CN109999754A - The preparation of polluted by copper material under a kind of environment for high-speed rail - Google Patents
The preparation of polluted by copper material under a kind of environment for high-speed rail Download PDFInfo
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- CN109999754A CN109999754A CN201910183594.7A CN201910183594A CN109999754A CN 109999754 A CN109999754 A CN 109999754A CN 201910183594 A CN201910183594 A CN 201910183594A CN 109999754 A CN109999754 A CN 109999754A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The present invention relates to a kind of silica gel load aminomethyl-pyridines for the highly selective preparation method except copper product.This method first prepares the alkoxy silane coupling agent with aminomethyl-pyridine, then aminomethyl-pyridine modified silane coupler is grafted to activated silica gel surface.Method of the invention is effectively increased except functional group's load capacity of copper product and its to the adsorption capacity of metal ion, reduces the cost of material, operating cost and disposal of pollutants of production.
Description
Technical field
The present invention relates to a kind of pair of copper ions the preparation method compared with strong selectivity adsorbent material, in particular to a kind of load
The silica gel material preparation method of the deep copper removal of aminomethyl-pyridine.
Background technique
In wet process iron-smelting copper, often by adding ferric iron that univalent copper ion is oxidized to bivalent cupric ion, generates pH value and arrived 1
3, the very high leachate of iron content, it is desirable to be able to selective extraction copper in such a case.Common purification copper-removing method master
There are electrolysis method, sulfurization-precipitation method, extraction and the adsorbent material method with chelation group etc..In these methods, chela is had
The adsorbent material for closing group has the characteristics that easy to use, pollution is small, selectively strong to copper ion.
Using 2- aminomethyl-pyridine class functional group as chelation group, have by the adsorbent material of substrate of organic polymer pellets
DOWEX M 4195, DOWEXXFS 43083, Lewatit TP 220 etc..U.S. Patent application US3873668A is (hereinafter referred to as
Document 1), US3873668A (hereinafter referred to as document 2), Chinese patent application CN101977689A (hereinafter referred to as document 3) discloses energy
At low ph conditions with high-selectivity adsorption copper ion, to the absorption very little of iron, to acid solution to be processed, without being turned up
PH, it is easy to use；The disadvantage is that polymer globules generally use hydrophobicity crosslinked polystyrene, resin is caused to use in aqueous solution
When be difficult to be made ion diffusion hindered inside chelating agent by water quick humidification, reduced adsorption rate and efficiency.In addition, polymerization
Object bead substrate bad mechanical strength, after filling column, the bead of lower layer is compressed, Adsorption and desorption characteristics further by
It influences.
Silica has good mechanical strength and biggish surface area, and the silicone hydroxyl on surface improves hydrophily,
And then substantially increase the rate of adsorption.It is negative that U.S. Patent application US 20020139753A1 (hereinafter referred to as document 4) discloses silica gel
Aminomethyl-pyridine chelating resin is carried, preparation step is complex, it may be assumed that is used first by alkyl halide base trichlorosilane, such as bromopropyl
Trichlorosilane is dissolved in anhydrous nonpolar solvent, and the silica gel reaction being hydrated to a certain degree, realizes surface modification alkylhalide group
Silica gel；It is reacted with polyamine compounds again, by surface modification amido；Substitution reaction occurs for last and chloromethylpyridine, repairs
Chelation group on decorations.This of alkyl halide base trichlorosilane and silica gel step reaction, violent releasing hydrogen chloride gas, to operation, equipment anticorrosion
Erosion, vent gas treatment have particular/special requirement.
Also mentioning in document 4 can be used alkylhalide group trialkoxy silane, but there is a problem of that reaction efficiency is low, when making
With bromopropyl trichlorosilane, increase weight 16-30% after reaction, but uses bromopropyl trimethoxy silane, and weight gain is less than after reaction
5%.
Chinese patent application CN102441367A (hereinafter referred to as document 5) discloses the defect for document 1 and improves: first making
Alkylhalide group trialkoxy silane and 2- aminomethyl-pyridine, in anhydrous non-protonic solvent, nitrogen protection, heating reaction adds
Alkali absorption hydrogen chloride generates aminomethyl-pyridine modified silane coupler；Again by aminomethyl-pyridine modified silane coupler with it is organic
The silica of amine activation, while the inert organic solvent of silane coupling agent and the mixed solution of acidic alcohol is added dropwise, heating is anti-
It answers 1 to 2 days.This set technique, which is directed to, uses alkylhalide group trialkoxy silane, improves the efficiency of graft reaction, but operate at
This document 4 similar with difficulty.
