CN108435137A - The support type reagent and preparation method of a kind of decoloration of hydrochloric acid and the removing of hydrochloric acid metal ion - Google Patents
The support type reagent and preparation method of a kind of decoloration of hydrochloric acid and the removing of hydrochloric acid metal ion Download PDFInfo
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- CN108435137A CN108435137A CN201810219654.1A CN201810219654A CN108435137A CN 108435137 A CN108435137 A CN 108435137A CN 201810219654 A CN201810219654 A CN 201810219654A CN 108435137 A CN108435137 A CN 108435137A
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Abstract
The present invention relates to a kind of novel supported reagents that can be used for hydrochloric acid decoloration and the removing of hydrochloric acid metal ion simultaneously and preparation method thereof and decoloration to remove metal ion technique.The reagent is provided simultaneously with the function of hydrochloric acid decoloration and the removing of hydrochloric acid metal ion.The reagent is by ordered mesoporous material MCM 41（By trimethoxy silicon substrate propyl amine and the processed MCM of trim,ethylchlorosilane 41）, 5@SiO of MOF2@Fe3O4, 2 pairs of bromomethyl second bipyridines, sulfurous acid, frerrous chloride, sodium thiosulfate, magnesium sulfate, stannous chloride, silica white, zinc powder, water, ethyl alcohol composition.The present invention can be used for simultaneously hydrochloric acid decoloration and hydrochloric acid metal ion removing novel supported reagent preparation process it is simple, it is with short production cycle, it is at low cost, use it for the removing of the decoloration and hydrochloric acid metal ion of hydrochloric acid, its bleaching time is short, the removing metal ion time is short, and effect is good, is not reduced to content of hydrochloric acid.
Description
Technical field
The present invention relates to technical field of fine, especially one kind being used for hydrochloric acid decoloration and hydrochloric acid metal ion simultaneously
Novel supported reagent of removing and preparation method thereof and decoloration remove metal ion technique.
Background technology
Hydrochloric acid is being commonly called as hydrochloric acid, is the aqueous solution of hydrogen chloride (HCl) gas.Pure hydrochloric acid be it is colorless and transparent or
It is unitary strong acid by yellow green transparence liquid.It is industrial generally to use electrolysis preparation, i.e. electrolytic sodium chloride aqueous solution,
Anode has chlorine generation.Chlorine can generate hydrogen chloride gas with hydrogen by ignition, and gained hydrogen chloride gas is through cooling
After be only absorbed by the water and obtain hydrochloric acid.Since hydrochloric acid has stronger corrosivity, understands the equipment such as pipeline of heavy corrosion irony and lead
Cause to produce in the technical hydrochloric acid prepared causes hydrochloric acid to be yellow containing a large amount of ferric ion.Meanwhile in recent years in essence
Thin chemical field has a large amount of by-product hydrochloric acid and generates, for example will produce a large amount of hydrochloric acid during preparing composite fertilizer.And it makes
During standby composite fertilizer raw material it is impure etc. due to can to contain a large amount of molecular bromine in the hydrochloric acid generated, bromine from
Son, magnesium ion, sodium ion, calcium ion, the organic-inorganics impurity such as potassium ion had both caused the decline of hydrochloric acid quality（I.e. produced salt
Acid be yellow either yellowish-brown some may be grey or black）, and cause environmental pollution and the wasting of resources.Therefore anxious
It needs to decolourize to technical hydrochloric acid and cleaned, produces and refine hydrochloric acid.And hydrochloric acid is decolourized and cleaned at present, production is refined
The method of hydrochloric acid is predominantly handled technical hydrochloric acid with various resins, and cost is higher during this, and treated
Resin is more intractable, causes the pollution of environment and the waste of resource.Therefore it is badly in need of the new side for wanting developing industry crude salt acid exquisite
Method.In this patent, we disclose a kind of can be used for the novel supported of hydrochloric acid decoloration and the removing of hydrochloric acid metal ion simultaneously
Reagent.The reagent can be used for hydrochloric acid decoloration and the removing of hydrochloric acid metal ion simultaneously, and the reagent is with short production cycle, at low cost,
The removing of the decoloration and hydrochloric acid metal ion of hydrochloric acid is used it for, bleaching time is short, and the removing metal ion time is short, effect
It is good, will not also content of hydrochloric acid be reduced.
