CN105597667B - The preparation method of suspension ball-type concave convex rod adsorbent and its application for handling heavy metals in industrial wastewater - Google Patents
The preparation method of suspension ball-type concave convex rod adsorbent and its application for handling heavy metals in industrial wastewater Download PDFInfo
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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
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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 present invention relates to the application of a kind of preparation method of suspension ball-type concave convex rod adsorbent and its processing heavy metals in industrial wastewater；Including the acid pretreatment of (1) concave convex rod；(2) preparation of concave convex rod mesoporous material；(3) preparation of functionalization concave convex rod mesoporous material and the preparation of (4) suspension ball-type concave convex rod adsorbent；And suspension ball-type concave convex rod sorbent treatment Industry Waste water law is applied, adsorbent is 1 by solid-to-liquid ratio:5 (g/L) are added to processing and purified industrial waste water in industrial wastewater.Compared with existing concave convex rod adsorbent：This adsorbent has high specific surface area by mesoporous material made from self assembly mode, and mesoporous material is connected with silane coupler as intermediate medium by the use of the acrylic acid of low cost, expand the inside aperture of mesoporous material, there is high selectivity, the absorption heavy metal ion that can be oriented.Adsorption efficiency is improved, secondary pollution is not produced in processing procedure, can repeatedly be recycled, recovery facilitates, and processing cost is low.
Description
Technical field
The invention belongs to adsorber technologies and technical field of sewage, and in particular to a kind of to be utilized by matrix of concave convex rod
Self-assembling technique and functional porous material and prepare a kind of be used to handle the adsorbent of heavy metal in waste water.
Background technology
It is well known that water is the basis that all life are depended on for existence on the earth.So populous in China, water resource needs
The big country of the amount of asking, the various water contamination accidents to emerge in an endless stream but make us startling, such as on April 27th, 2015, Yichang length sun
Covering special manganese industry blowdown causes water body blackening to foul, and then pollutes the mother river Qingjian River.River is practiced by tight on June 15th, 2015, Guangdong
High pollution, become bad V class water, according to the monitoring result of 2014, main contamination index was in exacerbation trend than 2013.
One of most heavy river is polluted as the whole nation, therefore two sides resident also endures it to the fullest extent bitter.Also on June 17th, 2015, Anhui Chizhou City
Mileage thousand mu of farmlands in town also become wasteland.Only because iirigation water source is polluted in chemical industry garden.Contain a large amount of Toxics in these water, it is multinomial
Pollutant is exceeded.Such case is innumerable, makes people worried.In the industrial production, a large amount of poisonous and harmful substances are irrational
Discharge exacerbates the deterioration of water environment and the shortage of water resource, most has influence on the existence and expanding economy of the mankind at last.2015
In on January 1, in, it is referred to as the new of " most tight in history "《Law on Environmental Protection》It is formal to implement, cause the concern of the public；In addition 2015
In on April 2, in, State Council has issued the notice on printing and distributing water prevention and cure of pollution action plan (ten, water), has all indicated water pollution
Problem extremely sternness, it is necessary to contain, and be badly in need of deploying Control Measures for Water Pollution immediately.
At present, heavy metal pollution serious threat the health of the mankind.Because it has high toxicity, non-biodegradation
Property, bioconcentration etc..Moreover, organism can also enriching heavy metal, eventually arrive inside people, it is extremely micro with regard to people can be caused
Death, or even the novel substance of more toxicity can also be converted into.Go water removal in heavy metal method it is numerous, have chemical precipitation method, from
Sub- exchange process, electrochemical process, bioanalysis, absorption method etc..Wherein absorption method is simple to operate so that its raw material sources is wide, cost is low, effect
Rate is high, selectivity is high, recyclable, gets most of the attention the advantages that non-secondary pollution, critical role is occupied in heavy metal in handling water.
