CN106140095B - The modified preparation and application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure - Google Patents
The modified preparation and application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/14—Fluorine or fluorine-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses the attapulgite modified preparation method and applications of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, belong to water source purifying and pollutant control technical field.The preparation method is as follows: being acidified, being fired to attapulgite to hydrochloric acid solution first；Again with the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure to attapulgite modified, the tertiary amine oxide that Abietyl-containing ternary phenanthrene ring structure is made is attapulgite modified.Adsorbent of the present invention is applicable to the removal of humic acid in drinking water, fluorine ion and the environmental contaminants such as Congo red.The advantages that preparation process of the present invention is simple, and utilization rate is high, and low in cost, widely applicable and easy to operate, modifying agent and matrix are environment-friendly material, easy to spread.
Description
Technical field
The invention belongs to water source purifying and pollutant control technical fields, are related to a kind of adsorbent, are specifically related to be modified
The modified preparation and application of attapulgite clay adsorbent.
Background technique
In recent years, with Chinese society rapid economic development, water pollutant discharge amount increases year by year, micro- in water environment
Pollution problem becomes increasingly conspicuous.The pollution that surface water body is subjected to not only constitutes a threat to aquatile, also destroys ecological environment,
And finally jeopardize the health of the mankind.Humic acid, fluorine ion are widely present in the surface water such as river, lake and the reservoir in China
And the multiple pollutants such as artificial synthetic organic materials such as dyestuff of industrial wastewater.Therefore developing effective processing method reduces corruption in water
Growing the artificial synthesized organic pollutants such as natural sex organic matter, inorganic anion (fluorine ion) and the dyestuff that acid is representative becomes one
The urgent task of item.
The method of tradition removal organic pollutants mainly includes absorption embrane method, bioanalysis, flocculence, advanced oxidation processes
With filter membrane method etc., but these types of method is all there is more or less limitation and to the secondary pollution problems of environment.It inhales
Attached rule is to rely on pore structure intensive on adsorbent, huge specific surface area, or by various active groups on surface and is inhaled
Various chemical bonds are formed by between attached matter, the organic pollutant and heavy metal contaminants that can be selectively enriched in water, into
And achieve the purpose that remove organic pollutants and heavy metal contaminants.In comparison, absorption method not only can avoid secondary dirt
Dye, and reduce costs to a certain extent.
Attapulgite is a kind of aqueous rich magnesium aluminosilicate clays mineral with chain layer structure, compares table with biggish
Area (300-400m2/ g) and more duct.Attapulgite itself have that large specific surface area, absorption property are strong, source is wide and
The features such as at low cost, therefore can be used for drinking water and sewage treatment.Although occurring both at home and abroad at present more attapulgite modified
Research to water pollutant absorption, mainly using chain alkyl as quaternary ammonium salt (e.g., the cetyl trimethyl chlorine of lipophilic group
(bromine) changes ammonium and brocide etc.) based on modified attapulgite, but above-mentioned surfactant has centainly environmental ecology
It is potentially hazardous.Currently, relating to how to utilize N, N-dimethyl dehydrogenation fir base amine oxide modified attapulgite Adsorption water
In the research of humic acid, anionic dye and anionic inorganic ion do not report still so far.
Rosin is a kind of renewable resources, and yield high price is low, and China's resin resource is abundant, and rosin accounts for about rosin
75%.From the demand of environmental protection, surfactant should have good ecological performance to reduce residual in the environment,
The scarcity of current petroleum-based energy at the same time, therefore be a kind of " green " by the Abietyl quaternary ammonium salt that rosin and its derivative synthesize
Surfactant generally has degradable, the small and ecological performance of pollution compared with chain alkyl cationoid surfactant
The features such as excellent, to have exploitation and application value well.
For background above, the invention proposes a kind of tertiary amine oxide modified attapulgites of Abietyl-containing ternary phenanthrene ring structure
The method of earth adsorbing, and it is applied to humic acid in water, inorganic anion (fluorine ion) and the anionic coloured dyestuff (the Congo
It is red) absorption.
