CN108264047A - A kind of sulphydryl activity charcoal and preparation method thereof and the application in alkyl mercury absorption - Google Patents
A kind of sulphydryl activity charcoal and preparation method thereof and the application in alkyl mercury absorption Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of sulphydryl activity charcoal, belong to activated carbon modified field.Methylolation and polycondensation reaction in absolute ethyl alcohol are occurred near amino thiophenols, melamine, formaldehyde, obtains carrying out modification after mixing with absorbent charcoal powder body after sulfydryl prepolymerization modification liquid, obtains near amino thiophenols polymer modified active carbon；Modified activated carbon is heat-treated, and obtains sulphydryl activity charcoal.The present invention is modified absorbent charcoal powder body using the sulfydryl prepolymerization modification liquid that near amino thiophenols, melamine and formaldehyde are formed, it can be in absorbent charcoal powder body Surface Creation nanoscale and the near amino thiophenols being evenly distributed polymeric layer, the content of mercapto functional group can be regulated and controled by adjusting the ratio of near amino thiophenols and absorbent charcoal powder body in wide range, and it is evenly distributed and regulatable sulfhydryl modified activated carbon eventually by sulfydryl is thermally treated resulting in, it realizes that the controllable of mercapto functional group introduces and be distributed, improves absorption property of the sulphydryl activity charcoal to alkyl mercury.
Description
Technical field
The present invention relates to activated carbon modified technical field more particularly to a kind of sulphydryl activity charcoal and preparation method thereof and in alkane
Application in the absorption of base mercury.
Background technology
Alkyl mercury (methyl mercury, ethyl mercury) is a kind of severe toxicity and has the organo-metallic compound of strong carcinogenesis, such
Compound is fat-soluble by force, easily remains in the biological body adipose tissue in natural water, and be enriched in aquatic food chain, and then
Serious harm is generated to the mankind and animal.
The technology of enrichment mercury compound can substantially be divided into acidolysis solvent rich in environmental sample, alkali digestion is enriched with, acid is waved
Send out preenrichment, cold trap trapping method, solid phase microemulsion preconcentrate method, 6 kinds of solid phase extraction.Wherein, what domestic application was relatively broad is solid phase
Alkyl mercury using the solid containing sulfydryl as filler, is carried out adsorbing separation by extraction from environmental sample.In the prior art, in
State patent CN 105771902A report a kind of sulfhydryl modified liquid formed using thioacetic acid, acetic anhydride and the concentrated sulfuric acid to work
Property charcoal be modified processing, reacted using hydroxyl and the thioacetic acid of activated carbon surface and sulfydryl be fixed on activated carbon,
It can be as the sulfhydryl modified activated carbon of mercury removal agent so as to be made；Xiao Lingling etc. (referring to《Mercapto-functionalized activated carbon is to mercury ion
Study on adsorption properties and Mechanisms》, modern chemical industry, 2013,33 (10):70~75) a kind of utilization γ-mercapto propyl three is disclosed
Methoxy silane carries out magnesium oxide/absorbent charcoal sulfhydryl modified novel mercapto functionalization activated carbon demercuration material, utilizes concentrated sulfuric acid etc.
Strong oxidizer to activated carbon carry out pre-oxidation treatment can improve the quantity of carbon surface hydroxy functional group, and be greatly promoted with
Mercury ion has the grafting in carbon surface of the mercapto functional group of strong affinity.At present, the prior art is mostly with or in activity
Carbon surface produces the special functional group of certain class, and such as active hydroxyl reacts with sulfydryl presoma, thus by sulfydryl official
Can group be grafted onto activated carbon surface, there are sulfydryl introduction volume is low, be unevenly distributed in carbon surface, finally the absorption of alkyl mercury imitated
The problem of fruit is poor.
Invention content
In consideration of it, the purpose of the present invention is to provide a kind of sulphydryl activity charcoal and preparation method thereof and in alkyl mercury absorption
Application.The introduction volume of sulfydryl is high in the sulphydryl activity charcoal that preparation method provided by the invention obtains, to the adsorption energy of alkyl mercury
Power is strong.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of preparation method of sulphydryl activity charcoal, includes the following steps：
(1) methylolation and polycondensation reaction in absolute ethyl alcohol are occurred near amino thiophenols, melamine, formaldehyde, obtained
To sulfydryl prepolymerization modification liquid；
(2) modification is carried out after the sulfydryl prepolymerization modification liquid that the step (1) obtains is mixed with absorbent charcoal powder body,
Obtain near amino thiophenols polymer modified active carbon；
(3) modified activated carbon that the step (2) obtains is heat-treated, obtains sulphydryl activity charcoal.
