CN102092787A - Method for continuously synthesizing vanadium trioxide - Google Patents
Method for continuously synthesizing vanadium trioxide Download PDFInfo
- Publication number
- CN102092787A CN102092787A CN 201010614020 CN201010614020A CN102092787A CN 102092787 A CN102092787 A CN 102092787A CN 201010614020 CN201010614020 CN 201010614020 CN 201010614020 A CN201010614020 A CN 201010614020A CN 102092787 A CN102092787 A CN 102092787A
- Authority
- CN
- China
- Prior art keywords
- reactor
- gas
- vanadous oxide
- product
- multicell
- 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.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a chemical material synthesis method, particularly a method for continuously synthesizing vanadium trioxide, which comprises steps as follows: after being preheated, the raw material polyammonium vanadate or vanadium pentoxide enters a multi-chamber boiling reactor of which the temperature is controlled at 600-750 DEG C; the solid raw material is fluidized by preheated reducing gas which is introduced from the bottom of the reactor; the solid material starts to move chamber by chamber from the first fluidization chamber at the inlet of the reactor; the material stays in the reactor for 10-30 minutes, and is reduced by the reducing gas to generate vanadium trioxide; the vanadium trioxide flows out of the outlet of the reactor and enters a product tank, thereby obtaining the black vanadium trioxide powder product; and part of the vanadium trioxide product, which enters a cyclone separator along with the reaction exhaust, also enters the product tank after being separated. Compared with the common fluidized reaction furnace, the multiple chambers of the multi-chamber boiling reactor reduce the back mixing of the material, thereby enhancing the quality of the product and forming a continuous production technique.
Description
Technical field
The present invention relates to a kind of chemical materials synthetic method, particularly relate to the method for the synthetic vanadous oxide of a kind of serialization.
Background technology
V
2O
3Character (being also referred to as MST or MIT) with metal-nonmetal transition, low temperature phase change feature have excellent light, electricity, magnetic property well.In the serial oxide compound of vanadium, vanadous oxide (V
2O
3) be a kind of crucial product, at electricity, magnetic, photoswitch, the multiple fields such as gas sensor, storage medium, resistive material that reach all are with a wide range of applications.V
2O
3It is the desirable feedstock of producing series alloys such as vanadium iron and nitrogen-vanadium alloy.
" Chengdu Univ. of Science ﹠ Technology's journal " (1984, (3): 27～30) introduced a kind of ammonium gas that utilizes to ammonium hexavanadate (NH
4)
2V
6O
16Carry out thermal reduction and prepare the method for vanadous oxide.This process is carried out in tube furnace, and the ammonium airshed is 10 ± 0.5 L/h, and temperature of reaction is controlled at 850 ± 50 ℃, and the reaction times is 30 min, and cooling can obtain vanadous oxide in ammonium gas atmosphere.This method have a too high problem of reaction process temperature, the consumption that reacts used reductive agent ammonium gas simultaneously is also bigger, the actual consumption amount of ammonium is 2 times of theoretical consumption.
Chinese patent CN1118765A discloses a kind of production method of vanadous oxide.This method adds the ammonium vanadate or the Vanadium Pentoxide in FLAKES of certain particle size in the external-heat container, in its container, feed industrial gas, make by outer heating that the high-temperature zone reaches 500～650 ℃ in the container, make furnace charge pass through this zone and reduction reaction takes place 15～40 minutes, making its decomposition-reduction is vanadous oxide.This document provides and has adopted common shaft furnace and the rotary kiln embodiment as production unit, can realize the serialization production of vanadous oxide, but there are some problems that are difficult to overcome in this method: the temperature of reaction general requirement is being carried out more than 900 ℃ in the actual industrial production implementation process, and the residence time of material in rotary kiln is also above one hour; Though the rotary kiln structure is simpler relatively simultaneously,, there are the technological difficulties of high temperature dynamic seal because the hot environment and the scantlings of the structure of its operation are bigger; Be subjected to the material selection of reacting in rotary kiln device and the restriction of manufacturing process and installation in addition, also have certain potential safety hazard in the production process; Reacting in rotary kiln device self character determines that the treatment capacity of its unit volume is less in addition, causes the production intensity of reactor and production efficiency all lower, and is simultaneously also bigger for the consumption of reducing gas such as industrial gas.
