothermal carbon substrate and an organic metal framework material, wherein the organic metal framework is organically combined with the hydrothermal carbon.
The invention also provides application of the hydrothermal carbon-based composite material, which is used as a heavy metal adsorbent to adsorb heavy metal ions in polluted water.
The invention utilizes the characteristics of large specific surface area and rich functional groups of the organic metal framework material and the characteristics of regeneration and strong water stability of the hydrothermal carbon to prepare the novel hydrothermal carbon-based composite material by a one-pot method so as to improve the adsorption effect of the composite material on heavy metals.
Specifically, the preparation method utilizes the characteristic that the preparation conditions of the hydrothermal carbon and the metal organic framework are similar, and adopts a one-pot method, namely, the metal organic framework precursor is added simultaneously in the process of preparing the hydrothermal carbon, so that the metal organic framework and the hydrothermal carbon can be organically combined. Firstly, the specific surface area of the hydrothermal carbon, particularly the number of micropores, can be increased, and the advantages of physical adsorption are fully utilized, so that the adsorption performance of the hydrothermal carbon on heavy metals in a liquid phase is improved. Secondly, the two are prepared by a one-pot method and grow in situ, so that the two are not simply mixed but closely connected, adsorption sites improved by rich oxygen-containing functional groups on the surface of the hydrothermal carbon can be effectively reserved, a metal organic framework can be better dispersed on the hydrothermal carbon, and the effect reduction caused by mutual coverage of the adsorption sites is avoided. In addition, considering that the hydrothermal carbon has excellent water stability, the hydrothermal carbon-based composite material can also greatly improve the water stability of the metal organic framework, thereby overcoming the defect of poor circulation stability of the metal organic framework used alone for adsorbing liquid phase pollutants.
To better explain the present invention, specific examples are given below, in which agricultural and forestry waste used in the present invention is collected from the local, and chemicals are purchased from national drug group or Aladdin company.
The following are examples:
a preparation method of a hydrothermal carbon-based composite material comprises the following steps:
(1) air drying bamboo sawdust and grinding into fine particles;
(2) respectively dissolving copper nitrate trihydrate and trimesic acid in a reaction solvent according to a certain proportion, and fully mixing, wherein the solvent is ethanol and deionized water (the mass ratio is 1: 1), and the mass ratio of the copper nitrate trihydrate, the trimesic acid and the solvent is 2: 1: 40;
(3) adding the bamboo dust particles obtained in the step (1) into the mixed solution obtained in the step (2), and fully mixing, wherein the mass ratio of the bamboo dust to the mixed solution is 1: 5;
(4) and (3) putting the mixed solution prepared in the step (3) into a closed reaction kettle with a stirrer for carbonization and crystallization reaction, wherein the heating rate is 10 ℃/min, the reaction temperature is 180 ℃, the reaction time is 18h, and the stirring rate is 800 rpm.
(5) After cooling, the solid obtained in step 4 was collected by centrifugation and washed 3 times with ethanol and deionized water.
(6) And (5) drying the solid obtained in the step (5) in vacuum to obtain the hydrothermal carbon-based composite material, wherein the vacuum drying temperature is 80 ℃.
As can be seen from table 1, the pore structure of the hydrothermal carbon itself is not good, but the pore structure of the hydrothermal carbon after being compounded with the MOFs material is significantly improved, and particularly, a large amount of microporous structures are introduced, which also greatly improves the physical adsorption performance of the hydrothermal carbon.
The heavy metal adsorption conditions in table 2 are as follows, adsorption temperature: normal temperature; initial concentration: 10 mg/L; the input amount of the adsorbent: 20 mg/L; reaction time: for 24 hours. As can be seen from the figure, the hydrothermal carbon-based composite material has a significantly improved heavy metal adsorption effect as compared with hydrothermal carbon, and is therefore suitable for use as a heavy metal adsorption material.
FIG. 1 is an X-ray diffraction diagram of a hydrothermal carbon-based composite material and a crystal diffraction peak of the hydrothermal carbon-based composite material after being soaked in water for 24 hours, wherein the intensity and the position of the crystal diffraction peak of the hydrothermal carbon-based composite material after being soaked in water for 24 hours are not changed, so that the crystal structure is still stable, and the high water stability of the composite material is also proved; fig. 2 is a fourier-infrared graph of a hydrothermal carbon-based composite material and a water immersion time thereof for 24 hours, and it can be seen that the composite material has rich surface functional groups and excellent water stability, and is therefore suitable for adsorption application of liquid-phase pollutants. Fig. 3 is a scanning electron microscope image of the hydrothermal carbon-based composite material, and it can be seen from the image that the regular octahedral structure of Cu-BTC is tightly combined with the structure of the hydrothermal carbon, thereby proving the feasibility of the method.
