CN108452824A - It is a kind of to prepare load pure rutile phase TiO2The method of the clinoptilolite of nanotube - Google Patents
It is a kind of to prepare load pure rutile phase TiO2The method of the clinoptilolite of nanotube Download PDFInfo
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- CN108452824A CN108452824A CN201710089732.6A CN201710089732A CN108452824A CN 108452824 A CN108452824 A CN 108452824A CN 201710089732 A CN201710089732 A CN 201710089732A CN 108452824 A CN108452824 A CN 108452824A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The present invention relates to zeolite, TiO2Nanotube preparation field, it is particularly a kind of to prepare load pure rutile phase TiO2The clinoptilolite preparation method of nanotube.The object of the present invention is to provide a kind of zeolite-loaded Rutile Type TiO2Nanotube and preparation method thereof, it can overcome the Rutile Type TiO for wastewater treatment effect in the plagioclase Zeolite support under prior art processing2The small and dispersed limitation of nanotube area is big, and prepares costly, and the ozone activity for passing through a kind of catalyst that this technology is prepared is high, energy high-efficient carrier TiO2Powder, chemical property is stablized after load, and can also promote TiO2The loads such as powder, body can be easily dispersed in water, to achieve the purpose that remove polluter in efficient row ozone catalyst joint ozone degradation sewage technique.
Description
Technical field
The present invention relates to zeolite, TiO2Nanotube preparation field, it is particularly a kind of to prepare load pure rutile phase TiO2
The clinoptilolite preparation method of nanotube.
Background technology
Zeolite（zeolite）It is a kind of ore, is found in earliest 1756.The mineralogist Leiderkranz of Sweden carries
（Cronstedt）It was found that there is a kind of natural aluminosilicate acid salt ore to will produce boiling phenomenon in calcination, therefore it is named as " zeolite "
（Swedish zeolit）.It is meant in Greek " boiling "（zeo）" stone "（lithos）.Hereafter, people grind zeolite
Study carefully and deepens continuously；The zeolite that nature has found has more than 80 kinds, it is more typical have analcime, chabasie, scolecite, heulandite,
Sodalite, modenite, foresite etc., all based on calcic, sodium.The number of their water content with ambient temperature and humidity change
Change and changes.The affiliated crystallographic system of crystal is with the different and different of mineral species, with monoclinic system and rhombic system（Orthorhombic system）Account for it is more
Number.Analcime, chabasie often in etc. shaft-like crystalline form, heulandite, foresite are plate-like, and erionite, modenite are in needle-shaped or fine
Shape is tieed up, phillipsite and foresite twin crystal are common.Pure various zeolites are colourless or white, but can be due to being mixed into impurity
In various light color.Glassy lustre.Cleavage is different with crystal structure.Mohs' hardness is medium.Proportion is between 2.0~2.3, and baric is then
Up to 2.5~2.8.Zeolite is mainly formed in the low temperature hot liquid stage, is common in effusive rock stomata, also sees hydrothermal deposit and close
In being deposited for hot spring.Zeolite can borrow the percolation of water, and to carry out the exchange of cation, sodium, calcium ion in ingredient can
It is exchanged with potassium, the magnesium plasma in aqueous solution, industrially to softening of water.The crystal structure of zeolite is by silicon（Aluminium）Oxygen four sides
Body is linked to be three-dimensional screen work, has hole and channel of all sizes in screen work, has prodigious opening.Alkali metal or alkali
Earthmetal cations and hydrone are distributed in hole and channel, weaker with contacting for screen work.Different ion exchanges are to zeolite
Structure influences very little, but the property of zeolite is made to change.Cavity of different sizes present in lattice can be drawn or filter and is big
The molecule of small other different substances.Industrially often as molecular sieve, to purify or detach the substance of blending constituent, such as gas
Body separation, petroleum cleanup, processing industrial pollution etc..
Clinoptilolite is one kind in zeolite group mineral, and most abundant one kind.Its crystal is transparent plate, also can be because
It is impure to form brown, red.Clinoptilolite is aqueous alkali metal aluminosilicate, it can be with the work(of molecular sieve after being dehydrated
Can, nitrogen can be selectively extracted from air and make oxygen coalescence.Clinoptilolite is alternatively arranged as ion-exchanger, is used for process cores
Waste material, it or the filler in paper industry and swelling agent；By TiO2It applies organic in ozone catalyst joint ozone degradation
When waste water technology, the ozone catalytic activity of catalyst, its recoverable efficiency and cost all leverage its application
In Practical Project.And research shows that TiO2When as ozone catalyst, if the ratio of catalyst Rutile Type itself is higher,
Specific surface area is bigger, and ozone cooperative efficiency is better.The prior art is by TiO2Load to activated carbon, potsherd, powder or preparation
Film forming, but the product being prepared but limits TiO2Active area and dispersibility, and costly, for preparing urges
The ozone activity of agent is not high.It is, thus, sought for one kind can either payload TiO2Powder, chemical property is steady after load
It is fixed, and can also promote load can easily be dispersed in water, facilitate recycling and it is cheap be to be applied to the technology
Necessity in Practical Project case.
Invention content
The object of the present invention is to provide a kind of zeolite-loaded Rutile Type TiO2Nanotube and preparation method thereof, it can gram
Take the Rutile Type TiO for wastewater treatment effect in the plagioclase Zeolite support under prior art processing2Nanotube area it is small and
Dispersibility limitation is big, and the ozone activity for preparing a kind of costly, to prepare by this technology catalyst is high, can be efficient
Load TiO2Powder, chemical property is stablized after load, and can also promote TiO2The loads such as powder, body can easily disperse
Yu Shuizhong, to achieve the purpose that remove polluter in efficient row ozone catalyst joint ozone degradation sewage technique.