Preferably, in the step (1) sulfydryl prepolymerization modification liquid a concentration of 100~200g/L, the sulfydryl pre-polymerization
It is 5 to close the molar ratio of near amino thiophenols and melamine in modification liquid：(1~5).
Preferably, the mixing in the step (1) specifically includes following steps：
Near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol are subjected to the first mixing, obtain sulfur-bearing prepolymerization
Liquid, the molar ratio of the near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol is 1:(1.2~2):(3~10)；
Melamine, surplus formaldehyde and second part of absolute ethyl alcohol are subjected to the second mixing, obtain nitrogenous prepolymerization liquid, it is described
The molar ratio of melamine, surplus formaldehyde and second part of absolute ethyl alcohol is 1:(2~3):(3~10)；
Obtained sulfur-bearing prepolymerization liquid, nitrogenous prepolymerization liquid and surplus absolute ethyl alcohol are mixed, sulfydryl prepolymerization is obtained and changes
Property liquid.
Preferably, in the step (2) in sulfydryl prepolymerization modification liquid the mass ratio of solute and absorbent charcoal powder body for 1~
30%..
Preferably, the granularity of absorbent charcoal powder body is 20~600 mesh in the step (2).
Preferably, the absorbent charcoal powder body includes wood activated charcoal, active fruit shell carbon, coaly activated carbon, pitch-based activated
Charcoal or resin matrix activated carbon.
Preferably, in the step (2) temperature of modification for 70~110 DEG C, time of the modification for 8~
48h。
Preferably, the temperature being heat-treated in the step (3) is 350~600 DEG C, and the time of the heat treatment is 2~6h.
The present invention also provides sulphydryl activity charcoal described made from preparation method described in above-mentioned technical proposal, including activity
Charcoal powder and the sulfhydryl modified layer that the absorbent charcoal powder body surface is obtained by near amino thiophenols Polymer-pyrolysis is distributed in, it is described
The doping of sulfydryl is 1~25wt% in sulphydryl activity charcoal.
The present invention also provides application of the sulphydryl activity charcoal described in above-mentioned technical proposal in alkyl mercury absorption.
The present invention provides a kind of preparation method of sulphydryl activity charcoal, by near amino thiophenols, melamine, formaldehyde in nothing
Methylolation and polycondensation reaction occur in water-ethanol, obtains sulfydryl prepolymerization modification liquid；By sulfydryl prepolymerization modification liquid with
Modification is carried out after absorbent charcoal powder body mixing, obtains near amino thiophenols polymer modified active carbon；Modified activated carbon carries out
Heat treatment, obtains sulphydryl activity charcoal.The present invention is changed using the sulfydryl prepolymerization that near amino thiophenols, melamine and formaldehyde are formed
Property liquid is modified absorbent charcoal powder body, can be in absorbent charcoal powder body Surface Creation nanoscale and the adjacent aminobenzene sulphur being evenly distributed
Phenol polymer layer, the content of mercapto functional group can be by adjusting the ratio of near amino thiophenols and absorbent charcoal powder body in wide range
Inside regulated and controled, and be evenly distributed and regulatable sulfhydryl modified activated carbon eventually by sulfydryl is thermally treated resulting in, realize mercapto
The controllable of base functional group introduces and is distributed；The present invention is using melamine-formaldehyde pre-polymer solution as resin matrix simultaneously, a side
Face can reduce heat treatment temperature because its carburizing temperature is relatively low, and stable matrix is formed in heat treatment process, be conducive to most
Mercapto functional group is preserved to limits, improves the doping of sulfydryl；On the other hand the most higher nitrogen-containing functional group of alkalinity at last
(melamine) is introduced into absorbent charcoal powder body surface, and nitrogen-containing functional group can directly receive from mercury atom electronically form from
Sub- dipolar bond further improves absorption property of the sulphydryl activity charcoal to alkyl mercury.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the flow chart that the present invention prepares sulphydryl activity charcoal；
Fig. 2 is the scanning electron microscope (SEM) photograph of sulphydryl activity charcoal of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of sulphydryl activity charcoal, include the following steps：
(1) methylolation and polycondensation reaction in absolute ethyl alcohol are occurred near amino thiophenols, melamine, formaldehyde, obtained
To sulfydryl prepolymerization modification liquid；
(2) modification is carried out after the sulfydryl prepolymerization modification liquid that the step (1) obtains is mixed with absorbent charcoal powder body,
Obtain near amino thiophenols polymer modified active carbon；
(3) modified activated carbon that the step (2) obtains is heat-treated, obtains sulphydryl activity charcoal.