Summary of the invention
The present invention uses abietyl tertiary amine oxide as modifier treatment attapulgite and then is prepared into adsorbent, it is therefore intended that
A kind of simple process, low in cost, absorption and good, the widely applicable adsorbent and this adsorbent of ecological performance are provided
The application of the inorganic anions pollutant such as organic matters and fluorine ion such as humic acid, congo red in going water removal.
The present invention can be realized by following technical side:
The preparation method of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure, this method include
Following steps:
(1) pretreatment of attapulgite: ground 20~200 mesh of attapulgite, then add it in acid solution,
At 60~80 DEG C, ultrasonic disperse reacts 15~30min, filters to take precipitating, and by washing of precipitate to neutrality, the bumps of acidification are made
Stick soil.
As a preferred option of the technical scheme, the acid adding amount of the attapulgite of step (1) be addition 10 in every gram of attapulgite~
20mL acid.Acid processing can make the K in attapulgite+、Mg2+Equal metal cations dissolution, and remove the carbonate for adhering to its surface
Equal impurity.Acid is one of hydrochloric acid, sulfuric acid and nitric acid, and concentration is 1~4mol/L, and the ultrasonic disperse time is 15~30min.
(2) it fires: adding water to be prepared into magma the attapulgite that step (1) obtains, be put into pipe after centrifugation removal supernatant
In formula furnace, high temperature fires 1-2h at 300~400 DEG C, is then down to room temperature, is ground up, sieved, obtains attapulgite powder, standby
With；
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, the tertiary amine oxide of 10mmol/L~100mmol/L Abietyl-containing ternary phenanthrene ring structure is formulated as with water
Surfactant-modified liquid, it is spare；
(4) attapulgite modified: the tertiary amine oxide surface of attapulgite powder and Abietyl-containing ternary phenanthrene ring structure is living
Property agent modification liquid according to mass volume ratio be that water-bath is vibrated after 1:2~9 (g/mL) mixing, washing is baked and banked up with earth to get to containing rosin
The oxidation of base ternary phenanthrene ring structure is tertiary attapulgite modified.
As a preferred option of the technical scheme, step (4) the water-bath vibration temperature be 15~60 DEG C, speed be 100~
250rpm/min, the time be 1~for 24 hours, the drying temperature be 60~80 DEG C.
The washing is the oxygen that resulting Abietyl-containing ternary phenanthrene ring structure is washed with appropriate distilled water or deionized water
Change the thick finished product of tertiary-amine modified attapulgite, is washed till the tertiary amine oxide surface that cleaning solution inspection does not measure Abietyl-containing ternary phenanthrene ring structure
Activating agent.The tertiary amine oxide method of the detection Abietyl-containing ternary phenanthrene ring structure is with ultraviolet-uisible spectrophotometer in λ
At=230nm detect abietyl ternary phenanthrene ring structure tertiary amine oxide absorption peak, when cleaning into supernatant in λ=230nm
Until place can't detect absorption peak.
As a preferred option of the technical scheme, the general structure of the tertiary amine oxide of the Abietyl-containing ternary phenanthrene ring structure are as follows:
Wherein, R isR1And R2Respectively C1~C2Alkyl.
As a preferred option of the technical scheme, the tertiary amine oxide of the Abietyl-containing ternary phenanthrene ring structure is N, and N-dimethyl is de-
Hydrogen fir base amine oxide, structural formula are as follows:
The application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure of the invention can be used
The humic acid, fluorine ion, Congo red in absorption water.Method are as follows:
(1) by the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure and pollutant water sample according to
Mass ratio is (0.4-2): 1 concentration range for being added to pollutant is in 1~100mg/L water sample；
(2) with acid or aqueous slkali adjust water sample pH value be 5~10, temperature control 20~50 DEG C, adsorption time be 0.5~
24 hours, 100~200rpm/min was vibrated in oscillation, the concentration of pollutant in separation determination supernatant, according in the water of absorption front and back
The concentration difference of pollutant, determines adsorbent to the adsorption effect of water pollutant, after processing pollutant concentration 0~3mg/L it
Between, removal rate is up to 90.0% or more.
As a preferred option of the technical scheme, the alkali be sodium hydroxide or potassium hydroxide, the acid be hydrochloric acid, sulfuric acid,
Any one of nitric acid.
