CN117247014A - Vanadium carbide powder and preparation method thereof - Google Patents
Vanadium carbide powder and preparation method thereof Download PDFInfo
- Publication number
- CN117247014A CN117247014A CN202311157235.7A CN202311157235A CN117247014A CN 117247014 A CN117247014 A CN 117247014A CN 202311157235 A CN202311157235 A CN 202311157235A CN 117247014 A CN117247014 A CN 117247014A
- Authority
- CN
- China
- Prior art keywords
- temperature
- vanadium
- phenolic resin
- carbon black
- powder
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 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 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 89
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005011 phenolic resin Substances 0.000 claims abstract description 51
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 51
- 239000006229 carbon black Substances 0.000 claims abstract description 44
- 238000003763 carbonization Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000002474 experimental method Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010586 diagram Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000007621 cluster analysis Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 235000019241 carbon black Nutrition 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- MCPTUMJSKDUTAQ-UHFFFAOYSA-N vanadium;hydrate Chemical compound O.[V] MCPTUMJSKDUTAQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 abstract description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 abstract description 3
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 11
- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 239000004484 Briquette Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000010426 asphalt Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of alloy smelting, in particular to vanadium carbide powder and a preparation method thereof; the method comprises the following steps: s1, raw material preparation, S2 one-stage pre-experiment and S3 actual production; according to the invention, carbon black and phenolic resin are used as composite carbon sources, the reduction and carbonization of vanadium oxide are promoted in different temperature ranges, and the overall efficiency is improved; the invention adopts a pre-experiment method, takes the gas production amount in unit time as a research basis, utilizes a scatter diagram of the gas production amount at the temperature to carry out curve fitting, carries out cluster analysis based on the tangential slope of the fitted curve, and determines the optimal temperature of one-stage reaction, thereby not only completing the carbonization of phenolic resin, but also ensuring the cracking flow of vanadium pentoxide to vanadium dioxide, vanadium trioxide and other low-valence vanadium oxides.
Description
Technical Field
The invention relates to the field of alloy smelting, in particular to vanadium carbide powder and a preparation method thereof.
Background
Metal matrix composite materials are receiving extensive attention from scientists in various material fields due to their unique advantages of high specific strength, high specific modulus, wear resistance, high temperature resistance, and the like.
Vanadium carbide (Vanadium carbide) is an transition metal carbide, the molecular formula is VC, the appearance is black gray powder, and the Vanadium carbide belongs to a sodium chloride type cubic crystal system structure, and the relative density is 5.77; melting point 2810 ℃; the boiling point is 3900 ℃, the thermal expansion coefficient is 7.2X10-6/K, the material is insoluble in water, soluble in nitric acid and decomposed, the chemical stability is good, and the high-temperature performance is good; vanadium carbide is prepared by fully mixing carbon powder with vanadium pentoxide, and reducing at 1300 ℃ or above under high vacuum condition; the vanadium carbide can be used as grain refiner in hard alloy, cutting tool and steelmaking industry, and can obviously improve the alloy performance.
Related art is disclosed in the prior art:
chinese patent publication No. CN113843382a discloses a process for producing vanadium-titanium carbide alloy; specifically disclosed is: the process comprises the following steps: s1: spraying an anti-oxidation coating on the surface of a vanadium-titanium alloy ingot to be processed, and starting a resistance furnace to preheat the inside of the furnace after the coating stands for 24 hours; s2: cleaning the inner surface of a cavity in the resistance furnace before preheating, starting preheating after cleaning, wherein the preheating time of the resistance furnace is at least 240 minutes, the preheating temperature is not lower than 700 ℃, and after preheating, feeding the vanadium-titanium alloy cast ingot to be processed into the resistance furnace; s3: after the vanadium-titanium alloy cast ingot to be processed is sent into a resistance furnace, the space between the heating parts is at least more than 100mm, the resistance furnace gradually increases the temperature to 900 ℃ within 360 minutes, and the temperature is kept for at least 240 minutes; s4: after the processing is finished, the resistance furnace is closed, the vanadium-titanium alloy cast ingot is kept in the cavity until the temperature in the cavity is reduced to 200 ℃, and the vanadium-titanium alloy cast ingot is taken out and carbon powder is sprayed on the surface; s5: and (3) placing the vanadium-titanium alloy cast ingot into an oil press for cogging.
