CN104923242A - Magnetic rare earth barium ferrite nano purifying catalyst, as well as preparation method and application thereof - Google Patents
Magnetic rare earth barium ferrite nano purifying catalyst, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic rare earth barium ferrite nano purifying catalyst, as well as a preparation method and application thereof. The catalyst is used for waste water treatment. The general formula of the catalyst is BaxReyMezFemOn, wherein x is 0.1-3.0, y is 0-2.0, z is 0-2, m is 1-24, n is 3-48, Me is Cu, Zn, Mn or Co, and Re is La, Ce, Nd, Pr, Sc or Y. The preparation method comprises the following steps: dissolving to prepare a solution, matching, mixing, carrying out high temperature ultrasonic dispersion for solation, carrying out microwave vacuum for gelation, carrying out microwave vacuum for denitration with less oxygen, and roasting; the method is characterized in that the high temperature ultrasonic dispersion, the microwave vacuum for gelation, the microwave vacuum for denitration with less oxygen and the roasting processes are performed after the matching and mixing processes. According to the invention, microwave vacuum for denitration with less oxygen is adopted to enable ammonium nitrate to be directly transformed into nitrogen, oxygen and water, no nitrogen oxide is generated during the preparation process, and secondary pollution caused by nitrogen oxide generated during a traditional preparation process is eliminated.
Description
Technical field
The present invention is used for chemical oxygen demand COD, sulphur-containing substance and nitrogenous thing process in metallurgical industry, chemical industry effluent, is specifically related to a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst.
Background technology
In metallurgy, the chemical industry strategy of sustainable development, the low cost purified treatment of waste water and waste gas is a wherein important ring.Process waste water, waste gas need just can be completed by the physical-chemical reaction process of complexity mostly, and this type of reaction needed catalytic purification agent most is done auxiliary, as the aspects such as exhaust fume catalytic reaction and liquid waste processing need environment protection catalytic cleanser in a large number.Environment protection catalytic cleanser require high, active high, the mithridatism of mechanical strength and stability strong, selective good, and to use by repeated regeneration.Require that equipment is simple, technique is terse in the application, do not produce secondary pollution to reduce environmental protection investments, be convenient to user and accept.But find and a kind ofly can meet all these catalytic purification agent required and be difficult to accomplish in one move, therefore scientific research personnel meets in exploitation the exploration that the new catalytic scavenging material of ecological requirements and new catalytic process aspect do one's utmost.
The catalysis material developed at present and researching and developing has precious metal catalytic material, Zeolite molecular sieve catalysis material, TiO
2catalysis material and electrode catalytic materials and living things catalysis biomaterial, ionic liquid at room temperature etc.Wherein noble metal catalyst has realized suitability for industrialized production and large-scale application, satisfactory for result, but because Precious Metals Resources is rare, be difficult to the requirement meeting environmental protection industry (epi) develop rapidly, in addition catalysis material is in development mostly, therefore develop the cheap and scope of application wide, respond well catalyst just becomes the task of top priority.
Summary of the invention
The invention provides a kind of cheap and innovative magnetic Nano rare earth barium ferrite cleaning catalyst.
Technical scheme of the present invention:
A preparation method for magnetic rare earth barium ferrite nanometer cleaning catalyst, comprises and moltenly joins solution, proportioning and mixing, high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of microwave negative pressure, calcining process; High temperature ultrasonic dispersion, the gelation of microwave negative pressure, the few oxygen denitration of microwave negative pressure, calcining process is carried out after it is characterized in that proportioning and mixed processes;
A kind of magnetic rare earth barium ferrite nanometer cleaning catalyst, general formula is Ba
xre
yme
zfe
mo
n, wherein x is 0.1 ~ 3.0, y be 0 ~ 2.0, z be 0 ~ 2, m be 1 ~ 24, n is 3 ~ 48; Wherein, Me is Cu or Zn or Mn or Co, Re is La or Ce or Nd or Pr or Sc or Y.
Magnetic rare earth barium ferrite nanometer cleaning catalyst is Ba
0.1nd
0.9fe
12o
19or Ba
0.8nd
0.2fe
2o
4or BaLa
0.1co
0.9fe
16o
27;
A kind of preparation method of magnetic rare earth barium ferrite nanometer cleaning catalyst, comprise and moltenly join solution, proportioning and mixing, high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of low-temperature microwave negative pressure, calcining process, make innovative magnetic rare earth barium ferrite nanometer cleaning catalyst, better applied in sewage disposal to make magnetic rare earth barium ferrite nanometer cleaning catalyst.
Preparation principle is for utilizing citric acid by metallic ion coordination, form chelate, by sol-gal process by its dispersing and disintegrating, obtain required magnetic rare earth barium ferrite nanometer cleaning catalyst finally by roasting, and utilize this magnetic rare earth barium ferrite nanometer cleaning catalyst to make cleaning catalyst to carry out catalytic purification reaction in disposing of sewage.
