阅读说明：本技术 一种固体硅基Anderson型含钼杂多酸催化剂及其应用 (A kind of solid silicon substrate 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硅基Anderson型含钼杂多酸催化剂及其应用。其制备步骤为将硅质多孔材料和胺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 silicon substrate Anderson type catalyst containing molybdenum heteropolyacid and its applications.Its preparation step is that siliceous porous material and amidine 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 solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid, which is characterized in that its preparation step are as follows: will be siliceous Porous material and amidine 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, table Face activating agent, magnetic agitation 12 ~ for 24 hours, 0.5 ~ 1h of ultrasonic vibration move into hydrothermal reaction kettle, utilize 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 by baking oven Room temperature rinses filtering for several times, dry 10 ~ 12h with ultrapure water and ethyl alcohol respectively.

2. solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid according to claim 1, which is characterized in that the silicon Matter porous material is one of silica, diatomite, bentonite.

3. solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid according to claim 1, which is characterized 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. solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid according to claim 1, which is characterized in that the amine Base functional group coupling agent is N- [3- (trimethoxy silicon substrate) propyl] ethylenediamine, N-(β-aminoethyl)-Y- aminopropyl-trimethoxy One or more of silane, Y- aminopropyl-trimethoxy silane, 3- aminopropyl triethoxysilane.

5. solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid according to claim 1, which is characterized in that the table Face activating agent is dodecyl trimethyl ammonium chloride .N, dinethylformamide, N, N dimethyl lauryl amine, octadecyl One or more of dimethyl hydroxyl second diyl ammonium nitrate.

6. application of the solid silicon substrate 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 silicon substrate 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 silicon substrate 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 silicon substrate 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 silicon substrate 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 system of solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid Preparation Method and its application.

Background technique

Iodine is a kind of important industrial chemicals, at the tips such as medicine, agricultural, dyestuff, metallurgy, synthetic rubber, science and techniques of defence Technology has extensive purposes.With the continuous expansion of iodine resource application field, the demand of global iodine is also increasingly powerful.Generation at present Mainly there are nitre, seaweed, subsurface brine and marine deposit rock phosphate in powder in the source of iodine in boundary.The popular feature of these propiodal is exactly Equivalent containing iodine is very low, and the rate for causing iodide ion to be oxidized to elemental iodine is very slow, and recovery rate is low, high production cost.Although can lead to Ion-exchange, precipitation method etc. are crossed to recycle iodine, but iodide ion is oxidized to by elemental iodine using oxidant, then by elemental iodine The method being collected, comparatively, cost is cheaper.There are many kinds of the oxidants that iodide ion can be aoxidized, but must It is noted that iodide ion is easily oxidized into the higher price such as acid iodide, need acid iodide being reduced into elemental iodine again.Such as Notification number is the Chinese invention patent of CN103183320A, disclose " a method of recycling iodine ", use sodium hypochlorite pair Inorganic iodine in waste liquid is aoxidized, then carries out enriching and recovering to this part iodine using strong-base anion-exchange resin, then One step of iodate ion is reduced to elemental iodine again, increases the complexity of technique, at the same the introducing of chlorate produce chlorine from Son generates volatile salts acid corrosion equipment, environmentally protective requirement is not achieved.

Hydrogen peroxide is a kind of Green Oxidant, and oxidation product is water, while hydrogen peroxide oxidation is moderate, can be incited somebody to action Iodide ion is oxidized to elemental iodine, without being oxidized to higher price, also can avoid environmental pollution and substitutes other oxidants in iodine processed It is widely used in industry.But the slow problem of oxidation rate is still remained, the equivalent of the iodine especially in propiodal compares When low, the technique duration for needing to grow could obtain the iodine of certain mass very much, cause iodine cost recovery height and yield is limited.Therefore it adopts The oxidation rate that hydrogen peroxide oxidation iodide ion is improved with catalyst is the key that solve the problems, such as this.But catalysis used at present The catalytic efficiency of agent is relatively low, and it is poor to recycle, at high cost.For example sulfuric acid recycles iodine oxidation as catalyst and has by Chen Xiao tiger etc. There is certain catalytic action, but oxidation rate is not significantly improved.

