CN110523434A - A kind of carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid and its application - Google Patents
A kind of carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid and its application Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C01B7/13—Iodine; Hydrogen iodide
- C01B7/14—Iodine
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention discloses a kind of carbon-based Keggin-type phosphato-molybdic heteropolyacid catalyst of solid 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, Keggin-type phosphato-molybdic heteropolyacid, inorganic metal salt, surfactant is added, 0.5 ~ 1h of ultrasonic vibration, it moves into hydrothermal reaction kettle, utilize the baking oven of temperature programming, reaction temperature is risen to 150 ~ 180 DEG C by room temperature in 0.5 ~ 1h, keep 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.
Description
Technical field
The invention belongs to catalytic fields, and in particular to a kind of carbon-based keggin type phosphato-molybdic heteropolyacid of solid for iodine recycling
The preparation of catalyst and application method.
Background technique
Iodine resource is one of world's scarce resource, in medicine, agricultural, dyestuff, metallurgy, synthetic rubber, national defence and tip skill
Art etc. has extensive purposes.China is the country of serious iodine deficiency, and according to statistics, the year demand of China's iodine is up to 4014 tons,
And the total productive capacity of national iodine is only 670 tons or so, much can not meet the demand in market, major part lean on from foreign countries into
Mouthful.Due to no special iodine ore resources, the iodine in China is mainly obtained from the resources such as seaweed, rock phosphate in powder, various natural bitterns,
But wherein the concentration of iodine is very low, and the speed for causing iodide ion to be oxidized to elemental iodine is very slow.For the oxidation rate for improving iodide ion, have
Research is reported Fe3+, chlorate, Cl2Deng the oxidizing iodide ion of conduct and corresponding catalyst is developed, but there are drawbacks
Such as cause environmental pollution and catalyst poisoning limitation.The oxidation product of hydrogen peroxide is water, since its product does not pollute,
And there is more appropriate oxidisability and be widely applied by industry, lack suitable catalyst, though such as the sodium molybdate of report
So there is preferable catalytic effect, but there is more apparent peroxidating phenomenon；The catalytic effect of sodium tungstate is by water body pH shadow
Ring larger, sour smaller scope of application, because its form under strongly acidic conditions wolframic acid it is not soluble in water and sour due to cause catalytic performance to drop
It is low.Therefore due to that can not overcome the problems, such as that iodide ion reaction rate is slow, it can only industrially rely on and extend the process time or to the greatest extent may be used
The concentration that iodide ion is improved by absorbing repeatedly of energy causes iodine cost recovery high, and yield is limited.Suitable catalyst is developed to mention
The rate of high hydrogen peroxide iodine oxide ion becomes the key to solve the problem.
Heteropoly acid is by hetero atom or central atom and the polyatom with coordination and oxygen atom are according to specific
The oxygen-containing polyacid that coordination bridging forms together, has very high catalytic activity.Keggin-type heteropoly acid is current using most
Extensive one kind heteropoly acid.Keggin-type heteropoly acid homogeneous catalysis efficiency is higher, but needs to carry out catalyst after reaction
Separation and recycling, this will increase equipment energy consumption and cost, therefore limit its wider course of industrialization.It is solid using carrier
It carries Keggin-type heteropoly acid and constitutes its expansible industrial applications after heterogeneous reaction catalyst, but Keggin-type heteropoly acid is readily soluble
Xie Yushui, and since structural stability height causes its active force between carrier small, it is easy to be lost during the reaction.Therefore
The invention proposes a kind of carbon-based Keggin-type catalyst containing molybdenum heteropolyacid of solid, be by Keggin-type heteropoly acid can with it is organic
Functional group's coupling porous carrier forms new effective catalyst and is catalyzed for iodide ion.
Summary of the invention
The invention solves a technical problem be to provide it is a kind of for iodine recycling the carbon-based keggin type phosphorus molybdenum of solid
Heteropolyacid catalyst.
A kind of carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid, preparation method are as follows: by carbonaceous porous material and carboxylic
Base functional group coupling agent is added in the dilute acid soln that pH is 3 ~ 4, and keggin type phosphato-molybdic heteropolyacid, inorganic metal salt, surface is added
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.
The carbonaceous porous material is active carbon through pre-treatment, multi-walled carbon nanotube, graphene, one in carbon fiber
Kind.The porous material pre-treatment of these carbonaceous is as follows: carbonaceous porous material is cleaned with the sodium hydroxide solution of 0.1M at normal temperature,
Then it is cleaned with the dilute hydrochloric acid of 0.1M to remove the soluble acid of carbonaceous porous material surface, alkaline impurities；Carbonaceous is porous
Material handles 12 ~ 15h in the nitric acid solution that concentration is 30%, and washing is heated to reflux 4 ~ 8h, dry 8 at 100 ~ 120 DEG C ~
12h obtains carbonaceous porous material sample.
