CN108311106A - A kind of expanded graphite-metal oxide sorbents and preparation method thereof - Google Patents
A kind of expanded graphite-metal oxide sorbents and preparation method thereof Download PDFInfo
- Publication number
- CN108311106A CN108311106A CN201810238850.3A CN201810238850A CN108311106A CN 108311106 A CN108311106 A CN 108311106A CN 201810238850 A CN201810238850 A CN 201810238850A CN 108311106 A CN108311106 A CN 108311106A
- Authority
- CN
- China
- Prior art keywords
- expanded graphite
- metal oxide
- solution
- dispersant
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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 present invention discloses a kind of expanded graphite metal oxide sorbents and preparation method thereof, including following components：Expanded graphite, metal oxide, dispersant, wherein the metal oxide is one kind in nanometer γ alundum (Al2O3)s or nanometer α manganese dioxide；The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1 1.5 mix.Preparation method is that expanded graphite is placed in metal-nitrate solutions, and the dispersant is added dropwise, and shakes drying；Product after drying is increased with per half an hour after 50 DEG C of speed is warming up to 350 450 DEG C and is kept the temperature, the expanded graphite metal oxide sorbents that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold are obtained.Expanded graphite metal oxide sorbents of the present invention are not influenced by solution ph, and convenient for recycling, the scope of application is wider.
Description
Technical field
The invention belongs to technical field of water pollution treatment more particularly to a kind of expanded graphite-metal oxide sorbents and
Preparation method.
Background technology
In past 30 years, Chinese industrialization and economy are developed rapidly, however, this quick development is
At the cost of the environment.According to the investigation statistics of State Environmental Protection Administration, so far from 2000, the whole nation has occurred more than 7000
Water pollution accident is played, the people's lives and property safety is seriously threatened.Wherein most commonly seen water pollution is Cr (VI) and F-It is dirty
Dye has a large amount of researcher to Cr (VI) and F in recent years-Removing method studied, such as：
Chinese CN201610938714.6 patents are related to a kind of mesoporous γ-Al of highly selective amino functional2O3Base is compound
The preparation method of adsorbent.This approach includes the following steps：It is stirred at room temperature down and dense nitre is added into the ethanol solution of P123 successively
Acid, aluminium isopropoxide form solution；The solution obtains gel after solvent-induced evaporation, and gained gel is fired to be made mesoporous γ-
Al2O3Original powder；A certain amount of amino silane is added dropwise in the above-mentioned original powder disperseed at room temperature to ethyl alcohol and stirs after a certain period of time,
Product is washed successively through separation, ethyl alcohol and dry, the obtained γ-Al2O3Base composite absorbent.This method preparation process letter
Single, mild condition；Prepared compound adsorbent reaches 67.0mg/g to the adsorbance of hypertoxic Cr (VI), still reaches after recycling three times
99.9% or more removal rate.But adsorbent is affected by solution ph in aqueous solution described in the patent, the γ-Al2O3
The soda acid being easy in solution, which reacts, causes secondary pollution, and is not easily recycled.
Chinese CN201010574158.1 patents are related to electricity and promote fluorine removal absorption composite particles, electricity rush fluorine removal absorbing composite plate
And preparation method.Electricity according to the present invention promotees fluorine removal absorption composite particles, electricity promotees fluorine removal absorbing composite plate and includes：Active metal oxygen
Compound, conducting medium, dispersant, wherein conducting medium: metal oxide: the ratio of dispersant is 5-45: 55-93: 2-10,
Dispersant is absolute ethyl alcohol and montmorillonite mixed liquor, and its ratio be 4mL: 1g.It is provided by the invention that compound electricity rush fluorine removal is provided
Sorbing material, defluorination effect is good, and the graininess electricity rush defluorination material grain density of preparation is moderate, and property is stablized, and not easily runs off, and fits
Promote fluorine removal process for fixed bed electricity；Electricity promotees fluorine removal plate as anode material, is directly used in electricity and promotees fluorine removal, also can be with other fluorine removals
Material is used in combination.The invention disperses the metal oxide using dispersant, and wherein dispersant additive amount is larger,
But still there is a situation where that dispersion is uneven causes absorption property poor.
Cr (VI) and F in removal solution at present-It mostly uses metal oxide being attached on carrier greatly and synthesizes composite adsorption
The method that agent carries out Adsorption, during preparing compound adsorbent, the metal oxide is easy in the carrier surface
Appearance stacks and reunites, and leads to the reduction of adsorbent specific surface area, to the Cr (VI) and F of low concentration-Removal effect it is poor；Big portion
Fractional bearer itself does not have surface-functionalized, binder is needed in preparation process so that preparation process is complex；In addition,
The bonding mode of metal oxide and carrier is insecure, and when adsorbent being caused to be acted in aqueous solution, metal oxide is easily from load
It falls off on body and reacts with other substances in solution, cause secondary pollution, the problem of be not easily recycled etc..Therefore, anxious
A kind of expanded graphite-metal oxide sorbents and preparation method thereof need to be designed to solve the above problems.