Cheap and easy to get due to concave convex rod rich reserves, specific surface area is big, and absorption property is excellent, the property such as pollution-free, makes it
As a kind of high-quality adsorbent.Concave convex rod is also known as palygorskite, is a kind of layer of chain with rich in the clay pit based on magnesium silicate
Thing, there is the brilliant bundle aggregate of filamentary structure.Fig. 1 is the SEM micrograph of concave convex rod.Nowadays prepared using concave convex rod for matrix
The method that adsorbent is used to handle heavy metal in water is a lot, but its technical merit is generally relatively low, and adsorption effect is not especially good, and
And majority is powdered, is unfavorable for reclaiming, receives certain limitation.CN104722265A discloses one kind and utilizes ethylenediamine tetraacetic
The attapulgite modified method and its application for preparing adsorbent of acetic acid.Ethylenediamine tetra-acetic acid almost can with so complexing of metal ion
Stable chelate is formed, selectivity is low, and dosage is big, flammable, less toxic, have excitant, potential safety hazard be present.
CN104707564A discloses one kind using concave convex rod as raw material, and by pretreatment, acid is modified, loads Fe3O4, activation heat treatment etc.
Concave convex rod/Fe prepared by technique3O4Composite.The method demand for control is high, low, the Fe of selectivity3O4It is unstable under the high temperature conditions
Fixed, absorption property is not high, it is difficult to extensive use.The CN104014299A one kind that discloses utilizes attapulgite and water certain proportion
It is prepared by mixing into the method for granule adsorbent.Though this method is simple, is easily recycled, energy resource consumption is big, is unfavorable for energy-saving ring
Protect, concave convex rod bad dispersibility, adsorption effect be not notable, it is impossible to realize the high-efficiency comprehensive utilization to all components in concave convex rod.
The content of the invention
The purpose of the present invention is the shortcomings that being to overcome prior art, there is provided one kind prepares adsorbent by matrix of concave convex rod
Method and the application using the sorbent treatment heavy metal in waste water, not only the cost of raw material is low for the adsorbent, enriches easy
, adsorptivity is strong, and larger interior external surface area, adsorption efficiency is greatly improved, and can repeatedly recycle, and environment will not be caused
Secondary pollution etc..
The purpose of the present invention is realized by following scheme：
A kind of preparation method of suspension ball-type concave convex rod adsorbent, comprises the following steps：
(1) the acid pretreatment of concave convex rod：Concave convex rod is ground and is added in high speed dispersor, distilled water is added, stirs
Mix, disperse, add hydrochloric acid stirring, filtering, be washed with distilled water to neutrality, then dry, cool down, grind acid treatment it is recessed
Convex rod；
(2) preparation of concave convex rod mesoporous material：The bumps of acid treatment are added in hexadecyltrimethylammonium chloride solution
Rod, pH=12 is adjusted with NaOH solution, stirs ultrasonic mixing thing；Then this mixture heats at 100~110 DEG C to 24 again~
36h, room temperature is cooled to, washs to neutrality, drying, 2~3h of roasting, cool down, grind to obtain concave convex rod mesoporous material；
(3) preparation of functionalization concave convex rod mesoporous material：Prepare coupling agent 1,3 2 mercaptopropyl trimethoxysilane, water and
Methanol solution, sulfuric acid solution regulation pH=4 is added, stirs and is heated to 70~80 DEG C, add acrylic acid and the concentrated sulfuric acid, temperature
Adjust to 80~90 DEG C, after reacting 1~1.5h, temperature is cooled to 15~30 DEG C, then add concave convex rod mesoporous material and second
Ether, in N2Protection under stir, then be passed through H2S, washed to neutrality, filtered with distilled water and absolute ethyl alcohol, drying, obtain functionalization
Concave convex rod mesoporous material；
(4) preparation of suspension ball-type concave convex rod adsorbent：Functionalization concave convex rod mesoporous material is taken to add flocculant polypropylene
Acid amides, it is put in magnetic stirring apparatus and stirs, then mixture is thrown in extruding machine, obtains suspension ball-type concave convex rod adsorbent.