Summary of the invention
The present invention provides a kind of method of the silica gel material of the deep copper removal of efficient preparation load aminomethyl-pyridine.
Of the invention includes: the step of being related to
(1) silane coupling agent is connect with silica gel: the group on silane coupling agent hydrolyzes, then the hydroxyl with Silica Surface
Condensation forms silicon oxygen bond connection；
(2) silane coupling agent is connect with aminomethyl-pyridine: by alkoxy silane coupling agent, 2- aminomethyl-pyridine, or
Again plus a kind of reaction of bridging agent connects aminomethyl-pyridine and silane coupling agent；
(3) it washing and processing: is washed with suitable solvent, the raw material of Silica Surface remnants and impurity is removed completely, obtained
The adsorbent material of the selective copper removal under high-speed rail environment must can be achieved.
It sequentially says, the first two steps sequence can be exchanged or be carried out simultaneously.
More specifically, the present invention can be realized by following preferred embodiment:
(1) silane coupling agent is connect with silica gel.
The present invention uses alkoxy silane coupling agent, and reaction is mild, can unlike using chlorosilane coupling agent in document 4
Corrosive hydrogen chloride gas is released, thus it is easy to operate, it pollutes small.The coupling agent with amino may be selected, comprising: 3- aminopropan
Base trimethoxy silane, 3-aminopropyltriethoxysilane, N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- ammonia
Ethyl -3- aminopropyltriethoxy diethoxy silane, or the coupling agent with epoxy group, including 3- (2,3- the third oxygen of epoxy) propyl three
Methoxy silane, 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicane, 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl diethoxy
Silane or 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane, the preferably silane coupling agent of three alkoxies of band.Silane
The mass ratio of coupling agent and silica gel is generally 20:1-1:1；More preferably the mass ratio of silane coupling agent and silica gel is 8:1-4:1.
Compared to document 5 in a large amount of atent solvents, including in acetone, toluene, n,N-Dimethylformamide, dimethyl sulfoxide
One kind, reaction is heated under nitrogen protection, the present invention is not necessarily to nitrogen protection, and the solvent used can also include tetrahydrofuran, first
One of alcohol, ethyl alcohol, isopropyl alcohol and water or mixture, for the consideration of environmental protection, preferentially use second to guarantee to be dissolved as standard
Alcohol.Specific reactive mode be will be dissolved with alkalescent group coupling agent with solvent, then be uniformly mixed with silica gel particle heat or
Person completes to react at room temperature.The soda acid of Silica Surface is too strong in this link can all have adverse effect on, and be preferably close to neutrality
Silica gel；Surface is conducive to react with a small amount of water, and the silica gel sand of usual technical grade shows just containing a small amount of water, without into
The drying of one step, can be used directly；The hydrochloric acid of 1N or the NaOH or KOH solution of nitric acid or pH=9-13 can also be used, 90 DEG C-
Washing reuses reaction temperature to close to after neutrality after 100 DEG C of activation, and generally between 0 DEG C -120 DEG C, the reaction time is 1 to 40
Between hour.
(2) silane coupling agent is connect with aminomethyl-pyridine.
The bridging agent that the present invention uses includes chloracetyl chloride, epoxychloropropane, 1,4-butanediol diglycidyl ether, second two
Alcohol diglycidyl ether, the epoxide diluents such as trihydroxymethylpropanyltri diglycidyl ether and they and ethylenediamine, triethylene two
Amine, tetraethylenepentamine, branched polyethylene imine, polyvinylamine, the product of the reactions such as polyallylamine.Reaction temperature can be -20
Between DEG C -80 DEG C, change between from 1 to 48 hour reaction time.Solvent includes acetone, toluene, methylene chloride, dichloroethanes, N,
One of dinethylformamide, dimethyl sulfoxide, tetrahydrofuran, methanol, ethyl alcohol, isopropyl alcohol and water or more than one is mixed
Close object.Specific reaction process is that 2- aminomethyl-pyridine and solvent are added in three-necked bottle, is uniformly mixed；Then under stiring,
Connection agent solution and silane coupler solution (or silica gel after silane coupling agent modification), room successively or is simultaneously added dropwise
Temperature perhaps 80 DEG C reaction 6-20 hour or only plus alkane coupling agent be dissolved in solution (or silane coupling agent modify after silicon
Glue).
(3) washing and processing.