" J. Photopolym. Sci. Technol. " (1997,10 (2): 211-215,) (Synthesis of fine particles of Sn, Ti, and V oxides by laser-induced vapor-phase reaction) introduced the method for the vanadous oxide that utilizes induced with laser method synthesis nano.Used raw material is VOCl
3, by with H
2, O
2With
:
After the mixed of=1.6 kpa:6.4 kpa:1.6 kpa, induced with laser generates V
2O
3The raw material VOCl that this method is used
3Itself add the water moulding after by pentachloro-ization two vanadium and coke burden, dry back introduce chlorine gas to make reaction makes, feedstock production cost height is not easy to obtain, and is subjected to the heat-flash decomposition can emit poisonous gas, easily set off an explosion.In addition, the raw material chance time of tide is corrosive to most of metals, and is therefore strict to production unit.
" mining metallurgical engineering " (2005,25 (6): 61～65) having introduced a kind of is that reducing gas is gone back the method for preparing vanadous oxide originally to ammonium meta-vanadate in the reacting in rotary kiln device with urban life coal gas.This method reaction times weak point be 50 min, but used reducing gas contains a large amount of CO toxic gases for life coal gas.There are the technological difficulties of high temperature dynamic seal in the reacting in rotary kiln device, so there is bigger potential safety hazard in this method; Also there is the low and energy consumption problem of higher of production efficiency in this method simultaneously.
Chinese patent CN101028938A provides a kind of method of utilizing fluidization technology to prepare vanadous oxide.This method is powder ammonium vanadate or Vanadium Pentoxide in FLAKES (granularity is between 0.05 mm～10.00 mm) to be joined as furnace charge add in the hot fluidized bed furnace boiler tube, makes the filling ratio of boiler tube reach 10%～55%; In boiler tube, feed industrial gas from the fluidized bed furnace bottom, simultaneously the fluidized bed furnace boiler tube is heated to 600～650 ℃, insulation reduction 3～9 minutes; Come out and the secluding air cooling from discharge port, promptly obtain product.In fact under the pellet density condition of determining, too small or excessive particle diameter all can be for the fluidized operation causes difficulty, and the wide meeting of feed particles diameter Distribution simultaneously brings bigger operation easier for the control of the residence time of feed particles in reactor.There is material back-mixing problem in this method, influences the quality of product, and tend to material for the quality that guarantees product and in reactor, stop the longer time, thereby make this technology be difficult to realize serialization; The used reducing gas consumption of this method simultaneously is bigger.
" steel vanadium titanium " (2008,29 (3): 27～30) introduced the method for utilizing fluidization technology reduction ammonium poly-vanadate (APV) to produce vanadous oxide.This method is similar to the method that patent CN101028938A introduces, different is: be controlled at 650 ℃～750 ℃ rather than 600 ℃～650 ℃, recovery time was controlled at 5～20 minutes rather than 3～9 minutes, and the grain graininess of used reactant is at 0.067 mm～0.25 mm rather than 0.05 mm～10.00 mm.What this method realized is a rhythmic reaction process, simultaneously the large usage quantity of reducing gas in this method.
Chinese patent CN101717117A provides a kind of ammonium vanadate or Vanadium Pentoxide in FLAKES and binding agent, carbon dust has been mixed and made into pelletizing, reacts the method for preparing vanadous oxide then in reducing gas.This method be with ammonium vanadate or Vanadium Pentoxide in FLAKES powder with make ball after binding agents such as dextrin, starch, wilkinite, water glass mix in mixing machine; join pelletizing in the reactor continuously after the drying; and reducing gas such as reverse feeding industrial gas, hydrogen, ammonium gas or Sweet natural gas; react 10～30 min down at 500～650 ℃, under the protection of secluding air or rare gas element argon gas, be cooled to 100 ℃ at last and obtain vanadous oxides.Because not only need to use binding agents such as dextrin, starch, water glass in the preparation process, this method will increase impurity to reaction system, thereby influence the quality of product, this technological process is complicated simultaneously, and the production cycle is longer.