Methylolation and polycondensation are occurred in ethanol solution near amino thiophenols, melamine, formaldehyde by the present invention
Reaction, obtains sulfydryl prepolymerization modification liquid.In the present invention, the concentration of the sulfydryl prepolymerization modification liquid be preferably 100~
200g/L, more preferably 120~180g/L, most preferably 150g/L；Near amino thiophenols in the sulfydryl prepolymerization modification liquid
Molar ratio with melamine is preferably 5：(1~5), more preferably 5：(1.5~4), most preferably 5：(2~3.5).
In the present invention, the formaldehyde adds in preferably in the form of formalin, and the mass fraction of the formalin is excellent
It is selected as 37%.
In the present invention, the mixing specifically includes following steps：
Near amino thiophenols (A), first part of formaldehyde (F) and first part of absolute ethyl alcohol are subjected to the first mixing, obtain sulfur-bearing
Prepolymerization liquid (AF prepolymerizations liquid), the molar ratio of the near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol is 1:
(1.2~2):(3~10)；
Melamine (M), surplus formaldehyde (F) and second part of absolute ethyl alcohol are subjected to the second mixing, obtain nitrogenous prepolymerization
Liquid (MF prepolymerizations liquid), the molar ratio of the melamine, surplus formaldehyde and second part of absolute ethyl alcohol is 1:(2~3):(3~
10)；
Obtained sulfur-bearing prepolymerization liquid, nitrogenous prepolymerization liquid and surplus absolute ethyl alcohol are mixed, sulfydryl prepolymerization is obtained and changes
Property liquid.
Near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol are carried out the first mixing by the present invention, obtain sulfur-bearing
Prepolymerization liquid, the molar ratio of the near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol is preferably 1:(1.2~2):
(3~10), more preferably 1:(1.5~2.6):(4~9).In the present invention, the temperature of first mixing is preferably 20~40
DEG C, more preferably 25~30 DEG C；The time of first mixing is preferably 0.5~4h, more preferably 1~3.5h, most preferably 2
~2.5h.The present invention does not have special restriction to the concrete mode of the described first mixing, and use is well known to those skilled in the art
Hybrid mode, specifically, as stirred.During the first mixing, it is anti-that with formaldehyde will methylolation occur for the near amino thiophenols
It should.Melamine, surplus formaldehyde and second part of absolute ethyl alcohol are carried out the second mixing by the present invention, obtain nitrogenous prepolymerization liquid, institute
The molar ratio for stating melamine, surplus formaldehyde and second part of absolute ethyl alcohol is preferably 1:(2~3):(3~10), more preferably 1:
(2.5~2.8):(4~8).In the present invention, the temperature of second mixing is preferably 40~60 DEG C, more preferably 45~58
DEG C, most preferably 55 DEG C；The time of second mixing is preferably 0.5~4h, more preferably 1.8~3.6h, most preferably 3h.
The present invention does not have special restriction to the concrete mode of the described second mixing, using hybrid mode well known to those skilled in the art
, specifically, as stirred.During the second mixing, with formaldehyde hydroxymethylation will occur for the melamine.
The present invention mixes obtained sulfur-bearing prepolymerization liquid, nitrogenous prepolymerization liquid and surplus absolute ethyl alcohol, and it is pre- to obtain sulfydryl
Polymeric modification liquid.The present invention does not have special restriction to the dosage of the surplus absolute ethyl alcohol, can be modified sulfydryl prepolymerization
The concentration of liquid reaches 100~200g/L.The present invention does not have the concrete mode of the mixing special restriction, using ability
Hybrid mode known to field technique personnel, specifically, as stirred at room temperature.
After obtaining sulfydryl prepolymerization modification liquid, after the present invention mixes the sulfydryl prepolymerization modification liquid with absorbent charcoal powder body
Processing is modified, obtains near amino thiophenols polymer modified active carbon.In the present invention, the sulfydryl prepolymerization modification liquid
The mass ratio of middle solute and absorbent charcoal powder body is preferably 1~30%, more preferably 5~25%.
In the present invention, the granularity of the absorbent charcoal powder body is preferably 20~600 mesh, more preferably 50~300 mesh, optimal
It is selected as 80~100 mesh.
In the present invention, the absorbent charcoal powder body preferably includes wood activated charcoal, active fruit shell carbon, coaly activated carbon, drip
Green matrix activated carbon or resin matrix activated carbon.The present invention does not have the source of the absorbent charcoal powder body special restriction, using ability
Commercial goods known to field technique personnel.