The solvent of washing include acetone, toluene, ethyl acetate, tetrahydrofuran, methanol, ethyl alcohol, in isopropyl alcohol and water
One or more kinds of mixtures.It can use 3 hours modes of Soxhlet extraction to wash, can also be stirred by solubilizer,
Suction filtration solid product, 3 times repeatedly.It is finally washed with water, dries, be exactly silica gel load aminomethyl-pyridine adsorbent material.
For material prepared by the present invention, the performance of its absorption is mainly characterized by Static Adsorption and desorption.Document 4
The result shows that this kind of material of silica gel base can show better height compared to the material of polymeric substrates under low copper concentration
Selectivity inhales copper performance, so the preparation of stoste simulates a kind of metallurgical leachate of low copper concentration in Static Adsorption test
(H2SO4 12.41g/L,Fe3+9.13g/L,Al3+1.06g/L,Cu2+110mg/L,Zn2+190mg/L,Mn2+30.2mg/L,Ca2+
320mg/L, pH=1.2), it takes 2g resin sample in ground conical flask, 200mL stoste is added, shakes 3 at 30 DEG C with shaking table
After a hour, 1.000mL is taken, dilutes 100 times with volumetric flask, guarantees that copper ion concentration between 0.5-2mg/L, is suitble to ICP-MS
Analytical concentration, by survey absorption front and back copper ion concentration combination moisture content measured value, calculating every gram of dry material to copper from
The adsorbance of son；This test is repeated 3 times, and is averaged.
Adsorbent material prepared by the present invention is attempted to use 1N respectively, the sulfuric acid of 2N, 4N desorb, it may be assumed that take 2g in desorption test
Sample adds the original liquid of 200mL, and 30 DEG C are shaken 3 hours, surveys solution concentration after absorption；Incline and fall residual solution, 100mL is washed 3 times, is added
200mL sulfuric acid, 30 degree are shaken 1 hour, survey stripping liquid concentration, resolution factor=stripping liquid concentration ÷ is (before adsorbing after solution concentration-absorption
Solution concentration)；This test is repeated 3 times, and is averaged.
Although above discussion and following example are concentrated on by adsorbing divalent under high concentration ferric ion environment
Copper ion, but it is noted that adsorbent material prepared by the present invention, it can also be used to the deep purifying copper removal under nickelic, high cobalt environment, or
Person is when pH is controlled 1.5 to 2.0, for removing nickel under high cobalt environment.
Method of the preparation provided by the invention for polluted by copper material under high-speed rail environment has the advantage that design of the present invention
Route reduce cost of material, operating cost, operation complexity, process cycle and environmental pollution.
Specific embodiment
Following implementation is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1: with after 3-aminopropyltriethoxysilane modified silica-gel, by with epoxychloropropane, 2- aminomethyl
Pyridine reaction preparation load aminomethyl-pyridine adsorbent material
1.0g 3-aminopropyltriethoxysilane (4.5mmol) is taken to be dissolved into 20mL Industrial Grade Tetrahydrofuran, and
(aqueous 10%) mixing, reacts at room temperature 3 hours the non-activated silica gel of 5.0g, and solvent is removed in vacuum distillation, and 105 drying 3 hours obtain
White solid particle, weight 5.4g, is exactly aminopropyl base silane SiClx glue；By silica gel and 0.5g 2- aminomethyl-pyridine
Three-necked bottle is added in (4.6mmol), 0.6g epoxychloropropane (7.4mmol), 20mL tetrahydrofuran, is stirred, after reflux 6 hours
Cooling, suction filtration obtains solid particle, and after being washed 3 times with 10mL, drying just obtains the silica gel material of load aminomethyl-pyridine.It surveys
The adsorbance of copper ion is 4.7mg/g, which can realize 85% desorption efficiency in the sulfuric acid of 2N.
The relationship of table 1 desorption efficiency and sulfuric acid concentration.
