CN108579684A - A method of being modified spherical porous silica removal heavy metal containing sewage and its organic pollution - Google Patents

A method of being modified spherical porous silica removal heavy metal containing sewage and its organic pollution Download PDF

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CN108579684A
CN108579684A CN201810430554.3A CN201810430554A CN108579684A CN 108579684 A CN108579684 A CN 108579684A CN 201810430554 A CN201810430554 A CN 201810430554A CN 108579684 A CN108579684 A CN 108579684A
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spherical porous
porous silica
heavy metal
modified
organic pollution
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CN108579684B (en
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李涛
葛秀珍
吴迪
郑春波
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HENAN LICHENG ENVIRONMENTAL TECHNOLOGY Co.,Ltd.
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李涛
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    • 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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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • 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
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
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    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
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Abstract

The invention belongs to new material technology fields, and in particular to a method of being modified spherical porous silica removal heavy metal containing sewage and its organic pollution.The present invention prepares the spherical porous silica of mesoporous specification, then surface modification is carried out in spherical porous silica silicon face and cavity by silane coupling agent, using 4,6 diamino resorcins and formaldehyde are polymerizer, the metal chelating sites such as amino and hydroxyl are introduced in spherical porous silica silicon face and cavity, to play the role of adsorbing heavy metal and organic pollution.The spherical porous silica of modification prepared by the present invention can be used for adsorbing Pb in water2+、Cd2+、Cr3+、Cu2+、Co2+Or Zn2+Etc. heavy metal ion and phenols and fragrant Amine Organic Pollutants.

Description

A kind of spherical porous silica removal heavy metal containing sewage of modification and its organic pollution Method
Technical field
The invention belongs to new material technology fields, and in particular to a kind of spherical porous silica removal of modification is heavy metal-polluted The method of water and its organic pollution.
Background technology
Heavy metal wastewater thereby causes extensive concern both domestic and external already to the serious harm of public health and ecological environment, this is Because heavy metal ion not only constitutes a threat to aquatile after entering environment, and participate in food chain can accumulate it is more highly concentrated Degree, and finally endanger human health.Heavy metal wastewater thereby pollution should earn widespread respect, and reduce or go heavy metal in water removal to seem non- It is often important and urgent.In numerous processing methods, absorption method will not introduce new chemical substance to institute compared with chemical precipitation method In the water of processing, energy consumption is significantly lower than evaporation concentration method, and effluent quality is better than Bubble-floating Method, and processing cost and operation complexity are remote Less than electrolysis, ion-exchange, solvent extraction and membrane separation process.In addition heavy metal ion is existed with dilute phase in waste water , adsorption technology has unrivaled advantage for deep purifying processing heavy metal wastewater thereby.
Activated carbon, flyash, activated sludge ash, zeolite, biomaterial, manganese oxide, peanut shell and kaolin etc. make a huge sum of money Belong to ion to be enriched with and detach under the action of the molecular attraction of surface of solids lack of equilibrium or chemical bond force.Since these adsorbents come Source is extensive and inexpensive, causes the extensive attention of field of water treatment, becomes a kind of very promising process for treating heavy-metal waste water. But these adsorbent generally existing adsorption capacities are relatively low, and dosage is big, it is not high enough to the removal efficiency of heavy metal the problems such as.If no It is handled through mode is effectively desorbed, often will produce a large amount of waste residues.
In terms of activated carbon adsorption research direction is concentrated mainly on modification at present, mainly increased using sour processing method Add surface functional group, such as carboxyl, quinone, carbonyl, lactone, hydroxyl and carboxylic acid anhydrides.Although these method of modifying increase surface Active group improves the adsorptivity to heavy metal ion, but has the following disadvantages：(1) its BET surface area and Kong Rong are reduced； (2) pore structure is destroyed, hole plug is caused, generates narrow microcellular structure, reduce adsorption capacity, be also unfavorable for ion in work The regeneration of transmission and activated carbon inside property charcoal.