The absorbent charcoal powder body is preferably immersed in sulfydryl prepolymerization modification liquid by the present invention to be mixed.When impregnating,
When the sulfydryl prepolymerization modification liquid can not be completely soaked absorbent charcoal powder body, preferably adding absolute ethyl alcohol makes active powdered carbon
Body is totally submerged in sulfydryl prepolymerization modification liquid.
After the completion of mixing, mixture is preferably placed in open-top receptacle by the present invention is modified processing.
In the present invention, the temperature of the modification is preferably 70~110 DEG C, and the time of the modification is preferably
8~48h.In the present invention, in the modification, methylolated near amino thiophenols and methylolated melamine will
Polycondensation reaction occurs, activated carbon surface is made to generate near amino thiophenols polymer modification layer.
In the present invention, the modification preferably includes evaporation and drying successively, obtains near amino thiophenols polymer
Modified activated carbon.In the present invention, the temperature of the evaporation is preferably 70~90 DEG C, more preferably 75~88 DEG C, most preferably
78~85 DEG C；The time of the evaporation is preferably the ethanol solution evaporating completely until in mixture.
After the completion of evaporation, preferably the product after evaporation is dried by the present invention, obtains the modified activated carbon.In this hair
In bright, the temperature of the drying is preferably 80~110 DEG C, more preferably 85~105 DEG C, most preferably 90~95 DEG C；It is described dry
The dry time is preferably 6~48h, more preferably 18~30h, most preferably 20~for 24 hours.After obtaining modified activated carbon, the present invention
The modified activated carbon is heat-treated, obtains sulphydryl activity charcoal.In the present invention, the heat-treating atmosphere is preferably lazy
Property gas, more preferably high pure nitrogen or high-purity argon gas；The temperature of the heat treatment is preferably 350~600 DEG C, more preferably
380~580 DEG C, most preferably 380~450 DEG C；The time of the heat treatment is preferably 2~6h, more preferably 3~4h.At this
In invention, in the heat treatment process, pyrolytic reaction occurs near amino thiophenols polymer modification layer, will give birth to activated carbon surface
Into it is fluffy, be evenly distributed the sulfhydryl modified layer of nanometer with high activity.
In the present invention, the heating rate for being warming up to the heat treatment temperature is preferably 1~5 DEG C/min, more preferably 3~
4℃/min。
After the completion of heat treatment, heat-treated products are preferably cooled to room temperature by the present invention, obtain sulphydryl activity charcoal.The present invention is right
The concrete mode of the cooling does not have special restriction, such as natural cooling under nitrogen protection.
The present invention also provides sulphydryl activity charcoal described made from preparation method described in above-mentioned technical proposal, including activity
Charcoal powder and the sulfhydryl modified layer that the absorbent charcoal powder body surface is obtained by near amino thiophenols Polymer-pyrolysis is distributed in, it is described
In sulphydryl activity charcoal the doping of sulfydryl for 1~25wt%, preferably 2.8~22.6wt%, more preferably 6.2~
12.7wt%.
In the present invention, nitrogen content is higher in the sulphydryl activity charcoal, and N doping amount is preferably 2.9~19.1wt%, more
Preferably 5.8~10.6wt%, the introducing of nitrogen-containing functional group greatly improve the surface alkalinty of activated carbon, can enhance modification
Activated carbon is to the adsorption capacity of mercury ion in aqueous solution.
In the present invention, in the heat treatment process of the near amino thiophenols polymer modified active carbon, in polymer
The pyrolysis temperature of the nitrogenous structural unit of melamine-formaldehyde class is relatively low, is conducive to preserve mercapto functional group to the maximum extent, and heat
In solution preocess, nitrogenous structural unit easily with certain active sites of activated carbon surface (such as hydroxyl, carboxyl oxygen-containing functional group, carbon
The edge carbons of carbon unsaturated bond or class graphite microcrystalline structure) complex reaction occurs, and in a manner of covalent bond or coordinate bond
With reference to significantly enhancing the binding force between sulfhydryl modified layer and Activated carbon matrix.
The present invention also provides application of the sulphydryl activity charcoal described in above-mentioned technical proposal in alkyl mercury absorption.
In the present invention, it is preferred to which the activated carbon fiber adsorbing substance is loaded in liquid phase fixed bed reactors, it is passed through alkane
Base mercury solution is adsorbed.
In the present invention, the temperature of the absorption is preferably 5~80 DEG C, more preferably 10~65 DEG C, most preferably 25~
35℃。
In the present invention, the absorption preferably carries out under the pressure of 0~20MPa, and more preferably 0.6~15MPa is optimal
It is selected as 0.8~3MPa.
In the present invention, the concentration of the alkyl mercury solution is preferably 0.1~1000ng/L, more preferably 20~700ng/
L, most preferably 200~500ng/L.
