CN102153135A - Method for preparing titanium carbonitride from ilmenite with high impurity content - Google Patents
Method for preparing titanium carbonitride from ilmenite with high impurity content Download PDFInfo
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- CN102153135A CN102153135A CN 201010615073 CN201010615073A CN102153135A CN 102153135 A CN102153135 A CN 102153135A CN 201010615073 CN201010615073 CN 201010615073 CN 201010615073 A CN201010615073 A CN 201010615073A CN 102153135 A CN102153135 A CN 102153135A
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Abstract
The invention provides a method for preparing titanium carbonitride from ilmenite with high impurity content, which comprises the following steps of: firstly, respectively drying ilmenite and graphite powder in a vacuum drying oven; weighing the dried ilmenite and graphite powder according to the molar ratio of 1:(3.25-3.75), and ball-milling the materials in a planetary ball mill; secondly, placing the ball-milled materials in a reaction vessel, putting the reaction vessel into a reaction furnace, vacuumizing the reaction furnace, introducing a running nitrogen gas into the reaction furnace, heating the reaction furnace to 1350-1600 DEG C, maintaining the temperature until the reaction is complete to obtain ferrous titanium carbonitride composite powder; and finally, after acid washing treatment, filtering, cleaning and drying the ferrous titanium carbonitride composite powder in sequence to obtain titanium carbonitride powder. The method provided by the invention has the characteristics of wide raw material sources, low cost, simple process and low energy consumption, and a new approach is especially developed for the comprehensive utilization of ilmenite with high impurity content.
Description
Technical field
The present invention relates to the utilization of ilmenite, specifically refer to a kind of method of utilizing the high impurity content ilmenite to prepare titanium carbonitride, belong to ilmenite and utilize technical field.Present method both can obtain the titanium carbonitride composite granule, also can obtain carbon titanium nitride powder, can make full use of the main body composition of raw material.
Background technology
The ilmenite resource reserve is big, and it is wide, almost all over the world to distribute.The titanium resource of China now occupies first of the world, 142 of total titanium deposits, and it is distributed in 20 provinces and regions, and the main place of production is provinces such as Sichuan, Hebei, Hainan.Ilmenite accounts for 98% of China's titanium resource total reserves, and rutile only accounts for 2%.Titanium resource reserves maximum be Panxi Diqu, the proven reserve of climbing big mining area, Xisi are with TiO
2Meter reaches 8.07 hundred million tons, and wherein Flos Bombacis Malabarici is 5.04 hundred million tons.
The main approach that utilizes of ilmenite is that concentrated ilmenite is produced the solubility in acid titanium slag with electric furnace smelting process, is used for sulfate process titanium dioxide production then.Another utilizes approach is that concentrated ilmenite is become titanium slag (TiO through the enrichment processing
2More than 90%) or artificial rutile (TiO
2More than 96%) afterwards, adopt fluidizing chlorination or fused salt chlorimation legal system to get TiCl
4Titanium sponge production also be ilmenite utilize one of approach.But, at present in the ilmenite comprehensive utilization process otherwise energy consumption too high, or the comprehensive utilization degree of iron is low, or the spent acid mother liquor is difficult, has influenced the efficient of ilmenite comprehensive utilization.
Particularly for the ilmenite (foreign matter content is greater than 10%) of high impurity content, because the fine fraction ilmenite is underutilized, make the application of many high impurity content ilmenites of having exploited out at present be subjected to greatly restriction, it is more that accumulation is shelved in the dressing-works, causes a large amount of wastings of resources.
Summary of the invention
At the prior art above shortcomings, the object of the present invention is to provide that a kind of technological process is simple, cost is low and can make full use of the method for iron and two kinds of main elements of titanium in the ilmenite, present method can be opened up a new approach for the comprehensive utilization of high impurity content ilmenite especially.
