CN104789780A - Method for recovering anatase-type titanium tungsten powder from waste vanadium-tungsten-titanium catalyst - Google Patents
Method for recovering anatase-type titanium tungsten powder from waste vanadium-tungsten-titanium catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000000843 powder Substances 0.000 title claims abstract description 57
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 6
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract 3
- 238000005406 washing Methods 0.000 abstract 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 1
- 238000001354 calcination Methods 0.000 description 21
- 239000011734 sodium Substances 0.000 description 14
- 238000002386 leaching Methods 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 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 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering anatase-type titanium tungsten powder from a waste vanadium-tungsten-titanium catalyst. The method comprises the following steps: performing ultrasonic cleaning on the waste vanadium-tungsten-titanium catalyst; mixing and grinding the catalyst, Na2CO3 and NaClO3; adding sodium chlorate into sodium carbonate to serve as a compound digesting agent by adopting a microwave roasting digesting method, wherein the reaction temperature of the sodium carbonate and the catalyst in a traditional high-temperature furnace roasting digesting process can be reduced from original 700 DEG C to 450 DEG C, and the reaction time is shortened from 3 hours to 30 minutes; finally, soaking by using warm water, acidizing, performing solid-liquid separation, performing acid washing and water washing, and roasting in a high-temperature furnace, wherein the obtained titanium dioxide powder contains a certain amount of tungsten oxide, and obtaining anatase-type titanium tungsten powder with high purity and high specific area. The method has the characteristics of energy conservation, environment friendliness, easiness in operation and high recovering efficiency; meanwhile, the recovered tungsten powder can serve as a raw material and can be directly used in the production of the vanadium-tungsten-titanium catalyst.
Description
Technical field
The invention belongs to catalyst recovery reutilization technology field, particularly utilize a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst of microwave calcining degestion.
Background technology
Oxynitride is that China " 12 " starts pollutent emphasis and reduces discharging object, requires that the thermoelectricity of all emphasis and the non-major area unit nitrogen oxide emission that puts into operation is reduced to 100mg/m respectively from 1 day January in 2014
3and 200mg/m
3.In addition, the limit value requirement that all will improve successively discharged nitrous oxides is estimated in each industrial source such as iron and steel, cement, glass, petrochemical industry and the civilian source such as waste incineration, district heating boiler.The demand of vanadium tungsten titanium denitrating catalyst increases thereupon greatly, estimates that its consumption will increase to 300,000 m
3more than/year.
In the out of stock catalyzer of vanadium tungsten titanium, TiO
2shared mass ratio is 85% ~ 90%, V
2o
5shared mass ratio is 1% ~ 5%, WO
3shared mass ratio is 5% ~ 10%.In actual applications, because vanadium tungsten titanium catalyst exists the factor such as poisoning of catalyst, duct blocking, high temperature sintering and scaling loss, cause catalyst activity reduction and structure deteriorate and be eliminated.The work-ing life of current catalyzer only has 1 ~ 3 year, and owing to may produce to environment the chemical element polluted containing vanadium, tungsten etc. in catalyzer, simultaneously vanadium, tungsten, titanium are all industrial raw material costly.Chinese Ministry of Environmental Protection clearly proposes in " notice about strengthening waste flue gas denitration catalyst supervision " of issue in 2014, and waste flue gas denitration catalyst management, regeneration, utilization are included in Hazardous wastes and managed, and requirement improves it and regenerates and utilize disposing capacity.Therefore, how to recycle useless vanadium tungsten titanium denitrating catalyst and become current problem demanding prompt solution.
