CN108889278A - A kind of preparation method of composite adsorption microballoon that removing mercury ion - Google Patents
A kind of preparation method of composite adsorption microballoon that removing mercury ion Download PDFInfo
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- CN108889278A CN108889278A CN201810748152.8A CN201810748152A CN108889278A CN 108889278 A CN108889278 A CN 108889278A CN 201810748152 A CN201810748152 A CN 201810748152A CN 108889278 A CN108889278 A CN 108889278A
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- cellulose
- illite
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- microballoon
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 82
- 239000001913 cellulose Substances 0.000 claims abstract description 82
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 78
- 229910052900 illite Inorganic materials 0.000 claims abstract description 64
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 235000010980 cellulose Nutrition 0.000 claims description 75
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000004005 microsphere Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 3
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 3
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical group CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 229920000875 Dissolving pulp Polymers 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 22
- 229910052753 mercury Inorganic materials 0.000 description 22
- 239000002351 wastewater Substances 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 17
- 230000010355 oscillation Effects 0.000 description 8
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QFAXIZQBSCGJMA-UHFFFAOYSA-N mercury;hydrate Chemical compound O.[Hg] QFAXIZQBSCGJMA-UHFFFAOYSA-N 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
Classifications
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of preparation method of composite adsorption microballoon that removing mercury ion, including illitic pretreatment；The preparation of cellulose ionic liquid；The preparation of illite cellulose mixed solution：The illite of different quality and the pore former of corresponding proportion are added into the cellulose ionic liquid of preparation, stirs evenly；The preparation of illite cellulose composite adsorption microballoon；The preparation of modified illite cellulose composite adsorption microballoon.Invention uses illite and cellulose for raw material, by ion liquid dissolving cellulose, illite is added and pore former prepares composite adsorption microballoon, raw material is cheap and easy to get, and nontoxic, ionic liquid is nontoxic, and dissolubility is strong, can be recycled, environmental-friendly；By the modified illite cellulose composite adsorption microballoon of graft N-methyl-1-methyl mercapto-2- nitroethylene amine, sulfydryl and amido are introduced to composite adsorption microballoon, greatly strengthens its adsorption efficiency to mercury ion.
Description
Technical field
The present invention relates to a kind of preparation methods of adsorbent, more particularly to the composite adsorption microballoon as mercury-removing adsorbent
Preparation method.
Background technique
In recent years, with the rapid development of society, environmental pollution caused by the discharge of industrial wastewater and sanitary sewage is further
Seriously, the mercury ion pollution problem wherein in water body is the most serious, it can cause serious harm to biology.Therefore it goes to remove water
Mercury ion in body has become an environmental problem urgently to be solved.
Illite is a kind of silicate mica-group clay minerals of rich potassium, and appearance off-white, property is crisp, frangible, partial size is small, tool
There are the properties such as specific surface is big, ion-exchange capacity is strong.Cellulose is most renewable resource in the world at present, nontoxic, duct
It is more.Illite and cellulose itself are used as adsorbent, not high to the adsorption efficiency of heavy metal ion, it is therefore desirable to carry out to it
It is modified to enhance its adsorption efficiency to heavy metal ion.Ionic liquid is research hotspot in recent years, using ionic liquid without
Poison, easily recycling, the features such as solvability is strong, prepare illite cellulose composite adsorption microballoon, and can be effective to its modification
Improve its adsorption efficiency to heavy metal ion in water.It is modified illite cellulose composite adsorption microballoon good dispersion in water,
Easily recycling has good effect to Heavy metal ions in water are solved.
Summary of the invention
The present invention is directed to prior art problem, provides a kind of preparation method of composite adsorption microballoon that can remove mercury ion,
Using illite and cellulose as raw material, by ion liquid dissolving cellulose, illite is added and pore former prepares composite adsorption
Microballoon；Sulfydryl and amido are introduced to composite adsorption microballoon by graft N-methyl-1-methyl mercapto-2- nitroethylene amine, to increase
Its strong adsorption efficiency to mercury ion.
