CN116850952A - Thallium removing agent for magnetic manganese dioxide, preparation method and application thereof - Google Patents
Thallium removing agent for magnetic manganese dioxide, preparation method and application thereof Download PDFInfo
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- CN116850952A CN116850952A CN202310948957.8A CN202310948957A CN116850952A CN 116850952 A CN116850952 A CN 116850952A CN 202310948957 A CN202310948957 A CN 202310948957A CN 116850952 A CN116850952 A CN 116850952A
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- thallium
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- manganese dioxide
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 229910052716 thallium Inorganic materials 0.000 title claims abstract description 120
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 108
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 14
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 14
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 14
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000004113 Sepiolite Substances 0.000 claims description 36
- 229910052624 sepiolite Inorganic materials 0.000 claims description 36
- 235000019355 sepiolite Nutrition 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000001568 sexual effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 39
- 239000000463 material Substances 0.000 description 26
- 239000006249 magnetic particle Substances 0.000 description 14
- -1 thallium ions Chemical class 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical group [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a thallium removing agent for magnetic manganese dioxide, a preparation method and application thereof, wherein the preparation method of the thallium removing agent for magnetic manganese dioxide comprises the following steps: adding a carrier into the solution with the dissolved iron source, stirring, adding ammonia water, and growing Fe on the carrier 3 O 4 The nano particles are subjected to solid-liquid separation to obtain a magnetic load nano material; will be magneticAdding the sexual loaded nano material into an acidic solution, stirring for reaction, adding potassium permanganate and manganese sulfate, and stirring or performing ultrasonic reaction to obtain a magnetic manganese dioxide thallium removal agent synthetic raw material; and heating the synthesized raw materials of the magnetic manganese dioxide thallium removal agent to 120-160 ℃ for reaction for 12-24 hours, recovering the solid in the solution by using a magnet or a centrifuge, washing the solid by pure water, and drying and grinding the solid to obtain the magnetic manganese dioxide thallium removal agent. The invention combines the magnetic nano material and the carrier, and can effectively disperse the nano particles by utilizing the space structure of the carrier, so that the nano particles can fully exert the efficacy, and the thallium treatment depth is high.
Description
Technical Field
The invention relates to thallium removal technology, in particular to a thallium removal agent for magnetic manganese dioxide, a preparation method and application thereof.
Background
Thallium is a trace element and depends on the existence of ores in the geochemical system, and has great harm to human bodies, thallium enters the human bodies to rapidly enter the body to circulate, damage the body systems and various organs of the human bodies, and the damage is irreversible, serious and even causes death. The thallium is strictly controlled in China, the solubility of thallium in drinking water is not allowed to exceed 0.1 mug/L, and in view of the harm and limiting standard of thallium, development of an efficient thallium removing agent which is efficient and convenient for recycling is urgently needed.
At present, nano materials are considered as ideal materials for emergency treatment of thallium, but due to smaller size, the nano materials are often gathered together in the synthesis process, so that the defects of buried adsorption active sites, poor mechanical stability and the like are caused.
In view of the above, it is highly desirable to research a high-efficiency nano thallium removing agent, which ensures environmental safety and human health, and provides a novel suitable emergency material for emergency treatment of thallium.
Disclosure of Invention
Aiming at the problems that the traditional thallium removing agent has buried adsorption active sites and poor mechanical stability, the invention provides a preparation method of the thallium removing agent of magnetic manganese dioxide.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of a thallium removing agent for magnetic manganese dioxide comprises the following steps:
step 1) preparation of magnetic carrier nano material, adding carrier (such as sepiolite) into solution dissolved with iron source, stirring while adding ammonia water, and growing Fe on the carrier 3 O 4 The nano particles are subjected to solid-liquid separation to obtain a magnetic load nano material;
step 2) adding the magnetic load nano material into an acidic solution, adding potassium permanganate and manganese sulfate under stirring, and stirring or performing ultrasonic treatment to obtain a magnetic manganese dioxide thallium removal agent synthetic raw material;
and 3) preparing the thallium removing agent of the magnetic manganese dioxide, heating the synthesized raw material of the thallium removing agent of the magnetic manganese dioxide to 120-160 ℃ for reaction for 12-24 hours (preferably to 120 ℃ for reaction for 20 hours), recovering the solid in the solution by using a magnet or a centrifuge, washing the solid by pure water, and drying and grinding the solid to obtain the thallium removing agent of the magnetic manganese dioxide.
