CN110354829A - For removing the preparation method of the water-fast carbon nanotube of load silver of Elemental Mercury in natural gas - Google Patents

For removing the preparation method of the water-fast carbon nanotube of load silver of Elemental Mercury in natural gas Download PDF

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CN110354829A
CN110354829A CN201910512987.8A CN201910512987A CN110354829A CN 110354829 A CN110354829 A CN 110354829A CN 201910512987 A CN201910512987 A CN 201910512987A CN 110354829 A CN110354829 A CN 110354829A
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carbon nanotube
solution
silver
natural gas
preparation
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CN110354829B (en
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张华伟
王娟
梁鹏
焦甜甜
张亚青
张文睿
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Shandong University of Science and Technology
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Shandong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/60—Heavy metals or heavy metal compounds
    • B01D2257/602—Mercury or mercury compounds

Abstract

The invention discloses a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Elemental Mercury in natural gas, is related to the preparation technical field of carbon nanotube.The following steps are included: selecting carbon nanotube for raw material, it is dissolved in a certain amount of n-hexane and carries out anhydrous dilution, be passivated with a certain amount of trim,ethylchlorosilane；Then a certain amount of concentrated nitric acid is gradually added dropwise and carries out acidification to the carbon nanotube after passivated；Carbon nanotube after acidification is dissolved in a certain amount of n-hexane stirring a period of time, certain density silver nitrate solution is prepared, a certain amount of silver nitrate is gradually added dropwise and is loaded to above-mentioned solution；Then it prepares certain density sodium borohydride solution and liquid-phase reduction is carried out to above-mentioned carbon nano-tube solution, finally obtain Ag and be supported in carbon nanotube duct.The Ag/CNTs that the present invention is prepared has biggish specific surface area, higher mechanical strength and good adsorption capacity, can form reproducible arquerite with the mercury in efficient absorption natural gas.

Description

For removing the preparation method of the water-fast carbon nanotube of load silver of Elemental Mercury in natural gas
Technical field
The present invention relates to the preparation technical fields of carbon nanotube, and in particular to a kind of for removing Elemental Mercury in natural gas The preparation method of carbon nanotube.
Background technique
The characteristics of mercury is that one kind has high toxicity, volatile, biological concentration, is one of most harmful element of human environment, Threaten the health of the mankind.The existence form of mercury in nature there are two types of, one is Elemental Mercuries, and one is organic mercuries.Naturally Mercury in gas mainly exists in the form of simple substance, and current Main Natural Gas demercuration technology is absorption method.
It is to carry sulphur/active carbon of silver, carry sulphur/silver aluminium oxide, carry silver-colored divide that more mercury removal agent is applied in natural gas mercury-removing device Son sieve, dedicated mercury removal agent.After active carbon is loaded into sulphur/silver, increase the surface area of reactive material, improves reactive material and mercury is steamed The adsorption capacity of gas, but active carbon loading silver cost is higher, repeats again the case where being suitable for big gas discharge, depth demercuration It is raw to use；Silver molecular sieve demercuration technology maturation has used for many years, and removal efficiency is high, invests larger；The ingredient one of dedicated mercury removal agent As be metal sulfide or oxide, sulfide is attached to mercury removal agent surface or under given conditions activated metal and hydrocarbon stream In H2S reaction generates sulfide.
Carbon nanotube is wound around central axis by certain helical angle by single-layer or multi-layer graphite hexagonal mesh plane Made of one-dimensional tubular nanometer material, both ends are bound by the pentagon of carbon atom.Its diameter is long from a few nanometers to tens of nanometers Several hundred nanometers are spent to several microns.In the prior art it is the most widely used have prepare antibacterial agent using carbon nanotube, or preparation is urged Agent is urged as the application text of application number 201811028249.8 discloses a kind of carbon multi-wall nano tube loaded nano silver hydrogen reduction Agent and preparation method, mainly with carbon multi-wall nano tube loaded nano silver oxygen reduction catalyst, nano silver having a size of 1~ 6nm, average-size 2.9nm；Nano silver is uniformly distributed on the carbon nanotubes, the load capacity of nano silver be mass percent 10~ 40%, the catalyst that the text is prepared can apply in direct methanol fuel cell in Cathodic oxygen reduction.