The present invention can make attapulgite's surface become loose more by the pretreatment of step (1) and (2) to attapulgite
Hole, thus the modification that the tertiary amine oxide for being conducive to next step Abietyl-containing ternary phenanthrene ring structure is attapulgite modified.
The beneficial effects of the present invention are:
1. the tertiary amine oxide solution for the Abietyl-containing ternary phenanthrene ring structure that the present invention uses changes natural attapulgite
Property is prepared into target affinity agent, the tertiary amine oxide solution and chain alkyl of used raw material Abietyl-containing ternary phenanthrene ring structure
Cationoid surfactant is compared, and with abundance, preparation method is simple, cheap and easy to get, processing cost is low, ecological
Can be superior, absorption property is good the advantages that, residual in the environment can be effectively reduced.
2. the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified with unmodified attapulgite
Adsorption capacity compare, adsorption capacity has obtained effective raising, especially has to humic acid, Congo red and fluorine ion stronger
Adsorption capacity.
3. the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified molten suitable for drinking water
The environmental pollutions such as anionic dye (Congo red) in solution property organic matter (humic acid), inorganic anion (fluorine ion) and dyeing waste water
The removal of object has good economical and environmentally friendly benefit.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) photograph, wherein (a) is unmodified attapulgite, it (b) is N of the invention, N-dimethyl dehydrogenation
Fir base amine oxide is attapulgite modified；
Fig. 2 is infrared spectrogram, wherein (a) is unmodified attapulgite, it (b) is the N as made from embodiment 1, N-diformazan
Base dehydrogenation fir base amine oxide modified attapulgite；It (c) is N, N-dimethyl dehydrogenation fir base amine oxide modifying agent；
Fig. 3 is X-ray powder diffraction figure, wherein (a) is unmodified attapulgite, it (b) is N of the invention, N-dimethyl
Dehydrogenation fir base amine oxide modified attapulgite earth adsorbing；
Fig. 4 is differential thermal-thermogravimetric map, wherein (a) is unmodified attapulgite, it (b) is N of the invention, N-dimethyl is de-
Hydrogen fir base amine oxide modified attapulgite earth adsorbing；
Fig. 5, which is that the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified, (implements humic acid
Example 1), the adsorption capacity histogram of fluorine ion (embodiment 2) and Congo red (embodiment 4).
Specific embodiment
Below in conjunction with technical solution and attached drawing, specific embodiment that the present invention will be described in detail.
Embodiment 1
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, includes the following steps:
(1) acid processing attapulgite
Attapulgite is fully ground, 200 meshes is crossed, the attapulgite powder after sieving is then added to 2mol/L salt
In acid solution, the mass volume ratio of the attapulgite powder and hydrochloric acid that add is 1:10, ultrasonic disperse at 60 DEG C of reaction temperature
15min, ultrasonic power 50W filter to take precipitating after the reaction was completed, and by washing of precipitate to neutrality, the attapulgite of acidification is made.
(2) it fires: adding water to be prepared into magma step (1) resulting attapulgite and be centrifuged removal under 5000rpm speed
It is fired in 400 DEG C of nitrogen environments in tube furnace after supernatant, adjusting heating rate is 50 DEG C/min, and the firing time is set to
2h is then same as being down to room temperature in nitrogen environment, grind into powder, and it is spare to cross 200 meshes.
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, is changed with the tertiary amine oxide surfactant that water is formulated as 30mmol/L Abietyl-containing ternary phenanthrene ring structure
Property liquid, it is spare.
(4) attapulgite modified: to weigh that attapulgite powder 9g obtained by step (1) is placed in 10mL ethyl alcohol and 45mL concentration is
After the tertiary amine oxide modification liquid and attapulgite of 30mmol/L Abietyl-containing ternary phenanthrene ring structure sufficiently shake up, by 40 DEG C of constant temperature
Water-bath is that 200rpm/min vibrates for 24 hours with revolving speed, then adopts the oxidation uncle of Abietyl-containing ternary phenanthrene ring structure wash with distilled water
Amine is attapulgite modified, until cleaning supernatant can't detect abietyl ternary in λ=230nm with ultraviolet-uisible spectrophotometer
After the tertiary amine oxide of phenanthrene ring structure, it is placed in a beaker and carries out vacuum drying drying at 60 DEG C, it is cooling luxuriant and rich with fragrance up to Abietyl-containing ternary
The attapulgite modified finished product of the tertiary amine oxide of ring structure.
