CN110102346A - A kind of silicon substrate germanomolybdate catalyst and preparation method thereof for iodine recycling - Google Patents
A kind of silicon substrate germanomolybdate catalyst and preparation method thereof for iodine recycling Download PDFInfo
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- CN110102346A CN110102346A CN201910448276.9A CN201910448276A CN110102346A CN 110102346 A CN110102346 A CN 110102346A CN 201910448276 A CN201910448276 A CN 201910448276A CN 110102346 A CN110102346 A CN 110102346A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/13—Iodine; Hydrogen iodide
- C01B7/14—Iodine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of silicon substrate germanomolybdate catalyst and preparation method thereof for iodine recycling.Its preparation step is that siliceous porous material and functional group's 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 germanomolybdate, inorganic metal salt, surfactant, dispersing agent is added, 0.5 ~ 1h of ultrasonic vibration, it moves into hydrothermal reaction kettle, utilize the baking oven of temperature programming, reaction temperature was risen to 150 DEG C by room temperature in 1 hour, keep the temperature 48 hours, then it is naturally cooling to room temperature, filtering for several times, dry 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 silicon substrate germanomolybdate catalyst and its system for iodine recycling
Preparation Method.
Background technique
Iodine is a kind of important industrial chemicals, and chemical products are widely used in food, medicine, dyestuff, metallurgy, synthesis rubber
All conglomeraties such as glue, agricultural, national defence hard-core technology.With the continuous expansion of iodine resource application field, the demand of global iodine also day
Tend to become strong strength.Iodine is scarce resource, and iodine ore resources in the world mainly have sodium nitrate, seaweed and subsurface brine and marine deposit
Rock phosphate in powder.Although iodine amount of storage is larger, and the situation of unresolved iodine resource scarcity.Trace it to its cause either from associated iodine still
Seaweed, brine and industrial wastewater extract recycling, although total amount is very big, the popular feature of these propiodal is exactly to contain iodine equivalent to compare
Low, the rate for causing iodide ion to be oxidized to elemental iodine is very slow, and recovery rate is low, high production cost.Although ion exchange can be passed through
Iodide ion is oxidized to elemental iodine using oxidant to recycle iodine by method, precipitation method etc., is then being collected elemental iodine
Method, comparatively, cost are cheaper.There are many kinds of the oxidants that iodide ion can be aoxidized, it is to be noted that,
Iodide ion is easily oxidized into the higher price such as acid iodide, needs acid iodide being reduced into elemental iodine again.For example notification number is
The Chinese utility model patent of CN103183320A, disclose " a method of recycling iodine ", use sodium hypochlorite to waste liquid
In inorganic iodine aoxidized, then using strong-base anion-exchange resin to this part iodine carry out enriching and recovering, then again will
One step of iodate ion is reduced to elemental iodine, increases the complexity of technique, while the introducing of chlorate produces chloride ion, produces
Raw volatile salts acid corrosion equipment, is not achieved environmentally protective requirement.
Hydrogen peroxide only produces water during iodide ion is oxidized to elemental iodine, other harmful without generating
Product, while hydrogen peroxide oxidation is moderate, iodide ion can be oxidized to elemental iodine, without being oxidized to higher price, so
And the rate of hydrogen peroxide oxidation iodide ion is relatively low, when the equivalent of the iodine especially in propiodal is relatively low, it is industrial need compared with
The long time could obtain the iodine of certain mass.Therefore it is using the oxidation rate that catalyst improves hydrogen peroxide oxidation iodide ion
Solve the problems, such as this key.But the catalytic efficiency of catalyst used at present is relatively low, and it is poor to recycle, at high cost.The present invention
A kind of new solid catalysis hydrogen peroxide oxidation iodide ion catalyst, high catalytic efficiency are proposed, good cycle is easy to back
It receives.
Summary of the invention
The purpose of the invention is to provide a kind of preparation of solid silicon substrate germanomolybdate catalyst for iodine recycling
And its iodine in phosphorus ore phosphoric acid by wet process recycles, iodine recycling, the extraction of marine product iodine and the recycling of the iodine of industrial wastewater containing iodine in brine
Method used in equal fields.