Invention content
The main purpose of the present invention is to provide it is a kind of can be used for simultaneously hydrochloric acid decoloration and hydrochloric acid metal ion removing it is new
Type support type reagent and preparation method thereof and decoloration remove metal ion technique.Simple production process, it is easy to use.Used work
The decoloration of hydrochloric acid and the removing of hydrochloric acid metal ion can be used in industry hydrochloric acid simultaneously.
The support type reagent of a kind of decoloration of hydrochloric acid and the removing of hydrochloric acid metal ion, the support type reagent are by mass fraction
10-40%'s passes through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane（Specific place
Reason process is：By trimethoxy silicon substrate propyl amine solvent in anhydrous methylene chloride, it is added to containing ordered mesoporous material MCM-
In the suspension of 41 anhydrous chloroform, stirred at 60-70 DEG C, obtain solid, be filtered, washed, dry solid is added to it is anhydrous
In chloroform, while trim,ethylchlorosilane is added, is stirred overnight at room temperature, filters, obtains solid, washing, be dried to obtain by three
Methoxyl group silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane.）Mass fraction is 10-40%'s
MOF-5@SiO2@Fe3O4（The reagent is had by a kind of porous metals loaded with the magnetic ferroferric oxide of Silica-coated
A kind of support materials obtained from machine frame frame material MOF-5）, mass fraction is the 2- of 3-15% to bromomethyl second bipyridine, quality
Score is the sulfurous acid of 1-10%, and mass fraction is the frerrous chloride of 1-10%, and mass fraction is the sodium thiosulfate of 1-10%, matter
The magnesium sulfate that score is 3-30% is measured, mass fraction is the stannous chloride of 3-30%, and mass fraction is the silica white of 10-40%, quality
Score is the zinc powder of 1-10%, and mass fraction is the ethyl alcohol of 5-40%, excess water composition.
The ordered mesoporous material MCM-41 is processed by trimethoxy silicon substrate propyl amine and trim,ethylchlorosilane
's（Concrete processing procedure is：It is by 20 grams of trimethoxy silicon substrate propyl amine solvents in 160 milliliters of anhydrous methylene chlorides, this is molten
Liquid is added in the suspension of 1600 milliliters of anhydrous chloroforms containing 28 grams of ordered mesoporous material MCM-41.Mixture is at 65 DEG C
Stirring 24 hours.Then solid is filtered and uses dichloromethane（2*200 milliliters）Washing, and vacuum drying 5 is small at 160 DEG C
When.Then the solid after drying is added in 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes is added, in room temperature
Lower stirring 24 hours.Then solid powder is filtered to obtain, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）
Washing, and be dried in vacuo at 120 DEG C and obtain within 5 hours above-mentioned pass through at trimethoxy silicon substrate propyl amine and trim,ethylchlorosilane
The ordered mesoporous material MCM-41 managed）.
The ordered mesoporous material MCM-41 that further preferably described support type reagent is 10% by mass fraction, matter
Measure the MOF-5@SiO that score is 10%2@Fe3O4（The reagent is loaded by a kind of with the magnetic ferroferric oxide of Silica-coated
Porous metals organic framework materials MOF-5 obtained from support materials）, the 2- that mass fraction is 3% is to bromomethyl bigeminy pyrrole
Pyridine, the sulfurous acid that mass fraction is 1%, the frerrous chloride that mass fraction is 1%, the sodium thiosulfate that mass fraction is 1%, quality
The magnesium sulfate that score is 3%, the stannous chloride that mass fraction is 3%, the silica white that mass fraction is 10%, mass fraction are 1%
Zinc powder, the ethyl alcohol that mass fraction is 5%, excess water composition.
The preparation side of the support type reagent of hydrochloric acid decoloration and the removing of hydrochloric acid metal ion described in technical scheme of the present invention
Method includes the following steps：
MCM-41 and 2- is dissolved in ethyl alcohol bromomethyl second bipyridine successively under stirring conditions, reacts 1- at 10-80 DEG C
48 hours；Sequentially add sulfurous acid, frerrous chloride, sodium thiosulfate, magnesium sulfate, stannous chloride, silica white, MOF-5@
SiO2@Fe3O4And water, the load for obtaining hydrochloric acid decoloration and the removing of hydrochloric acid metal ion for 1-24 hours is stirred at 20-90 DEG C
Type reagent.