Chinese patent CN101817558A discloses a kind of industrial microwave oven that utilizes ammonium vanadate has been reduced the method for preparing vanadous oxide.Ammonium vanadate is heated to 600～900 ℃ in the industrial microwave oven of reducing gas or inert atmosphere protection, the recovery time is 5～60 min, finally obtains vanadous oxide.The related technology of this method is intermittent process, and the industrial microwave oven performance is also unstable, and the gas volume that consumes in the reaction process is bigger simultaneously.
It is the method for feedstock production nano grade vanadium trioxide with the Vanadium Pentoxide in FLAKES that Chinese patent CN1300002C discloses a kind of.This method is earlier with V
2O
5And H
2C
2O
4In dehydrated alcohol, reflux and obtained VOC in 2 hours
2O
4Ethanolic soln, reduction obtains nano level V under the condition of High Temperature High Pressure then
2O
3This method steps complexity need prepare intermediate VOC in advance for obtaining nano grade vanadium trioxide
2O
4, increased preparation cost.In addition, the raw material of this method only is confined to Vanadium Pentoxide in FLAKES.
It is the method that feedstock production has the vanadous oxide of crystal formation with the Vanadium Pentoxide in FLAKES that Chinese patent CN1724385A discloses a kind of.It is that 200～300 ℃, pressure are 3～15 Mpa and reaction times to be to obtain vanadous oxide under the condition of 0.5～5 h in temperature that this method makes Vanadium Pentoxide in FLAKES by solvent method.This method reaction pressure is very high, and used raw material also only is limited as Vanadium Pentoxide in FLAKES.
It is the method for feedstock production vanadium sesquioxide powder with the vanadium tetraoxide that Chinese patent CN1974407A provides a kind of.Temperature of reaction is 550～600 ℃ in this method, and the reaction times is less than 3 min, and used reducing gas comprises industrial gas, hydrogen or ammonia.The raw materials used vanadium tetraoxide of this method is of little use, and need prepare by additive method.
" Zhongshan University's journal " (natural science edition) (2003,42 (1): 116～118) introduced: at H
2In the atmosphere to vanadyl (IV) basic carbonate ammonium (NH
4)
5[(VO)
6(CO
3)
4(OH)
9] 10H
2O obtains the spherical pure V of about 30 nm of granularity under the condition of 900 ℃ of insulation 30 min
2O
3Powder.There is the difficult acquisition of reaction raw materials vanadyl (IV) basic carbonate ammonium in this method, and more loaded down with trivial details, the synthetic cost of building-up process is higher.
In sum, when being the feedstock production vanadous oxide, needing to pass through the reduction reaction process as reducing gas such as life coal gas, industrial gas, hydrogen or carbonaceous reducing agent (600 ℃～1000 ℃) under the condition of high temperature and prepare with a large amount of reductive agents with ammonium meta-vanadate or ammonium poly-vanadate.The industrialization equipment used is used rotary reactor more at present, has the technological difficulties of high temperature dynamic seal, is easy to generate the leakage of reducing gas, makes Working environment have bigger danger and contaminative; The ammonium poly-vanadate of having reported prepares that the fluidization reaction process of vanadous oxide is actual to be intermittent process, there is material back-mixing problem in this method, tending to material for the quality that guarantees product stops the longer time in reactor, thereby make this technology be difficult to realize serialization, exist the reducing gas consumption simultaneously than problems such as height; Thereby the method that has also needs to use the binding agent granulation to introduce impurity element, influences quality product.On the other hand, some method uses Vanadium Pentoxide in FLAKES to be raw material, though can realize producing the simplification of vanadous oxide technological process.But industrial Vanadium Pentoxide in FLAKES is to be decomposed to produce by ammonium meta-vanadate or many (gathering) ammonium vanadate heated oxide to obtain, and just there is very high cost in itself, and the environmental pollution of suitability for industrialized production Vanadium Pentoxide in FLAKES process is bigger at present simultaneously.