The treatment technology of current existing useless vanadium tungsten titanium catalyst is mainly divided into two classes.The first kind is the regeneration of useless vanadium tungsten titanium catalyst, pickling the (the 4th can be passed through, 615, No. 991 United States Patent (USP)s), the method (Japanese Unexamined Patent Publication 6-170247 publication) of alkali cleaning (2002-0071244 Korean Patent) or surface layer peeling improves the catalytic performance of useless denitrating catalyst, continue to come into operation.But the regeneration efficiency of this reclaiming process is not high, and regeneration times is limited, finally will lose efficacy discarded.Equations of The Second Kind treatment technology is the recycling of useless vanadium tungsten titanium catalyst, both by the vanadium in a series of physico-chemical process purification spent catalyst, tungsten, titanium three kinds of elements.Current existing Patents, as CN101921916A---the method for Footwall drift oxide compound " from the waste flue gas denitration catalyst ", by catalyzer high temperature sodium roasting, (maturing temperature is 650 ~ 700 DEG C, soaking time is 3 ~ 6 hours), after leaching in water, regulate corresponding pH to obtain corresponding vanadium oxide, Tungsten oxide 99.999 and titanium oxide again, this method roasting soaking time is longer, and the product purity simultaneously prepared is general.For another example the method adopting High Temperature High Pressure to leach in CN102936039A---" recovery process of the honeycomb fashion SCR spent catalyst of tungstenic, vanadium, titanium " reclaims vanadium tungsten titanium catalyst.(leaching temperature is 130 ~ 220 DEG C to need high temperature in this method, leaching time is 1 ~ 6 hour) autoclaving (leaching pressure is 0.3 ~ 1.2MPa), the product simultaneously prepared is the Rutile type Titanium Dioxide that specific surface area is very low, again cannot be applied to the production of vanadium tungsten titanium catalyst.Therefore, how to reclaim the valuable element in useless vanadium tungsten titanium catalyst more energy-efficiently, and allow the recovery product obtained directly continue to be applied to the production of vanadium tungsten titanium catalyst, meet the growth requirement that useless vanadium tungsten titanium is at present recycled.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst utilizing microwave calcining degestion, the method significantly can reduce maturing temperature (can be down to 450 DEG C), shorten roasting time (to 30 minutes), the Detitanium-ore-type titanium tungsten powder of high purity, high-specific surface area can be obtained, the method has energy-conserving and environment-protective, the feature that simple to operate, organic efficiency is high, reclaim the titanium tungsten powder obtained simultaneously and can be used as raw material, be directly applied to the production of vanadium tungsten titanium catalyst again.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
From useless vanadium tungsten titanium catalyst, reclaim a method for Detitanium-ore-type titanium tungsten powder, comprise the steps:
Step one: useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, adds pore forming material and carry out sonic oscillation, utilizes ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dries after cleaning;
Step 2: by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na
2cO
3and NaClO
3, mix and be milled into 100 ~ 150 order powder, wherein Na
2cO
3be 1:1 ~ 2:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 0.1:100 ~ 10:100 with the mass ratio of useless vanadium tungsten titanium catalyst; Na
2cO
3add and the vanadium in spent catalyst, tungsten, titanium can be separately converted to corresponding sodium salt; And NaClO
3as fusing assistant, be conducive to the leaching of vanadium in spent catalyst, tungsten, titanium;
Step 3: mixed powder is put into microwave agglomerating furnace, with the heat-up rate microwave heating of 50 DEG C/min ~ 100 DEG C/min to 450 DEG C ~ 750 DEG C, insulation 0.5h ~ 2h cools to room temperature with the furnace again; Microwave calcining and composite digestion agent can make the V in spent catalyst
2o
5, WO
3and TiO
2be converted into corresponding sodium salt; Microwave calcining degestion has the advantages such as temperature rise rate is fast, heat-up time is short, selectivity heats, soaking time is short, relative to traditional High Temperature Furnaces Heating Apparatus roasting, adopt the combination technique of microwave calcining method and composite digestion agent, effectively can reduce maturing temperature, shorten roasting time, and effectively improve the leaching yield of tungsten titanium in spent catalyst;
Step 4: powder step 3 obtained is milled, joins in the warm water of 80 DEG C ~ 90 DEG C, and the mass ratio of powder and water is 1:5 ~ 1:10, fully stirs and is incubated 1 ~ 3 hour;
Step 5: adding sulfuric acid in the solution obtained in step 4 to pH is 1 ~ 2, solid-liquid separation after fully stirring, the solid phase obtained is titanate and tungstate, containing NaVO in liquid phase
3solid phase isolate mass concentration be 1% ~ 10% dilute sulphuric acid clean 3 times, wash 10 times, then dry in the baking oven being put into 80 DEG C ~ 130 DEG C, then roasting 4 ~ 5 hours in the retort furnace of 450 DEG C ~ 550 DEG C, can obtain the Detitanium-ore-type titanium tungsten powder of high purity, high-ratio surface;
Preferably, Na in step 2
2cO
3be 1.3:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3when being 1:100 with the mass ratio of useless vanadium tungsten titanium catalyst, good leaching effect can be reached.
Preferably, in step 3 with 100 DEG C/min microwave heating to 600 DEG C, when being incubated 30 minutes, leaching effect is better, can reduce power consumption simultaneously.
Preferably, in step 4, the mass ratio of powder and water is 1:5, and described soaking time is 3 hours.
Preferably, in step 5, the mass concentration of the dilute sulphuric acid that solid phase isolate adopts is 5%, and the maturing temperature of employing is 500 DEG C, and roasting time is 4 hours.
Compared with prior art, advantage of the present invention is: the method adopting microwave calcining in the digestion process of spent catalyst, simultaneously toward Na
2cO
3in add and help digestion agent NaClO
3, maturing temperature can be reduced preferably, shorten soaking time, save and to also improve titanium, the leaching yield of tungsten and the rate of recovery while the energy.The product that above method obtains is high-specific surface area (80 ~ 100m
2/ g) Detitanium-ore-type titanium tungsten powder, be the mass content 3%-5% of the mass content 90%-92% of anatase phase, titanium dioxide, tungstic oxide, specific surface is 80 ~ 100m
2/ g, can be used as the production that raw material directly can be used further to vanadium tungsten titanium denitrating catalyst, this recovery method technique is simple, workable, is applicable to heavy industrialization.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the titanium tungsten powder that 700 DEG C of microwave calcining degestions obtain.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, and following examples are explanation of the invention, and the present invention is not limited to following examples.
Embodiment one
The present embodiment comprises the following steps:
(1) useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, add pore forming material simultaneously and carry out sonic oscillation, utilize ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dry after cleaning; (2) by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na simultaneously
2cO
3and NaClO
3, mix and be milled to 100 ~ 150 orders, wherein Na
2cO
3be 1.5:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 1:100 with the mass ratio of useless vanadium tungsten titanium catalyst.(3) mixed powder is put in microwave baking furnace, with the heat-up rate microwave heating of 100 DEG C/min to 700 DEG C, be incubated 30 minutes, then cool to room temperature with the furnace; (4) being cleared up by microwave calcining after the powder obtained is milled joins in the warm water of about 90 DEG C, and the mass ratio of powder and water is 1:5, fully stirs and is incubated 3 hours.(5) in solution obtained above, the dilute sulphuric acid that mass concentration is 10% is added, regulate pH to 2, solid-liquid separation after abundant stirring, solid phase mass concentration be 5% dilute sulphuric acid clean 3 times, wash 10 times again, be put in the baking oven of 120 DEG C again and dry, then roasting 4 hours in the retort furnace of 500 DEG C, the powder obtained is the Detitanium-ore-type titanium tungsten powder of high-ratio surface.The specific surface area of the titanium tungsten powder wherein prepared is 90m
2/ g, the total mass content >95% of titanium oxide and Tungsten oxide 99.999.
Table 1 is the titanium tungsten powder product component that 700 DEG C of microwave calcining degestions obtain, and Fig. 1 is the XRD figure of the titanium tungsten powder that 700 DEG C of microwave calcining degestions obtain.
The titanium tungsten powder product component that table 1 700 DEG C of microwave calcining degestions obtain, XRF result
| Component | TiO 2 | WO 3 | NaO 2 | SiO 2 | CaO | SO 3 | Al 2O 3 |
| Content (%) | 90.7558 | 4.2763 | 0.3100 | 1.2562 | 0.6003 | 2.2632 | 0.2988 |
| Component | Fe 2O 3 | NbO | Cr 2O 3 | MgO | P 2O 5 | K 2O | |
| Content (%) | 0.1235 | 0.0886 | -- | -- | 0.0202 | 0.0071 |
Embodiment two
The present embodiment comprises the following steps:
(1) useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, add pore forming material simultaneously and carry out sonic oscillation, utilize ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dry after cleaning; (2) by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na simultaneously
2cO
3and NaClO
3, mix and be milled to 100 ~ 150 orders.Wherein Na
2cO
3be 1.3:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 1:100 with the mass ratio of useless vanadium tungsten titanium catalyst.(3) mixed powder is put in microwave baking furnace, with the heat-up rate microwave heating of 100 DEG C/min to 600 DEG C, be incubated 30 minutes, then cool to room temperature with the furnace.(4) being cleared up by microwave calcining after the powder obtained is milled joins in the warm water of about 90 DEG C, and the mass ratio of powder and water is 1:5, fully stirs and is incubated 3 hours.(5) in solution obtained above, the vitriol oil that mass concentration is 98% is added, regulate pH to 1, solid-liquid separation after abundant stirring, solid phase mass concentration be 5% dilute sulphuric acid clean 3 times, wash 10 times again, be put in the baking oven of 120 DEG C again and dry, then roasting 4 hours in the retort furnace of 500 DEG C, the powder obtained is the Detitanium-ore-type titanium tungsten powder of high-ratio surface.The specific surface area of the titanium tungsten powder wherein prepared is 99m
2/ g, the total mass content >95% of titanium oxide and Tungsten oxide 99.999.