A kind of solid silicon substrate germanomolybdate catalyst for iodine recycling the preparation method comprises the following steps: by siliceous porous material and
Functional group's coupling agent is added in the dilute acid soln that pH is 3 ~ 4, and addition Keggin-type germanomolybdate, inorganic metal salt, surface are living
Property agent, at room temperature magnetic agitation 12 ~ for 24 hours, 0.5 ~ 1h of ultrasonic vibration moves into hydrothermal reaction kettle, utilizes the baking of temperature programming
Reaction temperature is risen to 150 DEG C by room temperature in 1 hour, keeps the temperature 48 hours, is then naturally cooling to room temperature by case, point
Not Yong ultrapure water and ethyl alcohol rinse filtering for several times, dry 12h.
The siliceous porous material is silica, diatomite, bentonite.
Functional group's coupling agent be [3- (N,NDimethylamino) propyl] trimethyoxysilane, N, N- bis-
Ethyl -3- (trimethoxy silane base) propylamine, N- [3- (trimethoxy silicon substrate) propyl] ethylenediamine, urea propyl-triethoxysilicane
One or more of alkane, 3- aminopropyl triethoxysilane.
The inorganic metal salt is ferrous sulfate, in frerrous chloride, ferrous nitrate zinc sulfate, zinc chloride, zinc nitrate
It is one or more of.
The surfactant is octadecyldimethyl hydroxyl second diyl ammonium nitrate, N, N dimethyl lauryl amine, 2-
One or more of alkyl imidazoline.
Another object of the present invention is that solid silicon substrate germanomolybdate catalyst is used for iodine recycling, and removal process is
Catalyst is mixed with Biodine, adjusts pH value, hydrogen peroxide is added while stirring, reaction generates elemental iodine, and reaction is completed
It is passed through hot-air in the solution afterwards, elemental iodine forms iodine vapor distillation in solution, forms iodine crystallization to the cold.
The catalyst is required to recycle for iodine according to power 8, which is characterized in that in catalytic iodine removal process in iodine solution
The existence of iodine is iodide ion, 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 solid silicon substrate germanomolybdate catalyst for iodine recycling of the invention,
Preparation method is simple, forms extensive chemical absorption, stability by organo-functional group coupling agent between heteropoly acid and siliceous porous material
Good, cycle performance is good, is easy recycling.Keggin-type germanomolybdate effectively can aoxidize iodide ion by catalyzing hydrogen peroxide, and
Without peroxidating phenomenon.After being adulterated by Fe, Zn, the electronic property of germanomolybdate is finely tuned, germanium is further improved
The catalytic performance of molybdenum heteropolyacid.The amido in germanomolybdate and functional group's coupling agent that germanomolybdate and Fe, Zn are modified
Or imido grpup bonding, catalyzing cooperation effect occurs, further improves catalytic performance.It calculates and ties through first principles of quantum chemistry
Fruit discovery, amido or imido grpup in functional group's coupling agent make germanomolybdate and the modified germanomolybdate of Fe, Zn
Energy level of frontier orbital reduces, and is allowed to be more nearly the energy level of frontier orbital of hydrogen peroxide, therefore improve the kinetics of reaction
Energy.The catalyst can significantly improve in phosphorus ore phosphoric acid by wet process that iodine recycling, iodine recycling, marine product iodine extract and containing iodine in brine
Industrial wastewater iodine recycles the recovery rate of iodine, even if can also greatly speed up iodide ion under conditions of very low iodine concentration
Oxidation rate shortens the iodine recovery process time significantly, improves efficiency, reduces cost.
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 diatomite and 5ml urea propyl-triethoxysilicane solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type germanomolybdate, 1ml octadecyldimethyl hydroxyl second diyl ammonium nitrate, at room temperature magnetic force is added
For 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature at 1 hour for stirring
It is interior to rise to 150 DEG C by room temperature, it keeps the temperature 48 hours, is then naturally cooling to room temperature, rinsed respectively with ultrapure water and ethyl alcohol
For several times, it filters, it is spare to obtain sample by dry 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 1.65 × 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 diatomite
In the dilute acid soln that pH made of being deployed with sulfuric acid is 3,0.2gKeggin type germanomolybdate 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 1.2 times of hydrogen peroxide of theoretical amount, utilizes Iodide Ion Selective Electrode Bases real-time monitoring
Current potential, according to standard curve obtain iodide ion concentration variation with current potential corresponding relationship, and be calculated hydrogen peroxide oxidation iodine from
The reaction rate of son is 7.17 × 10-7mol·L-1·s-1。
C) other catalyst
The catalyst is the solid catalyst that functional group in coupling agent is sulfydryl, i.e., Keggin-type germanomolybdate and sulfydryl at
Key.By 1.000g diatomite and 5ml γ-mercaptopropyl trimethoxysilane solution be placed in pH made of being deployed with sulfuric acid be 2 it is dilute
In acid solution, be added 0.2gKeggin type germanomolybdate, 1mlN, N dimethyl lauryl amine, at room temperature magnetic agitation for 24 hours,
Then ultrasonic vibration 1h is moved into hydrothermal reaction kettle, using the baking oven of temperature programming, by reaction temperature by room temperature in 1 hour
120 DEG C are risen to, keeps the temperature 48 hours, is then naturally cooling to room temperature, is rinsed for several times with ultrapure water and ethyl alcohol respectively, mistake
Filter, 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 3.47 × 10-7mol·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 diatomite and 5ml γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane solution are placed in and are deployed with sulfuric acid
PH be 3 dilute acid soln in, be added 0.2gKeggin type germanomolybdate, 1mlN, N dimethyl lauryl amine, 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.