The present invention is achieved through the following technical solutions：The present invention, which is that invention is a kind of, preparing load pure rutile phase TiO2
Method of clinoptilolite of nanotube and preparation method thereof, steps are as follows for main preparation methods：
Step 1：If weighing the clinoptilolite particle of dry mass, it is 2% that clinoptilolite particle, which is integrally soaked into mass concentration,
It is impregnated 2 hours in NaCl solution, solid is with liquid fraction：1 to 50 to 1 to 27 or 1 to 60 to 1 to 30；Environment temperature is 10
Degree Celsius or more, 25 degrees Celsius or less；Drying and processing is carried out after dip time, and it is spare to take out surface modification zeolite.
Step 2：Weigh 2.5g titanium dioxide P25 powder and step 1 in the dipping zeolite 5g that is disposed while being added
To a concentration of 10molL of 180mL-1In NaOH solution, above-mentioned material is put in people's beaker, then by multiple or 1 above-mentioned processing material
Beaker is placed in oscillator concussion processing 30min together, will concussion treated that solid-liquid mixed solution is transferred out of beaker,
It imports in the polytetrafluoroethyllining lining reaction kettle that volume is 200mL and is handled.
Step 3：The suspended things that the step 2 has imported concussion treated the white emulsion that zeolite P 25 disperses are led
Enter and be put into air dry oven under the temperature conditions after reaction kettle continues to reaction, the temperature of air dry oven is set as 150
DEG C, and keep being cooled to reaction kettle at room temperature close or equal to after room temperature after being dried 48 hours, from air dry oven
Middle taking-up reaction kettle.
Step 4：By the step 3 final mean annual increment solution 0.1molL of taking-up-1The solution of HCl rinse repeatedly, solution and AgNO3
For solution until there is crystallization reaction object in step 3 final mean annual increment solution flushing process, it is anti-not generate new crystallization again after repeatedly rinsing
After answering object it is added that the crystallization reaction proposed out is entered AgNO is added3Solution is shaken in flask, is checked in AgNO3It is molten
Liquid does not have white depositions to occur, to complete step 4, otherwise continuing with AgNO after being added3Solution is repeatedly rinsed, finally
Remaining suspended sediment solution is subjected to desalination flushing with distilled water, until its acid-base value is reached pH=7 ~ 5.5.
Step 5：The last suspended sediment solution of step 4 is put it into vacuum drying chamber, after vacuumizing, temperature setting
It is 1000C keeps carrying out within 24 hours taking off doing, and until suspension solution is converted into powdered object, powdered object is that zeolite-titanate is received
Mitron powder.
Step 6：Powdered object is put into Muffle furnace and is calcined, the temperature rate that the setting of muffle furnace rises is set in
5°Cmin-1Until temperature is increased to 600oC, and processing 2 hours is maintained at such a temperature, after completing Muffle furnace processing, most
Obtained powder after Muffle furnace is calcined afterwards, powder are zeolite-rutile TiO2 nanometer tube composite materials powder, are cooled to room
Temperature is not examined finished product.
Step 7 does not examine finished product and screens several grams, is soaked into be contained in ionized water or pure water in container, container is put
Enter and has been set in 27 DEG C of constant temperature oscillation case, after starting constant temperature oscillation case to vibrate absorption under conditions of 160r/min 2 hours,
The measurement that extraction supernatant after container is stood carries out performance assessment criteria is taken out, nessler reagent is respectively adopted in wherein ammonia nitrogen, total nitrogen, total phosphorus
Spectrophotometry, potassium persulfate oxidation ultraviolet spectrophotometry, Ammonium Molybdate Spectrophotometric Method for Determination, ammonia nitrogen removal frank 94.2%
It is certified products above.
Step 8 certified products are packed.
