CN104046879B - Black ceramic material and preparation method thereof - Google Patents
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- CN104046879B CN104046879B CN201410309800.1A CN201410309800A CN104046879B CN 104046879 B CN104046879 B CN 104046879B CN 201410309800 A CN201410309800 A CN 201410309800A CN 104046879 B CN104046879 B CN 104046879B
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 129
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 129
- 238000000605 extraction Methods 0.000 claims abstract description 96
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 98
- 238000007885 magnetic separation Methods 0.000 claims description 85
- 239000008188 pellet Substances 0.000 claims description 51
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 47
- 239000010936 titanium Substances 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 33
- 239000000919 ceramic Substances 0.000 claims description 30
- 239000003638 chemical reducing agent Substances 0.000 claims description 30
- 159000000000 sodium salts Chemical class 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 20
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 16
- 239000002689 soil Substances 0.000 claims description 15
- 239000000440 bentonite Substances 0.000 claims description 13
- 229910000278 bentonite Inorganic materials 0.000 claims description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 10
- 229910021487 silica fume Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 16
- 235000011941 Tilia x europaea Nutrition 0.000 description 16
- 239000004571 lime Substances 0.000 description 16
- 230000005291 magnetic effect Effects 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 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
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 1
- 241000238590 Ostracoda Species 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种黑色陶瓷材料及其制备方法，属于无机非金属材料领域。The invention relates to a black ceramic material and a preparation method thereof, belonging to the field of inorganic non-metallic materials.
背景技术Background technique
我国钒钛磁铁矿经采选，分离出铁精矿、钛精矿后剩余的选矿尾矿到目前为止还无有效地综合利用方法，一直作为废物堆放，不但污染环境，而且还占用大量土地。my country's vanadium-titanium magnetite has been mined and selected, and the remaining ore tailings after separating iron concentrate and titanium concentrate have no effective comprehensive utilization methods so far. They have been piled up as waste, which not only pollutes the environment, but also occupies a large amount of land. .
提钒尾渣(以钒钛磁铁矿为原料制取钒渣，从钒渣中浸取钒盐，剩余的残渣称作提钒尾渣)也是一种大量堆放的工业废料，其中还含有32-37％的铁，对于提钒尾渣的综合利用，已有较多的方法。如文献[1]，公开号为CN86104984A，发明名称为“一种陶瓷粉末”的专利申请所公开的制取黑瓷材料的方法是将提钒尾渣粉碎至小于20目，加入或不加入添加剂，再在1000℃～1400℃下煅烧1～60分钟，再将煅烧产物粉碎至小于20目得到黑瓷粉末材料。又如文献[2]，公开号为CN102910892A，发明名称为“一种利用天然矿物及提钒尾渣制备的黑色陶板及其制备方法”的专利申请所公开的制取黑瓷陶板的方法是将原重量百分比为0～10％的提钒尾渣与一定比例的铬铁矿、氧化锰矿一起进行干燥脱水、破碎、过筛形成混合料，再将这种混合料按一定比例与粘土、长石、砂和其它添加剂进行混合制成含水率为14％～19％的泥团，这种泥团成型后经干燥、烧结后制成黑色陶瓷板。又如文献[3]，公开号为CN101713007A，发明名称为“一种提钒尾渣深度还原直接生产海绵铁的工艺方法”的专利申请所公开的方法是以煤为还原剂，同时添加CaO作为造渣剂，将提钒尾渣在高温下深度还原，还原产物经二段磨矿，二段弱磁选得到铁品位大于90％的海绵铁。又如文献[4],公开号为CN101280361A，发明名称为“一种提钒尾渣的处理方法”的专利申请所公开的方法是将提钒尾渣与碳源混合成混合物后，在高温下还原，所得还原产物经磁选分离得到磁性产物和非磁性产物，磁性产物用于钢铁冶炼，非磁性产物用于提取钒和钛。Vanadium extraction tailings (vanadium slag is prepared from vanadium-titanium magnetite, vanadium salts are leached from the vanadium slag, and the remaining residue is called vanadium extraction tailings) is also a large amount of industrial waste piled up, which also contains 32 -37% iron, for the comprehensive utilization of vanadium extraction tailings, there are many methods. Such as document [1], the publication number is CN86104984A, the patent application titled "a kind of ceramic powder" discloses the method of preparing black porcelain material by crushing the tailings of vanadium extraction to less than 20 meshes, adding or not adding additives , and then calcined at 1000° C. to 1400° C. for 1 to 60 minutes, and then pulverized the calcined product to less than 20 meshes to obtain black porcelain powder material. Another example is the document [2], the publication number is CN102910892A, and the patent application titled "a black ceramic plate prepared by utilizing natural minerals and vanadium extraction tailings and its preparation method" discloses a method for preparing a black ceramic plate. Vanadium extraction tailings with an original weight percentage of 0-10% and a certain proportion of chromite and manganese oxide ore are dried, dehydrated, crushed, and sieved to form a mixture, and then the mixture is mixed with clay and feldspar in a certain proportion , sand and other additives are mixed to form a mud ball with a moisture content of 14% to 19%. After the mud ball is formed, it is dried and sintered to make a black ceramic plate. Another example is the document [3], the publication number is CN101713007A, and the patent application titled "A Process Method for Direct Production of Sponge Iron by Deep Reduction of Vanadium Extraction Tailings" discloses that coal is used as a reducing agent, and CaO is added as a reducing agent. The slagging agent is used to deeply reduce the vanadium extraction tailings at high temperature, and the reduced products are subjected to secondary grinding and secondary weak magnetic separation to obtain sponge iron with an iron grade greater than 90%. Another example is document [4], the publication number is CN101280361A, the method disclosed in the patent application titled "a treatment method for vanadium extraction tailings" is to mix the vanadium extraction tailings and carbon source into a mixture, Reduction, the obtained reduction products are separated by magnetic separation to obtain magnetic products and non-magnetic products, the magnetic products are used for iron and steel smelting, and the non-magnetic products are used for extracting vanadium and titanium.
