CN110227459A - A kind of preparation method of tripolite loading solid super strong acids fenton catalyst - Google Patents
A kind of preparation method of tripolite loading solid super strong acids fenton catalyst Download PDFInfo
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- CN110227459A CN110227459A CN201910400445.1A CN201910400445A CN110227459A CN 110227459 A CN110227459 A CN 110227459A CN 201910400445 A CN201910400445 A CN 201910400445A CN 110227459 A CN110227459 A CN 110227459A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The present invention is a kind of preparation method of tripolite loading solid super strong acids fenton catalyst, its main feature is that, comprising the following steps: acidification is carried out in natural diatomaceous earth；Activated diatomaceous earth carrier is after heat treatment made in acidification diatomite；Insoluble sediment is made after activated diatomaceous earth carrier introduces molysite；Dipping synthesizes solid super strong acid precursor in situ；Heat treatment prepares tripolite loading solid super strong acids fenton catalyst.For solve the disadvantage that the existing catalyst low efficiency prepared using diatomite as carrier, synthesis step it is complicated, not environmentally the disadvantages of.Made catalyst is 93%-99% to rhodamine B degradation rate；It is 91%-96% to hydrogen peroxide resolution ratio.
Description
Technical field
The invention belongs to inorganic non-metallic material and class fenton catalyst fields, are related to a kind of tripolite loading solid super strong
The preparation method of acids fenton catalyst.
Background technique
China's organic wastewater is seriously polluted, and " three cause " is very big to human injury, and some organic matters have bioaccumulation,
Extremely difficult degradation in water, the processing method poor processing effect of traditional organic wastewater and not environmentally, some emerging method such as ultrasonic waves
Technology, microwave treatment technology also have the shortcomings that operating cost is high, and theoretical research is not enough.For above situation, by energy of oxidation
Power is strong, green non-pollution Fenton high-level oxidation technology is applied to treatment of Organic Wastewater.
Fenton oxidation technology is with the obvious advantage in terms of processing high concentration, difficult to degrade, poisonous and harmful waste water, is urged by catalyst
Change hydrogen peroxide (H2O2) generate high activity OH, can by useless Organic substance in water permineralization be H2O and CO2, it is a kind of environment
Friendly green water process new technology.But the technology is there is also catalyst recycling difficulty, and reaction rate is slow, organic matter mine
Change incomplete defect, hydrogen peroxide (H2O2) utilization rate is high, the hydrogen peroxide (H added2O2) water and oxygen can be decomposed into
Gas wastes oxidant, and iron cement presence is had after reaction, increases subsequent treatment cost.The class for preparing dynamical support type is fragrant
The catalyst that pauses can solve this defect.
For defect existing for Fenton oxidation technology, applicant Jilin English is up to water utilities science and technology limited Company 2013
Year has applied for application number " CN201310231119.5 ", a kind of title " tripolite loading solid superacid type Fenton catalyst
Preparation method " patent of invention, natural diatomaceous earth is carried out at acidification using 0.1~1mol/L inorganic 10~14h of acid dip
Reason, obtains active natural diatomite with 200~400 DEG C of 1~4h of temperature-activated, in 400~600 DEG C of 1~6h of temperature calcination
The heat treatment for carrying out presoma, obtains tripolite loading solid superacid type Fenton catalyst.Itself the problem is that: (1)
The natural diatomaceous earth acidification time is long；(2) activated diatomaceous earth carrier is one-part form temperature control activation processing, the activation rate of diatomite
It is low；(3) heat treatment of presoma is the heat treatment of one-part form temperature control, the low yield of finished catalyst；(4) although it improves degradation
Efficiency, but degradation efficiency is still lower.
Summary of the invention
Technical problem solved by the invention is: the shortcomings that overcoming the prior art, and it is super to provide a kind of tripolite loading solid
The preparation method of strong acid class fenton catalyst, solve the prior art prepared using diatomite as carrier catalyst low efficiency,
Synthesis step is complicated, not environmentally with traditional Fenton method to the demanding problem of pH value, using diatomite as catalyst carrier system
Standby heterogeneous catalyst, while absorption and catalysed oxidn are played, Fenton's reaction treatment effect is improved, while improving catalyst
Catalytic efficiency simplifies synthesis step, improves degradation efficiency, generates environmentally friendly synthetic.