| Test serial number | Sulfuric acid concentration (N) | Desorption efficiency (%) |
| 1 | 1.0 | 78 |
| 2 | 2.0 | 85 |
| 3 | 4.0 | 86 |
Embodiment 2: it with after 3-aminopropyltriethoxysilane modified silica-gel, is then modified with chloracetyl chloride, last 2-
Silica gel reaction preparation load aminomethyl-pyridine adsorbent material after aminomethyl-pyridine and modification
The non-activated silica gel of 5.0g is taken, 105 DEG C dry 3 hours；Take 1.0g 3-aminopropyltriethoxysilane
(4.5mmol) is dissolved into 20mL dichloroethanes and silica gel mixing, reacts at room temperature 3 hours, is evaporated under reduced pressure and removes solvent, and 105 DEG C
Drying 3 hours, obtains white solid particle, i.e. aminopropyl base silane SiClx glue；Silica gel and 1.0g Na2CO3 (9.4mmol) are existed
It is mixed in 20mL methylene chloride, 0.70g chloracetyl chloride (6.3mmol) is added dropwise in mixture, reacted at room temperature 30min, add
1.0mL water quenching is gone out, and suction filtration obtains solid particle, and after being washed 3 times with 10mL, drying just obtains what chloracetyl chloride was further modified
Silica gel；By silica gel, 0.5g aminomethyl-pyridine (4.6mmol), 1.0g Na2CO3 (9.4mmol) is mixed in 20mL ethyl alcohol, reflux
Cooling after 6 hours, suction filtration obtains solid particle, and after being washed 3 times with 10mL, drying just obtains the silica gel of load aminomethyl-pyridine
Material.The adsorbance for surveying copper ion is 9.2mg/g.
Embodiment 3: after 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 2- aminomethyl-pyridine, silica gel mixing
Single step reaction preparation load aminomethyl-pyridine adsorbent material
30g silica gel and the mixed in hydrochloric acid of 200mL1N are taken, in 90 DEG C of heating stirring 2h, 5 times is washed to neutrality with 200mL, gets rid of
Dry, room temperature dries 48h, obtains the silica gel of 1N hydrochloric acid activation, surveys aqueous 36%.
The NaOH solution for taking 30g silica gel and 200mL pH=11 washes 5 times into 200mL in 90 DEG C of heating stirring 2h
Property, drying, room temperature dries 48h, obtains the silica gel of pH=11NaOH solution activation, survey aqueous 37%.
The NaOH solution for taking 30g silica gel and 200mL pH=13 washes 5 times into 200mL in 90 DEG C of heating stirring 2h
Property, drying, room temperature dries 48h, obtains the silica gel of pH=13NaOH solution activation, survey aqueous 37%.
By 0.5g (4.6mmol) 2- aminomethyl-pyridine, 20mL tetrahydrofuran, the unactivated silica gel of 5.0g (or 7.0g 1 is added
The silica gel of silica gel or pH=11 the NaOH solution activation of N hydrochloric acid activation or the silica gel of pH=13NaOH solution activation), stirring
Mixing, 1.5g (65mmol) 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane is added dropwise in system, room temperature reaction 3
Hour, solvent is removed in vacuum distillation, and 65 drying 3 hours obtain yellow solid particle.With ethyl alcohol Soxhlet extraction 3h, filters solid and produce
Object is washed 3 times with 50mL, and drying obtains the silica gel material of load aminomethyl-pyridine.
The silica gel material of the load aminomethyl-pyridine for the silica gel preparation that table 2 activates in different ways and the pass of polluted by copper amount
System
| Test serial number | The activation method of silica gel | The adsorbance (mg/g) of copper ion |
| 1 | It is unactivated | 5.7 |
| 2 | 1N hydrochloric acid activation | 4.8 |
| 3 | The activation of pH=11NaOH solution | 5.2 |
| 4 | The activation of pH=13NaOH solution | 5.8 |
Embodiment 4: ammonia is prepared by 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and 2- aminomethyl-pyridine reaction
Picoline modified silane coupler, and then prepare silica gel load aminomethyl-pyridine adsorbent material
6g (56mmol) 2- aminomethyl-pyridine is taken, 20mL is diluted with ethanol to, allots solution A；Take 19g (80mmol) 3-
(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, is diluted with ethanol to 30mL, allots solution B；By solution B, at room temperature by
It is added dropwise to solution A, 12h is reacted at room temperature, just obtains the ethanol solution 50mL of aminomethyl-pyridine modified silane coupler；After taking modification
Coupling agent ethanol solution 1mL solution, after being diluted with ethyl alcohol be added the unactivated silica gel of 5g, room temperature reaction 12h simultaneously dry, obtain yellow
Color solid particle.With ethyl alcohol Soxhlet extraction 3h, solid product is filtered, is washed 3 times with 50mL, drying obtains load aminomethyl pyrrole
The silica gel material of pyridine.The adsorbance for surveying copper ion is 6.0mg/g.
