CN106492796B - A kind of tourmaline ceramic loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP - Google Patents

A kind of tourmaline ceramic loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP Download PDF

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CN106492796B
CN106492796B CN201610915728.6A CN201610915728A CN106492796B CN 106492796 B CN106492796 B CN 106492796B CN 201610915728 A CN201610915728 A CN 201610915728A CN 106492796 B CN106492796 B CN 106492796B
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tio
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tourmaline
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CN106492796A (en
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冯泽云
韩延昆
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Nature Environmental Protection Science And Technology Ltd Co
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656Manganese, technetium or rhenium
    • B01J23/6562Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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Abstract

TiO is loaded the present invention relates to a kind of tourmaline ceramic2The preparation technology of the immobilized photochemical catalysts of-NCP, belongs to water quality cleansing agent manufacture field;Described tourmaline ceramic load TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:1)The preparation of tourmaline ceramic;2)TiO2The preparation of-NCP composite photo-catalysts;3)Tourmaline ceramic loads TiO2The preparation of the immobilized photochemical catalysts of-NCP.The multi-element doping TiO that the present invention is prepared using tourmaline ceramic2/ TCB composite photo-catalysts, multielement codope TiO2/ TCB composite photo-catalysts, can carry out advanced treating to HOCs in water under field conditions (factors), and " zero " waste is produced, and belongs to environment-friendly Green Product.

Description

A kind of tourmaline ceramic loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP
Technical field
The invention belongs to water quality cleansing agent manufacture field, specifically, it is related to a kind of tourmaline ceramic load TiO2—NCP The preparation technology of immobilized photochemical catalyst.
Background technology
With the development of industrial or agricultural, substantial amounts of and ever-increasing HOCs finally necessarily enters the water circulation body of nature In system, and inevitably appear in drinking water;The particularly abuse of people's veterinary drug thing, electronics and plastic garbage spreads unchecked, and makes Emerging organic nuisance is continued to bring out in drinking water;High toxicity and extremely strong bioconcentration that they have, even if Content is atomic, also can constitute great risk to the health of the mankind.The water of indivedual persistence organic pollutants in China, water system Flat place in the world high-end.
The HOCs in drinking water is thoroughly removed to ensureing that human health is required, the drinking water treatment technique of current China In, the removing to HOCs is not accounted at all.Generally believe at present:To complicated component in water, the complicated HOCs's of physico-chemical property Remove, belong to the deep level of processing of drinking water, be very difficult.The adsorption method that some research institutes propose not only can not be thorough by its Bottom is disposed, and, simply serves the effect of concentration transfer from environment on the whole;The oxidation point that other research institutes use Solution, it is necessary to which using the extensive strong oxidizer of adaptation, and not only cost is high, operational hazards for strong oxidizer, and is easily caused water The secondary pollution of body.
Nano-TiO2Crystal is less than under the irradiation of 387.5nm ultraviolet in wavelength as photochemical catalyst, can produce electronics and Hole pair, i.e. carrier, can make oxygen molecule produce the hydroxyl radical free radical with strong oxidation, and then produce oxidation Decomposition work With the almost all of difficult organic compound decomposed including bacterium that decomposable asymmetric choice net is contacted finally is allowed to change into CO2, produce " zero " waste.But, because nano-particle hardly possible is reclaimed, it is impossible to reuse;Photo-generated carrier is easy to again multiple Close, light-catalysed quantum efficiency is very low;Pure nano-TiO2Catalytic reaction could be triggered by needing the auxiliary of ultraviolet, and actual Sunray middle-ultraviolet lamp only accounts for 3%~5%, and catalytic decomposition is extremely inefficient, etc. various reasons, makes to seem of great value new Material is very difficult to apply in the depths reason to HOCs in water.
We are by the nano-TiO of the miscellaneous element of the lot of trace that adulterates2It is supported on the material TCB with natural self-purification ability On (tourmaline ceramic), TiO has been made2/ TCB composite photo-catalysts, by the catalyticing decomposition action of nano TiO 2 and TCB absorption Effect and special chemical property are combined, and the decomposition damage capability to HOCs in environment greatly improved, can be visible Under light, significantly strengthen the decomposition efficiency of photochemical catalytic oxidation, be easy to reclaim again and use for a long time.It is demonstrated experimentally that applied in water Micro HOCs depths reason, is a kind of deep processing method close to natural auto purification.
