CN102872854A - Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof - Google Patents
Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof Download PDFInfo
- Publication number
- CN102872854A CN102872854A CN2012103758356A CN201210375835A CN102872854A CN 102872854 A CN102872854 A CN 102872854A CN 2012103758356 A CN2012103758356 A CN 2012103758356A CN 201210375835 A CN201210375835 A CN 201210375835A CN 102872854 A CN102872854 A CN 102872854A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- vanadium carbide
- carbide material
- titanium oxide
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 title abstract 6
- 230000000694 effects Effects 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 120
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000013078 crystal Substances 0.000 claims abstract description 60
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 16
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 claims description 87
- 230000015572 biosynthetic process Effects 0.000 claims description 45
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 5
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical group [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910010251 TiO2(B) Inorganic materials 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005755 formation reaction Methods 0.000 description 38
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 27
- 238000002803 maceration Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000007664 blowing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000003819 Madia Nutrition 0.000 description 1
- 240000004516 Madia sativa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 244000294611 Punica granatum Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a vanadium-titanium compound material with high thermal stability and high activity and a preparation method thereof. The vanadium-titanium compound material is mainly compounded by vanadium oxide and titanium oxide, wherein the content of the vanadium oxide is 0.5-30% of the mass of the vanadium-titanium compound material, and the crystal form of the titanium oxide in the vanadium-titanium compound material is anatase or TiO2(B) One or a mixture of both. Compared with the prior art, the vanadium-titanium compound material does not need to add any structural auxiliary agent, has good thermal stability and catalytic activity, and the generation temperature of rutile titanium oxide can reach more than 900 ℃. In addition, the material of the invention has simple preparation method and low cost, and is suitable for industrial mass production.
Description
Technical field
The invention belongs to technical field of material, be specifically related to highly active Vanadium Carbide material of a kind of high stability and preparation method thereof.
Background technology
According to statistics, between 1967～2000 years, about the paper that transition metal-catalyzed application is published, wherein 28% is relevant with vanadium, and 15% is relevant with titanium, and a large amount of reports shows that vanadium and titanium get more and more people's extensive concerning always in numerous catalystic converter systems
[1]Vanadium Carbide particularly has a good application prospect in the relevant catalyst system and catalyzing of selective oxidation of the SCR of nitrogen oxide, volatile organic matter oxidation, Oxidation of Hydrogen Sulfide, hydro carbons etc. and environmental protection, energy field than other materials.
The structure of the titanium oxide of one of the catalytic performance of Vanadium Carbide and its composition is closely related
[2]The titanium oxide of occurring in nature divides three kinds of conventional crystal formations: anatase, brockite and rutile, and wherein rutile is the steady phase of titanium oxide, anatase is mutually steady for being situated between with brockite.In high-temperature heat treatment process, anatase and brockite are finally converted into rutile.Catalytic performance difference after the titanium oxide of different crystal forms and vanadium oxide are compound is larger.Generally speaking, best with the Vanadium Carbide performance of the steady phase anatase type titanium oxide that is situated between.But in material preparation or application process, material often needs to face hot environment, and this easily causes the titanium oxide in the Vanadium Carbide brilliant phenomenon to occur turning, generates Titanium Dioxide Rutile Top grade.And vanadium oxide is easy and Titanium Dioxide Rutile Top grade forms solid solution, significantly reduces the catalytic performance of Vanadium Carbide
[3]In addition, vanadium oxide itself also can turn brilliant by the accelerating oxidation titanium, so that the generation temperature of Titanium Dioxide Rutile Top grade is lower than conventional titanium oxide in the Vanadium Carbide, further aggravates the decline of Vanadium Carbide catalytic performance
[4]
At present, a large amount of work concentrate on how to solve Vanadium Carbide poor stability to keep on its high performance problem.General way is to introduce the generation temperature that structural promoter (tungsten, molybdenum, aluminium, silicon, potassium etc.) improves Titanium Dioxide Rutile Top grade
[5]Change into Titanium Dioxide Rutile Top grade although the interpolation of structural promoter can be alleviated anatase-type titanium oxide to a certain extent, also have a series of problem.For example, some structural promoters are larger for the dispersity impact of vanadium oxide, and this easily causes the catalytic performance of Vanadium Carbide significantly to descend; In addition, for example be used for the Vanadium Carbide of denitration reaction, tungsten oxide or molybdenum oxide be as structural promoter, and its use amount reaches 8～10 times of vanadium oxide consumption in the compound often, and this causes the cost of Vanadium Carbide significantly to promote
[6]Therefore, keep again its good performance when how can improve Vanadium Carbide stability, remain the focus that industry is paid close attention to.