The technical solution that the present invention solves the problems, such as is: a kind of preparation of tripolite loading solid super strong acids fenton catalyst
Method, characterized in that the following steps are included:
1) natural diatomaceous earth acidification
Sulfuric acid, hydrochloric acid and citric acid are added in natural diatomaceous earth and carries out acidification, natural diatomaceous earth and sulfuric acid, hydrochloric acid
Mass parts ratio with citric acid is 1:0.5~2:1~1.5:0.5~1；
2) activated diatomaceous earth carrier
Activated diatomaceous earth carrier is after heat treatment made by the acidification diatomite that step 1) obtains；
3) insoluble sediment is made after introducing molysite in activated diatomaceous earth carrier
Ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate are introduced in the activated diatomaceous earth carrier that step 2) obtains
Be made insoluble sediment, activated diatomaceous earth carrier and ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate mass parts ratio
For 1:1~1.5:0.2~0.6:0.2~0.5:0.2~0.5:0.3~0.6；
4) solid super strong acid precursor in situ is synthesized
The insoluble sediment that step 3) obtains is mixed with maceration extract, impregnates and solid super strong acid precursor in situ is made, no
The mass parts of molten sediment and maceration extract ratio is 1:5~10；
5) tripolite loading solid super strong acids fenton catalyst is prepared
The solid super strong acid precursor in situ that step 4) obtains is heat-treated, tripolite loading solid super-strong acid is made
Class fenton catalyst.
Step 1) the natural diatomaceous earth acidification is: according to the matter of natural diatomaceous earth and sulfuric acid, hydrochloric acid and citric acid
Part is measured than being 1:0.5~2:1~1.5:0.5~1 ratio, it is 20%~30% that mass fraction is added in natural diatomaceous earth
Sulfuric acid, 10%~16% hydrochloric acid and 5%~10% citric acid stir 7~10h, stirring speed under the conditions of 25 DEG C~35 DEG C
Degree is 800~1000r/min.
Step 2) the activated diatomaceous earth carrier the following steps are included:
(1) the acidification diatomite obtained by step 1) carries out 1~4h vacuum filtration and leaves and takes unfiltered solid, and at 105 DEG C
It is sieved after~120 DEG C of 4~6h of freeze-day with constant temperature, 200~1000 mesh of aperture of sieve leaves and takes the lower diatomite of sieve；
(2) diatomite is in 200 DEG C~300 DEG C 1~2h of calcining of temperature under the sieve (1) step left and taken, then at 300 DEG C of temperature
~400 DEG C of 1~2h of calcining, are made activated diatomaceous earth carrier.
Step 3) the activated diatomaceous earth carrier insoluble sediment is made after introducing molysite the following steps are included:
(1) it is according to activated diatomaceous earth carrier and the mass parts ratio of ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate
1:1~1.5:0.2~0.6:0.2~0.5:0.2~0.5:0.3~0.6 ratio, introduces quality on activated diatomaceous earth carrier
Score be 5%~10% ferric sulfate, 4%~9% ferric nitrate, 10%~15% ferric acetate, 3%~6% iron chloride and 6%~
10% ferric oxalate obtains mixed solution；
(2) the pH value of the mixed solution (1) obtained with sodium hydroxide regulating step, make the pH 7.5 of mixed solution~
9.2；
(3) 10mL standard ammonia-ammonium chloride buffer solution is added in (2) mixed solution that step obtains；
(4) 8~ripening for 24 hours is carried out at 25 DEG C~35 DEG C of temperature, the mixed solution of ageing is filtered by vacuum, and is collected
Insoluble sediment.
