CN108927117A - A kind of preparation method of flyash-sodium alginate composite adsorbing material - Google Patents
A kind of preparation method of flyash-sodium alginate composite adsorbing material Download PDFInfo
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- CN108927117A CN108927117A CN201810870535.2A CN201810870535A CN108927117A CN 108927117 A CN108927117 A CN 108927117A CN 201810870535 A CN201810870535 A CN 201810870535A CN 108927117 A CN108927117 A CN 108927117A
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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
- B01J20/22—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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- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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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
- B01J20/06—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
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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
- B01J20/06—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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- 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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- 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 discloses a kind of flyash-sodium alginate composite adsorbing material preparation methods, using flyash as raw material, it activated, separated, since flyash has good pore structure, in wawter bloom reaction process, fly ash grain surface will appear abundant hydroxyl, make it have significant hydrophily, adsorptivity and chemical mobility of the surface, rhetorical function group prepares functionalization flyash afterwards, the flyash of functionalization, sodium alginate are prepared as graininess composite adsorbing material again, functionalization flyash has been given full play to and functional group (COO is enriched on sodium alginate surface‑Group) synergistic effect, can be used for adsorbing positively charged heavy metal ion, such as Cu2+、Ni2+、Zn2+、Pb2+、Cd2+Deng production cost is low, realizes the resource utilization of flyash, flyash specific surface area by activation processing can be improved 15-20 times, and absorption property greatly improved, and the composite material by this method preparation can be reused by desorption, it not will cause secondary pollution, reduce processing cost.
Description
Technical field
The invention belongs to industrial waste water treatments, are related to a kind of preparation method of adsorbent material, specifically relate to
And a kind of preparation method of functionalization flyash-sodium alginate composite adsorbing material.
Background technique
With the development of industrialization and urbanization, water environment pollution, water scarcity are got worse, water pollution control, water
Environmental protection is very urgent, and a major reason of water pollution is that various industrial wastewaters and sanitary sewage cannot effectively be located in
The heavy metal ion contained in reason and qualified discharge, especially industrial wastewater is huge to the harm of Environment-Ecosystem.In recent years
Come, plurality of heavy metal ion is discharged into water body, cannot be biodegradable in the natural environment, can be put aside in the environment, right
Human and animal has toxicity or carcinogenic influence.
Traditional wastewater treatment method is generally separated nuisance using various external forces from waste water, is such as changed
Precipitating, ion exchange, membrane filter method etc. are learned, but there are treatment effects to be not sufficiently stable, higher cost, easily causes two for the above method
The problem of secondary pollution.With the further promotion of heavy metal wastewater thereby discharge standard, develop a kind of economical, efficient for containing a huge sum of money
The technology for belonging to ion waste water processing is most important.Wherein, adsorption method is that a kind of equipment is simple, easily operated, without secondary pollution
Processing method, be the process for treating heavy-metal waste water of most application prospect at present, but existing common adsorbents have absorption and hold
Measure deficiency low, that parsing is difficult.
Flyash is one of biggish industrial residue of the current discharge capacity in China, is mainly derived from thermal power plant coal dust and is burning
When, the grey or grey black powder collected from boiler tail, main component Al2O3、SiO2, CaO and Fe2O3Deng largely
If flyash be not pocessed, be placed in outdoor occasion, can generate fugitive dust, pollute environment, be directly discharged into river, lake
In, it will cause rivers to silt up, polluted-water.But flyash surface porosity is porous, large specific surface area, while in flyash also
Containing a certain amount of uncompleted burned carbon, the active carbon that can be used as adsorbent is functioned as, these features have flyash
Very strong adsorptivity can be used as adsorbent material processing industrial wastewater, and the characteristics of porosity and large specific surface area of flyash makes it
Absorption can be generated by intermolecular attraction between contaminant molecule, while there are the ingredients such as a large amount of aluminium, iron, silicon for flyash, it can be right
Electronegative colloidal particles are adsorbed in water.But it is unsatisfactory that flyash is directly used in water treatment effect, or even can
Secondary pollution can be caused, therefore research is modified to flyash, so that it is more suitable for wastewater treatment and is especially suitable for containing weight
The wastewater treatment of metal ion, becomes a technical problem to be solved urgently.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in traditional Powder ash adsorption performance deficiency, it is outstanding in wastewater treatment
It is using being limited in the wastewater treatment containing heavy metal ion, to propose that one kind makes flyash by activation and functional modification
There is functionalization flyash-sodium alginate composite particles adsorbent material preparation method of preferable absorption property to heavy metal ion.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
The present invention provides a kind of preparation method of flyash-sodium alginate composite adsorbing material comprising following steps:
S1, activating fly ash is prepared, flyash is activated with activator；
S2, moisture is stood after the flyash after activation processing is washed with water, obtain weight after separating upper layer suspension flyash
Matter activating fly ash；
S3, preparation functionalization flyash, the heavy activating fly ash that step S2 is obtained is reacted jointly with silane coupling agent,
Functionalization flyash is made；
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, the functionalization flyash that step S3 is obtained with
Sodium alginate ripening in water jointly, obtains ageing liquid, the ageing drop is added to CaCl2After solidifying in solution, obtain
To flyash-sodium alginate composite adsorbing material.