Chinese patent publication No. CN106517201a discloses a method for producing vanadium carbide using a vertical intermediate frequency induction furnace; specifically disclosed is: the method comprises the following steps: (1) Mixing vanadium oxide and carbonaceous reducing agent uniformly, adding binder and water, mixing uniformly, and granulating to form pellets; (2) And (3) drying and screening the pellets, uniformly mixing the pellets with the additive until the additive is uniformly coated on the surfaces of the pellets, and then conveying the pellets into a vertical medium-frequency induction furnace for reaction to obtain vanadium carbide products. The vanadium carbide produced by the method has high vanadium conversion rate, is easy to realize mechanized continuous production, reduces the production cost, does not generate waste residues in the production process, and realizes the green production of the vanadium carbide.
Chinese patent publication No. CN104129994a discloses a method for preparing vanadium titanium carbide; specifically disclosed is: the preparation method of the vanadium titanium carbide comprises the following steps: a. and (3) batching: uniformly mixing ammonium metavanadate, titanium dioxide and carbon powder to obtain a mixture; b. and (5) press forming: pressing and forming the mixture to obtain a pressing block, wherein the density of the pressing block is 1.5-2.5 g cm < -3 >; c. primary carbonization: carbonizing the briquettes for the first time, removing ammonium and crystal water in the mixture, preserving heat and cooling; d. secondary carbonization: brushing off carbon powder on the surface of the briquette, grinding, crushing, screening, ball milling, and then compacting to obtain the briquette with the density of 1.5-2.5 g cm < -3 >; then preserving heat for 1-3 h at 1500-1800 ℃ under vacuum atmosphere, and cooling to obtain vanadium titanium carbide. The vanadium titanium carbide prepared by the method has good crystallinity, and the preparation method is simple and has lower energy consumption.
Chinese patent publication No. CN102225763B discloses a method for preparing vanadium carbide powder; specifically disclosed is: the preparation method comprises the steps of batching, mixing, solidifying, pulverizing, compression molding, sintering, decarburizing and pulverizing, and is characterized in that: mixing phenolic resin and vanadium pentoxide powder with the granularity of 0.1-3 mu m to form pug, solidifying at the temperature of 40-100 ℃, pulverizing, pressing into blocks, then firing for 6-8 hours in inert or reducing atmosphere at the temperature of 1300-1550 ℃ to obtain vanadium carbide blocks, decarburizing and crushing to obtain the vanadium carbide powder. The invention has the characteristics of simple process, high purity of vanadium carbide powder and low cost.
However: the above prior art still has the following problems:
1. in the prior art, graphite, carbon black, active carbon, coke, petroleum coke, asphalt, organic carbon, starch, paraffin, sugar and other single carbon sources are adopted, the carbonization interval is narrow, and the overall efficiency is low; especially when using organic carbon source, it needs to be cracked and carbonized, resulting in lower efficiency of overall reduction and vanadium carbonization.
2. Prior art carbonization generally uses an empirical temperature, and it is difficult to obtain the highest carbonization efficiency.