It is a kind of to utilize zeolite-loaded Rutile Type TiO2Nanotube carries out ozone as catalyst and is combined catalytic degradation ammonia nitrogen
The method of waste water：Include the following steps
It takes out a unit deionized water and the ammonia nitrogen waste water solution of a concentration of 100mgL-1 is added and be fabricated to pollutant simulated solution
Simulated solution is placed in reaction vessel, thermostat controlling reaction temperature is used in combination, puts into zeolite-loaded Rutile Type TiO2 nanotubes
In powder to organic pollution simulated solution, stir or be put into concussion instrument, formed liquid solid two-phase fully touch it is mixed suspended
Mixture is inserted into appendix in the reaction vessel, ozone is inputted into suspended mixture by appendix, ozone stability of flow exists
50mLmin-1 keeps reacting at least 3 hours under conditions of the stable output of ozone；
It is a kind of to carry out ozone combination catalytic degradation ammonia nitrogen waste water as catalyst using zeolite-loaded Rutile Type TiO2 nanotubes
And the method for the zeolite-loaded catalyst of recycling：
It builds at aeration tank 1, aeration tank uses concrete grade for C25, C30, and pond inner wall wall brush fills out seepage-resistant grade S5 or more
Impermeabilisation agent or coating, with armored concrete build aeration tank bottom wall, 400 ~ 620mm of bottom wall thickness, other pool walls 200mm
~ 400mm, every 8 squares of bottom wall build out 1 rectangular expansion joint；Setting masking net at the top of aeration tank, the top setting of masking net
Dry load lid is covered, setting contaminant water is introduced in aeration tank and is discharged into pipe and catalyst input pipe；
Several ozonation aerated devices are set in aeration tank, and the ozonation aerated device includes vertically arranged ozone air inlet master
The top of pipe, ozone air inlet supervisor connects ozone appendix, and the ozone air inlet supervisor whole body is circumferentially equidistantly positioned several ozone
Air intake branch, several aeration heads are additionally provided on the ozone air intake branch, and ozone air inlet supervisor bottom is additionally provided with rotation
Turn pedestal, and air inlet is arranged in ozone air inlet supervisor top, negative-pressure air fan or wine guide, the ozone air inlet branch is arranged in air inlet
Pipe is ceramic material, and the rotating base connects driving motor；The aeration head includes gas separating port, qi-regulating storehouse, qi-regulating orlop portion
Aeration head air inlet pipe is set, and qi-regulating storehouse is cone, and loudspeaker lid closes setting gas separating port, and spiral or ring shape is arranged in gas separating port
The stomata array of shape arrangement, setting Pneumatic rotary fan in the qi-regulating storehouse；
Bottom setting series connection fixing pipe is responsible in ozone air inlet, and water temperature heating is provided in fixing pipe of connecting；Series connection is opened to fix
It is provided with water temperature heating on pipe to control reaction temperature to 20 ~ 40 degrees Celsius and be always maintained at stabilization, opens contaminant water and is discharged into
Pipe is discharged into nitrogen-containing wastewater, and opens catalyst input pipe simultaneously, and input load Rutile Type TiO2 nanotube zeolite powders give up
Water and load Rutile Type TiO2 nanotube zeolite powders mixing, are pushed up in pending mixed liquor entirety liquid level and ozone air inlet supervisor
Portion maintains an equal level or opens ozone generating apparatus when being less than 10 ~ 40cm, is inputted into the ozone air inlet of ozonation aerated device supervisor smelly
Oxygen allows ozone to be distributed in pending mixed liquor by gas separating port, qi-regulating storehouse, with ammonia nitrogen waste water and load Rutile Type TiO2It receives
Mitron zeolite powder catalyst carries out hybrid reaction, reacts 3 ~ 5 hours, while covering and also setting up ozone time below dry load lid
It calls prisoners in after letting them out for exercise pipe device, recycles ozone, and re-inject in aerator, after the completion of the reaction time, take aeration tank mid-water and bottom
Water measures respectively, stops aeration and reaction after up to standard, carries out net liquid precipitation, surface sewage is discharged after the completion of precipitation, in dirt
Water is filtered when discharging, and recycles filter mud and glar, carry out cleaning in filter press or cleaning robot filter mud and
Glar recycles zeolite-loaded catalyst, in case next time uses.
After dip time as preferred step 1 zeolite, need to repeatedly it be rinsed with pure water or ionized water,
It is dry after impregnating zeolite acid-base property value and being down to 7 ~ 5.5, it is spare to step 2.
Zeolite entirety soaking technology as the preferred step 1 carries out in isothermal vibration device.
The clinoptilolite particle is the basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite particle as priority, picks up range
For：Ore NH4+Exchange capacity is 140mmol/100g~240mmol/100g, K+Exchange capacity is 22 × 10-3~14 × 10-3,
Adsorption capacity for nitrogen is 12mL/g~27mL/g.
It is 1.7 ~ 3.2mm as the preferred clinoptilolite grain diameter.
The specific surface area chosen as the preferred basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite is 530 ~ 830 ㎡/g.
It is air bath oscillator as the preferred oscillator, interior 200 standard vibration of setting XSB-70 (B) sieve.
Be conical flask beaker as the beaker in the preferred step 2, oscillator is air concussion device, air concussion device with
The speed of 200r/min is shaken.Processing 30min is rocked in concussion.
The beneficial effects of the invention are as follows：Present invention is generally directed to prepare one kind being exclusively used in ozone catalyst joint ozone degradation
The zeolite-loaded pure rutile phase TiO of organic wastewater technology2Nanotube, this technology be not it is simple in the prior art certain 1
Kind technique, but separately walk a technological approaches：In conjunction with hydrothermal synthesis method and infusion process, recycled after adjusting synthesis by infusion process
Hydrothermal synthesis method temperature the TiO of the mutually big specific surface area of pure rutile has been prepared with the temperature of calcining2Nanotube, and TiO2
Nanotube has been evenly distributed on zeolite surface very much, with material, reaction process pure rutile is not had to mutually by being accurately controlled
It stretches into as possible inside zeolite template,（Either with or without the product parameters contrast table specific surface area of this technology and usual technology in 300m2/
G, TiO2All Rutile Types are more advantageous to ozone catalytic performance）And it is controlled at zeolite surface and produces pure rutile phase
TiO2 nanotubes so that only need surface reaction can be carried out ozone catalyst joint ozone degradation technology can effectively into
Row, in pure rutile phase TiO2Its ozone catalytic activity is substantially increased on nanotube zeolitic material so that prepared product up to
On to extraordinary ozone catalyst joint ozone degradation treatment of Organic Wastewater in effect；
By TiO2It is even more pioneering to apply in ozone catalyst joint ozone degradation ammonia nitrogen waste water technology, possesses other catalyst highers
Efficiency and cheap cost, the ozone catalytic activity of catalyst, its recoverable efficiency and cost all largely effect on
It is applied in Practical Project.And research shows that TiO2When as ozone catalyst, if catalyst Rutile Type itself
Ratio is higher, and specific surface area is bigger, and ozone cooperative efficiency is better.The prior art is by TiO2Load to activated carbon, potsherd, powder
Or film forming is prepared, but the product being prepared but limits TiO2Active area and dispersibility, and costly, system
Ozone activity for the catalyst gone out is not high.