Invention content
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of expanded graphite-metal oxide absorption
Agent and preparation method thereof can select the metal oxide appropriate and expansion stone according to different pollutant and pollution level
Ink combines, to obtain adsorption effect well；The expanded graphite itself contain more organic group realize it is surface-functionalized,
Without additionally adding other binders in preparation process, at the same the covalent bond that is generated by organic group of the expanded graphite and
Metal oxide combines, and combination is stablized, and the metal oxide is not easily to fall off in aqueous solution, overcomes the metal oxygen
The problem of compound is affected by solution ph, is not easily recycled when being used alone, being not easy to reuse etc.；Pass through described point
Powder makes the metal oxide be uniformly dispersed in the expanded graphite lamella and fold, improves adsorption effect.
To achieve the above object, the technical solution adopted by the present invention is：
The present invention provides a kind of expanded graphite-metal oxide sorbents, including following components：
Expanded graphite 60-75wt%；
Metal oxide 29.9-39.9wt%；
Dispersant 0.05-0.1wt%；
Wherein, the metal oxide is one kind in nanometer γ-alundum (Al2O3) or nanometer α-manganese dioxide；Described point
Powder is polyvinyl alcohol and propylene glycol by weight 1:1-1.5 mixing.
Expanded graphite-metal oxide sorbents of the present invention are the toxic ions removed by absorption method in solution.
Expanded graphite-metal oxide sorbents of the present invention not only remain expanded graphite and the respective Optimality of metal oxide
Can, not available performance when also there is the two to be used alone；Contain more organic group energy on the expanded graphite lamella
Enough realize it is surface-functionalized, the metal oxide by covalent bond that organic group generates it is more stable be grafted on the expansion
On graphite, without additionally adding other binders；In addition, the metal oxide is poor separately as sorbing material stability,
It is affected by solution ph, is easily reacted with other substances in solution, generated secondary pollution, be unfavorable for recycling,
The metal oxide is combined with expanded graphite, bonding mode is stablized, the expanded graphite-metal oxide sorbents effect
When in solution, the metal oxide is not easily to fall off and reacts with soda acid in solution, to overcome the metal to aoxidize
The problem of stability difference and recycling hardly possible when object is used alone；
When the metal oxide content is 29.9-39.9wt%, the expanded graphite is cooperateed with metal oxide performance
Effect makes the expanded graphite-metal oxide be much larger than the metal oxide list to the removal rate of toxic ion in solution
The removal rate solely used, while the problem of metal oxide is affected by solution ph is overcome, the expanded graphite-
Metal oxide sorbents have preferable removal effect, the scope of application larger in acid or alkaline solution.
Wherein, the metal oxide is one kind in nanometer γ-alundum (Al2O3) or nanometer α-manganese dioxide, described
γ-alundum (Al2O3), to the toxic ion in solution have stronger adaptability, especially to fluorine ion have stronger affinity and
Selectivity；α-the manganese dioxide has stronger adsorption capacity to grease, fuel and the heavy metal ion in solution, especially to molten
Cadmium ion in liquid has excellent absorption property, cadmium ion that can be in specific adsorption aqueous solution.
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1-1.5 is mixed, and the polyvinyl alcohol has
The effect of dispersant can reduce the interfacial tension of solid-liquid in aqueous solution, and each substance in solution is made to form stable emulsion,
But since the metal oxide is nano level metal oxide, surface energy is larger, therefore dispersion is required in dispersion process
There is larger adhesive strength, the present invention to react to be formed with the polyvinyl alcohol in aqueous solution by the addition propylene glycol for agent
Carbon-carbon double bond, then combined with the metal oxide by carbon-carbon double bond, to improve the dispersant and the metal oxide
Adhesive strength, so that the metal oxide is evenly distributed on the expanded graphite surface lamella under the action of dispersant
And in fold, combined with the organic group on the expanded graphite, effectively prevents the metal oxide from occurring to stack and roll into a ball
It is poly-；In addition, the propylene glycol also has the function of bacteria mildew-proof, humidification, the expanded graphite-metal oxide can be extended and inhaled
Attached dose of service life.The polyvinyl alcohol and propylene glycol are by weight 1:1-1.5 mixes collective effect, can make the expansion
Organic group distribution in graphite surface and fold is more uniform, prevents the metal oxide from occurring to stack and reunite, moreover it is possible to
Extend the service life of the expanded graphite-metal oxide.
Expanded graphite-metal oxide sorbents of the present invention can be selected according to different pollutant and pollution level
The metal oxide appropriate is combined with the expanded graphite, to obtain adsorption effect well；In addition, the expansion stone
Ink and metal oxide have raw material sources extensive, cheap, easy to operate, will not cause secondary pollution, renewable to wait warp
Ji advantage；The two can be played into synergistic effect in conjunction with the expanded graphite-metal oxide sorbents are formed, made it have steady
It is qualitative it is good, the rate of adsorption is fast, adsorption capacity is big, density is low, convenient for recycling the advantages that, overcoming the metal oxide individually makes
Used time stability is poor, the problem of cannot reusing.
Preferably, a kind of expanded graphite-metal oxide sorbents, including following components：
Expanded graphite 65wt%；
Metal oxide 34.92wt%；
Dispersant 0.08wt%.
When the content of the metal oxide is 34.92wt%, the expanded graphite-metal oxide sorbents are in water
Solution ph has preferable absorption property in the case of being more than 2 less than 12.