However, also there is related scholar to point out, nanotube is in carried metal nano particle in the prior art, using common Its particle of dipping method can reunite or be more likely to cannot be introduced into duct at all, such as document " Highly dispersed Pd nanoparticles supported on1,10-phenanthroline-functionalized multi-walled Carbon nanotubes for electrooxidation of formic acid " it points out in page 6234: acidizing pretreatment The phenogram of carbon nanotube that is obtained using conventional impregnation mode of nanotube as shown in figure 4, as can be seen from Figure 4: nitric acid The surface CNTs of processing generates uneven defect, and Pd nanoparticle is unevenly distributed.Particle tends to deposit on these when load In local defect, lead to poor dispersion and extensive aggregation.
Summary of the invention
The purpose of the present invention is to provide a kind of for removing the preparation side of the water-fast carbon nanotube of load silver of Hg in natural gas Method, silver nano-grain are uniformly dispersed in carbon nanotube, form reproducible arquerite with the mercury simple substance in natural gas, reachable To the effect of efficient absorption mercury simple substance, demercuration efficiency is 96% or more.
Its technical solution includes:
It is a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, successively the following steps are included:
A, it is passivated, selects carbon nanotube for raw material, be dissolved in carrying out anhydrous dilution in a certain amount of hexane solution, lead to It crosses grafting silicon methyl functional group to be passivated carbon nanotube, obtains solution one；
B, step a acquired solution one is condensed back under conditions of 60~80 DEG C of temperature 10~12h, washed by washing, drying Carbon nanotube one is obtained after washing, drying；
C, it is acidified, is gradually added dropwise in carbon nanotube one obtained by a certain amount of concentrated nitric acid to step b, and carry out acidification, Then carbon nanotube two is obtained after washed, dry；
D, Double solvent method loads, and carbon nanotube two is distributed in hexane solution and stirring makes it be uniformly dispersed, and utilizes Double solvent method is by AgNO3Then solution loadings filter out n-hexane in the duct of carbon nanotube two, obtain carbon nanometer after drying Pipe three, wherein silver-colored load capacity is 1.5~2.5%, the AgNO3The concentration of solution is 0.1~0.16mol/L, described AgNO3The volume proportion of both the additional amount of solution and the hexane solution is 1.4:100；
E, carbon nanotube three obtained by step d is distributed in hexane solution, is added thereto excessive by liquid-phase reduction NaBH4Solution, it is washed, dry after to get.
Direct advantageous effects brought by above-mentioned technical proposal are as follows:
The first, above-mentioned technical proposal selects the silver-colored carbon nanotube of load to be used to remove the Elemental Mercury in natural gas for the first time, this is this Application an innovative point, need to consider among these the technical issues of have: first, the control to nano particle diameter.It receives The size of rice grain partial size influences demercuration efficiency, has confinement effect using the duct of carbon nanotube, can be by silver nano-grain Size effectively controlled.Second, the carbon nanotube for loading silver needs to have good hydrophobic performance, and vapor can make to urge Agent inactivation, efficiency are influenced.Original carbon nano tube surface has hydrophilic radical, keeps its hydrophobic performance poor.Above-mentioned technical side Case improves process conditions, the carbon nanotube being prepared both had had resistance to by comprehensively considering from raw material, process conditions It is aqueous, and higher demercuration rate can be kept.
The second, infusion process load silver same as the prior art is not used in above-mentioned technical proposal, but is selected double Solvent method loads, load principle are as follows:
Using the solvent of two kinds of opposed polarities by being successively added in carrier, the nonpolar solvent being first added is allowed sufficiently to moisten Wet carrier surface plays the role of covering carrier surface, another polar solvent containing predecessor is added, due to containing in carrier Large number of orifices, the solvent containing predecessor is entered in duct by capillary absorption and high degree of dispersion.