Product that is effective and successfully controlling its production, Production Time, technical difficulty are no longer needed in making, simultaneously
The problem of also can effectively solve the problem that recycling, by TiO2It applies last in ozone catalyst joint ozone degradation ammonia nitrogen waste water
Reactant be precipitation zeolite sludge mixture, it is only necessary to zeolite sludge mixture is recycled from aeration tank again,
After cleaning treatment, and it can reuse.
Description of the drawings
Fig. 1 is Aeration tank structure figure.
Fig. 2 is aerator structure chart.
Fig. 3 is aeration head structure chart.
Fig. 4 is aeration head internal structure chart.
Specific implementation mode
Below by embodiment, in conjunction with attached drawing, preferred specific description is used as to technical scheme of the present invention：
It is a kind of to prepare load pure rutile phase TiO2Method of clinoptilolite of nanotube and preparation method thereof, main preparation methods
Steps are as follows：
Step 1：If weighing the clinoptilolite particle of dry mass, it is 2% that clinoptilolite particle, which is integrally soaked into mass concentration,
It is impregnated 2 hours in NaCl solution, solid is with liquid fraction：1 to 50 to 1 to 27 or 1 to 60 to 1 to 30；Environment temperature is 10
Degree Celsius or more, 25 degrees Celsius or less；Drying and processing is carried out after dip time, and it is spare to take out surface modification zeolite.
Step 2：Weigh 2.5g titanium dioxide P25 powder and step 1 in the dipping zeolite 5g that is disposed while being added
To a concentration of 10molL of 180mL-1In NaOH solution, above-mentioned material is put in people's beaker, then by multiple or 1 above-mentioned processing material
Beaker is placed in oscillator concussion processing 30min together, will concussion treated that solid-liquid mixed solution is transferred out of beaker,
It imports in the polytetrafluoroethyllining lining reaction kettle that volume is 200mL and is handled.
Step 3：The suspended things that the step 2 has imported concussion treated the white emulsion that zeolite P 25 disperses are led
Enter and be put into air dry oven under the temperature conditions after reaction kettle continues to reaction, the temperature of air dry oven is set as 150
DEG C, and keep being cooled to reaction kettle at room temperature close or equal to after room temperature after being dried 48 hours, from air dry oven
Middle taking-up reaction kettle.
Step 4：Step 3 final mean annual increment solution of taking-up is rinsed repeatedly with the solution of the HCl of 0.1molL-1, solution and AgNO3
For solution until there is crystallization reaction object in step 3 final mean annual increment solution flushing process, it is anti-not generate new crystallization again after repeatedly rinsing
Addition enters to be added AgNO3 solution to the crystallization reaction proposed out after answering object, is shaken, is checked in AgNO3 in flask
Solution does not have white depositions to occur, to complete step 4, otherwise continuing with AgNO3 solution and repeatedly being rinsed, most after being added
Remaining suspended sediment solution is subjected to desalination flushing with distilled water afterwards, until its acid-base value is reached pH=7 ~ 5.5.
Step 5：The last suspended sediment solution of step 4 is put it into vacuum drying chamber, after vacuumizing, temperature setting
It keeps carrying out within 24 hours taking off doing for 1000C, until suspension solution is converted into powdered object, powdered object is that zeolite-titanate is received
Mitron powder.
Step 6：Powdered object is put into Muffle furnace and is calcined, the temperature rate that the setting of muffle furnace rises is set in
5°Cmin-1Until temperature is increased to 600oC, and processing 2 hours is maintained at such a temperature, after completing Muffle furnace processing, most
Obtained powder after Muffle furnace is calcined afterwards, powder is zeolite-rutile TiO2 nanometer tube composite materials powder herein）It is cooling
To room temperature, finished product is not examined.
Step 7 does not examine finished product and screens several grams, is soaked into be contained in ionized water or pure water in container, container is put
Enter and has been set in 27 DEG C of constant temperature oscillation case, after starting constant temperature oscillation case to vibrate absorption under conditions of 160r/min 2 hours,
The measurement that extraction supernatant after container is stood carries out performance assessment criteria is taken out, nessler reagent is respectively adopted in wherein ammonia nitrogen, total nitrogen, total phosphorus
Spectrophotometry, potassium persulfate oxidation ultraviolet spectrophotometry, Ammonium Molybdate Spectrophotometric Method for Determination, ammonia nitrogen removal frank 94.2%
It is certified products above.
Step 8 certified products are packed.
After dip time as preferred step 1 zeolite, need to repeatedly it be rinsed with pure water or ionized water,
It is dry after impregnating zeolite acid-base property value and being down to 7 ~ 5.5, it is spare to step 2.
Zeolite entirety soaking technology as the preferred step 1 carries out in isothermal vibration device.
The clinoptilolite particle is the basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite particle as priority, picks up range
For：Ore NH4+ exchange capacities be 140mmol/100g~240mmol/100g, K+ exchange capacities be 22 × 10-3~14 ×
10-3, adsorption capacity for nitrogen are 12ml/g~27ml/g.
It is 1.7 ~ 3.2mm as the preferred clinoptilolite grain diameter.
The specific surface area chosen as the preferred basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite is 530 ~ 830 ㎡/g.
It is air bath oscillator as the preferred oscillator, interior 200 standard vibration of setting XSB-70 (B) sieve.
Be conical flask beaker as the beaker in the preferred step 2, oscillator is air concussion device, air concussion device with
The speed of 200r/min is shaken.Processing 30min is rocked in concussion.