1. moltenly join solution
1. ferric nitrate deionized water is made into the iron nitrate solution that molar concentration is 0.4 ~ 0.8mol/L;
2. barium nitrate deionized water is made into the barium nitrate solution that molar concentration is 0.25 ~ 0.5mol/L;
3. rare earth oxide (as lanthanum, cerium, neodymium, praseodymium and mishmetal) is made into by deionized water the re chloride that mol ratio content concn is 0.03 ~ 0.10mol/L with after dissolving with hydrochloric acid;
2. proportioning and mixing
1. by barium nitrate solution, iron nitrate solution, earth solution, citric acid, according to Ba
2+: Fe
3+: Re
n+: the mol ratio of citric acid is (0.1 ~ 3.00): (1 ~ 24): (0 ~ 2.0): the proportioning of (3 ~ 20), measure solution respectively and weigh solid, then add citric acid after barium nitrate solution, iron nitrate solution and earth solution being mixed, be uniformly mixed solution until citric acid is complete clearly molten; Now Fe
3+, Ba
2+, Re
n+form chelating ion with citrate ion, reaction equation is as follows:
H
3L+Fe
3+→FeL+3H
+
H
3L+Ba
2+→(BaL)
-+3H
+
H
3L+Nd
3+→NdL+3H
+
In formula
2. with ammoniacal liquor, the mixed solution pH value of step 1. gained is transferred to 6.5 ~ 7.5,
NH
3·H
2O+HNO
3→NH
4NO
3+H
2O
NH
3·H
2O+HCl→NH
4Cl+H
2O
Treat that next step uses after mixed solution prepares;
3. high temperature ultrasonic dispersion sol
1. xanthans being added pH value by 1g ~ 5g/L or pickling elm rubber powder 10 ~ 25g/L is in the mixed solution of 6.5 ~ 7.5, continues to stir to become thick colloidal solution;
2. above-mentioned colloidal solution is placed in glass container, at the temperature of 50 ~ 80 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 60 ~ 120min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, treats that next step uses;
4. microwave negative pressure gelation:
1. step 3 gained colloidal solution being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.1 ~ 0.5) kPa;
2. be that in the microwave reactor of 2.45GHz, regulating power is 140 ~ 280w, carries out microwave drying treatment in frequency, control temperature 110 ~ 150 DEG C, time 10 ~ 35min, extracts the moisture evaporated out, makes gel after cooling during process;
3. obtained gel grinder ground, grind, sieve and repeatedly carry out, to making gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
5. the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be placed in microwave reactor, reactor internal gas pressure controls to-(1 ~ 2) KPa;
2. be that in the microwave reactor of 2.45GHz, setting power is 360 ~ 500w in frequency, carry out microwave denitration process, control temperature is 200 ~ 240 DEG C, and the time is 5 ~ 10min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
3. close microwave reactor, make it naturally cool to 25 DEG C;
4. from microwave reactor, take out ceramic vessel, collect fine powder also with grinder grinding, paper is by 200 eye mesh screens, and namely this fine powder is product after denitration and denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
6. roasting:
1. the crucible filling denitration gel fine powder is placed in the roaster after purification;
2. open roaster heater, control temperature is progressively warming up to 550 ~ 850 DEG C by 25 DEG C, at this temperature 60 ~ 120min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron, other metal ions and rare earth becomes the agent of nano rare earth barium ferrite catalytic purification through calcining;
3. close roaster heater, product powder is placed in crucible and naturally cools to 25 DEG C with stove;
4. open roaster, take out ceramic vessel, collect fine powder, this fine powder is nano-magnetic rare earth barium ferrite cleanser, and its character is as shown in table 1:
Table 1 nano-magnetic rare earth barium ferrite cleanser character
The method that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage:
By the waste water in storage tank with being pumped in suspended-bed reactor, and in proportion magnetic rare earth barium ferrite nanometer cleaning catalyst is joined in suspended-bed reactor, open compressed air require switch and supersonic generator simultaneously, make compressed air (or oxygen, ozone) through dispersion plate be separated into after fine gas bubbles with waste water, magnetic rare earth barium ferrite nanometer cleaning catalyst Homogeneous phase mixing, ultrasonic wave stirring rod starts vibration simultaneously, stir containing air (or oxygen, ozone) and the mixed liquor of magnetic rare earth barium ferrite nanometer cleaning catalyst, separator is entered through magnetic separation after gas and waste water fully react, Water Sproading through purification does it and uses, the magnetic rare earth barium ferrite nanometer cleaning catalyst that recovery obtains returns in suspended-bed reactor to be reused, the gas that purified treatment produces is emptying after inspection, if desired high temperature purification, then utilize steam(-)coil to heat, if there is accident, the waste water carrying out purified treatment enters as emergency pool from guard valve.
The step that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage is as follows:
(1) deliver in suspended-bed reactor by waste water pump from storage tank, flow is 80 ~ 150L/min;
(2) magnetic rare earth barium ferrite nanometer cleaning catalyst is pressed 100 ~ 300g/m
3add in suspended-bed reactor;
(3) by compressed air (or pure oxygen, ozone) with the flow of 20L/min through dispersion plate be separated into after fine gas bubbles with waste water, magnetic rare earth barium ferrite nanometer cleaning catalyst Homogeneous phase mixing;
(4) 20KHz/2000W ultrasonic stirrer agitated liquid is opened, COD (COD) in such waste water and oxygen adsorb at catalyst surface, enrichment, there is heterogeneous catalytic reaction, larger molecular organics valence link is ruptured, generate the organic oxygen compound of lower molecular weight, oxidation step of going forward side by side decomposes, and molecule is diminished.Organic matter is progressively from hydrocarbon → alcohol (aldehyde) → acid → CO
2+ H
2o, wherein acid degradation is controlling unit wherein; In processing procedure, reaction is as follows:
After purified treatment containing the water of the rare earth barium ferrite nanometer cleaning catalyst that is magnetic at separator through magnetic separation, reclaim magnetic rare earth barium ferrite nanometer cleaning catalyst and return in suspended-bed reactor and reuses, the gas CO that purified treatment produces
2through check harmless after emptying, recovery of purifying waste water do its use;
Beneficial effect of the present invention:
1, the present invention utilizes sol-gel method to prepare magnetic rare earth barium ferrite nanometer cleaning catalyst, utilize xanthans or pickling elm rubber powder as gelatinizing agent, ultrasonic wave does dispersion treatment, good dispersion, be conducive to the dispersiveness of crystal grain thinning and raising powder, reduce cost of material;
2, the present invention utilizes the gelation of microwave negative pressure, and compared with conventional method, gelation speed is fast, and technique is simple, and production efficiency is high;
3, the present invention utilizes the few oxygen denitration of microwave negative pressure, make ammonium nitrate be converted into nitrogen, oxygen and water, preparation process does not have the generation of nitrogen oxide, eliminates the secondary pollution phenomenon producing nitrogen oxide in conventional method preparation process, the denitration time is short, and denitration fine particle is even;
4, after roasting, gained magnetic rare earth barium ferrite nanometer cleaning catalyst cubic system spinel-type crystallite dimension is 40 ~ 90nm, and specific saturation magnetization is 28 ~ 40emu/g; Hexaplanar M type crystallite dimension is 30 ~ 80nm, and specific saturation magnetization is 20 ~ 50emu/g, stable chemical nature, and be easy to itself and liquid to separate by magnetic separation after catalytic reaction terminates, by washing methods Direct Regeneration, life cycle is long; Can be used for TOC, COD in process industrial wastewater, sulphur-containing substance and nitrogenous thing.