文献[1]和[2]的优点是将提钒尾渣制成了黑色陶瓷，缺点是提钒尾渣中的铁未加以利用，文献[2]还要配加铬铁矿和氧化锰矿，是对铬和锰资源的浪费。文献[3]和[4]的优点是提取了提钒尾渣中的铁，缺点是提铁后的剩余的渣未加以利用。而且文献[4]所述的可用磁选方法将还原后的提钒尾渣中的铁、锰和铬磁选出来，但只能磁选出铁，而锰和铬，因其原子间的自旋趋于反向排列，原子间磁矩互相低消，属反铁磁性物质，因此不可能用磁选方法磁选锰和铬。The advantage of literature [1] and [2] is that the vanadium extraction tailings are made into black ceramics, but the disadvantage is that the iron in the vanadium extraction tailings is not utilized, and the literature [2] also needs to add chromite and manganese oxide ore, It is a waste of chromium and manganese resources. The advantage of literature [3] and [4] is that the iron in the vanadium extraction tailings is extracted, and the disadvantage is that the remaining slag after iron extraction is not utilized. And the iron, manganese and chromium in the reduced vanadium extraction tailings can be magnetically separated out by the available magnetic separation method described in the document [4], but only iron can be magnetically separated out, and manganese and chromium, because of their interatomic The spin tends to be arranged in reverse, and the magnetic moments between atoms are low and cancel each other. It is an antiferromagnetic substance, so it is impossible to magnetically separate manganese and chromium by magnetic separation.
钒钛陶瓷可以用于制造太阳能热水器，太阳能房顶、远红外辐射元件、建筑装饰板等。钒钛陶瓷成本低、寿命长、效率高，和我国现有陶瓷产业的规模和产量结合，有可能发展成规模化生产的能源材料。目前钒钛陶瓷制备方法，主要是将提钒尾渣按照一定比例混合于普通陶瓷材料中烧结成瓷，或者在普通陶瓷坯体表面涂覆提钒尾渣浆料，再烧结成瓷。Vanadium-titanium ceramics can be used to make solar water heaters, solar roofs, far-infrared radiation elements, building decorative panels, etc. Vanadium-titanium ceramics have low cost, long life, and high efficiency. Combined with the scale and output of my country's existing ceramic industry, it is possible to develop into energy materials for large-scale production. At present, the preparation method of vanadium-titanium ceramics is mainly to mix vanadium-extracted tailings with ordinary ceramic materials in a certain proportion and sinter them into porcelain, or to coat the surface of ordinary ceramic body with vanadium-extracted tailings slurry, and then sinter them into porcelain.
发明内容Contents of the invention
本发明所要解决的技术问题提供一种黑色陶瓷材料，其以选矿尾矿和提钒尾渣为原料烧结成瓷，所得黑瓷材料的阳光吸收率为0.85～0.90。The technical problem to be solved by the present invention is to provide a black ceramic material, which is sintered into porcelain from ore dressing tailings and vanadium extraction tailings, and the sunlight absorption rate of the obtained black ceramic material is 0.85-0.90.
本发明的技术方案：Technical scheme of the present invention:
本发明提供一种黑色陶瓷材料，以重量份计，所述黑色陶瓷材料的成分包括：The present invention provides a kind of black ceramic material, by weight, the composition of described black ceramic material comprises:
Gr2O31.82-3.7份、TiO210.9-18.18份、V2O51.94-4.13份、MnO6.06-11.91份、Fe2O38-14份、Ni0.001-0.01份、SiO212-24.3份。Gr 2 O 3 1.82-3.7 parts, TiO 2 10.9-18.18 parts, V 2 O 5 1.94-4.13 parts, MnO6.06-11.91 parts, Fe 2 O 3 8-14 parts, Ni0.001-0.01 parts, SiO 2 12-24.3 parts.