In the present invention, the air speed that the alkyl mercury solution enters liquid phase fixed bed reactors is preferably 0.1~10h-1, more
Preferably 1~8h-1, most preferably 2~5h-1。
With reference to embodiment to sulphydryl activity charcoal provided by the invention and preparation method thereof and in alkyl mercury absorption
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Fig. 1 is the preparation method flow chart of sulphydryl activity charcoal of the present invention, and near amino thiophenols, formaldehyde and absolute ethyl alcohol are mixed
It closes, obtains sulfur-bearing prepolymerization liquid, melamine, formaldehyde and absolute ethyl alcohol are mixed, obtain nitrogenous prepolymerization liquid, sulfur-bearing prepolymerization
Liquid is mixed with nitrogenous prepolymerization liquid, obtains sulfydryl prepolymerization modification liquid, and sulfydryl prepolymerization modification liquid is mixed into absorbent charcoal powder body
Row modification obtains near amino thiophenols polymer modified active carbon, after modified activated carbon is dried and is heat-treated, obtains
Sulphydryl activity charcoal.
Embodiment 1
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:1.2：3 molar ratio weighs the adjacent amino of corrresponding quality
Benzenethiol, formalin (37wt.%) and absolute ethyl alcohol, 0.5h is kept stirring at 20 DEG C, obtains sulfur-bearing prepolymerization liquid, cooling
It is spare.
According to melamine (M):Formaldehyde (F)：Absolute ethyl alcohol=1:2：The melamine of 3 molar ratio weighing corrresponding quality
Amine:, formalin (37wt.%) and absolute ethyl alcohol, be kept stirring 0.5h at 40 DEG C, obtain nitrogenous prepolymerization liquid, cooling is standby
With.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous prepolymerization liquid by near amino thiophenols：The molar ratio of melamine is 5:
1 ratio is mixed, and is finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) concentration with absolute ethyl alcohol
It is 100g/L to get sulfydryl prepolymerization modification liquid.
Wood activated charcoal 100g is weighed, 20 mesh powder activated carbons are crushed to, according still further to total polymer (near amino thiophenols
+ melamine+formaldehyde)：The mass ratio of absorbent charcoal powder body is 1%, the sulfydryl prepolymerization modification liquid of 10mL is weighed, by active powdered carbon
Body is soaked in the sulfydryl prepolymerization modification liquid, and adds suitable absolute ethyl alcohol as diluent, it is ensured that absorbent charcoal powder body energy
It is totally submerged in dilute solution.
Said mixture is placed in open-top receptacle, and is stirred at 70 DEG C, until ethanol solution evaporating completely, then
Dry 6h, obtains modified activated carbon at 80 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 1 DEG C/min
Be heat-treated 2h to 350 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, log activated carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, loaded
100g is measured, at 5 DEG C, pressure control is 0.1h in 0MPa, air speed control for reaction temperature control-1, alkyl mercury concentration, which controls, to exist
0.1ng/L, the alkyl mercury rate of recovery of log activated carbon is 78%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 83%.
Embodiment 2
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:2：10 molar ratio weighs the adjacent amino of corrresponding quality
Benzenethiol, formalin (37wt.%) and absolute ethyl alcohol, 4h is kept stirring at 40 DEG C, obtains sulfur-bearing prepolymerization liquid, and cooling is standby
With.
According to melamine:Formaldehyde：Absolute ethyl alcohol=1:3：Melamine, the formaldehyde of 10 molar ratio weighing corrresponding quality
Solution (37wt.%) and absolute ethyl alcohol, 4h is kept stirring at 60 DEG C, obtains nitrogenous prepolymerization liquid, and cooling is spare.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous prepolymerization liquid, by near amino thiophenols：The molar ratio of melamine is
5:5 ratio is mixed, and it is dense to be finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) with absolute ethyl alcohol
Spend is 200g/L to get sulfydryl prepolymerization modification liquid.
Weigh active fruit shell carbon 100g, be crushed to 300 mesh, according still further to total polymer (near amino thiophenols+melamine+
Formaldehyde)：The mass ratio of absorbent charcoal powder body is 30%, weighs the sulfydryl prepolymerization modification liquid of 150mL, absorbent charcoal powder body is soaked in
In the sulfydryl prepolymerization modification liquid, and suitable absolute ethyl alcohol is added as diluent, it is ensured that absorbent charcoal powder body can be totally submerged
In dilute solution；
Said mixture is placed in open-top receptacle, and is stirred at 90 DEG C, until ethanol solution evaporating completely, then
Dry 48h, obtains modified activated carbon at 110 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 5 DEG C/min
Be heat-treated 6h to 600 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, former active fruit shell carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, loaded
1g is measured, at 80 DEG C, pressure control is 10h in 20MPa, air speed control for reaction temperature control-1, alkyl mercury concentration, which controls, to exist
1000ng/L, the alkyl mercury rate of recovery of former active fruit shell carbon is 80%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 93%.
