CN109692650A - The adsorbent and preparation method thereof of arsenite ion in efficient removal water - Google Patents
The adsorbent and preparation method thereof of arsenite ion in efficient removal water Download PDFInfo
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- CN109692650A CN109692650A CN201710982641.5A CN201710982641A CN109692650A CN 109692650 A CN109692650 A CN 109692650A CN 201710982641 A CN201710982641 A CN 201710982641A CN 109692650 A CN109692650 A CN 109692650A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The present invention is the adsorbent and preparation method thereof of arsenite ion in efficient removal water, is related to a kind of adsorbent and preparation method thereof of arsenite ion in efficient absorption water.Mainly solve the problems, such as that arsenite ion removal efficiency is not high in waste water solution existing in the prior art.The metal composite Cu that the present invention is prepared by using the method for co-precipitation plus hydro-thermal processxMn6‑xLa2(OH)18.4H2O or CuxMn6‑xFe2(OH)18.4H2O, wherein x=2~5 are that the technical solution of adsorbent preferably solves the problems, such as this.The adsorbent of the method for the present invention preparation has the characteristics that arsenous anion ion efficiency is high in removing water, can be used for environment protection field.
Description
Technical field
The present invention relates to a kind of adsorbents and preparation method thereof of arsenite ion in efficient removal water.
Background technique
Arsenic has attracted people's attention to the harm of environment, the weathering of the pollution of arsenic mainly from the geologic body containing arsenic.Certainly
The pollution of arsenic is widely present in right boundary.Constantly lead to the report being poisoned about arsenic polluted water is drunk all over the world, comprising: sub-
The ground such as India, Bangladesh, Vietnam, Thailand, the Taiwan of China, the Xinjiang in continent.Arsenic pollution is mainly carcinogenic to the harm of human body
And teratogenesis, wherein trivalent arsenic toxicity is most strong.At present both at home and abroad mainly using chemisorption, neutralization precipitation, flocculation sedimentation and
The methods of reverse osmosis improvement arsenic pollution.These methods respectively have advantage and disadvantage, and over all, absorption-deposition method is easy to operate, cost
It is lower, but still have much room for improvement in terms for the treatment of effect and waste residue disposition；And the equipment investment of hyperfiltration is big, operating cost is high,
For developing countries and regions, the especially outlying district of inhabitants live's dispersion, is administered and had using absorption-deposition method
There is realistic meaning.
CN103442801A disclose it is a kind of for adsorbing the iron coordination polymer of arsenate and phosphate radical, including by rich horse
Acid sodium aqueous solution and ferric chloride in aqueous solution are mixed to form mixture, and obtain from mixture as the non-of sediment formation
The method of the iron coordination polymer of crystalline compound form.The iron coordination polymer can be used to combine pollutant, Tathagata
From the arsenate and phosphate radical in water.
CN1835803 discloses a kind of ion-exchanger for being used to prepare and being loaded with carboxyl containing iron oxide/FeOOH
Method, which is characterized in that make carboxylic bead ion-exchanger contacted in water slurry with iron-(III)-salt or
A ') make the crosslinked polystyrene bead particle/polymer of aminomethylation in water slurry with iron-(III)-salt and and chloroethene
Acid contact and b) will be by step a) or a ' by the way that alkali metal hydroxide or alkaline earth metal hydroxide is added) resulting suspension
Being adjusted to pH value is 3-14, and separating obtained containing iron oxide/FeOOH ion-exchanger by known method.The present invention
Further relate to the ion-exchanger itself and its application in absorption heavy metal, especially arsenic.