In described step (1), the solid-to-liquid ratio of concave convex rod and distilled water is 1:20~1:30, the solid-liquid of concave convex rod and hydrochloric acid
Than for 1:5~1:15, concentration of hydrochloric acid is 9~12mol/L.
In described step (2), surfactant hexadecyltrimethylammonium chloride is 1 with distilled water solid-to-liquid ratio:30~
1:70；The concave convex rod of acid treatment and the mass ratio of surfactant are：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, the liquid liquor ratio of water and methanol is：1:8
~1:10, sulfuric acid solution concentration is 3mol/L；The solid-to-liquid ratio of coupling agent and acrylic acid is：1:1.5~1:4.5, the concentrated sulfuric acid adds
Amount accounts for the 1%~10% of mixed solution；The mass ratio of concave convex rod mesoporous material and coupling agent is：1:0.4~1:2, concave convex rod
The solid-to-liquid ratio of mesoporous material and ether is：1:50~1:60.
In described step (4), flocculant and functionalization concave convex rod mesoporous material mass ratio are 1:1~1:4.
In described step (4), Circularhole diameter be 1cm among extruding machine selection, and ball interior diameter is 3cm mould, temperature
For 100~110 DEG C.
Using the method for suspension ball-type concave convex rod sorbent treatment industrial wastewater, adsorbent is 1 by solid-to-liquid ratio:5 are added to
Processing and purified industrial waste water in industrial wastewater.
Compared with existing concave convex rod adsorbent, the present invention has the advantage that：
(1) this adsorbent has high specific surface area by mesoporous material made from self assembly mode, and utilizes low cost
Acrylic acid mesoporous material is connected with silane coupler as intermediate medium, expand the inside aperture of mesoporous material,
High selectivity is made it have, the absorption heavy metal ion that can be oriented.
(2) silane coupler utilized in this material contains two sulfydryls, and common silane coupled containing sulfydryl
Agent is compared, and greatly improves the absorption property of concave convex rod adsorbent.
(3) material makes suspension ball-type, increases its external surface area, improves adsorption efficiency, in processing procedure not
Secondary pollution is produced, can repeatedly be recycled, recovery facilitates, 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 for preparing the suspension ball-type concave convex rod adsorbent of the present invention.
Embodiment
Fig. 3 is the process chart of the present invention, and the present invention is further elaborated on below by specific case study on implementation.
The preparation method of adsorbent of the present invention, it comprises the following steps：
(1) the acid pretreatment of concave convex rod, detailed process are：Take concave convex rod to grind and cross 200~300 mesh sieves, and added
Enter into high speed dispersor, add distilled water, the solid-to-liquid ratio of concave convex rod and distilled water is 1:20~1:30, mixing speed is
10000~15000rpm, disperse 5~15min, add 9~12mol/L hydrochloric acid, the solid-to-liquid ratio of concave convex rod and hydrochloric acid is 1:5
~1:15,2000~4000rpm of rotating speed, 1~2h is rotated, filtering, neutrality is washed with distilled water to, is dried at 100~110 DEG C
It is dry, cooling, grinding, 200~300 mesh sieves are crossed, obtain the concave convex rod of acid treatment.
(2) preparation of concave convex rod mesoporous material, detailed process are：Take surfactant hexadecyltrimethylammonium chloride molten
In distilled water, solid-to-liquid ratio 1:30~1:70, add the concave convex rod of acid treatment, the concave convex rod and surfactant of acid treatment
Mass ratio be：1:0.5~1:1.5, with concentration be 6mol/L NaOH solution adjust pH=12, rotating speed be 1000~
10~25min of ultrasound is stirred under 2000rpm, then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave again, 100~
24~36h is heated at 110 DEG C, is cooled to room temperature, then is washed with distilled water and absolute ethyl alcohol to neutrality, is dried at 50~80 DEG C
0.5h~1h, 2~3h of roasting is then carried out at 200~400 DEG C, cooling, grinding, crosses 200~300 mesh sieves, obtains concave convex rod Jie
Porous materials.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process are：Take 1,3 2 mercaptopropyl trimethoxysilanes in
In round-bottomed flask, water and methanol are added, the solid-to-liquid ratio of coupling agent and water is：2:1~3:1, the liquid liquor ratio of water and methanol is：1:
8~1:10, add the sulfuric acid solution that concentration is 3mol/L and adjust pH=4, stir and be heated to 70~80 DEG C, rotating speed is 2000~
After 3000rpm, 0.5~1h, acrylic acid and the concentrated sulfuric acid are added, the solid-to-liquid ratio of coupling agent and acrylic acid is：1:1.5~1:4.5
Concentrated sulfuric acid addition accounts for the 1%~10% of above added mixed solution, and temperature adjustment is to 80~90 DEG C, after 1~1.5h, by temperature
15~30 DEG C are cooled to, then adds the stereoplasm amount of concave convex rod mesoporous material and ether, concave convex rod mesoporous material and coupling agent
The ratio between be：1:0.4~1:2, the solid-to-liquid ratio of concave convex rod mesoporous material and ether is：1:50~1:60 in N2Protection under, stirring 1
~2h, rotating speed is 3000~4000rpm, then is passed through 10~30min H2S, washed with distilled water and absolute ethyl alcohol to neutrality, mistake
Filter, dries at 100~110 DEG C, obtains functionalization concave convex rod mesoporous material, its structural representation such as Fig. 2.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process are：Functionalization concave convex rod mesoporous material is taken in round bottom
In flask, and flocculant polyacrylamide is added, flocculant and functionalization concave convex rod mesoporous material consolidate mass ratio as 1:1~1:
4,1~2h of stirring in magnetic stirring apparatus is put in, rotating speed is 800~2000rpm, then mixture is thrown in extruding machine, in selection
Between Circularhole diameter be 1cm, ball interior diameter is 3cm mould, and temperature is adjusted to 100~110 DEG C, and must can suspend ball-type concave convex rod
Adsorbent, its surface area is big, and excessively water-based energy is good.
The application of sorbent treatment industrial wastewater of the present invention, concrete operations are as follows：
Contain all kinds of heavy metal ion and some organic pollutions in industrial wastewater, adsorbent of the present invention is 1 by solid-to-liquid ratio:
5 are added in industrial wastewater, and under this ratio, this adsorbent is notable to the adsorption effect of heavy metal ions in wastewater, can be very big
Processing and purified industrial waste water in degree.
Embodiment 1
(1) the acid pretreatment of concave convex rod, detailed process are：Take 12g concave convex rods to grind and cross 250 mesh sieves, and be added into
Into high speed dispersor, 276mL distilled water is added, mixing speed 12000rpm, disperses 7min, adding 96mL concentration is
11mol/L hydrochloric acid, speed 3000rpm, 1.5h is rotated, filtering, neutrality is washed with distilled water to, is dried at 105 DEG C, it is cold
But, grind, cross 250 mesh sieves, obtain the concave convex rod of acid treatment.
(2) preparation of concave convex rod mesoporous material, detailed process are：Take 6g surfactant hexadecyltrimethylammonium chlorides
It is dissolved in 240mL distilled water, adds the concave convex rod of 4.8g acid treatments, the NaOH solution for being 6mol/L with concentration adjusts pH=
12, ultrasonic 15min is stirred in the case where rotating speed is 1300rpm, then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave again,
27h is heated at 103 DEG C, is cooled to room temperature, then is washed with distilled water and absolute ethyl alcohol to neutrality, 0.7h is dried at 60 DEG C, then
Roasting 2.4h is carried out at 250 DEG C, cooling, grinding, 250 mesh sieves is crossed, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process are：Take the mercapto propyl trimethoxy silicon of 2.7g1,3 bis-
Alkane adds 1.2mL water and 10.2mL ethanol in round-bottomed flask, adds the sulfuric acid solution that concentration is 3mol/L and adjusts pH=4,
Stir and be heated to 73 DEG C, after rotating speed 2200rpm, 0.7h, add 5.4mL acrylic acid and the 0.5mL concentrated sulfuric acids, temperature adjustment
To 83 DEG C, after 1.2h, temperature is cooled to 20 DEG C, 4.5g concave convex rod mesoporous material and 238.5mL ether are then added, in N2
Protection under, stir 1.3h, rotating speed 3400rpm, then be passed through 15min H2S, washed with distilled water and absolute ethyl alcohol into
Property, filtering is dried at 104 DEG C, obtains functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process are：5g functionalization concave convex rod mesoporous materials are taken in circle
In the flask of bottom, and 1.7g flocculant polyacrylamides are added, be put in magnetic stirring apparatus and stir 1.5h, rotating speed 1000rpm, then
Mixture is thrown in extruding machine, it is 1cm to select middle Circularhole diameter, and ball interior diameter is 3cm mould, and temperature is adjusted to
107 DEG C, must can suspend ball-type concave convex rod adsorbent, and its surface area is big, and excessively water-based energy is good.
Embodiment 2
(1) the acid pretreatment of concave convex rod, detailed process are：Take 14g concave convex rods to grind and cross 300 mesh sieves, and be added into
Into high speed dispersor, 350mL distilled water is added, mixing speed 14000rpm, disperses 10min, adds 140mL concentration
For 10.5mol/L hydrochloric acid, speed 3000rpm, 2h is rotated, filtering, neutrality is washed with distilled water to, is dried at 105 DEG C,
Cooling, grinding, cross 300 mesh sieves, obtain the concave convex rod of acid treatment.
(2) preparation of concave convex rod mesoporous material, detailed process are：Take 12g surfactant cetyl trimethyl chlorinations
Ammonium is dissolved in 600mL distilled water, adds the concave convex rod of 12g acid treatments, and the NaOH solution for being 6mol/L with concentration adjusts pH=
12, ultrasonic 20min is stirred in the case where rotating speed is 1600rpm, then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave again,
30h is heated at 105 DEG C, is cooled to room temperature, then is washed with distilled water and absolute ethyl alcohol to neutrality, 0.9h is dried at 70 DEG C, then
Roasting 2.8h is carried out at 300 DEG C, cooling, grinding, 300 mesh sieves is crossed, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process are：Take the mercapto propyl trimethoxy silicon of 9.6g1,3 bis-
Alkane adds 3.8mL water and 34.2mL ethanol in round-bottomed flask, adds the sulfuric acid solution that concentration is 3mol/L and adjusts pH=4,
Stir and be heated to 76 DEG C, after rotating speed 2500rpm, 0.9h, add 28.8mL acrylic acid and the 3.34mL concentrated sulfuric acids, temperature is adjusted
Save to 85 DEG C, after 1.4h, temperature is cooled to 25 DEG C, then add 12g concave convex rod mesoporous material and 660mL ether, stirring
1.6h, rotating speed 3600rpm, then it is passed through 20min H2S, washed with distilled water and absolute ethyl alcohol to neutrality, filtering, at 106 DEG C
Lower drying, obtain functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process are：Take 10g functionalization concave convex rod mesoporous materials in
In round-bottomed flask, and 4g flocculant polyacrylamides are added, be put in magnetic stirring apparatus and stir 2h, rotating speed 1500rpm, then will
Mixture is thrown in extruding machine, and it is 1cm to select middle Circularhole diameter, and ball interior diameter is 3cm mould, and temperature is adjusted to 105
DEG C, must can suspend ball-type concave convex rod adsorbent, and its surface area is big, and excessively water-based energy is good.
Embodiment 3
(1) the acid pretreatment of concave convex rod, detailed process are：Take 15g concave convex rods to grind and cross 300 mesh sieves, and be added into
Into high speed dispersor, 450mL distilled water is added, mixing speed 15000rpm, disperses 15min, adds 225mL concentration
For 9mol/L hydrochloric acid, speed 4000rpm, 2h is rotated, filtering, neutrality is washed with distilled water to, is dried at 110 DEG C, it is cold
But, grind, cross 300 mesh sieves, obtain the concave convex rod of acid treatment.