Preferably, the preparation method of the expanded graphite, includes the following steps：
(1) 0.5-2g natural flake graphites are soaked in aqueous solution, a concentration of 60%-70% Gao Meng of 30-40mL is added dropwise
Sour potassium solution is mixed；
(2) a concentration of 60%-70% salpeter solutions of 20-30mL are added dropwise into step (1) acquired solution；
(3) phosphoric acid solution of a concentration of 80%-90% of 20-30mL is added dropwise into step (2) acquired solution, is mixed
30-40min, filtering drying；
(4) crystalline flake graphite obtained by step (3) is calcined into 10-15s to get the expanded graphite in 900-1200 DEG C.
The present invention prepares expanded graphite using chemical oxidization method and secondary intercalation technique, and expansion multiple is up to 300mL/g, and
Not sulfur-bearing, corrosivity is small, and high temperature resistance, antioxygenic property are notable, and service life is long.
Preferably, the particle size range of the nanometer γ-alundum (Al2O3) is 20-50nm；The grain size of the α-manganese dioxide
Ranging from 30-50nm.
By size controlling in above range, the ratio table of the expanded graphite-metal oxide sorbents is further increased
Area makes the absorption property of the expanded graphite-metal oxide sorbents more to increase the contact area with aqueous solution
It is good.
A kind of preparation method of expanded graphite-metal oxide sorbents of the present invention, includes the following steps：
A, the expanded graphite is placed in the metal-nitrate solutions of 50-100mL, described point is added dropwise in 20-30min
Powder, room temperature shake drying after 1.5-3h；
B, by the product after drying in logical N2In the case of, 50 DEG C of speed is increased with per half an hour is warming up to 350-450
1-3h is kept the temperature after DEG C, obtains the expansion stone that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold
Ink-metal oxide sorbents.
The present invention carries out temperature programming in preparation process in such a way that per half an hour increases 50 DEG C, can make the metal
Nitrate obtains the metal oxide of specific modality and uniform particle diameter in decomposable process, while temperature programming and heat preservation
Process can make metal oxide active higher, without carrying out additional activation process, simplify preparation process.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) dispersant of the present invention can prevent the metal oxide from being sent out in the expanded graphite surface and fold
It is raw to stack and reunite, moreover it is possible to extend the service life of the expanded graphite-metal oxide；
(2) when expanded graphite-metal oxide sorbents of the present invention are acted in solution, there is preferable stablize
Property, all have higher removal rate in acid or alkaline solution, can be recycled, to overcome the metal oxide list
Stability is poor when solely using, the problem of being affected by solution ph；
(3) expanded graphite-metal oxide sorbents of the present invention can be selected according to different pollutant and pollution level
The metal oxide appropriate is selected to be combined with expanded graphite；The metal oxide is the metal oxide of specific morphology, right
Fluorine ion and cadmium ion have excellent compatibility and selectivity in solution, be suitable for removing solution the fluorine ion of low concentration with
Cadmium ion；
(4) on expanded graphite lamella of the present invention contain more organic group, itself can realize it is surface-functionalized,
The organic group by covalent bond effect in the metal oxide, in the expanded graphite-metal oxide preparation process
In without additional addition binder, you can realize that the metal oxide stability is grafted on the expanded graphite；
(5) present invention prepares the expanded graphite-metal oxide sorbents by the way of temperature programming, can obtain
Simplify and prepare without carrying out additional activation process with specific morphology, uniform particle diameter and the higher metal oxide of activity
Process；
(6) expanded graphite of the present invention-metal oxide sorbents production cost is relatively low, be harmful in removing solution from
It will not react with the substance of other in solution in the process of son, not will produce secondary pollution, convenient for recycling.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below, it is clear that described embodiment is only this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
The all other embodiment obtained under the conditions of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, including following components：
Expanded graphite 65wt%；
γ-alundum (Al2O3) 34.92wt%；
Dispersant 0.08wt%；
The γ-alundum (Al2O3) particle size range is 20-50nm；The dispersant be polyvinyl alcohol and propylene glycol by weight
Than 1:1 mixes.
The preparation method of the expanded graphite, includes the following steps：
(1) 1g natural flake graphites are soaked in aqueous solution, a concentration of 65% liquor potassic permanganates of 30mL, mixing is added dropwise
Stirring；
(2) a concentration of 65% salpeter solutions of 20mL are added dropwise into step (1) acquired solution；
(3) phosphoric acid solution of 20mL a concentration of 85% is added dropwise into step (2) acquired solution, 30min, filtering is mixed
Drying；
(4) crystalline flake graphite obtained by step (3) is calcined into 10s to get the expanded graphite in 900 DEG C.
A kind of preparation method of expanded graphite-metal oxide sorbents, includes the following steps：
A, expanded graphite is placed in the aluminum nitrate solution of 80mL, the dispersant is added dropwise in 25min, room temperature shakes 2h
After dry；
B, by the product after drying in logical N2In the case of, after being warming up to 400 DEG C with 50 DEG C of speed of raising of per half an hour
2h is kept the temperature, the expanded graphite-γ-three that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold is obtained
Al 2 O adsorbent.
Expanded graphite-γ described in the present embodiment-alundum (Al2O3) adsorbent has the toxic ion in solution stronger
Adaptability especially has stronger affinity and selectivity to fluorine ion, the expanded graphite-γ-alundum (Al2O3) adsorbent by
The influence of solution ph is smaller, has stronger absorption property to the fluorine ion in solution under acid and alkaline environment.