Therefore, the production of vanadous oxide needs a kind of above drawback that overcome, and realizes continuous production technology method safe, efficient, environmental protection.。
Summary of the invention
The object of the present invention is to provide the method for the synthetic vanadous oxide of a kind of serialization, can realize the serialization production of vanadous oxide by the multicell boiling reactor, thereby improved the production efficiency that vanadous oxide is produced greatly, improved quality product, formed the production technique of serialization.
The objective of the invention is to be achieved through the following technical solutions:
The method of the synthetic vanadous oxide of a kind of serialization, this method comprises following process: raw material many (gathering) ammonium vanadate or Vanadium Pentoxide in FLAKES are after preheating, enter the multicell boiling reactor, the temperature of reactor is controlled at 600-750 ℃, the reducing gas fluidisation of solid material after the preheating that the reactor bottom of associating feeds, solid materials begins to move by the chamber from first fluidising chamber of Reactor inlet, the residence time of material in reactor is 10-30 min, and through the reducing gas reduction, the final material reduction generates vanadous oxide and enters the product jar from the reactor outlet outflow, be the vanadous oxide powder-product of black, enter the part vanadous oxide product of cyclonic separator with reaction end gas, after separating, also enter into the product jar.
The method of the synthetic vanadous oxide of described a kind of serialization, reactor is the multicell boiling reactor, fluidising chamber is 10-20.
The method of the synthetic vanadous oxide of described a kind of serialization, raw material many (gathering) ammonium vanadate or Vanadium Pentoxide in FLAKES are through being preheating to 300-400 ℃, and the used thermal source of preheating is the tail gas of cyclonic separator.
The method of the synthetic vanadous oxide of described a kind of serialization, the used reducing gas of multicell boiling reactor is a kind of or its gas mixture of carbon monoxide, hydrogen, Sweet natural gas, petroleum refinery's gas, synthetic gas, blast furnace gas.
The method of the synthetic vanadous oxide of described a kind of serialization, reaction end gas are after cyclonic separator separates, and wherein 0-30% partly circulates and fresh feed gas is mixed into reactor bottom, behind the rest part preheating solid material, separates the CO that removes wherein
2Or H
2Impurity such as O return reactor.
The method of the synthetic vanadous oxide of described a kind of serialization, reaction reducing gas through the preheating of vanadous oxide product jar, are heated to 600-750 ℃ by process furnace earlier again.
Advantage of the present invention and effect are:
The present invention compares multicell boiling reactor multicellular and has the back-mixing that has reduced material with common fluidization Reaktionsofen, improved the quality of product, forms the production technique of serialization.Because the gas reduction of barium oxide does not belong to rapid reaction, need the certain reaction time, the multicell boiling reactor can be controlled the reaction times of material in reactor preferably makes raw material can access sufficient reaction, reducing gas contacts more abundant with solid material simultaneously, make the mass-transfer efficiency between gas-solid improve greatly, reaction rate accelerates is compared temperature of reaction with kiln rotaring process and is decreased.Owing to there is not dynamic seal under the hot conditions, though therefore use in the reaction or process in produce toxic gas such as CO, production process also can realize safety in production.The heat of reaction solid phase prod and reaction end gas rationally utilizes, and has improved the service efficiency of energy.The recycling of circulation of the part of reaction end gas and unreacting gas has improved the utilising efficiency of reducing gas, has reduced the gas unit consumption of device, has also reduced the raw material use cost of product.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings.
Sequence number explanation among the figure: 1 multicell boiling reactor, 2 primary cyclones, 3 secondary cyclones.