Embodiment 2：Step 1：If weighing the basins the Jinyun county, Zhejiang province Hu Zhen clinoptilolite particle of dry mass, pick up ranging from：Ore
NH4+ exchange capacities are 140mmol/100g~240mmol/100g, and K+ exchange capacities are 22 × 10-3~14 × 10-3, nitrogen
Gas adsorption capacity is 12mL/g~27mL/g.The clinoptilolite grain diameter is 1.7 ~ 3.2mm；Jinyun county, Zhejiang province pot town basin
The specific surface area that ground clinoptilolite is chosen is 530 ~ 830 ㎡/g；It is 2% that clinoptilolite particle, which is integrally soaked into mass concentration,
It is impregnated 2 hours in NaCl solution, solid is with liquid fraction：1 to 50 to 1 to 27 or 1 to 60 to 1 to 30；Environment temperature is 10
Degree Celsius or more, 25 degrees Celsius or less；After dip time, it is spare to take out dipping zeolite.The dip time knot of step 1 zeolite
Shu Hou need to repeatedly be rinsed with pure water or ionized water, dry wait impregnating after zeolite acid-base property value is down to 7 ~ 5.5, it is spare extremely
Step 2.
Step 2：Weigh 2.5g titanium dioxide P25 powder and step 1 in the dipping zeolite 5g that is disposed while being added
To a concentration of 10molL of 180mL-1In NaOH solution, above-mentioned material is put in people's beaker, then by the material beaker of multiple above-mentioned processing,
Beaker is conical flask beaker, and oscillator is air concussion device, and air concussion device is shaken with the speed of 200r/min.Place is rocked in concussion
Manage 30min, will concussion treated solid-liquid mixed solution is transferred out of beaker, import in the polytetrafluoroethylene (PTFE) that volume is 200mL
It is handled in lining reaction kettle.
Step 3：The step 2 has been imported concussion treated solid-liquid mixed solution reaction kettle maintain reaction after
Temperature conditions under be put into air dry oven, the temperature of air dry oven is set as 150oC, and keep that be dried 48 small
When, after reaction kettle is cooled at room temperature close or equal to after room temperature, reaction kettle is taken out from air dry oven.
Step 4：By the step 3 final mean annual increment solution 0.1molL of taking-up-1The solution of HCl rinse repeatedly, solution and AgNO3
For solution until there is crystallization reaction object in step 3 final mean annual increment solution flushing process, it is anti-not generate new crystallization again after repeatedly rinsing
The crystallization reaction addition AgNO to proposition is added after answering object3Solution is shaken in flask, is checked in AgNO3Solution adds
There is no white depositions to occur, to complete step 4, otherwise continuing with AgNO after entering3Solution is repeatedly rinsed, and will finally be remained
Under suspended sediment solution carry out desalination flushing with distilled water, until its acid-base value is reached pH=7 ~ 5.5.
Step 5：The last suspended sediment solution of step 4 is put it into vacuum drying chamber, after vacuumizing, temperature setting
It is 1000C keeps carrying out within 24 hours taking off doing, until suspension solution is converted into powdered object.
Step 6：Powdered object is put into Muffle furnace and is calcined, the temperature rate that the setting of muffle furnace rises is set in
5 ºC min-1Until temperature is increased to 600oC, and processing 2 hours is maintained at such a temperature, after completing Muffle furnace processing, finally
Obtained powder after Muffle furnace is calcined is cooled to room temperature, is not examined finished product.
Step 7 does not examine finished product screen and takes several grams of finished product, is soaked into ionized water or pure water, full temperature oscillation case 27
DEG C, oscillation absorption 2 hours under conditions of 160r/min, take out the measurement that extraction supernatant after standing carries out performance assessment criteria, wherein
Berthelot spectrophotometry, potassium persulfate oxidation ultraviolet spectrophotometry, ammonium molybdate point is respectively adopted in ammonia nitrogen, total nitrogen, total phosphorus
Light photometry measures, and it is certified products that ammonia nitrogen removal frank, which is 94.2% or more,.
Step 8 certified products are packed.