By the expanded graphite-γ-alundum (Al2O3) adsorbent for fluorine ion in adsorbent solution, selected using fluorine ion
The concentration of fluorine ion, experiment obtain in determination of electrode solution, as shown in table 1, when fluorinion concentration is 2mg/L, solution in solution
When pH value is 6, the expanded graphite-γ-alundum (Al2O3) adsorbent can reach 94.4% to the removal rate of fluorine ion in solution,
Maximal absorptive capacity reaches 0.3147mg/g；When solution ph is 2, the expanded graphite-γ-alundum (Al2O3) adsorbent is in solution
The removal rate of fluorine ion can reach 91%, and maximal absorptive capacity reaches 0.3033mg/g；When solution ph is 12, the expansion stone
Ink-γ-alundum (Al2O3) adsorbent can reach 91.5% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches 0.305mg/
g。
Therefore, the expanded graphite-γ-alundum (Al2O3) adsorbent has the fluorine ion in solution higher sensitive
Degree, the fluorine ion suitable for removing low concentration solution.
Embodiment 2
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 60wt%；
γ-alundum (Al2O3) 39.9wt%；
Dispersant 0.1wt%；
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1.5 mixing.
The preparation method of the expanded graphite is：
Qingdao day and the expansible graphite up to 50 mesh of graphite Co., Ltd, expansion multiplying power for 300-400mL/g are bought, it can
Expanded graphite is placed in 900 DEG C of calcining 10s, obtains expanded graphite.
A kind of preparation method of expanded graphite-metal oxide sorbents, includes the following steps：
γ-the alundum (Al2O3) is uniformly distributed in aqueous solution by dispersant, expanded graphite is immersed in
It states in dispersion solution, is stored at room temperature 10h, then in 200 DEG C of drying, obtain the expanded graphite-metal oxide sorbents.
By the expanded graphite-γ-alundum (Al2O3) adsorbent for adsorbing fluorine ion in solution, selected using fluorine ion
The concentration of fluorine ion, experiment obtain in determination of electrode solution, as shown in table 1, when fluorinion concentration is 2mg/L, solution in solution
When pH value is 6, the expanded graphite-γ-alundum (Al2O3) adsorbent can reach 93% to the removal rate of fluorine ion in solution, most
Big adsorbance reaches 0.31mg/g；Solution ph be 2 when, the expanded graphite-γ-alundum (Al2O3) adsorbent to fluorine in solution from
The removal rate of son can reach 90%, and maximal absorptive capacity reaches 0.3mg/g；When solution ph is 12, the expanded graphite-γ-three
Al 2 O adsorbent can reach 91.5% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches 0.305mg/g.
Therefore, fluorine ion of the expanded graphite-γ-alundum (Al2O3) adsorbent suitable for removing low concentration solution.
Embodiment 3
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 70wt%；
γ-alundum (Al2O3) 29.95wt%；
Dispersant 0.05wt%；
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1.2 mixing.
By the expanded graphite-γ-alundum (Al2O3) adsorbent for adsorbing fluorine ion in solution, selected using fluorine ion
The concentration of fluorine ion, experiment obtain in determination of electrode solution, as shown in table 1, when fluorinion concentration is 2mg/L, solution in solution
When pH value is 6, the expanded graphite-γ-alundum (Al2O3) adsorbent can reach 92% to the removal rate of fluorine ion in solution, most
Big adsorbance reaches 0.3067mg/g；When solution ph is 2, the expanded graphite-γ-alundum (Al2O3) adsorbent is to fluorine in solution
The removal rate of ion can reach 89%, and maximal absorptive capacity reaches 0.2967mg/g；When solution ph is 12, the expanded graphite-
γ-alundum (Al2O3) adsorbent can reach 90% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches 0.3mg/g.
Therefore, fluorine ion of the expanded graphite-γ-alundum (Al2O3) adsorbent suitable for removing low concentration solution.
Embodiment 4
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 65wt%；
α-manganese dioxide 34.92wt%；
Dispersant 0.08wt%；
The α-manganese dioxide particle size range is 30-50nm；The dispersant be polyvinyl alcohol and propylene glycol by weight
1:1 mixes.
The preparation method of the expanded graphite-metal oxide sorbents, includes the following steps：
A, expanded graphite is placed in the manganese nitrate solution of 80mL, the dispersant is added dropwise in 25min, room temperature shakes 2h
After dry；
B, by the product after drying in logical N2In the case of, after being warming up to 450 DEG C with 50 DEG C of speed of raising of per half an hour
2h is kept the temperature, the expanded graphite-α-two that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold is obtained
Manganese oxide sorbents adsorbent.
The present embodiment is using the expanded graphite-α-manganese dioxide adsorbent to grease, fuel and the heavy metal in solution
Ion has stronger adsorption capacity, especially has excellent absorption property to the cadmium ion in solution, can specifically adsorb water
Micro cadmium ion in solution.
By the expanded graphite-α-manganese dioxide adsorbent for the cadmium ion in adsorbent solution, using UV, visible light point
The concentration of cadmium ion, experiment obtain in light photometric determination solution, as shown in table 1, when in solution concentration of cadmium ions be 2mg/L,
When solution ph is 6, the expanded graphite-α-manganese dioxide adsorbent reaches 90.35% to the removal rate of cadmium ion in solution,
Maximal absorptive capacity reaches 0.3011mg/g；When solution ph is 2, the expanded graphite-α-manganese dioxide adsorbent is to cadmium in solution
The removal rate of ion can reach 88%, and maximal absorptive capacity reaches 0.2933mg/g；When solution ph is 12, the expanded graphite-
α-manganese dioxide adsorbent can reach 90% to the removal rate of cadmium ion in solution, and maximal absorptive capacity reaches 0.3mg/g.
