阅读说明：本技术 一种固体碳基Anderson型含钼杂多酸催化剂及其应用 (A kind of solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid and its application ) 是由 郭军 蔡丽丽 解田 史连军 张丹 李文飞 于 2019-09-02 设计创作，主要内容包括：本发明公开了一种固体碳基Anderson型含钼杂多酸催化剂及其应用。其制备步骤为将碳质多孔材料和羧基官能团偶联剂加入pH为3~4的稀酸溶液中,室温下磁力搅拌12~24h,加入Anderson型含钼杂多酸、表面活性剂,超声震荡0.5~1h,移入水热反应釜中,利用程序升温的烘箱,将反应温度在0.5~1h内由室温升至150~180℃,保持该温度48~72h,而后自然降温至室温,分别用超纯水和乙醇冲洗数次,过滤,干燥10~12h。本发明所述的催化剂能够在非均相条件下高效催化过氧化氢氧化碘离子生成碘单质,反应条件温和,过氧化氢利用率高,环境友好无污染,无过氧化,热稳定性好,可以重复循环使用多次,易回收利用。(The invention discloses a kind of solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid and its applications.Its preparation step is that carbonaceous porous material and carboxyl functional group coupling agent are added in the dilute acid soln that pH is 3 ~ 4, magnetic agitation 12 ~ for 24 hours at room temperature is added Anderson type and contains molybdenum heteropolyacid, surfactant, 0.5 ~ 1h of ultrasonic vibration, it moves into hydrothermal reaction kettle, using the baking oven of temperature programming, reaction temperature is risen to 150 ~ 180 DEG C by room temperature in 0.5 ~ 1h, keeps 48 ~ 72h of the temperature, then it is naturally cooling to room temperature, filtering for several times, dry 10 ~ 12h are rinsed with ultrapure water and ethyl alcohol respectively.Catalyst of the present invention can generate elemental iodine in efficient catalytic hydrogen peroxide oxidation iodide ion under heterogeneous conditions, and reaction condition is mild, and hydrogen peroxide utilization rate is high, environmental-friendly pollution-free, no peroxidating, thermal stability is good, it can be used with repetitive cycling repeatedly, it is easy to be recycled.)

1. a kind of carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid, it is characterised in that: its preparation step is that carbonaceous is more Porous materials and carboxyl functional group coupling agent are added in the dilute acid soln that pH is 3 ~ 4, and Anderson type is added and contains molybdenum heteropolyacid, surface Activating agent, magnetic agitation 12 ~ for 24 hours, 0.5 ~ 1h of ultrasonic vibration move into hydrothermal reaction kettle, utilize the baking of temperature programming at room temperature Reaction temperature is risen to 150 ~ 180 DEG C by room temperature in 0.5 ~ 1h, keeps 48 ~ 72h of the temperature, be then naturally cooling to room by case Temperature rinses filtering for several times, dry 10 ~ 12h with ultrapure water and ethyl alcohol respectively.

2. the carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid according to claim 1, it is characterised in that: the carbon Matter porous material is one of active carbon through pre-treatment, multi-walled carbon nanotube, graphene, fullerene, carbon fiber；The carbon Matter porous material pre-treatment is as follows: cleaning carbonaceous porous material with the sodium hydroxide solution of 0.1M at normal temperature, then uses 0.1M Dilute hydrochloric acid cleaning to remove soluble acid, the alkaline impurities of carbonaceous porous material surface；By carbonaceous porous material in concentration To handle 12-15h in 30% nitric acid solution, washs, be heated to reflux 4 ~ 8h, it is more to obtain carbonaceous by dry 8 ~ 12h at 100 ~ 120 DEG C Porous materials sample.

3. the carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid according to claim 1, it is characterised in that: described Anderson type is in Anderson type zinc ammonium molybdate heteropoly acid and Anderson sections ammonium molybdate heteropoly acid containing molybdenum heteropolyacid It is a kind of.

4. the carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid according to claim 1, it is characterised in that: described Carboxyl functional group coupling agent is 1,1- cyclobutane dioctyl phthalate benzene, o-carboxyl phenylacetic acid, 5- carboxyl -2- chlorophenylboronic acid, para hydroxybenzene One or more of formic acid.

5. the carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid according to claim 1, it is characterised in that: described Surfactant is N,N-dimethylformamide, N-Methyl pyrrolidone, N, N dimethyl lauryl amine, isopropanol, 2-alkane One or more of base imidazoline.

6. application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid in iodine recycling, specifically: it is used for phosphorus ore wet process Iodine recycles in phosphoric acid, iodine recycling, the extraction of marine product iodine and the iodine of industrial wastewater containing iodine recycle in brine.