Technical problem of the present invention is solved with following technical solution：
A kind of preparation method of composite adsorption microballoon that removing mercury ion, the preparation method are original with illite and cellulose
Material, preparation include the following steps：
A, illitic pretreatment：It weighs 10g illite and carries out cleaning removal of impurities, it is stand-by that 200 meshes are crossed after drying；
B, the preparation of cellulose ionic liquid：The cellulose of 1g is added into ionic liquid for the ionic liquid for measuring 40ml,
Constant temperature oil bath stirs 1h at 100 DEG C, so that cellulose is completely dissolved；
C, the preparation of illite cellulose mixed solution：0.5-2g is added in the cellulose ionic liquid prepared to the step b
Illite and mass fraction be 10%-50% pore former, stir evenly；
D, the preparation of illite cellulose composite adsorption microballoon：The hydrochloric acid that 150ml 1mol/L is prepared in the beaker of 250ml is molten
Liquid is placed the beaker and is stirred on magnetic stirring apparatus；Constant pressure leakage is added in the illite cellulose mixed solution of step c preparation
It in bucket, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, adsorption microspheres are washed to neutrality, be lyophilized,
Obtain illite cellulose composite adsorption microballoon；
E, the preparation of modified illite cellulose composite adsorption microballoon：The step d of 1g is added in the three-necked flask of 250ml
The illite cellulose composite adsorption microballoon of preparation, is added the ceric ammonium nitrate solution of 200ml, the pure nitric acid of 0.4ml, in N2Protection
Under, it is stirred to react 15min at 35 DEG C, 1g N- methyl-1-methyl mercapto-2- nitroethylene is then slowly added into three-necked flask
Amine is stirred to react 3h at 35 DEG C；It filters, products therefrom carries out Soxhlet extraction 12h, filters again, 45 in air dry oven
Dry drying 12h, obtains modified illite cellulose composite adsorption microballoon at DEG C.
The preparation method of the above-mentioned composite adsorption microballoon for removing mercury ion, the cellulose are microcrystalline cellulose, cotton fibre
One of dimension, stalk cellulose or paper fibre element.
The preparation method of the above-mentioned composite adsorption microballoon for removing mercury ion, the step b intermediate ion liquid are 1- allyl
- 3 methylimidazole villaumite of base or 1- butyl -3- methylimidazole villaumite.
The preparation method of the above-mentioned composite adsorption microballoon for removing mercury ion, in the step c, pore former is calcium carbonate.
The present invention uses illite and cellulose for raw material, by ion liquid dissolving cellulose, be added illite and at
Hole agent prepares composite adsorption microballoon, and raw material is cheap and easy to get, nontoxic, and ionic liquid is nontoxic, and dissolubility is strong, can be recycled, environment
It is friendly；By the modified illite cellulose composite adsorption microballoon of graft N-methyl-1-methyl mercapto-2- nitroethylene amine, to compound
Adsorption microspheres introduce sulfydryl and amido, greatly strengthen its adsorption efficiency to mercury ion, composite adsorption microballoon is to mercury ion
Maximum adsorption capacity is up to 350mg/g；The composite adsorption of the method for the present invention preparation is microsphere porous, and large specific surface area solves her
The disadvantages of sharp stone matter is crisp, and cellulose specific surface area is small；In addition, its good dispersion in water, the rate of adsorption is fast, in 10min or so
It can reach saturated adsorption capacity, and recyclable.The present invention takes full advantage of the reproducibility of illite and cellulose, for solution
Certainly heavy metal pollution has good application prospect in water；Preparation method of the present invention is simple, easy to operate, pollution-free, is easy to industry
Change, large-scale production.
Detailed description of the invention
Fig. 1 is influence diagram of the pH to composite adsorption microballoon absorption property；
Fig. 2 is influence diagram of the adsorption time to composite adsorption microballoon absorption property；
Fig. 3 is influence diagram of the mercury initial concentration to composite adsorption microballoon absorption property.
Specific embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, stirs 1h in 100 DEG C of constant temperature oil baths, so that cellulose is completely dissolved, is then added 0.5g's
The pore former calcium carbonate of illite and mass fraction 10%, stirs evenly, and obtains illite cellulose mixed solution；250ml's
The hydrochloric acid solution that 150ml 1mol/L is prepared in beaker, places the beaker and stirs on magnetic stirring apparatus；The illite of preparation is fine
It ties up plain mixed solution to be added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will inhale
Attached microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 83.4mg/g to the adsorption capacity of mercury-containing waste water.