Pass through the tertiary amine oxide of natural concave convex rod and Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified
Electron-microscope scanning obtains scanning electron microscope Fig. 1, and wherein Fig. 1 (a) is the scanning electron microscope (SEM) photograph of unmodified attapulgite, concave-convex as seen from the figure
There are apparent laminated structures on stick soil surface；Fig. 1 (b) is scanning electron microscope (SEM) photograph of the invention, and attapulgite is by containing as seen from the figure
The tertiary amine oxide of abietyl ternary phenanthrene ring structure is modified, and the apparent laminated structure of attapulgite's surface thickens, its surface
It is covered by the substance of one layer of cluster together, illustrates that modified natural attapulgite's surface has successfully been loaded containing pine
The tertiary amine oxide surfactant of perfume base ternary phenanthrene ring structure.Contain pine for what natural attapulgite, Examples 1 and 2 were prepared
The oxidation uncle of the surfactant-modified attapulgite of tertiary amine oxide of perfume base ternary phenanthrene ring structure, Abietyl-containing ternary phenanthrene ring structure
Amine is analyzed by infared spectrum, obtains infared spectrum as shown in Fig. 2, further demonstrating modified natural bumps with Fig. 2
Stick soil surface has successfully loaded the tertiary amine oxide surfactant of Abietyl-containing ternary phenanthrene ring structure.
Two, attapulgite modified the answering in absorption humic acid of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention
With
Weigh the attapulgite modified suction of tertiary amine oxide of the Abietyl-containing ternary phenanthrene ring structure of 0.0500g above method preparation
Attached dose, being placed in 50mL concentration is to be divided in 100mg/L humic acid solution with the pH that hydrochloric acid solution and sodium hydroxide solution adjust solution
Not Wei 5.0 and 7.0, solution is placed in 25 ± 1 DEG C, on water-bath constant temperature oscillator oscillation absorption 12h, oscillation rate 150rpm/
Min, the removal rate of humic acid reach 85% or more (as shown in Figure 3), after processing humic acid solution concentration 0~15mg/L it
Between, it is attapulgite modified that the unit adsorbance of humic acid respectively reaches 90 and 85mg humic acid/g.
Embodiment 2
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, includes the following steps:
(1) acid processing attapulgite
Attapulgite is fully ground, is sieved with 100 mesh sieve, the attapulgite powder after sieving is then added to 1mol/L nitre
In acid solution, the mass volume ratio of the attapulgite powder and nitric acid that add is 1:20, ultrasonic reaction at 80 DEG C of reaction temperature
30min, ultrasonic power 30W filter to take precipitating after the reaction was completed, and by washing of precipitate to neutrality, the attapulgite of acidification is made.
(2) fire: by the resulting attapulgite magma of step (1) be centrifuged under 5000rpm speed remove supernatant after in
It is fired in 300 DEG C of nitrogen environments in tube furnace, adjusting heating rate is 50 DEG C/min, and the firing time is set to 1h, is then same as
Room temperature, grind into powder are down in nitrogen environment, and it is spare to cross 200 meshes.
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, is changed with the tertiary amine oxide surfactant that water is formulated as 60mmol/L Abietyl-containing ternary phenanthrene ring structure
Property liquid, it is spare.
(4) attapulgite modified: to weigh that attapulgite powder 9g obtained by step (1) is placed in 10mL ethyl alcohol and 35mL concentration is
After the tertiary amine oxide modification liquid and attapulgite of 60mmol/L Abietyl-containing ternary phenanthrene ring structure sufficiently shake up, by 60 DEG C of constant temperature
Water-bath is that 150rpm/min vibrates 1~2h with revolving speed, then adopts the oxidation of Abietyl-containing ternary phenanthrene ring structure wash with distilled water
Tertiary-amine modified attapulgite, until cleaning supernatant can't detect abietyl three in λ=230nm with ultraviolet-uisible spectrophotometer
After the tertiary amine oxide of first phenanthrene ring structure, it is placed in a beaker and carries out vacuum drying drying at 80 DEG C, it is cooling up to Abietyl-containing ternary
The attapulgite modified finished product of the tertiary amine oxide of phenanthrene ring structure.