Silica is less directly as the research of heavy metal absorbent, the reason is that since its absorption property is low, mesoporous two Silica is used as sorbing material usually as template to prepare mesoporous activated carbon, and mesoporous silicon oxide is removed finally by HF Template silica (Ind.Eng. Chem.Res., 2011,50 (24), page 13825-13830)；Not only by template removal Atom utilization is low, and striping needs the HF using severe toxicity；Mesoporous silicon oxide is prepared into the spherical more of high-specific surface area Hole shape, the research for being then used as heavy metal absorbent to the modification of its surface have no document report.
Invention content
The object of the present invention is to provide the spherical porous silica silicon materials that a kind of surface is modified, and as heavy metal Its absorption property is studied with Adsorption of Organic agent.The present invention prepares the spherical porous silica of mesoporous specification, then Surface modification is carried out in spherical porous silica silicon face and cavity by silane coupling agent, using 4,6- diamino isophthalic two Phenol and formaldehyde are polymerizer, and the metal chelating sites such as amino and hydroxyl are introduced in spherical porous silica silicon face and cavity, To play the role of adsorbing heavy metal and organic pollution.
According to the first aspect of the invention, a kind of system for the spherical porous silica being modified the present invention provides surface Preparation Method includes the following steps：
(A) preparation of spherical porous silica：
1) 1795 type of 10.0g polyvinyl alcohol is dissolved in the aqueous acetic acid of 100ml 0.5mmol/L, and four ethoxies are then added dropwise Base silane 41.6g, hydrolysis 30-60min obtains translucent solution at 0-5 DEG C；
2) translucent solution is stirred to 5-6h plastics at 60-80 DEG C, is then cooled to and is stored at room temperature aging 16-18h, mistake Filter to obtain jelly；
3) jelly is placed in in the ammonia spirit of 2mol/L the 2-3h that flows back, it is molten using hydrochloric acid adjusting to be then cooled to room temperature Liquid pH is to neutrality, ultrasound 2-3h at 45-50 DEG C, filtering, and filter cake washing, 60-70 DEG C of drying is most gone through high-temperature calcination afterwards to constant weight Except organic matter obtains spherical porous silica；Conventional method prepare silica be chondritic, the present invention prepare two Silica contains a large amount of hole, is spherical porous shape, greatly enhances its specific surface area, is provided for follow-up function modification Possibility.
(B) preparation for the spherical porous silica that surface is modified：
A) the spherical porous silicas of 10.0g are placed in ultrasonic disperse in 500ml tetrahydrofurans at room temperature, 3- is then added Aminopropyltriethoxywerene werene 0.3-0.5g stirs 20-30min；
B) it is added in 1.5-2.0g 4,6-diaminoresorcinols to step a) solution, extremely with ammonia water conditioning system pH 8.5-9.0；
C) it is added dropwise in the formalin 40-60ml to step b) solution of a concentration of 37%wt, continues to surpass after completion of dropwise addition Sound 20-30min then heats to 70-80 DEG C of polymerization 6-8h；
D) it is cooled to room temperature, is filtered, filter cake is successively by washing and ethyl alcohol washing removal complete 4, the 6- diaminos of unreacted Base resorcinol and formaldehyde are subsequently placed in vacuum drying chamber drying to the constant weight at 70-80 DEG C and obtain the spherical more of surface modification Hole silica.
Preferably, the step 3) high-temperature calcination refers to the heating rate of 10 DEG C/min under air atmosphere by room temperature Heat preservation calcining 5-6h after being warming up to 700-800 DEG C；
Preferably, the addition of 4,6-diaminoresorcinol is 1.8g in step b), the formaldehyde of 37%wt in step c) The addition of aqueous solution is 50ml；The present invention obtains the spherical porous silica of high-specific surface area first, is connect on its surface The metal-chelators sites such as branch hydroxyl, amino, when the functional groups such as hydroxyl, the amino of grafting can excessively block porous silica Aperture reduces its specific surface area, and the activity of heavy metal ion is adsorbed to reduce it；Comprehensive its holds the absorption of heavy metal Amount, the formalin 50ml that 4,6-diaminoresorcinol 1.8g, 37%wt is added in 10.0g porous silicas of the present invention are It is optimal.