7. application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid according to claim 6 in iodine recycling, It is characterized in that, its removal process is to mix catalyst with Biodine, pH value is adjusted, hydrogen peroxide is added while stirring, Reaction generates elemental iodine, is passed through hot-air in the solution after the reaction was completed, and elemental iodine forms iodine vapor distillation in solution, to the cold shape It is crystallized at iodine.

8. application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid according to claim 7 in iodine recycling, It is characterized in that, in catalytic iodine removal process catalyst feed intake mass percent be 0.5%~10%.

9. application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid according to claim 7 in iodine recycling, It is characterized in that, the concentration of hydrogen peroxide put into removal process is 10%~30%, hydrogen peroxide input amount is theoretical input amount 1~1.5 times.

10. application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid according to claim 7 in iodine recycling, It is characterized in that reaction need to carry out in acid condition, pH value is adjusted between 1~3 using sulfuric acid or phosphoric acid.

Technical field

The invention belongs to catalytic fields, and in particular to a kind of carbon-based Anderson type of solid for iodine recycling is miscellaneous more containing molybdenum The preparation of acid catalyst and application method.

Background technique

Iodine is one of scarce resource in the world, is also important industrial chemicals, chemical products be widely used in food, All conglomeraties such as medicine, dyestuff, metallurgy, synthetic rubber, agricultural, national defence hard-core technology.Nature does not have special iodine mine, can only It is extracted from other iodine substances.The industrialized production of iodine is mainly the characteristic that is easily distilled according to iodine, using oxidant by seaweed, Iodide ion oxid-reclamatiom in the raw materials such as phosphorus ore.With the development of economy, traditional application field persistently increases the demand of iodine, And iodine is constantly applied to new field, the disparities between supply and demand of iodine will be protruded more.Although various iodine amount of storage are larger, do not solve The certainly situation of iodine resource scarcity.But various iodine recycling approach have that iodine resource equivalent containing iodine is low and recovery rate is low at present, produce It is at high cost.It is opposite using suitable oxidation although iodine can be recycled by ion-exchange, solvent signal suppression, precipitation method etc. For agent, higher cost.Suitable catalyst is selected it is noted that iodide ion is easily oxidized into the higher price such as acid iodide, is needed Acid iodide is reduced into elemental iodine again.For example notification number is the Chinese invention patent of CN103183320A, discloses a kind of " recycling The method of iodine " aoxidizes the inorganic iodine in waste liquid using sodium hypochlorite as oxidant, is exchanged and is set using strong alkalinity anion Rouge carries out enriching and recovering to this part iodine, one step of iodate ion is then reduced to elemental iodine again, this iodine recovery process is excessively Complexity, while chlorate produces chloride ion during oxidation, forms volatile salts acid corrosion equipment, green is not achieved The requirement of environmental protection.

Hydrogen peroxide is because its oxidation product is water, while hydrogen peroxide oxidation is moderate, its product will not be made to cause peroxide Change, but the rate of hydrogen peroxide oxidation iodide ion is relatively low, it is industrial to need when the equivalent of the iodine especially in propiodal is relatively low Longer time could obtain the iodine of certain mass.Therefore the oxidation rate of hydrogen peroxide oxidation iodide ion is improved using catalyst It is the key that solve the problems, such as this.But the catalytic efficiency of catalyst used at present is relatively low, and it is poor to recycle, at high cost.Such as Chen Xiaohu etc. has certain catalytic action to iodine oxidation recycling using sulfuric acid as catalyst, but there is no apparent for oxidation rate It improves.

Polyoxometallate collects acid base catalysator, oxidation reduction catalyst, metal oxide nanocatalyst etc. simultaneously Good characteristic is, it is considered to be a kind of multifunction catalyst of widely used green.Anderson type structure is polyacid Lesser one kind of structure in family, Anderson type heteropoly acid have homogeneous and multi-phase catalysis action.Due to D with higher_3d Symmetry, Anderson type heteropoly acid can carry out functionalization with organic ligand and form new effective catalyst.The present invention proposes one The kind carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid is for recycling iodide ion heterogeneous catalysis, high catalytic efficiency cyclicity Can be good, it is easily recycled.

Summary of the invention

The invention solves a technical problem be to provide it is a kind of for iodine recycling the carbon-based Anderson type of solid contain Molybdenum heteropolyacid catalyst.

A kind of carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid for iodine recycling, preparation method are as follows: by carbon Matter porous material and carboxyl functional group coupling agent are added in the dilute acid soln that pH is 3 ~ 4, be added Anderson type containing molybdenum heteropolyacid, Surfactant, magnetic agitation 12 ~ for 24 hours, 0.5 ~ 1h of ultrasonic vibration move into hydrothermal reaction kettle, utilize temperature programming at room temperature Baking oven, reaction temperature is risen to 150 ~ 180 DEG C by room temperature in 0.5 ~ 1h, keeps 48 ~ 72h of the temperature, then Temperature fall To room temperature, filtering for several times, dry 10 ~ 12h are rinsed with ultrapure water and ethyl alcohol respectively.