The carboxyl functional group coupling agent is 4,4- sulfonyl diphenyl acetic acid, 3-(4- carboxy phenyl) propionic acid, imidazoles -4,5-
The one or more of dicarboxylic acids.
The inorganic metal salt is nickel acetate, nickel sulfate, nickel chloride, nickel nitrate, zinc acetate, zinc sulfate, zinc chloride, nitre
One or more of sour zinc.
The surfactant is N,N-dimethylformamide, 2- alkyl imidazoline, isopropanol, octadecyldimethyl
One or more of hydroxyl second diyl ammonium nitrate.
The invention solves another technical problem be to be used for the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid
Iodine recycling.
Application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid in iodine recycling, specifically: in phosphorus ore wet process phosphorus
Iodine recycles in acid, iodine recycling, the extraction of marine product iodine and the iodine of industrial wastewater containing iodine recycle in brine.
Application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid in iodine recycling, removal process are by catalyst
It is mixed with Biodine, adjusts pH value, hydrogen peroxide is added while stirring, reaction generates elemental iodine, after the reaction was completed in solution
In be passed through hot-air, in solution elemental iodine formed iodine vapor distillation, to the cold formed iodine crystallization.
Application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid in iodine recycling, iodine is molten in catalytic iodine removal process
The existence of iodine is iodide ion in liquid, 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 keggin type phosphato-molybdic heteropolyacid of solid for iodine recycling of the invention
Catalyst, preparation method is simple, forms extensive chemical absorption by organo-functional group coupling agent between heteropoly acid and carbonaceous porous material,
Stability is good, and cycle performance is good, is easy recycling.Keggin type phosphato-molybdic heteropolyacid can effectively catalyzing hydrogen peroxide iodine oxide from
Son, and without peroxidating phenomenon.After being adulterated by Fe, Zn, the electronic property of keggin type phosphato-molybdic heteropolyacid is finely tuned, into
One step improves the catalytic performance of keggin type phosphato-molybdic heteropolyacid.What keggin type phosphato-molybdic heteropolyacid and Fe, Zn were modified
Carboxyl bonding in keggin type phosphato-molybdic heteropolyacid and functional group's coupling agent occurs catalyzing cooperation effect, further improves and urge
Change performance.It is found through first principles of quantum chemistry calculated result, the carboxyl in functional group's coupling agent makes keggin type phosphorus molybdenum
The energy level of frontier orbital for the keggin type phosphato-molybdic heteropolyacid that heteropoly acid and Fe, Zn are modified reduces, the modification group of carrier
Chemisorption occurs to be bonded with keggin type phosphato-molybdic heteropolyacid, changes keggin type phosphorus molybdenum while improving system stability
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% or more hydrogen peroxide use.
Specific embodiment
Below according to the detailed description present invention of embodiment, the objects and effects of the present invention will be more apparent.
Embodiment 1
Catalyst preparation:
1.000g active carbon and 5mL4,4- sulfonyl diphenyl acetic acid solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gkeggin type phosphato-molybdic heteropolyacid is added, 1ml2- alkyl imidazoline, magnetic agitation is for 24 hours, then ultrasonic at room temperature
1h is shaken, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, reaction temperature was risen to 150 by room temperature in 1 hour
DEG C, it keeps the temperature 48 hours, is then naturally cooling to room temperature, rinsed for several times, filtered with ultrapure water and ethyl alcohol respectively, it is dry
It is spare to obtain sample by 12h.
Evaluating catalyst:
(1) this CATALYST EXAMPLE:
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 2.26 ×
10-5mol·L-1·s-1。
(2) comparative example
A) do not add catalyst
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, are eventually adding theoretical amount
1.2 times of hydrogen peroxide obtains iodide ion concentration variation according to standard curve using Iodide Ion Selective Electrode Bases real-time monitoring current potential
With current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 1.0 × 10-8mol·L-1·s-1。
B) other catalyst
The catalyst is the common immobilized AlCl_3 catalyst of no functional group's coupling agent.Preparation method is to be placed in 1.000g active carbon
In the dilute acid soln that pH made of being deployed with sulfuric acid is 3,0.2gKeggin type phosphato-molybdic heteropolyacid is added, at room temperature magnetic agitation
For 24 hours, then ultrasonic vibration 1h, suction filtration are rinsed for several times with ultrapure water and ethyl alcohol respectively, are filtered, and dry 12h obtains sample.