The present invention at the same time decolourizes to hydrochloric acid the support type reagent of the hydrochloric acid decoloration and the removing of hydrochloric acid metal ion
And the application in the removing of hydrochloric acid metal ion.
The support type reagent is added in pending hydrochloric solution, is stood after being stirred to react 5min-60min,
Hydrochloric acid after decoloration and removing metal ion is obtained by filtration with support type reagent again.Institute is added in pending hydrochloric solution
The mass concentration of the support type reagent stated, the support type reagent is 0.1-30%；It uses again in the filtering of support type reagent, it is described
Support type reagent mass concentration be 1-50%.
The support type reagent of the hydrochloric acid decoloration and the removing of hydrochloric acid metal ion is at the same time to hydrochloric acid decoloration and hydrochloric acid gold
Belong to the application in ion removing, and decoloration to hydrochloric acid and synergy that metal ion is the decolorising agent each component, lacks and appoint
A kind of what component, effect can all be weakened.Bleaching principle is mainly：It is moderate due to adding several reproducibilities in the reagent,
The preferable reducing agent of selectivity can cooperate with and dispose the ferric ion that industry goes out hydrochloric acid, bivalent cupric ion and bromine molecule etc.
Coloured impurity.Removing metal ion principle be mainly：Due to adding several adsorptive agents in the reagent, in these types
Each metal ion species can be adsorbed under the synergistic effect of adsorptive agent.
The support type reagent is added in pending hydrochloric solution, uses support type reagent to filter again after stirring,
It can quickly be decolourized and remove the hydrochloric acid after metal ion.It decolourizes and the removing metal ion time is short, most fast only to need
5min generally requires 5min-60min.
The support type reagent is added in pending hydrochloric solution, uses support type reagent to filter again after stirring,
It can quickly be decolourized and remove the hydrochloric acid after metal ion.The concentration of hydrochloric acid range that it can be used to handle is wide, and mass concentration is
The industrial crude salt acid of 20-36% can be handled, and treated, and concentration of hydrochloric acid will not reduce, and mass concentration is maintained as 20-36%.
The support type reagent is added in pending hydrochloric solution, uses support type reagent to filter again after stirring,
It can quickly be decolourized and remove the hydrochloric acid after metal ion.It decolourizes and the effect of removing metal ion is good, treated salt
Acid is mostly colorless and transparent liquid（Part effect is slightly worse, still can reach light yellow clear liquid）, Fe in treated hydrochloric acid3 +, Cu2+,Fe2+,Pb2+,Co2+,Ni2+The content of equal metal ions all substantially reduces, above-mentioned metal ion in treated hydrochloric acid
Content be below 1mg/kg.
Specific implementation mode
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Instrument and reagent：
SHZ-E type circulating water type vacuum pumps（The biochemical instrument plants of Shanghai Rong Ya）；DZE-6120 type vacuum drying chambers（Shanghai perseverance day
Scientific instrument manufacturing company）；WRS-1A numeral melting point instruments（Shanghai Suoguang Optoelectronic Technology Co., Ltd.）；EB2005A electronic balances；
ZF-I type ultraviolet analysis instrument for three purposed；DE-102J heat collecting type constant-temperature heating magnetic stirring apparatus（Grey hair chemical apparatuses factory of Gongyi City）；
DFX-5L/30 cryogenic thermostat reactive bath techniques（Hundred river instrument plant of Wuxi City）；2YZ-4A type rotary vane type vacuum oil pumps（Sky is true forever for Linhai City
Null device factory）.
Embodiment 1
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
10% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
10%MOF-5@SiO2@Fe3O4, 3%2- is to bromomethyl second bipyridine, 1% sulfurous acid, 1% frerrous chloride, 1% sodium thiosulfate, 3% sulphur
Sour magnesium, 3% stannous chloride, 10% silica white, 1% zinc powder, 5% ethyl alcohol, excess water composition.
Embodiment 2
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
20% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
20%MOF-5@SiO2@Fe3O4, 6%2- is to bromomethyl second bipyridine, 2% sulfurous acid, 2% frerrous chloride, 2% sodium thiosulfate, 6% sulphur
Sour magnesium, 6% stannous chloride, 20% silica white, 1% zinc powder, 10% ethyl alcohol, excess water composition.