The carbonaceous porous material, for the active carbon through pre-treatment, multi-walled carbon nanotube, graphene, fullerene, carbon fiber One of dimension.The porous material pre-treatment of these carbonaceous is as follows: cleaning carbonaceous with the sodium hydroxide solution of 0.1M at normal temperature Then porous material is cleaned with the dilute hydrochloric acid of 0.1M to remove the soluble acid of carbonaceous porous material surface, alkaline impurities；It will Carbonaceous porous material handles 12 ~ 15h in the nitric acid solution that concentration is 30%, and washing is heated to reflux 4 ~ 8h, at 100 ~ 120 DEG C Dry 8 ~ 12h, obtains carbonaceous porous material sample.

The Anderson type is Anderson type zinc ammonium molybdate heteropoly acid and Anderson sections molybdic acid containing molybdenum heteropolyacid One of ammonium heteropoly acid.

The carboxyl functional group coupling agent is 1,1- cyclobutane dioctyl phthalate benzene, o-carboxyl phenylacetic acid, 5- carboxyl -2- chlorobenzene One or more of boric acid, P-hydroxybenzoic acid.

The surfactant is N,N-dimethylformamide, N-Methyl pyrrolidone, N, N dimethyl dodecyl One or more of amine, isopropanol, 2-alkyl imidazolines.

The invention solves another technical problem be to use the carbon-based Anderson type catalyst containing molybdenum heteropolyacid of solid It is recycled in iodine.

Application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid in iodine recycling, specifically: in phosphorus ore wet process Iodine recycles in phosphoric acid, iodine recycles in brine, marine product iodine extracts and the iodine recycling field of industrial wastewater containing iodine.

Application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid in iodine recycling, removal process are that will be catalyzed Agent is mixed with Biodine, adjusts pH value, hydrogen peroxide is added while stirring, reaction generates elemental iodine, after the reaction was completed molten Hot-air is passed through in liquid, elemental iodine forms iodine vapor distillation in solution, forms iodine crystallization to the cold.

Application of the solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid in iodine recycling, was recycled in catalytic iodine The existence of iodine is iodide ion in iodine solution in journey, and concentration is greater than 10ppm.

The Biodine, the existing forms of iodine are iodide ion, and concentration is greater than 10ppm.

The adjusting pH is mainly adjusted using sulfuric acid and phosphoric acid, pH value range 1-3.

In the catalytic oxidation process catalyst feed intake mass percent be 0.5%~10%.

The concentration of hydrogen peroxide put into the catalytic oxidation process is 10%~30%, and hydrogen peroxide input amount is theoretical throws Enter 1~1.5 times of amount.

Bring of the present invention is beneficial to benefit: the carbon-based Anderson type of solid for iodine recycling of the invention is miscellaneous more containing molybdenum Acid catalyst, preparation method is simple, forms extensive chemical by organo-functional group coupling agent between heteropoly acid and carbonaceous porous material and inhales Attached, stability is good, and cycle performance is good, is easy recycling.Anderson type being capable of effectively catalyzing hydrogen peroxide oxygen containing molybdenum heteropolyacid Change iodide ion, and without peroxidating phenomenon.Anderson type is urged containing the carboxyl bonding in molybdenum heteropolyacid and functional group's coupling agent Change synergistic effect, further improves catalytic performance.It is found through first principles of quantum chemistry calculated result, functional group's coupling agent In carboxyl energy level of frontier orbital of the Anderson type containing molybdenum heteropolyacid is reduced, the modification group of carrier can be with Containing molybdenum heteropolyacid bonding chemisorption occurs for Anderson type, and Anderson type is changed while improving system stability containing molybdenum The electronic property of heteropoly acid makes the reduction of its highest occupied molecular orbital energy level (HOMO), is conducive to the progress of catalysis reaction, therefore improve The dynamic performance of reaction.The catalyst can significantly improve iodine recycling in phosphorus ore phosphoric acid by wet process, iodine recycling, marine products in brine Product iodine extract and the iodine of industrial wastewater containing iodine recycling iodine recovery rate, average response rate relative to not plus catalyst improve 10⁴Times or more, even if the oxidation rate of iodide ion can also be greatly speeded up under conditions of very low iodine concentration, return iodine The receipts process time significantly shortens, and improves efficiency, and iodine cost recovery is made to reduce by 20% ~ 30%.The catalyst is significantly improving peroxidating While iodine hydroxide ionic oxide formation rate, the service efficiency of hydrogen peroxide is also significantly improved, reduces the throwing of hydrogen peroxide Enter amount, saves 8.6% or more hydrogen peroxide use.

Specific embodiment

Below according to the detailed description present invention of embodiment, effect of the invention be will be apparent.