The step 4) synthesizes solid super strong acid precursor in situ:
It (1) is that 20%~30% ammonium sulfate and 20%~35% sulfuric acid are mixed with maceration extract, sulfuric acid by mass fraction
The mass parts of ammonium and sulfuric acid ratio is 1:0.3~2；
(2) the mass parts of the maceration extract (1) obtained according to insoluble sediment and step are than the ratio for 1:5~10, by step
3) the insoluble sediment obtained is mixed with maceration extract, and dip time is 18~36h；
(3) after 105 DEG C~120 DEG C 2~3h of freeze-day with constant temperature, vacuum filtration leaves and takes unfiltered solid, and original position solid is made
Superpower acid precursor.
The step 5) prepare tripolite loading solid super strong acids fenton catalyst the following steps are included:
By step 4) obtain solid super strong acid precursor in situ carried out under the protection of nitrogen or argon gas 400 DEG C~
500 DEG C of 2~4h of calcining；
(2) under the protection of nitrogen or argon gas, continue that tripolite loading solid is made in 500 DEG C~600 DEG C 4~5h of calcining
Superpower acids fenton catalyst.
The diatom directly obtained by a kind of preparation method of tripolite loading solid super strong acids fenton catalyst
Native supported solid superacid acids fenton catalyst.
The beneficial effects of the present invention are: it not only solves the recycling difficulty of catalyst existing for Fenton oxidation technology,
Reaction rate is slow, the incomplete defect of mineralization of organic material, H2O2Utilization rate is not high, the H added2O2It can be decomposed into water and oxygen,
The problem of wasting oxidant, iron cement presence had after reaction, increases subsequent treatment cost, and solve the system of the prior art
The natural diatomaceous earth acidification time existing for the class fenton catalyst of standby dynamical support type is long, the activation rate of diatomite
It is low, the problem of the low yield of finished catalyst, and further improve degradation efficiency.Reach using diatomite as catalyst
Carrier prepares heterogeneous catalyst and plays absorption and catalysed oxidn, improves Fenton's reaction treatment effect, while improving catalyst
Catalytic efficiency, simplify synthesis step, improve degradation efficiency, generate the purpose of environmentally friendly synthetic.The diatomite of prepared acquisition
Supported solid superacid acids fenton catalyst is 98.12% to the removal rate of rhodamine B, to H2O2Resolution ratio be 93.73%.
Detailed description of the invention
Fig. 1 is that the activated diatomaceous earth of unsupported catalyst and the X of tripolite loading solid super strong acids fenton catalyst are penetrated
Ray diffraction diagram；
Fig. 2 is the Fourier infrared spectrum figure of tripolite loading solid super strong acids fenton catalyst；
Fig. 3 is removal rate of the comparative experiments with made catalyst in embodiment 1 to rhodamine B；
Fig. 4 is comparative experiments and the made catalyst of embodiment 1 to H2O2Resolution ratio.
Specific embodiment
Referring to figs. 1 to 4, embodiment 1, a kind of system of tripolite loading solid super strong acids fenton catalyst of the present embodiment
Preparation Method, comprising the following steps:
1) natural diatomaceous earth acidification
According to the mass parts of natural diatomaceous earth and sulfuric acid, hydrochloric acid and citric acid than the ratio for 1:0.5:1.5:1, natural
In diatomite be added mass fraction be 20% sulfuric acid, 10% hydrochloric acid and 5% citric acid, stir 10h under the conditions of 25 DEG C,
Mixing speed is 1000r/min；
2) activated diatomaceous earth carrier
Activated diatomaceous earth carrier is after heat treatment made by the acidification diatomite that step 1) obtains, comprising the following steps:
(1) the acidification diatomite obtained by step 1) carries out 2h vacuum filtration and leaves and takes unfiltered solid, and in 105 DEG C of perseverances
It is sieved after the dry 4h of temperature, 800 mesh of aperture of sieve leaves and takes the lower diatomite of sieve；
(2) diatomite is in 250 DEG C of calcining 1h of temperature under the sieve (1) step left and taken, then in 300 DEG C of calcining 1h of temperature, system
At activated diatomaceous earth carrier；
3) insoluble sediment is made after introducing molysite in activated diatomaceous earth carrier