Further, the support of step 1) includes, but is not limited to, sepiolite, activated carbon, or kaolin. The carrier in the step 1) is a nano material with high surface area and rich porosity, and the active carrier for preparing the thallium removing agent of the magnetic manganese dioxide must ensure that the active carrier has a large enough space structure, is favorable for the adhesion of the active material on the surface, and provides an adsorption site which is 4 times or more than that of the active material.
Further, the carrier of step 1) is preferably sepiolite, which has a three-dimensional network structure comprising a plurality of channels of different diameters and lengths, which cross each other and are connected to form a complex and stable spatial structure. And the channel structure can help the nano particles to be uniformly dispersed on the carrier, in addition, the size, the shape and the distribution of the loaded nano particles can be effectively controlled due to the highly stable skeleton structure of the sepiolite and the ion exchange sites, and the instability of the nano particles caused by surface free energy is reduced. Sepiolite is a material with high specific surface area and porosityThe inorganic nano material has a spatial structure which is favorable for the adhesion of nano particles and can be Fe 3 O 4 The nanoparticles provide loading sites, and subsequently formed manganese dioxide can also be attached to the surface or within the pores thereof.
Further, step 1) the iron source includes Fe 3+ Iron source and Fe 2+ An iron source of Fe 3+ With Fe 2+ The molar ratio of (2) is 1-3:1, preferably 3:2 or 2:1.
further, the iron source in step 1) is one or more of nitrate, sulfate and halide, preferably the Fe 3+ The iron source is FeCl 3 ·6H 2 O and/or FeCl 3 The Fe is 2+ The iron source is FeCl 2 ·4H 2 O and/or FeSO 4 。
Further, the dosage ratio of the iron source to the ammonia water in the step 1) is 0.5-1.5:1 (g/ml), the concentration of the ammonia water is 10-25%.
Further, the particle size of the magnetic loading nano material in the step 1) is 300-500nm, preferably 350-450nm.
Further, in the step 1), water is used for dissolving an iron source, heating is carried out to 70-90 ℃ and stirring is carried out to obtain Fe ion mixed solution, the carrier is dissolved in water and then added into the Fe ion mixed solution to obtain carrier-containing suspension, ammonia water is added while stirring, the ammonia water is added within 3-5 minutes, the suspension is completely blackened, constant-temperature stirring is continued for 2-4 hours (preferably 2.5-3.5 hours), and after solid-liquid separation of a centrifugal machine, pure water is used for washing and grinding to obtain the magnetic load nano material. The invention dissolves the carrier in water and then adds the carrier into the Fe ion mixed solution, which is beneficial for the carrier to be fully dispersed in the Fe ion mixed solution.
Further, step 2) adding the magnetic load nano material into an acidic solution, stirring and reacting for 15-25 min, adding potassium permanganate and manganese sulfate, stirring or ultrasonically reacting for 20-35 min, and obtaining the magnetic manganese dioxide thallium removal agent synthetic raw material.
Further, in the step 2), the mass ratio of the magnetic load nano material to the potassium permanganate is 0.5-3:1, and the preferred mass ratio is 1-2:1; the mass ratio of the potassium permanganate to the manganese sulfate is 1-8:1, and the preferable mass ratio is 3-6:1; the mass-volume ratio of the total mass of the magnetic load nano material, the potassium permanganate and the manganese sulfate to the acid solution is 1:20-60 (g/ml).
Further, the acid solution in the step 2) is a hydrochloric acid solution, and the concentration of the hydrochloric acid is 0.01-0.1M.
Further, the particle size of the thallium removing agent of the magnetic manganese dioxide in the step 3) is 100-1000nm.
Further, the drying temperature in the step 3) is 65-90 ℃ and the drying time is 18-24 hours.
Further, step 3) the magnetic manganese dioxide thallium removal agent is filled into a reaction kettle with a lining, and the reaction kettle is transferred to an oven.
The invention also discloses a thallium removing agent for magnetic manganese dioxide, which is prepared by the method.
Further, the particle size of the magnetic manganese dioxide thallium removal agent is 100-1000nm.