Technical scheme of the present invention is achieved in that a kind of high impurity content ilmenite prepares the method for titanium carbonitride, and it comprises the steps:
(1) earlier ilmenite and Graphite Powder 99 are dried in vacuum drying oven respectively; Bake out temperature is 100 ℃～150 ℃, is incubated 1～2 hour;
(2) ilmenite and the Graphite Powder 99 after will drying carries out weighing with the mole proportioning of 1:3.25～3.75, and carries out ball milling in planetary ball mill; Rotational speed of ball-mill is 250～450r/min, and the ball milling time is 2～6 hours;
(3) place reaction vessels (corundum/plumbago crucible) to put into Reaktionsofen in step (2) gained ball milling material, vacuumize the back and feed flowing nitrogen, Reaktionsofen is warming up to 1350～1600 ℃ of insulations down,, can obtains ferruginous titanium carbonitride composite granule until reacting completely.Its reaction formula is:
FeTiO
3?+（4-x）C+(x/2)N
2→Ti(C
1-x,N
x)+Fe+3CO（0.25<x<0.75）
So main component is Fe and TiCN in the composite granule that obtains, wherein the quality percentage composition of Fe and TiCN is respectively after testing: Fe:33.5～35.9%, TiCN:54.54～58.06% also contains impurity surpluses such as Mn, Si, Ca in addition.When being used to prepare iron base composite material in the composite granule, iron is the synthetic interface problem that adds avoided of original position, so the titanium carbonitride composite granule is a useful industrial raw material very.
If the titanium carbonitride composite granule of step (3) gained is filtered successively after cleanup acid treatment again, cleans and the dry carbon titanium nitride powder that gets final product purely.The specific acid washing method is: employing weight ratio concentration is 10%～20% hydrochloric acid, through 5～8 hours after-filtration of magnetic agitation, after again filter residue being stirred 3～5 hours in weight ratio concentration is 5%～10% hydrofluoric acid, successively after filtration, clean and be drying to obtain carbon titanium nitride powder.Wherein, hydrochloric acid and titanium carbonitride composite granule liquid-solid ratio are 5:1～10:1, and hydrofluoric acid and filter residue liquid-solid ratio are 2:1～5:1.After cleanup acid treatment, pure carbon titanium nitride powder granularity＜5 of gained micron, purity〉95%.
The present invention selects China's reserves abundant in conjunction with the china natural resources characteristics, includes the ilmenite (FeTiO of Fe and two kinds of main elements of Ti
3) as raw material, prepare the titanium carbonitride composite granule by carbothermic reduction.Present method both had been applicable to the ilmenite of high impurity content, and as the ilmenite that Flos Bombacis Malabarici produces, its foreign matter content also is applicable to the ilmenite of low impurity content up to more than 10%, so its practicality is stronger.
Present method can prepare iron content titanium carbonitride composite powder and two kinds of powders of titanium carbonitride.Titanium carbonitride is a kind of excellent property, broad-spectrum non-oxide ceramic material, have the advantage of TiC and TiN concurrently, have high-melting-point, high rigidity, wear-resisting, corrosion-resistant, characteristic such as anti-oxidant is again simultaneously heat, electric good conductor and be with a wide range of applications, and prepare corresponding matrix material with iron content titanium carbonitride composite granule, avoided common interface problem than the iron powder mode that adds of present commerce.In a single day accomplish scale production and to have great application value based on the technology of preparing of present method.At first, used starting material ilmenite be China be rich in one of resource, its price and TiC(or TiN) powder (hundreds of thousands of unit/ton) compares, and is very cheap.At present, because the fine fraction ilmenite is underutilized, the ilmenite of high impurity content particularly, the ilmenite that makes present major part exploit out have to be deposited in tailing dam as the dressing-works Litter.Secondly can directly fully effectively utilize the resource that is rich in--the main body composition of ilmenite of China again.Therefore, the present invention is for the effective comprehensive utilization that promotes the China's titanium iron ore deposit, and (C, N) widespread use in powder metallurgy and matrix material has very important significance to promote Ti.
In sum, the present invention has following advantage:
1. raw material sources are wide, and are cheap.The present invention selects the abundant ilmenite (FeTiO of China's reserves
3) as main raw material, particularly a large amount of high impurity content ilmenites, cost is lower.
2. technology is simple.The present invention utilizes cost-effective carbo-thermal process, is carbon source with graphite, normal pressure-sinteredly behind ball mill mixing can directly prepare the titanium carbonitride composite granule, obtains titanium carbonitride powder after pickling.Used preparation method's equipment is conventional general-purpose equipment, and technological process is simple, easy handling.