Summary of the invention
The objective of the invention is provides a kind of Vanadium Carbide material in order to address the above problem, this material has good heat endurance and catalytic activity concurrently, as catalyst removal of nitrogen oxide rate up to 98%, the volatile organic matter conversion ratio is more than 97%, and need not to add any structural promoter in the preparation process.
Another purpose of the present invention provides this Vanadium Carbide material preparation method, and it is simple that the method has process, and cost is lower, is fit to the advantages such as large-scale industrial production.
The object of the invention can reach by following measures:
The highly active Vanadium Carbide material of a kind of high thermal stability, this material mainly is to be composited by vanadium oxide and titanium oxide, wherein, the content of vanadium oxide is 0.5～30% of Vanadium Carbide quality of materials, and the titanium oxide crystal formation in the Vanadium Carbide material is anatase or TiO
2(B) a kind of or two kinds of mixing in.The content of vanadium oxide is 1～10% of Vanadium Carbide quality of materials in the preferred Vanadium Carbide material, and most preferably the content of vanadium oxide is 1～5% of Vanadium Carbide quality of materials in the Vanadium Carbide material.
The specific area of above-mentioned Vanadium Carbide material is 1～200m
2/ g, pore volume are 0.005～0.8cm
3/ g, the specific area of preferred Vanadium Carbide material is 1～120m
2/ g, pore volume are 0.01～0.4cm
3/ g.
The highly active Vanadium Carbide material preparation of above-mentioned high thermal stability method, the method may further comprise the steps: will contain TiO
2(B) titanium oxide of crystal formation joins in the precursor solution that contains vanadium, stirs, and leaves standstill 6～8 hours, and oven dry is obtaining after the roasting under 300～700 ℃ of conditions again.The TiO that contains of the present invention
2(B) titanium oxide of crystal formation is that a part of crystal formation is TiO
2(B) titanium oxide or whole crystal formation are TiO
2(B) titanium oxide.Preferred TiO
2(B) titanium oxide of crystal formation accounts for whole titanium oxide quality percentage compositions 1～100%, further preferred TiO
2(B) titanium oxide of crystal formation accounts for 5～100% of whole titanium oxide quality percentage compositions, most preferably TiO
2(B) titanium oxide of crystal formation accounts for whole titanium oxide quality percentage compositions 5%.
The above-mentioned TiO that contains
2(B) specific area of the titanium oxide of crystal formation is 10～300m
2/ g, pore volume are 0.02～1.0cm
3/ g, average pore size is 1.0～50nm.It is metavanadate, vanadic sulfate or oxalic acid vanadyl that the present invention selects the presoma that contains vanadium, the preferred ammonium metavanadate of described metavanadate.Containing the solvent that the precursor solution of vanadium selects is water or Organic Alcohol, and described Organic Alcohol is take ethanol as good, and the best is absolute ethyl alcohol.The precursor solution preferred concentration that contains vanadium is 1～6mol/L.
Said method can also may further comprise the steps: will contain the presoma of vanadium and cosolvent and together be dissolved in water or the organic alcohol solvent and make maceration extract, and join and contain TiO
2(B) stir in the titanium oxide of crystal formation, left standstill 6～8 hours, oven dry is obtaining after the roasting under 300～700 ℃ of conditions again.Contain the precursor solution of vanadium and contain TiO
2(B) amount ratio of the titanium oxide of crystal formation is 0.5～1.0mL/g, is preferably 0.7mL/g.
Usually titanium oxide has three kinds of crystal formations: anatase (anatase), rutile (rutile) and brockite (brookite).TiO
2(B) be a kind of new TiO that finds evening
2Crystal formation is found in 1980 first by people such as Marchand, four kinds of crystalline structure parameters such as table 1:
Table 1TiO
2The structural parameters of crystal formation
Utilize XRD or Raman spectrum to detect, the titanium oxide crystal formation in the Vanadium Carbide material of the present invention is anatase or TiO
2(B) a kind of in or two kinds.
Beneficial effect of the present invention compared with the prior art:
(1) need not to introduce the heat endurance that new structural promoter improves titanium oxide in the Vanadium Carbide material in the Vanadium Carbide material preparation process of the present invention, the generation temperature of Titanium Dioxide Rutile Top grade can be up to more than 900 ℃ in the Vanadium Carbide material.