Temperature is that before 20 ~ 70 DEG C of Industrial Wastewater Treatment, COD content is 500 ~ 800mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 100g/m
3, after the process of 0.5 ~ 1 hour, COD content mg/L is 10 ~ 20mg/L, COD clearance is 95%;
Temperature is that before 20 ~ 70 DEG C of Industrial Wastewater Treatment, COD content is 500 ~ 800mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 200g/m
3, after the process of 0.5 ~ 1 hour, industrial wastewater COD content is 3 ~ 5mg/L, COD clearance>=99%;
Accompanying drawing explanation
Fig. 1 is the process chart utilizing magnetic rare earth barium ferrite nanometer cleaning catalyst of the present invention to carry out suspension bed to dispose of sewage.
Fig. 2 is the TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst of the embodiment of the present invention 1.
Fig. 3 is the TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst of the embodiment of the present invention 2.
Fig. 4 is the magnetic rare earth barium ferrite nanometer cleaning catalyst X-ray diffractogram of the embodiment of the present invention 1.
Fig. 5 is the magnetic rare earth barium ferrite nanometer cleaning catalyst X-ray diffractogram of the embodiment of the present invention 2.
In Fig. 1: 1 is waste water, 2 is storage tank, and 3 is suction pump, 4 is suspended-bed reactor, and 5 is compressed air, and 6 is flow switch, 7 is ultrasonic wave stirring rod, and 8 is supersonic generator, and 9 is separator, 10 is the purified gas of discharging, and 11 for purifying waste water, and 12 is circulating pump, 13 is guard valve, and 14 is emergency pool, and 15 is steam(-)coil, 16 is magnetic rare earth barium ferrite nanometer cleaning catalyst, and 17 is dispersion plate.
Detailed description of the invention
Embodiment 1: preparation method is as follows for magnetic rare earth barium ferrite nanometer cleaning catalyst:
1, selected chemical substance material
To carry out selected to the chemical substance material needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Take neodymia 200g ± 5g and be placed in quartz boat, be placed in vacuum drying chamber dry, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, obtain solution
(1) taking 1 ± 0.001mol nine water ferric nitrate deionized water, to be prepared into 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
(2) take 0.25 ± 0.001mol barium nitrate deionized water to be prepared into 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and to prepare barium nitrate solution for later use;
(3) take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, be then prepared into 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
5, proportioning and mixing
By Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-be 2:0.8:0.2:6 by molal quantity ratio, measure iron nitrate solution, barium nitrate solution, re chloride weigh citric acid respectively:
Iron nitrate solution, barium nitrate solution and neodymium chloride solution are mixed and stir, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, adds deionized water by metal ion in solution concentration adjustment to 0.24 ± 0.01mol/L with 500ml volumetric flask; Treat after mixed solution prepares that next step operation uses;
6, high temperature ultrasonic dispersion sol
(1) xanthans being added pH value by 2 ± 0.001g/L is in the mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution;
(2) colloidal solution is placed in glass container, at the temperature of 60 ± 1 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.1min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, treats that next step uses;
7, microwave negative pressure gelation:
(1) step 6 gained colloidal solution being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
(2) in frequency be 2.45GHz microwave reactor in, carry out microwave drying treatment with the microwave that setting power is 200w, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture that evaporates out, after its cooling, make gel;
(3) made gel grinder ground, grind, sieve and repeatedly carry out, until make gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
8, the few oxygen denitration of microwave negative pressure:
(1) gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) KPa;
(2) in 2.45GHz frequency microwave reactor, setting power is that the microwave of 450w carries out denitration process, control temperature 220 ± 1 DEG C, time 6 ± 0.01min; In the process, in gel fine powder, ammonium chloride is decomposed into ammonia and hydrogen chloride, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(3) close microwave reactor, make it naturally cool to 25 DEG C;
(4) from microwave reactor, take out ceramic vessel, after collecting reaction, fine powder also grinds with grinder, and extremely by 200 mesh sieves, namely this fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
9, roasting:
(1) ceramic vessel filling denitration gel fine powder is placed in the roaster of purification;
(2) open roaster heater, control temperature is progressively warming up to 650 ± 1 DEG C by 25 DEG C, and in this temperature roasting, roasting time is 60 ± 0.01min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
(3) close roaster heater, make fine powder naturally cool to 25 DEG C with stove;
(4) open roaster, take out ceramic vessel, collect fine powder, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
(5) the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size: 75.5nm, structural formula is Ba
0.8nd
0.2fe
2o
4, be cubic system spinel ferrite body structure, specific saturation magnetization 37emu/g.
