CN105597667A - Preparation method of spherical suspending attapulgite adsorbent and application thereof for treating heavy metals in industrial wastewater - Google Patents
Preparation method of spherical suspending attapulgite adsorbent and application thereof for treating heavy metals in industrial wastewater Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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Abstract
The invention relates to a preparation method of a spherical suspending attapulgite adsorbent and application thereof for treating heavy metals in industrial wastewater. The method comprises the following steps: (1) attapulgite acid pretreatment; (2) preparation of an attapulgite mesoporous material; (3) preparation of a functional attapulgite mesoporous material; and (4) preparation of the spherical suspending attapulgite adsorbent. When used for treating industrial wastewater, the adsorbent in a solid-to-liquid ratio of 1:5 (g/L) is added into industrial wastewater for treating and purifying industrial wastewater. Compared with an existing attapulgite adsorbent, the adsorbent has the advantages that the mesoporous material prepared in a self-assembling manner has large specific surface area; and cheap acrylic acid is used as an intermediate for connecting the mesoporous material and a silane coupling agent, and the internal pore diameter of the mesoporous material is expanded, so that the adsorbent has high selectivity and can adsorb heavy metal ions directionally, the adsorption efficiency is improved and secondary pollution is not caused in a treatment process; and the spherical suspending attapulgite adsorbent can be recovered for multiple use, can be recovered conveniently, and has low treatment cost.
Description
Technical field
The invention belongs to adsorbent technology and technical field of sewage, be specifically related to one and utilize self assembly taking concave convex rod as matrixTechnology and functional porous material and a kind of adsorbent for the treatment of heavy metal in waste water of preparing.
Background technology
As everyone knows, water is the basis that on the earth, all life is depended on for existence. Populous like this in China, water demand amountLarge country, the various water contamination accidents that emerge in an endless stream but make us startling, and as on April 27th, 2015, the long sun in Yichang coveredThe blowdown of special manganese industry causes water body blackening and fouls, and then pollutes the mother river Qingjian River. On June 15th, 2015, Guangdong is practiced river and is subject to sternlyHigh pollution, has become bad V class water, and according to the monitoring result of 2014, main contamination index was and increases the weight of trend than 2013.Become the whole nation and pollute one of the heaviest river, therefore two sides resident also endures its hardship to the fullest extent. Also has on June 17th, 2015, An HuichiMileage thousand mu of farmlands in state town have also become wasteland. Only because iirigation water source is polluted in chemical industry garden. In these water, contain a large amount of Toxics, manyItem pollutant exceeds standard. Such case is innumerable, makes people worried. In industrial production, a large amount of poisonous and harmful substances are unreasonableDischarge aggravated the deterioration of water environment and the shortage of water resource, have influence on the most at last the mankind's existence and expanding economy. 2015In on January 1, in, new " Law on Environmental Protection " that be called as " the tightest in history " formally implemented, and caused the public's concern; In additionOn April 2nd, 2015, State Council issued about the notice of printing and distributing water prevention and cure of pollution action plan (ten, water), all showsWater pollution problems extremely severe, need to contain immediately, and be badly in need of launching Control Measures for Water Pollution.
At present, the healthy of the mankind in heavy metal pollution serious threat. Because it has high toxicity, non-biodegradation, lifeThing enriching etc. And organism can also enriching heavy metal, finally arrive in intelligent's body, extremely trace just can causing death,Even can also be converted into the more novel substance of toxicity. The method of removing heavy metal in water is numerous, has chemical precipitation method, ion-exchangeMethod, electrochemical process, bioanalysis, absorption method etc. Wherein absorption method is wide with its raw material sources, cost is low, simple to operate, efficiencyHigh, selectively high, recyclable, the advantages such as non-secondary pollution get most of the attention, and in processing water, in heavy metal, occupy critical role.