(2) the superior catalytic performance of Vanadium Carbide material performance of the present invention, as catalyst, the conversion ratio of its nitrogen oxide is better than existing industrial index up to more than 98%; In addition, the conversion ratio of volatile organic matter reaches more than 97%.
(3) Vanadium Carbide material preparation procedure of the present invention is simple, and cost is lower, is fit to large-scale industrial production.
Description of drawings
Fig. 1: the XRD spectra of the embodiment 1 Vanadium Carbide material that the process heat endurance is investigated.
Fig. 2: the XRD spectra that obtains the Vanadium Carbide material through the conventional method of heat endurance investigation.
Shown in Fig. 1-2, through 500～800 ℃ of heat treatment tests, Vanadium Carbide material prepared in accordance with the present invention does not demonstrate Rutile Type, is pure anatase, when temperature is higher than 900 ℃, just occurs Rutile Type in the sample; And the Vanadium Carbide material of conventional method preparation Rutile Type just occurs through 600 ℃ the time.
Fig. 3: the TPR spectrogram of the embodiment 1 Vanadium Carbide material that the process heat endurance is investigated.
Fig. 4: the TPR spectrogram that obtains the Vanadium Carbide material through the conventional method of heat endurance investigation.
Shown in Fig. 3-4, Vanadium Carbide material prepared in accordance with the present invention reduction peak all occurs through 500～1000 ℃ of processing.And the Vanadium Carbide material of preparation according to conventional methods, it is very many that 600 ℃ reduction peak intensity has weakened than the sample of 500 ℃ of processing, and reduction peak does not appear in the sample of 700 ℃ of processing.These difference show that the Vanadium Carbide material of the inventive method preparation has good heat endurance.
The specific embodiment
The invention will be further described according to embodiment for the below, and the specific embodiments of following examples just is described more specifically the present invention, and the present invention is not limited to the content of following examples.
Embodiment 1:
According to the described method of patent (ZL0315827.5) with anatase type titanium oxide, technical grade K
2CO
3(purity 98wt%), H
2O evenly mixes, wherein TiO
2/ K
2The O mol ratio is 1.9, water content 20wt%; The reaction mass that mixes evenly is applied to the aluminium oxide backing plate, 880 ℃ of reaction temperatures, the reaction time is 2 hours, sintered product is two potassium titanates; After sintered product disperses in water, place the aqueous solution reaction 8 hours of 50 ℃, 5 times pH=8, filtering and being placed on pH is that 3 aqueous hydrochloric acid solution stirred 8 hours, to potassium content admittedly less than the 0.5wt% of product weight; Washing is filtered, and 20～50 ℃ of dryings obtained hydrated product in 12 hours; Crystallization is 2 hours in 500 ℃ of air, obtains containing TiO
2(B) titanium oxide of crystal formation, this titanium oxide contain 95% anatase crystal and 5% TiO
2(B) crystal formation, specific area are 105m
2/ g, average pore size is 6.2nm, pore volume is 0.23cm
3/ g.Adopting ammonium metavanadate is the precursor that contains vanadium, and oxalic acid is cosolvent, and both mol ratios are 1:2, are dissolved in and are made into the maceration extract that concentration is 0.2M (precursor solution that namely contains vanadium) in the deionized water; Maceration extract joined contain TiO
2(B) in the titanium dioxide powder of crystal formation, liquid-solid ratio is that 0.7mL/g(is that every mL maceration extract and 0.7g all are TiO
2(B) titanium oxide of crystalline form mixes), stir, leave standstill 8 hours after, place baking oven to dry, and then place tube furnace, 500 ℃ of roastings of blowing air obtain the Vanadium Carbide material.
The heat stability testing of Vanadium Carbide material: the Vanadium Carbide material is placed Muffle furnace, respectively through 500,600,700,800,900 and 1000 ℃ of six temperature roastings, the time was respectively 2 hours.
Method one: after cooling, with 6 sample porphyrizes, be the crystal formation of X-ray powder diffraction (XRD) test sample of D8Adavance by model, test condition is that sweep limits is between 5 °～60 °, speed is 0.5 second/step, it is that 40 kilovolts of electric currents are 30 milliamperes that voltage is set, and experimental result is seen Fig. 1.