About the TiO of multielement codope2The photochemical catalyst on TCB is supported on, and is applied to the health environment-friendly of water In deep level of processing, both at home and abroad without document report.
The content of the invention
In order to overcome problem present in background technology, TiO is loaded the invention provides a kind of tourmaline ceramic2—NCP The preparation technology of immobilized photochemical catalyst;Multielement codope TiO2The many factors synergy of/TCB composite photo-catalysts, energy Under visible light, decomposition of organic matter, not only substantially increases the utilization ratio of photocatalysis efficiency and sunshine, and is easy to back Receive and long-term utilization, can be applied in various water treatments.
In order to achieve the above object, the present invention proposes following technical scheme:
Described tourmaline ceramic load TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:
1) preparation of tourmaline ceramic
A. by dravite, schorl, elbaite and tsilaisite through over cleaning, dry, crush, covered by thunder Machine or air-flow crushing are machined to 2000~2500 mesh;
B. by 10kg polycrystals tourmaline powder and clay, blended stirring 60 minutes, in uniform shape;
C. 1 is pressed by concentration 0.85~0.90wt% titanium hydroxide inorganic sols are water-soluble:3~5 parts by weight, which are slowly injected, beats In pulp grinder, make tourmaline powder and solid-like of the clay formation containing moisture 30%;
D. through high-pressure extrusion, granulation forms the tourmaline ceramic ball of 3~8mm particle diameters;
2)TiO2The preparation of-NCP composite photo-catalysts
A. precursor substance TiC1 is weighed4+H2The chemistry of O formation 50% is pure, and in injection reactor, it is 28% to be dissolved in chemistry pure Ethanol acidic aqueous solution in, obtain mixture one;Under high velocity agitation, by hydrogen peroxide and the pure ethanol solution of 30% chemistry In proportion 1:2.8 mixing, obtain mixture two;Mixture two is slowly dropped in mixture one by constant pressure funnel, The ratio of mixture one and mixture two is 1:0.8, translucent pale yellow solution is made, 1~2 is stood after the completion of reaction small When, fully precipitation after discharge supernatant liquor, by 3 times centrifugation, clean it is highly purified after, while stirring inject 40 DEG C~60 DEG C deionized water, Hydrothermal Synthesiss process for dispersing produces pH value 3~5;1.0~1.4wt% of concentration titanium hydroxide inorganic sol The aqueous solution, is designated as normalization product NT-D1;
B. by the normalization product NT-D1 weighed, in injection autoclave, through high temperature, high-pressure sinter, its temperature control Between 500 DEG C~600 DEG C, 30 minutes temperature controls are shut down after constant pressure and stood, plus nitrogen cooling, stand aging 10~12 hours, by Titanium hydroxide changes system into Detitanium-ore-type crystalline solid TiO2, concentration is adjusted to 0.85~1.0wt%;PH value 3~5, is designated as normalization Product NT-D2;
C. 50 kilograms of normalization product NT-D2 are weighed, through more than 800 DEG C of high temperature sintering, optimal sintering temperature temperature control 850 DEG C, nitrogen cooling is added after standing, by anatase crystal TiO2Change into rutile ore type crystalline solid TiO2The aqueous solution, concentration is adjusted Whole is 0.9~1.0wt%;
D. the rutile ore type crystalline solid TiO after normalization product NT-D2 and concentration adjustment after concentration is adjusted2It is water-soluble Liquid presses 7:3~4 ratio is stirred 30~45 minutes using solution manufacturing method altogether under the conditions of 40 DEG C~60 DEG C, plus nitrogen is cold But after, 10~12 hours are stood, milky mixed crystal TiO is formed2Compound aqueous solution, is set as compound NT-D2F;
E. normalization product NT-D1,450g are weighed;Compound NT-D2F, 950g;Deionized water 8000g~9000g, mixes Miscellaneous water-soluble platinum gold ionization compound 25g is configured to the concentration 2.5wt% aqueous solution, and water-soluble platinum gold ionization compound is commercially available Commodity, using hydrothermal synthesis method and common solution doping technique, are made precious metal ion doping specialization product TiO2/ NCP is combined Photochemical catalyst;
3) tourmaline ceramic load TiO2The preparation of the immobilized photochemical catalysts of-NCP
Using 2.5MM-3.5MM step 1) prepared by tourmaline ceramic ball through cleaning, dry, by dried electricity Gas stone is from step 2) prepared by TiO2The aqueous solution of-NCP inorganic sol is with 1min/m immersion process, then by 500 DEG C -600 DEG C of high temperature sintering 3 minutes, cooling packing.