Abundant due to concave convex rod reserves, cheap and easy to get, specific area is large, absorption property excellence, and the character such as pollution-free, makes its one-tenthFor a kind of adsorbent of high-quality. Concave convex rod claims again palygorskite, is a kind of layer of chain to be rich in magnesium silicate as main clay mineral,There is the brilliant bundle aggregate of filamentary structure. Fig. 1 is the SEM micrograph of concave convex rod. Nowadays utilize concave convex rod for matrix preparation suctionThe attached dose of method for the treatment of heavy metal in water is a lot, but its technical merit is generally on the low side, and adsorption effect is not good especially, andMajority is Powdered, is unfavorable for reclaiming, and has been subject to certain limitation. CN104722265A discloses one and has utilized ethylenediamine tetraaceticAttapulgite modified method and the application thereof of preparing adsorbent of acetic acid. So ethylenediamine tetra-acetic acid almost can with complexing of metal ion shapeBecome stable chelate, selectively low, dosage is large, flammable, low toxicity, has excitant, has potential safety hazard. CN104707564ADisclose a kind of taking concave convex rod as raw material, by pretreatment, sour modification, load Fe3O4, the technique such as activation heat treatment prepare recessedProtruding rod/Fe3O4Composite. The method demand for control is high, selectively low, Fe3O4Unstable under hot conditions, absorption propertyNot high, be difficult to extensive use. The one that discloses of CN104014299A utilizes attapulgite to be mixed with into water certain proportionThe method of granule adsorbent. Though this method is simple, be easy to reclaim, energy resource consumption is large, is unfavorable for energy-conserving and environment-protective, concave convex rodBad dispersibility, adsorption effect are not remarkable, can not realize the high-efficiency comprehensive utilization to all components in concave convex rod.
Summary of the invention
The object of the invention is to be to overcome the shortcoming of prior art, a kind of method of preparing adsorbent taking concave convex rod as matrix is providedAnd adopting the application of this sorbent treatment heavy metal in waste water, this adsorbent not only cost of raw material is low, rich and easy to get, absorptionThe interior external surface area that property is strong, larger, adsorption efficiency improves greatly, can repeatedly recycle, and can not cause secondary dirt to environmentDye etc.
Object of the present invention realizes by following scheme:
The suspend preparation method of ball-type concave convex rod adsorbent, comprises the following steps:
(1) the acid pretreatment of concave convex rod: concave convex rod is ground and joined in high speed dispersor, then add distilled water, stir,Disperse, then add hydrochloric acid to stir, filter, be washed with distilled water to neutrality, then dry, cooling, grind acid-treated recessedlyProtruding rod;
(2) preparation of concave convex rod mesoporous material: in hexadecyltrimethylammonium chloride solution, add the concave convex rod after acidic treatment,With NaOH solution adjusting pH=12, stir ultrasonic mixture; And then this mixture is heated at 100～110 DEG C to 24～36h, is cooled to room temperature, and washing is to neutral, dries, roasting 2～3h, cooling, grind to obtain concave convex rod mesoporous material;
(3) preparation of functionalization concave convex rod mesoporous material: preparation coupling agent 1,3 two mercaptopropyl trimethoxysilane, water and methyl alcoholSolution, adds sulfuric acid solution to regulate pH=4, stirs and is heated to 70～80 DEG C, then add acrylic acid and the concentrated sulfuric acid, and temperature is adjustedJoint, to 80～90 DEG C, after reaction 1～1.5h, is cooled to 15～30 DEG C by temperature, then adds concave convex rod mesoporous material and ether,At N2Protection under stir, then pass into H2S,, filter to neutral with distilled water and absolute ethanol washing, dry, obtain functionalizationConcave convex rod mesoporous material;
(4) preparation of suspension ball-type concave convex rod adsorbent: get functionalization concave convex rod mesoporous material and add flocculant polyacrylamide,Be put in magnetic stirring apparatus and stir, then mixture is thrown in extruding machine, obtain suspension ball-type concave convex rod adsorbent.
In described step (1), the solid-to-liquid ratio of concave convex rod and water is 1:20～1:30 (g/ml), the solid-to-liquid ratio of concave convex rod and hydrochloric acidFor=1:5～1:15 (g/ml), concentration of hydrochloric acid is 9～12mol/L.
In described step (2), surfactant hexadecyltrimethylammonium chloride and distilled water solid-to-liquid ratio are 1:30～1:70(g/ml); The mass ratio of concave convex rod and surfactant is: 1:0.5～1:1.5, NaOH solution concentration is 6mol/L.
In described step (3), the solid-to-liquid ratio of coupling agent and water is: 2:1～3:1 (g/ml), and the liquid liquor ratio of water and methyl alcohol is:1:8～1:10 (ml/ml), sulfuric acid solution concentration is 3mol/L; Coupling agent and acrylic acid solid-to-liquid ratio are: 1:1.5～1:4.5 (g/ml),Concentrated sulfuric acid addition accounts for 1%～10% of mixed solution; The mass ratio of concave convex rod and coupling agent is: 1:0.4～1:2 (g/g), and recessedThe solid-to-liquid ratio of protruding rod and ether is: 1:50～1:60.