Embodiment 3
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
20% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
20%MOF-5@SiO2@Fe3O4, 6%2- is to bromomethyl second bipyridine, 1% sulfurous acid, 1% frerrous chloride, 1% sodium thiosulfate, 3% sulphur
Sour magnesium, 10% stannous chloride, 20% silica white, 1% zinc powder, 10% ethyl alcohol, excess water composition.
Embodiment 4
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
10% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
10%MOF-5@SiO2@Fe3O4, 3%2- is to bromomethyl second bipyridine, 1% sulfurous acid, 1% frerrous chloride, 1% sodium thiosulfate, 3% sulphur
Sour magnesium, 10% stannous chloride, 10% silica white, 1% zinc powder, 5% ethyl alcohol, excess water composition.
Embodiment 5
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
40% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
10%MOF-5@SiO2@Fe3O4, 6%2- is to bromomethyl second bipyridine, 1% sulfurous acid, 1% frerrous chloride, 1% sodium thiosulfate, 3% sulphur
Sour magnesium, 3% stannous chloride, 20% silica white, 1% zinc powder, 5% ethyl alcohol, excess water composition.
Embodiment 6
It can be used for hydrochloric acid decoloration simultaneously and the novel supported reagent each component of hydrochloric acid metal ion removing is by weight percentage：
10% passes through trimethoxy silicon substrate propyl amine and the processed MCM-41 of trim,ethylchlorosilane（Concrete processing procedure is：By 20 gram three
Methoxyl group silicon substrate propyl amine solvent is added to 1600 milliliters in 160 milliliters of anhydrous methylene chlorides, the solution to be had containing 28 grams
In the suspension of the anhydrous chloroform of sequence Mesoporous silica MCM 41.Mixture stirs 24 hours at 65 DEG C.Then solid is filtered
Dichloromethane is used in combination（2*200 milliliters）Washing, and be dried in vacuo 5 hours at 160 DEG C.Then the solid after drying is added to
In 1000 milliliters of anhydrous chloroforms, while 50 grams of trim,ethylchlorosilanes are added, stir 24 hours at room temperature.Then solid is filtered to obtain
Powder, the solid powder acetone（3*200 milliliters）And ether（3*200 milliliters）Washing, and vacuum drying 5 is small at 120 DEG C
When obtain it is above-mentioned pass through trimethoxy silicon substrate propyl amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane）,
40%MOF-5@SiO2@Fe3O4, 3%2- is to bromomethyl second bipyridine, 1% sulfurous acid, 1% frerrous chloride, 1% sodium thiosulfate, 6% sulphur
Sour magnesium, 6% stannous chloride, 20% silica white, 1% zinc powder, 5% ethyl alcohol, excess water composition.
By embodiment 1-6 can be used for simultaneously hydrochloric acid decoloration and hydrochloric acid metal ion removing novel supported reagent by with
It is prepared by lower section method：
Under stirring conditions, successively by MCM-41（It is processed by trimethoxy silicon substrate propyl amine and trim,ethylchlorosilane
MCM-41）Bromomethyl second bipyridine is dissolved in ethyl alcohol with 2-, is reacted 24 hours at 40 DEG C.Then sulfurous acid, chlorine are sequentially added
Change ferrous, sodium thiosulfate, magnesium sulfate, stannous chloride, silica white, MOF-5@SiO2@Fe3O4And the water of surplus, in temperature 25
The novel supported reagent for obtaining that this can be used for hydrochloric acid decoloration simultaneously and hydrochloric acid metal ion removes for 2 hours is stirred at DEG C.
The novel supported reagent that can be used for hydrochloric acid decoloration and the removing of hydrochloric acid metal ion simultaneously prepared is by with lower section
Method to hydrochloric acid decolourize and remove hydrochloric acid metal ion.
Embodiment 7
Reagent prepared by 0.1% above-described embodiment 1 is added in pending hydrochloric acid, is stood after being stirred to react 60min, then with 1%
Above-described embodiment 1 prepare reagent be obtained by filtration decoloration and remove metal ion after hydrochloric acid.