Preferably, the step S4 specifically comprises the following steps:
S41,1-4 parts by weight sodium alginate powder and 5-20 parts by weight functionalization flyash are placed in 100-300 parts by weight
Stirring to sodium alginate dissolves in deionized water, is aged 4-24h after mixing, obtains ageing liquid；
S42, the CaCl that the ageing drop is added to 100-1000 parts by weight2Curing process 1-6h in solution, is granulated into
After ball, it is washed with deionized to neutrality, up to flyash-sodium alginate composite adsorbing material after drying.
Preferably, the activator be at least one of sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, the flyash with
The volume ratio of the activator is 1:2-10, and the molar concentration of the activator is 1-5mol/L.
Preferably, the step S1 is specifically, flyash is mixed in proportion with activator, and at 20-100 DEG C with
The mixing speed stir-activating 1-6h of 50-100r/min.
Preferably, the step S3 specifically comprises the following steps:
S31, heavy activating fly ash described in 5-10 parts by weight is placed in 100-200 weight parts organic solvent；
3-15 parts by weight silane coupling agent is added in S32, the mixture obtained to step S31, is condensed back reaction；
It dries after S33, the reaction product organic solvent washing for obtaining step S32 at 40-80 DEG C to get functionalization
Fly ash material.
Preferably, the density of the heavy activating fly ash is 1.9-2.3cm3/g。
Preferably, the silane coupling agent is γ-aminoethyl amino propyl trimethoxy silane, three ethoxy of γ-aminopropyl
At least one of base silane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane.
Preferably, after the step S32 is specifically, alkyl coupling agent is mixed with the mixture of step S31, in 60-
Oil bath is condensed back reaction 10-24h at 120 DEG C.
Preferably, the organic solvent is at least one of benzene,toluene,xylene, dehydrated alcohol, methanol.
Preferably, the viscosity of the sodium alginate is 0.83-1.15Pas, the CaCl2The mass concentration of solution is
1-10%.
The above technical solution of the present invention has the following advantages over the prior art:
Flyash of the present invention-sodium alginate composite adsorption granular materials preparation method, using flyash as raw material,
After being activated, being separated, since flyash has good pore structure, and in wawter bloom reaction process, fly ash grain table
Face will appear abundant hydroxyl, make it have significant hydrophily, adsorptivity and chemical mobility of the surface, by rhetorical function group
It is prepared as functionalization flyash, then the flyash of functionalization, sodium alginate are prepared as graininess composite adsorbing material, by filling
Functionalization flyash is waved in distribution and functional group (COO is enriched on sodium alginate surface-Group) quantity synergistic effect, can be used for adsorbing
Positively charged heavy metal ion, such as Cu2+、Ni2+、Zn2+、Pb2+、Cd2+Deng, therefore can be applied to technical field of sewage, it goes
Heavy metal ion in water removal, this adsorbent material raw material are discarded flyash, and low manufacture cost realizes the resource of flyash
To change and utilizes, the flyash specific surface area by activation processing can be improved 15-20 times, the absorption property of flyash greatly improved,
In addition, functionalization flyash-sodium alginate material by this method preparation can be reused by desorption, not will cause secondary
Pollution, further reduced processing cost, and activating fly ash surface can be by grafting different functional groups, for handling containing difference
The waste water of charging property heavy metal compensates for the problem of conventional adsorbent wide spectrum formula handles heavy metal ion.The preparation method technique
And it is easy to operate, preparation efficiency is high, and it is with short production cycle, it is not necessarily to special chemical industry equipment, is easy to industrialized mass production.