In described step (4), flocculant and concave convex rod mass ratio are 1:1～1:4 (g/g).
In described step (4), it is 1cm that extruding machine is selected middle circle bore dia, the mould that ball interior diameter is 3cm, temperatureIt is 100～110 DEG C.
The method of application suspension ball-type concave convex rod sorbent treatment industrial wastewater, adsorbent is that 1:5 (g/L) is added to by solid-to-liquid ratioIn industrial wastewater, process and purified industrial waste water.
Compared with existing concave convex rod adsorbent, the present invention has following advantage:
(1) mesoporous material that this adsorbent makes by self assembly mode has high specific area, and utilizes propylene cheaplyAcid is connected mesoporous material as intermediate medium with silane coupler, expanded the aperture, inside of mesoporous material, also makes it haveHigh is selective, Adsorption of Heavy Metal Ions that can be directed.
(2) silane coupler utilizing in this material contains two sulfydryls, compared with the common silane coupler that contains a sulfydryl,Improve greatly the absorption property of concave convex rod adsorbent.
(3) this material is made suspension ball-type, has increased its external surface area, has improved adsorption efficiency, in processing procedure, does not produceSecondary pollution, can repeatedly recycle, and it is convenient to reclaim, and processing cost is low.
Brief description of the drawings
Fig. 1 is the SEM micrograph of concave convex rod;
Fig. 2 is the structural representation of functionalization concave convex rod mesoporous material;
Fig. 3 is the process chart of preparation suspension ball-type concave convex rod adsorbent of the present invention.
Detailed description of the invention
Fig. 3 is process chart of the present invention, below by concrete case study on implementation, the present invention is further elaborated.
The preparation method of adsorbent of the present invention, it comprises the following steps:
(1) the acid pretreatment of concave convex rod, detailed process is: get concave convex rod and grind and cross 200～300 mesh sieves, and joinedIn high speed dispersor, then add distilled water, the solid-to-liquid ratio of concave convex rod and water is 1:20～1:30 (g/ml), mixing speed is 10000～15000rpm, disperses 5～15min, then adds the hydrochloric acid of 9～12mol/L, and the solid-to-liquid ratio of concave convex rod and hydrochloric acid is=1:5～1:15(g/ml), rotating speed 2000～4000rpm, rotates 1～2h, filters, and is washed with distilled water to neutrality, at 100～110 DEG CDry, cooling, grinding, crosses 200～300 mesh sieves, obtains acid-treated concave convex rod.
(2) preparation of concave convex rod mesoporous material, detailed process is: get surfactant hexadecyltrimethylammonium chloride and be dissolved in distillationIn water, solid-to-liquid ratio is 1:30～1:70 (g/ml), then adds the concave convex rod after acidic treatment, the matter of concave convex rod and surfactantAmount is than being: NaOH solution that 1:0.5～1:1.5 (g/g) is 6mol/L by concentration adjusting pH=12, be 1000 at rotating speed～Under 2000rpm, stir ultrasonic 10～25min, and then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave, 100～At 110 DEG C, heat 24～36h, be cooled to room temperature, then use distilled water and absolute ethanol washing to neutral, at 50～80 DEG C, dry0.5h～1h then carries out roasting 2～3h at 200～400 DEG C, and cooling, grinding, crosses 200～300 mesh sieves, obtains concave convex rodMesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process is: get 1,3 two mercaptopropyl trimethoxysilane and burn in round bottomIn bottle, then add water and methyl alcohol, the solid-to-liquid ratio of coupling agent and water is: 2:1～3:1 (g/ml), and the liquid liquor ratio of water and methyl alcohol is:1:8～1:10 (ml/ml), adding concentration is the sulfuric acid solution adjusting pH=4 of 3mol/L, stirs and be heated to 70～80 DEG C, turnsSpeed is 2000～3000rpm, after 0.5～1h, then adds acrylic acid and the concentrated sulfuric acid, and coupling agent and acrylic acid solid-to-liquid ratio are:1:1.5～1:4.5 (g/ml), concentrated sulfuric acid addition account for above add 1%～10% of mixed solution, temperature is adjusted to 80～90 DEG C,After 1～1.5h, temperature is cooled to 15～30 DEG C, then adds concave convex rod mesoporous material and ether, concave convex rod and coupling agentAdmittedly Gu mass ratio is: 1:0.4～1:2 (g/g), the solid-to-liquid ratio of concave convex rod and ether is: 1:50～1:60 (g/ml) is at N2'sUnder protection, stir 1～2h, rotating speed is 3000～4000rpm, then passes into the H of 10～30min2S, by distilled water and anhydrous secondAlcohol washing, to neutral, is filtered, and at 100～110 DEG C, dries, and obtains functionalization concave convex rod mesoporous material, and its structural representation is as Fig. 2.