Polyacid or polyoxoanion possess physics abundant and chemically as a kind of important inorganic metal compound Matter is widely used in catalysis, material and biomedicine field.Anderson type structure is tied in polyacid family Lesser one kind of structure, by six coplanar MoO₆Or WO₆Side connects into a closed similar annular plane to octahedron altogether, Hetero atom is located in the octahedral voids of annular central.Due to D with higher_3dSymmetry, the heteropoly acid of Anderson type More stable structure is formed by organo-functional group coupling agent between siliceous porous material, generates efficient heterogeneous catalysis material Material.The invention proposes a kind of solid silicon substrate Anderson type catalyzing hydrogen peroxides containing molybdenum heteropolyacid to aoxidize iodide ion, catalysis effect Rate is high, and good cycle is easily recycled.

Summary of the invention

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

A kind of solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid for iodine recycling, preparation method are as follows: by silicon Matter porous material and amidine 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 siliceous porous material is one of silica, diatomite, bentonite.

The Anderson type is that Anderson sections molybdenum heteropolyacid and Anderson type zinc molybdenum are miscellaneous more containing molybdenum heteropolyacid One of acid.

Functional group's coupling agent is N- [3- (trimethoxy silicon substrate) propyl] ethylenediamine, N-(β-aminoethyl)-Y- ammonia One or more of propyl-trimethoxysilane, Y- aminopropyl-trimethoxy silane, 3- aminopropyl triethoxysilane.

The surfactant is dodecyl trimethyl ammonium chloride, N,N-dimethylformamide, N, N dimethyl 12 One or more of alkylamine, octadecyldimethyl hydroxyl second diyl ammonium nitrate.

The invention solves another technical problem be by solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid use It is recycled in iodine.

Solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid is used for iodine recycling, specifically it is in phosphorus ore phosphoric acid by wet process Iodine recycling, the extraction of marine product iodine and the recycling of the iodine of industrial wastewater containing iodine in middle iodine recycling, brine.

By solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid be used for iodine recycling, removal process be by catalyst with Biodine mixing, adjusts pH value, and hydrogen peroxide is added while stirring, and reaction generates elemental iodine, after the reaction was completed in the solution It is passed through hot-air, elemental iodine forms iodine vapor distillation in solution, forms iodine crystallization to the cold.

The catalyst is recycled for iodine, and the existence of iodine is iodide ion in iodine solution in catalytic iodine removal process, 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 solid silicon substrate Anderson type 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 siliceous porous material and inhales Attached, stability is good, and cycle performance is good, is easy recycling.Anderson type catalyst containing molybdenum heteropolyacid can effectively be catalyzed peroxide Change iodine hydroxide ion, and without peroxidating phenomenon.Anderson type containing in molybdenum heteropolyacid and functional group's coupling agent amido or Asia Amido bonding occurs catalyzing cooperation effect, further improves catalytic performance.It is sent out through first principles of quantum chemistry calculated result Existing, amido or imido grpup in functional group's coupling agent reduce energy level of frontier orbital of the Anderson type containing molybdenum heteropolyacid, make Be more nearly the energy level of frontier orbital of hydrogen peroxide, therefore improve the dynamic performance of reaction.The catalyst can be obvious Improve iodine recycling in phosphorus ore phosphoric acid by wet process, iodine recycles, marine product iodine extracts and the iodine of industrial wastewater containing iodine recycles iodine in brine Recovery rate, average response rate relative to not plus catalyst improve 10⁴Times or more, even if in the item of very low iodine concentration Under part, the oxidation rate of iodide ion can also be greatly speeded up, shortens the iodine recovery process time significantly, improves efficiency, returns iodine Harvest this reduction by 20% ~ 30%.The catalyst also obviously mentions while significantly improving hydrogen peroxide oxidation iodide ion oxidation rate The high service efficiency of hydrogen peroxide, reduces the input amount of hydrogen peroxide, saves 8% 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.