Step 2) obtain activated diatomaceous earth carrier introduce molysite after insoluble sediment is made the following steps are included:
(1) it is according to activated diatomaceous earth carrier and the mass parts ratio of ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate
1:1:0.2:0.2:0.2:0.3 ratio, on activated diatomaceous earth carrier introduce mass fraction be 5% ferric sulfate, 4% nitric acid
Iron, 10% ferric acetate, 3% iron chloride and 6% ferric oxalate obtain mixed solution；
(2) the pH value of the mixed solution (1) obtained with sodium hydroxide regulating step makes the pH 7.5 of mixed solution；
(3) 10mL standard ammonia-ammonium chloride buffer solution is added in (2) mixed solution that step obtains；
(4) the ripening that 8h is carried out at 25 DEG C of temperature, is filtered by vacuum the mixed solution of ageing, collects insoluble sediment；
4) solid super strong acid precursor in situ is synthesized
The insoluble sediment that step 3) obtains is mixed with maceration extract, impregnates and solid super strong acid precursor in situ, packet is made
Include following steps:
It (1) is that 20% ammonium sulfate and 20% sulfuric acid are mixed with maceration extract, the matter of ammonium sulfate and sulfuric acid by mass fraction
Amount part is compared for 1:0.5；
(2) the mass parts of the maceration extract (1) obtained according to insoluble sediment and step obtain step 3) than the ratio for 1:5
The insoluble sediment obtained is mixed with maceration extract, dip time 18h；
(3) after 105 DEG C of freeze-day with constant temperature 2h, vacuum filtration leaves and takes unfiltered solid, and original position solid super-strong acid forerunner is made
Body；5) tripolite loading solid super strong acids fenton catalyst is prepared
The solid super strong acid precursor in situ that step 4) obtains is heat-treated, tripolite loading solid super-strong acid is made
Class fenton catalyst, comprising the following steps:
(1) the solid super strong acid precursor in situ that step 4) obtains is subjected to 400 DEG C of calcinings under the protection of nitrogen or argon gas
2h；
(2) under the protection of nitrogen or argon gas, continue that it is fragrant that tripolite loading solid super strong acids is made in 600 DEG C of calcining 4h
Pause catalyst.
Made tripolite loading solid super strong acids fenton catalyst is 98.12% to the removal rate of rhodamine B, to H2O2
Resolution ratio be 93.73%.
As shown in Figure 1, a is the activated diatomaceous earth X-ray diffraction line chart of unsupported catalyst, and b is tripolite loading solid
The X-ray diffraction line chart of superpower acids fenton catalyst；There is spreading out for solid strong acid in diatomite after a and b compares visible load
Penetrate peak.
As shown in Figure 2, Fourier infrared spectrum figure shows that tripolite loading solid super strong acids fenton catalyst occurs
Asymmetric S=O stretching vibration has superpower acidity.
From the figure 3, it may be seen that the initial concentration of rhodamine B is 0.5mmol/L in degradation experiment, it is separately added into 40mg embodiment 1
The diatomite that made tripolite loading solid super strong acids fenton catalyst and 40mg comparative experiments obtain-iron oxide support type is urged
Agent, initial pH=3,15 DEG C of reaction temperature, for reaction 6h to the percent of decolourization of rhodamine B, the diatomite for comparing visible embodiment 1 is negative
Carrying solid super strong acids fenton catalyst is 98.12% to the percent of decolourization of rhodamine B, than diatomite-oxygen of comparative experiments preparation
Change iron loaded catalyst and is higher by 63%.
As shown in Figure 4, in decomposition experiment, the dosage of hydrogen peroxide is 15mmol/L, is then respectively adding 40mg implementation
The diatomite that the made tripolite loading solid super strong acids fenton catalyst of example 1 and 40mg comparative experiments obtain-iron oxide load
Type catalyst, initial pH=3,15 DEG C of reaction temperature, reaction two experiments of 6h are catalyzed H2O2Resolution ratio, compare visible embodiment 1
Tripolite loading solid super strong acids fenton catalyst be catalyzed H2O2Resolution ratio be 93.73%, and diatomite-iron oxide is negative
Supported catalyst is catalyzed H2O2Resolution ratio be only 17.98%.