本发明上述黑色陶瓷材料，其以磁选尾渣和钒钛磁铁矿选钛矿尾渣为原料烧结成瓷，磁选尾渣和钒钛磁铁矿选钛矿尾渣的重量比为：2-10︰1；其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～8％。Above-mentioned black ceramic material of the present invention, it is sintered into porcelain with magnetic separation tailings and vanadium-titanium magnetite beneficiation titanium ore tailings as raw material, the weight ratio of magnetic separation tailings and vanadium-titanium magnetite beneficiation titanium ore tailings is: 2-10︰1; Among them, the magnetic separation tailings are made by the following method: mixing the vanadium extraction tailings, carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets, and the pellets are dried and reduced , and then through crushing and magnetic separation, reduced iron powder and magnetic separation tailings are obtained. The consumption of each raw material is as follows: the vanadium extraction tailings are based on 100 parts, and the carbonaceous reducing agent (in terms of its carbon content) is used in the amount of vanadium extraction tailings 10.5-25% of the weight, the amount of sodium salt is 1-4% of the weight of the tailings for vanadium extraction, the amount of iron powder is 0-2% of the weight of the tailings for vanadium extraction, and the amount of lime is 0-8% of the weight of the tailings for vanadium extraction .
优选的，各原料的用量为：提钒尾渣以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的15％，钠盐用量为提钒尾渣重量的4％，铁粉用量为提钒尾渣重量的2％，石灰用量为提钒尾渣重量的7.5％。Preferably, the consumption of each raw material is: the amount of vanadium extraction tailings is based on 100 parts, the amount of carbonaceous reducing agent (in terms of its carbon content) is 15% of the weight of vanadium extraction tailings, and the amount of sodium salt is 100% of the weight of vanadium extraction tailings. 4%, the amount of iron powder is 2% of the weight of the tailings for vanadium extraction, and the amount of lime is 7.5% of the weight of the tailings for vanadium extraction.
优选的，所述提钒尾渣的粒度为0.165-0.417mm。Preferably, the particle size of the vanadium extraction tailings is 0.165-0.417mm.
所述碳质还原剂为焦碳、煤、碳黑、木炭中至少一种。The carbonaceous reducing agent is at least one of coke, coal, carbon black and charcoal.
优选的，所述碳质还原剂的粒度为0.25～0.05mm。Preferably, the particle size of the carbonaceous reducing agent is 0.25-0.05mm.
所述铁粉中铁含量在90％以上。The iron content in the iron powder is above 90%.
优选的，所述铁粉的粒度为0.063～0.125mm。Preferably, the particle size of the iron powder is 0.063-0.125 mm.
所述钠盐为Na2CO3、NaCl、Na2SO4中至少一种。The sodium salt is at least one of Na 2 CO 3 , NaCl, and Na 2 SO 4 .
优选的，所述钠盐溶液的浓度为1.5～3mol·L-1。Preferably, the concentration of the sodium salt solution is 1.5-3 mol·L -1 .
所述石灰为熟石灰，CaO的含量为66.45％以上。The lime is slaked lime, and the content of CaO is more than 66.45%.
上述磁选尾渣的制备方法中，球团采用的干燥方式为日晒12～72小时或于50～250℃下保温2小时～42小时烘干。In the above preparation method of magnetic separation tailings, the pellets are dried in the sun for 12-72 hours or at 50-250° C. for 2 hours-42 hours.
上述磁选尾渣的制备方法中，球团采用还原炉进行还原，所述还原炉为转底炉、管式炉或马弗炉。In the above preparation method of magnetic separation tailings, the pellets are reduced in a reduction furnace, and the reduction furnace is a rotary hearth furnace, a tube furnace or a muffle furnace.
优选的，球团在马弗炉内还原时，球团周围应充填碳质还原剂。Preferably, when the pellets are reduced in the muffle furnace, a carbonaceous reducing agent should be filled around the pellets.
优选的，为了使球团还原时金属不被氧化，球团在炉内的气氛为非氧化性气氛。Preferably, in order to prevent the metal from being oxidized when the pellets are reduced, the atmosphere of the pellets in the furnace is a non-oxidizing atmosphere.
上述磁选尾渣的制备方法中，球团破碎为粒度≤0.165mm粉末。In the above method for preparing magnetically separated tailings, the pellets are broken into powders with a particle size of ≤0.165 mm.
上述磁选尾渣的制备方法中，磁选强度为50-65mT(毫斯特拉)。In the above preparation method of magnetic separation tailings, the magnetic separation intensity is 50-65mT (milliStra).