Embodiment 5: pass through 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane and 2- aminomethyl-pyridine reaction system
Standby aminomethyl-pyridine modified silane coupler, and then prepare silica gel load aminomethyl-pyridine adsorbent material
6g (56mmol) 2- aminomethyl-pyridine is taken, 20mL is diluted with ethanol to, allots solution A；Take 19.8g (80mmol) 3-
(2,3- the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane, is diluted with ethanol to 30mL, allots solution B；By solution B, in room temperature
Under be added dropwise solution A, react at room temperature 12h, just obtain the ethanol solution 50mL of aminomethyl-pyridine modified silane coupler；It takes and repairs
The unactivated silica gel of 5g is added in the ethanol solution 1mL solution of coupling agent after decorations after being diluted with ethyl alcohol, react at room temperature 12h and dry,
Obtain yellow solid particle.With ethyl alcohol Soxhlet extraction 3h, solid product is filtered, is washed 3 times with 50mL, drying obtains load ammonia first
The silica gel material of yl pyridines.The adsorbance for surveying copper ion is 5.8mg/g.
Embodiment 6: pass through 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl
Diethoxy silane and 2- aminomethyl-pyridine reaction prepare aminomethyl-pyridine modified silane coupler, and then prepare silica gel load ammonia
Picoline adsorbent material
6g (56mmol) 2- aminomethyl-pyridine is taken, 20mL is diluted with ethanol to, allots solution A；Take 9.5g (40mmol) 3-
(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane and 9.9g (40mmol) 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy
Silane is diluted with ethanol to 30mL, allots solution B；By solution B, solution A is added dropwise at room temperature, reacts at room temperature 12h, just
Obtain the ethanol solution 50mL of aminomethyl-pyridine modified silane coupler；The ethanol solution 1mL solution of coupling agent after taking modification,
The unactivated silica gel of 5g is added after being diluted with ethyl alcohol, react at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet extraction
3h filters solid product, is washed 3 times with 50mL, and drying obtains the silica gel material of load aminomethyl-pyridine.Survey the suction of copper ion
Attached amount is 6.4mg/g.
Embodiment 7: pass through N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane, 1,4-butanediol diglycidyl ether
Simultaneously and aminomethyl-pyridine reaction prepares 2- aminomethyl-pyridine modified silane coupler, and then prepares silica gel load aminomethyl-pyridine
Adsorbent material
Take 1.95g 2- aminomethyl-pyridine (18mmol) and 3.0g N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane
(14.4mmol) mixing, is diluted with ethanol to 20mL, allots solution A；Take 4.7g 1,4- butanediol diglycidyl ether
(23.4mmol) is diluted with ethanol to 10mL, allots solution B, by solution B, solution A is added dropwise at room temperature, after being added dropwise to complete
Continue to react at room temperature 12h, just obtains the ethanol solution of aminomethyl-pyridine modified silane coupler；The second of coupling agent after taking modification
Alcoholic solution 4mL solution is added the unactivated silica gel of 4g, stirs evenly after being diluted with ethyl alcohol, react at room temperature 12h and dry, obtain yellow
Solid particle.With ethyl alcohol Soxhlet extraction 3h, solid product is filtered, is washed 3 times with 50mL, drying loads the silicon of aminomethyl-pyridine
Glue material, the adsorbance for surveying copper ion is 4.0mg/g.
Embodiment 8: by 3-aminopropyltriethoxysilane, 1,4-butanediol diglycidyl ether while and aminomethyl
Pyridine reaction preparation 2- aminomethyl-pyridine modified silane coupler, and then prepare silica gel load aminomethyl-pyridine adsorbent material
Take 1.95g 2- aminomethyl-pyridine (18mmol) and 3.2g 3-aminopropyltriethoxysilane (14.4mmol) mixed
It closes, is diluted with ethanol to 20mL, allots solution A；Take 4.7g 1,4- butanediol diglycidyl ether (23.4mmol) dilute with ethyl alcohol
10mL is released, solution B is allotted, by solution B, solution A is added dropwise at room temperature, continues to react at room temperature 12h after being added dropwise to complete, just
Obtain the ethanol solution of aminomethyl-pyridine modified silane coupler；The ethanol solution 4mL solution of coupling agent after taking modification, uses second
The unactivated silica gel of 4g is added after alcohol dilution, stirs evenly, react at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet
3h is extracted, solid product is filtered, is washed 3 times with 50mL, drying loads the silica gel material of aminomethyl-pyridine, surveys the suction of copper ion
Attached amount is 4.3mg/g.