On the whole, above-mentioned technical proposal can make silver-colored uniform load in carbon nanotube, can be with efficient removal natural gas In mercury, form reproducible arquerite.
As a preferred solution of the present invention, in step a, methyl functional group is provided by trim,ethylchlorosilane, carbon is received Mitron is passivated, and the mass volume ratio of the carbon nanotube and the hexane solution is 3:80g/mL, the carbon The mass volume ratio of nanotube and the trim,ethylchlorosilane is 3:7g/mL.
In above-mentioned technical proposal, raw material carbon nanotube is one-dimensional tubular nanometer material, can be by grafting silicon methyl function Roll into a ball the passivation to realize carbon nanotube.
As another preferred embodiment of the invention, in step b, n-hexane and dehydrated alcohol is selected to be washed, it is dry Temperature is 80 DEG C, dry 12h.
Further, in step c, the mass volume ratio of carbon nanotube one and concentrated nitric acid is 1:50g/mL, select distilled water, Dehydrated alcohol is washed, and drying temperature is 60 DEG C.
In above-mentioned technical proposal, it is acidified carbon nanotube one using concentrated nitric acid, reaches and removes agraphitic carbon, shearing carbon is received The purpose of mitron.
Further, in step d, using Double solvent method by AgNO3Solution loadings are logical in the duct of carbon nanotube two It crosses and AgNO is added dropwise into finely dispersed solution3Solution is obtained through magnetic agitation 5h；Drying temperature is 40 DEG C, dry Time is 12h.
In above-mentioned technical proposal, slight excess of NaBH is added dropwise4Solution carries out liquid-phase reduction, makes AgNO3It is reduced into Ag completely Nano particle.
Further, in step e, distilled water and dehydrated alcohol is selected to be washed, drying temperature is 60 DEG C, drying time For 12h.
Further, in step d, silver-colored load capacity is 2%.
It in above-mentioned technical proposal, finds, when silver-colored load capacity is higher than 2%, the removal efficiency of mercury is influenced during the experiment Less, therefore, optimum load amount can be 2%.
Compared with prior art, present invention offers following advantageous effects:
The first, first in terms of raw material selection, having selected the relatively wide carbon nanotube in source is raw material, carbon nanotube table Face activity is strong, can graft the functionalization that various functional groups realize carbon nanotube；Silver nano-grain is supported on carbon nanotube In duct, using the confinement effect in carbon nanotube duct, effective control to nano particle diameter is realized；The carbon of grafting methyl is received Mitron has good hydrophobic performance.
The second, the silver on catalyst is supported in the duct of carbon nanotube.The present invention is realized by Double solvent method, Wherein the high interfacial tension between salting liquid and hydrophobic organic solvent drives a certain amount of metal nanoparticle to enter in duct Portion and high degree of dispersion, and can inhibit metal in the growth of carrier bracket outer surface.Silver nano-grain on catalyst uniformly divides It dissipates, forms reproducible arquerite with the mercury simple substance in natural gas, achieve the effect that efficient absorption mercury simple substance.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing:
Fig. 1 is that the XRD of raw material carbon nanotube of the present invention, Ag nano particle and the silver-colored carbon nanotube of load being finally prepared spreads out Penetrate figure；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph for the silver-colored carbon nanotube of load that the present invention is finally prepared；
Fig. 3 is demercuration efficiency figure under embodiment difference water vapour content；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph for the silver-colored carbon nanotube of load that the prior art is obtained using conventional impregnation mode.
Specific embodiment
The invention proposes a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Elemental Mercury in natural gas, is Keep advantages of the present invention, technical solution clearer, clear, elaborates combined with specific embodiments below to the present invention.
Raw material needed for the present invention can be bought by commercial channel and be obtained.