Table 2 is the titanium tungsten powder product component that 600 DEG C of microwave calcining degestions obtain.
The titanium tungsten powder product component that table 2 600 DEG C of microwave calcining degestions obtain, XRF result
| Component | TiO 2 | WO 3 | NaO 2 | SiO 2 | CaO | SO 3 | Al 2O 3 |
| Content (%) | 91.8184 | 3.4221 | 0.4943 | 2.4202 | 0.8262 | 0.1903 | 0.5816 |
| Component | Fe 2O 3 | NbO | Cr 2O 3 | MgO | P 2O 5 | K 2O | |
| Content (%) | 0.0494 | 0.0471 | 0.0294 | 0.0711 | 0.0372 | 0.0048 |
Embodiment three
The present embodiment comprises the following steps:
(1) useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, add pore forming material simultaneously and carry out sonic oscillation, utilize ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dry after cleaning; (2) by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na simultaneously
2cO
3and NaClO
3, mix and be milled to 100 ~ 150 orders.Wherein Na
2cO
3be 1.5:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 5:100 with the mass ratio of useless vanadium tungsten titanium catalyst.(3) mixed powder is put in microwave baking furnace, with the heat-up rate microwave heating of 100 DEG C/min to 500 DEG C, be incubated 30 minutes, then cool to room temperature with the furnace.(4) being cleared up by microwave calcining after the powder obtained is milled joins in the warm water of about 90 DEG C, and the mass ratio of powder and water is 1:5, fully stirs and is incubated 3 hours.(5) in solution obtained above, the vitriol oil that mass concentration is 98% is added, regulate pH to 1, solid-liquid separation after abundant stirring, solid phase mass concentration be 5% dilute sulphuric acid clean 3 times, wash 10 times again, be put in the baking oven of 120 DEG C again and dry, then roasting 4 hours in the retort furnace of 500 DEG C, the powder obtained is the Detitanium-ore-type titanium tungsten powder of high-ratio surface.The specific surface area of the titanium tungsten powder wherein prepared is 90m
2/ g, the total mass content >95% of titanium oxide and Tungsten oxide 99.999.
Table 3 is the titanium tungsten powder product component that 500 DEG C of microwave calcining degestions obtain.
The titanium tungsten powder product component that table 3500 DEG C microwave calcining degestion obtains, XRF result
| Component | TiO 2 | WO 3 | NaO 2 | SiO 2 | CaO | SO 3 | Al 2O 3 |
| Content (%) | 91.8588 | 3.3083 | 0.3449 | 2.0261 | 0.8403 | 0.7540 | 0.6310 |
| Component | Fe 2O 3 | NbO | Cr 2O 3 | MgO | P 2O 5 | K 2O | |
| Content (%) | 0.0470 | 0.0623 | 0.0206 | 0.0556 | 0.0373 | 0.0063 |
Embodiment four
The present embodiment comprises the following steps:
A kind of method that microwave calcining degestion reclaims Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst comprises the following steps successively:
(1) useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, add pore forming material simultaneously and carry out sonic oscillation, utilize ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dry after cleaning; (2) by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na simultaneously
2cO
3and NaClO
3, mix and be milled to 100 ~ 150 orders.Wherein Na
2cO
3be 1.3:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 10:100 with the mass ratio of useless vanadium tungsten titanium catalyst.(3) mixed powder is put in microwave baking furnace, with the heat-up rate microwave heating of 100 DEG C/min to 450 DEG C, be incubated 30 minutes, then cool to room temperature with the furnace.(4) being cleared up by microwave calcining after the powder obtained is milled joins in the warm water of about 90 DEG C, and the mass ratio of powder and water is 1:5, fully stirs and is incubated 3 hours.(5) in solution obtained above, the dilute sulphuric acid that mass concentration is 10% is added, regulate pH to 1, solid-liquid separation after abundant stirring, solid phase mass concentration be 5% dilute sulphuric acid clean 3 times, then wash 10 times, then dry in the baking oven being put into 120 DEG C, then roasting 4 hours in the retort furnace of 500 DEG C, the powder obtained is the Detitanium-ore-type titanium tungsten powder of high-ratio surface.The specific surface area of the titanium tungsten powder wherein prepared is 82m
2/ g, the total mass content >95% of titanium oxide and Tungsten oxide 99.999.