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process is: get functionalization concave convex rod mesoporous material in round-bottomed flask,And adding flocculant polyacrylamide, flocculant and concave convex rod admittedly mass ratio are that 1:1～1:4 (g/g) is put in magnetic stirring apparatusStir 1～2h, rotating speed is 800～2000rpm, then mixture is thrown in extruding machine, and selecting middle circle bore dia is 1cm,Ball interior diameter is the mould of 3cm, and temperature is adjusted to 100～110 DEG C, the ball-type concave convex rod adsorbent that can suspend, its surface areaGreatly, crossing water-based can be good.
The application of sorbent treatment industrial wastewater of the present invention, concrete operations are as follows:
In industrial wastewater, contain all kinds of heavy metal ion and some organic pollutions, adsorbent of the present invention is 1:5 (g/L) by solid-to-liquid ratioBe added in industrial wastewater, under this ratio, in this Adsorbent For Removal of Heavy, the adsorption effect of heavy metal ion is remarkable, greatly journeyOn degree, process and purified industrial waste water.
Embodiment 1
(1) the acid pretreatment of concave convex rod, detailed process is: get 10g concave convex rod and grind and cross 200 mesh sieves, and joined heightIn speed dispersion machine, then 200ml adds distilled water, and mixing speed is 10000rpm, disperses 5min, then adds 50ml concentration to beThe hydrochloric acid of 12mol/L, speed is 2000rpm, rotates 1h, filters, and is washed with distilled water to neutrality, at 100 DEG C, dry,Cooling, grinding, cross 200 mesh sieves, obtains acid-treated concave convex rod.
(2) preparation of concave convex rod mesoporous material, detailed process is: get 6g surfactant hexadecyltrimethylammonium chloride and be dissolved inIn 180ml distilled water, then add the concave convex rod after 3g acidic treatment, the NaOH solution that is 6mol/L by concentration regulates pH=12,Be under 1000rpm, to stir ultrasonic 10min at rotating speed, and then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave,At 100 DEG C, heat 24h, be cooled to room temperature, then use distilled water and absolute ethanol washing to neutral, at 50 DEG C, dry 0.5h, connectAnd at 500 DEG C, carry out roasting 2h, cooling, grinding, crosses 200 mesh sieves, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process is: get 1.2g1,3 two mercaptopropyl trimethoxysilanes are in circleIn end flask, then add 0.6ml water and 4.8ml ethanol, adding concentration is the sulfuric acid solution adjusting pH=4 of 3mol/L, stirs alsoBe heated to 70 DEG C, rotating speed is 2000rpm, after 0.5h, then adds 1.8ml acrylic acid and the 72ul concentrated sulfuric acid, and temperature is adjusted to80 DEG C, after 1h, temperature is cooled to 15 DEG C, then add that 3g's is recessed
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process is: get 4g functionalization concave convex rod mesoporous material and burn in round bottomIn bottle, and add 1g flocculant polyacrylamide, be put in magnetic stirring apparatus and stir 1h, rotating speed is 800rpm, then will mixThing is thrown in extruding machine, and selecting middle circle bore dia is 1cm, the mould that ball interior diameter is 3cm, and temperature is adjusted to 100 DEG C,The ball-type concave convex rod adsorbent that can suspend, its surface area is large, and crossing water-based can be good.
Embodiment 2
(1) the acid pretreatment of concave convex rod, detailed process is: get 12g concave convex rod and grind and cross 250 mesh sieves, and joined heightIn speed dispersion machine, then to add 276ml distilled water, mixing speed be 12000rpm, disperses 7min, then add 96ml concentration to beThe hydrochloric acid of 11mol/L, speed is 3000rpm, rotates 1.5h, filters, and is washed with distilled water to neutrality, at 105 DEG C, dry,Cooling, grinding, cross 250 mesh sieves, obtains acid-treated concave convex rod.