Embodiment 9: first being reacted with 1,4-butanediol diglycidyl ether by 2- aminomethyl-pyridine, then with 3- (2,3- rings
The third oxygen of oxygen) propyl trimethoxy silicane reaction, aminomethyl-pyridine modified silane coupler is prepared, last and silica gel reaction prepares silicon
Glue loads aminomethyl-pyridine adsorbent material
1.95g 2- aminomethyl-pyridine (18mmol) is taken, 10mL is diluted with ethanol to, allots solution A；Take 2.80g 1,4-
Butanediol diglycidyl ether (13.8mmol) is diluted with ethanol to 10mL, allots solution B, is added dropwise under room temperature (26 DEG C)
Solution A continues to react at room temperature 12h after being added dropwise to complete；Take 1.70g 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane
(7.2mmol) is diluted with ethanol to 10mL, allots solution C, and solution above is added dropwise, and continues to react at room temperature after being added dropwise to complete
12h just obtains the ethanol solution of aminomethyl-pyridine modified silane coupler；The ethanol solution 4mL of coupling agent after taking modification is molten
Liquid is added the unactivated silica gel of 4g, stirs evenly after being diluted with ethyl alcohol, react at room temperature 12h and dry, obtain yellow solid particle.With
Ethyl alcohol Soxhlet extraction 3h filters solid product, is washed 3 times with 50mL, and drying obtains the silica gel material of load aminomethyl-pyridine.
The adsorbance for surveying copper ion is 8.9mg/g.
Embodiment 10: pass through 3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 1,4- butanediol diglycidyl ether
It is reacted simultaneously with 2- aminomethyl-pyridine, prepares aminomethyl-pyridine modified silane coupler, it is last to prepare load ammonia with silica gel reaction
Picoline adsorbent material
1.95g 2- aminomethyl-pyridine (18mmol) is taken, 10mL is diluted with ethanol to, allots solution A；Take 2.8g 1,4- fourth
Hexanediol diglycidyl ether (13.8mmol), 1.70g 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (7.2mmol) are used
Ethyl alcohol is diluted to 10mL, allots solution B；Solution A is added dropwise in solution B, is reacted 12 hours, it is modified just to obtain aminomethyl-pyridine
The ethanol solution of silane coupling agent；The ethanol solution 4mL solution of coupling agent after taking modification is added 4g and does not live after being diluted with ethyl alcohol
SiClx glue, stirs evenly, and reacts at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet extraction 3h, filters solid and produce
Object is washed 3 times with 50mL, and drying obtains the silica gel material of load aminomethyl-pyridine.The adsorbance for surveying copper ion is 8.5mg/g.
Embodiment 11: being reacted by ethylene glycol diglycidylether, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane
It is reacted simultaneously with 2- aminomethyl-pyridine, prepares aminomethyl-pyridine modified silane coupler, it is negative that silica gel is finally prepared with silica gel reaction
Carry aminomethyl-pyridine adsorbent material
1.95g 2- aminomethyl-pyridine (18mmol) is taken, 10mL is diluted with ethanol to, allots solution A；Take 2.6g ethylene glycol
Diglycidyl ether (15mmol), 1.70g 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (7.2mmol) are dilute with ethyl alcohol
10mL is released, solution B is allotted；Solution A is added dropwise in solution B, is reacted 12 hours, it is even just to obtain aminomethyl-pyridine modified silane
Join the ethanol solution of agent；The unactivated silicon of 4g is added in the ethanol solution 4mL solution of coupling agent after taking modification after being diluted with ethyl alcohol
Glue stirs evenly, and reacts at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet extraction 3h, solid product is filtered, is used
50mL is washed 3 times, and drying obtains the silica gel material of load aminomethyl-pyridine.The adsorbance for surveying copper ion is 5.2mg/g.
Embodiment 12: being reacted by trihydroxymethylpropanyltri diglycidyl ether, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy
Base silane is reacted with 2- aminomethyl-pyridine simultaneously, prepares aminomethyl-pyridine modified silane coupler, last to prepare with silica gel reaction
Silica gel load aminomethyl-pyridine adsorbent material
1.95g 2- aminomethyl-pyridine (18mmol) is taken, 20mL is diluted with ethanol to, allots solution A；Take tri- hydroxyl first of 3.05g
Base propane triglycidyl ether (15mmol), 1.70g 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (7.2mmol) are used
Ethyl alcohol is diluted to 10mL, allots solution B；Solution A is added dropwise in solution B, is reacted 12 hours, it is modified just to obtain aminomethyl-pyridine
The ethanol solution of silane coupling agent；The ethanol solution 4mL solution of coupling agent after taking modification is added 4g and does not live after being diluted with ethyl alcohol
SiClx glue, stirs evenly, and reacts at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet extraction 3h, filters solid and produce
Object is washed 3 times with 50mL, and drying obtains the silica gel material of load aminomethyl-pyridine.The adsorbance for surveying copper ion is 7.0mg/g.