It is a kind of to carry out ozone combination catalytic degradation ammonia nitrogen as catalyst using zeolite-loaded Rutile Type TiO2 nanotubes
The method of pollutant：Include the following steps
It takes out a unit deionized water and the stupid phenol solution of a concentration of 100mgL-1 is added and be fabricated to organic pollution simulated solution
Organic pollution simulated solution is placed in reaction vessel, low temperature thermostat bath controlling reaction temperature is used in combination, puts into zeolite-loaded golden red
In stone phase TiO2 nanotube powders to organic pollution simulated solution, stirs or be put into concussion instrument, form liquid solid two-phase
Mixed suspended mixture is fully touched, appendix is inserted into the reaction vessel, ozone is inputted into suspended mixture by appendix,
Ozone stability of flow keeps reacting at least 3 hours under conditions of the stable output of ozone in 50mLmin-1；
It is a kind of organic as catalyst progress ozone combination catalytic degradation phenols using zeolite-loaded Rutile Type TiO2 nanotubes
The method of pollutant and the zeolite-loaded catalyst of recycling：
As shown in Figs 1-4, it builds at aeration tank 1, aeration tank uses concrete grade for C25, C30, and pond inner wall wall brush is filled out anti-
Impermeabilisation agent or the coating for oozing grade S5 or more, with armored concrete build aeration tank bottom wall, 400 ~ 620mm of bottom wall thickness,
Other pool walls 200mm ~ 400mm, every 8 squares of bottom wall build out 1 rectangular expansion joint；Setting masking net at the top of aeration tank
（1）, masking net top setting masking dry load lid（2）, setting contaminant water is introduced in aeration tank is discharged into pipe（101）, and catalysis
Agent input pipe；
Several ozonation aerated devices are set in aeration tank（3）, the ozonation aerated device includes vertically arranged ozone air inlet
Supervisor（4）, the top of ozone air inlet supervisor connects ozone appendix（5）, the ozone air inlet supervisor whole body is circumferentially equidistantly positioned
Several ozone air intake branches（6）, several aeration heads are additionally provided on the ozone air intake branch（7）, the ozone air inlet supervisor
Bottom is additionally provided with rotating base（8）, and air inlet is arranged in ozone air inlet supervisor top, negative-pressure air fan or air inducing is arranged in air inlet
Device（9）, the ozone air intake branch is ceramic material, and the rotating base connects driving motor；The aeration head includes dividing gas
Head（10）, qi-regulating storehouse（11）, aeration head air inlet pipe is arranged in qi-regulating orlop portion（12）, qi-regulating storehouse is cone, and loudspeaker lid is closed
Gas separating port is set, and the stomata array of spiral or circle shaped formation is arranged in gas separating port（13a）, the pneumatic rotation of setting in the qi-regulating storehouse
Turn fan（13b）；
Bottom setting series connection fixing pipe is responsible in ozone air inlet, and water temperature heating is provided in fixing pipe of connecting（14）；
Water temperature heating is provided in unlatching series connection fixing pipe to control reaction temperature to 20 ~ 40 degrees Celsius and be always maintained at steady
Fixed, unlatching contaminant water is discharged into pipe and is discharged into waste water containing ammonia nitrogen pollutant, and opens catalyst input pipe simultaneously, input load rutile
Phase TiO2 nanotube zeolite powders, organic wastewater and load Rutile Type TiO2 nanotube zeolite powders mixing, pending
Mixed liquor entirety liquid level maintains an equal level with ozone air inlet supervisor top or opens ozone generating apparatus when being less than 10 ~ 40cm, to ozone
Ozone is inputted in the ozone air inlet supervisor of aerator, ozone is allowed to be distributed in pending mixed liquor by gas separating port, qi-regulating storehouse,
With containing stupid phenol organic wastewater and load Rutile Type TiO2Nanotube zeolite powder catalyst carries out hybrid reaction, reaction 3 ~ 5
Hour, while covering and also setting up ozone recycling air pipe device below dry load lid, ozone is recycled, and re-inject aerator
In, after the completion of the reaction time, aeration tank mid-water and bottom water is taken to measure respectively, stops aeration and reaction after up to standard, into
Row net liquid precipitates, and surface sewage is discharged after the completion of precipitation, is filtered in sewage discharge, recycled filter mud and glar,
It carries out cleaning filter mud and glar in filter press or cleaning robot, recycles zeolite-loaded catalyst, in case next time uses.
Specific embodiment described herein is only an example for the spirit of the invention.Technology belonging to the present invention is led
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of preparing load pure rutile phase TiO2Method of clinoptilolite of nanotube and preparation method thereof, it is characterized in that：System
Steps are as follows for Preparation Method,
Step 1：If weighing the clinoptilolite particle of dry mass, it is 2% that clinoptilolite particle, which is integrally soaked into mass concentration,
It is impregnated 2 hours in NaCl solution, solid is with liquid fraction：1 to 50 to 1 to 27 or 1 to 60 to 1 to 30；Environment temperature is 10
Degree Celsius or more, 25 degrees Celsius or less；Drying and processing is carried out after dip time, and it is spare to take out surface modification zeolite；
Step 2：Weigh 2.5g titanium dioxide P25 powder and step 1 in the dipping zeolite 5g that is disposed while being added to
A concentration of 10molL of 180mL-1In NaOH solution, above-mentioned material is put in people's beaker, then multiple or 1 above-mentioned processing material is burnt
Cup is placed in oscillator concussion processing 30min together, will concussion treated that solid-liquid mixed solution is transferred out of beaker, lead
Enter and is handled in the polytetrafluoroethyllining lining reaction kettle that volume is 200mL；
Step 3：The step 2 has been imported concussion treated the white emulsion that zeolite P 25 disperses suspended things import it is anti-
It is put into air dry oven under temperature conditions after answering kettle to continue to reaction, the temperature of air dry oven is set as 150 DEG C, and
Reaction kettle is cooled at room temperature close or equal to after room temperature by holding after being dried 48 hours, is taken out from air dry oven
Reaction kettle；
Step 4：Step 3 final mean annual increment solution of taking-up is rinsed repeatedly with the solution of the HCl of 0.1molL-1, solution and AgNO3 solution
Up to there is crystallization reaction object in step 3 final mean annual increment solution flushing process, new crystallization reaction object is not generated again after repeatedly rinsing
It is added afterwards and enters to be added AgNO3 solution to the crystallization reaction proposed out, shaken in flask, checked in AgNO3 solution
There is no white depositions to occur after addition to complete step 4, otherwise continue with AgNO3 solution and repeatedly rinsed, finally will
Remaining suspended sediment solution carries out desalination flushing with distilled water, until its acid-base value is reached pH=7 ~ 5.5；
Step 5：The last suspended sediment solution of step 4 is put it into vacuum drying chamber, after vacuumizing, temperature is set as
1000C keeps carrying out within 24 hours taking off doing, and until suspension solution is converted into powdered object, powdered object is zeolite-titanate nanometer
Pipe powder；
Step 6：Powdered object is put into Muffle furnace and is calcined, the temperature rate that the setting of muffle furnace rises is set in 5 °
Cmin-1Until temperature is increased to 600oC, and processing 2 hours is maintained at such a temperature, after completing Muffle furnace processing, finally
Obtained powder after Muffle furnace is calcined, powder is zeolite-rutile TiO2 nanometer tube composite materials powder herein）It is cooled to
Room temperature is not examined finished product；
Step 7 does not examine finished product and screens several grams, is soaked into be contained in ionized water or pure water in container, container is put into
It is set as in 27 DEG C of constant temperature oscillation case, after starting constant temperature oscillation case to vibrate absorption under conditions of 160r/min 2 hours, takes out
Extraction supernatant carries out the measurement of performance assessment criteria after container is stood, and nessler reagent light splitting is respectively adopted in wherein ammonia nitrogen, total nitrogen, total phosphorus
Photometry, potassium persulfate oxidation ultraviolet spectrophotometry, Ammonium Molybdate Spectrophotometric Method for Determination, ammonia nitrogen removal frank are 94.2% or more
For certified products；
Step 8 certified products are packed.
2. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：After the dip time of step 1 zeolite, need to repeatedly it be rushed with pure water or ionized water
It washes, it is dry after impregnating zeolite acid-base property value and being down to 7 ~ 5.5, it is spare to step 2.
3. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：The zeolite entirety soaking technology of the step 1 carries out in isothermal vibration device.
4. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：The clinoptilolite particle is the basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite particle, picks up range
For：Ore NH4+ exchange capacities be 140mmol/100g~240mmol/100g, K+ exchange capacities be 22 × 10-3~14 ×
10-3, adsorption capacity for nitrogen are 12ml/g~27ml/g.
5. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：The clinoptilolite grain diameter is 1.7 ~ 3.2mm.
6. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：The specific surface area that the basins Jinyun county, Zhejiang province Hu Zhen clinoptilolite is chosen is 530 ~ 830 ㎡/g.
7. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：The oscillator is air bath oscillator, interior 200 standard vibration of setting XSB-70 (B) sieve.
8. a kind of prepare according to claim 1 loads pure rutile phase TiO2The method of the clinoptilolite of nanotube and its
Preparation method, it is characterized in that：Beaker in the step 2 is conical flask beaker, and oscillator is air concussion device, air concussion device
It is shaken with the speed of 200r/min, processing 30min is rocked in concussion.
9. preparing load pure rutile phase TiO according to claim 4 is a kind of2The method of the clinoptilolite of nanotube and its preparation side
Method, it is characterized in that：Step 1：If weighing the basins the Jinyun county, Zhejiang province Hu Zhen clinoptilolite particle of dry mass, pick up ranging from：Ore
NH4+ exchange capacities are 140mmol/100g~240mmol/100g, and K+ exchange capacities are 22 × 10-3~14 × 10-3, nitrogen
Gas adsorption capacity is 12mL/g~27mL/g, and the clinoptilolite grain diameter is 1.7 ~ 3.2mm；Jinyun county, Zhejiang province pot town basin
The specific surface area that ground clinoptilolite is chosen is 530 ~ 830 ㎡/g；It is 2% that clinoptilolite particle, which is integrally soaked into mass concentration,
It is impregnated 2 hours in NaCl solution, solid is with liquid fraction：1 to 50 to 1 to 27 or 1 to 60 to 1 to 30；Environment temperature is 10
Degree Celsius or more, 25 degrees Celsius or less；After dip time, taking-up dipping zeolite is spare, the dip time knot of step 1 zeolite
Shu Hou need to repeatedly be rinsed with pure water or ionized water, dry wait impregnating after zeolite acid-base property value is down to 7 ~ 5.5, it is spare extremely
Step 2；
Step 2：Weigh 2.5g titanium dioxide P25 powder and step 1 in the dipping zeolite 5g that is disposed while being added to
A concentration of 10molL of 180mL-1In NaOH solution, above-mentioned material is put in people's beaker, then by the material beaker of multiple above-mentioned processing, is burnt
Cup is conical flask beaker, and oscillator is air concussion device, and air concussion device is shaken with the speed of 200r/min, and processing is rocked in concussion
30min, will concussion treated solid-liquid mixed solution is transferred out of beaker, import the polytetrafluoroethyllining lining that volume is 200mL
It is handled in reaction kettle；
Step 3：The reaction kettle that the step 2 has been imported to concussion treated solid-liquid mixed solution maintains the temperature after reaction
It is put into air dry oven in the case of degree, the temperature of air dry oven is set as 150oC, and keep being dried 48 hours, after
Reaction kettle is cooled at room temperature close or equal to after room temperature, reaction kettle is taken out from air dry oven；
Step 4：By the step 3 final mean annual increment solution 0.1molL of taking-up-1The solution of HCl rinse repeatedly, solution and AgNO3Solution
Up to there is crystallization reaction object in step 3 final mean annual increment solution flushing process, new crystallization reaction object is not generated again after repeatedly rinsing
It is added afterwards and AgNO is added to the crystallization reaction of proposition3Solution is shaken in flask, is checked in AgNO3After solution is added
There is no white depositions to occur, to complete step 4, otherwise continuing with AgNO3Solution is repeatedly rinsed, finally will be remaining
Suspended sediment solution carries out desalination flushing with distilled water, until its acid-base value is reached pH=7 ~ 5.5；
Step 5：The last suspended sediment solution of step 4 is put it into vacuum drying chamber, after vacuumizing, temperature is set as
1000C keeps carrying out within 24 hours taking off doing, until suspension solution is converted into powdered object；
Step 6：Powdered object is put into Muffle furnace and is calcined, the temperature rate that the setting of muffle furnace rises is set in 5 oC
min-1Until temperature is increased to 600oC, and processing 2 hours is maintained at such a temperature, after completing Muffle furnace processing, finally by Muffle
Obtained powder after stove calcining is cooled to room temperature, is not examined finished product；
Step 7 does not examine finished product screen and takes several grams of finished product, is soaked into ionized water or pure water, complete 27 DEG C of case of temperature oscillation,
The measurement that extraction supernatant after standing carries out performance assessment criteria, wherein ammonia are taken out in oscillation absorption 2 hours under conditions of 160r/min
Berthelot spectrophotometry, potassium persulfate oxidation ultraviolet spectrophotometry, ammonium molybdate light splitting is respectively adopted in nitrogen, total nitrogen, total phosphorus
Photometry measures, and it is certified products that ammonia nitrogen removal frank, which is 94.2% or more,；
Step 8 certified products are packed.