Adsorbent activity of the present invention evaluation method is as follows:
Detection method: fixed bed reactors, the detection architecture of mercury vapourmeter are used.
Adsorbent activity detecting step: preparation gained loads the tubular type that silver-colored carbon nanotube adsorption agent is placed in fixed bed reactors In furnace, the N of air inlet is carried out using mass flowmenter2Flow control, mercury generator bath temperature control at 30 DEG C, use Mercury vapourmeter measures mercury concentration.
Evaluation method: demercuration efficiency can be obtained by the variation of front and back mercury content.Calculation method such as formula (1):
Embodiment 1:
The first step, passivation: selecting quality is the carbon nanotube of 3g, is dissolved in the n-hexane of 80mL and in ultrasonic disperse instrument Ultrasonic disperse 15min is carried out, 7mL trim,ethylchlorosilane (TCMS) is gradually added dropwise under conditions of ultrasonic disperse and is passivated, holds Continuous ultrasonic disperse 30min；
Carbon nano-tube solution after passivation is condensed back 10h under conditions of temperature 70 C by second step, with n-hexane, Dehydrated alcohol washs several times, and 12h is dried under conditions of oven temperature is 80 DEG C；
Third step, acidification: selecting quality is the above-mentioned carbon nanotube of 1g, is dissolved in the concentrated nitric acid of 50mL, is in temperature Be condensed back 12h under conditions of 100 DEG C, with distilled water, dehydrated alcohol wash several times, oven temperature be 60 DEG C under conditions of into The dry 12h of row；
The load of 4th step, silver nitrate: above-mentioned carbon nanotube is distributed in 100mL n-hexane, and magnetic agitation 1h is being stirred The AgNO of 1.4mL is gradually added dropwise under conditions of mixing to it3Solution (0.0254g AgNO3It is dissolved in 1.4mL H2O), continue magnetic force to stir 5h is mixed, n-hexane is filtered, 12h is dried under conditions of temperature is 40 DEG C；
5th step, reduction Argent grain: above-mentioned carbon nanotube is distributed in 30mL n-hexane, under stirring conditions to it The NaBH that 1.5mL concentration is 0.3M is gradually added dropwise4Solution stirs 1h, is washed with distilled water and dehydrated alcohol, is 60 DEG C in temperature Item under 12h is dried.Finally obtain the carbon nanotube that silver load capacity is 1.5%.
Demercuration experiment is carried out to the load silver carbon nanotube that the present embodiment is prepared, selects simulation natural gas methane content 85%, remaining is N2Carry out demercuration experiment.CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is 400mL/min, into The experiment of row demercuration.Experimental result is that demercuration efficiency is about 97%.Carbon nanotube, Ag nano particle and the silver being finally prepared are born The carbon nanotube XRD diffraction pattern that carrying capacity is 1.5% is as shown in Figure 1.
Embodiment 2:
Difference from Example 1 is:
The carbon nanotube that the load capacity of silver is 2% is controlled in 4th step,
It is 2mL that sodium borohydride solution is added dropwise in 5th step.
Select simulation natural gas methane content 85%.Remaining is N2Carry out demercuration experiment.CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is that 400mL/min carries out demercuration experiment.Experimental result demercuration efficiency is 98%.Finally it is prepared into The carbon nanotube SEM scanning electron microscope (SEM) photograph that the silver load capacity arrived is 2% is as shown in Figure 2.
Embodiment 3:
Difference from Example 1 is:
The carbon nanotube that silver load capacity is 2.5% is controlled in 4th step,
It is 3mL that sodium borohydride solution is added dropwise in 5th step.
Select simulation natural gas methane content 85%.Remaining is N2Demercuration experiment is carried out, CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is that 400mL/min carries out demercuration experiment.Experimental result demercuration efficiency is 98%.
From above-described embodiment 1- embodiment 3 it is found that it is 1.5%~2.5% that silver carrying amount of the present invention, which preferably controls, most preferably 2%.