(2) preparation of concave convex rod mesoporous material, detailed process is: get 6g surfactant hexadecyltrimethylammonium chloride and be dissolved inIn 240ml distilled water, then add the concave convex rod after 4.8g acidic treatment, the NaOH solution that is 6mol/L by concentration regulates pH=12,Be under 1300rpm, to stir ultrasonic 15min at rotating speed, and then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave,At 103 DEG C, heat 27h, be cooled to room temperature, then use distilled water and absolute ethanol washing to neutral, at 60 DEG C, dry 0.7h, connectAnd at 250 DEG C, carry out roasting 2.4h, cooling, grinding, crosses 250 mesh sieves, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process is: get 2.7g1,3 two mercaptopropyl trimethoxysilanes are in circleIn end flask, then add 1.2ml water and 10.2ml ethanol, adding concentration is the sulfuric acid solution adjusting pH=4 of 3mol/L, stirsAnd be heated to 73 DEG C, and rotating speed is 2200rpm, after 0.7h, then adds 5.4ml acrylic acid and the 0.5ml concentrated sulfuric acid, temperature regulatesTo 83 DEG C, after 1.2h, temperature is cooled to 20 DEG C, then add concave convex rod mesoporous material and the 238.5ml ether of 4.5g,At N2Protection under, stir 1.3h, rotating speed is 3400rpm, then passes into the H of 15min2S, washes with distilled water and absolute ethyl alcoholWash to neutrality, filter, at 104 DEG C, dry, obtain functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process is: get 5g functionalization concave convex rod mesoporous material and burn in round bottomIn bottle, and add 1.7g flocculant polyacrylamide, be put in magnetic stirring apparatus and stir 1.5h, rotating speed is 1000rpm, then willMixture is thrown in extruding machine, and selecting middle circle bore dia is 1cm, the mould that ball interior diameter is 3cm, and temperature is adjusted to107 DEG C, the ball-type concave convex rod adsorbent that can suspend, its surface area is large, and crossing water-based can be good.
Embodiment 3
(1) the acid pretreatment of concave convex rod, detailed process is: get 14g concave convex rod and grind and cross 300 mesh sieves, and joined heightIn speed dispersion machine, then to add 350ml distilled water, mixing speed be 14000rpm, disperses 10min, then add 140ml concentrationFor the hydrochloric acid of 10.5mol/L, speed is 3000rpm, rotates 2h, filters, and is washed with distilled water to neutrality, at 105 DEG CDry, cooling, grinding, crosses 300 mesh sieves, obtains acid-treated concave convex rod.
(2) preparation of concave convex rod mesoporous material, detailed process is: get 12g surfactant hexadecyltrimethylammonium chloride and be dissolved inIn 600ml distilled water, then add the concave convex rod after 12g acidic treatment, the NaOH solution that is 6mol/L by concentration regulates pH=12,Be under 1600rpm, to stir ultrasonic 20min at rotating speed, and then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave,At 105 DEG C, heat 30h, be cooled to room temperature, then use distilled water and absolute ethanol washing to neutral, at 70 DEG C, dry 0.9h, connectAnd at 300 DEG C, carry out roasting 2.8h, cooling, grinding, crosses 300 mesh sieves, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process is: get 9.6g1,3 two mercaptopropyl trimethoxysilanes are in circleIn end flask, then add 3.8ml water and 34.2ml ethanol, adding concentration is the sulfuric acid solution adjusting pH=4 of 3mol/L, stirsAnd be heated to 76 DEG C, and rotating speed is 2500rpm, after 0.9h, then adds 28.8ml acrylic acid and the 3.34ml concentrated sulfuric acid, temperature is adjustedJoint, to 85 DEG C, after 1.4h, is cooled to 25 DEG C by temperature, then adds concave convex rod mesoporous material and the 660ml ether of 12g,Stir 1.6h, rotating speed is 3600rpm, then passes into the H of 20min2S, extremely neutral with distilled water and absolute ethanol washing, filter,At 106 DEG C, dry, obtain functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process is: get 10g functionalization concave convex rod mesoporous material and burn in round bottomIn bottle, and add 4g flocculant polyacrylamide, be put in magnetic stirring apparatus and stir 2h, rotating speed is 1500rpm, then will mixThing is thrown in extruding machine, and selecting middle circle bore dia is 1cm, the mould that ball interior diameter is 3cm, and temperature is adjusted to 105 DEG C,The ball-type concave convex rod adsorbent that can suspend, its surface area is large, and crossing water-based can be good.