Embodiment 2, a kind of preparation method of tripolite loading solid super strong acids fenton catalyst of the present embodiment, including with
Lower step:
1) natural diatomaceous earth acidification
According to the mass parts of natural diatomaceous earth and sulfuric acid, hydrochloric acid and citric acid than the ratio for 1:0.5:1:0.8, natural
In diatomite be added mass fraction be 25% sulfuric acid, 15% hydrochloric acid and 8% citric acid, stir 9h under the conditions of 30 DEG C,
Mixing speed is 800r/min；
2) activated diatomaceous earth carrier
Activated diatomaceous earth carrier is after heat treatment made by the acidification diatomite that step 1) obtains, comprising the following steps:
(1) the acidification diatomite obtained by step 1) carries out 3h vacuum filtration and leaves and takes unfiltered solid, and in 115 DEG C of perseverances
It is sieved after the dry 5h of temperature, 900 mesh of aperture of sieve leaves and takes the lower diatomite of sieve；
(2) under the sieve (1) step left and taken then diatomite is calcined in 200 DEG C of calcining 1.5h of temperature at 350 DEG C of temperature
Activated diatomaceous earth carrier is made in 1.5h；
3) insoluble sediment is made after introducing molysite in activated diatomaceous earth carrier
Step 2) obtain activated diatomaceous earth carrier introduce molysite after insoluble sediment is made the following steps are included:
(1) it is according to activated diatomaceous earth carrier and the mass parts ratio of ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate
1:1.2:0.4:0.3:0.3:0.4 ratio, on activated diatomaceous earth carrier introduce mass fraction be 7% ferric sulfate, 7% nitric acid
Iron, 12% ferric acetate, 4% iron chloride and 6% ferric oxalate obtain mixed solution；
(2) the pH value of the mixed solution (1) obtained with sodium hydroxide regulating step makes the pH 8.3 of mixed solution；
(3) 10mL standard ammonia-ammonium chloride buffer solution is added in (2) mixed solution that step obtains；
(4) the ripening that 12h is carried out at 30 DEG C of temperature, is filtered by vacuum the mixed solution of ageing, collects insoluble precipitating
Object；
4) solid super strong acid precursor in situ is synthesized
The insoluble sediment that step 3) obtains is mixed with maceration extract, impregnates and solid super strong acid precursor in situ, packet is made
Include following steps:
It (1) is that 28% ammonium sulfate and 25% sulfuric acid are mixed with maceration extract, the matter of ammonium sulfate and sulfuric acid by mass fraction
Amount part is compared for 1:1；
(2) the mass parts of the maceration extract (1) obtained according to insoluble sediment and step obtain step 3) than the ratio for 1:8
The insoluble sediment obtained is mixed with maceration extract, dip time 20h；
(3) after 115 DEG C of freeze-day with constant temperature 2.5h, vacuum filtration leaves and takes unfiltered solid, before original position solid super-strong acid is made
Drive body；5) tripolite loading solid super strong acids fenton catalyst is prepared
The solid super strong acid precursor in situ that step 4) obtains is heat-treated, tripolite loading solid super-strong acid is made
Class fenton catalyst, comprising the following steps:
(1) the solid super strong acid precursor in situ that step 4) obtains is subjected to 450 DEG C of calcinings under the protection of nitrogen or argon gas
3h；
(2) under the protection of nitrogen or argon gas, continue that tripolite loading solid super strong acids is made in 550 DEG C of calcining 4.5h
Fenton catalyst.
Made tripolite loading solid super strong acids fenton catalyst is 95.49% to the removal rate of rhodamine B, to H2O2
Resolution ratio be 93.11%.