Embodiment 8
Reagent prepared by 1% above-described embodiment 1 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 1 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 9
Reagent prepared by 5% above-described embodiment 1 is added in pending hydrochloric acid, is stood after being stirred to react 5min, then with 10%
Reagent prepared by above-described embodiment 1 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 10
Reagent prepared by 1% above-described embodiment 2 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 2 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 11
Reagent prepared by 1% above-described embodiment 3 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 3 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 12
Reagent prepared by 1% above-described embodiment 4 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 4 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 13
Reagent prepared by 1% above-described embodiment 5 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 5 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
Embodiment 14
Reagent prepared by 1% above-described embodiment 6 is added in pending hydrochloric acid, is stood after being stirred to react 10min, then with 5%
Reagent prepared by above-described embodiment 6 is obtained by filtration decoloration and removes the hydrochloric acid after metal ion.
The novel supported reagent that can be used for hydrochloric acid decoloration and the removing of hydrochloric acid metal ion simultaneously of embodiment 1 to 6 is in reality
It applies and preferable hydrochloric acid decolorizing effect and hydrochloric acid metal ion removal effect can be obtained under the use proportioning of a 7-14.Quality is dense
Degree, which is the industrial crude salt acid of 20-36%, to be handled, and treated, and concentration of hydrochloric acid will not reduce, and mass concentration is maintained as 20-
36%.Treated, and hydrochloric acid is mostly colorless and transparent liquid（Part effect is slightly worse, still can reach light yellow clear liquid）, place
Fe in hydrochloric acid after reason3+, Cu2+,Fe2+,Pb2+,Co2+,Ni2+The content of equal metal ions all substantially reduces, and content is below
1mg/kg。
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the limitation for the present invention, this Shen
Please in embodiment and embodiment in feature in the absence of conflict, mutually can arbitrarily combine.The protection model of the present invention
Enclose the equivalent replacement side of technical characteristic in the technical solution that should be recorded with claim, including the technical solution of claim record
Case is protection domain.Equivalent replacement i.e. within this range is improved, also within protection scope of the present invention.
Claims (7)
1. the support type reagent of a kind of hydrochloric acid decoloration and the removing of hydrochloric acid metal ion, which is characterized in that the support type reagent is by matter
The ordered mesoporous material MCM-41 that score is 10-40% is measured, mass fraction is the MOF-5@SiO of 10-40%2@Fe3O4, mass fraction
For 3-15% 2- to bromomethyl second bipyridine, mass fraction is the sulfurous acid of 1-10%, and mass fraction is the protochloride of 1-10%
Iron, mass fraction are the sodium thiosulfate of 1-10%, and mass fraction is the magnesium sulfate of 3-30%, and mass fraction is the chlorination of 3-30%
Stannous, mass fraction are the silica white of 10-40%, and mass fraction is the zinc powder of 1-10%, and mass fraction is the ethyl alcohol of 5-40%, remaining
Measure water composition.
2. the support type reagent of hydrochloric acid decoloration described in claim 1 and the removing of hydrochloric acid metal ion, which is characterized in that the load
The ordered mesoporous material MCM-41 that type reagent is 10% by mass fraction, the MOF-5@SiO that mass fraction is 10%2@Fe3O4, quality
The 2- that score is 3% is to bromomethyl second bipyridine, the sulfurous acid that mass fraction is 1%, the frerrous chloride that mass fraction is 1%, quality
The sodium thiosulfate that score is 1%, the magnesium sulfate that mass fraction is 3%, the stannous chloride that mass fraction is 3%, mass fraction are
10% silica white, the zinc powder that mass fraction is 1%, the ethyl alcohol that mass fraction is 5%, excess water composition.
3. the support type reagent of hydrochloric acid decoloration as claimed in claim 1 or 2 and the removing of hydrochloric acid metal ion, which is characterized in that institute
The ordered mesoporous material MCM-41 stated is processed by trimethoxy silicon substrate propyl amine and trim,ethylchlorosilane, specifically will
Trimethoxy silicon substrate propyl amine solvent is added to the anhydrous chloroform containing ordered mesoporous material MCM-41 in anhydrous methylene chloride
Suspension in, stirred at 60-70 DEG C, obtain solid, be filtered, washed, dry solid is added in anhydrous chloroform, simultaneously plus
Enter trim,ethylchlorosilane, be stirred overnight at room temperature, filters, obtains solid, washing, be dried to obtain by trimethoxy silicon substrate propyl
Amine and the processed ordered mesoporous material MCM-41 of trim,ethylchlorosilane.