The concrete steps of the synthetic vanadous oxide method of serialization are:
Raw material many (gathering) ammonium vanadate or Vanadium Pentoxide in FLAKES are after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 600-750 ℃, the reducing gas fluidisation of solid material after the preheating of the multicell boiling reactor 1 bottom feeding of associating, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of material in multicell boiling reactor 1 is 10-30 min, and through the reducing gas reduction, the final material reduction generates vanadous oxide and enters the product jar from the 1 outlet outflow of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar cools off through the fresh reactant reducing gas, fresh reduction reaction gas is heated, further arrive 600-750 ℃ by heater heats, enter multicell boiling reactor 1 fluidisation, the reduction solid material, and then enter from cyclonic separator 2,3 isolate solid particulate wherein, the 0-30% recirculation of tail gas discharged enters well heater and is warmed up to 600-750 ℃, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material, enter gas separation unit then, separate the impurity of removing wherein, enter into vanadous oxide product jar cooling vanadous oxide product again, and be mixed into multicell boiling reactor 1 reduction raw material many (gathering) ammonium vanadate with fresh feed gas.
Reducing gas is a kind of or its gas mixture of carbon monoxide, hydrogen, Sweet natural gas, petroleum refinery's gas, synthetic gas, blast furnace gas.
Embodiment 1:
Raw material many (gathering) ammonium vanadate is after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 750 ℃, the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 750 ℃ a reducing gas CO fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 15 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar cools off through fresh reducing gas CO, fresh reducing gas CO is heated, further by heater heats to 750 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter from cyclonic separation 2,3 isolate solid particulate wherein, 20% recirculation of tail gas discharged enters 750 ℃ of well heaters, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate, enter gas separation unit then, separate and remove wherein CO
2Deng impurity, enter into vanadous oxide product jar cooling vanadous oxide product again and be mixed into multicell boiling reactor 1 reduction raw material many (gathering) ammonium vanadate with fresh CO.The content of vanadium of vanadous oxide product can reach 67.6%.
Embodiment 2:
Raw material many (gathering) ammonium vanadate enters multicell boiling reactor 1 after preheating, the temperature of multicell boiling reactor 1 is controlled at 620 ℃, and the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 620 ℃ reducing gas H
2Fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 10 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter the part vanadous oxide product of cyclonic separator 2,3 with reaction end gas, after separating, also enter into the product jar.Vanadous oxide product in the product jar is through fresh reducing gas H
2Cooling, fresh reducing gas H
2Be heated, further by heater heats to 620 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter the solid particulate of isolating wherein from cyclonic separator 2,3, enter solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate again, enter gas separation unit then, separate the impurity H that removes wherein
2O, enter into again vanadous oxide product jar cooling vanadous oxide product and with fresh H
2Be mixed into multicell boiling reactor 1 reduction raw material many (gathering) ammonium vanadate.The content of vanadium of vanadous oxide product can reach 67.7%.
Embodiment 3:
Raw material many (gathering) ammonium vanadate is after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 650 ℃, the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 650 ℃ a Sweet natural gas fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 12 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar is through new Sweet natural gas cooling, fresh Sweet natural gas is heated, further by heater heats to 650 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter the solid particulate of isolating wherein from cyclonic separation 2,3,10% recirculation of tail gas discharged enters 650 ℃ of well heaters, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate, enter gas separation unit then, separate and remove wherein CO
2And H
2Impurity such as O enter into vanadous oxide product jar cooling vanadous oxide product again and are mixed into multicell boiling reactor 1 reduction raw material many (gathering) ammonium vanadate with fresh Sweet natural gas.The content of vanadium of vanadous oxide product can reach 67.4%.