Embodiment 3
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:1.5:5 molar ratio weighs the adjacent amino of corrresponding quality
Benzenethiol, formalin (37wt.%) and absolute ethyl alcohol, 1h is kept stirring at 30 DEG C, obtains sulfur-bearing prepolymerization liquid, and cooling is standby
With.
According to melamine:Formaldehyde：Absolute ethyl alcohol=1:2.5:The melamine of 8 molar ratio weighing corrresponding quality, first
Aldehyde solution (37wt.%) and absolute ethyl alcohol, 3h is kept stirring at 60 DEG C, obtains nitrogenous prepolymerization liquid, and cooling is spare.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous pre-polymer solution by near amino thiophenols：The molar ratio of melamine
It is 5:2 ratio is mixed, and is finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) with absolute ethyl alcohol
A concentration of 150g/L is to get sulfydryl prepolymerization modification liquid.
Coaly activated carbon 100g is weighed, is crushed to 100 mesh powder activated carbons, according still further to total polymer (adjacent aminobenzene sulphur
Phenol+melamine+formaldehyde)：The mass ratio of absorbent charcoal powder body is 10%, the sulfydryl prepolymerization modification liquid of 66.7mL is weighed, by work
Property charcoal powder be soaked in the sulfydryl prepolymerization modification liquid, and add suitable absolute ethyl alcohol as diluent, it is ensured that activated carbon
Powder can be totally submerged in dilute solution；
Said mixture is placed in open-top receptacle, and is stirred at 85 DEG C, until ethanol solution evaporating completely, then
Dry 30h, obtains modified activated carbon at 90 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 3 DEG C/min
Be heat-treated 3h to 400 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, raw coal activated carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, loaded
10g is measured, at 10 DEG C, pressure control is 1h in 0.6MPa, air speed control for reaction temperature control-1, the control of alkyl mercury concentration is in 20ng/
L, the alkyl mercury rate of recovery of raw coal activated carbon is 83%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 97%.
Embodiment 4
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:2：6 molar ratio weighs the adjacent aminobenzene of corrresponding quality
Thiophenol, formalin (37wt.%) and absolute ethyl alcohol, 2.5h is kept stirring at 25 DEG C, obtains sulfur-bearing prepolymerization liquid, and cooling is standby
With.
According to melamine:Formaldehyde：Absolute ethyl alcohol=1:2.8:The melamine of 7 molar ratio weighing corrresponding quality, first
Aldehyde solution (37wt.%) and absolute ethyl alcohol, 1.8h is kept stirring at 58 DEG C, obtains nitrogenous prepolymerization liquid, and cooling is spare.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous prepolymerization liquid by near amino thiophenols：The molar ratio of melamine is 5:
4 ratio is mixed, and is finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) concentration with absolute ethyl alcohol
It is 100g/L to get sulfydryl prepolymerization modification liquid.
Asphalt based active carbon 100g is weighed, is crushed to 80 mesh powder activated carbons, according still further to total polymer (adjacent aminobenzene sulphur
Phenol+melamine+formaldehyde)：The mass ratio of absorbent charcoal powder body is 20%, weighs the sulfydryl prepolymerization modification liquid of 200mL, will be active
Charcoal powder is soaked in the sulfydryl prepolymerization modification liquid, and adds suitable absolute ethyl alcohol as diluent, it is ensured that active powdered carbon
Physical efficiency is totally submerged in dilute solution；
Said mixture is placed in open-top receptacle, and is stirred at 75 DEG C, until ethanol solution evaporating completely, then
Drying for 24 hours, obtains modified activated carbon at 85 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 4 DEG C/min
Be heat-treated 4h to 380 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, protobitumen matrix activated carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, filled
The amount of filling out 5g, at 25 DEG C, pressure control is 2h in 0.8MPa, air speed control for reaction temperature control-1, alkyl mercury concentration, which controls, to exist
200ng/L, the alkyl mercury rate of recovery of protobitumen matrix activated carbon is 85%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 98%.
Embodiment 5
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:2：4 molar ratio weighs the adjacent aminobenzene of corrresponding quality
Thiophenol, formalin (37wt.%) and absolute ethyl alcohol, 2h is kept stirring at 35 DEG C, obtains sulfur-bearing prepolymerization liquid, and cooling is standby
With.