Therefore, the expanded graphite-α-manganese dioxide adsorbent has higher selectivity to cadmium ion in solution, is applicable in
In the cadmium ion for removing low concentration in solution.
Embodiment 5
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 60wt%；
α-manganese dioxide 39.9wt%；
Dispersant 0.1wt%；
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1.5 mixing.
The preparation method of the expanded graphite is：
Qingdao day and the expansible graphite up to 50 mesh of graphite Co., Ltd, expansion multiplying power for 300-400mL/g are bought, it can
Expanded graphite is placed in 900 DEG C of calcining 10s, obtains expanded graphite.
A kind of preparation method of expanded graphite-metal oxide sorbents, includes the following steps：
α-the manganese dioxide is uniformly distributed in aqueous solution by dispersant, expanded graphite is immersed in above-mentioned point
It dissipates in solution, is stored at room temperature 10h, then in 200 DEG C of drying, obtain the expanded graphite-metal oxide sorbents.
By the expanded graphite-α-manganese dioxide adsorbent for Adsorption of Cadmium in solution, it is divided using UV, visible light
The concentration of cadmium ion, experiment obtain in photometric determination solution, as shown in table 1, when in solution concentration of cadmium ions be 2mg/L, it is molten
When liquid pH value is 6, the expanded graphite-α-manganese dioxide adsorbent can reach 88% to the removal rate of cadmium ion in solution, most
Big adsorbance reaches 0.29mg/g；When solution ph is 2, the expanded graphite-α-manganese dioxide adsorbent is to cadmium ion in solution
Removal rate can reach 86%, maximal absorptive capacity reaches 0.2867mg/g；When solution ph is 12, the expanded graphite-α-two
Manganese oxide sorbents can reach 86.7% to the removal rate of cadmium ion in solution, and maximal absorptive capacity reaches 0.289mg/g.
Therefore, cadmium ion of the expanded graphite-α-manganese dioxide adsorbent suitable for removing low concentration solution.
Embodiment 6
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 70wt%；
α-manganese dioxide 29.95wt%；
Dispersant 0.05wt%；
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1.2 mixing.
By the expanded graphite-α-manganese dioxide adsorbent for Adsorption of Cadmium in solution, it is divided using UV, visible light
The concentration of cadmium ion, experiment obtain in photometric determination solution, as shown in table 1, when in solution concentration of cadmium ions be 2mg/L, it is molten
Expanded graphite-α-the manganese dioxide adsorbent can reach 85% to the removal rate of cadmium ion in solution when liquid pH value is 6, maximum
Adsorbance reaches 0.28mg/g；When solution ph is 2, the expanded graphite-α-manganese dioxide adsorbent is to cadmium ion in solution
Removal rate can reach 83%, and maximal absorptive capacity reaches 0.2767mg/g；When solution ph is 12, the expanded graphite-α-dioxy
Change manganese adsorbent and 84% can reach to the removal rate of cadmium ion in solution, maximal absorptive capacity reaches 0.28mg/g.
Therefore, cadmium ion of the expanded graphite-α-manganese dioxide adsorbent suitable for removing low concentration solution.
Embodiment 7
The present embodiment provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
The preparation method of the expanded graphite-metal oxide sorbents, includes the following steps：
A, expanded graphite is placed in the aluminum nitrate solution of 80mL, the dispersant, room temperature concussion is added dropwise in 25min
It is dry after 1.5-3h；
B, by the product after drying in logical N2In the case of, 2h is calcined at 400 DEG C, obtains the metal oxide insertion
Expanded graphite-γ-alundum (Al2O3) adsorbent in the expanded graphite sheet surfaces and lamella fold.
By the expanded graphite-γ-alundum (Al2O3) adsorbent for fluorine ion in adsorbent solution, selected using fluorine ion
The concentration of fluorine ion, experiment obtain in determination of electrode solution, as shown in table 1, when fluorinion concentration is 2mg/L, solution in solution
When pH value is 6, the expanded graphite-γ-alundum (Al2O3) adsorbent can reach 89% to the removal rate of fluorine ion in solution, most
Big adsorbance reaches 0.2967mg/g；When solution ph is 2, the expanded graphite-γ-alundum (Al2O3) adsorbent is to fluorine in solution
The removal rate of ion can reach 87%, and maximal absorptive capacity reaches 0.29mg/g；When solution ph is 12, the expanded graphite-γ-
Alundum (Al2O3) adsorbent can reach 88% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches 0.2933mg/g.
From experimental result as can be seen that the expanded graphite-γ-alundum (Al2O3) activity obtained without temperature programming
And expanded graphite-γ-the alundum (Al2O3) that the pattern and grain size of the metal oxide are prepared slightly poorer to embodiment 1,
But still there is preferable absorption property, it is suitable for removing the toxic ion of low concentration.
Comparative example 1
This comparative example provides a kind of expanded graphite-γ-alundum (Al2O3) adsorbent, and compared with Example 1, difference exists
In the dispersant is only polyvinyl alcohol.
By the expanded graphite-γ-alundum (Al2O3) adsorbent for fluorine ion in adsorbent solution, selected using fluorine ion
The concentration of fluorine ion, experiment obtain in determination of electrode solution, as shown in table 1, when fluorinion concentration is 2mg/L, solution in solution
When pH value is 6, the expanded graphite-γ-alundum (Al2O3) adsorbent can reach 65% to the removal rate of fluorine ion in solution, most
Big adsorbance reaches 0.2167mg/g；When solution ph is 2, the expanded graphite-γ-alundum (Al2O3) adsorbent is to fluorine in solution
The removal rate of ion can reach 43%, and maximal absorptive capacity reaches 0.1433mg/g；When solution ph is 12, the expanded graphite-
γ-alundum (Al2O3) adsorbent can reach 30% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches 0.1mg/g.
It can be obtained from experimental result, when the weight ratio of the polyvinyl alcohol and propylene glycol is outside range of the present invention,
The adsorbent being prepared is affected by solution ph.
Comparative example 2
The present embodiment provides a kind of expanded graphite-γ-alundum (Al2O3) adsorbents, and compared with Example 1, difference exists
In the dispersant is polyvinyl alcohol and propylene glycol by weight 1:3 mix.
By expanded graphite-γ-alundum (Al2O3) prepared by this comparative example for the fluorine ion in adsorbent solution, test
It arrives, as shown in table 1, for the expanded graphite-γ-alundum (Al2O3) when solution ph is 6, fluorinion concentration is 2mg/ in solution
L, the expanded graphite-γ-alundum (Al2O3) can reach 70% to the removal rate of fluorine ion in solution, and maximal absorptive capacity reaches
0.233mg/g；When solution ph is 2, the expanded graphite-γ-alundum (Al2O3) is to the removal rate of fluorine ion in solution
60%；When solution ph is 12, the expanded graphite-γ-alundum (Al2O3) is 58% to the removal rate of fluorine ion in solution.
And expanded graphite-γ-the alundum (Al2O3) occurs concussion with soda acid in the solution and causes secondary pollution.
It can be obtained from experimental result, the weight ratio of the polyvinyl alcohol and propylene glycol is less than 1:When 1.5, the metal oxygen
Compound easily occurs to stack and reunite, and specific surface area is caused to decline, and absorption property reduces.
Comparative example 3
This comparative example provides a kind of expanded graphite-metal oxide sorbents, compared with Example 1, the difference is that,
Including following components：
Expanded graphite 65wt%；
γ-alundum (Al2O3) 35wt%；
The preparation method of the expanded graphite-metal oxide sorbents, includes the following steps：
A, expanded graphite is placed in the aluminum nitrate solution of 80mL, room temperature shakes drying after 1.5-3h；
B, by the product after drying in logical N2In the case of, after being warming up to 400 DEG C with 50 DEG C of speed of raising of per half an hour
2h is kept the temperature, the expanded graphite-γ-three that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold is obtained
Al 2 O adsorbent.
By expanded graphite-γ-alundum (Al2O3) prepared by this comparative example for the cadmium ion in adsorbent solution, test
It arrives, as shown in table 1, expanded graphite-γ-alundum (Al2O3) Adsorption of Cadmium in the solution, when concentration of cadmium ions in solution
For 2mg/L, the expanded graphite-γ-alundum (Al2O3) can reach 50% to the removal rate of cadmium ion in solution, maximal absorptive capacity
Up to 0.1667mg/g；When solution ph is 2, removal rate of the expanded graphite-γ-alundum (Al2O3) to cadmium ion in solution
It is 15%；When solution ph is 12, the expanded graphite-γ-alundum (Al2O3) is to the removal rate of cadmium ion in solution
18%
In the case where being not added with dispersant, the metal oxide is embedded in the expanded graphite sheet surfaces and fold
When easily occur accumulation and reunite, reduce the specific surface area of the adsorbent, absorption property caused to reduce.
Test result
The present invention is used for the expanded graphite-metal oxide to remove fluorine ion and cadmium ion in solution, and adopts respectively
Fluorine ion in solution and cadmium ion are detected with fluoride ion selective electrode and ultraviolet specrophotometer, testing result such as table 1
It is shown：
1 Experimental Comparison data of table
Above-described embodiment is that transformation parameter obtains in range of the present invention, expanded graphite-metal oxygen of the present invention
Compound adsorbent can select the metal oxide appropriate to be combined with expanded graphite according to different pollutants and pollution level,
Expanded graphite-the metal oxide sorbents are obtained to the selective Adsorption of noxious material in solution, to take
Obtain good adsorption effect.The expanded graphite-as described in optimal preparation method preparation is respectively adopted in embodiment 1 and embodiment 4
γ-alundum (Al2O3) and expanded graphite-α-manganese dioxide respectively in solution fluorine ion and cadmium ion have stronger affinity
And absorption property, embodiment 2 are to buy the common expansible graphite in market to prepare expanded graphite, then pass through current conventional preparation
Method, which prepares the expanded graphite-metal oxide sorbents, still has preferable adsorption effect；In range of the present invention
Expanded graphite-the metal oxide sorbents being inside prepared are to have higher removal within the scope of 2-12 in solution ph
Rate；Embodiment 7 does not prepare the expanded graphite-metal oxide sorbents in preparation process by the way of temperature programming,
The homogeneity of the activity of the metal oxide, grain size and pattern is slightly less than embodiment 1, but still has preferable adsorptivity
Energy.Above-mentioned comparative example 1 and comparative example 2 change the composition and content of dispersant outside range of the present invention, and experiment obtains, removal
Rate is affected by pH value of solution, and relatively low to the toxic ion remaval rate of low concentration in neutral solution, and recycles difficulty, cannot
Secondary use；Difference lies in the expanded graphite-metal oxide sorbents in preparation process with embodiment 1 for comparative example 3
It is not added with dispersant, is disperseed when the metal oxide being caused to be attached in the expanded graphite sheet surfaces and fold uneven
It is even, accumulation easily occurs and reunites so that the expanded graphite-metal oxide being prepared using preparation method described in comparative example 3
Specific surface area less than expanded graphite-metal oxide that addition dispersant is prepared in preparation process, so as to cause absorption
The adsorption effect of agent reduces.
In conclusion expanded graphite-metal oxide sorbents of the present invention not only have the expanded graphite and gold
Belong to the respective excellent performance of oxide, moreover it is possible to which the synergistic effect for playing the two makes the composite material be acted on as sorbing material
There is higher stability in solution, hardly influenced by solution ph, there is higher parent to specific noxious material
With power and adsorption capacity, the removal of low concentration noxious material suitable for solution；Without additional addition binder in preparation process
And additional activation act, simplify material composition and operating process.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of expanded graphite-metal oxide sorbents, which is characterized in that include following components：
Expanded graphite 60-70wt%；
Metal oxide 29.9-39.9wt%；
Dispersant 0.05-0.1wt%；
Wherein, the metal oxide is one kind in nanometer γ-alundum (Al2O3) or nanometer α-manganese dioxide；The dispersant
It is polyvinyl alcohol and propylene glycol by weight 1:1-1.5 mixing.
2. a kind of expanded graphite-metal oxide sorbents according to claim 1, which is characterized in that comprising with the following group
Point：
Expanded graphite 65wt%；
Metal oxide 34.92wt%；
Dispersant 0.08wt%；
The dispersant is polyvinyl alcohol and propylene glycol by weight 1:1 mixes.
3. a kind of expanded graphite-metal oxide sorbents according to claim 1, which is characterized in that the expansion stone
The preparation method of ink, includes the following steps：
(1) 0.5-2g natural flake graphites are soaked in aqueous solution, a concentration of 60%-70% potassium permanganate of 30-40mL is added dropwise
Solution is mixed；
(2) a concentration of 60%-70% salpeter solutions of 20-30mL are added dropwise into step (1) acquired solution；
(3) phosphoric acid solution of a concentration of 80%-90% of 20-30mL is added dropwise into step (2) acquired solution, 30- is mixed
40min, filtering drying；
(4) crystalline flake graphite obtained by step (3) is calcined into 10-15s to get the expanded graphite in 900-1200 DEG C.
4. a kind of preparation method of expanded graphite-metal oxide sorbents according to claim 1, which is characterized in that
The particle size range of the γ-alundum (Al2O3) is 20-50nm.
5. a kind of preparation method of expanded graphite-metal oxide sorbents according to claim 1, which is characterized in that
The particle size range of the nanometer α-manganese dioxide is 30-50nm.
6. the preparation method of any one expanded graphite-metal oxide sorbents of claim 1-5, which is characterized in that including
Following steps：
A, the expanded graphite is placed in the metal-nitrate solutions of 50-100mL, the dispersion is added dropwise in 20-30min
Agent, room temperature shake drying after 1.5-3h；
B, by the product after drying in logical N2In the case of, it is protected after being warming up to 350-450 DEG C with 50 DEG C of speed of raising of per half an hour
Warm 1-3h obtains expanded graphite-metal that the metal oxide is embedded in the expanded graphite sheet surfaces and lamella fold
Oxide adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810238850.3A CN108311106A (en) | 2018-03-22 | 2018-03-22 | A kind of expanded graphite-metal oxide sorbents and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810238850.3A CN108311106A (en) | 2018-03-22 | 2018-03-22 | A kind of expanded graphite-metal oxide sorbents and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108311106A true CN108311106A (en) | 2018-07-24 |
Family
ID=62898031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810238850.3A Pending CN108311106A (en) | 2018-03-22 | 2018-03-22 | A kind of expanded graphite-metal oxide sorbents and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108311106A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248662A (en) * | 2018-09-17 | 2019-01-22 | 明光市飞洲新材料有限公司 | A kind of adsorbent and preparation method thereof for building |
| CN111135794A (en) * | 2020-01-13 | 2020-05-12 | 唐山师范学院 | Alumina modified expanded graphite adsorbent and preparation method and application thereof |
| CN111170420A (en) * | 2020-01-20 | 2020-05-19 | 中南大学 | Method for removing fluorine ions in solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817441A (en) * | 2006-01-16 | 2006-08-16 | 上海自来水市北科技有限公司 | Adsorbing material for removing cadmium in water and production thereof |
| CN101104523A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院大连化学物理研究所 | Method for preparing high specific surface area high thermal stability aluminum oxide |
| RU2429906C1 (en) * | 2009-12-29 | 2011-09-27 | Общество с ограниченной ответственностью Научно-производственное предприятие "Лисскон" | Complex granular nanosorbent |
| CN102335590A (en) * | 2010-07-27 | 2012-02-01 | 北京林业大学 | Efficient electric promoting absorptive fluorine removal adsorbent and preparation method thereof |
| CN103920449A (en) * | 2014-04-24 | 2014-07-16 | 云南大学 | Self-assembled nano film MnO2 adsorption agent capable of high-efficiently adsorbing heavy metals and preparation method of adsorption agent |
| CN105903435A (en) * | 2016-04-12 | 2016-08-31 | 北京化工大学 | Sulfenyl group modified expandable graphite adsorbent used for efficient treatment of heavy metal wastewater |
-
2018
- 2018-03-22 CN CN201810238850.3A patent/CN108311106A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817441A (en) * | 2006-01-16 | 2006-08-16 | 上海自来水市北科技有限公司 | Adsorbing material for removing cadmium in water and production thereof |
| CN101104523A (en) * | 2006-07-14 | 2008-01-16 | 中国科学院大连化学物理研究所 | Method for preparing high specific surface area high thermal stability aluminum oxide |
| RU2429906C1 (en) * | 2009-12-29 | 2011-09-27 | Общество с ограниченной ответственностью Научно-производственное предприятие "Лисскон" | Complex granular nanosorbent |
| CN102335590A (en) * | 2010-07-27 | 2012-02-01 | 北京林业大学 | Efficient electric promoting absorptive fluorine removal adsorbent and preparation method thereof |
| CN103920449A (en) * | 2014-04-24 | 2014-07-16 | 云南大学 | Self-assembled nano film MnO2 adsorption agent capable of high-efficiently adsorbing heavy metals and preparation method of adsorption agent |
| CN105903435A (en) * | 2016-04-12 | 2016-08-31 | 北京化工大学 | Sulfenyl group modified expandable graphite adsorbent used for efficient treatment of heavy metal wastewater |
Non-Patent Citations (6)
| Title |
|---|
| HONGYUN JIN ET AL: ""research on removal of fluoride in aqueous solution by alumina-modified expanded graphite composite"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 乔延江: "《中华医学百科全书 中药制剂学》", 30 April 2017, 中国协和医科大学出版社 * |
| 胡功政等: "《新全使用兽药手册》", 30 September 2009, 河南科学技术出版社 * |
| 郑水林等: "《非金属矿加工技术与应用手册》", 31 May 2005, 冶金工业出版社 * |
| 韦军: "《高分子合成工艺学》", 28 February 2011, 华东理工大学出版社 * |
| 高滋等: "《固体酸催化》", 31 May 2016, 复旦大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248662A (en) * | 2018-09-17 | 2019-01-22 | 明光市飞洲新材料有限公司 | A kind of adsorbent and preparation method thereof for building |
| CN111135794A (en) * | 2020-01-13 | 2020-05-12 | 唐山师范学院 | Alumina modified expanded graphite adsorbent and preparation method and application thereof |
| CN111170420A (en) * | 2020-01-20 | 2020-05-19 | 中南大学 | Method for removing fluorine ions in solution |
| CN111170420B (en) * | 2020-01-20 | 2021-08-17 | 中南大学 | Method for removing fluorine ions in solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108311106A (en) | A kind of expanded graphite-metal oxide sorbents and preparation method thereof | |
| CN108905999B (en) | Novel biochar composite gel and preparation method and application thereof | |
| CN106000299B (en) | A kind of preparation method of the activated carbon supported type adsorbent of wool | |
| CN102614854A (en) | Method for preparaing dephosphorized and ferrum-carried activated carbon adsorbent | |
| CN107362823B (en) | Catalytic material for degrading indoor formaldehyde at room temperature and preparation method thereof | |
| CN107867688A (en) | A kind of preparation method for the shaddock peel activated carbon for being used for purification of air and sewage disposal | |
| CN1935355A (en) | Manganese bioxide/carbon nano tube composite adsorbent and its preparing method | |
| CN108939910B (en) | Sticking film for catalyzing and oxidizing indoor formaldehyde and preparation and application methods thereof | |
| CN104667860A (en) | Adsorbent and preparation method thereof | |
| CN109833849A (en) | Modification biological charcoal and the preparation method and application thereof for As polluted soil reparation | |
| CN110314640A (en) | The preparation process and application of the preparation process of conch meal adsorbent, shell powder supported nano zero-valence iron adsorbent | |
| CN107983320A (en) | Preparation method of difunctional film removed for formaldehyde and products thereof and application | |
| CN107774232A (en) | A kind of magnetic active carbon mixture of the ball containing charcoal and preparation method thereof | |
| CN106311135A (en) | Composite material for removing fluorinion in water and preparation method thereof | |
| CN107952289A (en) | A kind of filter screen with purifying formaldehyde and preparation method thereof | |
| CN113441142B (en) | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst | |
| CN104667985A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN107051194A (en) | A kind of purification particle being filled in filter screen | |
| CN109499563A (en) | A kind of preparation method of zinc oxide-active carbon composite catalyst | |
| CN108940349A (en) | The method of carbonitride Z-type photochemical catalyst removal dyestuff contaminant is mixed using siliver chromate/sulphur | |
| CN107837819B (en) | MnY catalyst for indoor formaldehyde catalytic removal and preparation method thereof | |
| CN115353189B (en) | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen | |
| WO2021139416A1 (en) | Composite functional material for simultaneous denitrification and dephosphorization and preparation method therefor | |
| CN114870845A (en) | Preparation method of catalyst for removing ciprofloxacin by efficient Fenton-like method | |
| CN104607160A (en) | Difunctional water phase adsorbing material with characteristic of zwitterion coadsorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180724 |