Detailed description of the invention
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is flyash described in the embodiment of the present invention 1-sodium alginate composite adsorbing material infared spectrum；
Fig. 2 is flyash described in the embodiment of the present invention 1-sodium alginate composite adsorbing material to different equilibrium concentration Cu2+、
Ni2+Absorption property curve graph.
Specific embodiment
Embodiment 1
The present embodiment provides a kind of flyash-sodium alginate composite adsorbing material preparation methods comprising following steps:
S1, flyash is taken from thermal power plant, after removing impurity and drying, cross 200 meshes, using the hydrochloric acid of 1mol/L as work
Agent is activated flyash: by flyash and hydrochloric acid solution according to the volume ratio of 1:2 at 20 DEG C with 50r/min
Mixing speed stir-activating 6h, obtain activating fly ash.
S2, the activating fly ash obtained after activation processing is washed with deionized to neutrality, then in deionized water
Natural subsidence separates upper layer suspension flyash after sedimentation, lower layer's sedimentation flyash filtering drying is taken to activate fine coal to get to heavy
Ash, the density of the heavy activating fly ash are 1.9cm3/ g, flyash specific surface area about 3.0~5.2m before activating2/ g, through work
Gained heavy activating fly ash specific surface area about 37.1~64.90m after change2/g。
S3, preparation functionalization flyash, take heavy activating fly ash, it are reacted jointly with silane coupling agent, by silane
The functional group of coupling agent grafts in heavy activating fly ash, obtains the functionalization flyash with selective absorption heavy metal ion
Adsorbent material, specifically, including following preparation step:
S31,5 parts by weight heavy activating fly ash are stirred evenly in there-necked flask with 100 parts by weight of toluene.
Coupling agent γ-aminoethylaminopropyl trimethoxy of 3 parts by weight is added in S32, the mixture obtained to step S31
Silane (KH792), oil bath is condensed back reaction for 24 hours at 60 DEG C.
S33, the obtained reaction product of step S32 is washed twice with toluene, and is done in the vacuum oven at 40 DEG C
It is dry, obtain amino functional flyash.
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, the functionalization flyash that step S33 is obtained
With sodium alginate powder ripening in water jointly, ageing liquid is obtained, the ageing drop is added into CaCl2Solidify in solution
Afterwards, flyash-sodium alginate composite adsorbing material is obtained, is specifically included the following steps:
S41,1 parts by weight sodium alginate powder and 5 parts by weight functionalization flyash are placed in 100 parts by weight of deionized water
Stirring is completely dissolved to sodium alginate, is aged 4h after mixing, obtains ageing liquid, wherein the sodium alginate powder glues
Degree is 0.83Pas.
S42, the CaCl for being drawn with syringe by the ageing liquid and being added dropwise to 100 parts by weight2In solution at solidification
6h is managed, wherein the CaCl2The concentration of solution is 1%, and during curing process, continuous uniform stirring generates after avoiding solidification
Sphere be adhered, after solidification is granulated balling-up, be washed with deionized to neutrality, it is compound up to flyash-sodium alginate after dry
Particulate adsorbent material.
Embodiment 2
The present embodiment provides a kind of preparation methods of functionalization flyash comprising following steps:
S1, flyash is taken from thermal power plant, after removing impurity and drying, cross 200 meshes, using the sulfuric acid of 5mol/L as work
Agent is activated flyash: by flyash and sulfuric acid solution according to the volume ratio of 1:10 at 100 DEG C with 100r/
The mixing speed stir-activating 1h of min, obtains activating fly ash.
S2, the activating fly ash obtained after activation processing is washed with deionized to neutrality, then in deionized water
Natural subsidence separates upper layer suspension flyash after sedimentation, lower layer's sedimentation flyash filtering drying is taken to activate fine coal to get to heavy
Ash, the density of the heavy activating fly ash are 2.3cm3/ g, flyash specific surface area about 3.0~5.2m before activating2/ g, through work
Gained heavy activating fly ash specific surface area about 37.1~64.90m after change2/g。
S3, preparation functionalization flyash, take heavy activating fly ash, it are reacted jointly with silane coupling agent, by silane
The functional group of coupling agent grafts in heavy activating fly ash, obtains the functionalization flyash with selective absorption heavy metal ion
Adsorbent material, specifically, including following preparation step:
S31, by the mixed solution of 10 parts by weight heavy activating fly ash and 200 parts by weight benzene and dimethylbenzene in there-necked flask
It stirs evenly, the volume ratio of the benzene and dimethylbenzene is 2:1.