Disclosure of Invention
In order to achieve the purpose of the invention, the invention is realized by the following technical scheme: a method for preparing vanadium carbide powder, comprising the following steps:
s1, preparing raw materials; cleaning, grinding, solidifying and crushing carbon black, vanadium pentoxide and water-soluble phenolic resin to obtain ternary mixed furnace burden powder;
s2, a one-stage pre-experiment; comprising the following steps:
s21, taking out a certain mass of sample powder from the ternary mixed furnace burden powder, placing the sample powder into a vacuum heating furnace, vacuumizing the vacuum heating furnace, sealing and heating;
s22, the vacuum heating furnace is used for carrying out the process according to a parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 Performing a "heat-soak" cycling operation to perform a one-stage pre-experiment;
wherein T is 1 Is the initial temperature of the experiment;
delta T is the experimental temperature step and represents the temperature increase at each cycle operation;
t 0 the heat preservation time is the same time of heat preservation of the vacuum heating furnace in each cycle operation;
T i is the temperature at the ith cycle operation, satisfies T i ＝T 1 +i·ΔT；
T 2 For the experimental termination temperature, satisfy T 2 ＝T 1 ++ (N-1). DELTA.T, which means that the temperature reached T after N-1 cycles of the one-stage pre-experiment were performed 2 Stopping the experiment after the Nth heat preservation is executed;
s23, recording gas yield V when the vacuum heating furnace executes each cycle operation i ，V i Represents the gas production rate in the ith cyclic operation, wherein i is a natural number and satisfies i E [1, N]；
S24, at a temperature T i On the abscissa, gas yield V i Drawing a scatter diagram with the ordinate;
s25, performing curve fitting on the scatter diagram, solving the slope of each tangent line of the fitted curve, and obtaining a tangent point slope set { k ] according to the sequence from low temperature to high temperature j -wherein j is the number of tangent points;
s26, cutting point slope set { k ] j Performing cluster analysis, dividing into three cluster groups to obtain three temperature points T corresponding to the separation points of the three cluster groups a 、T b And T c Three temperature intervals were obtained, wherein [ T ] a ,T b ]Is phenolic resin charring area, [ T ] b ,T c ]Phenolic resin carbonization+vanadium pentoxide cracking interval, [ T ] c ,T 2 ]Is a vanadium pentoxide volatilization zone;
s3, actual production; and carbonizing the ternary mixed furnace burden powder according to the phenolic resin carbonization and vanadium pentoxide cracking zone to finish actual production.
Further, the step S1 specifically includes:
s11, cleaning carbon black; placing carbon black into an acid solution, and cleaning grease on the surface of the carbon black by utilizing the corrosion action of acid; washing the carbon black subjected to acid washing, wherein the carbon black is not dried after washing;
s12, preparing binary mixed furnace burden; pouring vanadium pentoxide powder into wet carbon black according to a proportion to form a mixture, pouring the mixture into a ball mill for barreling and stirring, and combining the vanadium pentoxide powder with the carbon black by taking water as a medium to obtain a mixed mixture;
s13, preparing ternary mixed furnace burden; adding water-soluble phenolic resin into the ball mill according to a certain proportion, and continuously barreling to obtain ternary mixed furnace burden
S14, curing ternary mixed furnace burden; pouring the ternary mixed furnace burden with the water-soluble phenolic resin, the carbon black and the vanadium pentoxide, solidifying at a certain temperature, smashing the solidified ternary mixed furnace burden, and pouring the smashed ternary mixed furnace burden into a mixing mill for milling until the average diameter is reached, so as to obtain ternary mixed furnace burden powder.
Further, step S3 specifically includes:
s31, a stage; cracking zone [ T ] of phenolic resin carbonization and vanadium pentoxide b ,T c ]The temperature is selected as a first-stage temperature, and the ternary mixed furnace burden powder is heated at a low temperature and kept warm;
s32, two stages; after the first stage is completed, raising the furnace temperature to 1000 ℃ to start raising the temperature to 1300 ℃ in a sectional way, and continuously vacuumizing to complete carbonization until the vacuum degree is lower than 5 Pa to complete the reaction;
s33, ball milling is carried out on the furnace burden according to a certain ball-material ratio after carbon removal and temperature reduction, and actual production is completed after batch mixing, sieving and packaging.
Further, the particle size of the vanadium pentoxide powder is 0.1-3 mu m; weight based on the weight of the composition; 3-7 parts of vanadium carbide, 6-10 parts of carbon black and 15-20 parts of water-soluble phenolic resin
Further, all carbon blacks are any one of national brands N110, N115, N121, N134, N219, N220, N231, N234, N326, N330, N339, N347, N351, N375, N539, N550, N650, N660, N762, N774.