According to melamine:Formaldehyde：Absolute ethyl alcohol=1:3：Melamine, the formaldehyde of 10 molar ratio weighing corrresponding quality
Solution (37wt.%) and absolute ethyl alcohol, 3.6h is kept stirring at 55 DEG C, obtains nitrogenous prepolymerization liquid, and cooling is spare.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous prepolymerization liquid by near amino thiophenols：The molar ratio of melamine is 5:
3.5 ratio is mixed, and it is dense to be finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) with absolute ethyl alcohol
Spend is 120g/L to get sulfydryl prepolymerization modification liquid.
Resin matrix activated carbon 100g is weighed, is crushed to 300 mesh powder activated carbons, according still further to total polymer (adjacent aminobenzene
Thiophenol+melamine+formaldehyde)：The mass ratio of absorbent charcoal powder body is 25%, the sulfydryl prepolymerization modification liquid of 208mL is weighed, by work
Property charcoal powder be soaked in the sulfydryl prepolymerization modification liquid, and add suitable absolute ethyl alcohol as diluent, it is ensured that activated carbon
Powder can be totally submerged in dilute solution；
Said mixture is placed in open-top receptacle, and is stirred at 78 DEG C, until ethanol solution evaporating completely, then
Dry 20h, obtains modified activated carbon at 105 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 5 DEG C/min
Be heat-treated 2h to 580 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, primary resin matrix activated carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, filled
The amount of filling out 2g, at 35 DEG C, pressure control is 5h in 3MPa, air speed control for reaction temperature control-1, the control of alkyl mercury concentration is in 500ng/
L, the alkyl mercury rate of recovery of primary resin matrix activated carbon is 82%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 99%.
Embodiment 6
According near amino thiophenols:Formaldehyde：Absolute ethyl alcohol=1:2：9 molar ratio weighs the adjacent aminobenzene of corrresponding quality
Thiophenol, formalin (37wt.%) and absolute ethyl alcohol, 3.5h is kept stirring at 28 DEG C, obtains sulfur-bearing prepolymerization liquid, and cooling is standby
With.
According to melamine:Formaldehyde：Absolute ethyl alcohol=1:3：Melamine, the formaldehyde of 4 molar ratio weighing corrresponding quality
Solution (37wt.%) and absolute ethyl alcohol, 1h is kept stirring at 60 DEG C, obtains nitrogenous prepolymerization liquid, and cooling is spare.
By obtained sulfur-bearing prepolymerization liquid and nitrogenous prepolymerization liquid by near amino thiophenols：The molar ratio of melamine be for
5:1.5 ratio is mixed, and is finally diluted to total polymer (near amino thiophenols+melamine+formaldehyde) with absolute ethyl alcohol
A concentration of 180g/L is to get sulfydryl prepolymerization modification liquid.
Wood activated charcoal 100g is weighed, is crushed to 200 mesh powder activated carbons, according still further to total polymer (adjacent aminobenzene sulphur
Phenol+melamine+formaldehyde)：The mass ratio of absorbent charcoal powder body is 15%, weighs the sulfydryl prepolymerization modification liquid of 83mL, will be active
Charcoal powder is soaked in the sulfydryl prepolymerization modification liquid, and adds suitable absolute ethyl alcohol as diluent, it is ensured that active powdered carbon
Physical efficiency is totally submerged in dilute solution；
Said mixture is placed in open-top receptacle, and is stirred at 88 DEG C, until ethanol solution evaporating completely, then
Dry 18h, obtains modified activated carbon at 95 DEG C.
Above-mentioned modified activated carbon is placed in tube furnace, nitrogen is passed through and heats up as protection gas, and with the rate of 3 DEG C/min
Be heat-treated 3h to 450 DEG C, continue thereafter under nitrogen protection cooled to room temperature to get sulphydryl activity charcoal.
Finally, protolignin's matrix activated carbon and the sulphydryl activity charcoal are respectively placed in liquid phase fixed bed reactors, filled
The amount of filling out 1.25g, at 65 DEG C, pressure control is 8h in 15MPa, air speed control for reaction temperature control-1, alkyl mercury concentration, which controls, to exist
700ng/L, the alkyl mercury rate of recovery of primary resin matrix activated carbon is 77%, and the alkyl mercury rate of recovery of sulphydryl activity charcoal is 95%.