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to
The iodine solution of 0.01mol/L takes the iodine solution of 10mL, and phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole are added, and is added above-mentioned
The catalyst of 0.5g preparation, is eventually adding the hydrogen peroxide of theoretical amount, utilizes Iodide Ion Selective Electrode Bases real-time monitoring current potential, root
Iodide ion concentration variation and current potential corresponding relationship are obtained according to standard curve, and the reaction of hydrogen peroxide oxidation iodide ion is calculated
Rate is 9.87 × 10-6mol·L-1·s-1。
C) other catalyst
The catalyst is the solid catalyst that functional group in coupling agent is ammonium, i.e., Keggin-type phosphato-molybdic heteropolyacid and sulfydryl at
Key.By 1.000g activated carbon and three ethoxy solution of silane of 5ml γ-aminopropyl be placed in pH made of being deployed with sulfuric acid be 2 it is dilute
In acid solution, be added 0.2gKeggin type phosphato-molybdic heteropolyacid, 1mlN, dinethylformamide, at room temperature magnetic agitation for 24 hours, so
Ultrasonic vibration 1h afterwards is moved into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature by room temperature liter in 1 hour
To 120 DEG C, the temperature is kept 48 hours, is then naturally cooling to room temperature, rinse filtering for several times with ultrapure water and ethyl alcohol respectively,
Dry 12h, it is spare to obtain sample.
1.6667g potassium iodide is taken to be dissolved in appropriate amount of deionized water, until constant volume is configured to 0.01mol/L in the volumetric flask of 100mL
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 1.35 ×
10-5mol·L-1·s-1。
D) other catalyst
The catalyst is the solid catalyst that functional group in coupling agent is hydroxyl, i.e., Keggin-type germanomolybdate and hydroxyl at
Key.1.000g activated carbon and 5ml polyglycol solution are placed in the dilute acid soln that pH made of being deployed with sulfuric acid is 3, are added
0.2gKeggin type phosphato-molybdic heteropolyacid, 1mlN, dinethylformamide, at room temperature magnetic agitation for 24 hours, then ultrasonic vibration 1h,
It moves into hydrothermal reaction kettle, using the baking oven of temperature programming, reaction temperature was risen to 150 DEG C by room temperature in 1 hour, keeping should
Temperature 48 hours, it is then naturally cooling to room temperature, rinses filtering for several times with ultrapure water and ethyl alcohol respectively, dry 12h obtains sample
Product are spare.
1.6667g potassium iodide is taken to be dissolved in appropriate amount of deionized water, until constant volume is configured to 0.01mol/L in the volumetric flask of 100mL
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 1.12 ×
10-5mol·L-1·s-1。
Embodiment 2
Catalyst preparation:
1.000g active carbon and 5ml4,4- sulfonyl diphenyl acetic acid solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type phosphato-molybdic heteropolyacid is added, 1ml2- alkyl imidazoline, 0.04g ferrous sulfate, magnetic force stirs at room temperature
It mixes for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature in 1 hour
150 DEG C are risen to by room temperature, keeps the temperature 48 hours, is then naturally cooling to room temperature, rinses number with ultrapure water and ethyl alcohol respectively
Secondary, it is spare to obtain sample by filtering, dry 12h.
Evaluating catalyst:
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 2.35 ×
10-5mol·L-1·s-1。
Carry out circulation experiment: it is as shown in the table for its empirical value:
Case study on implementation 3
Catalyst preparation:
1.000g activated carbon and 5ml4,4- sulfonyl diphenyl acetic acid solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type phosphato-molybdic heteropolyacid is added, 1ml2- alkyl imidazoline, 0.0456g zinc sulfate, magnetic force stirs at room temperature
It mixes for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature in 1 hour
150 DEG C are risen to by room temperature, keeps the temperature 48 hours, is then naturally cooling to room temperature, rinses number with ultrapure water and ethyl alcohol respectively
Secondary, it is spare to obtain sample by filtering, dry 12h.
Evaluating catalyst:
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 2.50 ×
10-5mol·L-1·s-1。
Carry out circulation experiment: it is as shown in the table for its empirical value:
Case study on implementation 4
Catalyst preparation:
It is 3 that 1.000g multi-walled carbon nanotube and 5ml4,4- sulfonyl diphenyl acetic acid solution, which are placed in pH made of being deployed with sulfuric acid,
Dilute acid soln in, be added 0.2gKeggin type phosphato-molybdic heteropolyacid, 1ml2- alkyl imidazoline, 0.0456g zinc sulfate, at room temperature
For 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature 1 magnetic agitation
150 DEG C are risen to by room temperature in hour, the temperature is kept 48 hours, is then naturally cooling to room temperature, uses ultrapure water and ethyl alcohol respectively
Filtering for several times is rinsed, it is spare to obtain sample by dry 12h.
Evaluating catalyst:
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 2.25 ×
10-5mol·L-1·s-1。
Carry out circulation experiment: it is as shown in the table for its empirical value:
Case study on implementation 5
Catalyst preparation:
1.000g graphene and 5ml4,4- sulfonyl diphenyl acetic acid solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type phosphato-molybdic heteropolyacid is added, 1ml2- alkyl imidazoline, 0.0456g zinc sulfate, magnetic force stirs at room temperature
It mixes for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature in 1 hour
150 DEG C are risen to by room temperature, keeps the temperature 48 hours, is then naturally cooling to room temperature, rinses number with ultrapure water and ethyl alcohol respectively
Secondary, it is spare to obtain sample by filtering, dry 12h.
Evaluating catalyst:
It takes 1.6667g potassium iodide to be dissolved in appropriate amount of deionized water, is transferred in the volumetric flask of 100mL, constant volume is configured to 0.01mol/L
Iodine solution, take the iodine solution of 10mL, phosphorus acid for adjusting pH=2.5 of stoichiometric ratio mole be added, urging for above-mentioned 0.5g preparation is added
Agent is eventually adding the hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, is obtained according to standard curve
Iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodide ion reaction rate be 1.97 ×
10-5mol·L-1·s-1。
Carry out circulation experiment: it is as shown in the table for its empirical value:
Above-described embodiment and experimental example are used to illustrate the present invention and technical concept and feature, its purpose is allow ripe
The understanding for knowing technique can understand the content of present invention and implement accordingly, can not be limited the invention with this, at this
In the protection scope that the Spirit Essence and rights protection of invention require, to any modifications and changes that the present invention makes, both fall within
In protection scope of the present invention.
Claims (10)
1. a kind of carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid, it is characterised in that: its preparation step is that carbonaceous is porous
Material and carboxyl functional group coupling agent are added in the dilute acid soln that pH is 3 ~ 4, and keggin type phosphato-molybdic heteropolyacid, inorganic metal is added
Salt, surfactant, magnetic agitation 12 ~ for 24 hours, 0.5 ~ 1h of ultrasonic vibration move into hydrothermal reaction kettle, utilize program 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 by the baking oven of heating, then natural
It is cooled to room temperature, rinses filtering for several times, dry 10 ~ 12h with ultrapure water and ethyl alcohol respectively.
2. the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 1, it is characterised in that: the carbonaceous
Porous material is one of active carbon through pre-treatment, multi-walled carbon nanotube, graphene, carbon fiber；The porous material of carbonaceous
Material pre-treatment is as follows: cleaning carbonaceous porous material with the sodium hydroxide solution of 0.1M at normal temperature, then uses the dilute hydrochloric acid of 0.1M
It cleans to remove soluble acid, the alkaline impurities of carbonaceous porous material surface；
Carbonaceous porous material is handled into 12 ~ 15h in the nitric acid solution that concentration is 30%, washing is heated to reflux 4 ~ 8h, and 100
Dry 8 ~ 12h obtains carbonaceous porous material sample at ~ 120 DEG C.
3. the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 1, it is characterised in that: the carboxyl
Functional group's coupling agent be 4,4- sulfonyl diphenyl acetic acid, 3-(4- carboxy phenyl) propionic acid, imidazoles -4,5- dicarboxylic acids one kind or several
Kind.
4. the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 1, it is characterised in that: the nothing
Machine metal salt is one of nickel acetate, nickel sulfate, nickel chloride, nickel nitrate, zinc acetate, zinc sulfate, zinc chloride, zinc nitrate or several
Kind.
5. the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 1, it is characterised in that: the table
Face activating agent is N,N-dimethylformamide, in 2- alkyl imidazoline, isopropanol, octadecyldimethyl hydroxyl second diyl ammonium nitrate
One or more.
6. application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid in iodine recycling, specifically: it is used for phosphorus ore wet process phosphorus
Iodine recycles in acid, iodine recycling, the extraction of marine product iodine and the iodine of industrial wastewater containing iodine recycle in brine.
7. application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 6 in iodine recycling,
It is characterized in that, removal process is to mix catalyst with Biodine, adjusts pH value, hydrogen peroxide is added while stirring, instead
Elemental iodine should be generated, is passed through hot-air in the solution after the reaction was completed, elemental iodine forms iodine vapor distillation in solution, is formed to the cold
Iodine crystallization.
8. application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid in iodine recycling according to claim 7, special
Sign is, the catalyst mass percent that feeds intake is 0.5%~10% in catalytic iodine removal process.
9. application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 7 in iodine recycling,
It is characterized in that, the concentration of hydrogen peroxide put into removal process is 10%~30%, and hydrogen peroxide input amount is the 1 of theoretical input amount
~1.5 times.
10. application of the carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid according to claim 7 in iodine recycling,
Feature is that reaction need to carry out in acid condition, and pH value is adjusted between 1~3 using sulfuric acid or phosphoric acid.
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