CN109251331A - A kind of Polyamine capsule dispersion liquid removing underwater gold category ion - Google Patents
A kind of Polyamine capsule dispersion liquid removing underwater gold category ion Download PDFInfo
- Publication number
- CN109251331A CN109251331A CN201811090700.9A CN201811090700A CN109251331A CN 109251331 A CN109251331 A CN 109251331A CN 201811090700 A CN201811090700 A CN 201811090700A CN 109251331 A CN109251331 A CN 109251331A
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- CN
- China
- Prior art keywords
- metal ion
- dispersion liquid
- solution
- capsule
- piperazine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
A kind of Polyamine capsule dispersion liquid removing underwater gold category ion, is related to the complexometric extraction of polymer and metal ion, belongs to water process absorption complexing field of functional materials.Lower edge four replaces calixarenes acyl chlorides and piperazine to carry out polycondensation, directly obtains submicron order capsule dispersant liquid of poly- (calixarenes-piperazine) amide as wall material.The aqueous solution of metal ion is added on this dispersion liquid, supermolecule crosslink complex can be formed at phase interface by the complexing of capsule wall and metal, metal ion is fixed on phase interface region, realizes the removing of metal ion in water phase.After removing processed water, hydrochloric acid is added into the organic liquid containing complex compound, complex compound is dissociated, Metal ion release to aqueous hydrochloric acid solution phase, and discontinuous organic phase restores to original state, realizes that the recycling of dispersion liquid uses.
Description
Technical field
The present invention relates to a kind of Polyamine capsule dispersion liquids for removing underwater gold category ion, in particular to polymer and metal
The complexometric extraction of ion belongs to water process absorption complexing field of functional materials.
Background technique
Heavy metal is industrially widely used, and is inevitably dissolved in water, thus is entered in natural water, to ring
Border, ecology and human health damage.On the one hand the recycling of Heavy Metals in Waters ion can effectively prevent environmental pollution, separately
On the one hand can also waste utilization, turn waste into wealth, save the cost.Therefore, there is heavy metal ions removal in water to recycle ability for exploitation
Material, existing social value has an economic benefit again.Some high polymers have special binding site and complexing power, can pass through
Noncovalent interaction and metal ion form co-ordination complex, to remove it from water in conjunction with the metal ion in water.
The high-polymer molecule binding site is more, with the heavy metal ion effect with variable valence, can form supermolecule cross-linked structure,
It is precipitated from solution, generates insoluble complex compound.By shirtsleeve operation, such as filters, these solid matters can be removed.These
Processing of the solid matter through acid or aqueous slkali, dissociates, utilizes by polymer recovery and again.Thus using immiscible with water
The polymer substance of stable dispersion in liquid is complexed with the harmful heavy metal ions in water, make its there is precipitating in phase interface and
Capture heavy metal ion simultaneously recycles, and is a kind of convenient, environmentally friendly extraction recovery method.
This patent is by preparing polyamide glue to tert-butyl p tertButylcalixarene-O- tetraethyl acyl chlorides acyl chlorides (I) and piperazine polycondensation
Capsule organic dispersions.In a variety of and immiscible organic solvent of water parents' self assembly can occur for I, form the poly- of certain shapes
Collective.It is spontaneous to obtain using polyamide as cyst wall without stirring due to the presence of aggregation when polycondensation reaction occurs with piperazine
Microcapsules, size may be homogenously dispersed in solvent in 500nm or so, do not precipitate, and form uniform dispersion.Capsule
It is formed unrelated with piperazine solution.Piperazine can be aqueous solution, be also possible to the solution that solvent identical with I solution is prepared.Due to
The wall material of microcapsules is the polyamide containing calixarenes, can be with the heavy metal ion or rare earth that are dissolved in water by interfacial effect
Metal ion generates metal-organic complex effect, forms the crosslink complex by supermolecular mechanism connection, is precipitated from liquid
And it floats at phase interface.To remove underwater gold category ion, it is purified water phase.After removing water phase, to precipitate and organic
It is added to hydrochloric acid, complexing is destroyed and is recycled by Metal ion release into acid.Polyamine capsule is also dispersed to again
It in organic liquid, returns to original state dispersion liquid and is regenerated, reuse.
Summary of the invention
The meaning of the invention is to prepare a kind of polyamide glue for removing underwater gold category ion in view of the deficiencies of the prior art
Capsule dispersion liquid.