10. a kind of zeolite-loaded Rutile Type TiO2 nanotubes prepared using claim 1 carry out ozone connection as catalyst
With the method for catalytic degradation ammonia nitrogen pollutant, it is characterized in that：Include the following steps,
It takes out a unit deionized water and the stupid phenol solution of a concentration of 100mgL-1 is added and be fabricated to organic pollution simulated solution
Organic pollution simulated solution is placed in reaction vessel, low temperature thermostat bath controlling reaction temperature is used in combination, puts into zeolite-loaded golden red
In stone phase TiO2 nanotube powders to organic pollution simulated solution, stirs or be put into concussion instrument, form liquid solid two-phase
Mixed suspended mixture is fully touched, appendix is inserted into the reaction vessel, ozone is inputted into suspended mixture by appendix,
Ozone stability of flow keeps reacting at least 3 hours under conditions of the stable output of ozone in 50mLmin-1；
It is a kind of organic as catalyst progress ozone combination catalytic degradation phenols using zeolite-loaded Rutile Type TiO2 nanotubes
The method of pollutant and the zeolite-loaded catalyst of recycling：
It builds at aeration tank 1, aeration tank uses concrete grade for C25, C30, and pond inner wall wall brush fills out seepage-resistant grade S5 or more
Impermeabilisation agent or coating, with armored concrete build aeration tank bottom wall, 400 ~ 620mm of bottom wall thickness, other pool walls 200mm
~ 400mm, every 8 squares of bottom wall build out 1 rectangular expansion joint；Setting masking net at the top of aeration tank（1）, masking net top
Setting masking dry load lid（2）, setting contaminant water is introduced in aeration tank is discharged into pipe（101）And catalyst input pipe；
Several ozonation aerated devices are set in aeration tank（3）, the ozonation aerated device includes vertically arranged ozone air inlet
Supervisor（4）, the top of ozone air inlet supervisor connects ozone appendix（5）, the ozone air inlet supervisor whole body is circumferentially equidistantly positioned
Several ozone air intake branches（6）, several aeration heads are additionally provided on the ozone air intake branch（7）, the ozone air inlet supervisor
Bottom is additionally provided with rotating base（8）, and air inlet is arranged in ozone air inlet supervisor top, negative-pressure air fan or air inducing is arranged in air inlet
Device（9）, the ozone air intake branch is ceramic material, and the rotating base connects driving motor；The aeration head includes dividing gas
Head（10）, qi-regulating storehouse（11）, aeration head air inlet pipe is arranged in qi-regulating orlop portion（12）, qi-regulating storehouse is cone, and loudspeaker lid is closed
Gas separating port is set, and the stomata array of spiral or circle shaped formation is arranged in gas separating port（13a）, the pneumatic rotation of setting in the qi-regulating storehouse
Turn fan（13b）；
Bottom setting series connection fixing pipe is responsible in ozone air inlet, and water temperature heating is provided in fixing pipe of connecting（14）；
Water temperature heating is provided in unlatching series connection fixing pipe to control reaction temperature to 20 ~ 40 degrees Celsius and be always maintained at steady
Fixed, unlatching contaminant water is discharged into pipe and is discharged into waste water containing ammonia nitrogen pollutant, and opens catalyst input pipe simultaneously, input load rutile
Phase TiO2 nanotube zeolite powders, organic wastewater and load Rutile Type TiO2 nanotube zeolite powders mixing, pending
Mixed liquor entirety liquid level maintains an equal level with ozone air inlet supervisor top or opens ozone generating apparatus when being less than 10 ~ 40cm, to ozone
Ozone is inputted in the ozone air inlet supervisor of aerator, ozone is allowed to be distributed in pending mixed liquor by gas separating port, qi-regulating storehouse,
With containing stupid phenol organic wastewater and load Rutile Type TiO2Nanotube zeolite powder catalyst carries out hybrid reaction, reaction 3 ~ 5
Hour, while covering and also setting up ozone recycling air pipe device below dry load lid, ozone is recycled, and re-inject aerator
In, after the completion of the reaction time, aeration tank mid-water and bottom water is taken to measure respectively, stops aeration and reaction after up to standard, into
Row net liquid precipitates, and surface sewage is discharged after the completion of precipitation, is filtered in sewage discharge, recycled filter mud and glar,
It carries out cleaning filter mud and glar in filter press or cleaning robot, recycles zeolite-loaded catalyst, in case next time uses.
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Application publication date: 20180828 |