The TEM figure of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 2 shows Ba
0.8nd
0.2fe
2o
4for irregular class square sheet-like particle, crystallite dimension between 40 ~ 90nm, average-size 75.5nm.
The XRD diffracted intensity collection of illustrative plates of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 4, ordinate is diffracted intensity, abscissa is the angle of diffraction 2 θ, peak value has been there is at the angle of diffraction 28.428 °, 32.716 °, 33.266 °, 42.464 °, 46.405 °, 54.906 °, 62.515 °, 65.743 ° places, match with standard x RD spectrogram PDF46-0113, for Bb21m (36) type cubic crystal structure, in magnetic rare earth barium ferrite nanometer cleaning catalyst, introduce Nd
3+, both do not caused the disappearance of diffraction maximum also obviously not occur other diffraction maximums, whole series of samples is single-phase, and Nd is described
3+occupy part Ba
2+position.
Embodiment 2:
With embodiment 1 unlike Fe in material composition proportioning
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 9:0.8:0.2:20, calcining process sintering temperature is 750 DEG C, and other techniques are identical with embodiment 1.
1, selected chemical substance material
To carry out selected to the chemical substance material needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Takes neodymia 200g ± 5g and be placed in quartz boat, and it is dry quartz boat to be placed in vacuum drying chamber, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, obtain solution
(1) taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
(2) take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
(3) take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
5, proportioning and mixing
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 9:0.8:0.2:20, measure iron nitrate solution, barium nitrate solution respectively, weigh citric acid containing neodymium solution:
By iron nitrate solution, barium nitrate solution and mix and stir containing neodymium solution, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, add deionized water at 500ml volumetric flask and solution concentration is adjusted to 0.4 ± 0.01mol/L, treat that subsequent processing uses;
6, high temperature ultrasonic dispersion sol
(1) 1 ± 0.001g xanthans being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
(2) above-mentioned colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, and treats that next step uses;
7, microwave negative pressure gelation:
(1) 6 gained colloidal solutions being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
(2) in frequency be 2.45GHz microwave reactor in, carry out microwave drying treatment with the microwave that setting power is 200w, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture that evaporates out, after its cooling, make gel;
(3) made gel grinder is ground, cross 200 mesh sieves; Grind, sieve and repeatedly carry out, become gel fine powder, gel fine particle diameter≤0.075mm;
8, the few oxygen denitration of microwave negative pressure
(1) gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) KPa;
(2) in 2.45GHz frequency microwave reactor, use the microwave that setting power is 450w to carry out denitration process, treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(3) close microwave reactor, make it naturally cool to 25 DEG C;
(4) from microwave reactor, take out ceramic vessel, fine powder after collecting reaction also grinds with grinder, and cross 200 mesh sieves, namely gained fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
9, roasting
(1) ceramic vessel filling denitration gel fine powder is placed in the roaster after purification;
(2) open roaster heater, regulate temperature to be progressively warming up to 750 ± 1 DEG C by 25 DEG C, at this temperature, roasting time 60 ± 0.1min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
(3) close roaster heater, make fine powder naturally cool to 25 DEG C with stove;
(4) open roaster, take out ceramic vessel and interior fine powder thereof, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
(5) the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size is 62.3nm, and structural formula is Ba
0.8nd
0.2fe
9o
19,belong to hexaplanar M type ferrite structure, magnetic saturation intensity 37emu/g;
10, product storage
To the rare earth barium ferrite cleanser powder storage of preparation in water white glass container, be airtightly stored in cool place, drying, clean environment, the erosion of moistureproof, sun-proof, anti-acid-alkali salt, storage temperature 20 DEG C ± 10 DEG C, relative humidity≤10%.
Magnetic rare earth barium ferrite nanometer cleaning catalyst TEM figure shown in Fig. 3 shows Ba
0.8nd
0.2fe
12o
19for irregular class hexagon sheet-like particle, crystallite dimension between 30 ~ 80nm, average-size 62.3nm;
The XRD diffracted intensity collection of illustrative plates of the magnetic rare earth barium ferrite nanometer cleaning catalyst shown in Fig. 5, ordinate is diffracted intensity, abscissa is the angle of diffraction 2 θ, the angle of diffraction 22.972 °, 30.295 °, 31.261 °, 32.148 °, 34.089 °, 35.571 °, 37.046 °, 40.278 °, 42.758 °, 49.992 °, 50.252 °, 55.005 °, 56.886 °, there is peak value in 63.002 ° of places, coincide with XRD standard spectrogram PDF39-1433, for P63/M-mmc (194)) type M type hexagonal system structure, Nd in magnetic rare earth barium ferrite nanometer cleaning catalyst
3+existence, both do not caused the disappearance of diffraction maximum also obviously not occur other diffraction maximums, whole series of samples is single-phase, and Nd is described
3+occupy part Ba
2+position.
Embodiment 3:
The present embodiment and embodiment 1 are unlike Fe in material composition proportioning
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio 2:0.9:0.1:6, adopt pickling elm rubber powder to carry out solation process, other techniques are identical with embodiment 1.
1, selected chemical substance material
To carry out selected to the chemical substance needed for preparation, and carry out quality purity control:
2, roaster is cleared up
To clear up the roaster that preparation uses, remove in-furnace dust dirt and harmful gas material with compressed air, make in stove clean;
3, dry process
Take neodymia 200g ± 5g and be placed in quartz boat respectively, be placed in vacuum drying chamber dry, baking temperature 120 DEG C ± 2 DEG C, vacuum-18Pa, drying time 30min;
4, pickling elm rubber powder preparation
1. choose 5 years raw elm extra dry white wine skin 2000g ± 5g and be broken into the fritter that granularity is 2 ~ 3mm;
2. by step 1. gained elm extra dry white wine skin fritter 0.1mol/L hydrochloric acid 3L repeatedly clean three times, remove Ca wherein
2+, Mg
2+; And then by washed with de-ionized water three times;
3. by step 2. gained pickling Radix Ulmi Tonkinesis Rhizoma Euonymus to be again placed in vacuum drying chamber dry, baking temperature 110 DEG C ± 2 DEG C, vacuum-18Pa, drying time 60 ± 2min;
4. pickling Radix Ulmi Tonkinesis Rhizoma Euonymus after step 3. gained drying is placed in grinding machine for grinding, cross the fine powder that 200 mesh sieves obtain particle diameter≤0.075mm, this fine powder is pickling elm rubber powder, is placed in drier and treats that next step uses;
5, obtain solution
1. taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
2. take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
3. take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
6, proportioning and mixing
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 2:0.9:0.1:6, measure iron nitrate solution, barium nitrate solution respectively, weigh citric acid containing neodymium solution:
By iron nitrate solution, barium nitrate solution and mix and stir containing neodymium solution, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, add deionized water at 500ml volumetric flask and solution concentration is adjusted to 0.6 ± 0.01mol/L, treat that next step uses;
7, high temperature ultrasonic dispersion sol
1. 12 ± 0.001g pickling elm rubber powder being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
2. above-mentioned colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution, and treats that next step uses;
8, microwave negative pressure gelation:
1. 6 gained colloidal solutions being placed in ceramic vessel with cover is placed in microwave reactor, and stove internal gas pressure controls to-(0.2 ± 0.01) kPa;
2. be in the microwave reactor of 2.45GHz in frequency, carry out microwave drying treatment with the microwave that setting power is 200w, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, during process, extract the moisture evaporated out, after its cooling, make gel;
3. made gel grinder ground, grind, sieve and repeatedly carry out, to making gel fine powder by 200 mesh sieves, gel fine particle diameter≤0.075mm;
9, the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be placed on microwave reactor, reactor internal gas pressure controls to-(1.5 ± 0.01) KPa;
2., in 2.45GHz frequency microwave reactor, use the microwave that setting power is 450w to carry out denitration process, treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; In gel fine powder, a small amount of ammonium chloride is decomposed into ammonia and hydrogen chloride in the process, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
3. close microwave reactor, make it naturally cool to 25 DEG C;
4. from microwave reactor, take out ceramic vessel, fine powder after collecting reaction also grinds with grinder, and cross 200 mesh sieves, namely gained fine powder is the product after denitration is denitration gel fine powder, and particle diameter≤0.075mm, treats that next step uses;
10, roasting:
1. the ceramic vessel filling denitration gel fine powder is placed in the roaster after purification;
2. open roaster heater, regulate temperature to be progressively warming up to 650 ± 1 DEG C by 25 DEG C, at this temperature, roasting time 60 ± 0.1min; In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining;
3. close roaster heater, make fine powder naturally cool to 25 DEG C with stove;
4. open roaster, take out ceramic vessel and interior fine powder thereof, this fine powder is nano-magnetic rare earth barium ferrite cleanser;
5. the nano-magnetic rare earth barium ferrite cleanser that this technique is produced is powdery, and its average-size: 65.7nm, structural formula is Ba
0.9nd
0.1fe
2o
4,hexaplanar M type ferrite structure, magnetic saturation intensity 45emu/g;
(11) product storage
To the rare earth barium ferrite cleanser powder storage of preparation in the glass container of amber transparent, be airtightly stored in cool place, drying, clean environment, the erosion of moistureproof, sun-proof, anti-acid-alkali salt, storage temperature 20 DEG C ± 10 DEG C, relative humidity≤10%.