进一步，上述黑色陶瓷中，其原料还包括普通陶瓷料，各原料的重量比为：磁选尾渣︰钒钛磁铁矿选钛矿尾渣︰普通陶瓷料＝2-10︰1︰0.0001-0.5其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣用量以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～5％。Further, among the above-mentioned black ceramics, the raw materials also include ordinary ceramic materials, and the weight ratio of each raw material is: magnetic separation tailings: vanadium titanomagnetite titanium ore tailings: ordinary ceramic materials = 2-10: 1: 0.0001- 0.5 Among them, the magnetic separation tailings are made by the following method: mixing the vanadium extraction tailings, carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets, the pellets are dried, reduced, and then crushed, Magnetic separation obtains reduced iron powder and magnetic separation tailings. The consumption of each raw material is: the amount of tailings for vanadium extraction is based on 100 parts, and the amount of carbonaceous reductant (in terms of its carbon content) is 10.5 to 10.5% of the weight of tailings for vanadium extraction. 25%, the amount of sodium salt is 1-4% of the weight of the tailings for vanadium extraction, the amount of iron powder is 0-2% of the weight of the tailings for vanadium extraction, and the amount of lime is 0-5% of the weight of the tailings for vanadium extraction.
优选的，各原料的重量比为：磁选尾渣︰钒钛磁铁矿选钛矿尾渣︰普通陶瓷料＝2-6︰1︰0.0001-0.4。Preferably, the weight ratio of each raw material is: magnetic separation tailings: vanadium-titanium magnetite titanium ore tailings: common ceramic material = 2-6: 1: 0.0001-0.4.
所述普通陶瓷料为昔格达土、硅铁灰或膨润土中的至少一种。The common ceramic material is at least one of Xigeda clay, ferrosilicon ash or bentonite.
优选的，所述黑色陶瓷中，当原料为昔格达土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝2-6︰1。Preferably, in the black ceramics, when the raw material is Xigeda soil, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=2-6:1.
优选的，所述黑色陶瓷中，当原料为硅灰和昔格达土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝3-10︰1。Preferably, in the black ceramics, when the raw materials are silica fume and Xigeda soil, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=3-10:1.
优选的，所述黑色陶瓷中，当原料为硅粉和膨润土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝2-10︰1。Preferably, in the black ceramics, when the raw materials are silicon powder and bentonite, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=2-10:1.
优选的，所述黑色陶瓷中，当原料为昔格达土时，其粒度为0.074-0.165mm。Preferably, in the black ceramics, when the raw material is Xigeda clay, its particle size is 0.074-0.165mm.
优选的，所述黑色陶瓷中，当原料为硅灰时，其粒度为0.074-0.165mm。Preferably, in the black ceramics, when the raw material is silica fume, its particle size is 0.074-0.165 mm.
优选的，所述黑色陶瓷中，当原料为膨润土时，其粒度为0.061-0.074mm。Preferably, in the black ceramics, when the raw material is bentonite, its particle size is 0.061-0.074mm.
本发明还提供了上述黑色陶瓷材料的制备方法为：将磁选尾渣与钒钛磁铁矿选钛矿尾渣混匀，球磨至粒径0.025-0.05mm得球磨混合料，再压制成型，然后于1000℃～1100℃烧结0.5-1小时，冷却即得黑色陶瓷材料。The present invention also provides a preparation method for the above-mentioned black ceramic material: mixing the tailings from magnetic separation with the tailings from vanadium-titanium-magnetite and titanium ore, ball milling to obtain a ball-milling mixture with a particle size of 0.025-0.05 mm, and then pressing to form, Then sinter at 1000°C to 1100°C for 0.5-1 hour, and cool to obtain a black ceramic material.
进一步，烧结冷却后再粉碎至0.025-0.09mm得黑色陶瓷材料末。Further, after sintering and cooling, it is pulverized to 0.025-0.09mm to obtain black ceramic material powder.
本发明还提供了钒钛磁铁矿选钛矿尾渣的用途，其与提钒尾渣作为原料制备黑色陶瓷，具体方法为：以磁选尾渣和钒钛磁铁矿选钛矿尾渣为原料烧结成瓷，磁选尾渣和钒钛磁铁矿选钛矿尾渣的重量比为：2-10︰1；其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣用量以100计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～5％。The present invention also provides the use of vanadium-titanium-magnetite beneficiation titanium ore tailings, which and vanadium extraction tailings are used as raw materials to prepare black ceramics. The specific method is: using magnetic separation tailings and vanadium-titanium-magnetite beneficiation titanium ore tailings The raw material is sintered into porcelain, the weight ratio of magnetic separation tailings and vanadium-titanium-magnetite titanium ore tailings is: 2-10:1; wherein, the magnetic separation tailings are made by the following method: the vanadium extraction tailings, Mix carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets. The pellets are dried, reduced, crushed, and magnetically separated to obtain reduced iron powder and magnetic separation tailings. The dosage of each raw material is: The amount of tailings for vanadium extraction is calculated as 100, the amount of carbonaceous reducing agent (calculated by its carbon content) is 10.5-25% of the weight of tailings for vanadium extraction, the amount of sodium salt is 1-4% of the weight of tailings for vanadium extraction, iron powder The dosage is 0-2% of the weight of the tailings for vanadium extraction, and the dosage of lime is 0-5% of the weight of the tailings for vanadium extraction.