Embodiment 4:
The raw material Vanadium Pentoxide in FLAKES is after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 720 ℃, the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 720 ℃ a synthetic gas fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 15 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar cools off through fresh synthesis gas, synthetic gas is heated, further by heater heats to 720 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter the solid particulate of isolating wherein from cyclonic separation 2,3,30% recirculation of tail gas discharged enters 720 ℃ of well heaters, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate, enter gas separation unit then, separate and remove wherein CO
2And H
2Impurity such as O enter into vanadous oxide product jar cooling vanadous oxide product again and are mixed into multicell boiling reactor 1 reduction raw material Vanadium Pentoxide in FLAKES with fresh synthesis gas.
Embodiment 5:
Raw material many (gathering) ammonium vanadate is after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 670 ℃, the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 670 ℃ reducing gas (Sweet natural gas is pressed 1 to 3 blended gas mixture with a petroleum refinery's gas) fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 15 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar cools off through fresh reducing gas, fresh reducing gas is heated, further by heater heats to 670 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter from cyclonic separation 2,3 isolate solid particulate wherein, 25% recirculation of tail gas discharged enters 670 ℃ of well heaters, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate, enter gas separation unit then, separate the impurity of removing wherein, enter into vanadous oxide product jar cooling vanadous oxide product again, and be mixed into multicell boiling reactor 1 reduction raw material many (gathering) ammonium vanadate with fresh feed gas.The content of vanadium of vanadous oxide product can reach 66.9%.
Embodiment 6:
Raw material many (gathering) ammonium vanadate is after preheating, enter multicell boiling reactor 1, the temperature of multicell boiling reactor 1 is controlled at 750 ℃, the temperature that solid material feeds through multicell boiling reactor 1 bottom of associating is 750 ℃ a blast furnace gas fluidisation, solid materials begins to move by the chamber from first fluidising chamber of multicell boiling reactor 1 ingress, the residence time of solid materials in multicell boiling reactor 1 is 25 min, raw material many (gathering) ammonium vanadate finally is reduced to vanadous oxide, the vanadous oxide that reduction generates enters into the product jar from 1 outlet of multicell boiling reactor, be the vanadous oxide powder-product of black, enter cyclonic separator 2 with reaction end gas, 3 part vanadous oxide product also enters into the product jar after separating.Vanadous oxide product in the product jar cools off through fresh blast furnace gas, fresh blast furnace gas is heated, further by heater heats to 750 ℃, enter multicell boiling reactor 1 fluidisation, reduction solid many (gathering) ammonium vanadate, and then enter from cyclonic separation 2,3 isolate solid particulate wherein, 30% recirculation of tail gas discharged enters 750 ℃ of well heaters, enter into multicell boiling reactor 1 again and participate in reaction, rest part enters solid material hold-up vessel preheating solid material many (gathering) ammonium vanadate, enters combustion unit recovery heating unit then heat is provided.
Claims (6)
1. the method for the synthetic vanadous oxide of a serialization, it is characterized in that, this method comprises following process: raw material many (gathering) ammonium vanadate or Vanadium Pentoxide in FLAKES are after preheating, enter the multicell boiling reactor, the temperature of reactor is controlled at 600-750 ℃, the reducing gas fluidisation of solid material after the preheating that the reactor bottom of associating feeds, solid materials begins to move by the chamber from first fluidising chamber of Reactor inlet, the residence time of material in reactor is 10-30 min, and through the reducing gas reduction, the final material reduction generates vanadous oxide and enters the product jar from the reactor outlet outflow, be the vanadous oxide powder-product of black, enter the part vanadous oxide product of cyclonic separator with reaction end gas, after separating, also enter into the product jar.
2. the method for the synthetic vanadous oxide of a kind of serialization according to claim 1, it is characterized in that: reactor is the multicell boiling reactor, fluidising chamber is 10-20.
3. the method for the synthetic vanadous oxide of a kind of serialization according to claim 1, it is characterized in that: raw material many (gathering) ammonium vanadate or Vanadium Pentoxide in FLAKES are through being preheating to 300-400 ℃, and the used thermal source of preheating is the tail gas of cyclonic separator.