Embodiment 3, a kind of preparation method of tripolite loading solid super strong acids fenton catalyst of the present embodiment, including with
Lower step:
1) natural diatomaceous earth acidification
According to the mass parts of natural diatomaceous earth and sulfuric acid, hydrochloric acid and citric acid than the ratio for 1:2:1.5:1, in natural silicon
In diatomaceous earth be added mass fraction be 30% sulfuric acid, 16% hydrochloric acid and 10% citric acid, stir 10h under the conditions of 35 DEG C,
Mixing speed is 900r/min；
2) activated diatomaceous earth carrier
Activated diatomaceous earth carrier is after heat treatment made by the acidification diatomite that step 1) obtains, comprising the following steps:
(1) the acidification diatomite obtained by step 1) carries out 4h vacuum filtration and leaves and takes unfiltered solid, and in 120 DEG C of perseverances
It is sieved after the dry 6h of temperature, 1000 mesh of aperture of sieve leaves and takes the lower diatomite of sieve；
(2) diatomite is in 300 DEG C of calcining 2h of temperature under the sieve (1) step left and taken, then in 400 DEG C of calcining 2h of temperature, system
At activated diatomaceous earth carrier；
3) insoluble sediment is made after introducing molysite in activated diatomaceous earth carrier
Step 2) obtain activated diatomaceous earth carrier introduce molysite after insoluble sediment is made the following steps are included:
(1) it is according to activated diatomaceous earth carrier and the mass parts ratio of ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate
1:1.5:0.5:0.5:0.3:0.6 ratio, on activated diatomaceous earth carrier introduce mass fraction be 10% ferric sulfate, 9% nitre
Sour iron, 15% ferric acetate, 6% iron chloride and 10% ferric oxalate obtain mixed solution；
(2) the pH value of the mixed solution (1) obtained with sodium hydroxide regulating step makes the pH 9.2 of mixed solution；
(3) 10mL standard ammonia-ammonium chloride buffer solution is added in (2) mixed solution that step obtains；
(4) ripening for 24 hours is carried out at 35 DEG C of temperature, and the mixed solution of ageing is filtered by vacuum, collects insoluble precipitating
Object；
4) solid super strong acid precursor in situ is synthesized
The insoluble sediment that step 3) obtains is mixed with maceration extract, impregnates and solid super strong acid precursor in situ, packet is made
Include following steps:
It (1) is that 30% ammonium sulfate and 35% sulfuric acid are mixed with maceration extract, the matter of ammonium sulfate and sulfuric acid by mass fraction
Amount part is compared for 1:2；
(2) the mass parts of the maceration extract (1) obtained according to insoluble sediment and step obtain step 3) than the ratio for 1:10
The insoluble sediment obtained is mixed with maceration extract, dip time 36h；
(3) after 120 DEG C of freeze-day with constant temperature 3h, vacuum filtration leaves and takes unfiltered solid, and original position solid super-strong acid forerunner is made
Body；5) tripolite loading solid super strong acids fenton catalyst is prepared
The solid super strong acid precursor in situ that step 4) obtains is heat-treated, tripolite loading solid super-strong acid is made
Class fenton catalyst, comprising the following steps:
(1) the solid super strong acid precursor in situ that step 4) obtains is subjected to 500 DEG C of calcinings under the protection of nitrogen or argon gas
4h；
(2) under the protection of nitrogen or argon gas, continue that it is fragrant that tripolite loading solid super strong acids is made in 600 DEG C of calcining 4h
Pause catalyst.
Made tripolite loading solid super strong acids fenton catalyst is 98.01% to the removal rate of rhodamine B, to H2O2
Resolution ratio be 95.27%.
Claims (7)
1. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst, characterized in that the following steps are included:
1) natural diatomaceous earth acidification
Sulfuric acid, hydrochloric acid and citric acid are added in natural diatomaceous earth and carries out acidification, natural diatomaceous earth and sulfuric acid, hydrochloric acid and lemon
The mass parts ratio of lemon acid is 1:0.5~2:1~1.5:0.5~1；
2) activated diatomaceous earth carrier
Activated diatomaceous earth carrier is after heat treatment made by the acidification diatomite that step 1) obtains；
3) insoluble sediment is made after introducing molysite in activated diatomaceous earth carrier
Ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate is introduced in the activated diatomaceous earth carrier that step 2) obtains to be made
The mass parts ratio of insoluble sediment, activated diatomaceous earth carrier and ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate is 1:1
~1.5:0.2~0.6:0.2~0.5:0.2~0.5:0.3~0.6；
4) solid super strong acid precursor in situ is synthesized
The insoluble sediment that step 3) obtains is mixed with maceration extract, impregnates and solid super strong acid precursor in situ is made, it is insoluble heavy
Starch and the mass parts of maceration extract ratio are 1:5~10；
5) tripolite loading solid super strong acids fenton catalyst is prepared
The solid super strong acid precursor in situ that step 4) obtains is heat-treated, it is fragrant that tripolite loading solid super strong acids is made
Pause catalyst.
2. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst as described in claim 1, feature
It is that step 1) the natural diatomaceous earth acidification is: according to the mass parts ratio of natural diatomaceous earth and sulfuric acid, hydrochloric acid and citric acid
For 1:0.5~2:1~1.5:0.5~1 ratio, be added in natural diatomaceous earth sulfuric acid that mass fraction is 20%~30%,
10%~16% hydrochloric acid and 5%~10% citric acid, 7~10h is stirred under the conditions of 25 DEG C~35 DEG C, mixing speed is
800~1000r/min.
3. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst as described in claim 1, feature
Be, step 2) the activated diatomaceous earth carrier the following steps are included:
(1) the acidification diatomite obtained by step 1) carries out 1~4h vacuum filtration and leaves and takes unfiltered solid, 105 DEG C~120
It is sieved after DEG C 4~6h of freeze-day with constant temperature, 200~1000 mesh of aperture of sieve leaves and takes the lower diatomite of sieve；
(2) diatomite is in 200 DEG C~300 DEG C 1~2h of calcining of temperature under the sieve (1) step left and taken, then 300 DEG C of temperature~
400 DEG C of 1~2h of calcining, are made activated diatomaceous earth carrier.
4. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst as described in claim 1, feature
Be, step 3) the activated diatomaceous earth carrier insoluble sediment is made after introducing molysite the following steps are included:
It (1) is 1:1 according to the mass parts ratio of activated diatomaceous earth carrier and ferric sulfate, ferric nitrate, ferric acetate, iron chloride and ferric oxalate
~1.5:0.2~0.6:0.2~0.5:0.2~0.5:0.3~0.6 ratio introduces quality point on activated diatomaceous earth carrier
Number is 5%~10% ferric sulfate, 4%~9% ferric nitrate, 10%~15% ferric acetate, 3%~6% iron chloride and 6%~10%
Ferric oxalate obtains mixed solution；
(2) the pH value of the mixed solution (1) obtained with sodium hydroxide regulating step makes the pH 7.5~9.2 of mixed solution；
(3) 10mL standard ammonia-ammonium chloride buffer solution is added in (2) mixed solution that step obtains；
(4) 8~ripening for 24 hours is carried out at 25 DEG C~35 DEG C of temperature, the mixed solution of ageing is filtered by vacuum, and is collected insoluble
Sediment.
5. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst as described in claim 1, feature
Being that the step 4) synthesizes solid super strong acid precursor in situ is:
(1) be that 20%~30% ammonium sulfate and 20%~35% sulfuric acid are mixed with maceration extract by mass fraction, ammonium sulfate and
The mass parts ratio of sulfuric acid is 1:0.3~2；
(2) the mass parts of the maceration extract (1) obtained according to insoluble sediment and step obtain step 3) than the ratio for 1:5~10
The insoluble sediment obtained is mixed with maceration extract, and dip time is 18~36h；
(3) after 105 DEG C~120 DEG C 2~3h of freeze-day with constant temperature, vacuum filtration leaves and takes unfiltered solid, and original position solid super strong is made
Acid precursor.
6. a kind of preparation method of tripolite loading solid super strong acids fenton catalyst as described in claim 1, feature
Be, the step 5) prepare tripolite loading solid super strong acids fenton catalyst the following steps are included:
(1) the solid super strong acid precursor in situ that step 4) obtains is carried out 400 DEG C~500 DEG C under the protection of nitrogen or argon gas
Calcine 2~4h；
(2) under the protection of nitrogen or argon gas, continue that tripolite loading solid super strong is made in 500 DEG C~600 DEG C 4~5h of calcining
Acids fenton catalyst.
7. a kind of silicon of the preparation method preparation of tripolite loading solid super strong acids fenton catalyst as described in claim 1
Diatomaceous earth supported solid superacid acids fenton catalyst.
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