本发明的有益效果：Beneficial effects of the present invention:
1、本发明采用钠盐和铁粉联合催化，有效地降低了还原温度，缩短了还原时间，降低了能耗，提高了生产效率。1. The present invention adopts the joint catalysis of sodium salt and iron powder, which effectively reduces the reduction temperature, shortens the reduction time, reduces energy consumption, and improves production efficiency.
2、本发明将钠盐溶解于水，然后和碳质还原剂、提钒尾渣、铁粉、熟石灰混合均匀，再将此混合料和粘结剂混合均匀后压制成球团；这种混料方式保证了钠盐能均匀地分布于提钒尾渣中，从而充分保证了钠盐对提钒尾渣还原的催化作用。2. The present invention dissolves the sodium salt in water, then mixes it evenly with carbonaceous reducing agent, vanadium extraction tailings, iron powder, and slaked lime, and then presses the mixture into pellets after being evenly mixed with the binder; The feeding method ensures that the sodium salt can be evenly distributed in the vanadium extraction tailings, thereby fully ensuring the catalytic effect of the sodium salt on the reduction of the vanadium extraction tailings.
3、本发明使用的钠盐量少，钠盐混合均匀，球团在还原过程中不会产生崩溃或粉化。3. The amount of sodium salt used in the present invention is small, the sodium salt is mixed evenly, and the pellets will not collapse or pulverize during the reduction process.
4、本发明综合利用提钒尾渣、选矿尾矿和硅灰三种工业废料，制取出的黑瓷可用于生产太阳能集热材料，同时附产的铁粉可用于钢铁生产。4. The present invention comprehensively utilizes three kinds of industrial wastes including vanadium extracting tailings, ore dressing tailings and silica fume, and the black porcelain produced can be used to produce solar energy heat collecting materials, and the iron powder produced by it can be used in steel production at the same time.
本发明以选矿尾矿和提钒尾渣相结合，既提取提钒尾渣中的铁，又将提铁后产生的非磁性物和选矿尾矿相结合，生产黑瓷材料的方法，达到全部利用提钒尾渣、选矿尾矿，彻底解决两种渣形成的污染问题。The present invention combines ore dressing tailings and vanadium extraction tailings, not only extracts the iron in the vanadium extraction tailings, but also combines the non-magnetic substances produced after iron extraction with the ore dressing tailings to produce black porcelain materials, achieving all Utilize vanadium extraction tailings and mineral processing tailings to completely solve the pollution problem caused by the two kinds of slags.
现有的钒钛陶瓷制备方法，没有将提钒尾渣中的铁和镓提取出来，其中的资源未得到充分利用；本发明的对提钒尾渣先进行还原磁选处理，将其中的铁提取出来，镓则溶入铁的晶格中随铁一起提取出来，铁提取出来后，可采用水溶液电解法分离出铁粉和氧化镓。而磁选产生的磁选尾渣则断续用于制取黑瓷粉末，使提钒尾渣得到了更好的利用，并且还可附产高纯电解铁粉和稀贵的氧化镓。本发明还利用了另两种难以处理的工业废渣即钒钛磁铁矿选钛矿尾渣和硅铁灰，从而有废渣处理、循环经济的环保社会效益。本发明所制成的黑瓷材料的阳光吸收率为0.85～0.90。The existing method for preparing vanadium-titanium ceramics does not extract iron and gallium from the tailings of vanadium extraction, and the resources therein are not fully utilized; in the present invention, the tailings of vanadium extraction are first subjected to reduction magnetic separation treatment, and the iron After extraction, gallium is dissolved in the iron lattice and extracted together with iron. After the iron is extracted, iron powder and gallium oxide can be separated by aqueous solution electrolysis. The magnetic separation tailings produced by magnetic separation are intermittently used to produce black porcelain powder, which makes better use of the vanadium extraction tailings, and can also produce high-purity electrolytic iron powder and rare gallium oxide. The invention also utilizes other two kinds of industrial waste slags that are difficult to handle, that is, vanadium-titanium magnetite beneficiation titanium ore tailings and ferrosilicon ash, so as to have environmental protection and social benefits of waste slag treatment and circular economy. The solar absorptivity of the black porcelain material prepared by the invention is 0.85-0.90.