Embodiment 2
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, stirs 1h in 100 DEG C of constant temperature oil baths, so that cellulose is completely dissolved, 1g she is then added
The pore former calcium carbonate of sharp stone and mass fraction 10%, stirs evenly, and obtains illite cellulose mixed solution；In the burning of 250ml
The hydrochloric acid solution that 150ml 1mol/L is prepared in cup, places the beaker and stirs on magnetic stirring apparatus；By Erie's mineral wool of preparation
Plain mixed solution is added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will adsorb
Microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 85.2mg/g to the adsorption capacity of mercury-containing waste water.
Embodiment 3
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, stirs 1h in 100 DEG C of constant temperature oil baths, so that cellulose is completely dissolved, is then added 1.5g's
The pore former calcium carbonate of illite and mass fraction 10%, stirs evenly, and obtains illite cellulose mixed solution；250ml's
The hydrochloric acid solution that 150ml 1mol/L is prepared in beaker, places the beaker and stirs on magnetic stirring apparatus；The illite of preparation is fine
It ties up plain mixed solution to be added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will inhale
Attached microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 81.4mg/g to the adsorption capacity of mercury-containing waste water.
Embodiment 4
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, stirs 1h in 100 DEG C of constant temperature oil baths, so that cellulose is completely dissolved, is then added 1.5g's
The pore former calcium carbonate of illite and mass fraction 30%, stirs evenly, and obtains illite cellulose mixed solution；250ml's
The hydrochloric acid solution that 150ml 1mol/L is prepared in beaker, places the beaker and stirs on magnetic stirring apparatus；The illite of preparation is fine
It ties up plain mixed solution to be added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will inhale
Attached microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 83.8mg/g to the adsorption capacity of mercury-containing waste water.
Embodiment 5
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, stirs 1h in 100 DEG C of constant temperature oil baths, so that cellulose is completely dissolved, is then added 1.5g's
The pore former calcium carbonate of illite and mass fraction 50%, stirs evenly, and obtains illite cellulose mixed solution；250ml's
The hydrochloric acid solution that 150ml 1mol/L is prepared in beaker, places the beaker and stirs on magnetic stirring apparatus；The illite of preparation is fine
It ties up plain mixed solution to be added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will inhale
Attached microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 87.5mg/g to the adsorption capacity of mercury-containing waste water.
Embodiment 6
Experimental rig platform is built, illite is cleaned and is cleaned, 200 meshes are crossed after drying, for use；Take 40ml ionic liquid, to from
1g cellulose is added in sub- liquid, 1 g she is then added so that cellulose is completely dissolved in 100 DEG C of constant temperature oil bath stirring 1h
The pore former calcium carbonate of sharp stone and mass fraction 30%, stirs evenly, and obtains illite cellulose mixed solution；In the burning of 250ml
The hydrochloric acid solution that 150ml 1mol/L is prepared in cup, places the beaker and stirs on magnetic stirring apparatus；By Erie's mineral wool of preparation
Plain mixed solution is added in constant pressure funnel, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, will adsorb
Microballoon is washed to neutrality, and freeze-drying obtains illite cellulose composite adsorption microballoon.
It is put into the illite cellulose composite adsorption microballoon of 1g preparation in the three-necked flask of 250ml, the nitre of 200ml is added
Sour cerium ammonium salt solution, the pure nitric acid of 0.4ml, in N2Under protection, 15min is stirred to react at 35 DEG C, then slowly into three-necked flask
1g N- methyl-1-methyl mercapto-2- nitroethylene amine is added, is stirred to react 3h at 35 DEG C；It filters, products therefrom soxhlet extraction
12h；It filters again, dry drying 12h at 45 DEG C, it is micro- to obtain modified illite cellulose composite adsorption in air dry oven
Ball.
Mercury-containing waste water is prepared with mercuric acetate in laboratory, is 1g/L for 100ppm mercury-containing waste water adsorption microspheres dosage,
Oscillation absorption 2h, is filtered with filter needle tubing, is detected after diluting several times step by step with atomic fluorescence spectrophotometer, it is flat to obtain absorption
Weigh concentration, so that calculating modified composite adsorption microballoon is 86.1mg/g to the adsorption capacity of mercury-containing waste water.
Referring to table 1, how empty the modification composite adsorption microballoon of the method for the present invention preparation is, and large specific surface area solves illite
Matter is crisp, the small disadvantage of cellulose specific surface area.