CN105879836A discloses a kind of method of modifying for enhancing granular activated carbon arsenic-adsorbing ability and modified particles are living
The application of property charcoal, method includes the following steps: the 1) purification of granular activated carbon: granular activated carbon is rinsed with deionized water,
Remove upper layer impurity, ash content and supernatant after static, it is dry；2) granular activated carbon for having purified step 1) is added to iron ion
In solution, stands or stir, filter out solid；3) solid that step 2) filters out is cleaned with deionized water, it is dry.Modified activated carbon
Application be the As (III) and As (V) that can be removed in solution, pass through it is a kind of enhancing granular activated carbon arsenic-adsorbing ability modification
Method, which prepares a kind of pair of arsenic, adsorbent material excellent adsorption effect, at low cost, and water body arsenic pollution is controlled and purified.
But above-mentioned technological invention has deficiency, is difficult as adsorbent prepares the problems such as complicated or adsorption efficiency is not high in reality
It is applied in the case of border, in view of the above deficiencies, proposes that preparation is simple, the arsenous in the high new adsorbent removing waste water of adsorption efficiency
Acid ion.
Summary of the invention
The first technical problem to be solved by the present invention is to overcome in industrial wastewater existing in the prior art
The not high problem of arsenite ion removal efficiency provides a kind of new adsorbent for adsorbing arsenite ion in water.The suction
Attached dose has the characteristics that arsenous anion ion efficiency is high in removing water.
The second technical problem to be solved by the present invention is to provide the corresponding absorption of one of one kind and solution technical problem
The preparation method of the adsorbent of arsenite ion in water.
The third technical problem to be solved by the present invention is to provide the corresponding absorption of one of one kind and solution technical problem
The application method of the adsorbent of arsenite ion in water.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: arsenous anion in a kind of absorption water
The adsorbent of ion, composition include CuxMn6-xLa2(OH)18.4H2O or CuxMn6-xFe2(OH)18.4H2O, wherein x=2~5.
In above-mentioned technical proposal, the adsorbent has hydrotalcite-like compound.Preferably, the hydrotalcite-like compound is nitre
Acid group intercalation.
In above-mentioned technical proposal, the crystal grain of the adsorbent is less than 500nm.Preferably, 100-500nm.
In above-mentioned technical proposal, the CuxMn6-xLa2(OH)18.4H2O or CuxMn6-xFe2(OH)18.4H2O, wherein x is excellent
Select 3~5.
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: arsenite ion in absorption water
Adsorbent preparation method, comprising the following steps:
1. mantoquita, manganese salt, lanthanum salt or mantoquita, manganese salt, molysite is soluble in water, it is denoted as solution A；
2. alkali source is soluble in water, it is denoted as solution B；
3. solution B is added in solution A, pH value of solution is 6~11 to stop, stirring, solution is poured into crystallizing kettle in 60~
150 DEG C of 1~36h of hydro-thermal process, be filtered, washed, in dry to get adsorbent product.
In above-mentioned technical proposal, the mantoquita is at least one of copper nitrate, copper sulphate or copper chloride.
In above-mentioned technical proposal, the manganese salt is at least one of manganese acetate, manganese nitrate or manganese chloride.
In above-mentioned technical proposal, the lanthanum salt is at least one of lanthanum nitrate or lanthanum chloride.
In above-mentioned technical proposal, the molysite is at least one of ferric nitrate or iron chloride.
In above-mentioned technical proposal, the molar ratio of the mantoquita and manganese salt is 1:2~5:1, and preferred molar ratio is 1:1~5:1.
In above-mentioned technical proposal, the alkali source is at least one of sodium hydroxide, potassium hydroxide or ammonium hydroxide.
In above-mentioned technical proposal, mixed solution pH value 6.5~9.5 is controlled.
In above-mentioned technical proposal, hydro-thermal process temperature is 65~120 DEG C, 3~12h of time.It is further preferable that 90-120
DEG C, time 3-5h.To obtain the houghite crystal grain less than 500 nanometers, adsorption efficiency is helped to improve.
In above-mentioned technical proposal, the drying condition is 60-150 DEG C, 1-24h.
In above-mentioned technical proposal, the step is stopped 3. by solution B fast drop into solution A, to solution ph to 6~11
Only.