具体实施方式detailed description
本发明提供一种黑色陶瓷材料，以重量份计，所述黑色陶瓷材料的成分包括：The present invention provides a kind of black ceramic material, by weight, the composition of described black ceramic material comprises:
Gr2O31.82-3.7份、TiO210.9-18.18份、V2O51.94-4.13份、MnO6.06-11.91份、Fe2O38-14份、Ni0.001-0.01份、SiO212-24.3份。Gr 2 O 3 1.82-3.7 parts, TiO 2 10.9-18.18 parts, V 2 O 5 1.94-4.13 parts, MnO6.06-11.91 parts, Fe 2 O 3 8-14 parts, Ni0.001-0.01 parts, SiO 2 12-24.3 parts.
本发明上述黑色陶瓷材料，其以磁选尾渣和钒钛磁铁矿选钛矿尾渣为原料烧结成瓷，磁选尾渣和钒钛磁铁矿选钛矿尾渣的重量比为：2-10︰1；其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～8％。Above-mentioned black ceramic material of the present invention, it is sintered into porcelain with magnetic separation tailings and vanadium-titanium magnetite beneficiation titanium ore tailings as raw material, the weight ratio of magnetic separation tailings and vanadium-titanium magnetite beneficiation titanium ore tailings is: 2-10︰1; Among them, the magnetic separation tailings are made by the following method: mixing the vanadium extraction tailings, carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets, and the pellets are dried and reduced , and then through crushing and magnetic separation, reduced iron powder and magnetic separation tailings are obtained. The consumption of each raw material is as follows: the vanadium extraction tailings are based on 100 parts, and the carbonaceous reducing agent (in terms of its carbon content) is used in the amount of vanadium extraction tailings 10.5-25% of the weight, the amount of sodium salt is 1-4% of the weight of the tailings for vanadium extraction, the amount of iron powder is 0-2% of the weight of the tailings for vanadium extraction, and the amount of lime is 0-8% of the weight of the tailings for vanadium extraction .
优选的，各原料的用量为：提钒尾渣以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的15％，钠盐用量为提钒尾渣重量的4％，铁粉用量为提钒尾渣重量的2％，石灰用量为提钒尾渣重量的7.5％。Preferably, the consumption of each raw material is: the amount of vanadium extraction tailings is based on 100 parts, the amount of carbonaceous reducing agent (in terms of its carbon content) is 15% of the weight of vanadium extraction tailings, and the amount of sodium salt is 100% of the weight of vanadium extraction tailings. 4%, the amount of iron powder is 2% of the weight of the tailings for vanadium extraction, and the amount of lime is 7.5% of the weight of the tailings for vanadium extraction.
本发明所述的提钒尾渣是指用钒钛磁铁矿为原料冶炼钢铁过程中产生的钒渣为原料，提取五氧化二钒后剩余的渣。The tailings for vanadium extraction in the present invention refer to the vanadium slag produced in the process of smelting iron and steel with vanadium-titanium magnetite as raw material, and the remaining slag after extracting vanadium pentoxide.
优选的，所述提钒尾渣的粒度为0.165-0.417mm。本发明中，若粒度过大，还原时间太长，料度过小，压制难以成型。Preferably, the particle size of the vanadium extraction tailings is 0.165-0.417mm. In the present invention, if the particle size is too large, the reduction time will be too long, and if the material is too small, it will be difficult to form by pressing.
所述碳质还原剂为焦碳、煤、碳黑、木炭中至少一种。The carbonaceous reducing agent is at least one of coke, coal, carbon black and charcoal.
优选的，所述碳质还原剂的粒度为0.25～0.05mm。本发明中，粒度过大，还原时间太长，料度过小，压制难以成型。Preferably, the particle size of the carbonaceous reducing agent is 0.25-0.05 mm. In the present invention, if the particle size is too large, the reduction time is too long, and the material is too small, so it is difficult to form by pressing.
所述铁粉中铁含量在90％以上。The iron content in the iron powder is above 90%.
优选的，所述铁粉的粒度为0.063～0.125mm；加入的铁粉作为生成金属铁晶种的作用，并与钠盐起联合催化作用，提高还原效率，缩短还原时间；本发明中，铁粉粒度过大，不易混匀，且起不到晶种作用，粒度过小，表面能过高，在空气就发生了氧化，成为氧化铁，同样起不到晶种作用。Preferably, the particle size of the iron powder is 0.063-0.125mm; the added iron powder acts as a metal iron seed crystal, and acts as a joint catalyst with the sodium salt to improve the reduction efficiency and shorten the reduction time; in the present invention, the iron powder If the particle size is too large, it is not easy to mix, and it cannot play the role of seed crystal. If the particle size is too small, the surface energy is too high. It will be oxidized in the air and become iron oxide, which also cannot play the role of seed crystal.
所述钠盐为Na2CO3、NaCl、Na2SO4中至少一种；Na2CO3、NaCl、Na2SO4在高温还原过程中能破坏氧化铁中的晶格，从而起到催化氧化铁还原的作用。The sodium salt is at least one of Na 2 CO 3 , NaCl, and Na 2 SO 4 ; Na 2 CO 3 , NaCl, and Na 2 SO 4 can destroy the lattice in iron oxide during the high-temperature reduction process, thereby acting as a catalyst The role of iron oxide reduction.