Embodiment 4
(1) the acid pretreatment of concave convex rod, detailed process is: get 15g concave convex rod and grind and cross 300 mesh sieves, and joined heightIn speed dispersion machine, then to add 450ml distilled water, mixing speed be 15000rpm, disperses 15min, then add 225ml concentrationFor the hydrochloric acid of 9mol/L, speed is 4000rpm, rotates 2h, filters, and is washed with distilled water to neutrality, at 110 DEG C, dry,Cooling, grinding, cross 300 mesh sieves, obtains acid-treated concave convex rod.
(2) preparation of concave convex rod mesoporous material, detailed process is: get 16g surfactant hexadecyltrimethylammonium chloride and be dissolved inIn 1120ml distilled water, then add the concave convex rod after 24g acidic treatment, the NaOH solution that is 6mol/L by concentration regulatesPH=12, is under 2000rpm, to stir ultrasonic 25min at rotating speed, and then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave,At 110 DEG C, heat 36h, be cooled to room temperature, then use distilled water and absolute ethanol washing to neutral, at 80 DEG C, dry 1h, connectAnd at 400 DEG C, carry out roasting 3h, cooling, grinding, crosses 300 mesh sieves, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process is: get 24g1,3 two mercaptopropyl trimethoxysilanes are in circleIn end flask, then add 8ml water and 80ml ethanol, adding concentration is the sulfuric acid solution adjusting pH=4 of 3mol/L, stirs and addsHeat is to 80 DEG C, and rotating speed is 3000rpm, after 1h, then adds 108ml acrylic acid and the 19.6ml concentrated sulfuric acid, and temperature is adjusted to 90 DEG C,After 1.5h, temperature is cooled to 30 DEG C, then adds concave convex rod mesoporous material and the 1800ml ether of 20g, at N2ProtectionUnder, stirring 2h, rotating speed is 4000rpm, then passes into the H of 30min2S, extremely neutral with distilled water and absolute ethanol washing, mistakeFilter is dried at 110 DEG C, obtains functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process is: get 20g functionalization concave convex rod mesoporous material and burn in round bottomIn bottle, and add 20g flocculant polyacrylamide, be put in magnetic stirring apparatus and stir 1.8h, rotating speed is 2000rpm, then willMixture is thrown in extruding machine, and selecting middle circle bore dia is 1cm, the mould that ball interior diameter is 3cm, and temperature is adjusted to110 DEG C, the ball-type concave convex rod adsorbent that can suspend, its surface area is large, and crossing water-based can be good.
Embodiment 5
Suspension ball-type concave convex rod adsorbent is to removing the effect detection experiment of heavy metal in waste water, and detailed process is:
Utilize the suspension ball-type concave convex rod adsorbent of preparation in embodiment 1～4 to adsorb respectively Cd in waste water2+、Pb2+And Hg+. RespectivelyThe adsorption experiment condition of embodiment is as follows:
Compound concentration is the Cd that contains of 60mg/L, 80mg/L and 40mg/L respectively2+The aqueous solution, containing Pb2+The aqueous solution and containing Hg+The aqueous solution, the waste water of sample content simulation China city industrial area. Take respectively the Cd that contains of 4 parts of 0.5L2+The aqueous solution, containPb2+The aqueous solution and containing Hg+The aqueous solution is designated as A, B, C, D, E. A is blank solution, in B, C, D, E, distinguishesAdd suspension ball-type concave convex rod adsorbent prepared in 0.1g embodiment 1～4, at 25 DEG C, stir 30min, rotating speed500rpm, centrifugal, measure respectively Cd in supernatant2+、Pb2+And Hg+Content.
Cd in each suspension ball-type concave convex rod adsorbent difference adsorbed water in embodiment 1～42+、Pb2+And Hg+After each aqueous solution inContent of beary metal is as follows:
From above adsorption experiment result, the adsorbent adsorption effect of preparing by the method is fine, especially sample D coupleCd2+、Pb2+And Hg+Adsorbance reaches respectively 225mg/g, 180mg/g and 113.5mg/g, and all kinds of heavy metals are hadWell adsorption effect, can also process multiclass organic matter as phenols, dyestuff etc. simultaneously, can extensively and effectively process all kinds ofWaste water.