Two, attapulgite modified the answering in absorption humic acid of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention
With
(1) the modified attapulgite earth adsorbing for weighing the preparation of the 0.0500g above method, being placed in 50mL concentration is 100mg/L
In humic acid solution, pH value of solution=6.0 are adjusted with sodium hydroxide solution and hydrochloric acid solution, solution are placed in 25 ± 1 DEG C, water-bath is permanent
It is vibrated on warm oscillator for 24 hours, oscillation rate 200rpm/min, the removal rate of humic acid reaches 85% or more, rotten after processing
Acid solutions are grown between 1~15mg/L, and it is attapulgite modified that the unit adsorbance of humic acid reaches 85mg humic acid/g.
Embodiment 3
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, including walk as follows
It is rapid:
(1) acid processing attapulgite:
Attapulgite is fully ground, 200 meshes is crossed, the attapulgite powder after sieving is then added to 4mol/L sulphur
In acid solution, the quality of the attapulgite powder added and the mass volume ratio of hydrochloric acid are 1:15, ultrasound at 70 DEG C of reaction temperature
20min is reacted, ultrasonic power 60W filters to take precipitating after the reaction was completed, and by washing of precipitate to neutrality, the bumps of acidification are made
Stick soil.
(2) fire: by the resulting attapulgite magma of step (1) be centrifuged under 5000rpm speed remove supernatant after in
It is fired in 350 DEG C of nitrogen environments in tube furnace, adjusting heating rate is 50 DEG C/min, and the firing time is set to 1h, is then same as
Room temperature, grind into powder are down in nitrogen environment, and it is spare to cross 200 meshes；
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, the tertiary amine oxide surfactant of 100mmol/L Abietyl-containing ternary phenanthrene ring structure is formulated as with water
Modification liquid, it is spare.
(4) attapulgite modified: to weigh that attapulgite powder 9g obtained by step (1) is placed in 10mL ethyl alcohol and 20mL concentration is
After the tertiary amine oxide modification liquid and attapulgite of 100mmol/L Abietyl-containing ternary phenanthrene ring structure sufficiently shake up, by 15 DEG C of perseverances
Tepidarium is that 250rpm/min vibrates 16h with revolving speed, then adopts the oxidation of Abietyl-containing ternary phenanthrene ring structure wash with distilled water
Tertiary-amine modified attapulgite, until cleaning supernatant can't detect abietyl three in λ=230nm with ultraviolet-uisible spectrophotometer
After the tertiary amine oxide of first phenanthrene ring structure, it is placed in a beaker, cooling to obtain the final product Abietyl-containing ternary dry dry in 70 DEG C of progress vacuum dryings
The attapulgite modified finished product of the tertiary amine oxide of phenanthrene ring structure.
Two, the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified is adsorbing in Congo red
Using
(1) the modified attapulgite earth adsorbing for weighing the preparation of the 0.1000g above method, being placed in 50mL concentration is 100mg/L
In Congo red solution, pH value of solution=6.0 are adjusted with sodium hydroxide solution and hydrochloric acid solution.Solution is placed in 20 ± 1 DEG C, constant temperature water bath
10h, oscillation rate 200rpm/min are vibrated on oscillator, Congo red removal rate reached for 95% or more (as shown in Figure 3),
Congo red solution concentration is between 2~3mg/L after processing, Congo red unit adsorbance reach 120mg it is Congo red/g is modified concave-convex
Stick soil.
Embodiment 4
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, includes the following steps:
(1) acid processing attapulgite:
Attapulgite is fully ground, 200 meshes is crossed, the attapulgite powder after sieving is then added to 3mol/L salt
In acid solution, the mass volume ratio of the attapulgite powder and hydrochloric acid that add is 1:12, ultrasonic disperse at 65 DEG C of reaction temperature
30min, ultrasonic power 40W filter to take precipitating after the reaction was completed, and by washing of precipitate to neutrality, the attapulgite of acidification is made.