The specific surface area and pore structure of the hydrothermal carbon and hydrothermal carbon-based composite material in example 1 are as follows:
TABLE 1
The adsorption efficiency of hydrothermal carbon and hydrothermal carbon-based composite material in example 1 to various liquid-phase heavy metals is as follows:
TABLE 2
Example 2
A preparation method of a hydrothermal carbon-based composite material comprises the following steps:
(1) air drying the straws and grinding into fine particles;
(2) respectively dissolving aluminum nitrate nonahydrate and trimesic acid in a reaction solvent according to a certain proportion, and fully mixing, wherein the solvent is deionized water, and the mass ratio of the aluminum nitrate nonahydrate to the trimesic acid to the solvent is 5: 1: 8;
(3) adding the straw particles obtained in the step (1) into the mixed solution obtained in the step (2), and fully mixing; the mass ratio of the straw to the mixed solution is 1: 1;
(4) and (3) putting the mixed solution prepared in the step (3) into a closed reaction kettle with a stirrer for carbonization and crystallization reaction, wherein the heating rate is 5 ℃/min, the reaction temperature is 250 ℃, the reaction time is 48h, and the stirring speed is 300 rpm.
(5) After cooling, the solid obtained in step 4 was collected by centrifugation and washed 3 times with deionized water.
(6) And (5) drying the solid obtained in the step (5) in vacuum to obtain the hydrothermal carbon-based composite material, wherein the vacuum drying temperature is 100 ℃.
Example 3
A preparation method of a hydrothermal carbon-based composite material comprises the following steps:
(1) air drying sawdust and grinding into fine particles;
(2) respectively dissolving ferric chloride hexahydrate and terephthalic acid in a reaction solvent according to a certain proportion, and fully mixing, wherein the solvent is deionized water, and the mass ratio of the ferric chloride hexahydrate to the terephthalic acid to the solvent is 3: 1: 10;
(3) adding the wood dust particles obtained in the step (1) into the mixed solution obtained in the step (2), and fully mixing; the mass ratio of the wood chips to the mixed solution is 2: 1;
(4) and (3) putting the mixed solution prepared in the step (3) into a closed reaction kettle with a stirrer for carbonization and crystallization reaction, wherein the heating rate is 20 ℃/min, the reaction temperature is 150 ℃, the reaction time is 24h, and the stirring rate is 0 rpm.
(5) After cooling, the solid obtained in step 4 was collected by centrifugation and washed 3 times with deionized water.
(6) And (5) drying the solid obtained in the step (5) in vacuum to obtain the hydrothermal carbon-based composite material, wherein the vacuum drying temperature is 60 ℃.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a hydrothermal carbon-based composite material is characterized by comprising the following steps:
(1) mixing biomass with a metal organic framework material precursor solution to obtain a raw material mixed solution;
(2) carrying out hydrothermal reaction on the raw material mixed solution in a closed reactor, wherein carbonization of biomass and crystallization reaction of the metal organic framework material occur in the hydrothermal reaction process; and after the hydrothermal reaction is finished, carrying out solid-liquid separation, and cleaning and drying the obtained solid material to obtain the hydrothermal carbon-based composite material, wherein the biomass is granular biomass with the particle size of 1-10 mm.
2. The method of claim 1, wherein the biomass is one or more of straw, wood chips, and bamboo chips.
3. The method according to claim 1, wherein the metal-organic framework material precursor solution includes a metal salt solution obtained by dissolving a metal salt in a solvent and an organic framework ligand solution obtained by dissolving an organic framework ligand in a solvent; the metal salt is copper nitrate trihydrate, cobalt nitrate hexahydrate, ferric chloride hexahydrate or aluminum nitrate nonahydrate; the organic framework ligand is trimesic acid, terephthalic acid or 2-amino terephthalic acid.
4. The method according to claim 3, wherein the solvent is water and/or ethanol.
5. The method according to claim 3, wherein the mass ratio of the metal salt to the organic skeleton ligand is 1:5 to 5:1, and the mass ratio of the solvent to the metal salt is 1:1 to 10: 1.
6. The preparation method according to claim 1, wherein the mass ratio of the biomass to the metal organic framework material precursor solution is 1:1 to 1: 10.
7. The preparation method according to claim 1, wherein the reaction temperature in the hydrothermal reaction is 150 ℃ to 300 ℃ and the reaction time is 8h to 48 h.
8. The hydrothermal carbon-based composite material prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the hydrothermal carbon-based composite material according to claim 8 as a heavy metal adsorbent.
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