Fig. 2 is the scanning electron microscope (SEM) photograph of sulphydryl activity charcoal：A) unmodified activated carbon；B) 10% polymer fluid is modified sulphydryl activity
Charcoal；C) 20% polymer fluid is modified sulphydryl activity charcoal；D) 30% polymer fluid is modified sulphydryl activity charcoal, and as shown in Figure 2, the present invention can obtain
To the acticarbon of the sulfhydryl modified coating with nanoscale, it is evenly distributed, is tightly combined in activated carbon surface.
EDS analysis result of the table 1 for different sulfhydryl modified activated carbons, as can be seen from Table 1, sulfydryl produced by the present invention is lived
Property charcoal, the doping ratio of surface sulfydryl is adjustable between 2.8~22.6wt%, with sulfydryl prepolymerization modification liquid and activated carbon
The raising of ratio, the surface sulfhydryl content in sulphydryl activity charcoal obtained also greatly increase.
The EDS analysis results of 1 sulfhydryl modified activated carbon of table
Table 2 is absorption result of the different sulfhydryl modified activated carbons to methyl mercury, as can be seen from Table 2, produced by the present invention
Sulphydryl activity charcoal is excellent to the absorption property of alkyl mercury.
2 sulfhydryl modified activated carbon of table is to the absorption result of methyl mercury
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulphydryl activity charcoal, includes the following steps：
(1) methylolation and polycondensation reaction in absolute ethyl alcohol are occurred near amino thiophenols, melamine, formaldehyde, obtains mercapto
Base prepolymerization modification liquid；
(2) modification is carried out after the sulfydryl prepolymerization modification liquid that the step (1) obtains is mixed with absorbent charcoal powder body, is obtained
Near amino thiophenols polymer modified active carbon；
(3) modified activated carbon that the step (2) obtains is heat-treated, obtains sulphydryl activity charcoal.
2. preparation method according to claim 1, which is characterized in that sulfydryl prepolymerization modification liquid in the step (1)
A concentration of 100~200g/L, the molar ratio of near amino thiophenols and melamine is 5 in the sulfydryl prepolymerization modification liquid：(1
~5).
3. preparation method according to claim 1 or 2, which is characterized in that the mixing in the step (1) specifically include with
Lower step：
Near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol are subjected to the first mixing, obtain sulfur-bearing prepolymerization liquid, institute
The molar ratio for stating near amino thiophenols, first part of formaldehyde and first part of absolute ethyl alcohol is 1:(1.2~2):(3~10)；
Melamine, surplus formaldehyde and second part of absolute ethyl alcohol are subjected to the second mixing, obtain nitrogenous prepolymerization liquid, the trimerization
The molar ratio of cyanamide, surplus formaldehyde and second part of absolute ethyl alcohol is 1:(2~3):(3~10)；
The sulfur-bearing prepolymerization liquid, the nitrogenous prepolymerization liquid and surplus absolute ethyl alcohol are mixed, obtain sulfydryl prepolymerization modification
Liquid.
4. preparation method according to claim 1, which is characterized in that in the step (2) in sulfydryl prepolymerization modification liquid
The mass ratio of solute and absorbent charcoal powder body is 1~30%.
5. preparation method according to claim 1, which is characterized in that the granularity of absorbent charcoal powder body is in the step (2)
20~600 mesh.
6. preparation method according to claim 1 or 5, which is characterized in that the absorbent charcoal powder body include wood activated charcoal,
Active fruit shell carbon, coaly activated carbon, asphalt based active carbon or resin matrix activated carbon.
7. preparation method according to claim 1, which is characterized in that the temperature of modification is 70 in the step (2)
~110 DEG C, the time of the modification is 8~48h.
8. the preparation method according to claim 1 or 7, which is characterized in that the temperature of heat treatment is in the step (3)
350~600 DEG C, the time of the heat treatment is 2~6h.
9. the sulphydryl activity charcoal made from preparation method described in claim 1~8 any one, which is characterized in that including
Absorbent charcoal powder body and the sulfhydryl modified layer that the absorbent charcoal powder body surface is obtained by near amino thiophenols Polymer-pyrolysis is distributed in,
The doping of sulfydryl is 1~25wt% in the sulphydryl activity charcoal.
10. application of the sulphydryl activity charcoal in alkyl mercury absorption described in claim 9.
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| CN112499626A (en) * | 2020-11-11 | 2021-03-16 | 陕西浦士达环保科技有限公司 | Preparation process of active coke |
| CN118005017A (en) * | 2024-01-23 | 2024-05-10 | 浙江佶竹生物科技有限公司 | Preparation and application of bamboo activated carbon capable of serving as catalyst carrier |
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| CN118005017A (en) * | 2024-01-23 | 2024-05-10 | 浙江佶竹生物科技有限公司 | Preparation and application of bamboo activated carbon capable of serving as catalyst carrier |
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