Further, the adsorption capacity of the magnetic manganese dioxide thallium removing agent to thallium is 400-600mg/g.
The invention also discloses an application of the magnetic manganese dioxide thallium removal agent in the field of thallium removal of wastewater.
The invention also discloses a thallium removing method of the thallium removing agent for magnetic manganese dioxide, which comprises the following steps: and directly adding the thallium removing agent of the magnetic manganese dioxide into the polluted water body, and stirring for 20min-4h to complete thallium removal.
Furthermore, the input amount of the thallium-removing magnetic manganese dioxide in the polluted water body is 0.1-0.5g/L, and the dosage can be properly increased or decreased according to the thallium content of the actual polluted water body.
Further, the stirring rotation speed is 200-300r/min.
The reaction principle of the preparation method of the thallium removing agent for the magnetic manganese dioxide is as follows:
wherein, step 1)
4OH - +2Fe 2+ +Fe 3+ →Fe 3 O 4 +2H 2 O
Wherein, step 3
2MnO 4 - +3Mn 2+ +2H 2 O→5MnO 2 +4H +
The preparation method of the thallium removing agent for magnetic manganese dioxide has the advantages of simple operation, stable product property, and capability of meeting the requirement of large-scale generation and application, and particularly, compared with the prior art, the preparation method of the thallium removing agent for magnetic manganese dioxide has the following advantages:
1) The invention relates to a preparation method of a thallium removing agent for magnetic manganese dioxide, which comprises the steps of firstly growing Fe on a carrier (such as sepiolite) 3 O 4 The nano particles are used for obtaining the magnetic carrier nano material with magnetism. Then dissolving the magnetic carrier nano material, adding manganese dioxide synthesis raw material into the solution, using a reaction kettle to make manganese dioxide fully grow between the vacancies of the magnetic carrier nano material, adopting stepwise synthesis can reduce the interference to the synthesis of manganese dioxide when the magnetic particle raw material coexist, and using sepiolite can reduce the agglomeration of magnetic particles, and manganese dioxide part also grows near the magnetic particles on the sepiolite surface. The sepiolite is introduced to not only space the magnetic particles, but also disperse the synthesized manganese dioxide, so that the aggregation of the magnetic particles due to paramagnetic property and the aggregation of the nano particles due to smaller size are solved, the adsorption performance of the material is obviously improved, and the active adsorption material fully exerts the performance of the material. The thallium removing agent for magnetic manganese dioxide has extremely strong thallium adsorption capacity, and the used adsorption material can be easily recovered from the solution by using the magnet. The adsorption performance of the material is obviously improved by stepwise preparation in the preparation process, and the adsorption effect of the material is far greater than that of sepiolite, magnetic particles and magnetic sepiolite, which shows that manganese dioxide is the main active substance for adsorbing thallium.
2) The invention relates to a preparation method of a thallium removing agent for magnetic manganese dioxide, which utilizes sepiolite nano-carriers to grow Fe 3 O 4 The nano particles are also beneficial to the subsequent utilization of the Fe-Nd magnet and Fe 3 O 4 The magnetic force between the nano particles is used for recovering the nano composite thallium removing agent, so that secondary pollution to the environment after thallium in the wastewater is adsorbed is effectively avoided.
3) The nano composite thallium removing agent prepared by the preparation method of the nano composite thallium removing agent comprehensively utilizes sepiolite, magnetic particles and the thallium removing capability of manganese dioxide, wherein manganese dioxide is a main active thallium adsorption substance, the thallium removing efficiency of the magnetic manganese dioxide thallium removing agent is extremely high, the sepiolite not only has a certain adsorption effect on thallium, but also can be used as a carrier to disperse the magnetic particles and manganese dioxide by virtue of a space structure, and the problem that adsorption active sites cannot be fully utilized due to agglomeration and the utilization rate of materials is low is solved.
4) The thallium removing agent of the magnetic manganese dioxide has extremely high thallium adsorption capacity which is higher than that of most reported adsorption materials at present, the thallium adsorption capacity is up to 585mg/g, the wastewater can meet the discharge standard by low-dose addition, more than 99% of thallium ions in the wastewater can be removed in 5min, and the residual adsorption solubility can be as low as 0.1 mug/L.