Further, all carbon blacks are under the national standard number N330.
Further, the curing temperature of the water-soluble phenolic resin is 120-200 ℃.
Further, the curing temperature of the water-soluble phenolic resin is 180 ℃.
Further, the parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 In }, T 1 Selecting 300 ℃, selecting 50 ℃ for DeltaT, and T 2 Selecting 800 ℃ t 0 Selecting for 1min.
The invention also provides vanadium carbide powder, which is prepared by adopting the preparation method, completing one stage in a phenolic resin carbonization and vanadium pentoxide cracking zone after one-stage pre-experiment and performing two-stage high-temperature carbonization.
The beneficial effects of the invention are as follows:
1. compared with the prior art which only uses carbon black or phenolic resin as a carbon source, the invention can provide carbon sources with different characteristics, promotes the reduction and carbonization of vanadium oxide in different temperature ranges, improves the overall efficiency, and particularly comprises the steps that the carbon black can be utilized to promote the cracking of vanadium pentoxide in one stage to obtain vanadium dioxide, vanadium trioxide and other low-valence vanadium oxides, and simultaneously complete the carbonization of the phenolic resin, and the phenolic resin which is completed by the carbon black and the carbonization simultaneously carries out the carbonization of vanadium to obtain vanadium carbide in the two stages, thereby improving the overall reaction efficiency.
2. The invention adopts a pre-experiment method, takes the gas production amount per unit time as a research basis, determines the optimal temperature of one-stage reaction, not only completes the carbonization of phenolic resin, but also ensures the cracking flow of vanadium pentoxide to vanadium dioxide, vanadium trioxide and other low-valence vanadium oxides.
3. According to the invention, curve fitting is performed by using a scatter diagram of gas production under temperature, clustering analysis is performed based on the tangential slope of a fitted curve, a phenolic resin carbonization and vanadium pentoxide cracking interval can be rapidly and accurately obtained, the temperature of the interval is used as a one-stage temperature, and carbonization of phenolic resin serving as a dual carbon source and cracking of vanadium pentoxide can be simultaneously completed.
Drawings
FIG. 1 is a graph showing the relationship between gas production per unit time and temperature.
Detailed Description
The present invention will be further described in detail with reference to the following examples, which are only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The invention adopts carbon black and phenolic resin as dual carbon sources, and needs to consider the coordinated working temperature of the carbon black and the phenolic resin, especially when the carbon black has an overlapping reduction temperature and the phenolic resin carbonization temperature in one stage, but the phenolic resin carbonization degree is lower or not if the temperature is too low, and volatilization of vanadium pentoxide can occur if the temperature is too high, generally, the phenolic resin carbonization temperature is between 250 and 800 ℃, and the vanadium pentoxide volatilizes back when the temperature is above 700 ℃, and the proper temperature under a specific proportion needs to be studied how to obtain, the invention takes gas production per unit time as a research object, and the total process of the reaction of the vanadium pentoxide and C is divided into the following stages: v (V) 2 O 5 →VO 2 →V 2 O 3 →VO x →V 8 C 7 (reaction procedure for carbothermic synthesis of vanadium carbide powder by V205); when the temperature is too low, vanadium pentoxide is not reduced and phenolic resin is not carbonized to produce gas, after the temperature is gradually increased, the vanadium pentoxide starts to be reduced but the phenolic resin is not carbonized to produce gas, the temperature is increased again, the vanadium pentoxide starts to be reduced and the phenolic resin starts to be carbonized to produce gas, the temperature is increased again, the vanadium pentoxide is reduced and volatilized and the phenolic resin is carbonized to produce gas, and the gas is produced in unit timeThe amount is gradually increased, so that the state of the reaction can be judged by the gas production amount per unit time so as to obtain the optimal reaction temperature under the current proportion.