Method two: after cooling, with 6 sample porphyrizes, it is the reducing power of vanadium oxide on multi-functional absorption instrument (TPR) test sample of TP-5000 by model, taking by weighing 0.05 gram sample joins in the test quartz ampoule, gas speed with 20 ml/min passes into air first, with 10 ℃/minute speed temperature is risen to 300 ℃ from room temperature and carry out preliminary treatment, be incubated 0.5 hour; After temperature is down to room temperature, pass into 20% hydrogen/nitrogen gaseous mixture with the gas speed of 20 ml/min after the end, open thermal conductivity detector (TCD), bridge stream is set to 90 milliamperes, and the conductance cell temperature is 60 ℃; After device to be detected is stable, with 10 ℃/minute speed temperature is risen to 800 ℃ from room temperature, and by the thermal conductivity detector (TCD) collection signal, experimental result is seen Fig. 2.
The removal of nitrogen oxide performance test of Vanadium Carbide material: evaluating apparatus is the quartz tube reactor of internal diameter 8mm; Vanadium Carbide material compressing tablet is crushed to the particle that granularity is 1.25 ~ 3mm, places the reactor constant temperature zone, piling up length is about 18cm; Unstripped gas consist of NO(700ppm), NH
3(700ppm), 5%O
2, all the other are nitrogen; Air speed is 5000h
-1, reaction temperature is 300 ℃.
The volatile organic matter of Vanadium Carbide material removes performance test: this performance evaluation is to be the fixed-bed micro-reactor of 4mm at internal diameter; Take by weighing a certain amount of Vanadium Carbide material and join constant temperature zone in the reactor; Volatile organic matter is toluene, and the content of toluene is 1000ppm in the unstripped gas, and all the other are air; Reaction temperature is 400 ℃, and the unstripped gas air speed is 12000h
-1
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 2:
With anatase titanium dioxide TiO
2, technical grade K
2CO
3(purity 98wt%), H
2O evenly mixes, wherein TiO
2/ K
2The O mol ratio is 3, water content 20wt%; The reaction mass that mixes evenly is applied to the aluminium oxide backing plate, 1000 ℃ of reaction temperatures, the reaction time is 2 hours, sintered product is potassium tetratitanate; Sintered product is broken, and placing pH is that 3 the HCl aqueous solution stirred 24 hours, to potassium content admittedly less than the 0.5wt% of product weight; Washing is filtered, and 20～50 ℃ of dryings obtained hydrated product in 12 hours; Crystallization is 2 hours in 400 ℃ of air, and obtaining all is TiO
2(B) titanium oxide of crystalline form, specific area are 20m
2/ g, pore volume are 0.03cm
3/ g.Adopting vanadic sulfate is the precursor that contains vanadium, is dissolved in and is made into the maceration extract that concentration is 1mol/L in the deionized water; It all is TiO that maceration extract is joined
2(B) in the titanium oxide of crystalline form, liquid-solid ratio is that 0.7g/mL(is that every mL maceration extract and 0.7g all are TiO
2(B) titanium oxide of crystalline form mixes), stir, leave standstill 8 hours after, place baking oven to dry; And then placing tube furnace, 600 ℃ of roastings of blowing air obtain the Vanadium Carbide material.
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 3:
Anatase-type titanium oxide is scattered in the 10M NaOH aqueous solution, and liquid-solid ratio is 100mL/g, then mixed solution is stirred, and places water heating kettle, is heated to 180 ℃ of insulations 48 hours.To be cooled to room temperature, the collecting precipitation thing is immersed in the excessive 0.1M HCl aqueous solution, stirs 24 hours; After the end, use deionized water washing sediment, collect, under 80 ℃ of conditions, dry.Powder is again through 400 ℃ of roastings 2 hours, and obtaining whole crystal formations is TiO
2(B) titanium dioxide powder, crystal formation are TiO
2(B) titanium oxide specific area is 50m
2/ g, pore volume are 0.15cm
3/ g, average pore size is 12nm.Adopting the oxalic acid vanadyl is the precursor that contains vanadium, is dissolved in and is made into maceration extract in the deionized water, and concentration is 0.6mol/L; Measure maceration extract and join in the above-mentioned titanium oxide, liquid-solid ratio stirs as described in the example 1, leave standstill 8 hours after, place baking oven to dry; And then placing tube furnace, 400 ℃ of roastings of blowing air obtain the Vanadium Carbide material.
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 4:
Contain TiO according to what embodiment 1 prepared
2(B) the twin crystal titanium oxide of crystal formation and anatase crystal, (commercially available titanium ore type titanium oxide specific area is 200m with itself and commercially available anatase-type titanium oxide
2/ g, pore volume are 0.35cm
3/ g, average pore size is 5nm) carry out compositely, both mass ratioes are 1:1,, acquisition contain TiO
2(B) TiO in crystal formation and the anatase crystal twin crystal titanium oxide
2(B) content of crystal formation is about 2.5%.Adopting ammonium metavanadate is the precursor that contains vanadium, joins in the absolute ethyl alcohol, adds thermal agitation, is made into the maceration extract that concentration is 0.1mol/L; Measure maceration extract and join in the above-mentioned titanium oxide, liquid-solid ratio is 0.7mL/g, stirs, leave standstill 8 hours after, place baking oven to dry; And then place tube furnace, 700 ℃ of roastings of blowing air.Obtain the Vanadium Carbide material.