3. this technology can obtain the titanium carbonitride composite granule, also can prepare carbon titanium nitride powder.Composite granule main body composition quality percentage composition is: Fe:33.5～35.9%, TiCN:54.54～58.06%.When being used to prepare iron base composite material in the composite granule, wherein original position synthetic iron can avoid adding the interface problem that iron exists.
4. present method has made full use of the main element iron and the titanium of ilmenite, for ilmenite, the particularly comprehensive utilization of high impurity content ilmenite open up a new way, also is that (C, N) powder provides novel method to low-cost preparation Ti.
Description of drawings
The XRD figure of the titanium carbonitride composite granule of Fig. 1-embodiment of the invention preparation.
The secondary electron scanned photograph of the titanium carbonitride composite granule of Fig. 2-embodiment of the invention preparation.
The XRD figure of the titanium carbonitride powder of Fig. 3-embodiment of the invention preparation.
The secondary electron scanned photograph of the titanium carbonitride powder of Fig. 4-embodiment of the invention preparation.
Embodiment
The invention will be further described below by specific embodiment.
Embodiment 1:The oven dry respectively in vacuum drying oven with ilmenite and Graphite Powder 99 earlier, bake out temperature is 110 ℃, soaking time is 2 hours.Then, the material of drying is carried out weighing with the mole proportioning of 1:3.25, in planetary ball mill, carry out ball milling.Rotational speed of ball-mill is 350r/min, and the ball milling time is 4 hours.Place corundum crucible to put into Reaktionsofen in the ball milling material, vacuumize the through-flow moving nitrogen in back.Reaktionsofen is warming up to 1350 times insulations to react completely in 6 hours.Be cooled to room temperature then product is taken out acquisition titanium carbonitride composite granule.Fig. 1 is the XRD figure of titanium carbonitride composite granule, and Fig. 2 is the secondary electron scanning pattern of composite granule.
Again composite granule is carried out pickling: adopting weight ratio concentration is 20% hydrochloric acid, through 6 hours after-filtration of magnetic agitation, again filter residue is stirred 3 hours in weight ratio concentration is 10% hydrofluoric acid after, successively after filtration, clean and be drying to obtain carbon titanium nitride powder.Wherein, hydrochloric acid and titanium carbonitride composite granule liquid-solid ratio are 10:1, and hydrofluoric acid and filter residue liquid-solid ratio are 3:1.Fig. 3 is the XRD figure of carbon titanium nitride powder, and Fig. 4 is the secondary electron shape appearance figure of carbon titanium nitride powder.
Embodiment 2:The oven dry respectively in vacuum drying oven with ilmenite and Graphite Powder 99 earlier, bake out temperature is 110 ℃, soaking time is 2 hours.Then, the material of drying is carried out weighing with the mole proportioning of 1:3.5, in planetary ball mill, carry out ball milling.Rotational speed of ball-mill is 350r/min, and the ball milling time is 4 hours.Place corundum crucible to put into Reaktionsofen in the ball milling material behind the batch mixing, vacuumize back through-flow moving nitrogen, Reaktionsofen is warming up to 1400 ℃ of following insulations reacted completely in 4 hours.Be cooled to room temperature then product is taken out acquisition titanium carbonitride composite granule.
Again composite granule is carried out pickling: adopting weight ratio concentration is 15% hydrochloric acid, through 8 hours after-filtration of magnetic agitation, again filter residue is stirred 3 hours in weight ratio concentration is 10% hydrofluoric acid after, successively after filtration, clean and be drying to obtain carbon titanium nitride powder.Wherein, hydrochloric acid and titanium carbonitride composite granule liquid-solid ratio are 10:1, and hydrofluoric acid and filter residue liquid-solid ratio are 3:1.