Embodiment 13: by 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 1,4-butanediol diglycidyl ether,
Tetraethylenepentamine and 2- aminomethyl-pyridine reaction prepare aminomethyl-pyridine modified silane coupler, and then prepare silica gel load ammonia first
Yl pyridines adsorbent material
Tetraethylenepentamine (0.90g) and 2- aminomethyl-pyridine (2.11g) are taken, 20mL is diluted with ethanol to, allots solution A；
3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (0.71g) and 1,4-butanediol diglycidyl ether (3.33g) are taken, second is used
Alcohol is diluted to 20mL, allots solution B；Solution A is added dropwise in solution B by (0~10 DEG C) under ice-water bath, after dripping, room temperature
It is stirred overnight, just obtains the ethanol solution of aminomethyl-pyridine modified silane coupler；The ethanol solution of coupling agent after taking modification
8mL solution is added the unactivated silica gel of 4g, stirs evenly, and reacts at room temperature 12h and dries, obtains yellow solid particle.With ethyl alcohol Soxhlet
3h is extracted, solid product is filtered, is washed 3 times with 50mL, drying obtains the silica gel material of load aminomethyl-pyridine, surveys copper ion
Adsorbance be 6.5mg/g.
Embodiment 14: by 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 1,4-butanediol diglycidyl ether,
Branched polyethylene imine and 2- aminomethyl-pyridine reaction prepare aminomethyl-pyridine modified silane coupler, and then prepare silica gel load
Aminomethyl-pyridine adsorbent material
Branched polyethylene imine (0.90g, molecular weight 600) and 2- aminomethyl-pyridine (2.11g) are taken, is diluted with ethanol to
20mL allots solution A；3- (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane (0.71g) and 1,4- butanediol two is taken to shrink sweet
Oily ether (3.33g), is diluted with ethanol to 20mL, allots solution B；Solution is added dropwise in solution B by (0-10 DEG C) under ice-water bath
A, after dripping, is stirred overnight at room temperature, and just obtains the ethanol solution of aminomethyl-pyridine modified silane coupler；Idol after taking modification
Join the ethanol solution 8mL solution of agent, the unactivated silica gel of 4g is added, stirs evenly, react at room temperature 12h and dry, obtains yellow solid
Particle.With ethyl alcohol Soxhlet extraction 3h, solid product is filtered, is washed 3 times with 50mL, drying obtains the silicon of load aminomethyl-pyridine
Glue material, the adsorbance for surveying copper ion is 7.3mg/g.
Above embodiments are only for the purpose of description not intended to restrict the invention, it is all the spirit and principles in the present invention it
Interior, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of for the highly selective preparation method except copper product, which comprises the following steps:
(1) silane coupling agent is connect with silica gel: the group on silane coupling agent hydrolyzes, then contracts with the hydroxyl of Silica Surface
It closes, forms silicon oxygen bond connection；
(2) silane coupling agent is connect with aminomethyl-pyridine: by alkoxy silane coupling agent, 2- aminomethyl-pyridine, or being added again
A kind of reaction of bridging agent connects aminomethyl-pyridine and silane coupling agent；
(3) washing and processing: being washed with suitable solvent, and the raw material of Silica Surface remnants and impurity are removed completely, institute is obtained
State the adsorbent material of highly selective copper removal.
2. preparation method according to claim 1, which is characterized in that step (1) and (2) can sequentially be exchanged or simultaneously
It carries out.
3. -2 described in any item preparation methods according to claim 1, which is characterized in that silane coupling agent described in step (1)
Mass ratio with silica gel is 20:1-1:1；It is preferred that 8:1-4:1.
4. -2 described in any item preparation methods according to claim 1, which is characterized in that silica gel described in step (1) is table
What face was in neutrality, the hydrochloric acid of 1N or the NaOH or KOH solution of nitric acid or pH=9-13 can also be used, in 90 DEG C of -100 DEG C of work
Washing is reused to close to after neutrality after change.
5. -2 described in any item preparation methods according to claim 1, which is characterized in that alkoxy silane described in step (2)
Coupling agent is selected from: the coupling agent with amino or the coupling agent with epoxy group；It preferably is selected from: 3- TSL 8330,
3-aminopropyltriethoxysilane, N- aminoethyl -3- aminopropyltriethoxy dimethoxysilane, N- aminoethyl -3- ammonia
Hydroxypropyl methyl diethoxy silane, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, 3- (2,3- the third oxygen of epoxy) third
Ethyl triethoxy silicane alkane, 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane or 3- (2,3- the third oxygen of epoxy) third
Any one in ylmethyl dimethoxysilane.