To solve above-mentioned technical problem three, The technical solution adopted by the invention is as follows: arsenous anion in a kind of absorption water
Adsorbent is mixed with the aqueous solution containing arsenite ion at 5~35 DEG C and mixes slowly 10~30min by the method for ion,
Arsenite ion in water can be removed.
In above-mentioned technical proposal, the concentration ratio of arsenite ion is 5~40:1 in adsorbent and water.
Adsorbent provided by the invention can arsenite ion in efficient absorption water, can be used for environment protection field.
Using technical solution of the present invention, with the metal composite Cu being co-precipitated plus prepared by hydro-thermal treatment methodxMn6-xLa2
(OH)18.4H2O or CuxMn6-xFe2(OH)18.4H2O is active component, and since it is with layer structure, and interlayer can accommodate friendship
Anion is changed, therefore shows the good adsorption properties to anion.The metal composite of copper, manganese, lanthanum or copper, manganese, iron composition
In object, copper, manganese have synergistic effect under certain proportion, have compared with other adsorbent materials more preferably to arsenite ion
Adsorption capacity, be embodied in that adsorbent amount is few, and adsorption rate is fast, 10~30min, can remove in water arsenous anion from
It is high-efficient to take off arsenous anion for son.By controlling the materials synthesis technological parameter, the optimization such as crystal form, pore structure can be effectively controlled
Removal efficiency achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
By copper nitrate, manganese nitrate and ferric nitrate, 4.5:1.5:2 is dissolved in deionized water in molar ratio, stir at room temperature to
Clarification, is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is fast
Speed is added dropwise in solution A, is stopped to solution ph to 8.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermals
Handle 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product A.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent A, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 2]
By copper nitrate, manganese nitrate and ferric nitrate, 3:3:2 is dissolved in deionized water in molar ratio, is stirred at room temperature to clear
Clearly, it is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is quick
It is added dropwise in solution A, stops to solution ph to 8.0, continue to stir 2h, solution is poured into crystallizing kettle at 105 DEG C of hydro-thermals
Manage 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product B.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent B, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 3]
By copper nitrate, manganese nitrate and lanthanum nitrate, 4.5:1.5:2 is dissolved in deionized water in molar ratio, stir at room temperature to
Clarification, is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is fast
Speed is added dropwise in solution A, is stopped to solution ph to 8.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermals
Handle 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product C.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent C, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 4]
By copper nitrate, manganese nitrate and lanthanum nitrate, 3:3:2 is dissolved in deionized water in molar ratio, is stirred at room temperature to clear
Clearly, it is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is quick
It is added dropwise in solution A, stops to solution ph to 8.0, continue to stir 2h, solution is poured into crystallizing kettle at 105 DEG C of hydro-thermals
Manage 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product D.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent D, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 5]
By copper nitrate, manganese nitrate and ferric nitrate, 4.5:1.5:2 is dissolved in deionized water in molar ratio, stir at room temperature to
Clarification, is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is fast
Speed is added dropwise in solution A, is stopped to solution ph to 9.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermals
Handle 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product E.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent E, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 6]
By copper nitrate, manganese nitrate and ferric nitrate, 4.5:1.5:2 is dissolved in deionized water in molar ratio, stir at room temperature to
Clarification, is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is fast
Speed is added dropwise in solution A, is stopped to solution ph to 7.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermals
Handle 5h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product F.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent F, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[embodiment 7]
By copper nitrate, manganese nitrate and ferric nitrate, 4.5:1.5:2 is dissolved in deionized water in molar ratio, stir at room temperature to
Clarification, is denoted as solution A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；Solution B is fast
Speed is added dropwise in solution A, is stopped to solution ph to 8.0, continues to stir 2h, solution is poured into crystallizing kettle at 70 DEG C of hydro-thermals
Manage 10h, be filtered, washed, in 100 DEG C of dry 10h up to adsorbent product G.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent G, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[comparative example 1]
By copper nitrate and ferric nitrate, 6:2 is dissolved in deionized water in molar ratio, is stirred to clarify at room temperature, and solution is denoted as
A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；By solution B fast drop to solution A
In, stop to solution ph to 8.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermal process 5h, filters, wash
Wash, in 100 DEG C of dry 10h up to adsorbent product.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
[comparative example 2]
By manganese nitrate and ferric nitrate, 6:2 is dissolved in deionized water in molar ratio, is stirred to clarify at room temperature, and solution is denoted as
A；Sodium hydroxide is dissolved in deionized water, is stirred to clarify at room temperature, solution B is denoted as；By solution B fast drop to solution A
In, stop to solution ph to 8.0, continues to stir 2h, solution is poured into crystallizing kettle in 105 DEG C of hydro-thermal process 5h, filters, wash
Wash, in 100 DEG C of dry 10h up to adsorbent product.