4. claim 1-3 any one of them hydrochloric acid decolourizes and the preparation side of the support type reagent of hydrochloric acid metal ion removing
Method, which is characterized in that include the following steps：
Ordered mesoporous material MCM-41 and 2- is dissolved in ethyl alcohol bromomethyl second bipyridine successively under stirring conditions, 10-
It is reacted 1-48 hours at 80 DEG C；Sequentially add sulfurous acid, frerrous chloride, sodium thiosulfate, magnesium sulfate, stannous chloride, silica gel
Powder, MOF-5@SiO2@Fe3O4And water, it is to obtain hydrochloric acid decoloration and hydrochloric acid metal ion to take off that 1-24 hours are stirred at 20-90 DEG C
The support type reagent removed.
5. claim 1-3 any one of them hydrochloric acid decolourizes and the support type reagent of hydrochloric acid metal ion removing is at the same time to salt
Application in acid decoloration and the removing of hydrochloric acid metal ion.
6. the application described in claim 5, which is characterized in that the support type examination is added in pending hydrochloric solution
Agent is filtered with support type reagent after stirring 5min-60min, can quickly be decolourized and remove the hydrochloric acid after metal ion.
7. the application described in claim 6, which is characterized in that the support type examination is added in pending hydrochloric solution
The mass concentration of agent, the support type reagent is 0.1-30%；It uses again in the filtering of support type reagent, the support type reagent
Mass concentration be 1-50%.
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|---|---|---|---|---|
| CN115770575A (en) * | 2022-11-18 | 2023-03-10 | 深圳技术大学 | Use and recovery method of magnetic contact electrocatalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0735242B2 (en) * | 1989-06-21 | 1995-04-19 | 日本錬水株式会社 | Crude hydrochloric acid purification method |
| CN1104992A (en) * | 1994-07-08 | 1995-07-12 | 山东新华制药厂 | Method for treating ferrous salt in industrial halogen hydrogen acid |
| CN1128978A (en) * | 1994-06-03 | 1996-08-14 | 挪威海德罗公司 | Method for removing unwanted color from hydrochloric acid |
| CN102249190A (en) * | 2011-07-25 | 2011-11-23 | 国药集团化学试剂有限公司 | Method for purifying hydroiodic acid |
| CN105478086A (en) * | 2015-12-24 | 2016-04-13 | 淄博永辰环境影响评价有限公司 | Preparation method of composite adsorbing material of industrial wastewater heavy metal ions |
| CN106732345A (en) * | 2016-12-29 | 2017-05-31 | 河南水晶头文化传媒有限公司 | A kind of composite adsorbing material for heavy metal containing wastewater treatment and preparation method thereof |
-
2018
- 2018-03-16 CN CN201810219654.1A patent/CN108435137A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0735242B2 (en) * | 1989-06-21 | 1995-04-19 | 日本錬水株式会社 | Crude hydrochloric acid purification method |
| CN1128978A (en) * | 1994-06-03 | 1996-08-14 | 挪威海德罗公司 | Method for removing unwanted color from hydrochloric acid |
| CN1104992A (en) * | 1994-07-08 | 1995-07-12 | 山东新华制药厂 | Method for treating ferrous salt in industrial halogen hydrogen acid |
| CN102249190A (en) * | 2011-07-25 | 2011-11-23 | 国药集团化学试剂有限公司 | Method for purifying hydroiodic acid |
| CN105478086A (en) * | 2015-12-24 | 2016-04-13 | 淄博永辰环境影响评价有限公司 | Preparation method of composite adsorbing material of industrial wastewater heavy metal ions |
| CN106732345A (en) * | 2016-12-29 | 2017-05-31 | 河南水晶头文化传媒有限公司 | A kind of composite adsorbing material for heavy metal containing wastewater treatment and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李朝略等: "《化工小商品生产法 第一集》", 31 March 1993, 湖南科学技术出版社 * |
| 马世昌: "《化学物质辞典》", 30 April 1999, 陕西科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115770575A (en) * | 2022-11-18 | 2023-03-10 | 深圳技术大学 | Use and recovery method of magnetic contact electrocatalyst and preparation method thereof |
| CN115770575B (en) * | 2022-11-18 | 2024-02-23 | 深圳技术大学 | Use and recovery method of magnetic contact electrocatalyst and preparation method thereof |
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