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 5:
The whole TiO of being that prepare according to embodiment 2 methods
2(B) titanium oxide of crystalline form carries out itself and commercially available anatase-type titanium oxide (with embodiment 4) composite, and mass ratio is 1:5, acquisition contain TiO
2(B) TiO in crystal formation and the anatase crystal twin crystal titanium oxide
2(B) content of crystal formation is about 16%.Adopting ammonium metavanadate is the precursor that contains vanadium, and oxalic acid is cosolvent, and both mol ratios are 1:2, are dissolved in being made into maceration extract in the deionized water, and concentration is 3mol/L; Measure maceration extract, join above-mentioned TiO
2(B) content of crystal formation is that liquid-solid ratio is 0.7mL/g, stirs in about 16% the titanium oxide, leave standstill 8 hours after, place baking oven to dry; And then place tube furnace, 500 ℃ of roastings of blowing air.Obtain the Vanadium Carbide material.
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 6:
The whole TiO of being that prepare according to embodiment 3 methods
2(B) titanium oxide of crystalline form carries out itself and commercially available anatase-type titanium oxide (with embodiment 4) composite, and mass ratio is 1:10, acquisition contain TiO
2(B) TiO in crystal formation and the anatase crystal twin crystal titanium oxide
2(B) content of crystal formation is 10%.Adopting vanadic sulfate is the precursor that contains vanadium, is dissolved in being made into maceration extract in the deionized water, and concentration is 2mol/L; Measure maceration extract and join above-mentioned TiO
2(B) content of crystal formation is that liquid-solid ratio is 0.7mL/g, stirs in 10% the titanium oxide, leave standstill 8 hours after, place baking oven to dry; And then place tube furnace, 400 ℃ of roastings of blowing air.Obtain the Vanadium Carbide material.
Every structural parameters and the catalytic performance test result of Vanadium Carbide material are as shown in table 1.
Embodiment 7:
Contain TiO according to what embodiment 1 prepared
2(B) the twin crystal titanium oxide of crystal formation and anatase crystal carries out itself and commercially available amorphous hydrated titanium oxide composite, and mass ratio is 1:8, through 500 ℃ of roastings after 2 hours, acquisition contain TiO
2(B) TiO in crystal formation and the anatase crystal twin crystal titanium oxide
2(B) content of crystal formation is about 1%, and the specific area of material is 150m
2/ g, pore volume are 0.35cm
3/ g, the aperture is 8nm.Adopting vanadic sulfate is the precursor that contains vanadium, is dissolved in being made into maceration extract in the deionized water, and concentration is 6mol/L; Measure maceration extract and join above-mentioned TiO
2(B) content of crystal formation is that liquid-solid ratio is 1mL/g, stirs in about 1% the titanium oxide, leave standstill 8 hours after, place baking oven to dry; And then place tube furnace, 550 ℃ of roastings of blowing air.Obtain the Vanadium Carbide material.
Embodiment 8:
Butyl titanate and acetylacetone,2,4-pentanedione are slowly joined in the absolute ethyl alcohol simultaneously, at room temperature stir 1h; Prepare in addition ethanol-aqueous hydrochloric acid solution, its speed with 1 ~ 2 of per second is joined in the butyl titanate and acetylacetone,2,4-pentanedione ethanolic solution of vigorous stirring, continue to stir 4h, obtain the sol solutions of transparent and stable, the mol ratio of each material is Ti: absolute ethyl alcohol: water: acetylacetone,2,4-pentanedione=1:20:5:0.3; Behind the sample gel, more at ambient temperature ageing 2 days, the colloidal sol of making.
Then the whole crystalline forms that prepare according to embodiment 2 methods are TiO
2(B) titanium oxide drops in the above-mentioned colloidal sol, and mass ratio is 1:20, stirs 6h, places baking oven to dry; 400 ℃ of roasting 2h, making all is TiO
2(B) titanium oxide of crystal formation.Adopting ammonium metavanadate is the precursor that contains vanadium, is dissolved in being made into maceration extract in the deionized water, and concentration is 4mol/L; Measure maceration extract and join in the above-mentioned titanium oxide, liquid-solid ratio is 0.5mL/g, stirs, leave standstill 8 hours after, place baking oven to dry, and then place tube furnace, 300 ℃ of roastings of blowing air. obtain the Vanadium Carbide material.