(2) preparation of concave convex rod mesoporous material, detailed process are：Take 16g surfactant cetyl trimethyl chlorinations
Ammonium is dissolved in 1120mL distilled water, adds the concave convex rod of 24g acid treatments, and the NaOH solution for being 6mol/L with concentration adjusts pH=
12, ultrasonic 25min is stirred in the case where rotating speed is 2000rpm, then this mixture is transferred in polytetrafluoroethylene (PTFE) autoclave again,
36h is heated at 110 DEG C, is cooled to room temperature, then is washed with distilled water and absolute ethyl alcohol to neutrality, 1h is dried at 80 DEG C, is then existed
Roasting 3h is carried out at 400 DEG C, cooling, grinding, 300 mesh sieves is crossed, obtains concave convex rod mesoporous material.
(3) preparation of functionalization concave convex rod mesoporous material, detailed process are：Take the mercaptopropyl trimethoxysilanes of 24g1,3 bis-
In round-bottomed flask, 8mL water and 80mL ethanol are added, the sulfuric acid solution that concentration is 3mol/L is added and adjusts pH=4, stirring is simultaneously
Be heated to 80 DEG C, after rotating speed 3000rpm, 1h, add 108mL acrylic acid and the 19.6mL concentrated sulfuric acids, temperature adjustment to 90 DEG C,
After 1.5h, temperature is cooled to 30 DEG C, 20g concave convex rod mesoporous material and 1800mL ether are then added, in N2Protection under,
2h, rotating speed 4000rpm are stirred, then is passed through 30min H2S, washed with distilled water and absolute ethyl alcohol to neutrality, filtering, 110
Dried at DEG C, obtain functionalization concave convex rod mesoporous material.
(4) preparation of suspension ball-type concave convex rod adsorbent, detailed process are：Take 20g functionalization concave convex rod mesoporous materials in
In round-bottomed flask, and 20g flocculant polyacrylamides are added, be put in magnetic stirring apparatus and stir 1.8h, rotating speed 2000rpm,
Mixture is thrown in extruding machine again, it is 1cm to select middle Circularhole diameter, and ball interior diameter is 3cm mould, and temperature is adjusted to
110 DEG C, must can suspend ball-type concave convex rod adsorbent, and its surface area is big, and excessively water-based energy is good.
Embodiment 4
Suspension ball-type concave convex rod adsorbent is tested to the effect detection for removing heavy metal in waste water, and detailed process is：
Cd in waste water is adsorbed respectively using the suspension ball-type concave convex rod adsorbent prepared in embodiment 1~32+、Pb2+And Hg+。
The adsorption experiment condition of each embodiment is as follows：
Compound concentration contains Cd for 60mg/L, 80mg/L and 40mg/L respectively2+The aqueous solution, containing Pb2+The aqueous solution and containing Hg+Water
Solution, sample content simulate the waste water of China's city industrial area.Weigh 3 parts of 0.5L respectively contains Cd2+The aqueous solution, containing Pb2+Water
Solution and containing Hg+The aqueous solution is designated as A, B, C, D.A is blank solution, and institute in 0.1g embodiments 1~3 is separately added into B, C, D
The suspension ball-type concave convex rod adsorbent of preparation, stirs 30min, rotating speed 500rpm at 25 DEG C, centrifugation, determines respectively in supernatant
Cd2+、Pb2+And Hg+Content.
Each suspension ball-type concave convex rod adsorbent adsorbs Cd in water respectively in embodiment 1~32+、Pb2+And Hg+Afterwards each water-soluble
Content of beary metal is as follows in liquid：
It was found from above Adsorption experimental results, the adsorbent adsorption effect prepared by this method is fine, especially sample C
To Cd2+、Pb2+And Hg+Adsorbance respectively reaches 225mg/g, 180mg/g and 113.5mg/g, and has very to all kinds of heavy metals
Good adsorption effect, while more type organics such as phenols, dyestuff etc. can also be handled, can extensively and effectively it handle all kinds of useless
Water.