(2) fire: by the resulting attapulgite magma of step (1) be centrifuged under 5000rpm speed remove supernatant after in
It is fired in 400 DEG C of nitrogen environments in tube furnace, adjusting heating rate is 50 DEG C/min, and the firing time is set to 1h, is then same as
Room temperature, grind into powder are down in nitrogen environment, and it is spare to cross 200 meshes.
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, is changed with the tertiary amine oxide surfactant that water is formulated as 70mmol/L Abietyl-containing ternary phenanthrene ring structure
Property liquid, it is spare.
(4) attapulgite modified: to weigh that attapulgite powder 9g obtained by step (1) is placed in 10mL ethyl alcohol and 45mL concentration is
After the tertiary amine oxide modification liquid and attapulgite of 70mmol/L Abietyl-containing ternary phenanthrene ring structure sufficiently shake up, by 40 DEG C of constant temperature
Water-bath is that 200rpm/min vibrates 20h with revolving speed, then adopts the oxidation uncle of Abietyl-containing ternary phenanthrene ring structure wash with distilled water
Amine is attapulgite modified, until cleaning supernatant can't detect abietyl ternary in λ=230nm with ultraviolet-uisible spectrophotometer
After the tertiary amine oxide of phenanthrene ring structure, it is placed in a beaker and carries out vacuum drying drying at 60 DEG C, it is cooling luxuriant and rich with fragrance up to Abietyl-containing ternary
The attapulgite modified finished product of the tertiary amine oxide of ring structure.
Two, attapulgite modified the answering in absorption fluorine ion of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention
The modified attapulgite earth adsorbing that the preparation of the 0.0500g above method is weighed with (1), being placed in 50mL concentration is that 20mg/L copper ion is molten
In liquid, pH value of solution=6.0 are adjusted with sodium hydroxide solution and hydrochloric acid solution.Solution is placed in 40 ± 1 DEG C, on water-bath constant temperature oscillator
Oscillation 20 hours, oscillation rate 100rpm/min, the removal rate of fluorine ion reaches 90.0% or more (as shown in Figure 3), processing
For fluorinion concentration between 2~3mg/L, it is attapulgite modified that the unit adsorbance of fluorine ion reaches 18mg fluorine ion/g afterwards.
Embodiment 5
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, includes the following steps:
(1) acid processing attapulgite:
Attapulgite is fully ground, 160 meshes is crossed, the attapulgite powder after sieving is then added to 2mol/L salt
In acid solution, the quality of the attapulgite powder added and the mass volume ratio of hydrochloric acid are 1:10, are stirred at 60 DEG C of reaction temperature
3h is reacted, and is placed on ultrasound 25min in ultrasonic generator, adjusting generator power is 50W.Precipitating is filtered to take, precipitating is washed
It washs to neutrality, the attapulgite of acidification is made.
(2) fire: by the resulting attapulgite magma of step (1) be centrifuged under 5000rpm speed remove supernatant after in
It is fired in 400 DEG C of nitrogen environments in tube furnace, adjusting heating rate is 50 DEG C/min, and the firing time is set to 2h, is then same as
Room temperature, grind into powder are down in nitrogen environment, and it is spare to cross 200 meshes；
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxygen of Abietyl-containing ternary phenanthrene ring structure is weighed
Change tertiary amine surfactant, is changed with the tertiary amine oxide surfactant that water is formulated as 10mmol/L Abietyl-containing ternary phenanthrene ring structure
Property liquid, it is spare.
(4) attapulgite modified: to weigh that attapulgite powder 9g obtained by step (1) is placed in 10mL ethyl alcohol and 80mL concentration is
After the tertiary amine oxide modification liquid and attapulgite of 10mmol/L Abietyl-containing ternary phenanthrene ring structure sufficiently shake up, by 35 DEG C of constant temperature
Water-bath is that 200rpm/min vibrates 10h with revolving speed, then adopts the oxidation uncle of Abietyl-containing ternary phenanthrene ring structure wash with distilled water
Amine is attapulgite modified, until cleaning supernatant can't detect abietyl ternary in λ=230nm with ultraviolet-uisible spectrophotometer
After the tertiary amine oxide of phenanthrene ring structure, it is placed in a beaker and carries out vacuum drying drying at 65 DEG C, it is cooling luxuriant and rich with fragrance up to Abietyl-containing ternary
The attapulgite modified finished product of the tertiary amine oxide of ring structure.
Two, the attapulgite modified fluorine ion in absorption water of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention
Application
(1) the modified attapulgite earth adsorbing for weighing the preparation of the 0.1000g above method, being placed in 50mL concentration is 30mg/L fluorine
In solion, pH value of solution=8.0 are adjusted with sodium hydroxide solution and hydrochloric acid solution.Solution is placed in 30 ± 1 DEG C, constant temperature water bath vibration
It swings and is vibrated 1-2 hours, oscillation rate 100rpm/min on device, the removal rate of fluorine ion reaches 92.0% or more, fluorine after processing
For ion concentration between 2~3mg/L, it is attapulgite modified that the unit adsorbance of fluorine ion reaches 12mg fluorine ion/g.
Embodiment 6
One, the attapulgite modified preparation method of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure, includes the following steps:
(1) acid processing attapulgite:
Attapulgite is fully ground, 200 meshes is crossed, the attapulgite powder after sieving is then added to 2mol/L salt
In acid solution, the mass volume ratio of the quality of the attapulgite powder added and hydrochloric acid solution is 1:10, at 60 DEG C of reaction temperature
It is stirred to react 3h, and is placed on ultrasound 30min in ultrasonic generator, adjusting generator power is 30W.Precipitating is filtered to take, will be sunk
Washing form sediment to neutrality, the attapulgite of acidification is made.
(2) fire: by the resulting attapulgite magma of step (1) be centrifuged under 5000rpm speed remove supernatant after in
It is fired in 400 DEG C of nitrogen environments in tube furnace, adjusting heating rate is 50 DEG C/min, and the firing time is set to 1.5h, then together
Room temperature, grind into powder are down in nitrogen environment, and it is spare to cross 200 meshes.
(3) attapulgite modified
It weighs the attapulgite 9g that the ground rear partial size of step (2) is 200 purposes to be placed in conical flask, be pipetted with pipette
After 55mL concentration sufficiently shakes up for the tertiary amine oxide modification liquid and attapulgite of 30mmol/L Abietyl-containing ternary phenanthrene ring structure, warp
It is that 200rpm/min vibrates 12h that 50 DEG C of waters bath with thermostatic control, which are crossed, with revolving speed, is then divided using until cleaning supernatant with UV, visible light
Photometer is placed in a beaker and carries out very at 60 DEG C after the tertiary amine oxide that λ=230nm can't detect abietyl ternary phenanthrene ring structure
The dry drying of sky, the cooling attapulgite modified finished product of tertiary amine oxide up to Abietyl-containing ternary phenanthrene ring structure.
Two, the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure of the invention is attapulgite modified is adsorbing in Congo red
Using
(1) the modified attapulgite earth adsorbing for weighing the preparation of the 0.0500g above method, being placed in 50ml concentration is 100mg/L
In Congo red solution, pH value of solution=9.0 are adjusted with nitric acid solution.Solution is placed in 50 DEG C, and it is small that 15 are vibrated on water-bath constant temperature oscillator
When, oscillation rate 150rpm/min, Congo red removal rate reaches 95% or more, and Congo red solution concentration is 2 after processing
Between~20mg/L, Congo red unit adsorbance reach 80mg it is Congo red/g is attapulgite modified.