Technical solution of the present invention is summarized as follows:
A kind of Polyamine capsule dispersion liquid removing underwater gold category ion, it is characterized in that with poly- (calixarenes-piperazine) amide
The dispersion liquid that submicron order capsule as wall material is formed in organic solvent；The water-soluble of metal ion is added to this dispersion liquid
Liquid forms supermolecule linked solid with capsule wall and metal complex, metal ion is fixed on to the interface zone of two liquid phases, realizes
The removing of underwater gold category ion；After removing water, hydrochloric acid is added to remaining system, dissociates complex compound, Metal ion release to hydrochloric acid
Water-soluble liquid phase, and organic dispersions restore to original state.
The preparation method of capsule dispersant liquid is added drop-wise to piperazine solution to tert-butyl p tertButylcalixarene-O- tetraethyl acyl chlorides
In the organic solution of acyl chlorides (I), I polymerize to form submicron order capsule in the solution with piperazine, obtains dispersion liquid；The structural formula of I
It is as follows:
Solvent used in the organic solution of I is that one or more of methylene chloride, chloroform, carbon tetrachloride are mixed
It closes；Piperazine solution can be aqueous solution, be also possible to the organic solution with I same solvent.
Piperazine concentration is 2 × 10-2Mol/L~10-1mol/L；The concentration of I is 2~7 × 10-3mol/L；Removable metal
Ion includes heavy metal ion Hg (II), Pb (II), Cu (II) and rare earth ion Ce (III) and La (III).
Embodiment
The preparation of dispersion liquid
Embodiment 1
It is 3 × 10 to 5mL concentration-32.75mL 3.48 × 10 is added dropwise in the dichloromethane solution of the I of mol/L-2Mol/L piperazine
The dichloromethane solution of piperazine reacts 60s under static condition, and deionized water 10mL is added on dispersion liquid, 12h is stood, to go
Except by-product HCl.Water layer is removed, Polyamine capsule methylene chloride dispersion liquid is made.
Embodiment 2
It is 2 × 10 to 5mL concentration-35mL 4 × 10 is added dropwise on the chloroform soln of the I of mol/L-2The water of mol/L piperazine
Solution reacts 60s under static condition, removes water layer, and Polyamine capsule chloroform dispersion liquid is made.
Embodiment 3
It is 7 × 10 to 5mL concentration-37.15mL 3.13 × 10 is added dropwise in the carbon tetrachloride solution of the I of mol/L-2Mol/L piperazine
The carbon tetrachloride solution of piperazine reacts 60s under static condition.Deionized water 10mL is added on dispersion liquid, 12h is stood, to go
Except by-product HCl.Water layer is removed, Polyamine capsule carbon tetrachloride dispersion liquid is made.
Embodiment 4
It is 5 × 10 to 5mL concentration-3The methylene chloride of the I of mol/L-chloroform mixed solution and dripping 10mL 10- 2Mol/L piperazine aqueous solution reacts 60s under stirring, removes water layer, and-three chloromethane of Polyamine capsule methylene chloride is made
Alkane mixed dispersion liquid.
The complexing of metal ion is enriched with and recycling
Embodiment 5
By the Pb (NO of 10mL 0.56mg/L3)2Aqueous solution is poured into 10mL methylene chloride capsules disperse described in embodiment 1
On liquid, stands at room temperature for 24 hours, occur white fluffy solid substance at phase interface.Remove upper layer aqueous solution, inductively coupled plasma
Emission spectrum (ICP-OES) testing result shows, Pb2+Concentration is lower than 0.01mg/L.It is added on the flocculent substance of organic phase
10mL concentration is the hydrochloric acid of 5wt%, is stood for 24 hours.Detect Pb in hydrochloric acid phase2+Concentration is 0.48mg/L, Pb2+The rate of recovery be
85.7%.
Embodiment 6
By the Ce (NO of 10mL 0.17mg/L3)3With the La (NO of 0.13mg/L3)3Mixed aqueous solution is poured into 10mL implementation
On chloroform capsule dispersant liquid described in example 2,12h is stood at room temperature, occurs white fluffy solid substance at phase interface.It removes
Layer aqueous solution, ICP-OES do not detect Ce3+With La3+.It is 5wt%'s that 10mL concentration is added on the flocculent substance of organic phase
Hydrochloric acid is stood for 24 hours.Detect Ce in hydrochloric acid phase3+With La3+Concentration is respectively 0.15mg/L and 0.11mg/L, Ce3+And La3Return
Yield is respectively 88.2% and 84.6%.