The different content of vapor is smaller on demercuration efficiency influence,
Present invention research preparation carries silver-colored carbon nanotube in different H2The shadow of water-fast demercuration performance under the atmosphere of O content It rings.
Embodiment 4:
Difference from Example 1 is that silver load capacity is 2%.
Selecting simulation gas water vapor content is 3%, methane content 85%.Remaining is N2Carry out demercuration experiment.
CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is that 400mL/min carries out demercuration experiment.Experimental result It is about 97.5% for demercuration efficiency.
Embodiment 5:
Difference from Example 1 is that silver load capacity is 2%.
Select simulation natural gas H2O content is 4%, methane content 85%.Remaining is N2Carry out demercuration experiment.
H is passed through when experiment2It is about 4% that O, which controls content, CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is 400mL/min carries out demercuration experiment.Experimental result is that demercuration efficiency is about 97%.
Embodiment 6:
Difference from Example 1 is that silver load capacity is 2%.
Select simulation natural gas H2O content is 5%, methane content 85%.Remaining is N2Carry out demercuration experiment.
H is passed through when experiment2It is about 5% that O, which controls content, CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is 400mL/min carries out demercuration experiment.Experimental result is that demercuration efficiency is about 96.7%.
Embodiment 7:
Difference from Example 1 is that silver load capacity is 2%.
Select simulation natural gas H2O content is 6%, methane content 85%.Remaining is N2Carry out demercuration experiment.
H is passed through when experiment2It is about 6% that O, which controls content, CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is 400mL/min carries out demercuration experiment.Experimental result is that demercuration efficiency is about 96.3%.
Embodiment 8:
Difference from Example 1 is that silver load capacity is 2%.
Select simulation natural gas H2O content is 7%, methane content 85%.Remaining is N2Carry out demercuration experiment.
H is passed through when experiment2It is about 7% that O, which controls content, CH when experiment4It is passed through flow 600mL/min, carrier gas N2Flow is 400mL/min carries out demercuration experiment.Experimental result is that demercuration efficiency is about 96%.
From embodiment 4-8 it is found that, under different water vapour content atmosphere, demercuration efficiency exists when load silver content is 2% 96% or more, vapor influences the demercuration performance of catalyst smaller.Carbon nanotube water resistance prepared by the present invention is good, takes off Mercury is high-efficient, and specific data are as shown in Figure 3.
Comparative example 1:
Difference from Example 1 are as follows:
4th step comprises the concrete steps that: infusion process used, the carbon nanotube of functionalization is distributed in 100mL dehydrated alcohol, Weigh 0.0318g AgNO3It is dissolved in 30mL distilled water, is added drop-wise in CNTs, persistently stir 5h, wash several times, in 60 DEG C of temperature Lower drying.
Other steps are identical, finally obtain the carbon nanotube that silver load capacity is 2%.
Demercuration experiment is carried out to the load silver carbon nanotube that the comparative example 1 is prepared, selects simulation natural gas methane content 85%；Remaining is N2Carry out demercuration experiment；Experimental result is that demercuration efficiency is about 92%.
Comparative example 2:
Difference from Example 1 are as follows:
5th step comprises the concrete steps that: using calcining reduction method, the carbon nanotube for loading silver nitrate is ground and is put into tube furnace In, in N2The lower 350 DEG C of calcinings 3h of atmosphere, take out cooling.
Demercuration experiment is carried out to the load silver carbon nanotube that the comparative example 1 is prepared, selects simulation natural gas methane content 85%；Remaining is N2Carry out demercuration experiment；Experimental result is that demercuration efficiency is about 97%.