Claims (7)
1. the preparation method of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure, it is characterised in that:
This method comprises the following steps:
(1) pretreatment of attapulgite: attapulgite is ground up, sieved, then is added it in acid solution, at 60~80 DEG C,
Ultrasonic disperse reacts 15min~30min, filters to take precipitating, and by washing of precipitate to neutrality, the attapulgite of acidification is made；It is described
Acid solution is sulfuric acid, nitric acid, and concentration is 1~4mol/L, and ultrasonic generator power is 30~60W；
(2) it fires: adding water to be prepared into magma the attapulgite that step (1) obtains, be put into tube furnace after centrifugation removal supernatant
In, high temperature fires 1-2h at 300~400 DEG C, is then down to room temperature, is ground up, sieved, obtains attapulgite powder, spare；
(3) preparation of the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure: the oxidation uncle of Abietyl-containing ternary phenanthrene ring structure is weighed
Amine surfactant is formulated as the tertiary amine oxide surface of 10mmol/L~100mmol/L Abietyl-containing ternary phenanthrene ring structure with water
Activating agent modification liquid, it is spare；
(4) attapulgite modified: by the tertiary amine oxide surfactant of attapulgite powder and Abietyl-containing ternary phenanthrene ring structure
Modification liquid is that water-bath is vibrated after 1:2~9g/mL is mixed according to mass volume ratio, and washing is dried to get Abietyl-containing ternary is arrived
The oxidation of phenanthrene ring structure is tertiary attapulgite modified.
2. the system of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure according to claim 1
Preparation Method, it is characterised in that: using the tertiary amine oxide of Abietyl-containing ternary phenanthrene ring structure as modifying agent, the Abietyl-containing three
The general structure of the tertiary amine oxide of first phenanthrene ring structure are as follows:
Wherein, R isR1And R2Respectively C1~C2Alkyl.
3. the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure according to claim 1 or 2
Preparation method, it is characterised in that: the tertiary amine oxide of the Abietyl-containing ternary phenanthrene ring structure be N, N-dimethyl dehydrogenation fir base
Amine oxide, structural formula are as follows:
4. the system of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure according to claim 1
Preparation Method, it is characterised in that: the acid adding amount of the attapulgite of the step (1) is that 10~20mL is added in every gram of attapulgite
Acid.
5. the system of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure according to claim 1
Preparation Method, it is characterised in that: step (4) the water-bath vibration temperature is 15~60 DEG C, and speed is 150~250rpm, time 1
~for 24 hours, the drying temperature is 60~80 DEG C.
6. the tertiary amine oxide of the resulting Abietyl-containing ternary phenanthrene ring structure of method a method as claimed in any one of claims 1 to 5 is modified concave-convex
The application of stick earth adsorbing, it is characterised in that: the tertiary amine oxide of the Abietyl-containing ternary phenanthrene ring structure is attapulgite modified
Humic acid in the adsorbable water of adsorbent, fluorine ion is Congo red, method are as follows:
(1) by the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure and pollutant water sample according to quality
Than being added in pollutant water sample for 0.4-2:1, pollutant water sample concentration range is 1~100mg/L；
(2) pH value of water sample being adjusted as 5~9 with acid or aqueous slkali, temperature controls 20~50 DEG C, and adsorption time is 1~24 hour,
100~200rpm is vibrated, the concentration of pollutant in separation determination supernatant, according to the concentration difference of absorption front and back water pollutant,
Determine adsorbent to the adsorption effect of water pollutant.
7. the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure according to claim 6 is answered
It is sodium hydroxide or potassium hydroxide with, it is characterised in that: the alkali, the acid is hydrochloric acid, sulfuric acid, any in nitric acid
Kind.
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| CN102247799A (en) * | 2011-07-12 | 2011-11-23 | 陕西科技大学 | Method for removing humic acid in water by utilizing surfactant modified attapulgite |
| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
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| CN102247799A (en) * | 2011-07-12 | 2011-11-23 | 陕西科技大学 | Method for removing humic acid in water by utilizing surfactant modified attapulgite |
| CN103086927A (en) * | 2012-12-06 | 2013-05-08 | 广西民族大学 | Tertiary amine oxide with rosinyl three-membered phenanthrene ring structure and preparation method of tertiary amine oxide |
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| "Adsorption of the anionic dye Congo red from aqueous solution onto natural zeolites modified with N,N-dimethyl dehydroabietylamine oxide";Shaogang Liu et al.;《Chemical Engineering Journal》;20140318;第248卷;第135-144页 |
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