优选的，所述钠盐溶液的浓度为1.5～3mol·L-1。Preferably, the concentration of the sodium salt solution is 1.5-3 mol·L -1 .
所述石灰为熟石灰，CaO的含量为66.45％以上。The lime is slaked lime, and the content of CaO is more than 66.45%.
上述磁选尾渣的制备方法中，球团采用的干燥方式为日晒12～72小时或于50～250℃下保温2小时～42小时烘干。In the above preparation method of magnetic separation tailings, the pellets are dried in the sun for 12-72 hours or at 50-250° C. for 2 hours-42 hours.
优选的，上述磁选尾渣的制备方法中，球团采用的干燥方式为100℃的下保温12小时。Preferably, in the above-mentioned method for preparing tailings from magnetic separation, the pellets are dried at 100° C. for 12 hours.
上述磁选尾渣的制备方法中，球团采用还原炉进行还原，所述还原炉为转底炉、管式炉或马弗炉。In the above preparation method of magnetic separation tailings, the pellets are reduced in a reduction furnace, and the reduction furnace is a rotary hearth furnace, a tube furnace or a muffle furnace.
优选的，球团在马弗炉内还原时，球团周围应充填碳质还原剂。Preferably, when the pellets are reduced in the muffle furnace, a carbonaceous reducing agent should be filled around the pellets.
优选的，为了使球团还原时金属不被氧化，球团在炉内的气氛为非氧化性气氛。Preferably, in order to prevent the metal from being oxidized when the pellets are reduced, the atmosphere of the pellets in the furnace is a non-oxidizing atmosphere.
上述磁选尾渣的制备方法中，球团破碎为粒度≤0.165mm粉末。In the above method for preparing magnetically separated tailings, the pellets are broken into powders with a particle size of ≤0.165 mm.
上述磁选尾渣的制备方法中，磁选强度为50-65mT(毫斯特拉)。强度过小，则还原所得的金属铁不能充分选出，强度过大，刚非磁性粉末附在金属铁粉表面一起带出，起不到分离的目的。In the above preparation method of magnetic separation tailings, the magnetic separation intensity is 50-65mT (milliStra). If the strength is too small, the metal iron obtained by reduction cannot be fully separated; if the strength is too high, the non-magnetic powder will be attached to the surface of the metal iron powder and carried out together, and the purpose of separation will not be achieved.
进一步，上述黑色陶瓷中，其原料还包括普通陶瓷料，各原料的重量比为：磁选尾渣︰钒钛磁铁矿选钛矿尾渣︰普通陶瓷料＝2-10︰1︰0.0001-0.5其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣用量以100份计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～5％。Further, among the above-mentioned black ceramics, the raw materials also include ordinary ceramic materials, and the weight ratio of each raw material is: magnetic separation tailings: vanadium titanomagnetite titanium ore tailings: ordinary ceramic materials = 2-10: 1: 0.0001- 0.5 Among them, the magnetic separation tailings are made by the following method: mixing the vanadium extraction tailings, carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets, the pellets are dried, reduced, and then crushed, Magnetic separation obtains reduced iron powder and magnetic separation tailings. The consumption of each raw material is: the amount of tailings for vanadium extraction is based on 100 parts, and the amount of carbonaceous reductant (in terms of its carbon content) is 10.5 to 10.5% of the weight of tailings for vanadium extraction. 25%, the amount of sodium salt is 1-4% of the weight of the tailings for vanadium extraction, the amount of iron powder is 0-2% of the weight of the tailings for vanadium extraction, and the amount of lime is 0-5% of the weight of the tailings for vanadium extraction.
优选的，各原料的重量比为：磁选尾渣︰钒钛磁铁矿选钛矿尾渣︰普通陶瓷料＝2-6︰1︰0.0001-0.4。Preferably, the weight ratio of each raw material is: magnetic separation tailings: vanadium-titanium magnetite titanium ore tailings: common ceramic material = 2-6: 1: 0.0001-0.4.
所述普通陶瓷料为昔格达土、硅铁灰或膨润土中的至少一种。The common ceramic material is at least one of Xigeda clay, ferrosilicon ash or bentonite.
优选的，所述黑色陶瓷中，当原料为昔格达土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝2-6︰1。Preferably, in the black ceramics, when the raw material is Xigeda soil, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=2-6:1.
优选的，所述黑色陶瓷中，当原料为硅灰和昔格达土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝3-10︰1。Preferably, in the black ceramics, when the raw materials are silica fume and Xigeda soil, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=3-10:1.