Embodiment 7
By the Cu (NO of 10mL 1.49mg/L3)2With the Hg (NO of 1.35mg/L3)2Mixed aqueous solution is poured into 10mL implementation
On carbon tetrachloride capsule dispersant liquid described in example 3, stands at room temperature for 24 hours, occur thin film at phase interface.Remove upper water
Solution, ICP-OES detection display Cu2+And Hg2+Concentration is below 0.01mg/L.10mL concentration is added on film is
The hydrochloric acid of 5wt% is stood for 24 hours.Detect Cu in hydrochloric acid phase2+And Hg2+Concentration is respectively 1.36mg/L and 1.27mg/L, Cu2+With
Hg2+The rate of recovery be respectively 91.3% and 94.1%.
Claims (4)
1. a kind of Polyamine capsule dispersion liquid for removing underwater gold category ion, it is characterized in that with poly- (calixarenes-piperazine) amide work
The dispersion liquid formed in organic solvent for the submicron order capsule of wall material；The water-soluble of metal ion is added to this dispersion liquid
Liquid, capsule wall and metal complex form supermolecule linked solid, and metal ion is fixed on to the interface zone of two liquid phases, realize water
The removing of middle metal ion；After removing water, hydrochloric acid is added to remaining system, dissociates complex compound, Metal ion release to hydrochloric acid water
Solution phase, dispersion liquid restore to original state.
2. the preparation method of the capsule dispersant liquid is that piperazine solution is added drop-wise to tert-butyl-calix according to claims 1
[4] in the organic solution of aromatic hydrocarbons-O- tetraethyl acyl chlorides acyl chlorides (I), I polymerize in the solution with piperazine, forms submicron order capsule,
Obtain dispersion liquid；The structural formula of I is as follows:
3. solvent used in the organic solution of the I is methylene chloride, chloroform, four according to claims 1 and 2
The mixing of one or more of chlorination carbon；Piperazine solution can be aqueous solution, be also possible to the organic solution with I same solvent.
4. the concentration of the piperazine solution is 2 × 10 according to claims 1 and 2-2Mol/L~10-1mol/L；I solution it is dense
Degree is 2~7 × 10-3mol/L；Removable metal ion soluble in water includes heavy metal ion Hg (II), Pb (II), Cu
(II) and rare earth ion Ce (III) and La (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811090700.9A CN109251331A (en) | 2018-09-19 | 2018-09-19 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811090700.9A CN109251331A (en) | 2018-09-19 | 2018-09-19 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
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| Publication Number | Publication Date |
|---|---|
| CN109251331A true CN109251331A (en) | 2019-01-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811090700.9A Pending CN109251331A (en) | 2018-09-19 | 2018-09-19 | A kind of Polyamine capsule dispersion liquid removing underwater gold category ion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473180A (en) * | 2020-11-09 | 2021-03-12 | 中国工程物理研究院核物理与化学研究所 | Method for separating metal ions in solution based on supermolecule self-assembly |
| CN115231673A (en) * | 2022-06-08 | 2022-10-25 | 广州市浪奇实业股份有限公司 | Quantitative dispensing capsule with water treatment function |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781199A (en) * | 2010-01-30 | 2010-07-21 | 浙江工业大学 | Chemical synthesis method of O-acylcalix[4]arene |
| CN104132920A (en) * | 2014-08-07 | 2014-11-05 | 贵州大学 | Method for measuring Ag<+> or F<-> through fluorescence quenching |
| CN108164696A (en) * | 2018-01-11 | 2018-06-15 | 天津工业大学 | A kind of polyamide detected with extracting metals ion |
| CN108445155A (en) * | 2018-03-13 | 2018-08-24 | 天津工业大学 | A kind of test paper of detection benzene reagent |
-
2018
- 2018-09-19 CN CN201811090700.9A patent/CN109251331A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781199A (en) * | 2010-01-30 | 2010-07-21 | 浙江工业大学 | Chemical synthesis method of O-acylcalix[4]arene |
| CN104132920A (en) * | 2014-08-07 | 2014-11-05 | 贵州大学 | Method for measuring Ag<+> or F<-> through fluorescence quenching |
| CN108164696A (en) * | 2018-01-11 | 2018-06-15 | 天津工业大学 | A kind of polyamide detected with extracting metals ion |
| CN108445155A (en) * | 2018-03-13 | 2018-08-24 | 天津工业大学 | A kind of test paper of detection benzene reagent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112473180A (en) * | 2020-11-09 | 2021-03-12 | 中国工程物理研究院核物理与化学研究所 | Method for separating metal ions in solution based on supermolecule self-assembly |
| CN115231673A (en) * | 2022-06-08 | 2022-10-25 | 广州市浪奇实业股份有限公司 | Quantitative dispensing capsule with water treatment function |
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Application publication date: 20190122 |
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