According to fig. 1, this embodiment provides a method for preparing vanadium carbide powder, which includes the following steps:
s1, preparing raw materials; cleaning, grinding, solidifying and crushing carbon black, vanadium pentoxide and water-soluble phenolic resin to obtain ternary mixed furnace burden powder;
s2, a one-stage pre-experiment; comprising the following steps:
s21, taking out a certain mass of sample powder from the ternary mixed furnace burden powder, placing the sample powder into a vacuum heating furnace, vacuumizing the vacuum heating furnace, sealing and heating;
s22, the vacuum heating furnace is used for carrying out the process according to a parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 Performing a "heat-soak" cycling operation to perform a one-stage pre-experiment;
wherein T is 1 Is the initial temperature of the experiment;
delta T is the experimental temperature step and represents the temperature increase at each cycle operation;
t 0 the heat preservation time is the same time of heat preservation of the vacuum heating furnace in each cycle operation;
T i is the temperature at the ith cycle operation, satisfies T i ＝T 1 +i·ΔT；
T 2 For the experimental termination temperature, satisfy T 2 ＝T 1 ++ (N-1). DELTA.T, which means that the temperature reached T after N-1 cycles of the one-stage pre-experiment were performed 2 Stopping the experiment after the Nth heat preservation is executed;
s23, recording gas yield V when the vacuum heating furnace executes each cycle operation i ，V i Represents the gas production rate in the ith cyclic operation, wherein i is a natural number and satisfies i E [1, N]；
S24, at a temperature T i On the abscissa, gas yield V i Drawing powder with ordinateA dot diagram;
s25, performing curve fitting on the scatter diagram, solving the slope of each tangent line of the fitted curve, and obtaining a tangent point slope set { k ] according to the sequence from low temperature to high temperature j -wherein j is the number of tangent points;
s26, cutting point slope set { k ] j Performing cluster analysis, dividing into three cluster groups to obtain three temperature points T corresponding to the separation points of the three cluster groups a 、T b And T c Three temperature intervals were obtained, wherein [ T ] a ,T b ]Is phenolic resin charring area, [ T ] b ,T c ]Phenolic resin carbonization+vanadium pentoxide cracking interval, [ T ] c ,T 2 ]Is a vanadium pentoxide volatilization zone;
s3, actual production; and carbonizing the ternary mixed furnace burden powder according to the phenolic resin carbonization and vanadium pentoxide cracking zone to finish actual production.
Further, the step S1 specifically includes:
s11, cleaning carbon black; placing carbon black into an acid solution, and cleaning grease on the surface of the carbon black by utilizing the corrosion action of acid; washing the carbon black subjected to acid washing, wherein the carbon black is not dried after washing;
s12, preparing binary mixed furnace burden; pouring vanadium pentoxide powder into wet carbon black according to a proportion to form a mixture, pouring the mixture into a ball mill for barreling and stirring, and combining the vanadium pentoxide powder with the carbon black by taking water as a medium to obtain a mixed mixture;
s13, preparing ternary mixed furnace burden; adding water-soluble phenolic resin into the ball mill according to a certain proportion, and continuously barreling to obtain ternary mixed furnace burden
S14, curing ternary mixed furnace burden; pouring the ternary mixed furnace burden with the water-soluble phenolic resin, the carbon black and the vanadium pentoxide, solidifying at a certain temperature, smashing the solidified ternary mixed furnace burden, and pouring the smashed ternary mixed furnace burden into a mixing mill for milling until the average diameter is reached, so as to obtain ternary mixed furnace burden powder.
Further, step S3 specifically includes:
s31, one stageThe method comprises the steps of carrying out a first treatment on the surface of the Cracking zone [ T ] of phenolic resin carbonization and vanadium pentoxide b ,T c ]The temperature is selected as a first-stage temperature, and the ternary mixed furnace burden powder is heated at a low temperature and kept warm;
s32, two stages; after the first stage is completed, raising the furnace temperature to 1000 ℃ to start raising the temperature to 1300 ℃ in a sectional way, and continuously vacuumizing to complete carbonization until the vacuum degree is lower than 5 Pa to complete the reaction;
s33, ball milling is carried out on the furnace burden according to a certain ball-material ratio after carbon removal and temperature reduction, and actual production is completed after batch mixing, sieving and packaging.
Further, the particle size of the vanadium pentoxide powder is 0.1-3 mu m; weight based on the weight of the composition; 3-7 parts of vanadium carbide, 6-10 parts of carbon black and 15-20 parts of water-soluble phenolic resin
Further, all carbon blacks are any one of national brands N110, N115, N121, N134, N219, N220, N231, N234, N326, N330, N339, N347, N351, N375, N539, N550, N650, N660, N762, N774.
Further, all carbon blacks are under the national standard number N330.
Further, the curing temperature of the water-soluble phenolic resin is 120-200 ℃.
Further, the curing temperature of the water-soluble phenolic resin is 180 ℃.
Further, the parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 In }, T 1 Selecting 300 ℃, selecting 50 ℃ for DeltaT, and T 2 Selecting 800 ℃ t 0 Selecting for 1min.
Example two
The invention also provides vanadium carbide powder, which is prepared by adopting the preparation method, completing one stage in a phenolic resin carbonization and vanadium pentoxide cracking zone after one-stage pre-experiment and performing two-stage high-temperature carbonization.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for preparing vanadium carbide powder, comprising the steps of:
s1, preparing raw materials; cleaning, grinding, solidifying and crushing carbon black, vanadium pentoxide and water-soluble phenolic resin to obtain ternary mixed furnace burden powder;
s2, a one-stage pre-experiment; comprising the following steps:
s21, taking out a certain mass of sample powder from the ternary mixed furnace burden powder, placing the sample powder into a vacuum heating furnace, vacuumizing the vacuum heating furnace, sealing and heating;
s22, the vacuum heating furnace is used for carrying out the process according to a parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 Performing a "heat-soak" cycling operation to perform a one-stage pre-experiment;
wherein T is 1 Is the initial temperature of the experiment;
delta T is the experimental temperature step and represents the temperature increase at each cycle operation;
t 0 the heat preservation time is the same time of heat preservation of the vacuum heating furnace in each cycle operation;
T i is the temperature at the ith cycle operation, satisfies T i ＝T 1 +i·ΔT；
T 2 For the experimental termination temperature, satisfy T 2 ＝T 1 ++ (N-1). DELTA.T, which means that the temperature reached T after N-1 cycles of the one-stage pre-experiment were performed 2 Stopping the experiment after the Nth heat preservation is executed;
s23, recording gas yield V when the vacuum heating furnace executes each cycle operation i ，V i Represents the gas production rate in the ith cyclic operation, wherein i is a natural number and satisfies i E [1, N]；
S24, at a temperature T i On the abscissa, gas yield V i Drawing a scatter diagram with the ordinate;
s25, performing curve fitting on the scatter diagram, solving the slope of each tangent line of the fitted curve, and obtaining a tangent point slope set { k ] according to the sequence from low temperature to high temperature j -wherein j is the number of tangent points;
s26, cutting point slope set { k ] j Performing cluster analysis, dividing into three cluster groups to obtain three temperature points T corresponding to the separation points of the three cluster groups a 、T b And T c Three temperature intervals were obtained, wherein [ T ] a ,T b ]Is phenolic resin charring area, [ T ] b ,T c ]Phenolic resin carbonization+vanadium pentoxide cracking interval, [ T ] c ,T 2 ]Is a vanadium pentoxide volatilization zone;
s3, actual production; and carbonizing the ternary mixed furnace burden powder according to the phenolic resin carbonization and vanadium pentoxide cracking zone to finish actual production.