Embodiment 3:The oven dry respectively in vacuum drying oven with ilmenite and Graphite Powder 99 earlier, bake out temperature is 110 ℃, soaking time is 2 hours.Then, the material of drying is carried out weighing with the mole proportioning of 1:3.75, in planetary ball mill, carry out ball milling.Rotational speed of ball-mill is 350r/min, and the ball milling time is 4 hours.Place corundum crucible to put into Reaktionsofen in the ball milling material behind the batch mixing, vacuumize the through-flow moving nitrogen in back.Reaktionsofen is warming up to 1450 ℃ of following insulations to react completely in 3 hours.Be cooled to room temperature then product is taken out acquisition titanium carbonitride composite granule.
Again composite granule is carried out pickling: adopting weight ratio concentration is 10% hydrochloric acid, through 8 hours after-filtration of magnetic agitation, again filter residue is stirred 5 hours in weight ratio concentration is 5% hydrofluoric acid after, successively after filtration, clean and be drying to obtain carbon titanium nitride powder.Wherein, hydrochloric acid and titanium carbonitride composite granule liquid-solid ratio are 10:1, and hydrofluoric acid and filter residue liquid-solid ratio are 5:1.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (3)
1. a high impurity content ilmenite prepares the method for titanium carbonitride, and it is characterized in that: it comprises the steps:
(1) earlier ilmenite and Graphite Powder 99 are dried in vacuum drying oven respectively;
(2) ilmenite and the Graphite Powder 99 after will drying carries out weighing with the mole proportioning of 1:3.25～3.75, and carries out ball mill mixing in planetary ball mill; Rotational speed of ball-mill is 250～450r/min, and the ball milling time is 2～6 hours;
(3) place reaction vessels to put into Reaktionsofen in the ball milling material, vacuumize the through-flow moving nitrogen in back, Reaktionsofen is warming up to 1350～1600 ℃ of insulations down,, can obtain ferruginous titanium carbonitride composite powder until reacting completely.
2. high impurity content ilmenite according to claim 1 prepares the method for titanium carbonitride, it is characterized in that: the titanium carbonitride composite powder of gained is filtered, cleans and be drying to obtain carbon titanium nitride powder successively after cleanup acid treatment.
3. high impurity content ilmenite according to claim 2 prepares the method for titanium carbonitride, it is characterized in that: described acid washing method is: employing weight ratio concentration is 10%～20% hydrochloric acid, through 5～8 hours after-filtration of magnetic agitation, after again filter residue being stirred 3～5 hours in weight ratio concentration is 5%～10% hydrofluoric acid, successively after filtration, clean and be drying to obtain carbon titanium nitride powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983688A (en) * | 2015-03-04 | 2016-10-05 | 海南大学 | Fast preparation method for Ti(C1-x, Nx) (0<=x<=1)-Fe composite powder |
| WO2020170223A1 (en) * | 2019-02-22 | 2020-08-27 | University Of Johannesburg | Titanium carbonitride |
| CN115821140A (en) * | 2022-11-24 | 2023-03-21 | 河南融发新材料科技有限公司 | Titanium-containing alloy for metallurgy and low-cost production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055957A (en) * | 1991-04-20 | 1991-11-06 | 中国科学院电工研究所 | Ion plating technology for titanium carbonitride coatings |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
-
2010
- 2010-12-30 CN CN 201010615073 patent/CN102153135A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055957A (en) * | 1991-04-20 | 1991-11-06 | 中国科学院电工研究所 | Ion plating technology for titanium carbonitride coatings |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库 工程科技I辑》 20091215 张龙柱 低成本制备TiCN粉及复合粉的工艺优化 第8～11页，表2.1，表3.1-3.5，图3.19 1-3 , 第12期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983688A (en) * | 2015-03-04 | 2016-10-05 | 海南大学 | Fast preparation method for Ti(C1-x, Nx) (0<=x<=1)-Fe composite powder |
| WO2020170223A1 (en) * | 2019-02-22 | 2020-08-27 | University Of Johannesburg | Titanium carbonitride |
| CN115821140A (en) * | 2022-11-24 | 2023-03-21 | 河南融发新材料科技有限公司 | Titanium-containing alloy for metallurgy and low-cost production method thereof |
| CN115821140B (en) * | 2022-11-24 | 2024-04-30 | 河南融发新材料科技有限公司 | Titanium-containing alloy for metallurgy and low-cost production method thereof |
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Application publication date: 20110817 |