Comparative example 3:
Difference from Example 1 are as follows:
Step 1: acidification: selecting quality is the carbon nanotube of 3g, is dissolved in the concentrated nitric acid of 150mL and in ultrasonic disperse Instrument carries out ultrasonic disperse 15min, and 140 DEG C of oil baths are condensed back 12h, washing to neutrality, dry 12h at being 80 DEG C in temperature；
Step 2: the load of silver nitrate: above-mentioned carbon nanotube is distributed in 100mL dehydrated alcohol, magnetic agitation 1h, AgNO is added to it under conditions of stirring3Solution (0.0318g AgNO3It is dissolved in 30mL H2O), continue magnetic agitation 12h, washing Several times, 12h is dried under conditions of temperature is 80 DEG C；
Step 3: reduction Argent grain: above-mentioned carbon nanotube being distributed in 30mL n-hexane, under stirring conditions to it The NaBH that 2mL concentration is 0.3M is gradually added dropwise4Solution stirs 1h, is washed with distilled water and dehydrated alcohol, is 60 DEG C in temperature 12h is dried under item.Finally obtain the carbon nanotube that silver load capacity is 2%.
Demercuration experiment is carried out to the load silver carbon nanotube that the comparative example 1 is prepared, selects simulation natural gas methane content 85%；Remaining is N2Carry out demercuration experiment；Experimental result is that demercuration efficiency is about 90%.
It uses for reference the prior art and can be realized in the part that do not addressed in the present invention.
It should be noted that any equivalent way that those skilled in the art are made under the introduction of this specification, or Obvious variant should all be within the scope of the present invention.

Claims (7)

1. a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, which is characterized in that successively include Following steps:
A, it is passivated, selects carbon nanotube for raw material, be dissolved in carrying out anhydrous dilution in a certain amount of hexane solution, by transferring It meets silicon methyl functional group to be passivated carbon nanotube, obtains solution one；
B, step a acquired solution one is condensed back 10~12h by washing, drying under conditions of 60~80 DEG C of temperature, wash, Carbon nanotube one is obtained after drying；
C, it is acidified, is gradually added dropwise in carbon nanotube one obtained by a certain amount of concentrated nitric acid to step b, and carry out acidification, then Carbon nanotube two is obtained after washed, dry；
D, Double solvent method loads, and carbon nanotube two is distributed in hexane solution and stirring makes it be uniformly dispersed, using double molten Agent method is by AgNO3Then solution loadings filter out n-hexane in the duct of carbon nanotube two, obtain carbon nanotube after drying Three, wherein silver-colored load capacity is 1.5~2.5%, the AgNO3The concentration of solution is 0.1~0.16mol/L, described AgNO3The volume proportion of the additional amount of solution and the hexane solution is 1.4:100；
E, carbon nanotube three obtained by step d is distributed in hexane solution, excessive NaBH is added thereto by liquid-phase reduction4It is molten Liquid, it is washed, dry after to get.
2. it is according to claim 1 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: provide methyl functional group in step a by trim,ethylchlorosilane and carbon nanotube is passivated, the carbon The mass volume ratio of nanotube and the hexane solution is 3:80g/mL, the carbon nanotube and the trimethyl chlorine The mass volume ratio of silane is 3:7g/mL.
3. it is according to claim 2 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: selecting n-hexane and dehydrated alcohol to be washed in step b, drying temperature is 80 DEG C, dry 12h.
4. it is according to claim 3 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: the mass volume ratio of carbon nanotube one and concentrated nitric acid is 1:50g/mL in step c, distilled water, anhydrous second are selected Alcohol is washed, and drying temperature is 60 DEG C.
5. it is according to claim 4 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: in step d, using Double solvent method by AgNO3Solution loadings be in the duct of carbon nanotube two by point It dissipates in uniform solution and AgNO is added dropwise3Solution is obtained through magnetic agitation 5h；Drying temperature is 40 DEG C, and drying time is 12h。
6. it is according to claim 5 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: selecting distilled water and dehydrated alcohol to be washed in step e, drying temperature is 60 DEG C, drying time 12h.
7. it is according to claim 6 a kind of for removing the preparation method of the water-fast carbon nanotube of load silver of Hg in natural gas, It is characterized by: silver-colored load capacity is 2% in step d.
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