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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 6.42 × 10-7mol·L-1·s-1。
Embodiment 2
Catalyst preparation:
1.000g diatomite and 5ml urea propyl-triethoxysilicane solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type germanomolybdate, 1ml octadecyldimethyl hydroxyl second diyl ammonium nitrate, 0.04g sulfuric acid Asia is added
Iron, for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle magnetic agitation at room temperature, will be anti-using the baking oven of temperature programming
It answers temperature to rise to 150 DEG C by room temperature in 1 hour, keeps the temperature 48 hours, room temperature is then naturally cooling to, respectively with ultrapure
Water and ethyl alcohol rinse filtering for several times, and 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 1.98 × 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 diatomite and 5ml urea propyl-triethoxysilicane solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type germanomolybdate, 1ml octadecyldimethyl hydroxyl second diyl ammonium nitrate, 0.0456g sulfuric acid is added
Zinc, for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle magnetic agitation at room temperature, will be anti-using the baking oven of temperature programming
It answers temperature to rise to 150 DEG C by room temperature in 1 hour, keeps the temperature 48 hours, room temperature is then naturally cooling to, respectively with ultrapure
Water and ethyl alcohol rinse filtering for several times, and 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 2.03 × 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:
1.000g bentonite and 5ml urea propyl-triethoxysilicane solution are placed in the diluted acid that pH made of being deployed with sulfuric acid is 3
In solution, 0.2gKeggin type germanomolybdate, 1ml octadecyldimethyl hydroxyl second diyl ammonium nitrate, 0.0456g sulfuric acid is added
Zinc, for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle magnetic agitation at room temperature, will be anti-using the baking oven of temperature programming
It answers temperature to rise to 150 DEG C by room temperature in 1 hour, keeps the temperature 48 hours, room temperature is then naturally cooling to, respectively with ultrapure
Water and ethyl alcohol rinse filtering for several times, and 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 1.56 × 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:
By 1.000g silica and 5ml urea propyl-triethoxysilicane solution be placed in pH made of being deployed with sulfuric acid be 3 it is dilute
In acid solution, 0.2gKeggin type germanomolybdate, 1ml octadecyldimethyl hydroxyl second diyl ammonium nitrate, 0.0456g sulphur is added
Sour zinc, for 24 hours, then ultrasonic vibration 1h, moves into hydrothermal reaction kettle magnetic agitation at room temperature, will using the baking oven of temperature programming
Reaction temperature rose to 150 DEG C by room temperature in 1 hour, kept the temperature 48 hours, was then naturally cooling to room temperature, respectively with super
Pure water and ethyl alcohol rinse filtering for several times, and 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 1.2 times of hydrogen peroxide of theoretical amount, using Iodide Ion Selective Electrode Bases real-time monitoring current potential, according to mark
Directrix curve obtains iodide ion concentration variation and current potential corresponding relationship, and the reaction rate of hydrogen peroxide oxidation iodide ion is calculated
It is 1.41 × 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, and its purpose is, which allows, is familiar with this
The understanding of item technology can understand the content of present invention and implement accordingly, can not be limited the invention with this, in the present invention
Spirit Essence and the desired protection scope of rights protection in, to any modifications and changes for making of the present invention, both fall within this hair
In bright protection scope.