2. The method for producing vanadium carbide powder according to claim 1, wherein: the step S1 specifically comprises the following steps:
s11, cleaning carbon black; placing carbon black into an acid solution, and cleaning grease on the surface of the carbon black by utilizing the corrosion action of acid; washing the carbon black subjected to acid washing, wherein the carbon black is not dried after washing;
s12, preparing binary mixed furnace burden; pouring vanadium pentoxide powder into wet carbon black according to a proportion to form a mixture, pouring the mixture into a ball mill for barreling and stirring, and combining the vanadium pentoxide powder with the carbon black by taking water as a medium to obtain a mixed mixture;
s13, preparing ternary mixed furnace burden; adding water-soluble phenolic resin into the ball mill according to a certain proportion, and continuously barreling to obtain ternary mixed furnace burden
S14, curing ternary mixed furnace burden; pouring the ternary mixed furnace burden with the water-soluble phenolic resin, the carbon black and the vanadium pentoxide, solidifying at a certain temperature, smashing the solidified ternary mixed furnace burden, and pouring the smashed ternary mixed furnace burden into a mixing mill for milling until the average diameter is reached, so as to obtain ternary mixed furnace burden powder.
3. The method for producing vanadium carbide powder according to claim 2, wherein: the step S3 specifically comprises the following steps:
s31, a stage; cracking zone [ T ] of phenolic resin carbonization and vanadium pentoxide b ,T c ]The temperature is selected as a first-stage temperature, and the ternary mixed furnace burden powder is heated at a low temperature and kept warm;
s32, two stages; after the first stage is completed, raising the furnace temperature to 1000 ℃ to start raising the temperature to 1300 ℃ in a sectional way, and continuously vacuumizing to complete carbonization until the vacuum degree is lower than 5 Pa to complete the reaction;
s33, ball milling is carried out on the furnace burden according to a certain ball-material ratio after carbon removal and temperature reduction, and actual production is completed after batch mixing, sieving and packaging.
4. The method for producing vanadium carbide powder according to claim 2, wherein: the particle size of the vanadium pentoxide powder is 0.1-3 mu m; weight based on the weight of the composition; 3-7 parts of vanadium carbide, 6-10 parts of carbon black and 15-20 parts of water-soluble phenolic resin.
5. The method for producing vanadium carbide powder according to claim 2, wherein: all carbon blacks are any one of national brands N110, N115, N121, N134, N219, N220, N231, N234, N326, N330, N339, N347, N351, N375, N539, N550, N650, N660, N762 and N774.
6. The method for producing vanadium carbide powder according to claim 5, wherein: all carbon blacks are national standard number N330.
7. The method for producing vanadium carbide powder according to claim 5, wherein: the curing temperature of the water-soluble phenolic resin is 120-200 ℃.
8. The method for producing vanadium carbide powder according to claim 7, wherein: the curing temperature of the water-soluble phenolic resin is 180 ℃.
9. The method for producing vanadium carbide powder according to claim 1, wherein: the parameter table T i ∈{T 1 ,ΔT,t 0 ,T 2 In }, T 1 Selecting 300 ℃, selecting 50 ℃ for DeltaT, and T 2 Selecting 800 ℃ t 0 Selecting for 1min.