4. the method for the synthetic vanadous oxide of a kind of serialization according to claim 1, it is characterized in that: the used reducing gas of multicell boiling reactor is a kind of or its gas mixture of carbon monoxide, hydrogen, Sweet natural gas, petroleum refinery's gas, synthetic gas, blast furnace gas.
5. the method for the synthetic vanadous oxide of a kind of serialization according to claim 1, it is characterized in that: reaction end gas is after cyclonic separator separates, wherein 0-30% partly circulates and fresh feed gas is mixed into reactor bottom, behind the rest part preheating solid material, separates the CO that removes wherein
2Or H
2Impurity such as O return reactor.
6. the method for the synthetic vanadous oxide of a kind of serialization according to claim 1 is characterized in that: the reaction reducing gas through the preheating of vanadous oxide product jar, is heated to 600-750 ℃ by process furnace earlier again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010614020XA CN102092787B (en) | 2010-12-30 | 2010-12-30 | Method for continuously synthesizing vanadium trioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010614020XA CN102092787B (en) | 2010-12-30 | 2010-12-30 | Method for continuously synthesizing vanadium trioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102092787A true CN102092787A (en) | 2011-06-15 |
| CN102092787B CN102092787B (en) | 2012-07-18 |
Family
ID=44126078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010614020XA Expired - Fee Related CN102092787B (en) | 2010-12-30 | 2010-12-30 | Method for continuously synthesizing vanadium trioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102092787B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583537A (en) * | 2012-02-27 | 2012-07-18 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN103663555A (en) * | 2012-09-19 | 2014-03-26 | 大连博融新材料有限公司 | Granular vanadium oxide and production method thereof |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| CN104445401A (en) * | 2013-09-25 | 2015-03-25 | 攀钢集团攀枝花钢钒有限公司 | Vanadium trioxide for vanadium alloy smelting and preparation method thereof |
| WO2016018165A1 (en) * | 2014-07-31 | 2016-02-04 | Instituto Superior Técnico | Simplified process for preparing electrolyte for vanadium redox batteries |
| CN105969984A (en) * | 2016-05-16 | 2016-09-28 | 武汉理工大学 | Preparation method of vanadium trioxide |
| CN106006735A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid |
| CN107055611A (en) * | 2017-03-02 | 2017-08-18 | 河钢股份有限公司承德分公司 | A kind of method of link production vanadic anhydride and vanadium trioxide |
| CN107434259A (en) * | 2017-08-09 | 2017-12-05 | 河钢股份有限公司承德分公司 | A kind of method by preparing vanadium trioxide containing vanadium solution |
| CN111892085A (en) * | 2020-07-21 | 2020-11-06 | 河北宏钛科技有限公司 | Vanadium trioxide preparation system and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3650680A (en) * | 1964-04-07 | 1972-03-21 | Teeg Research Inc | Processes for obtaining vanadium suboxides |
| CN1118765A (en) * | 1994-09-15 | 1996-03-20 | 攀枝花钢铁(集团)公司 | Method for producing V2O3 |
-
2010
- 2010-12-30 CN CN201010614020XA patent/CN102092787B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3650680A (en) * | 1964-04-07 | 1972-03-21 | Teeg Research Inc | Processes for obtaining vanadium suboxides |
| CN1118765A (en) * | 1994-09-15 | 1996-03-20 | 攀枝花钢铁(集团)公司 | Method for producing V2O3 |
Non-Patent Citations (1)
| Title |
|---|
| 《制药设备与工程设计》 20040731 朱宏吉等 卧式多室流化床干燥器 化学工业出版社 , 第1版 1 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583537A (en) * | 2012-02-27 | 2012-07-18 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN102583537B (en) * | 2012-02-27 | 2014-03-05 | 南通汉瑞实业有限公司 | Production process of vanadium trioxide |
| CN103663555A (en) * | 2012-09-19 | 2014-03-26 | 大连博融新材料有限公司 | Granular vanadium oxide and production method thereof |