Further, described step 1) b step in the composition of raw material be tourmaline 60%~70%, clay 30%~ 40% is constituted.
Further, described step 1) step c in titanium hydroxide inorganic sol be by the ammoniacal liquor of titanium tetrachloride+35%+mistake Hydrogen oxide 50%, by high-speed stirred, constant temperature and pressure is centrifuged, natural sedimentation, and 3 times clean, highly purified, 40 DEG C of vacuum Dry 8 hours, after crushed using hydrothermal preparing process, disperseed with 120 DEG C of deionized waters, be made translucent light yellow The aqueous solution.
Percentage in file is mass percent without special instruction.
Beneficial effects of the present invention:
(1) the multi-element doping TiO prepared using tourmaline ceramic2/ TCB composite photo-catalysts, multielement codope TiO2/ TCB composite photo-catalysts, can carry out advanced treating to HOCs in water under field conditions (factors), and " zero " waste is produced, and is belonged to Environment-friendly Green Product.
(2) performance for making modern nanometer technology improve water quality with tourmaline ceramic is organically combined, and the effect of synergy is not Only substantially increase nano-TiO2The ability of degraded Organic substance in water, and be expected to handle out the health with certain physiological action Drinking water.
(3) the multielement codope TiO prepared by2/ TCB composite photo-catalysts, not only purify ring with utilization sunshine The premium properties in border, and be easy to reclaim and reuse, be conducive to being widely used in various green technologies.
Brief description of the drawings
Fig. 1 is the immobilized photochemical catalyst schematic diagram of tourmaline ceramic;
Fig. 2 is tourmaline ceramic carrier schematic diagram;
Fig. 3 is TiO2- NCP is in tourmaline ceramic surface microscope schematic diagram;
Fig. 4 is that tourmaline ceramic loads TiO2The immobilized photochemical catalysts of-NCP;
Fig. 5 is purification of water quality experimental provision I;
Fig. 6 is purification of water quality experimental provision II;
Fig. 7 is purification of water quality experimental provision III.
Embodiment
Below in conjunction with embodiments of the invention and accompanying drawing, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments, is based on Embodiment in the present invention, it is all other that this area control technical staff is obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
Described tourmaline ceramic load TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:
1) preparation of tourmaline ceramic
A. by dravite, schorl, elbaite and tsilaisite through over cleaning, dry, crush, covered by thunder Machine or air-flow crushing are machined to 2000 mesh;
B. by 6kg polycrystals tourmaline powder and 4kg clay, blended stirring 60 minutes, in uniform shape;
C. 1 is pressed by concentration 0.85wt% titanium hydroxide inorganic sols are water-soluble:3 parts by weight are slowly injected in beater, make Tourmaline powder and solid-like of the clay formation containing moisture content 30%, titanium hydroxide inorganic sol is by the ammonia of titanium tetrachloride+35% Water+hydrogen peroxide 50%, by high-speed stirred, constant temperature and pressure is centrifuged, natural sedimentation, and 3 times are clean, highly purified, and 40 DEG C vacuum drying 8 hours, after crushed using hydrothermal preparing process, disperseed with 120 DEG C of deionized waters, be made translucent Shape light yellow solution;
D. through high-pressure extrusion, granulation forms the tourmaline ceramic ball of 5mm particle diameters;
2)TiO2The preparation of-NCP composite photo-catalysts
A. precursor substance TiC1 is weighed4+H2The chemistry of O formation 50% is pure, and in injection reactor, it is 28% to be dissolved in chemistry pure Ethanol acidic aqueous solution in, obtain mixture one;Under high velocity agitation, by hydrogen peroxide and the pure ethanol solution of 30% chemistry In proportion 1:2.8 mixing, obtain mixture two;Mixture two is slowly dropped in mixture one by constant pressure funnel, The ratio of mixture one and mixture two is 1:0.8, translucent pale yellow solution is made, stands 1 hour after the completion of reaction, fills Supernatant liquor is discharged after fractional precipitation, by 3 centrifugations, clean it is highly purified after, 40 DEG C of deionization is injected while stirring Water, Hydrothermal Synthesiss process for dispersing produces pH value 3;The concentration 1.0wt% titanium hydroxide inorganic sol aqueous solution, is designated as normalization production Product NT-D1;
B. by the normalization product NT-D1 weighed, in injection autoclave, through high temperature, high-pressure sinter, its temperature control Between 500 DEG C, 30 minutes temperature controls are shut down after constant pressure and stood, plus nitrogen cooling, are stood aging 10 hours, are changed by titanium hydroxide Detitanium-ore-type crystalline solid TiO is made2, concentration is adjusted to 0.85wt%;PH values 3, are designated as normalization product NT-D2;
C. 50 kilograms of normalization product NT-D2 are weighed, through more than 800 DEG C of high temperature sintering, optimal sintering temperature temperature control 850 DEG C, nitrogen cooling is added after standing, by anatase crystal TiO2Change into rutile ore type crystalline solid TiO2The aqueous solution, concentration is adjusted Whole is 0.9wt%;
D. the rutile ore type crystalline solid TiO after normalization product NT-D2 and concentration adjustment after concentration is adjusted2It is water-soluble Liquid presses 7:3 ratio is stirred 30 minutes using solution manufacturing method altogether under the conditions of 40 DEG C, plus after nitrogen cooling, stands 10 small When, form milky mixed crystal TiO2Compound aqueous solution, is set as compound NT-D2F;
E. normalization product NT-D1,450g are weighed;Compound NT-D2F, 950g;Deionized water 8000g~9000g, mixes Miscellaneous water-soluble platinum gold ionization compound 25g is configured to the concentration 2.5wt% aqueous solution, and water-soluble platinum gold ionization compound is commercially available Commodity, using hydrothermal synthesis method and common solution doping technique, are made precious metal ion doping specialization product TiO2/ NCP is combined Photochemical catalyst;
3) tourmaline ceramic load TiO2The preparation of the immobilized photochemical catalysts of-NCP
Using 2.5MM step 1) prepared by tourmaline ceramic ball through cleaning, dry, by dried tourmaline from Step 2) prepared by TiO2The aqueous solution of-NCP inorganic sol is with 1min/m immersion process, then by 500 DEG C of high temperature Sintering 3 minutes, cooling packing.
Embodiment 2
Described tourmaline ceramic load TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:
1) preparation of tourmaline ceramic
A. by dravite, schorl, elbaite and tsilaisite through over cleaning, dry, crush, covered by thunder Machine or air-flow crushing are machined to 2200 mesh;
B. by 6.5kg polycrystals tourmaline powder and 3.5kg clay, blended stirring 60 minutes, in uniform shape;
C. 1 is pressed by concentration 0.87wt% titanium hydroxide inorganic sols are water-soluble:4 parts by weight are slowly injected in beater, make Tourmaline powder and solid-like of the clay formation containing moisture content 30%, titanium hydroxide inorganic sol is by the ammonia of titanium tetrachloride+35% Water+hydrogen peroxide 50%, by high-speed stirred, constant temperature and pressure is centrifuged, natural sedimentation, and 3 times are clean, highly purified, and 40 DEG C vacuum drying 8 hours, after crushed using hydrothermal preparing process, disperseed with 120 DEG C of deionized waters, be made translucent Shape light yellow solution;
D. through high-pressure extrusion, granulation forms the tourmaline ceramic ball of 5mm particle diameters;
2)TiO2The preparation of-NCP composite photo-catalysts
A. precursor substance TiC1 is weighed4+H2The chemistry of O formation 50% is pure, and in injection reactor, it is 28% to be dissolved in chemistry pure Ethanol acidic aqueous solution in, obtain mixture one;Under high velocity agitation, by hydrogen peroxide and the pure ethanol solution of 30% chemistry In proportion 1:2.8 mixing, obtain mixture two;Mixture two is slowly dropped in mixture one by constant pressure funnel, The ratio of mixture one and mixture two is 1:0.8, translucent pale yellow solution is made, 1.5 hours are stood after the completion of reaction, Fully precipitation after discharge supernatant liquor, by 3 times centrifugation, clean it is highly purified after, while stirring inject 50 DEG C go from Sub- water, Hydrothermal Synthesiss process for dispersing produces pH value 4;The concentration 1.2wt% titanium hydroxide inorganic sol aqueous solution, is designated as normalization Product NT-D1;
B. by the normalization product NT-D1 weighed, in injection autoclave, through high temperature, high-pressure sinter, its temperature control Between 550 DEG C, 30 minutes temperature controls are shut down after constant pressure and stood, plus nitrogen cooling, are stood aging 11 hours, are changed by titanium hydroxide Detitanium-ore-type crystalline solid TiO is made2, concentration is adjusted to 0.90wt%;PH values 4, are designated as normalization product NT-D2;
C. 50 kilograms of normalization product NT-D2 are weighed, through more than 800 DEG C of high temperature sintering, optimal sintering temperature temperature control 850 DEG C, nitrogen cooling is added after standing, by anatase crystal TiO2Change into rutile ore type crystalline solid TiO2The aqueous solution, concentration is adjusted Whole is 0.95wt%;
D. the rutile ore type crystalline solid TiO after normalization product NT-D2 and concentration adjustment after concentration is adjusted2It is water-soluble Liquid presses 7:3 ratio is stirred 40 minutes using solution manufacturing method altogether under the conditions of 50 DEG C, plus after nitrogen cooling, stands 11 small When, form milky mixed crystal TiO2Compound aqueous solution, is set as compound NT-D2F;
E. normalization product NT-D1,450g are weighed;Compound NT-D2F, 950g;Deionized water 8000g~9000g, mixes Miscellaneous water-soluble platinum gold ionization compound 25g is configured to the concentration 2.5wt% aqueous solution, and water-soluble platinum gold ionization compound is commercially available Commodity, using hydrothermal synthesis method and common solution doping technique, are made precious metal ion doping specialization product TiO2/ NCP is combined Photochemical catalyst;
3) tourmaline ceramic load TiO2The preparation of the immobilized photochemical catalysts of-NCP
Using 3.0MM step 1) prepared by tourmaline ceramic ball through cleaning, dry, by dried tourmaline from Step 2) prepared by TiO2The aqueous solution of-NCP inorganic sol is with 1min/m immersion process, then by 550 DEG C of high temperature Sintering 3 minutes, cooling packing.
Embodiment 3
Described tourmaline ceramic load TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:
1) preparation of tourmaline ceramic
A. by dravite, schorl, elbaite and tsilaisite through over cleaning, dry, crush, covered by thunder Machine or air-flow crushing are machined to 2500 mesh;
B. by 7kg polycrystals tourmaline powder and 3kg clay, blended stirring 60 minutes, in uniform shape;
C. 1 is pressed by concentration 0.90wt% titanium hydroxide inorganic sols are water-soluble:5 parts by weight are slowly injected in beater, make Tourmaline powder and solid-like of the clay formation containing moisture content 30%, titanium hydroxide inorganic sol is by the ammonia of titanium tetrachloride+35% Water+hydrogen peroxide 50%, by high-speed stirred, constant temperature and pressure is centrifuged, natural sedimentation, and 3 times are clean, highly purified, and 40 DEG C vacuum drying 8 hours, after crushed using hydrothermal preparing process, disperseed with 120 DEG C of deionized waters, be made translucent Shape light yellow solution;
D. through high-pressure extrusion, granulation forms the tourmaline ceramic ball of 5mm particle diameters;
2)TiO2The preparation of-NCP composite photo-catalysts
A. precursor substance TiC1 is weighed4+H2The chemistry of O formation 50% is pure, and in injection reactor, it is 28% to be dissolved in chemistry pure Ethanol acidic aqueous solution in, obtain mixture one;Under high velocity agitation, by hydrogen peroxide and the pure ethanol solution of 30% chemistry In proportion 1:2.8 mixing, obtain mixture two;Mixture two is slowly dropped in mixture one by constant pressure funnel, The ratio of mixture one and mixture two is 1:0.8, translucent pale yellow solution is made, stands 2 hours after the completion of reaction, fills Supernatant liquor is discharged after fractional precipitation, by 3 centrifugations, clean it is highly purified after, 60 DEG C of deionization is injected while stirring Water, Hydrothermal Synthesiss process for dispersing produces pH value 5;The concentration 1.4wt% titanium hydroxide inorganic sol aqueous solution, is designated as normalization production Product NT-D1;
B. by the normalization product NT-D1 weighed, in injection autoclave, through high temperature, high-pressure sinter, its temperature control Between 600 DEG C, 30 minutes temperature controls are shut down after constant pressure and stood, plus nitrogen cooling, are stood aging 12 hours, are changed by titanium hydroxide Detitanium-ore-type crystalline solid TiO is made2, concentration is adjusted to 1.0wt%;PH values 5, are designated as normalization product NT-D2;
C. 50 kilograms of normalization product NT-D2 are weighed, through more than 800 DEG C of high temperature sintering, optimal sintering temperature temperature control 850 DEG C, nitrogen cooling is added after standing, by anatase crystal TiO2Change into rutile ore type crystalline solid TiO2The aqueous solution, concentration is adjusted Whole is 1.0wt%;
D. the rutile ore type crystalline solid TiO after normalization product NT-D2 and concentration adjustment after concentration is adjusted2It is water-soluble Liquid presses 7:4 ratio is stirred 45 minutes using solution manufacturing method altogether under the conditions of 60 DEG C, plus after nitrogen cooling, stands 12 small When, form milky mixed crystal TiO2Compound aqueous solution, is set as compound NT-D2F;
E. normalization product NT-D1,450g are weighed;Compound NT-D2F, 950g;Deionized water 8000g~9000g, mixes Miscellaneous water-soluble platinum gold ionization compound 25g is configured to the concentration 2.5wt% aqueous solution, and water-soluble platinum gold ionization compound is commercially available Commodity, using hydrothermal synthesis method and common solution doping technique, are made precious metal ion doping specialization product TiO2/ NCP is combined Photochemical catalyst;
3) tourmaline ceramic load TiO2The preparation of the immobilized photochemical catalysts of-NCP
Using 3.5MM step 1) prepared by tourmaline ceramic ball through cleaning, dry, by dried tourmaline from Step 2) prepared by TiO2The aqueous solution of-NCP inorganic sol is with 1min/m immersion process, then by 600 DEG C of high temperature Sintering 3 minutes, cooling packing.
Experimental analysis:
1. different catalyst is tested the degradation efficiency of HOCs in water under visible light.
1) catalyst:
Using specification, weight be same as tourmaline ceramic ball preparation method (step 1) prepare) prepare Chinese medicine stone ceramic Ball and thunder feldspar ball are in same step 1) prepare, its purpose passes through different carrier material carried metal element codopes TiO2/ NCP composite photo-catalysts, analysis 5 kinds of samples of contrast:1. market sale tourmaline ceramic ball product;②TiO2/ electrically Prepared by feldspar ball (pressing step 1) .C.);3. metallic element codope TiO2Prepared by/tourmaline ceramic ball (pressing step 3));④ Metallic element codope TiO2Prepared by/Chinese medicine stone ceramic ball (pressing step 3));5. metallic element codope TiO2/ radium feldspar ball Prepared by (pressing step 3))
1. market sale tourmaline ceramic ball product TCB;Particle diameter 2.5~3.5mm, 500g;
②TiO2/ tourmaline ceramic ball TiO2Prepared by/TCB (pressing step 1) .C.);Particle diameter 2.5~3.5mm, 500g;
③TiO2- NCP/ tourmaline ceramic balls TiO2Prepared by-NCP/TCB (pressing step 3));2.5~3.5mm of particle diameter, 500g;
④TiO2- NCP/ Chinese medicine stone ceramic balls TiO2Prepared by-NCP/ medical stones (pressing step 3));2.5~3.5mm of particle diameter, 500g;
⑤TiO2- NCP/ radium feldspar balls TiO2Prepared by-NCP/ radium stone (pressing step 3));Particle diameter 2.5~3.5mm, 500g;
2) experimental method:
The experimental analysis carried out in homemade reactor, the reagent used is that micro HOCs is added in pure water Afterwards, light is radiated at the above sample in water, experimental analysis photocatalysis HOCs oxidation Decomposition efficiency, to evaluate invention system respectively The TiO obtained2/ TCB composite photo-catalysts also have naturally-produced representative to the degradation efficiency of the HOCs in drinking water Microcystin-LR (is purchased from ALEXIS companies).The existing artificial synthesized several class POPs of selected HOCs (such as polycyclic aromatic hydrocarbon, Polychlorinated biphenyl (being purchased from State center for standard matter)).
3) reactor:
Reactor is made up of reactive tank, light source, constant temperature dashpot and circulating pump.All components are saturating using stainless steel and height Quartz glass depending on rate is manufactured.Wherein light source (is purchased from the limited public affairs of the special Optoelectronics Technology share of Guangdong Shelley for 8*5W from colour filter lamp Department), wavelength is respectively from 365nm ultraviolets and 420nm visible ray, and the HOCs contents added in water refer to national standard GB/T5750-2006《Drinking water standard experimental method》Use HPLC and GC/MS (imported from America liquid chromatograph and gas phase Chromatograph) detection is sampled before illumination and after illumination two hours respectively, represented with the elimination factor of harmful substance before and after the processing with The degradation efficiency of upper sample.
4) experimentation:
Water quality experiment purifier be by the high 320mm of diameter 158mm thickness 2mm stainless steel can open from colour filter lamp Tower cover, built with 8 5W from colour filter lamp.The photo catalysis reactor of the high 250mm quartz glass of built-in diameter 67mm thickness 3mm, And equipped with reactive tank, constant temperature dashpot and circulating pump.Purification style is circularly purifying, sewage sample:Added in pure water micro- HOCs, total amount 1.5kg are measured,
Laboratory sample:5 kinds of 2.5~3.5mm of diameter, weight 500g catalyst prods
Experimental situation humidity:30%~40%
Experimental situation temperature:25℃
Test radiation source:Wavelength 365nm (ultraviolet)~420nm (visible ray)
Purification style:Circularly purifying 2h.
5) experimental result:
5 kinds of different catalysts under wavelength 365nm~420nm illumination to water in HOCs degradation efficiency contrast table 1:
The degradation efficiency contrast table of the different catalysts of table 1 under visible light to HOCs in water
As can be seen from Table 1, under 420nm light action, degradation efficiency of several composite photo-catalysts to POPs in water.Its In, CO is that initial concentration CO about 1mg/L C/CO are the ratio between HOCs contents and initial content, the smaller table of ratio in water after effect 2h Show that degradation efficiency is higher.It can be seen that, 1. TCB slightly has adsorption capacity, pure TiO to HOCs in water2After being supported on TCB, can In the presence of seeing under light, though HOCs concentration has further decline, the limited extent declined;2. it is supported on TCB TiO2Adulterate after Fe, N, S, POPs concentration declines obvious, and 2h is acted under visible light close to being completely eliminated;③Fe、N、S The TiO of codope2On different carriers, the eradicating efficacy difference to HOCs is obvious, demonstrates the special electrochemical properties of TCB To TiO2- NCP photocatalysis has cooperative effect.
The multi-element doping TiO that the present invention is prepared using natural Tourmaline2/ TCB composite photo-catalysts, multielement codope TiO2/ TCB composite photo-catalysts, can carry out advanced treating to HOCs in water under field conditions (factors), and " zero " waste is produced, and is belonged to Environment-friendly Green Product;The performance for making modern nanometer technology improve water quality with tourmaline ceramic is organically combined, collaboration The effect of effect not only substantially increases nano-TiO2The ability of degraded Organic substance in water, and be expected to handle out with certain raw The healthy drinking water of reason effect;Prepared multielement codope TiO2/ TCB composite photo-catalysts, not only with utilizing the sun The premium properties of light environment purification, and be easy to reclaim and reuse, be conducive to being widely used in various green technologies.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (3)

1. a kind of tourmaline ceramic loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP, it is characterised in that:Described is electric Feldspar loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP includes step in detail below:
1)The preparation of tourmaline ceramic
A. by dravite, schorl, elbaite and tsilaisite through over cleaning, dry, crush, by Raymond machine or Person's air-flow crushing is machined to 2000 ~ 2500 mesh;
B. by 10kg polycrystals tourmaline powder and clay, blended stirring 60 minutes, in uniform shape, the polycrystal tourmaline The composition of powder and clay is tourmaline 60%~70%, and clay 30%~40% is constituted;