10. Vanadium carbide powder, characterized in that the preparation method according to any one of claims 1-9 is adopted, after one-stage pre-experiment, one-stage is completed in the phenolic resin carbonization and vanadium pentoxide cracking zone, and the preparation is carried out after two-stage high-temperature carbonization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311157235.7A CN117247014A (en) | 2023-09-08 | 2023-09-08 | Vanadium carbide powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311157235.7A CN117247014A (en) | 2023-09-08 | 2023-09-08 | Vanadium carbide powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247014A true CN117247014A (en) | 2023-12-19 |
Family
ID=89127264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311157235.7A Pending CN117247014A (en) | 2023-09-08 | 2023-09-08 | Vanadium carbide powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247014A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884063A (en) * | 2006-07-06 | 2006-12-27 | 四川大学 | Process for preparing nano vanadium carbide powder |
| CN102225763A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of vanadium carbide powder |
| CN102275918A (en) * | 2011-05-31 | 2011-12-14 | 攀枝花学院 | Method of producing vanadium carbide |
| CN106517201A (en) * | 2016-10-25 | 2017-03-22 | 河钢股份有限公司承德分公司 | Method for producing vanadium carbide through vertical medium-frequency induction furnace |
| CN107282079A (en) * | 2017-08-08 | 2017-10-24 | 陕西科技大学 | The preparation method and product of a kind of banding vanadium carbide elctro-catalyst |
| CN108002383A (en) * | 2017-12-21 | 2018-05-08 | 芜湖人本合金有限责任公司 | Vanadium carbide and preparation method thereof |
-
2023
- 2023-09-08 CN CN202311157235.7A patent/CN117247014A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884063A (en) * | 2006-07-06 | 2006-12-27 | 四川大学 | Process for preparing nano vanadium carbide powder |
| CN102225763A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of vanadium carbide powder |
| CN102275918A (en) * | 2011-05-31 | 2011-12-14 | 攀枝花学院 | Method of producing vanadium carbide |
| CN106517201A (en) * | 2016-10-25 | 2017-03-22 | 河钢股份有限公司承德分公司 | Method for producing vanadium carbide through vertical medium-frequency induction furnace |
| CN107282079A (en) * | 2017-08-08 | 2017-10-24 | 陕西科技大学 | The preparation method and product of a kind of banding vanadium carbide elctro-catalyst |
| CN108002383A (en) * | 2017-12-21 | 2018-05-08 | 芜湖人本合金有限责任公司 | Vanadium carbide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106564894B (en) | Isotropism isostatic pressing formed graphite material and preparation method are prepared using graphene oxide | |
| CN105272287B (en) | A method of preparing graphite crucible with recycled graphite | |
| CN110845237B (en) | High-entropy ceramic powder, preparation method thereof and high-entropy ceramic block | |
| CN100503434C (en) | Method of preparing isotropic carbon material and prepared carbon material | |
| CN107244924B (en) | A kind of high micropore electric forging coal base brick fuel of high thermal conductivity and preparation method thereof | |
| CN103572087A (en) | Preparation method of boron carbide particle enhanced aluminum-based composite material | |
| CN109097563B (en) | Preparation method of vanadium-nitrogen alloy | |
| CN106048284A (en) | Vanadium-nitrogen alloy and preparation method thereof | |
| CN107602125A (en) | A kind of fine grained, high density, the preparation method of high purity graphite material | |
| CN101638733B (en) | Vanadium nitrogen alloy preparing method | |
| CN101319282B (en) | Method for manufacturing high-density vanadium-nitrogen alloy | |
| CN106517201A (en) | Method for producing vanadium carbide through vertical medium-frequency induction furnace | |
| CN104018056A (en) | Preparation method of nitrided ferrovanadium with high quality and low cost | |
| CN108083803A (en) | A kind of preparation method and graphite product of mold compression moulding graphite product | |
| CN102936678B (en) | Vanadium-nitrogen alloy production method | |
| CN100494507C (en) | High-density semi-graphite cathode carbon block and method for producing same | |
| CN1478915A (en) | Process and device for continuous production of vanadium nitride alloy | |
| CN101591190B (en) | Novel Si3N4-SiC-C refractory brick for sidewall of aluminum electrolysis bath and preparation method thereof | |
| CN110184521B (en) | Composite densifier and method for preparing vanadium-nitrogen alloy by adopting same | |
| CN117247014A (en) | Vanadium carbide powder and preparation method thereof | |
| WO2024000872A1 (en) | Ultra-coarse tungsten powder and ultra-coarse tungsten carbide powder, and preparation method therefor | |
| CN112795794B (en) | Method for preparing high-purity metal chromium block by adopting wet-process mixed metal powder | |
| CN114182152B (en) | Preparation method of vanadium-nitrogen alloy | |
| JPH0234508A (en) | Preparation of isotropic carbon material having high density | |
| CN111847458B (en) | Preparation method of high-purity and low-cost molybdenum disilicide |
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 |