The every structure of table 2 Vanadium Carbide material and catalytic performance parameter thereof
Comparative example 1:
Take hydrous titanium oxide (Zhenjiang, Jiangsu Province titanium dioxide limited company) as raw material, obtain anatase-type titanium oxide through 500 ℃ of roastings after 2 hours, specific area is 150m
2/ g, pore volume are 0.3cm
3/ g, average pore size is 6.5nm.As the base material of Vanadium Carbide material, identical among Vanadium Carbide material preparation method and the embodiment 1.According to material structure and the method for evaluating performance of embodiment 1, by test as can be known, material Rutile Type just occurs through 600 ℃ of heat treatments, and the removal efficiency of nitrogen oxide is 60%.
Comparative example 2:
According to document
[7]The report precipitation method prepare titanium oxide.Measure the 20mL butyl titanate and join in the absolute ethyl alcohol of 100mL, then this mixed solution is joined in the 100mL ethanol water, mix solution, the mol ratio of water/butyl titanate is 75.After the white depositions to be formed, continue to stir 24 hours, then the collecting precipitation thing washs sediment with the 400mL ethanol water.After washing finishes, sediment is placed 80 ℃ of baking oven bakings 24 hours, after 2 hours, obtain whole crystal formations is anatase-type titanium oxide to the driest powder through 400 ℃ of heat treatments, and the specific area of this material is 130m
2/ g, pore volume are 0.25cm
3/ g, average pore size is 7nm.According to material structure and the method for evaluating performance of embodiment 1, by test as can be known, material Rutile Type just occurs through 500 ℃ of heat treatments, and the removal efficiency of nitrogen oxide is 60%.
Comparative example 3:
Commercial oxidation titanium nano particle (Hangzhou ten thousand scape new material Co., Ltds); Specific area is 88.3m
2/ g, pore volume are 0.05cm
3/ g, granular size is about 10nm.According to material structure and the method for evaluating performance of embodiment 1, by test as can be known, material Rutile Type just occurs through 550 ℃ of heat treatments, and the removal efficiency of nitrogen oxide is 68%.
Comparative example 4:
Document
[8]The Vanadium Carbide material of report, titanium oxide crystal formation wherein is anatase, has added the 9wt% tungstic acid in the compound as the heat endurance of structural promoter with raising Vanadium Carbide material.It is 600 ℃ that the rutile of this compound generates temperature, and the conversion ratio of nitrogen oxide is 95%.
Comparative example 5:
According to bibliographical information
[9]Improve one's methods, the silica that adds 5wt% content as structural promoter to improve the heat endurance of Vanadium Carbide material.It is 730 ℃ that the rutile of this compound generates temperature, and the conversion ratio of nitrogen oxide only is 30%, and the removal efficiency of volatile organic matter is 45%.
Reference:
[1]Weckhuysen?BM,Keller?DE(2003)Catalysis?Today78:25
[2]Wachs?IE,Weckhuysen?BM(1997)Appl?Catal?A?Gen157:67
[3]Saleh?RY，Wachs?IE,Chan?SS,Chersich?CC(1986)Journal?ofCatalysis98:102
[4]
MA,Alemany?L,amp,x,s?J,Jiménez?MC,Larrubia?MA,Delgado?F,Granados?ML,Marti,nez-Arias?A,Blasco?JM,Fierro?JL,s?G(1996)Journal?of?Solid?State?Chemistry124:69
[5]Reddy?BM,Ganesh?I,Chowdhury?B(1999)Catalysis?Today49:115
[6]Madia?G，Elsener?M,Koebel?M,Raimondi?F,Wokaun?A(2002)Applied?Catalysis?B:Environmental39:181
[7]Zhang?J,Li?M,Feng?Z,Chen?J,Li?C(2006)Journal?of?Physical?Chemistry?B110:927
[8]Djerad?S,Tifouti?L,Crocoll?M,Weisweiler?W(2004)Journal?of?Molecular?Catalysis?A:Chemical208:257
[9]Okada?K,Yamamoto?N,Kameshima?Y，Yasumori?A,MacKenzie?KJD(2001)Journal?of?the?American?Ceramic?Society84:1591
Claims (10)
1. highly active Vanadium Carbide material of high thermal stability, it is characterized in that described Vanadium Carbide material mainly is to be composited by vanadium oxide and titanium oxide, wherein, the content of vanadium oxide is 0.5～30% of Vanadium Carbide quality of materials, and the titanium oxide crystal formation in the Vanadium Carbide material is anatase or TiO
2(B) a kind of or two kinds of mixing in.