C. 1 is pressed by concentration 0.85 ~ 0.90wt% titanium hydroxide inorganic sols are water-soluble:3 ~ 5 parts by weight are slowly injected in beater, Make tourmaline powder and solid-like of the clay formation containing moisture 30%;
D. through high-pressure extrusion, granulation forms the tourmaline ceramic ball of 3 ~ 8mm particle diameters;
2)TiO2The preparation of-NCP composite photo-catalysts
A weigh precursor substance TiC14+H2O formation 50% chemistry it is pure, injection reactor in, be dissolved in chemistry it is pure be 28% ethanol In acidic aqueous solution, mixture one is obtained;Under high velocity agitation, by hydrogen peroxide and the pure ethanol solution of 30% chemistry in proportion 1:2.8 mixing, obtain mixture two;Mixture two is slowly dropped in mixture one by constant pressure funnel, mixture One is 1 with the ratio of mixture two:0.8, translucent pale yellow solution is made, 1 ~ 2 hour is stood after the completion of reaction, it is fully heavy Supernatant liquor is discharged behind shallow lake, by 3 centrifugations, clean it is highly purified after, 40 DEG C ~ 60 DEG C of deionization is injected while stirring Water, Hydrothermal Synthesiss process for dispersing produces pH value 3 ~ 5;1.0 ~ 1.4wt% of the concentration titanium hydroxide inorganic sol aqueous solution, is designated as rule Format product NT-D1;
B. by the normalization product NT-D1 weighed, in injection autoclave, through high temperature, high-pressure sinter, its temperature control exists Between 500 DEG C ~ 600 DEG C, 30 minutes temperature controls are shut down after constant pressure and stood, plus nitrogen cooling, aging 10 ~ 12 hours are stood, by hydrogen-oxygen Change titanium and change system into Detitanium-ore-type crystalline solid TiO2, concentration is adjusted to 0.85 ~ 1.0wt%;PH value 3 ~ 5, is designated as normalization product NT- D2;
C. 50 kilograms of normalization product NT-D2 are weighed, through more than 800 DEG C of high temperature sintering, after standing plus nitrogen cooling, by anatase Type crystal TiO2Change into rutile ore type crystalline solid TiO2The aqueous solution, concentration is adjusted to 0.9 ~ 1.0wt%;
D concentration is adjusted after normalization product NT-D2 and concentration adjustment after rutile ore type crystalline solid TiO2The aqueous solution is pressed 7:3 ~ 4 ratio is stirred 30 ~ 45 minutes using solution manufacturing method altogether under the conditions of 40 DEG C ~ 60 DEG C, plus after nitrogen cooling, it is quiet Put 10 ~ 12 hours, form milky mixed crystal TiO2Compound aqueous solution, is set as compound NT-D2F;
E. normalization product NT-D1,450g are weighed;Compound NT-D2F, 950g;Deionized water 8000g ~ 9000g, adulterates water-soluble Property platinum ionic compound 25g be configured to the concentration 2.5wt% aqueous solution, water-soluble platinum gold ionization compound is commercial goods, is adopted With hydrothermal synthesis method and common solution doping technique, precious metal ion doping specialization product TiO is made2/ NCP composite photocatalysts Agent;
3)Tourmaline ceramic loads TiO2The preparation of the immobilized photochemical catalysts of-NCP
Using 2.5-3.5mm step 1)Prepared tourmaline ceramic ball by cleaning, drying, by dried tourmaline from Step 2)Prepared TiO2The aqueous solution of-NCP inorganic sol is with 1min/m immersion process, then by 500 DEG C -600 DEG C High temperature sintering 3 minutes, cooling packing.
2. a kind of tourmaline ceramic load TiO according to claim 12The preparation technology of the immobilized photochemical catalysts of-NCP, its It is characterised by:Described step 1)Step c in titanium hydroxide inorganic sol be by the ammoniacal liquor of titanium tetrachloride+35%+hydrogen peroxide 50%, by high-speed stirred, constant temperature and pressure is centrifuged, natural sedimentation, and 3 times clean, highly purified, and 40 DEG C of vacuum drying 8 are small When, after crushed using hydrothermal preparing process, disperseed with 120 DEG C of deionized waters, translucent light yellow solution is made.
3. a kind of tourmaline ceramic load TiO according to claim 12The preparation technology of the immobilized photochemical catalysts of-NCP, its It is characterised by:Described step 2)Step c in 850 DEG C of sintering temperature temperature control.
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