Embodiment above has carried out specific description, but content of the present invention to the method for the present invention
Above case study on implementation is not restricted to, as long as in the main scope without departing from the present invention, experiment condition and method can be entered
The flexible change of row, these belong to protection scope of the present invention.Therefore, patent of the present invention and protection domain should be with appended rights
Claim is defined.
Claims (6)
1. a kind of preparation method of suspension ball-type concave convex rod adsorbent, it is characterised in that comprise the following steps：
(1) the acid pretreatment of concave convex rod：Concave convex rod is ground and is added in high speed dispersor, distilled water is added, stirring, divides
Dissipate, add hydrochloric acid stirring, filtering, be washed with distilled water to neutrality, then dry, cool down, grind acid treatment concave convex rod；
(2) preparation of concave convex rod mesoporous material：Take hexadecyltrimethylammonium chloride to be dissolved in distilled water, add acid treatment
Concave convex rod, pH=12 is adjusted with NaOH solution, stirs ultrasonic mixing thing；Then this mixture is heated at 100~110 DEG C again
24~36h, room temperature is cooled to, washs to neutrality, drying, 2~3h of roasting, cool down, grind to obtain concave convex rod mesoporous material；
(3) preparation of functionalization concave convex rod mesoporous material：Prepare the mercaptopropyl trimethoxysilane of coupling agent 1,3 2, water and methanol
Solution, sulfuric acid solution regulation pH=4 is added, stirs and is heated to 70~80 DEG C, add acrylic acid and the concentrated sulfuric acid, temperature adjustment
To 80~90 DEG C, after reacting 1~1.5h, temperature is cooled to 15~30 DEG C, then adds concave convex rod mesoporous material and ether,
N2Protection under stir, then be passed through H2S, washed to neutrality, filtered with distilled water and absolute ethyl alcohol, drying, obtain functionalization concave convex rod
Mesoporous material；
(4) preparation of suspension ball-type concave convex rod adsorbent：Functionalization concave convex rod mesoporous material is taken to add flocculant polyacrylamide,
It 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 as described in claim 1, it is characterized in that in described step (1), the solid-to-liquid ratio of concave convex rod and distilled water is
1:20~1:30g/mL；The solid-to-liquid ratio of concave convex rod and hydrochloric acid is=1:5~1:15g/mL, concentration of hydrochloric acid are 9~12mol/L.
3. the method as described in claim 1, it is characterized in that in described step (2), surfactant cetyl trimethyl
Ammonium chloride is 1 with distilled water solid-to-liquid ratio:30~1:70g/mL；The concave convex rod of acid treatment and the mass ratio of surfactant are：1:
0.5~1:1.5, NaOH solution concentration is 6mol/L.
4. the method as described in claim 1, it is characterized in that in described step (3), the solid-to-liquid ratio of coupling agent and water is：2:1
~3:The liquid liquor ratio of 1g/mL, water and methanol is：1:8~1:10mL/mL, sulfuric acid solution concentration are 3mol/L；Coupling agent and propylene
Acid solid-to-liquid ratio be：1:1.5~1:4.5g/mL, concentrated sulfuric acid addition account for the 1%~10% of mixed solution；The mesoporous material of concave convex rod
Material and the mass ratio of coupling agent are：1:0.4~1:The solid-to-liquid ratio of 2g/g, concave convex rod mesoporous material and ether is：1:50~1:
60。
5. the method as described in claim 1, it is characterized in that in described step (4), flocculant and functionalization concave convex rod are mesoporous
Quality of materials ratio is 1:1~1:4g/g.
6. the method as described in claim 1, it is characterized in that in described step (4), among extruding machine selection Circularhole diameter for
1cm, ball interior diameter are 3cm mould, and temperature is 100~110 DEG C.
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| CN111659344A (en) * | 2020-06-16 | 2020-09-15 | 明光春计高分子材料有限公司 | Modified attapulgite adsorbent and production process thereof |
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