In the 1L aqueous solution that the arsenite ion containing 500mg is added in 20 DEG C in 12g adsorbent, detected after stirring 20min
As a result arsenous anion ion concentration in water is listed in table 1.
Table 1
[embodiment 8~10]
Adsorbent A is subjected to arsenous anion ion core in removing water under conditions of different amounts, temperature, mixing time
It tests, is as a result listed in table 2.
Table 2
Claims (10)
1. the adsorbent of arsenite ion, composition include Cu in a kind of absorption waterxMn6-xLa2(OH)18·4H2O or
CuxMn6-xFe2(OH)18·4H2O, wherein x=2~5.
2. the preparation method of the adsorbent of arsenite ion in absorption water described in claim 1, comprising the following steps:
1. mantoquita, manganese salt, lanthanum salt or mantoquita, manganese salt, molysite is soluble in water, it is denoted as solution A；
2. alkali source is soluble in water, it is denoted as solution B；
3. solution B is added in solution A, solution ph is 6~11, and stirring pours into solution in crystallizing kettle in 60~150 DEG C of water
It is heat-treated 1~36h, is filtered, washed, dries to get adsorbent product.
3. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that institute
The mantoquita stated is at least one of copper nitrate, copper sulphate or copper chloride.
4. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that institute
The manganese salt stated is at least one of manganese acetate, manganese nitrate or manganese chloride.
5. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that institute
The lanthanum salt stated is at least one of lanthanum nitrate or lanthanum chloride；Molysite is at least one of ferric nitrate or iron chloride.
6. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that institute
The alkali source stated is at least one of sodium hydroxide, potassium hydroxide or ammonium hydroxide.
7. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that control
Mixed solution pH value 6.5~9.5 processed.
8. the preparation method of the adsorbent of arsenite ion in absorption water according to claim 2, it is characterised in that water
Heat treatment temperature is 65~120 DEG C, 3~12h of time.
9. a kind of method of arsenite ion in absorption water, by adsorbent and the aqueous solution containing arsenite ion 5~
35 DEG C of 10~30min of mixing, can remove arsenite ion in water.
10. the method for arsenite ion in absorption water according to claim 9, it is characterised in that adsorbent and the water Central Asia
The concentration ratio of arsenic acid radical ion is 5~40:1.
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| CN114515562A (en) * | 2020-11-18 | 2022-05-20 | 中国石油化工股份有限公司 | Adsorbent for removing benzene, toluene and xylene in fluid and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112675806A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Adsorbent for removing carbon monoxide in gas, preparation method and application |
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| CN110947395A (en) * | 2019-12-03 | 2020-04-03 | 中化环境控股有限公司 | Preparation method of Fenton-like catalytic material and sewage treatment method |
| CN114515562A (en) * | 2020-11-18 | 2022-05-20 | 中国石油化工股份有限公司 | Adsorbent for removing benzene, toluene and xylene in fluid and preparation method and application thereof |
| CN114515562B (en) * | 2020-11-18 | 2023-09-29 | 中国石油化工股份有限公司 | Adsorbent for removing benzene, toluene and xylene in fluid, and preparation method and application thereof |
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