2. the highly active Vanadium Carbide material of high thermal stability according to claim 1, the content that it is characterized in that vanadium oxide in the described Vanadium Carbide material is 1～10% of Vanadium Carbide quality of materials.
3. the highly active Vanadium Carbide material of high thermal stability according to claim 1, the content that it is characterized in that vanadium oxide in the described Vanadium Carbide material is 1～5% of Vanadium Carbide quality of materials.
4. highly active Vanadium Carbide material of high thermal stability, the specific area that it is characterized in that described Vanadium Carbide material is 1～200m
2/ g, pore volume are 0.005～0.8cm
3/ g.
5. the highly active Vanadium Carbide material preparation of a high thermal stability method is characterized in that the method may further comprise the steps: will contain TiO
2(B) titanium oxide of crystal formation joins in the precursor solution that contains vanadium, stirs, and leaves standstill 6～8 hours, and oven dry is obtaining after the roasting under 300～700 ℃ of conditions again.
6. Vanadium Carbide material preparation method according to claim 5 is characterized in that containing TiO
2(B) in the titanium oxide of crystal formation, crystal formation is TiO
2The content of titanium oxide (B) is 1～100%, and preferred crystal formation is TiO
2The content of titanium oxide (B) is 5～100%.
7. Vanadium Carbide material preparation method according to claim 5 is characterized in that the TiO that contains that selects
2(B) specific area of the titanium oxide of crystal formation is 10～300m
2/ g, pore volume are 0.02～1.0cm
3/ g, average pore size is 1.0～50nm.
8. Vanadium Carbide material preparation method according to claim 5, it is characterized in that selecting the presoma that contains vanadium is metavanadate, vanadic sulfate or oxalic acid vanadyl, containing the solvent that the precursor solution of vanadium selects is water or Organic Alcohol; Organic Alcohol is preferably ethanol.
9. Vanadium Carbide material preparation method according to claim 5, the concentration that it is characterized in that containing the precursor solution of vanadium is 1～6mol/L.
10. Vanadium Carbide material preparation method according to claim 5 is characterized in that containing the precursor solution of vanadium and contains TiO
2(B) crystal formation the amount ratio of titanium oxide be 0.5～1.0mL/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103758356A CN102872854A (en) | 2012-09-29 | 2012-09-29 | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103758356A CN102872854A (en) | 2012-09-29 | 2012-09-29 | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102872854A true CN102872854A (en) | 2013-01-16 |
Family
ID=47474500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103758356A Pending CN102872854A (en) | 2012-09-29 | 2012-09-29 | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102872854A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047937A1 (en) * | 2012-09-29 | 2014-04-03 | 南京工业大学 | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
| CN104817107A (en) * | 2015-03-31 | 2015-08-05 | 吉林大学 | Method for preparing black titanium dioxide B phase and anatase phase nanoparticles |
| CN105126813A (en) * | 2015-10-09 | 2015-12-09 | 清华大学 | High-specific-surface denitration catalyst and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58188834A (en) * | 1982-04-27 | 1983-11-04 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of anthraquinone |
| CN101480611A (en) * | 2009-02-04 | 2009-07-15 | 北京科技大学 | Vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof |
| CN102367180A (en) * | 2011-03-17 | 2012-03-07 | 中国科学院过程工程研究所 | Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source |
-
2012
- 2012-09-29 CN CN2012103758356A patent/CN102872854A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58188834A (en) * | 1982-04-27 | 1983-11-04 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of anthraquinone |
| CN101480611A (en) * | 2009-02-04 | 2009-07-15 | 北京科技大学 | Vanadium-doped titanium-base flue gas denitration catalyst material and preparation method thereof |
| CN102367180A (en) * | 2011-03-17 | 2012-03-07 | 中国科学院过程工程研究所 | Method for preparing high-pore order degree nano mesoporous TiO2 material with low-priced industrial titanium source |