6. -2 described in any item preparation methods according to claim 1, which is characterized in that alkoxy silane described in step (2)
Coupling agent is selected from the silane coupling agent of three alkoxies of band.
7. -2 described in any item preparation methods according to claim 1, which is characterized in that the choosing of bridging agent described in step (2)
From: epoxide diluent and its and ethylenediamine, triethylene diamine, tetraethylenepentamine, branched polyethylene imine, polyvinylamine, polyene
Any one in the product of the reactions such as propylamine.
8. preparation method according to claim 7, which is characterized in that the bridging agent is selected from: chloracetyl chloride, epoxy chlorine
Propane, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether and its
With ethylenediamine, triethylene diamine, tetraethylenepentamine, branched polyethylene imine, polyvinylamine, in the product of the reactions such as polyallylamine
Any one.
9. -2 described in any item preparation methods according to claim 1, which is characterized in that silane coupling agent described in step (2)
For the reaction temperature connecting with aminomethyl-pyridine between -20 DEG C to 80 DEG C, the reaction time is 1 to 48 hour.
10. -2 described in any item preparation methods according to claim 1, which is characterized in that silane coupled described in step (2)
Solvent used in the reaction that agent is connect with aminomethyl-pyridine is selected from: acetone, toluene, methylene chloride, dichloroethanes, N, N- bis-
One of methylformamide, dimethyl sulfoxide, tetrahydrofuran, methanol, ethyl alcohol, isopropyl alcohol and water or more than one mixing
Object.
11. -2 described in any item preparation methods according to claim 1, which is characterized in that silane coupled described in step (1)
For the reaction temperature of agent and silica gel connection between 0 DEG C to 120 DEG C, the reaction time is 1 to 40 hour.
12. -2 described in any item preparation methods according to claim 1, which is characterized in that silane coupled described in step (1)
Solvent used in the reaction that agent is connect with silica gel is selected from: acetone, toluene, n,N-Dimethylformamide, dimethyl sulfoxide, four
One of hydrogen furans, methanol, ethyl alcohol, isopropyl alcohol and water or more than one mixture.
13. according to claim 1 or 2 described in any item preparation methods, which is characterized in that the use of the 2- aminomethyl-pyridine
Amount are as follows: 0.02-0.2 grams of 2- aminomethyl-pyridine is corresponded on every gram of silica gel.
14. preparation method according to claim 1, which is characterized in that specific step is as follows for the method:
(1) silane coupling agent is connect with silica gel: the solution of silane coupling agent being uniformly mixed with silica gel, room temperature reaction 12-20 is small
When, it is exactly the silica gel after silane coupling agent modification that solid particle is obtained after dry；
(2) silane coupling agent is connect with aminomethyl-pyridine: 2- aminomethyl-pyridine and solvent being added in three-necked bottle, mixing is equal
It is even；Then under stiring, connection agent solution and silane coupler solution (or silane coupling agent successively or is simultaneously added dropwise
Silica gel after modification), it reacts at room temperature 6-20 hours, the solution for either only alkane coupling agent being added to be dissolved in (or silane coupling agent modification
Silica gel afterwards)；Yellow thick liquid (or yellow solid particle) is obtained after reaction, is as connect with aminomethyl-pyridine
The solution (or surface modification the silica gel adsorptive material of aminomethyl-pyridine) of silane coupling agent；
(3) it washing and processing: uses ethyl alcohol Soxhlet extraction 3 hours, filters solid product, be washed with water 3 times, dry, be exactly silica gel
Load aminomethyl-pyridine adsorbent material.
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| CN112717892A (en) * | 2020-11-19 | 2021-04-30 | 江苏海普功能材料有限公司 | Copper-removing adsorbent for purifying cobalt-nickel electrolyte and preparation method thereof |
| EP4223409A1 (en) * | 2022-02-02 | 2023-08-09 | Conductive Energy Inc. | Lithium ion adsorbents |
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| CN112717892A (en) * | 2020-11-19 | 2021-04-30 | 江苏海普功能材料有限公司 | Copper-removing adsorbent for purifying cobalt-nickel electrolyte and preparation method thereof |
| EP4223409A1 (en) * | 2022-02-02 | 2023-08-09 | Conductive Energy Inc. | Lithium ion adsorbents |
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