Table 4 is the titanium tungsten powder product component that 450 DEG C of microwave calcining degestions obtain.
The titanium tungsten powder product component that table 4450 DEG C microwave calcining degestion obtains, XRF result
| Component | TiO 2 | WO 3 | NaO 2 | SiO 2 | CaO | SO 3 | Al 2O 3 |
| Content (%) | 91.9977 | 3.2517 | 0.4462 | 2.0004 | 0.8808 | 0.6074 | 0.6226 |
| Component | Fe 2O 3 | NbO | Cr 2O 3 | MgO | P 2O 5 | K 2O | |
| Content (%) | 0.0496 | 0.0563 | 0.0222 | 0.0595 | 0.0332 | 0.0047 |
These are only the preferred embodiments of the present invention, do not limit to scope of patent protection of the present invention.In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation, all in protection scope of the present invention.
Claims (5)
1. from useless vanadium tungsten titanium catalyst, reclaim a method for Detitanium-ore-type titanium tungsten powder, it is characterized in that, comprise the steps:
Step one: useless vanadium tungsten titanium catalyst is put into ultrasonic oscillator, adds pore forming material and carry out sonic oscillation, utilizes ultrasonic wave removing to be adsorbed in dust and other materials of catalyst surface, dries after cleaning;
Step 2: by levigate for the useless vanadium tungsten titanium catalyst after drying, add Na
2cO
3and NaClO
3, mix and be milled into 100 ~ 150 order powder, wherein Na
2cO
3be 1:1 ~ 2:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 0.1:100 ~ 10:100 with the mass ratio of useless vanadium tungsten titanium catalyst;
Step 3: mixed powder is put into microwave agglomerating furnace, with the heat-up rate microwave heating of 50 DEG C/min ~ 100 DEG C/min to 450 DEG C ~ 750 DEG C, insulation 0.5h ~ 2h cools to room temperature with the furnace again;
Step 4: powder step 3 obtained is milled, joins in the warm water of 80 DEG C ~ 90 DEG C, and the mass ratio of powder and water is 1:5 ~ 1:10, fully stirs and is incubated 1 ~ 3 hour;
Step 5: adding sulfuric acid in the solution obtained in step 4 to pH is 1 ~ 2, solid-liquid separation after fully stirring, the solid phase obtained is titanate and tungstate, containing NaVO in liquid phase
3solid phase isolate mass concentration be 1% ~ 10% dilute sulphuric acid clean 3 times, wash 10 times, then dry in the baking oven being put into 80 DEG C ~ 130 DEG C, then roasting 4 ~ 5 hours in the retort furnace of 450 DEG C ~ 550 DEG C, can obtain the Detitanium-ore-type titanium tungsten powder of high purity, high-ratio surface.
2. a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst according to claim 1, is characterized in that, Na in step 2
2cO
3be 1.3:1, NaClO with the mass ratio in useless vanadium tungsten titanium catalyst
3be 1:100 with the mass ratio of useless vanadium tungsten titanium catalyst.
3. a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst according to claim 1, is characterized in that, in step 3 with 100 DEG C/min microwave heating to 600 DEG C, be incubated 30 minutes.
4. a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst according to claim 1, it is characterized in that, in step 4, the mass ratio of powder and water is 1:5, and described soaking time is 3 hours.
5. a kind of method reclaiming Detitanium-ore-type titanium tungsten powder from useless vanadium tungsten titanium catalyst according to claim 1, it is characterized in that, in step 5, the mass concentration of the dilute sulphuric acid that solid phase isolate adopts is 5%, and the maturing temperature of employing is 500 DEG C, and roasting time is 4 hours.
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| CN106622284A (en) * | 2016-12-05 | 2017-05-10 | 清华大学 | Recovery and utilization technology of waste titanium-vanadium based SCR catalyst capable of being applied to reproduction |
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