The specific surface area and aperture contrast table of 1 adsorbent of table
| Illite | Microcrystalline cellulose | Illite cellulose composite microsphere | |
| Specific surface area（m2/g） | 23.11 | 1.167 | 4.299 |
| Aperture（nm） | 26.19 | 17.51 | 19.07 |
It is 100 mg/L in mercury initial concentration, the dosage of composite adsorption microballoon is 1g/L, the item of oscillation absorption 2h referring to Fig. 1
Under part, composite adsorption microballoon increases the adsorption capacity of mercury ion with the increase of pH value of solution.Simultaneously as can be seen that being in pH
When 1, adsorption capacity can also reach 65mg/g, show that the composite adsorption microballoon also has good absorption property under strong acid, answer
With in extensive range.
It is 100mg/L in mercury initial concentration, composite adsorption microballoon dosage is 1g/L, and solution ph is 3 referring to Fig. 2
Under the conditions of, composite adsorption microballoon with adsorption time increase plus and increases the adsorption capacity of mercury ion.As seen from the figure, multiple
It closes adsorption microspheres and basically reaches balance when adsorbing 10min, show that the rate of adsorption of composite adsorption microballoon is fast.
It referring to Fig. 3, is 1g/L in composite adsorption microballoon dosage, 2h is adsorbed in oscillation, multiple under conditions of solution ph is 3
Adsorption microspheres are closed to the adsorption capacity of mercury difference initial concentration.As seen from the figure, maximum adsorption of the composite adsorption microballoon to mercury ion
Capacity is 350mg/g, shows that composite adsorption microballoon has very big adsorption capacity, has a good application prospect.
Claims (4)
1. one kind can remove the preparation method of the composite adsorption microballoon of mercury ion, the preparation method is with illite and cellulose
Raw material, which is characterized in that preparation includes the following steps：
A, illitic pretreatment：It weighs 10g illite and carries out cleaning removal of impurities, 200 meshes are crossed after drying, for use；
B, the preparation of cellulose ionic liquid：The cellulose of 1g is added into ionic liquid for the ionic liquid for measuring 40ml,
Constant temperature oil bath stirs 1h at 100 DEG C, so that cellulose is completely dissolved；
C, the preparation of illite cellulose mixed solution：0.5-2g is added in the cellulose ionic liquid prepared to the step b
Illite and mass fraction be 10%-50% pore former, stir evenly；
D, the preparation of illite cellulose composite adsorption microballoon：The hydrochloric acid that 150ml 1mol/L is prepared in the beaker of 250ml is molten
Liquid is placed the beaker and is stirred on magnetic stirring apparatus；Constant pressure leakage is added in the illite cellulose mixed solution of step c preparation
It in bucket, is slowly dropped in hydrochloric acid solution, stirs 1h, adsorption microspheres are obtained by filtration, adsorption microspheres are washed to neutrality, be lyophilized,
Obtain illite cellulose composite adsorption microballoon；
E, the preparation of modified illite cellulose composite adsorption microballoon：The step d of 1g is added in the three-necked flask of 250ml
The illite cellulose composite adsorption microballoon of preparation, is added the ceric ammonium nitrate solution of 200ml, the pure nitric acid of 0.4ml, in N2Protection
Under, it is stirred to react 15min at 35 DEG C, 1g N- methyl-1-methyl mercapto-2- nitroethylene is then slowly added into three-necked flask
Amine is stirred to react 3h at 35 DEG C；It filters, products therefrom carries out Soxhlet extraction 12h, filters again, 45 in air dry oven
Dry drying 12h, obtains modified illite cellulose composite adsorption microballoon at DEG C.
2. the preparation method of the composite adsorption microballoon according to claim 1 for removing mercury ion, it is characterised in that：It is described
Cellulose is one of microcrystalline cellulose, cotton fiber, stalk cellulose or paper fibre element.
3. the preparation method of the composite adsorption microballoon according to claim 2 for removing mercury ion, it is characterised in that：It is described
Step b intermediate ion liquid is -3 methylimidazole villaumite of 1- allyl or 1- butyl -3- methylimidazole villaumite.
4. the preparation method of the composite adsorption microballoon according to claim 3 for removing mercury ion, it is characterised in that：It is described
In step c, the pore former is calcium carbonate.
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| CN115430407A (en) * | 2022-09-16 | 2022-12-06 | 华北电力大学（保定） | Preparation method of fluorescence response type water phase adsorbent, product and application thereof |
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