Drawings
FIG. 1 shows sepiolite, fe 3 O 4 Adsorption quantity analysis chart of thallium in wastewater removed by nano particles, magnetic sepiolite and the thallium removing agent of the magnetic manganese dioxide of example 1;
FIG. 2 is a graph showing the adsorption amount of thallium ions by the magnetic manganese dioxide thallium removal agent of example 1 at different pH values;
FIG. 3 is a schematic diagram of the particle size distribution of the thallium removal agent for magnetic manganese dioxide of example 1;
FIG. 4 is an electron micrograph of a magnetic manganese dioxide thallium removal agent of example 1.
Detailed Description
The invention is further illustrated by the following examples:
example 1
Referring to fig. 1 and 2, the present embodiment discloses a preparation method of a nanocomposite thallium removal agent, comprising the following steps:
step 1) preparing a magnetic sepiolite nano material: the molar ratio of the configuration is Fe 3+ ：Fe 2+ =3: fe of 2 3+ And Fe (Fe) 2+ Wherein Fe is 3+ The solution is FeCl 3 ，Fe 2+ The solution is FeSO 4 A solution;specifically, 2.43g FeCl was dissolved in 40ml of water, respectively 3 6H 2 O and 1.67g FeSO 4 ·7H 2 And O, heating to 90 ℃ under stirring to obtain an iron ion mixed solution, and keeping the temperature at 90 ℃ for later use.
Dissolving 1g sepiolite in 30ml water, adding into the above iron ion mixture, adding 2.5ml 25% concentrated ammonia water, stirring for 3 hr, and centrifuging to obtain supernatant 3 O 4 And (3) carrying out centrifugation on the suspension to collect solid, washing the solid with ultrapure water for multiple times, and drying and grinding the solid at 105 ℃ to obtain the magnetic sepiolite nanomaterial. Sepiolite has a network structure, contains a large number of pores, can provide a sufficient adhesion platform for magnetic particles, and has a space structure capable of fixing the magnetic particles.
2) The acidic solution dissolves the magnetic sepiolite nano material, and the manganese dioxide synthetic raw material is dissolved in the solution: the mass ratio of the magnetic sepiolite nano material to the potassium permanganate is 0.8:1, and the mass ratio of the potassium permanganate to the manganese sulfate is 5:1. Specifically, firstly dissolving a magnetic sepiolite nano material in 0.01M 80ml hydrochloric acid solution, then adding potassium permanganate and manganese sulfate raw materials, stirring and dissolving for 30min to obtain a synthetic raw material of a magnetic manganese dioxide thallium removal agent; the mass-volume ratio of the total mass of the magnetic sepiolite, the potassium permanganate and the manganese sulfate to the acid solution is 1:30 (g/ml);
3) Preparing a magnetic manganese dioxide thallium removal agent: and (3) loading the synthetic raw materials of the magnetic manganese dioxide thallium removal agent into a reaction kettle with a lining, transferring the reaction kettle into an oven, maintaining the temperature at 120 ℃ for 24 hours to obtain a material, recovering or centrifugally separating solid by using a magnet, washing the solid with distilled water until the supernatant is colorless, finally, placing the obtained solid into the oven, drying the obtained solid at 65 ℃ for 24 hours, and grinding to obtain the magnetic manganese dioxide thallium removal agent.
The thallium ion adsorption test result of the magnetic manganese dioxide thallium removal agent prepared in this example is shown in fig. 1, and the test method is as follows: respectively taking 10mg of the thallium removing agent, sepiolite and Fe of the magnetic manganese dioxide prepared by the embodiment 3 O 4 Nanoparticle, magnetic sepiolite nanomaterial prepared in step 1 (abbreviated as Fe) 3 O 4 SEP) was added to 50ml of 50ppmtl solution, ph=7, and shake-absorbed for 2h.