Above detailed description of the invention has been carried out concrete description to method of the present invention, but content of the present invention also not onlyOnly limit to above case study on implementation, as long as do not exceeding within the scope of purport of the present invention, can carry out flexibly experiment condition and methodChange, these all belong to protection scope of the present invention. Therefore, patent of the present invention and protection domain should taking appended claims asAccurate.
Claims (7)
1. the suspend preparation method of ball-type concave convex rod adsorbent, is characterized in that, comprises the following steps:
(1) the acid pretreatment of concave convex rod: concave convex rod is ground and joined in high speed dispersor, then add distilled water, stirMix, disperse, then add hydrochloric acid to stir, filter, be washed with distilled water to neutrality, then dry, cooling, grind to obtain sour placeThe concave convex rod of reason;
(2) preparation of concave convex rod mesoporous material: add recessed after acidic treatment in hexadecyltrimethylammonium chloride solutionProtruding rod, with NaOH solution adjusting pH=12, stirs ultrasonic mixture; And then by this mixture at 100～110 DEG CHeating 24～36h, is cooled to room temperature, and washing is to neutral, dries, roasting 2～3h, cooling, grind to such an extent that concave convex rod is mesoporousMaterial;
(3) preparation of functionalization concave convex rod mesoporous material: preparation coupling agent 1,3 two mercaptopropyl trimethoxysilane, Shui HejiaAlcoholic solution, adds sulfuric acid solution to regulate pH=4, stirs and is heated to 70～80 DEG C, then add acrylic acid and the concentrated sulfuric acid, temperatureDegree is adjusted to 80～90 DEG C, after reaction 1～1.5h, temperature is cooled to 15～30 DEG C, then adds concave convex rod mesoporous materialAnd ether, at N2Protection under stir, then pass into H2S, extremely neutral with distilled water and absolute ethanol washing, filter, dry,Obtain functionalization concave convex rod mesoporous material;
(4) preparation of suspension ball-type concave convex rod adsorbent: get functionalization concave convex rod mesoporous material and add flocculant polyacrylamideAmine, is put in magnetic stirring apparatus and stirs, then mixture is thrown in extruding machine, obtains suspension ball-type concave convex rod adsorbent.
2. the method for claim 1, is characterized in that in described step (1), the solid-to-liquid ratio of concave convex rod and water is1:20～1:30 (g/ml), the solid-to-liquid ratio of concave convex rod and hydrochloric acid is=1:5～1:15 (g/ml) that concentration of hydrochloric acid is 9～12mol/L.
3. the method for claim 1, is characterized in that in described step (2) surfactant cetyl threeAmmonio methacrylate and distilled water solid-to-liquid ratio are 1:30～1:70 (g/ml); The mass ratio of concave convex rod and surfactant is: 1:0.5～1:1.5, NaOH solution concentration is 6mol/L.
4. the method for claim 1, is characterized in that in described step (3), the solid-to-liquid ratio of coupling agent and water is:2:1～3:1 (g/ml), the liquid liquor ratio of water and methyl alcohol is: 1:8～1:10 (ml/ml), sulfuric acid solution concentration is 3mol/L; EvenConnection agent and acrylic acid solid-to-liquid ratio are: 1:1.5～1:4.5 (g/ml), and concentrated sulfuric acid addition accounts for 1%～10% of mixed solution;The mass ratio of concave convex rod and coupling agent is: 1:0.4～1:2 (g/g), the solid-to-liquid ratio of concave convex rod and ether is: 1:50～1:60.
5. the method for claim 1, is characterized in that in described step (4) flocculant and concave convex rod mass ratioFor 1:1～1:4 (g/g).
6. the method for claim 1, is characterized in that in described step (4), and extruding machine selects middle circular hole straightFootpath is 1cm, the mould that ball interior diameter is 3cm, and temperature is 100～110 DEG C.
7. the method for application suspension ball-type concave convex rod sorbent treatment heavy metals in industrial wastewater, is characterized in that adsorbent is by solid-liquidThan processing and purified industrial waste water for 1:5 (g/L) is added in industrial wastewater.
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