The embodiment utilizing magnetic rare earth barium ferrite nanometer cleaning catalyst to dispose of sewage is:
1, utilize technological process that magnetic rare earth barium ferrite nanometer cleaning catalyst is disposed of sewage as shown in Figure 1, the waste water 1 in storage tank 2 is delivered in suspended-bed reactor 4 with pump 3, and by 100 ~ 300g/ waste water m
3ratio magnetic rare earth barium ferrite nanometer cleaning catalyst 16 is joined in suspended-bed reactor 4, open compressed air 5 flow switch 6 and supersonic generator 8 simultaneously, make compressed air (or oxygen, ozone) 5 through dispersion plate 17 be separated into after fine gas bubbles with waste water 1, magnetic rare earth barium ferrite nanometer cleaning catalyst 16 Homogeneous phase mixing, simultaneously ultrasonic wave stirring rod 7 starts Vibratory Mixing and contains air (or oxygen, ozone) 5 and the mixed liquor of magnetic rare earth barium ferrite nanometer cleaning catalyst 16, separator 9 is entered through magnetic separation after air and waste water fully react, water 11 through purification reclaims and does its use, magnetic rare earth barium ferrite nanometer cleaning catalyst is returned in suspended-bed reactor 4 by circulating pump 13 to be reused, the gas 10 that purified treatment produces is emptying after inspection, if desired high temperature purification, then utilize steam(-)coil 15 to heat, if there is accident, the waste water carrying out purified treatment enters as emergency pool 14 from guard valve 13,
2, magnetic rare earth barium ferrite nanometer cleaning catalyst is pressed 200 ± 0.01g/m
3add in suspension bed;
3, the waste water containing COD is delivered in suspended-bed reactor by pump from storage tank, and flow velocity is 100 ± 0.01L/min;
4, by oxygen (or ozone) with the flow of 20 ± 0.01L/min through dispersion plate be separated into after fine gas bubbles with waste water, catalyst granules three-phase Homogeneous phase mixing; Open 20KHZ/2000w ultrasonic stirrer agitated liquid simultaneously, make COD and oxygen by being adsorbed on catalyst surface enrichment like this, there is heterogeneous catalytic reaction, larger molecular organics valence link is ruptured, generate the organic oxygen compound of lower molecular weight, oxidation step of going forward side by side decomposes, and makes molecule continue to diminish.Organic matter is progressively from hydrocarbon → alcohol (aldehyde) → acid → CO
2+ H
2o, wherein acid degradation is controlling unit wherein; In processing procedure, reaction is as follows, as:
Through the water of purified treatment at separator through magnetic separation, reuse in reclaiming clean catalyst Returning reactor; The gas that reaction produces is harmless rear directly emptying after testing;
5, COD index contrast in waste water before and after process:
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 723mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 100g/m
3, after the process of 45 ± 0.01 minutes, COD content is 30mg/L, COD clearance is 95.85%;
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 732mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 200g/m
3, after the process of 45 ± 0.01 minutes, industrial wastewater COD content is 7mg/L, COD clearance is 99.04%;
Temperature is that before 50 ± 0.01 DEG C of Industrial Wastewater Treatment, COD content is 728mg/L; Add magnetic rare earth barium ferrite nanometer cleaning catalyst 300g/m
3, after the process of 45 ± 0.01 minutes, industrial wastewater COD content is 6mg/L, COD clearance is 99.18%.
The process of magnetic rare earth barium ferrite nanometer cleaning catalyst is containing NO
x, VOC and CO exhaust-gas treatment method:
1, magnetic rare earth barium ferrite nanometer cleaning catalyst is placed in porous material, and the porous material that magnetic rare earth barium ferrite nanometer cleaning catalyst is housed is made the cylindrical form matched with discharge duct, this cylinder is reactor; Reactor is placed in discharge duct, when the gas containing nitrogen oxide, carbon monoxide, hydrocarbon passes through, gas molecule is adsorbed on its surface and produces Local enrichment by magnetic rare earth barium ferrite nanometer cleaning catalyst, and it is N that nitrogen oxide, carbon monoxide, hydrocarbon a series of redox reaction can occur by gas transition
2, water and CO
2, as:
2, before and after process, in waste gas, gas is at 180 ~ 300 DEG C, CO entrance concentration 8000 ~ 15000mg/m
3, exit concentration 75 ~ 120mg/m
3, conversion ratio>=99%, HC entrance concentration 500 ~ 1000mg/m
3, exit concentration 0.00mg/m
3, conversion ratio 100%, NO
xentrance concentration 300 ~ 1000mg/m
3, exit concentration 2.5 ~ 8mg/m
3, conversion ratio>=99%.
Claims (9)
1. a magnetic rare earth barium ferrite nanometer cleaning catalyst, general formula is Ba
xre
yme
zfe
mo
n, wherein x is 0.1 ~ 3.0, y be 0 ~ 2.0, z be 0 ~ 2, m be 1 ~ 24, n is 3 ~ 48; Me is Cu or Zn or Mn or Co, Re is La or Ce or Nd or Pr or Sc or Y.
2. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1, is characterized in that described barium ferrite nanometer cleaning catalyst is Ba
0.1nd
0.9fe
12o
19or Ba
0.8nd
0.2fe
2o
4or BaLa
0.1co
0.9fe
16o
27.
3. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1, is characterized in that its preparation technology comprises high temperature ultrasonic dispersion sol, the gelation of microwave negative pressure, the few oxygen denitration of low-temperature microwave negative pressure, roasting;
Described high temperature ultrasonic dispersion sol chemical industry sequence is:
(1) xanthans 1g ~ 5g/L or pickling elm rubber powder 10 ~ 5g/L being added pH value is in the mixed solution of 6.5 ~ 7.5, stirs and becomes colloidal solution;
(2) described mixed solution is mol ratio is barium nitrate solution: iron nitrate solution: earth solution: citric acid=0.1 ~ 3.00:1 ~ 24:0 ~ 2.0:3 ~ 20;
(3) colloidal solution is placed in glass container, at the temperature of 50 ~ 80 DEG C, carry out ultrasonic disperse with 600W/40kHz ultrasonic disperse instrument, jitter time is 60 ~ 120min; After High Temperature Disperse process, metal ion fully disperses in colloidal solution;
The step of described microwave negative pressure gel process is:
(1) colloidal solution after high temperature ultrasonic dispersion sol be placed in ceramic vessel with cover and be placed on the microwave reactor that air pressure is-0.1 ~-0.5KPa;
(2) in frequency be 2.45GHz microwave reactor in, regulating power is 140 ~ 280w, carries out microwave drying treatment, control temperature 110 ~ 150 DEG C, time 10 ~ 35min, extracts the moisture that evaporates out during process, after its cooling, become gel;
(3) obtained gel is carried out grind, sieve as the gel fine powder of particle diameter≤0.075mm;
The step of the few oxygen denitration operation of described microwave negative pressure is:
(1) gel fine powder is put into ceramic vessel with cover and be placed in the microwave reactor that setting power is 360 ~ 500w, frequency is 2.45GHz, air pressure is-1 ~-2KPa, carry out microwave denitration process; The control temperature of microwave denitration process is 200 ~ 240 DEG C, and the time is 5 ~ 10min;
In microwave denitration processing procedure, in gel fine powder, ammonium chloride is decomposed into ammonia and hydrogen chloride, and decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reaction equation is as follows:
(2) close microwave reactor, make it naturally cool to 25 DEG C;
(3) from microwave reactor, take out ceramic vessel, collect fine powder, grind, sieve, make the denitration gel fine powder of particle diameter≤0.075mm;
The step of described calcining process is:
(1) crucible filling denitration gel fine powder is placed in the roaster after purification;
(2) open roaster heater, control temperature is 550 ~ 850 DEG C, at this temperature 60 ~ 120min; Obtained nano rare earth barium ferrite catalytic purification agent.
4. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1, is characterized in that its preparation method comprises the steps:
(1) material purity requires:
Neodymia purity is 99.9%;
Nine water ferric nitrate purity are 99.9%;
Barium nitrate purity is 99.9%;
Ammoniacal liquor purity is 28%;
Citric acid purity is 99.9%;
Hydrochloric acid purity is 40%;
Pickling elm glue purity is 99.5%;
(2) dry process:
Taking neodymia 200g ± 5g, to be placed in vacuum be that the vacuum drying chamber of-18Pa is dry, baking temperature 120 DEG C ± 2 DEG C, drying time 30min;
(3) pickling elm rubber powder preparation:
1. choose 5 years raw elm extra dry white wine skin 2000g ± 5g and be broken into the fritter that granularity is 2 ~ 3mm;
2. by step 1. gained elm extra dry white wine skin fritter 0.1mol/L hydrochloric acid 3L repeatedly clean three times, remove Ca wherein
2+, Mg
2+; And then by washed with de-ionized water three times;
3. by step 2. gained pickling Radix Ulmi Tonkinesis Rhizoma Euonymus to be again placed in vacuum drying chamber dry, baking temperature 110 DEG C ± 2 DEG C, vacuum-18Pa, drying time 60 ± 2min; Grind and the pickling elm rubber powder of the obtained particle diameter≤0.075mm that sieves;
(4) obtain solution:
1. taking 1 ± 0.001mol nine water ferric nitrate deionized water, to prepare 0.5 ± 0.001mol/L iron nitrate solution at 2000 milliliters of volumetric flasks stand-by;
2. take 0.25 ± 0.001mol barium nitrate deionized water to prepare 0.25 ± 0.001mol/L at 1000 milliliters of volumetric flasks and prepare barium nitrate solution for later use;
3. take 0.05 ± 0.001mol neodymia, 0.1 ± 0.001mol/L dissolving with hydrochloric acid, then prepare 0.05 ± 0.001mol/L neodymium chloride solution by deionized water at 1000 milliliters of volumetric flasks stand-by;
(5) proportioning and mixing:
According to Fe
3+, Ba
2+, Nd
3+, (C
6h
5o
7)
3-molal quantity ratio be 2:0.9:0.1:6, measure iron nitrate solution, barium nitrate solution, neodymium chloride solution respectively, weigh citric acid simultaneously;
Iron nitrate solution, barium nitrate solution and neodymium chloride solution are mixed and stir, then citric acid is added, continue to stir until solution is clarified completely, dripping ammoniacal liquor regulates solution ph to 7.0 ± 0.01, adds at 500ml volumetric flask the mixed solution that solution concentration to be adjusted to 0.6 ± 0.01mol/L by deionized water;
(7) high temperature ultrasonic dispersion sol
1. 12 ± 0.001g pickling elm rubber powder being added pH value is in 500 ± 0.01ml mixed solution of 7.0 ± 0.01, continues stirring and makes it be dissolved into colloidal solution gradually;
2. colloidal solution is placed in glass container, at the temperature of 60 ± 0.01 DEG C, carry out ultrasonic disperse with the ultrasonic disperse instrument of 600W/40kHz, jitter time is 90 ± 0.01min; After High Temperature Disperse process, metal ion is fully separated into High Temperature Disperse colloidal solution in colloidal solution;
(8) microwave negative pressure gelation:
1. High Temperature Disperse colloidal solution is placed in ceramic vessel with cover to put into the microwave reactor that air pressure is-0.2 ± 0.01kPa, frequency is 2.45GHz, setting power is 200w and carry out microwave drying treatment, treatment temperature 125 ± 1 DEG C, time 25 ± 0.01min, extract the moisture evaporated during process out, after it cools naturally, make gel;
2. by gel abrasive, the gel fine powder being screened into particle diameter≤0.075mm;
(9) the few oxygen denitration of microwave negative pressure:
1. gel fine powder is put into ceramic vessel with cover and be-(1.5 ± 0.01) KPa at air pressure, frequency is 2.45GHz, setting power is 450w microwave reactor carries out denitration and is treated to denitration gel fine powder; Wherein denitration treatment temperature is 220 ± 1 DEG C, and the time is 6 ± 0.1min; Have ammonium chloride to be decomposed into ammonia and hydrogen chloride in the process in gel fine powder, decomposing ammonium nitrate is nitrogen, oxygen and water, the gas that in processing procedure, extraction produces, and reacts as follows:
(10) roasting:
1. the ceramic vessel filling denitration gel fine powder is placed in roaster;
2. roaster heater is opened, at 650 ± 1 DEG C of roasting temperature 60 ± 0.1min; Naturally being cooled to average-size is 58.6nm, and molecular formula is Ba
0.9nd
0.1fe
2o
4,, magnetic saturation intensity is the nano-magnetic rare earth barium ferrite cleanser of the hexaplanar M type ferrite structure of 45emu/g;
In the process, organic substance decomposing is carbon dioxide and water, and the chelating ion of baric, iron and rare earth synthesizes the agent of nano rare earth barium ferrite catalytic purification through calcining.
5. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1 or 3 or 4, it is characterized in that it is cubic system spinel-type, its molecular formula is Ba
xnd
yfe
2o
4, crystallite dimension is 40 ~ 90nm, and specific saturation magnetization is 28 ~ 40emu/g.
6. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 1 or 3, it is characterized in that it is hexaplanar M type, its molecular formula is Ba
xnd
yfe
12o
19, crystallite dimension is 30 ~ 80nm, and specific saturation magnetization is 20 ~ 50emu/g.
7. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to any one of Claims 1 to 4, is characterized in that for Industrial Wastewater Treatment.
8. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 7, is characterized in that the processing step for Industrial Wastewater Treatment is:
(1) deliver in suspended-bed reactor by waste water pump from storage tank, flow is 80 ~ 150L/min;
(2) magnetic rare earth barium ferrite nanometer cleaning catalyst is pressed 100 ~ 300g/m
3add in suspended-bed reactor;
(3) by compressed air or pure oxygen or ozone with the flow of 20L/min through dispersion plate be separated into after fine gas bubbles with waste water, magnetic rare earth barium ferrite nanometer cleaning catalyst Homogeneous phase mixing;
(4) 20KHz/2000W ultrasonic stirrer agitated liquid is opened, COD in such waste water and oxygen adsorb at catalyst surface, enrichment, there is heterogeneous catalytic reaction, larger molecular organics valence link is ruptured, generate the organic oxygen compound of lower molecular weight, oxidation step of going forward side by side decomposes, and molecule is diminished; Organic matter is progressively from hydrocarbon → alcohol or aldehyde → acid → CO
2+ H
2o, in processing procedure, reaction is as follows:
(5) after purified treatment containing the water of the rare earth barium ferrite nanometer cleaning catalyst that is magnetic at separator through magnetic separation, reclaim magnetic rare earth barium ferrite nanometer cleaning catalyst and return in suspended-bed reactor and reuses, the gas CO that purified treatment produces
2through check harmless after emptying, recovery of purifying waste water do its use.
9. a kind of magnetic rare earth barium ferrite nanometer cleaning catalyst according to claim 7, is characterized in that for NO
x, VOC and CO process process be by the gas containing nitrogen oxide, carbon monoxide, hydrocarbon by place in flue containing the perforated reactor of catalyst, gas molecule is adsorbed on its surface and produces Local enrichment by magnetic rare earth barium ferrite nanometer cleaning catalyst, and it is N that nitrogen oxide, carbon monoxide, hydrocarbon redox reaction can occur by gas transition
2, water and CO
2, reaction equation is as follows:
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| CN105289634A (en) * | 2015-06-08 | 2016-02-03 | 太原理工大学 | Magnetic rare earth barium ferrite nanometer purifying catalyst |
| CN108675501A (en) * | 2018-06-06 | 2018-10-19 | 全椒县花溪湖特种水产专业合作社 | A kind of processing method of Chinese turtle aquaculture effluent |
| CN109437880A (en) * | 2018-12-10 | 2019-03-08 | 合肥学院 | Method for preparing Ce-Sm-Fe composite solid electrolyte ceramic material by ultrasonic-microwave sol-gel method |
| CN115475745A (en) * | 2022-10-26 | 2022-12-16 | 鞍钢集团北京研究院有限公司 | Preparation process and coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry |
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| US7276254B2 (en) * | 2002-05-07 | 2007-10-02 | Xerox Corporation | Emulsion/aggregation polymeric microspheres for biomedical applications and methods of making same |
| CN101367647B (en) * | 2008-09-19 | 2011-12-14 | 西北工业大学 | Lanthanum doped nano barium ferrite film and method of manufacturing the same |
| CN101452756B (en) * | 2008-09-19 | 2011-04-13 | 西北工业大学 | Cerium-doped nanometer barium ferrite thin film and method for making same |
| CN103435798B (en) * | 2013-07-24 | 2016-04-06 | 中北大学 | A kind of rare earth codoped barium ferrite/polyaniline composite material |
| CN104437502B (en) * | 2014-12-15 | 2017-01-04 | 南京理工大学 | Magnetic fenton catalyst ferrospinel with Fenton iron containing sludge as source of iron and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105289634A (en) * | 2015-06-08 | 2016-02-03 | 太原理工大学 | Magnetic rare earth barium ferrite nanometer purifying catalyst |
| CN108675501A (en) * | 2018-06-06 | 2018-10-19 | 全椒县花溪湖特种水产专业合作社 | A kind of processing method of Chinese turtle aquaculture effluent |
| CN108675501B (en) * | 2018-06-06 | 2021-04-02 | 全椒县花溪湖特种水产专业合作社 | Treatment method of turtle breeding wastewater |
| CN109437880A (en) * | 2018-12-10 | 2019-03-08 | 合肥学院 | Method for preparing Ce-Sm-Fe composite solid electrolyte ceramic material by ultrasonic-microwave sol-gel method |
| CN109437880B (en) * | 2018-12-10 | 2021-06-22 | 合肥学院 | Method for preparing Ce-Sm-Fe composite solid electrolyte ceramic material by ultrasonic-microwave sol-gel method |
| CN115475745A (en) * | 2022-10-26 | 2022-12-16 | 鞍钢集团北京研究院有限公司 | Preparation process and coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry |
| CN115475745B (en) * | 2022-10-26 | 2023-10-20 | 鞍钢集团北京研究院有限公司 | Preparation process and coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry |
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