Claims (11)
1. a kind of solid silicon substrate germanomolybdate catalyst for iodine recycling, it is characterised in that: its preparation step is will be siliceous
Porous material and functional group's coupling agent are added in the dilute acid soln that pH is 3 ~ 4, and Keggin-type germanomolybdate, 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 DEG C by room temperature in 1 hour, keeps the temperature 48 hours, is then naturally cooling to by the baking oven of heating
Room temperature rinses filtering for several times, dry 12h with ultrapure water and ethyl alcohol respectively.
2. siliceous porous material according to claim 1, it is characterized in that silica, diatomite, bentonite.
3. functional group's coupling agent according to claim 1, it is characterized in that [3- (N,NDimethylamino) propyl] trimethoxy
Monosilane, N, N- diethyl -3- (trimethoxy silane base) propylamine, N- [3- (trimethoxy silicon substrate) propyl] ethylenediamine, urea third
One or more of ethyl triethoxy silicane alkane, 3- aminopropyl triethoxysilane.
4. inorganic metal salt according to claim 1, it is characterized in that ferrous sulfate, frerrous chloride, ferrous nitrate zinc sulfate,
One or more of zinc chloride, zinc nitrate.
5. surfactant according to claim 1, it is characterized in that octadecyldimethyl hydroxyl second diyl ammonium nitrate, N, N
One or more of dimethyl dodecylamine, 2-alkyl imidazolines.
6. requiring the catalyst to recycle for iodine according to power 1, which is characterized in that the catalyst can be 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. according to power 1 require the catalyst for iodine recycle, which is characterized in that its removal process be by catalyst with contain
Iodine solution mixing, adjusts pH value, and hydrogen peroxide is added while stirring, and reaction generates elemental iodine, leads in the solution after the reaction was completed
Enter hot-air, elemental iodine forms iodine vapor distillation in solution, forms iodine crystallization to the cold.
8. requiring the catalyst to recycle for iodine according to power 7, which is characterized in that iodine in iodine solution in catalytic iodine removal process
Existence be iodide ion, concentration be greater than 10ppm.
9. requiring the catalyst to recycle for iodine according to power 7, which is characterized in that catalyst feeds intake in catalytic iodine removal process
Mass percent is greater than 0.01%.
10. requiring the catalyst to recycle for iodine according to power 7, which is characterized in that the hydrogen peroxide put into removal process
Concentration is 10%~30%, and hydrogen peroxide input amount is 1~1.5 times of theoretical input amount.
11. require the catalyst to recycle for iodine according to power 7, it is characterized in that, reaction need to carry out in acid condition, utilize
PH value is adjusted between 1~3 by sulfuric acid or phosphoric acid.
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Cited By (8)
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| CN110420660A (en) * | 2019-08-09 | 2019-11-08 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate germanomolybdate catalyst and its application |
| CN110508329A (en) * | 2019-09-02 | 2019-11-29 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate Waugh type catalyst containing molybdenum heteropolyacid and its application |
| CN110508321A (en) * | 2019-09-02 | 2019-11-29 | 瓮福（集团）有限责任公司 | A kind of solid carbon-based Waugh type catalyst containing molybdenum heteropolyacid and its application |
| CN110523437A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate keggin type phosphato-molybdic heteropolyacid catalyst and its application |
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| CN110523405A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid and its application |
| CN115636396A (en) * | 2022-10-18 | 2023-01-24 | 厦门大学 | Hydrogen peroxide generation method |
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| CN110420660A (en) * | 2019-08-09 | 2019-11-08 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate germanomolybdate catalyst and its application |
| CN110508329A (en) * | 2019-09-02 | 2019-11-29 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate Waugh type catalyst containing molybdenum heteropolyacid and its application |
| CN110508321A (en) * | 2019-09-02 | 2019-11-29 | 瓮福（集团）有限责任公司 | A kind of solid carbon-based Waugh type catalyst containing molybdenum heteropolyacid and its application |
| CN110523437A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate keggin type phosphato-molybdic heteropolyacid catalyst and its application |
| CN110523434A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of carbon-based keggin type phosphato-molybdic heteropolyacid catalyst of solid and its application |
| CN110523406A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of solid carbon-based Anderson type catalyst containing molybdenum heteropolyacid and its application |
| CN110523405A (en) * | 2019-09-02 | 2019-12-03 | 瓮福（集团）有限责任公司 | A kind of solid silicon substrate Anderson type catalyst containing molybdenum heteropolyacid and its application |
| CN115636396A (en) * | 2022-10-18 | 2023-01-24 | 厦门大学 | Hydrogen peroxide generation method |
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