| CN103663555B (en) * | 2012-09-19 | 2015-11-18 | 大连博融新材料有限公司 | A kind of Granular vanadium oxide and production method thereof |
| CN104445401A (en) * | 2013-09-25 | 2015-03-25 | 攀钢集团攀枝花钢钒有限公司 | Vanadium trioxide for vanadium alloy smelting and preparation method thereof |
| CN104118910A (en) * | 2014-06-24 | 2014-10-29 | 中国科学院过程工程研究所 | Method for selectively preparing vanadium oxides and recovering hydroxides through vanadate hydrogen reduction method |
| WO2016018165A1 (en) * | 2014-07-31 | 2016-02-04 | Instituto Superior Técnico | Simplified process for preparing electrolyte for vanadium redox batteries |
| CN105969984A (en) * | 2016-05-16 | 2016-09-28 | 武汉理工大学 | Preparation method of vanadium trioxide |
| CN106006735A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method for preparing vanadium trioxide through bone coal vanadium extracting vanadium-rich liquid |
| CN107055611A (en) * | 2017-03-02 | 2017-08-18 | 河钢股份有限公司承德分公司 | A kind of method of link production vanadic anhydride and vanadium trioxide |
| CN107434259A (en) * | 2017-08-09 | 2017-12-05 | 河钢股份有限公司承德分公司 | A kind of method by preparing vanadium trioxide containing vanadium solution |
| CN111892085A (en) * | 2020-07-21 | 2020-11-06 | 河北宏钛科技有限公司 | Vanadium trioxide preparation system and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102092787B (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102092787B (en) | Method for continuously synthesizing vanadium trioxide | |
| CN102363837B (en) | A kind of powdery manganese oxide ore fluidization low-temperature reduction method | |
| CN101880059B (en) | Method for producing vanadium trioxide by adopting fluidized bed reactor | |
| CN102557134B (en) | Fluidized reduction furnace for producing high-purity vanadium trioxide and production method | |
| CN103130279B (en) | A kind of method of chlorination production high purity vanadic anhydride | |
| CN103667571B (en) | System and method of fluidized direct reduction of iron ore concentrate powder | |
| CN109621847B (en) | System and method for coating lithium ion battery anode material by compounding carbon and metal oxide | |
| AU2016212453B2 (en) | System and method for producing high-purity vanadium tetraoxide powder | |
| CA2973499A1 (en) | System and method for producing high-purity vanadium pentoxide powder | |
| CN105984900A (en) | System and method for preparing high-purity vanadium pentoxide powder | |
| CN103708461B (en) | The method preparing calcium carbide | |
| CN104197323A (en) | Inner and outer circulation coupled device for separating carbon dioxide by burning coal-based chemical loopings | |
| CN101844809A (en) | System and method for producing vanadium trioxide | |
| CN105861080A (en) | Rapid catalytic pyrolysis system of biomass downward bed and biomass pyrolysis method | |
| CN104878193A (en) | Fluidized reduction roasting system and method for low-grade manganese oxide ores | |
| CN102427128B (en) | Device and process for manufacturing positive/negative electrode material of lithium battery | |
| CN1048038C (en) | Process for treating ash | |
| EP1529121A1 (en) | Process and apparatus for the direct reduction of iron oxides in an electrothermal fluidized bed and resulant product | |
| CN100457635C (en) | Production process of vanadium sesquioxide powder | |
| CN205803398U (en) | A kind of low order fine coal hydrogenation pressurization fast low temperature destructive distillation device | |
| CN115490249B (en) | Method and system for preparing metal oxide powder and regenerating nitric acid by fractional pyrolysis of nitrate | |
| CN103803650B (en) | A kind of method of producing molybdic oxide | |
| JPS6251900B2 (en) | ||
| CN101962207A (en) | Method for preparing vanadium trioxide powder | |
| CN108622935B (en) | System and method for preparing high-purity low-valence vanadium oxide by efficient clean chlorination method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120718 Termination date: 20171230 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |