CN111004964A - A kind of method for producing vanadium nitrogen alloy - Google Patents
A kind of method for producing vanadium nitrogen alloy Download PDFInfo
- Publication number
- CN111004964A CN111004964A CN202010039364.6A CN202010039364A CN111004964A CN 111004964 A CN111004964 A CN 111004964A CN 202010039364 A CN202010039364 A CN 202010039364A CN 111004964 A CN111004964 A CN 111004964A
- Authority
- CN
- China
- Prior art keywords
- kiln
- vanadium
- kiln chamber
- heating
- heating section
- 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
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910001199 N alloy Inorganic materials 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 139
- 238000010438 heat treatment Methods 0.000 claims abstract description 105
- 239000002994 raw material Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 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 10
- 239000011819 refractory material Substances 0.000 claims abstract description 10
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 20
- 230000002829 reductive effect Effects 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 230000001960 triggered effect Effects 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000628 Ferrovanadium Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 238000005121 nitriding Methods 0.000 abstract description 8
- 238000005485 electric heating Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000002354 daily effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000019580 granularity Nutrition 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 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 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- VUPFAQJTTFZEQH-UHFFFAOYSA-N [N].[C].[V] Chemical compound [N].[C].[V] VUPFAQJTTFZEQH-UHFFFAOYSA-N 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/02—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/10—Rotary-drum furnaces, i.e. horizontal or slightly inclined internally heated, e.g. by means of passages in the wall
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
- F27B7/32—Arrangement of devices for charging
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
- F27B7/32—Arrangement of devices for charging
- F27B7/3205—Charging
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
- F27B7/33—Arrangement of devices for discharging
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
- F27B7/34—Arrangements of heating devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories or equipment specially adapted for rotary-drum furnaces
- F27B7/42—Arrangement of controlling, monitoring, alarm or like devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/02—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type
- F27B2007/022—Rotary-drum furnaces, i.e. horizontal or slightly inclined of multiple-chamber or multiple-drum type the drum having a non-uniform section along its length
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明提供了一种生产钒氮合金的方法，是将氧化钒与碳质还原剂混合成型形成原料球，将原料球进料到直热式回转窑中，在氮气气氛下原料球依次经过直热式回转窑的升温段、加热段和降温段然后出窑。通过在回转窑窑膛壁用耐材设置炒料槽、在窑膛出口设置挡料板，将回转窑加热段中的物料填充率提高到25%以上，并对加热段中的原料球通入2000安培以上的电流直接对原料球自身通电使其发热并升温到1200℃以上，还原氮化生成钒氮合金。本发明的优点是电热效率高、电耗低、生产连续稳定，产品氮含量高、密度大,生产过程安全环保。The invention provides a method for producing vanadium-nitrogen alloy, which comprises the steps of mixing vanadium oxide and carbonaceous reducing agent to form raw material balls, feeding the raw material balls into a direct-heating rotary kiln, and in a nitrogen atmosphere, the raw material balls pass through a direct-heating rotary kiln in sequence. The heating section, heating section and cooling section of the thermal rotary kiln are then discharged from the kiln. The material filling rate in the heating section of the rotary kiln is increased to more than 25% by setting the frying trough with refractory materials on the wall of the rotary kiln and the baffle plate at the outlet of the kiln, and the raw material balls in the heating section are fed into the rotary kiln. The current above 2000 amperes directly energizes the raw material ball itself to make it heat up and heat up to above 1200 ℃, reducing and nitriding to form a vanadium-nitrogen alloy. The invention has the advantages of high electric heating efficiency, low power consumption, continuous and stable production, high nitrogen content and high density in the product, and safe and environmentally friendly production process.
Description
Technical Field
The invention belongs to the field of ferrous metallurgy, and relates to a method for producing a vanadium-nitrogen alloy.
Background
The vanadium-nitrogen alloy is an excellent steel-making additive, and can obviously raise and improve comprehensive mechanical property and welding property of steel. Compared with the use of ferrovanadium, the method can save 20 to 40 percent of vanadium resources, thereby reducing the production cost of steel making. Taking the construction industry as an example, the new three-grade steel bar produced by using the vanadium-nitrogen alloying technology not only enhances the safety, shock resistance, toughness and welding performance of buildings due to the improvement of the strength, but also has the advantages of saving steel by 10 to 12 percent compared with the common steel bar, and the like.
U.S. Pat. No. 3,982,181 Kg of V was introduced into U.S. Pat. No. 3,983,992 by J.H. Dowaning et al in 19672O562Kg of carbon powder, 4.1Kg of gum resin and 3Kg of iron powder were mixed and molded under 20.68MPa, the sample size was 51X 38 mm. And (3) carrying out carbon reduction at 1385 ℃ under 22.7Pa, reducing the vacuum degree of the system to 2666Pa during reduction, keeping the vacuum degree for 60 hours, and reducing the vacuum degree of the system to 22.7Pa again, namely marking the end of the reduction process. At this time, the furnace is stopped from heating, and when the sample is cooled to room temperature, the sample is taken out of the furnace, and vanadium carbide (VCx) is obtained. When the vacuum degree is restored to 22.7Pa, the furnace is not stopped heating and the temperature is reduced to 1100 ℃, nitrogen is sent into the furnace and the partial pressure of nitrogen is kept at PN2700 to 1000 Pa. Nitriding at constant temperature for 2h, adjusting the furnace temperature to 1000 ℃, nitriding for 6h, stopping heating by an electric furnace, cooling to room temperature in a helium atmosphere, and discharging, wherein the chemical composition of the product is as follows: 78.75% V-10.5% C-7.3% N, so this VN is also referred to as VCN.
1999 Wang Gong Dai et al, with V2O5And forming with an active carbon briquette, carrying out carbothermic reduction under experimental conditions, firstly reducing to generate VC under the vacuum of 1673K and 1.333Pa, then introducing nitrogen, and nitriding under the nitrogen pressure of 101325Pa for 1.5 hours to obtain samples of 86% V, 7% C, 9.069% -9.577% N and 2% O. In order to improve the strength of the vanadium-nitrogen alloy, 3 percent of iron powder is added into the raw materials.
The two processes require high vacuum degree, the equipment cost and the running cost are higher, and the heating mode of the reaction process is not involved.
In 1977 United states Co, United states carbide, Inc., was disclosed in U.S. Pat. No. 4,40814, to V2O3And reducing and nitriding the vanadium-nitrogen alloy and carbon at 1100-1500 ℃ to produce the vanadium-nitrogen alloy containing 12% of nitrogen.
2001 Sunshun Hui et al in Chinese patent CN1422800A, powdered vanadium oxide, carbonaceous powder and binder are mixed uniformly and pressed into blocks, formed, the formed material is continuously added into a production furnace, ammonia gas or nitrogen gas is introduced into the production furnace as reaction and protective gas, the production furnace is heated to 1000-1800 ℃, the material is carbonized and nitrogenized in the furnace, the duration is less than 3 hours, the material is cooled to 100-250 ℃ in protective atmosphere before being taken out of the furnace, and vanadium-nitrogen alloy products are obtained.
The two processes described above do not address the problem of the heating pattern, and are actually heating in the manner required by the resistance pusher kiln.
The two processes described above and the process disclosed in CN1587064 are actually implemented with V2O3As raw material, if V is used2O5As the raw material is not subjected to the pre-reduction process, the raw material can be melted and hardened at 670 ℃, namely, the melting point of the raw material is close to the melting point of the raw material, so that the subsequent reduction process is prevented and the product agglomeration phenomenon is formed. And the lower the oxidation state of vanadium in the vanadium feedstock, the higher the feedstock cost.
U.S. Pat. No. 4,000,62057 to Goddard et al, United states of United carbide corporation, 1985, discloses the higher oxides of vanadium V2O5Or ammonium vanadate is used as a raw material, mixed gas (nitrogen and ammonia) is used as a reducing agent and a nitriding agent, the mixed gas is firstly pre-reduced for 1 hour at 675-700 ℃, low-melting-point high-valence vanadium oxide is reduced to high-melting-point low-valence vanadium oxide, then reduction and nitriding are simultaneously carried out for 3-4 hours at 950 ℃, products with 73.3% of V, 12.6% of N and 15.35% of O can be obtained, and then a great amount of oxygen is removed at 1400 ℃ by using a carbothermic reduction method to obtain a carbon vanadium nitrogen alloy product. The process is subjected to pre-reduction, temperature reduction, batching and high-temperature carbon thermal reduction, so that the energy consumption is high, the production efficiency is low, and the heating mode is not described.
Galesic et al (Thin Solid Films, 349(1999) 14-18) published 1999 a method for producing vanadium-nitrogen alloy Films at 1100 ℃ using rapid thermal processing.
In 2000, Prabhat Kumar Tripathy in J. Mater. chem., 2001, 11, 691-695 discloses the use of V at 1500 ℃2O5As raw materials of carbon heat and N2Reducing to produce the vanadium-nitrogen alloy.
Both of the above processes are small-scale non-continuous processes of investigational nature.
The vanadium-nitrogen alloy production method disclosed in Chinese patents CNl478915A and CN2690415 is to pre-reduce vanadium pentoxide and carbon powder into VO at 400-800 ℃ after briquetting2Or V2O3, and finally reducing the alloy into vanadium-nitrogen alloy at 1000-1500 ℃. Because the mixture of the vanadium oxide raw material and the carbon powder is good in magnetic conductivity after being pressed into a block and is difficult to heat in an induction mode, the process adopts the heating mode that the alloy resistance wire heats in a resistance heating mode and combines the induction heating mode in the pre-reduction process, and the process is different from the heating mode that the electrode directly supplies electricity to the solid raw material in the pre-reduction and reduction nitridation processes. In addition, in order to avoid the blockage of the hearth by the materials, the process actually uses an additional graphite sagger to contain the materials, and then uses the graphite sagger to move in the furnace to complete the pre-reduction and reduction nitridation processes. Therefore, the production process is complicated, the cost of the graphite sagger is increased, the inner diameter of the furnace hearth of the furnace is smaller and is generally not more than 400mm, and the thermal efficiency is relatively lower. CN1757606A and CN101082089 also mention the use of induction furnaces.
Suizitong in 2003 and the like is disclosed in Chinese patent CNl212416A, and vanadium-nitrogen alloy is produced by reducing and nitriding at 1300-1500 ℃ for 0.5-8 h in the presence of a density enhancer. The process does not involve the problem of the mode of addition, and is actually completed by heating the pushed slab kiln with a resistance wire.
In 1973, Servaas middlelhoek et al disclose in US3745209 that vanadium pentoxide is used as a raw material, and the vanadium-nitrogen alloy is synthesized by reductive nitridation of ammonia gas and natural gas at 800-1250 ℃. The process is not carried out by carbothermic reduction, and is actually completed by using a resistance type rotary kiln.
Chinese patents CN1562770 and CNl644510 disclose that vanadium-nitrogen alloy containing about 14% nitrogen is produced by using vanadium trioxide as raw material at a temperature above 1420 ℃ by microwave heating. The microwave heating has high thermal efficiency, but because the power of a single microwave tube cannot be too large, the power of the single microwave tube is generally larger to achieve 5kw of power, under the condition that the power density of the whole kiln is required to be larger, a plurality of microwave tubes are generally adopted, but when the number of the microwave tubes is too large, the different microwave tubes are easy to heat mutually, so that the service life of the microwave tubes is reduced, and the thermal efficiency is reduced. Too large a furnace results in uneven heating due to limited microwave penetration (typically less than 5 cm). The above two reasons make the production scale of a single device limited. The annual production of about 100 tons of vanadium-nitrogen alloy is generally achieved by a single furnace. In addition, in the production process of the vanadium-nitrogen alloy, along with the deepening of the reduction degree, the reaction medium has the property of metal more and more, so that the reflection of the medium to microwaves is stronger in the later reaction stage, the reaction is not easy to complete, and more oxygen can be remained in the product. Unlike the heating mode of the present invention in which electricity is directly applied to the solid raw material.
Zhengchen collusion in 2002 is disclosed in Chinese patent CNl380247A (NH)4)5[(VO)6(CO3)4(OH)9]10H2And O is used as a raw material, and vanadium-nitrogen alloy is synthesized at 750-1100 ℃.
High curtain, 2003, et al, in chinese patent CNl431146A, disclose a special process for producing vanadium pentoxide (V) containing a crystal water2O5·H2O, the mass percentage of the crystal water is about 9%) as a raw material, and the vanadium-nitrogen alloy is produced by keeping the temperature of 500-800 ℃ for 3-5 hours.
In 1991 Arai, Tohru, in EP471276, disclosed the vapor deposition of vanadium-nitrogen alloys on metal surfaces at 700 ℃.
The three methods adopt special synthetic raw materials, and the raw materials are difficult to obtain and have high price.
Christopher Allen Bennett in 2002, and its doctor's paper H. Kwon, S. Choi et al in Journal of Catalysis 184, 236-246 (1999), disclosed that vanadium-nitrogen alloys with high specific surface area for use as catalysts were produced in trace amounts at 800-1000 ℃. The disadvantage of this process is the production on a thermal analyzer, whose throughput is very small, only in the milligram range.
The current mainstream method for producing vanadium-nitrogen alloy is also a pushed slab kiln method, vanadium oxide and a carbonaceous reducing agent are mixed and pressed into a graphite crucible and then are intermittently pushed into a pushed slab kiln for heating, a 46m long double-channel pushed slab kiln is generally heated by a silicon-molybdenum rod, about 4 tons of vanadium-nitrogen alloy is produced daily, the best pushed slab kiln has the advantages that the power consumption of the vanadium-nitrogen alloy per ton is 4000-5000 kwh, 1000 crucibles are consumed in one pushed slab kiln per year, the value is ￥ 80-100 ten thousand, after the temperature is raised to the reaction temperature, if the production is stopped and reduced to below 900 ℃, the silicon-molybdenum rod is completely damaged, a 46m double-pushed slab kiln has the total price of the silicon-molybdenum rod of about ￥ 20 ten thousand, after the vanadium-nitrogen product is discharged from the kiln, the graphite crucible needs to be manually removed, the vanadium-nitrogen alloy is knocked off, sorted and then packaged, and partial fine crushed aggregates can be produced in the knocking-off process, and the national standard of the vanadium-nitrogen alloy stipulates that the ratio of the fine crushed aggregates with.
In summary, because the high-valence vanadium oxide raw material has poor electrical conductivity and magnetic property, in the existing production method, the heating mode of an electric heating element heating furnace such as an alloy resistance wire, a silicon-carbon rod or a silicon-molybdenum rod is generally adopted for industrial mass production, or the heating mode of heating a graphite lining by induction heating and heating a graphite lining to heat a solid raw material is adopted for heating. There are also small scale devices that use microwave heating. The resistance heating equipment has slow heat transfer and high heat loss, and the power consumption of each ton of vanadium-nitrogen alloy in the double-channel pushed slab kiln process is about 4000-5000 kWh. The microwave heating is not easy to be enlarged, and the reduction nitridation reaction is not complete enough. The induction heating needs to adopt graphite material with good conductivity and high temperature resistance as the lining, and the short wear-resisting life of the graphite lining is always a constraint factor of the long-term operation of the reaction furnace.
After many years of exploration, the inventor successively adopts methods such as an external heating rotary kiln CN1775661A and an induction vertical kiln CN101372321A to produce vanadium-nitrogen alloy, innovatively proposes a method for producing vanadium-nitrogen alloy by directly heating materials through electrification in 2009 for the first time in the world, submits an application of Chinese patent CN103466569A, and unfortunately is rejected. The inventor builds the first practical direct-heating rotary kiln producing 3 tons of vanadium-nitrogen alloy every day in 2012, successfully reaches the standard in 2014 to produce vanadium-nitrogen alloy, and applies for direct-heating rotary kiln patent CN103335513B for producing vanadium-nitrogen alloy in 2013 in the meantime. The inventor improves the direct-heating rotary kiln equipment and the vanadium-nitrogen alloy production process from 2014, further improves the production efficiency, and realizes safe, environment-friendly, continuous and stable production. However, in the process of popularizing the direct-heating rotary kiln equipment and the vanadium-nitrogen alloy production process, a great deal of technical secret is stolen and the patent rights are infringed, and the obtained technical progress is further patented only by disclosing the technical secret, so that the protection is expected to be realized in a patent form.
Disclosure of Invention
The invention aims to provide a vanadium-nitrogen alloy production process which has the advantages of easily obtained raw materials, stable process, high electrothermal efficiency and low energy consumption and takes a vanadium-and-oxygen-containing compound as a raw material. In the direct-heating rotary kiln, materials containing vanadium and carbonaceous reducing agents are directly electrified through positive and negative electrodes, and then the resistance of the materials or the contact resistance between material particles or blocks generates heat under the action of current to heat the materials.
The purpose of the invention is realized as follows: mixing vanadium oxide and a carbonaceous reducing agent to form raw material balls (hereinafter called material balls), feeding the material balls into a direct-heating rotary kiln, sequentially passing the material balls through a heating section, a heating section and a cooling section of the direct-heating rotary kiln under the nitrogen atmosphere, and then discharging the material balls out of the kiln. The material filling rate in the heating section of the rotary kiln is improved to more than 25% by arranging a material frying groove on the wall of the kiln chamber of the rotary kiln and arranging a material baffle plate at the outlet of the kiln chamber, and the raw material ball in the heating section is electrified by more than 2000 amperes of current to heat the raw material ball and raise the temperature to 1200-1600 ℃, so that vanadium-nitrogen alloy is generated by reduction and nitridation.
The specific technical scheme of the invention is as follows:
a method for producing vanadium-nitrogen alloy, mix vanadium oxide and carbonaceous reducing agent raw materials to form the pellet of material, heat it to above 1200 duC to reduce and nitrogenize gradually in the atmosphere of nitrogen, then cool and get vanadium-nitrogen alloy product gradually, characterized by that:
the reduction nitridation process is carried out in a direct-heating rotary kiln device; the direct-heating rotary kiln is provided with a kiln head box, a kiln tail box, a rotary pipe and a refractory material close to the inner wall of the rotary pipe, wherein a cylindrical or prismatic cavity surrounded by the refractory material is a kiln chamber, and the kiln chamber is divided into a kiln chamber feeding hole, a temperature rising section, a heating section, a temperature reducing section and a kiln chamber discharging hole; the material balls reach the kiln chamber feed inlet from a feed channel and enter the kiln chamber, sequentially pass through the temperature rising section, the heating section and the temperature reduction section, are withdrawn from the kiln chamber discharge outlet, fall into a kiln tail box and are temporarily stored and intermittently discharged from the kiln tail box; the nitrogen enters the kiln chamber from a kiln chamber discharge port, sequentially passes through a cooling section, a heating section and a heating section, and is withdrawn from the kiln chamber from a kiln chamber feed port; the rotary pipe at the feed port end of the kiln chamber is in rotary sealing connection with the kiln head box, and the rotary pipe at the discharge port end of the kiln chamber is in rotary sealing connection with the kiln tail box;
positive and negative electrodes, namely a positive electrode and a negative electrode, are fixed on the kiln chamber walls at two ends of the kiln chamber heating section of the directly-heated rotary kiln, the positive electrode and the negative electrode are in contact with the material balls in the kiln chamber, direct current of more than 2000 amperes is introduced into the material balls in the heating section through the positive electrode and the negative electrode, and the material balls are heated by the resistance of the material balls;
the inner wall of the kiln chamber of the direct heating rotary kiln is provided with a material-resisting material and/or an electrode material protruding towards the kiln chamber to form a material-frying groove; a material baffle plate is arranged at the discharge port of the kiln chamber; the material level of the material balls in the kiln chamber is improved through the material frying groove and the material baffle plate, so that the filling rate of the material balls in the heating section is improved to more than 25%; the ratio of the length of the heating section kiln chamber to the equivalent diameter thereof is 5-30;
when the direct-heating rotary kiln is started, namely in the temperature rise process of the heating section of the direct-heating rotary kiln from room temperature to over 1200 ℃, resistance materials capable of generating heat under the condition that the positive electrode and the negative electrode are electrified are placed in the heating section, the resistance materials are electrified and heated, the heating section is preheated to a certain temperature, and then the resistance materials are gradually replaced by the material balls; or the material balls are directly added to the heating section, then a part of the material balls are short-circuited by using a conductive material or the resistance material, and the resistance of the material ball material pile of the heating section is reduced, so that the material ball material pile can be electrified under the voltages of the positive electrode and the negative electrode to heat and raise the temperature. The conductive material is generally a steel bar, or a vanadium-nitrogen alloy product, or a partially reduced raw material ball; of course, it can also be a vanadium-nitrogen alloy product or a mixed material ball pile of partially reduced raw material balls and completely unreduced raw material balls.
Further, a sieve hole pipe is arranged between the kiln chamber discharge hole and the material baffle plate and/or a sieve plate is arranged on a path through which the material passes between the material baffle plate and the temporary storage position of the kiln tail box material. The two ends of the sieve tube are provided with a feed inlet and a discharge outlet. And sieve holes with the same aperture are distributed on the pipe wall of the sieve hole pipe, and the equivalent diameter of each sieve hole is 5-30 mm. When the material balls discharged from the discharge port of the kiln chamber pass through the sieve hole pipe, the large material balls with the granularity larger than the sieve meshes fall into the kiln tail box from the discharge port of the sieve hole pipe, and the fine material balls with the granularity smaller than the sieve meshes fall into the kiln tail box from the sieve meshes. The sieve plate is obliquely arranged on a path where the materials fall to the kiln tail box. Sieve pores with the same size are distributed on the sieve plate, and the equivalent diameter of the sieve pores is between 5 and 30 mm. During the falling process of the material, the material is divided into two parts of large block material and small block material with different particle size ranges. A partition board is arranged in the kiln tail box to separate materials with different particle sizes; more than two discharge ports are correspondingly arranged on the kiln tail box and are respectively used for discharging materials with different particle sizes.
Further, the material ball enters a kiln chamber feed inlet through a feed channel, and a material level detection or observation device is arranged on the feed channel and is higher than the highest point of the kiln chamber feed inlet; when the material level of the material ball falls to the material level detection or observation device, an alarm is triggered and/or manual or automatic mechanical feeding is triggered, or the feeding speed is accelerated during continuous feeding.
Furthermore, the refractory material forming the kiln chamber wall is a non-metallic material with the resistivity more than 5 times that of the material ball in the heating section.
Further, iron oxide or a mixture thereof is added to the material ball in an amount of not more than 100% by weight of vanadium in terms of iron, and an iron-containing vanadium-nitrogen alloy or iron vanadium nitride is produced.
Furthermore, the power applied to the anode and the cathode is an adjustable direct current power supply, the voltage range of the power supply is adjustable between 0V and 200V, and the current range is adjustable between 0 Ampere and 20000 Ampere. The adjustable power supply is suitable for adjusting the large-range change of the material resistance material when the directly-heated rotary kiln is started and the change of the daily output of the stable production.
Further, the pressure of the atmosphere in the kiln chamber is higher than the atmospheric pressure by more than 5Pa at the discharge port of the kiln chamber. The micro-positive pressure in the directly-heated rotary kiln is maintained, air is prevented from being leaked into the kiln, and the sealing requirement between the rotary pipe and the kiln tail box is lowered.
Compared with the prior art, the invention has the following characteristics:
1) the occupied area is less than 18m by 6m, the installed capacity is less than or equal to 450kVA, and the daily output is more than or equal to 4 tons. The pusher kiln length was 46m for comparative equal production.
2) The material directly heats, the heat transfer process from the heating element to the material is avoided, the electric heating efficiency is high, the material balls are uniformly heated, and the power consumption of the product per ton is less than or equal to 3000 kWh. And the power consumption of the pushed slab kiln per ton product with the same yield is 4000-5000 kwh as comparison.
3) Heating elements such as silicon carbide rods and silicon molybdenum rods are not used, and consumables such as graphite crucibles are not used. And the furnace blockage caused by the problems of crucible cracking, scaling and the like can be avoided. These are all the ones of the pusher kiln as a comparison.
4) The start and stop are flexible, and the loss is small. The temperature is raised to the reaction temperature for only 4 days, and the heating power supply is cut off when the vehicle is stopped. The parking can not damage the silicon-molybdenum rod of the silicon-carbon rod. As a comparative pushed slab kiln with the same yield, the temperature needs to be raised for 14-21 days when the kiln is started, and the heating element silicon-molybdenum rod in the high-temperature area needs to be completely replaced when the shutdown temperature is reduced to be below 900 ℃.
5) The temperature of the material is higher than the temperature of the refractory (the highest temperature of the refractory is 60-80 ℃ lower than that of the pushed slab kiln), and the service life of the refractory is long. The pusher kiln as a comparison heats the material and the refractory material indiscriminately, and the temperature of the refractory material is higher than that of the material.
6) The maintenance cost is low, and the overhaul cost is not as much as 1/5 of the pushed slab kiln.
7) The problems of uneven heating of different parts in the pushed slab kiln crucible and poor product consistency are avoided. The product has high density, high nitrogen content and 100 percent of pass rate.
8) The product is discharged without bonding, and the discharged material is a single material ball, so that the product is convenient to package automatically. The pusher kiln products used as comparison need to be moved out of the crucible, and can be unpacked after being manually knocked apart and sorted.
9) The vanadium-nitrogen alloy product has high density, and the density is about 4.0 g/ml. When the vanadium-nitrogen mixed catalyst is added into molten steel during use, the yield of vanadium and nitrogen is greatly improved. The density of the vanadium-nitrogen alloy product produced by the push plate kiln as a comparison is only 3.0-3.5 g/ml.
10) In the vanadium-nitrogen alloy production process, a material frying groove, a material baffle plate and a material level detection device are adopted, so that the material filling rate in the heating section of the kiln chamber of the directly-heated rotary kiln is improved, and compared with the directly-heated rotary kiln process without the material frying groove and the material baffle plate, the filling rate of the heating section is improved by 60-100%, the voltage of the heating section is reduced by 30%, and the power consumption and the gas consumption of a ton product are reduced by more than 40%. Is safer and more energy-saving.
11) And a screening device is arranged between a kiln chamber discharge port and a temporary storage position of kiln tail box materials, and products with different granularities are separated and taken out of the kiln after the products are subjected to granularity classification. The dust and the process of classification after the kiln is taken out are reduced, the production efficiency is improved, and the dust pollution and waste are reduced.
Detailed Description
The specific technical solution of the present invention will now be described with reference to the embodiments. The following examples are merely illustrative of the reliable and effective implementation of the technical solution of the present invention, but the technical solution of the present invention is not limited to the following examples.
Example 1
3000kg of flaky vanadium pentoxide with the content of more than 98 percent, 855kg of graphite and 10kg of iron scale are proportioned, all the raw materials are crushed, mixed and briquetted to form material balls. Intermittently adding the material balls into a feeding channel of the direct heating rotary kiln. When the material in the feeding channel falls to the position of the material level detection device, the alarm is triggered, and the material is fed again manually. The finely crushed materials fall to the temporary storage position of the finely crushed materials in the kiln tail box through the sieve holes of the sieve hole pipe. Along with the rotation of the rotary kiln, the material level of the material balls in the feeding channel descends, and the material balls sequentially enter a kiln chamber feeding port, a preheating section, a heating section, a cooling section, a kiln chamber discharging port and a sieve hole pipe feeding port of the direct-heating rotary kiln, cross a material baffle plate and fall to a large-granularity material temporary storage position in a kiln tail box. Discharging from the kiln tail box every half hour or 1 hour. The maximum temperature at which the batch passed through the heating zone was 1500 ℃. The kiln chamber of the direct heating rotary kiln is provided with a frying trough built by refractory materials. The filling rate of the material balls in the heating section is about 45%, the voltage between the anode and the cathode at two ends of the heating section is about 70V, the current is about 4500A, and the power is stabilized at 310-320 kw. The equivalent inner diameter of the heating section kiln chamber is 60cm (because a stir-frying groove is arranged in the kiln chamber, the kiln chamber can be cylindrical or prismatic, and the like, so that the kiln chamber is not a regular cylinder, and is expressed by the equivalent inner diameter), and the length of the heating section kiln chamber is 6.6 m. The daily yield of vanadium-nitrogen alloy is 3-3.5 tons, and the typical product analysis result is as follows: the V content is 77.2%, the nitrogen content is 15.7%, and the carbon content is 4.1%. The density of the product is controllable between 3.6 and 4.2 g/ml. The proportion of the fine crushed aggregates is about 3 percent.
Example 2
On the basis of the embodiment 1, the voltage between the anode and the cathode at the two ends of the heating section is about 70V, the current is about 6000A, and the power is stabilized at 420 kw. The equivalent inner diameter of the heating section kiln chamber is 70cm (because a stir-frying groove is arranged in the kiln chamber, the kiln chamber can be cylindrical or prismatic, and the like, so that the kiln chamber is not a regular cylinder, and is expressed by the equivalent inner diameter), and the length of the heating section kiln chamber is 7 m. The daily yield of vanadium-nitrogen alloy is 4-4.5 tons, and the analysis result of a typical product is as follows: the V content is 77.5%, the nitrogen content is 18.7%, and the carbon content is 2.1%. The density of the product is controllable between 3.6 and 4.2 g/ml. The proportion of the fine crushed aggregates is about 3 percent.
Claims (7)
1. A method for producing vanadium-nitrogen alloy, mix vanadium oxide and carbonaceous reducing agent raw materials to form the pellet of material, heat it to above 1200 duC to reduce and nitrogenize gradually in the atmosphere of nitrogen, then cool and get vanadium-nitrogen alloy product gradually, characterized by that:
the reduction nitridation process is carried out in a direct-heating rotary kiln device; the direct-heating rotary kiln is provided with a kiln head box, a kiln tail box, a rotary pipe and a refractory material close to the inner wall of the rotary pipe, wherein a cylindrical or prismatic cavity surrounded by the refractory material is a kiln chamber, and the kiln chamber is divided into a kiln chamber feeding hole, a temperature rising section, a heating section, a temperature reducing section and a kiln chamber discharging hole; the material balls reach the kiln chamber feed inlet from a feed channel and enter the kiln chamber, sequentially pass through the temperature rising section, the heating section and the temperature reduction section, are withdrawn from the kiln chamber discharge outlet, fall into a kiln tail box and are temporarily stored and intermittently discharged from the kiln tail box; the nitrogen enters the kiln chamber from a kiln chamber discharge port, sequentially passes through a cooling section, a heating section and a heating section, and is withdrawn from the kiln chamber from a kiln chamber feed port; the rotary pipe at the feed port end of the kiln chamber is in rotary sealing connection with the kiln head box, and the rotary pipe at the discharge port end of the kiln chamber is in rotary sealing connection with the kiln tail box;
positive and negative electrodes, namely a positive electrode and a negative electrode, are fixed on the kiln chamber walls at two ends of the kiln chamber heating section of the directly-heated rotary kiln, the positive electrode and the negative electrode are in contact with the material balls in the kiln chamber, direct current of more than 2000 amperes is introduced into the material balls in the heating section through the positive electrode and the negative electrode, and the material balls are heated by the resistance of the material balls;
the inner wall of the kiln chamber of the direct heating rotary kiln is provided with a material-resisting material and/or an electrode material protruding towards the kiln chamber to form a material-frying groove; a material baffle plate is arranged at the discharge port of the kiln chamber; the material level of the material balls in the kiln chamber is improved through the material frying groove and the material baffle plate, so that the filling rate of the material balls in the heating section is improved to more than 25%; the ratio of the length of the heating section kiln chamber to the equivalent diameter thereof is 5-30;
when the direct-heating rotary kiln is started, namely in the temperature rise process of the heating section of the direct-heating rotary kiln from room temperature to over 1200 ℃, resistance materials capable of generating heat under the condition that the positive electrode and the negative electrode are electrified are placed in the heating section, the resistance materials are electrified and heated, the heating section is preheated to a certain temperature, and then the resistance materials are gradually replaced by the material balls; or the material balls are directly added to the heating section, then a part of the material balls are short-circuited by using a conductive material or the resistance material, and the resistance of the material ball material pile of the heating section is reduced, so that the material ball material pile can be electrified under the voltages of the positive electrode and the negative electrode to heat and raise the temperature.
2. A method for producing vanadium-nitrogen alloy according to claim 1, characterized in that:
a sieve hole pipe is arranged between the kiln chamber discharge hole and the material baffle plate and/or a sieve plate is arranged on a path through which materials pass between the material baffle plate and the temporary material storage position of the kiln tail box;
the pipe orifices at the two ends of the sieve pore pipe are a feed inlet and a discharge outlet of the sieve pore pipe; sieve pores with the same pore diameter are distributed on the pipe wall of the sieve pore pipe, and the equivalent diameter of each sieve pore is 5-30 mm; when the material balls discharged from the discharge port of the kiln chamber pass through the sieve hole pipe, large material balls with the granularity larger than that of the sieve holes fall into the kiln tail box from the discharge port of the sieve hole pipe, and fine material balls with the granularity smaller than that of the sieve holes fall into the kiln tail box from the sieve holes;
the sieve plate is obliquely arranged on a path of the material falling to the kiln tail box; sieve pores with the same size are distributed on the sieve plate, and the equivalent diameter of each sieve pore is between 5 and 30 mm; during the falling process of the materials, the materials are divided into large materials and small materials with different particle size ranges;
a partition board is arranged in the kiln tail box to separate materials with different particle sizes; more than two discharge ports are correspondingly arranged on the kiln tail box and are respectively used for discharging materials with different particle sizes.
3. A method of producing a vanadium-nitrogen alloy according to claim 1 or 2, characterized in that: the material ball enters the kiln chamber feed inlet through a feed channel, and a material level detection or observation device is arranged on the feed channel and is higher than the highest point of the kiln chamber feed inlet; when the material level of the material ball falls to the material level detection or observation device, an alarm is triggered and/or manual or automatic mechanical feeding is triggered, or the feeding speed is accelerated during continuous feeding.
4. A method of producing a vanadium-nitrogen alloy according to claim 1 or 2, characterized in that: the refractory material forming the kiln chamber wall is a non-metallic material with the resistivity more than 5 times that of the material ball pile in the heating section.
5. A method of producing a vanadium-nitrogen alloy according to claim 1 or 2, characterized in that: adding iron, ferric oxide or a mixture thereof which does not exceed 100 percent of the weight of vanadium calculated by iron into the material ball to produce the vanadium-nitrogen alloy containing iron or the nitrided ferrovanadium.
6. A method of producing a vanadium-nitrogen alloy according to claim 1 or 2, characterized in that: the power applied to the anode and the cathode is an adjustable direct current power supply, the voltage range of the power is adjustable between 0V and 200V, and the current range is adjustable between 0 Ampere and 20000 Ampere.
7. A method of producing a vanadium-nitrogen alloy according to claim 1 or 2, characterized in that: the pressure of the atmosphere in the kiln chamber is higher than the atmospheric pressure by more than 5Pa at the discharge port of the kiln chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019224211318 | 2019-12-30 | ||
| CN201922421131 | 2019-12-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111004964A true CN111004964A (en) | 2020-04-14 |
Family
ID=70120704
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202020077103.9U Active CN210602747U (en) | 2019-12-30 | 2020-01-15 | Directly-heated rotary kiln for reduction nitridation reaction |
| CN202010039364.6A Pending CN111004964A (en) | 2019-12-30 | 2020-01-15 | A kind of method for producing vanadium nitrogen alloy |
| CN202011419086.3A Pending CN112880389A (en) | 2019-12-30 | 2020-12-07 | Directly-heated rotary kiln for reduction nitridation reaction |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202020077103.9U Active CN210602747U (en) | 2019-12-30 | 2020-01-15 | Directly-heated rotary kiln for reduction nitridation reaction |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011419086.3A Pending CN112880389A (en) | 2019-12-30 | 2020-12-07 | Directly-heated rotary kiln for reduction nitridation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN210602747U (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111879110A (en) * | 2020-08-24 | 2020-11-03 | 马鞍山中科冶金材料科技有限公司 | A hybrid electric heating shaft furnace kiln |
| CN111854418A (en) * | 2020-08-24 | 2020-10-30 | 马鞍山中科冶金材料科技有限公司 | A resistance heating shaft furnace |
| CN111854419A (en) * | 2020-08-24 | 2020-10-30 | 马鞍山中科冶金材料科技有限公司 | A direct heating electric heating shaft kiln |
| CN117781670A (en) * | 2022-11-29 | 2024-03-29 | 冯良荣 | A complete set of equipment for carbothermal reduction reaction |
| CN115772624A (en) * | 2022-11-29 | 2023-03-10 | 冯良荣 | Method for producing vanadium-nitrogen alloy |
| CN116534810A (en) * | 2023-03-13 | 2023-08-04 | 中铝山东有限公司 | Continuous high-efficiency decarburization method and equipment for aluminum nitride powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201808121U (en) * | 2010-10-22 | 2011-04-27 | 横店集团东磁股份有限公司 | Improved furnace presintering material sieving automatic mechanical rapping system |
| CN103466569A (en) * | 2009-10-12 | 2013-12-25 | 冯良荣 | Method for preparing vanadium nitride |
| CN208846932U (en) * | 2018-08-26 | 2019-05-10 | 冯良荣 | A kind of directly-heated type rotary kiln |
| CN208846929U (en) * | 2018-08-26 | 2019-05-10 | 冯良荣 | A kind of directly-heated type rotary kiln |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040202A (en) * | 2009-10-13 | 2011-05-04 | 冯良荣 | Method for preparing vanadium nitride |
| CN103335513B (en) * | 2012-12-10 | 2015-07-15 | 冯良荣 | Electric heating rotary kiln |
| CN208846933U (en) * | 2018-08-26 | 2019-05-10 | 冯良荣 | A kind of directly-heated type rotary kiln |
-
2020
- 2020-01-15 CN CN202020077103.9U patent/CN210602747U/en active Active
- 2020-01-15 CN CN202010039364.6A patent/CN111004964A/en active Pending
- 2020-12-07 CN CN202011419086.3A patent/CN112880389A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103466569A (en) * | 2009-10-12 | 2013-12-25 | 冯良荣 | Method for preparing vanadium nitride |
| CN201808121U (en) * | 2010-10-22 | 2011-04-27 | 横店集团东磁股份有限公司 | Improved furnace presintering material sieving automatic mechanical rapping system |
| CN208846932U (en) * | 2018-08-26 | 2019-05-10 | 冯良荣 | A kind of directly-heated type rotary kiln |
| CN208846929U (en) * | 2018-08-26 | 2019-05-10 | 冯良荣 | A kind of directly-heated type rotary kiln |
Non-Patent Citations (1)
| Title |
|---|
| 杨保祥等: "《钒钛清洁生产》", 31 January 2017 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112880389A (en) | 2021-06-01 |
| CN210602747U (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111004964A (en) | A kind of method for producing vanadium nitrogen alloy | |
| CN101392333B (en) | Vanadium-nitrogen alloy preparation method and device | |
| CN107008914B (en) | A production process of reduced iron powder for improving the performance of reduced iron powder | |
| WO2020059630A1 (en) | Method for smelting oxide ore | |
| CN102187001A (en) | Method for processing solid or molten materials | |
| CN101372321A (en) | Method for preparing vanadium nitride | |
| CN101082089A (en) | Preparation method of nitriding vanadium alloy | |
| CN103436699B (en) | A kind of microwave silicothermic process produces the method for low carbon ferrochromium | |
| CN106044771B (en) | A kind of titanium carbide preparation method that titanium processing is proposed based on titanium-containing blast furnace slag carbonization | |
| CN104046824A (en) | Ferrovanadium nitride and preparation method thereof | |
| CN101693529A (en) | Method for preparing vanadium nitride | |
| CN103193231B (en) | Prepare the method for titanium carbide or titanium carbonitride | |
| CN109402315A (en) | A method of preparing reduced iron or nitrided iron | |
| CN109536815A (en) | A method of preparing nitridation manganese alloy | |
| CN103602773B (en) | Method for comprehensive utilization of paigeite through direct reduction-electric furnace melting separation of rotary hearth furnace | |
| CN111872414B (en) | Preparation method of micro-nano pre-alloyed powder | |
| CN109399586A (en) | A method of preparing carbon tungsten nitride | |
| CN113735126A (en) | Method for preparing calcium carbide at low temperature by utilizing electromagnetic induction technology | |
| CN110184521B (en) | Composite densifier and method for preparing vanadium-nitrogen alloy by adopting same | |
| CN107460309A (en) | A kind of method that microwave heating chromite powder prepares ferrochrome | |
| CN109354020A (en) | A method of preparing chromium carbide or chromium nitride | |
| CN101845566A (en) | Method for continuous reduction production of VN alloy | |
| CN103466569A (en) | Method for preparing vanadium nitride | |
| CN102040202A (en) | Method for preparing vanadium nitride | |
| CN110373603A (en) | The method that vananum fine powder is used for vanadium iron spray refining |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200414 |