The coupling agent gamma-aminopropyl-triethoxy-silane of 15 parts by weight is added in S32, the mixture obtained to step S31
(KH550), oil bath is condensed back reaction 10h at 120 DEG C.
S33, the obtained reaction product of step S32 is washed twice with benzene, and dry in the vacuum oven at 80 DEG C,
Obtain amino functional flyash.
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, the functionalization flyash that step S33 is obtained
With sodium alginate powder ripening in water jointly, ageing liquid is obtained, the ageing drop is added into CaCl2Solidify in solution
Afterwards, flyash-sodium alginate composite adsorbing material is obtained, is specifically included the following steps:
S41,4 parts by weight sodium alginate powders and 20 parts by weight functionalization flyash are placed in 300 parts by weight of deionized water
Middle stirring is completely dissolved to sodium alginate, is aged after mixing for 24 hours, obtains ageing liquid, wherein the sodium alginate powder
Viscosity is 1.15Pas.
S42, the CaCl for being drawn with syringe by the ageing liquid and being added dropwise to 1000 parts by weight2In solution at solidification
2h is managed, wherein the CaCl2The concentration of solution is 10%, and during curing process, continuous uniform stirring generates after avoiding solidification
Sphere be adhered, after solidification is granulated balling-up, be washed with deionized to neutrality, it is compound up to flyash-sodium alginate after dry
Adsorb granular materials.
Embodiment 3
The present embodiment provides a kind of preparation methods of functionalization flyash comprising following steps:
S1, flyash is taken from thermal power plant, after removing impurity and drying, 200 meshes are crossed, using the sulfuric acid of 3mol/L, hydrochloric acid
Mixed solution as activator (sulfuric acid, hydrochloric acid volume ratio be 1:1), flyash is activated: by flyash
With sulfuric acid, mixed in hydrochloric acid liquid solution according to the volume ratio of 1:5 at 70 DEG C with the mixing speed stir-activating 3h of 80r/min,
Obtain activating fly ash.
S2, the activating fly ash obtained after activation processing is washed with deionized to neutrality, then in deionized water
Natural subsidence separates upper layer suspension flyash after sedimentation, lower layer's sedimentation flyash filtering drying is taken to activate fine coal to get to heavy
Ash, the density of the heavy activating fly ash are 2.1cm3/ g, flyash specific surface area about 3.0~5.2m before activating2/ g, through work
Gained heavy activating fly ash specific surface area about 37.1~64.90m after change2/g。
S3, preparation functionalization flyash, take heavy activating fly ash, it are reacted jointly with silane coupling agent, by silane
The functional group of coupling agent grafts in heavy functionalization flyash, obtains the functionalization fine coal with selective absorption heavy metal ion
Grey adsorbent material, specifically, including following preparation step:
S31,8 parts by weight heavy activating fly ash are stirred evenly in there-necked flask with 150 parts by weight of xylene.
The coupling agent of 10 parts by weight: γ-mercaptopropyl trimethoxysilane is added in S32, the mixture obtained to step S31
(KH590) with the mixture of gamma-mercaptopropyltriethoxysilane (KH580), the mass ratio of the two is 1:1, then at 90 DEG C
Oil bath is condensed back reaction 18h.
S33, the obtained reaction product of step S32 is washed twice with dimethylbenzene, and in the vacuum oven at 60 DEG C
It is dry, obtain functionalization flyash.
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, the functionalization flyash that step S33 is obtained
With sodium alginate powder ripening in water jointly, ageing liquid is obtained, the ageing drop is added into CaCl2Solidify in solution
Afterwards, flyash-sodium alginate composite adsorbing material is obtained, is specifically included the following steps:
S41,3 parts by weight sodium alginate powders and 15 parts by weight functionalization flyash are placed in 200 parts by weight of deionized water
Middle stirring is completely dissolved to sodium alginate, is aged 16h after mixing, obtains ageing liquid, wherein the sodium alginate powder
Viscosity is 1Pas.
S42, the CaCl for being drawn with syringe by the ageing liquid and being added dropwise to 700 parts by weight2In solution at solidification
4h is managed, wherein the CaCl2The concentration of solution is 5%, and during curing process, continuous uniform stirring generates after avoiding solidification
Sphere be adhered, after solidification is granulated balling-up, be washed with deionized to neutrality, it is compound up to flyash-sodium alginate after dry
Adsorb granular materials.
Embodiment 4
The present embodiment provides a kind of preparation methods of functionalization flyash comprising following steps:
S1, flyash is taken from thermal power plant, after removing impurity and drying, cross 200 meshes, it is molten using the sodium hydroxide of 4mol/L
Liquid is activated flyash as activator: by flyash and sodium hydroxide solution according to the volume ratio of 1:7 at 55 DEG C
Under with the mixing speed stir-activating 3.5h of 80r/min, obtain activating fly ash.
S2, the activating fly ash obtained after activation processing is washed with deionized to neutrality, then in deionized water
Natural subsidence separates upper layer suspension flyash after sedimentation, lower layer's sedimentation flyash filtering drying is taken to activate fine coal to get to heavy
Ash, the density of the heavy activating fly ash are 2.2cm3/ g, flyash specific surface area about 3.0~5.2m before activating2/ g, through work
Gained heavy activating fly ash specific surface area about 37.1~64.90m after change2/g。
S3, preparation functionalization flyash, take heavy activating fly ash, it are reacted jointly with silane coupling agent, by silane
The functional group of coupling agent grafts in heavy activating fly ash, obtains the functionalization flyash with selective absorption heavy metal ion
Adsorbent material, specifically, including following preparation step:
S31, by 7 parts by weight heavy activating fly ash and 155 parts by weight Methanol, dehydrated alcohol mixed solution in there-necked flask
In stir evenly, the volume ratio of the methanol and dehydrated alcohol is 2:1.
The coupling agent of 11.5 parts by weight: γ-aminoethylaminopropyl front three is added in S32, the mixture obtained to step S31
Oxysilane (KH792), then oil bath is condensed back reaction 20h at 105 DEG C.
S33, the mixed solution of reaction product methanol and dehydrated alcohol that step S32 is obtained is washed twice, and 75
It is dry in vacuum oven at DEG C, obtain amino functional flyash.
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, the functionalization flyash that step S33 is obtained
With sodium alginate powder ripening in water jointly, ageing liquid is obtained, the ageing drop is added into CaCl2Solidify in solution
Afterwards, flyash-sodium alginate composite adsorbing material is obtained, is specifically included the following steps:
S41,2.5 parts by weight sodium alginate powders and 16 parts by weight functionalization flyash are placed in 170 parts by weight deionizations
Stirring is completely dissolved to sodium alginate in water, is aged 9h after mixing, obtains ageing liquid, wherein the sodium alginate powder
Viscosity be 1.12Pas.
S42, the CaCl for being drawn with syringe by the ageing liquid and being added dropwise to 700 parts by weight2In solution at solidification
2h is managed, wherein the CaCl2The concentration of solution is 2.5%, and during curing process, continuous uniform stirring produces after avoiding solidification
Raw sphere is adhered, and after solidification is granulated balling-up, is washed with deionized to neutrality, multiple up to flyash-sodium alginate after dry
Close absorption granular materials.
Experimental example
1, infared spectrum is tested
Flyash-sodium alginate composite adsorbing material infared spectrum that test is prepared using method described in embodiment 1,
As shown in Figure 1, test result shows in 1650-1550cm-1(1601.35cm-1) at there are COO-The strong asymmetry of group is stretched
Contracting vibration peak, the absorption peak of presence-OH at 3881.87cm-1, it is abundant that this shows that flyash-sodium alginate obtained has
Functional group is conducive to absorb different types of heavy metal ion.
2, flyash-sodium alginate composite adsorbing material adsorptivity is tested
Using the functionalization flyash Treatment of Copper (II) of the preparation of embodiment 1, nickel (II) waste water, 100mL Cu is taken2+、Ni2+
Initial concentration is the waste water of 10,20,50,100,200,300,400,500mg/L, and 0.1g is added after pH value of waste water is transferred to 5.5
Flyash-sodium alginate composite adsorbing material, it is anti-with the vibration velocity absorption of 120r/min in 25 DEG C of water bath with thermostatic control shaking table
After answering for 24 hours, residue Cu in sample detection solution2+、Ni2+Heavy metal concentration, testing result are as shown in table 1.
Table 1
It can be seen that by the above results, using the flyash of functionalization made from method described in the embodiment of the present invention-alginic acid
Cu of the sodium composite adsorbing material to low concentration2+、Ni2+There is higher removal rate, to the Cu of high concentration2+、Ni2+It shows higher
Adsorptive value.Flyash-sodium alginate composite adsorbing material is to heavy metal ion (Cu2+、Ni2+) adsorption curve as shown in Fig. 2,
Pass through the analysis to adsorption isotherm fitting data, the results showed that, the composite adsorbing material is to Cu2+Maximum adsorption value be
82.6mg/g, to Ni2+Maximum adsorption value be 37.6mg/g.
3, regenerability is tested
It is test flyash-sodium alginate absorption property with absorption, the variation of parsing number, by adsorption saturation Cu2+
Flyash-sodium alginate composite adsorbing material (0.1g) recycling, be placed in 250ml conical flask, be added 100ml 1M HCl
It is placed in shaking bath and parses 30min under the vibration velocity of 150r/min, after parsing completely, will be answered with a large amount of deionized waters
It closes adsorbent material to wash to neutrality, then material is added to the Cu of 100ml 500mg/L containing concentration2+Waste water in, material is continuous
Absorption-parsing 6 times, each maximum adsorption value is measured respectively, the results are shown in Table 2.
Table 2
As can be seen from the above test results that maximum adsorption value after the flyash-sodium alginate composite adsorbing material parsing 6 times
It is the 89% of original material, there is good regeneration to reuse property.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of flyash-sodium alginate composite adsorbing material preparation method, which comprises the steps of:
S1, activating fly ash is prepared, flyash is activated with activator；
S2, moisture is stood after the flyash after activation processing is washed with water, it is living to obtain heavy after separation upper layer suspension flyash
Change flyash；
S3, preparation functionalization flyash, the heavy activating fly ash that step S2 is obtained is reacted jointly with silane coupling agent, is made
Functionalization flyash；
S4, preparation functionalization flyash-sodium alginate composite adsorbing material, by the obtained functionalization flyash of step S3 and seaweed
Sour sodium ripening in water jointly, obtains ageing liquid, the ageing drop is added to CaCl2After solidifying in solution, powder is obtained
Coal ash-sodium alginate composite adsorbing material.
2. flyash according to claim 1-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
Step S4 is stated to specifically comprise the following steps:
S41,1-4 parts by weight sodium alginate powder and 5-20 parts by weight functionalization flyash are placed in 100-300 parts by weight go from
Stirring to sodium alginate dissolves in sub- water, is aged 4-24h after mixing, obtains ageing liquid；
S42, the CaCl that the ageing drop is added to 100-1000 parts by weight2Curing process 1-6h in solution, after being granulated balling-up,
It is washed with deionized to neutrality, up to flyash-sodium alginate composite adsorbing material after drying.
3. flyash according to claim 2-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
Stating activator is at least one of sulfuric acid, hydrochloric acid, nitric acid, sodium hydroxide, the volume ratio of the flyash and the activator
For 1:2-10, the molar concentration of the activator is 1-5mol/L.
4. flyash according to claim 3-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
Step S1 is stated specifically, flyash is mixed in proportion with activator, and with the stirring speed of 50-100r/min at 20-100 DEG C
Spend stir-activating 1-6h.
5. flyash according to claim 1-4-sodium alginate composite adsorbing material preparation method, feature
It is, the step S3 specifically comprises the following steps:
S31, heavy activating fly ash described in 5-10 parts by weight is placed in 100-200 weight parts organic solvent；
3-15 parts by weight silane coupling agent is added in S32, the mixture obtained to step S31, is condensed back reaction；
It dries after S33, the reaction product organic solvent washing for obtaining step S32 at 40-80 DEG C to get functionalization fine coal
Putty material.
6. flyash according to claim 5-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
The density for stating heavy activating fly ash is 1.9-2.3cm3/g。
7. flyash according to claim 6-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
Stating silane coupling agent is γ-aminoethyl amino propyl trimethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-mercapto propyl front three
At least one of oxysilane, gamma-mercaptopropyltriethoxysilane.
8. flyash according to claim 7-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
After step S32 is stated specifically, alkyl coupling agent is mixed with the mixture of step S31, oil bath is condensed back at 60-120 DEG C
React 10-24h.
9. flyash according to claim 8-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
Stating organic solvent is at least one of benzene,toluene,xylene, dehydrated alcohol, methanol.
10. flyash according to claim 9-sodium alginate composite adsorbing material preparation method, which is characterized in that institute
The viscosity for stating sodium alginate is 0.83-1.15Pas, the CaCl2The mass concentration of solution is 1-10%.
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