As can be seen from FIG. 1, the magnetic manganese dioxide thallium removal agent prepared in this example shows excellent adsorption performance in adsorption capacity, and its adsorption capacity to thallium is far greater than that of sepiolite and Fe 3 O 4 After the nano particles and the magnetic sepiolite are introduced into the manganese dioxide, the adsorption performance is greatly improved, which shows that the adsorption of the manganese dioxide to thallium in the magnetic manganese dioxide thallium removal agent prepared by the invention is dominant. Meanwhile, after the adsorption is finished, the magnetic particles are introduced, so that the adsorption material can be easily recovered by introducing the magnetic environment, and secondary pollution caused by residual environment of the adsorption material is avoided. The magnetic sepiolite has an adsorption capacity greater than that of Fe alone in the presence of sepiolite 3 O 4 The nano particles show that the space structure of the sepiolite avoids the agglomeration of magnetic particles, so that adsorption active sites can better contact thallium ions, and the rest effective space can also be used for dispersing active material manganese dioxide, so that the synthesis process of manganese dioxide can be prevented from being interfered by the existence of a large number of synthesis raw materials of the magnetic particles in the step-by-step synthesis, and the generation of the manganese dioxide structure is better ensured.
The detection results of thallium adsorption amounts of the magnetic manganese dioxide thallium removal agent prepared in the embodiment at different pH values are shown in figure 2. The test method is as follows: after the adsorption was completed, the adsorption material was settled to the bottom by a magnet, 8ml of supernatant was collected by a syringe, and then the supernatant was filtered by a 0.22 μm disposable syringe, and 30. Mu.L of an equivalent amount of nitric acid solution (50%, v/v) was added to preserve the sample. The thallium residual concentration was determined by inductively coupled plasma spectrometry (ICP), and the experiment was repeated three times with the addition of an error bar.
As can be seen from fig. 2, in the pH range of 1-11, the thallium ion removal efficiency of the magnetic manganese dioxide thallium removal agent prepared in this example is higher than 95%, and the thallium ion adsorption of the magnetic manganese dioxide thallium removal agent is not affected in a wide pH environment, which may cause that the material has a low charge zero point, which is only 2.14, and this indicates that at a pH value of more than 2.14, the material surface is always negatively charged, which makes positively charged thallium ions very easy to reach the material surface through electrostatic attraction, and the affinity of the manganese dioxide host material to thallium is very strong, so that the material always maintains high removal efficiency at a wide pH.
As can be seen from FIG. 3, the magnetic manganese dioxide thallium removing agent prepared in this example is typical nanoparticles, the particle diameter is distributed between 1-1000nm, the main particle diameter is about 100-600nm, the average particle diameter is 419.5nm, the adsorption material cannot be recovered by conventional filtration, and the present invention introduces magnetic particles, so that the defect of difficult recovery of the nano material can be solved to a great extent.
As can be seen from fig. 4, the magnetic manganese dioxide thallium removing agent prepared in this embodiment has a rich pore structure, the material is of a typical gully structure, the surface of the material is extremely uneven, and thallium ions easily reach the surface of the material in the thallium adsorption process, so that thallium ions enter the material space, and are favorable for adsorption and removal of thallium.
Example 2
The embodiment discloses a preparation method of a thallium removing agent for magnetic manganese dioxide, which comprises the following steps:
1) The molar ratio of the configuration is Fe 3+ ：Fe 2+ Fe=2:1 3+ Salt solution and Fe 2+ Salt solution and mixing Fe therein 3+ The solution is FeCl 3 ·6H 2 O，Fe 2+ The solution is FeCl 2 ·4H 2 An O solution; specifically, 3.24g FeCl was dissolved in 40ml of water, respectively 3 6H 2 O and 1.19g FeCl 2 ·4H 2 And O, heating to 90 ℃ under stirring to obtain an iron ion mixed solution, and keeping the temperature at 90 ℃ for later use.
Dissolving 1.5g sepiolite in 30ml water, adding into the above iron ion mixture, adding 4ml 25% concentrated ammonia water, stirring for 3 hr, and centrifuging to obtain supernatant 3 O 4 And (3) carrying out centrifugation on the suspension to collect solid, washing the solid with ultrapure water for multiple times, and drying and grinding the solid at 105 ℃ to obtain the magnetic sepiolite nanomaterial. .