The present invention prepares the spherical porous silica of mesoporous specification, then by silane coupling agent spherical porous two Surface modification is carried out in silicon oxide surface and cavity, uses 4,6-diaminoresorcinol and formaldehyde for polymerizer, spherical more The metal chelating sites such as amino and hydroxyl are introduced in hole silica surface and cavity, to play the role of adsorbing heavy metal.
According to an aspect of the present invention, a kind of use for the spherical porous silica being modified the present invention provides surface On the way, it is used for the absorption of heavy metal ion and organic pollution in water.
Preferably, the heavy metal ion is Pb2+、Cd2+、Cr3+、Cu2+、Co2+Or Zn2+, further preferably Pb2+With Cr3+；The spherical porous silica that surface prepared by the present invention is modified can be used for the absorption of contents of many kinds of heavy metal ion, especially right Pb2+And Cr2+Adsorption efficiency highest.
Preferably, the organic pollution can be arylamine or aldehydes matter, such as phenol, p-nitrophenol, aniline, adjacent nitre Base aniline or paranitroanilinum；Especially paranitroanilinum its can be all had within the scope of wider pH 96% or more absorption Rate；
The invention has the advantages that：
1) present invention has prepared a kind of spherical porous silica, than the ratio that conventional commercial mesoporous silicon oxide has bigger Surface area about 1360m2/ g (BET method measurement)；
2) present invention is using the spherical porous silica prepared as carrier, with silane coupling agent in spherical porous silica Surface modification is carried out in silicon face and cavity, uses 4,6-diaminoresorcinol and formaldehyde for polymerizer, spherical porous two The metal chelating sites such as amino and hydroxyl are introduced in silicon oxide surface and cavity forms a kind of novel heavy metal and organic pollution Sorbing material；
3) the spherical porous silica that surface prepared by the present invention is modified has heavy metal and organic pollution larger Adsorption capacity；
4) the spherical porous silica that the surface for preparing of the present invention is modified to can be desorbed after heavy metal adsorption, it can be achieved that Recovery.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of spherical porous silica；
Fig. 2 is the scanning electron microscope (SEM) photograph for the spherical porous silica that surface is modified；
Fig. 3 is the overlapping infrared spectrogram of spherical porous silica and spherical porous silica that surface is modified.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
One, the detection method of heavy metal ion and organic removal rate R：
Take heavy metal ion solution or organic matter in conical flask, with the H of 0.1mol/L2SO4Or 0.1mol/LNaOH is water-soluble Liquid adjusts solution ph, and the spherical porous silica that a certain amount of surface is modified is added, conical flask is put into 40 DEG C of waters bath with thermostatic control In oscillator, control temperature filters after stirring 12h under the rotating speed of 200r/min, using atom extinction spectrum instrument (AA- 6300F, Japanese Shimadzu Corporation's production) concentration of heavy metal ion in filtrate is measured, using the dense of HPLC external standard method organic matters Degree.The removal rate R (%) of heavy metal ion and organic matter is calculated with formula (1) in aqueous solution：
In formula, C0It is respectively heavy metal ion mass concentration or organic matter mass concentration in initial and filtrate, mg/L with C.
Two, heavy metal ion and organic matter adsorbance qtDetection method：
Adsorbance qtIt is calculated according to formula (2)：
In formula, C0And CtRespectively initial and t moment heavy metal ion or organic matter mass concentration, mg/L；W changes for surface The spherical porous silica quality of property, g；V is liquor capacity, L.
Embodiment 1 prepares the spherical porous silica adsorbent that surface is modified
(A) preparation of spherical porous silica：
1) 10.0g polyvinyl alcohol (1795 type) is dissolved in the aqueous acetic acid of 100ml 0.5mmol/L, and tetrem is then added dropwise Oxysilane 41.6g, hydrolysis 30-60min obtains translucent solution at 0-5 DEG C；
2) translucent solution is stirred to 5-6h plastics at 60-80 DEG C, is then cooled to and is stored at room temperature aging 16-18h, mistake Filter to obtain jelly；
3) jelly is placed in in the ammonia spirit of 2mol/L the 2-3h that flows back, is then cooled to the salt that room temperature uses 2mol/L Aqueous acid adjusts pH value of solution to neutrality, ultrasound 2-3h at 45-50 DEG C, filtering, and filter cake is washed, and 60-70 DEG C of drying is to constant weight, most Had afterwards by room temperature to heat preservation calcining 5-6h removals after 700-800 DEG C with the heating rate of 10 DEG C/min under air atmosphere Machine object obtains spherical porous silica；Its scanning electron microscope (SEM) photograph as shown in Figure 1, as can be seen from Figure 1 the present invention prepare it is spherical Porous silica contains a large amount of open-celled structure, than conventional spherical mesoporous silica specific surface area bigger, specific surface area For 1360m2/ g (BET method measurement)；
(B) preparation for the spherical porous silica that surface is modified：
A) the spherical porous silicas of 10.0g are placed in ultrasonic disperse in 500ml tetrahydrofurans at room temperature, 3- is then added Aminopropyltriethoxywerene werene 0.4g stirs 20-30min；
B) 1.8g4 is added, in 6- diamino resorcins to step a) solution, extremely with the ammonia water conditioning system pH of 5mol/L 8.5-9.0；
C) it is added dropwise in the formalin 50ml to step b) solution of a concentration of 37%wt, continues ultrasound after completion of dropwise addition 20-30min then heats to 70-80 DEG C of polymerization 6-8h；
D) it is cooled to room temperature, is filtered, filter cake is successively by washing and ethyl alcohol washing removal complete 4, the 6- diaminos of unreacted Base resorcinol and formaldehyde are subsequently placed in vacuum drying chamber drying to the constant weight at 70-80 DEG C and obtain the spherical more of surface modification Hole silica.
Surface be modified spherical porous silica scanning electron microscope (SEM) photograph as shown in Fig. 2, it can be seen from the figure that it is modified still Retain vesicular texture, specific surface area 1280m2, only there is slight drop in/g (BET method measurement).
The overlapping infrared spectrogram such as Fig. 3 institutes for the spherical porous silica and spherical porous silica that surface is modified Show, wherein (i) be spherical porous silica, (ii) be surface be modified spherical porous silica；Its modified infrared light There is the characteristic absorption peak of N-H and O-H in spectrogram, shows that 4,6-diaminoresorcinol has been grafted to spherical porous silica On.
The removal rate of different heavy metals and organic matter under 2 difference pH of embodiment
Due to surface be modified spherical porous silica contain hydroxyl and amino, when being adsorbed with heavy metal chelating by The influence that pH is adjusted, so emphasis of the present invention screens pH conditions：
Take commercially available Pb2+、Cr3+、Cu2+、Ni2+、Zn2+、Hg2+、Cd2+And Co2+Chloride or nitrate be configured to 60- The aqueous solution of 100mg/L difference pH value simulates heavy metal aqueous solution, is added surface prepared by 2.0g embodiments 1 in 1L aqueous solutions Modified spherical porous silica tests its removal rate R under different pH environment, and the results are shown in Table 1：
Removal rate of the spherical porous silica that the 1 difference lower surfaces pH of table are modified to heavy metal ion
The above test results show that it is different to the suction-operated of different heavy metals under different pH value, generally speaking to Pb2+、 Cr3+、Cu2+、Zn2+、Cd2+And Co2+Higher removal rate can be obtained under certain pH value；Such as Pb2+(± 0.2 conditions of pH=6.0 Under) and Cr3+(under the conditions of pH=8.0 ± 0.2) ion has nearly reached the effect of complete absorption；But for Ni2+And Hg2+ Adsorption rate is undesirable in the range of pH=2-10.
Adsorption effect of the embodiment 3 to arylamine and aldehydes matter
Phenol, p-nitrophenol, aniline, ortho-nitraniline and paranitroanilinum are configured to the water-soluble of 100mg/L with water Liquid, then tests the removal rate R values of each organic matter under different pH condition, and statistical result is shown in Table 2：
Removal rate of the spherical porous silica that the 2 difference lower surfaces pH of table are modified to organic matter
The above result shows that the spherical porous silica that surface prepared by the present invention is modified has phenyl amines and phenol Machine pollutant all has stronger absorption property, but needs to use under certain pH environment mostly, therefore actual treatment organic contamination It needs to be adjusted to specific pH ranges first when object, wherein paranitroanilinum has wider pH use scopes, in pH=6-9 All have higher absorption property.
Embodiment 4Cr3+The detection of adsorbance
Take Cr (NO3)3Nonahydrate is soluble in water, using the sodium hydrate aqueous solution regulation system pH to 8.0 of 0.5mol/L ± 0.2, it is prepared into the aqueous solution of a concentration of 120mg/L, pH=8.0 ± 0.2, is separately added into prepared by the present invention spherical porous two The spherical porous silica (being abbreviated as MPS) and commercially available mesoporous silicon oxide that silica (being abbreviated as PS), surface are modified (Sigma-Aldrich (Shanghai) trade Co., Ltd, is abbreviated as MCM-41, SBET~1000m2/ g) between 4,6- diamino Benzenediol (being abbreviated as N/O-L) is used as adsorbent, tests Cr3+Adsorbance qt, the results are shown in Table 3：
The different adsorbents of table 3 correspond to qtCorrection data
Note：qtMiddle t is 12h.
The above test results show that spherical porous silica prepared by the present invention is to Cr3+Removal rate be far longer than city Mesoporous silicon oxide (MCM-41) is sold, it is suitable with the absorption property of organic polymer 4,6-diaminoresorcinol, when to spherical After porous silica is modified, adsorbance is greatly improved, surface be modified spherical porous silica with it is spherical Porous silica is compared, and is not only provided with physisorption, but also be provided with chemisorption, i.e. physical absorption at this time Synergistic effect is played with chemisorption, substantially increases the spherical porous silica of surface modification to Cr3+Suction Attached amount.
The spherical porous silica that test surfaces are modified is to paranitroanilinum (under pH=8.0), PbCl2(pH=6.0 Under) adsorbance be respectively 236.2mg/g and 315.8mg/g.
5 recovery situation of embodiment
To study the spherical porous silica of surface modification prepared by the present invention to various heavy metal ion or organic dirt Contaminate object recovery situation, the present invention will use after surface be modified spherical porous silica filter recycling, to recycling The spherical porous silica that is modified of surface carry out the desorption of heavy metal to achieve the purpose that activating adsorbent, investigate desorption Afterwards to Cr (NO3)3, paranitroanilinum and PbCl2Adsorbance；
Desorption method is as follows：The spherical porous silica that the surface of recycling is modified is placed in the hydrochloric acid of 1mol/L, in Ultrasound 2-3h, is then filtered at 50-60 DEG C, the spherical porous dioxy that the surface that being dried at 70-80 DEG C must activate to constant weight is modified SiClx.
The spherical porous silica that surface is modified every time after use is desorbed it, and table 4 is different heavy metals Adsorbance with activation number relation table：
The adsorbance of the different heavy metals of table 4 with access times variation
Note：It applies mechanically absorption heavy metal or organic matter carries out under its optimal pH environment in the process, i.e. Cr (NO3)3With Paranitroanilinum is in pH=8.0 ± 0.2, PbCl2Under pH=6.0 ± 0.2.
The above result shows that acid lower high temperature ultrasonic desorption can make the spherical porous silica that surface is modified through the invention The absorption property of silicon is activated, especially for PbCl2Absorption, only have dropped about 6% using adsorbance after five times；But Paranitroanilinum adsorbance, which has dropped about 49%, can not continue recovery, Cr (NO3)3Adsorbance has dropped about 24%.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.

Claims (10)

1. a kind of preparation method for the spherical porous silica that surface is modified, includes the following steps：
(A) preparation of spherical porous silica：
1）Polyvinyl alcohol is dissolved in aqueous acetic acid, is then added dropwise tetraethoxysilane, and hydrolysis 30-60min is obtained semi-transparent at 0-5 DEG C Bright solution；
2）Translucent solution is stirred into 5-6h plastics at 60-80 DEG C, is then cooled to and is stored at room temperature aging 16-18h, filter Jelly；
3）Jelly is placed in ammonia spirit the 2-3h that flows back, is then cooled to room temperature using hydrochloric acid conditioning solution pH to neutrality, Ultrasound 2-3h at 45-50 DEG C, filtering, filter cake washing, 60-70 DEG C of drying are most obtained through high-temperature calcination organics removal afterwards to constant weight Spherical porous silica；
(B) preparation for the spherical porous silica that surface is modified：
A) the spherical porous silicas of 10.0g are placed in ultrasonic disperse in tetrahydrofuran at room temperature, 3- aminopropyls is then added Triethoxysilane 0.3-0.5g stirs 20-30min；
B) 1.5-2.0g 4,6- diamino resorcins are added to step a）In solution, with ammonia water conditioning system pH to 8.5- 9.0；
C) the formalin 40-60ml to step b of a concentration of 37%wt is added dropwise）In solution, continue ultrasound 20- after completion of dropwise addition 30min then heats to 70-80 DEG C of polymerization 6-8h；
D) it is cooled to room temperature, is filtered, filter cake is successively by between washing and ethyl alcohol washing removal complete 4, the 6- diamino of unreacted Benzenediol and formaldehyde are subsequently placed in vacuum drying chamber drying to the constant weight at 70-80 DEG C obtains surface modification spherical porous two Silica.
2. preparation method according to claim 1, it is characterised in that：Step 3）The high-temperature calcination refers in air atmosphere Under with the heating rate of 10 DEG C/min by room temperature to heat preservation calcining 5-6h after 700-800 DEG C.
3. preparation method according to claim 1, it is characterised in that：Step b）The addition of middle 4,6- diamino resorcins It is 1.8g to measure, and the addition of the formalin of 37%wt is 50ml in step c).
4. the purposes for the spherical porous silica that surface described in a kind of claim 1 is modified, it is characterised in that：For weight in water The absorption of metal ion and organic pollution.
5. purposes according to claim 4, it is characterised in that：The heavy metal ion is Pb2+、Cd2+、Cr3+、Cu2+、Co2+ Or Zn2+。
6. purposes according to claim 5, it is characterised in that：The heavy metal ion Pb2+Or Cr3+。
7. purposes according to claim 4, it is characterised in that：The organic pollution is that organic pollution is arylamine or phenol Substance.
8. purposes according to claim 7, it is characterised in that：The arylamine is aniline, ortho-nitraniline or p-nitrophenyl Amine.
9. purposes according to claim 8, it is characterised in that：The arylamine is paranitroanilinum.
10. purposes according to claim 7, it is characterised in that：The aldehydes matter is phenol or p-nitrophenol.
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CN110075807A (en) * 2019-05-20 2019-08-02 云南大学 A kind of modified Nano porous silicon adsorbent and the preparation method and application thereof
CN110075807B (en) * 2019-05-20 2022-06-07 云南大学 Modified nano porous silicon adsorbent and preparation method and application thereof
CN110756177A (en) * 2019-10-24 2020-02-07 齐鲁工业大学 Preparation method and application of functionalized nano silicon dioxide/resorcinol-formaldehyde microspheres
CN110756177B (en) * 2019-10-24 2022-08-30 齐鲁工业大学 Preparation method and application of functionalized nano silicon dioxide/resorcinol-formaldehyde microspheres
CN111569824A (en) * 2020-05-29 2020-08-25 河北工业大学 Three-dimensional reticular hierarchical pore silicon dioxide heavy metal ion adsorbent and preparation method thereof
CN111569824B (en) * 2020-05-29 2023-04-18 河北工业大学 Three-dimensional reticular hierarchical pore silicon dioxide heavy metal ion adsorbent and preparation method thereof
CN113049651A (en) * 2021-03-15 2021-06-29 重庆大学 In-situ electrochemical immunosensor for simultaneously detecting four breast cancer markers
CN112931934A (en) * 2021-03-24 2021-06-11 湖北中烟工业有限责任公司 Fragrance-holding and cooling additive and preparation method and application thereof
CN114053859A (en) * 2021-11-17 2022-02-18 重庆科技学院 Hydrogen sulfide remover and preparation method thereof
CN114053859B (en) * 2021-11-17 2023-08-18 重庆科技学院 Hydrogen sulfide remover and preparation method thereof
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