Non-Patent Citations (4)
| Title |
|---|
| 向辉等: "钒钛催化剂制备工艺对表面结构与催化分解气相二噁英的影响", 《中国科技论文在线》, vol. 6, no. 3, 31 March 2011 (2011-03-31), pages 220 - 225 * |
| 徐云龙等: "V2O5/TiO2催化剂用于烟气同时脱硫脱硝的研究", 《环境科学与技术》, vol. 30, no. 11, 30 November 2007 (2007-11-30), pages 83 - 85 * |
| 田晓宁等: "单斜相态TiO2(B)的制备和应用研究进展", 《应用化工》, vol. 38, no. 4, 30 April 2009 (2009-04-30), pages 588 - 591 * |
| 陈闪山等: "含TiO2(B)介孔氧化钛材料的制备、特性和应用", 《催化学报》, vol. 31, no. 6, 30 June 2010 (2010-06-30), pages 605 - 614 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014047937A1 (en) * | 2012-09-29 | 2014-04-03 | 南京工业大学 | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
| US9856149B2 (en) | 2012-09-29 | 2018-01-02 | Nanjing Tech University | Vanadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
| CN104817107A (en) * | 2015-03-31 | 2015-08-05 | 吉林大学 | Method for preparing black titanium dioxide B phase and anatase phase nanoparticles |
| CN104817107B (en) * | 2015-03-31 | 2016-05-04 | 吉林大学 | A kind of method of preparing black titanium dioxide B phase and anatase-phase nano particle |
| CN105126813A (en) * | 2015-10-09 | 2015-12-09 | 清华大学 | High-specific-surface denitration catalyst and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tahir | Hierarchical 3D VO2/ZnV2O4 microspheres as an excellent visible light photocatalyst for CO2 reduction to solar fuels | |
| He et al. | Z-scheme SnO2− x/g-C3N4 composite as an efficient photocatalyst for dye degradation and photocatalytic CO2 reduction | |
| He et al. | The key surface species and oxygen vacancies in MnOx (0.4)-CeO2 toward repeated soot oxidation | |
| Zhou et al. | Photocatalytic reduction of CO2 into CH4 over Ru-doped TiO2: Synergy of Ru and oxygen vacancies | |
| Li et al. | Sol–gel combustion synthesis and visible-light-driven photocatalytic property of perovskite LaNiO3 | |
| Ning et al. | Selective catalytic reduction of NO with NH3 over CeO2–ZrO2–WO3 catalysts prepared by different methods | |
| Zhang et al. | UV Raman spectroscopic study on TiO2. I. Phase transformation at the surface and in the bulk | |
| Reddy et al. | Structural characterization of CeO2− MO2 (M= Si4+, Ti4+, and Zr4+) mixed oxides by Raman spectroscopy, X-ray photoelectron spectroscopy, and other techniques | |
| Zhao et al. | Promotion effects of SiO2 or/and Al2O3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NO by NH3 | |
| González-Rovira et al. | Single-step process to prepare CeO2 nanotubes with improved catalytic activity | |
| Reddy et al. | Investigation of surface structures of dispersed V2O5 on CeO2− SiO2, CeO2− TiO2, and CeO2− ZrO2 mixed oxides by XRD, Raman, and XPS techniques | |
| Rao et al. | Structural characterization and catalytic evaluation of supported copper–ceria catalysts for soot oxidation | |
| Kumari et al. | Dependence of photoactivity of niobium pentoxide (Nb2O5) on crystalline phase and electrokinetic potential of the hydrocolloid | |
| Xu et al. | NH3-SCR denitration catalyst performance over vanadium–titanium with the addition of Ce and Sb | |
| CN103641165B (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| Huang et al. | Praseodymium hydroxide and oxide nanorods and Au/Pr6O11 nanorod catalysts for CO oxidation | |
| CN104069848B (en) | The hot legal system of a kind of alcohol is for the method for pure phase bismuth titanates and titanium oxide composite material | |
| Lv et al. | Synthesis and characterisation of Gd3+-doped mesoporous TiO2 materials | |
| CN103086435A (en) | Preparation method of molybdenum trioxide nanorod | |
| Yang et al. | Catalytic activity and crystal structure modification of Pd/γ-Al2O3–TiO2 catalysts with different Al2O3 contents | |
| CN107321351A (en) | A kind of method for preparing high-efficient catalyst of methane/carbon dioxide reforming reaction | |
| CN104888767A (en) | Noble metal oxide catalyst, and preparation and application thereof | |
| CN105800676A (en) | Two-dimensional titanate nanometer material and preparation method thereof | |
| Yuan et al. | CuO quantum dots supported by SrTiO3 perovskite using the flame spray pyrolysis method: Enhanced activity and excellent thermal resistance for catalytic combustion of CO and CH4 | |
| CN102861605A (en) | Diesel vehicle oxidation catalyst with low SO2 oxidation activity and preparation method of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130116 |