2) Dissolving the magnetic sepiolite in a hydrochloric acid solution of 0.05M, then adding the potassium permanganate and the manganese sulfate raw materials, wherein the volume of the hydrochloric acid solution is 5 times of the sum of the volumes of the magnetic sepiolite, the potassium permanganate and the manganese sulfate, stirring and dissolving for 45min, and obtaining a synthetic raw material of the magnetic manganese dioxide thallium removal agent;
3) Preparing a magnetic manganese dioxide thallium removal agent: adding the synthetic raw material of the thallium removing agent of the magnetic manganese dioxide into a reaction kettle, wherein the volume ratio of the synthetic raw material of the thallium removing agent of the magnetic manganese dioxide to the reaction kettle is 1:1.3, heating the reaction kettle, maintaining the constant temperature at 120 ℃ for 24 hours, settling the adsorption material by using a magnetic device, adding pure water, stirring and washing, continuing to settle by using the magnetic device, washing until supernatant fluid is clear after settling, separating solid materials, and grinding by using a grinder to obtain the magnetic manganese dioxide thallium removal agent.
The thallium removing agent of the magnetic manganese dioxide synthesized by the embodiment has optimized thallium adsorption performance, can meet the removal requirement under wide pH, has residual solubility lower than 2ug/L for removing thallium solution with initial solubility of 200ug/L, and meets the emission requirements of various industrial activities.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the thallium removing agent for the magnetic manganese dioxide is characterized by comprising the following steps:
step 1) adding a carrier into the solution dissolved with the iron source, stirring and adding ammonia water to grow Fe on the carrier 3 O 4 The nano particles are subjected to solid-liquid separation to obtain a magnetic load nano material;
step 2) adding the magnetic load nano material into an acidic solution, adding potassium permanganate and manganese sulfate under stirring, and stirring or performing ultrasonic treatment to obtain a magnetic manganese dioxide thallium removal agent synthetic raw material;
and 3) heating the synthesized raw materials of the magnetic manganese dioxide thallium removal agent to 120-160 ℃ for reaction for 12-24 hours, recovering the solid in the solution by using a magnet or a centrifuge, washing the solid by pure water, and drying and grinding the solid to obtain the magnetic manganese dioxide thallium removal agent.
2. The method for preparing the thallium removing agent for magnetic manganese dioxide according to claim 1, wherein the carrier in the step 1) is sepiolite, activated carbon or kaolin.
3. The method for preparing a thallium removal agent for magnetic manganese dioxide as defined in claim 1, wherein in step 1) the iron source comprises Fe 3+ Iron source and Fe 2+ An iron source of Fe 3+ With Fe 2+ The molar ratio of (2) is 1-3:1.
4. The method for preparing the thallium removing agent for magnetic manganese dioxide according to claim 1, wherein the dosage ratio of the iron source to the ammonia water in the step 1) is 0.5-1.5:1 (g/ml), the concentration of the ammonia water is 10-25%.
5. The method for preparing the thallium removing agent for magnetic manganese dioxide according to claim 1, characterized in that in step 1), water is used for dissolving an iron source, heating is carried out to 70-90 ℃ and stirring is carried out to obtain an Fe ion mixed solution, the carrier is dissolved in water and then added into the Fe ion mixed solution to obtain a carrier-containing suspension, ammonia water is added while stirring, the ammonia water is added within 3-5 minutes, stirring is continued for 2-4 hours at constant temperature, and after solid-liquid separation of a centrifuge, pure water is washed and ground to obtain the magnetic load nanomaterial.
6. The method for preparing the thallium removing agent for magnetic manganese dioxide according to claim 1, wherein in the step 2), the magnetic load nano material is added into an acidic solution, stirred and reacted for 15-25 min, potassium permanganate and manganese sulfate are added, and stirred or ultrasonically reacted for 20-35 min, so as to obtain the synthetic raw material of the thallium removing agent for magnetic manganese dioxide.
7. The method for preparing the thallium removal agent for magnetic manganese dioxide according to claim 1, wherein in the step 2), the mass ratio of the magnetic load nanomaterial to potassium permanganate is 0.5-3:1; the mass ratio of the potassium permanganate to the manganese sulfate is 1-8:1; the mass-volume ratio of the total mass of the magnetic load nano material, the potassium permanganate and the manganese sulfate to the acid solution is 1:20-60 (g/ml).
8. The method for preparing a thallium removing agent for magnetic manganese dioxide according to claim 1, wherein the acidic solution in the step 2) is a hydrochloric acid solution, and the concentration of hydrochloric acid is 0.01 to 0.1M.
9. A thallium removal agent for magnetic manganese dioxide, characterized in that it is prepared by the method of any one of claims 1-8.
10. Use of the magnetic manganese dioxide thallium removal agent of claim 9 in the wastewater thallium removal field.
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