优选的，所述黑色陶瓷中，当原料为硅粉和膨润土时，磁选尾渣︰钒钛磁铁矿选钛矿尾渣＝2-10︰1。Preferably, in the black ceramics, when the raw materials are silicon powder and bentonite, magnetic separation tailings:vanadium titanomagnetite titanium ore tailings=2-10:1.
优选的，所述黑色陶瓷中，当原料为昔格达土时，其粒度为0.074-0.165mm。Preferably, in the black ceramics, when the raw material is Xigeda clay, its particle size is 0.074-0.165mm.
优选的，所述黑色陶瓷中，当原料为硅灰时，其粒度为0.074-0.165mm。Preferably, in the black ceramics, when the raw material is silica fume, its particle size is 0.074-0.165 mm.
优选的，所述黑色陶瓷中，当原料为膨润土时，其粒度为0.061-0.074mm。Preferably, in the black ceramics, when the raw material is bentonite, its particle size is 0.061-0.074mm.
本发明还提供了上述黑色陶瓷材料的制备方法为：将磁选尾渣与钒钛磁铁矿选钛矿尾渣混匀，球磨至粒径0.025-0.05mm得球磨混合料，再压制成型，然后于1000℃～1100℃烧结0.5-1小时，冷却即得黑色陶瓷材料。The present invention also provides a preparation method for the above-mentioned black ceramic material: mixing the tailings from magnetic separation with the tailings from vanadium-titanium-magnetite and titanium ore, ball milling to obtain a ball-milling mixture with a particle size of 0.025-0.05 mm, and then pressing to form, Then sinter at 1000°C to 1100°C for 0.5-1 hour, and cool to obtain a black ceramic material.
进一步，烧结冷却后再粉碎至0.025-0.09mm得黑色陶瓷材料末。Further, after sintering and cooling, it is pulverized to 0.025-0.09mm to obtain black ceramic material powder.
本发明还提供了钒钛磁铁矿选钛矿尾渣的用途，其与提钒尾渣作为原料制备黑色陶瓷，具体方法为：以磁选尾渣和钒钛磁铁矿选钛矿尾渣为原料烧结成瓷，磁选尾渣和钒钛磁铁矿选钛矿尾渣的重量比为：2-10︰1；其中，磁选尾渣由以下方法制成：将提钒尾渣、碳质还原剂、铁粉、石灰和钠盐溶液混匀制成球团，球团经干燥、还原，再经破碎、磁选，得到还原铁粉和磁选尾渣，各原料的用量为：提钒尾渣用量以100计，碳质还原剂(以其碳含量计)用量为提钒尾渣重量的10.5～25％，钠盐用量为提钒尾渣重量的1～4％，铁粉用量为提钒尾渣重量的0～2％，石灰用量为提钒尾渣重量的0～5％。The present invention also provides the use of vanadium-titanium-magnetite beneficiation titanium ore tailings, which and vanadium extraction tailings are used as raw materials to prepare black ceramics. The specific method is: using magnetic separation tailings and vanadium-titanium-magnetite beneficiation titanium ore tailings The raw material is sintered into porcelain, the weight ratio of magnetic separation tailings and vanadium-titanium-magnetite titanium ore tailings is: 2-10:1; wherein, the magnetic separation tailings are made by the following method: the vanadium extraction tailings, Mix carbonaceous reducing agent, iron powder, lime and sodium salt solution to form pellets. The pellets are dried, reduced, crushed, and magnetically separated to obtain reduced iron powder and magnetic separation tailings. The dosage of each raw material is: The amount of tailings for vanadium extraction is calculated as 100, the amount of carbonaceous reducing agent (calculated by its carbon content) is 10.5-25% of the weight of tailings for vanadium extraction, the amount of sodium salt is 1-4% of the weight of tailings for vanadium extraction, iron powder The dosage is 0-2% of the weight of the tailings for vanadium extraction, and the dosage of lime is 0-5% of the weight of the tailings for vanadium extraction.
昔格达土：岩性下部以砾岩为主，泥钙质胶结，成分复杂；中部为灰色、杂色条带状粘土岩与黄色细砂岩互层，其顶部为紫红色厚层状钙质粘土岩，含介形虫、硅藻及孢粉等化石；上部以黄色厚，巨厚层细砂岩为主，夹杂色条带状粘土岩，含钙质结核。Xigeda soil: The lower part of the lithology is dominated by conglomerate, muddy calcareous cementation, and complex composition; the middle part is interbedded with gray and variegated banded claystone and yellow fine sandstone, and the top is purple-red thick-bedded calcareous Claystone, containing fossils such as ostracods, diatoms and sporopollen; the upper part is dominated by yellow thick, ultra-thick fine sandstone, mixed with colored banded claystone, containing calcareous concretions.
膨润土：分析值：Al2O3：16.54％、FeO：0.26％、SiO2：50.95％、Fe2O3：1.36％、MgO：4.65％、CaO：2.26％、K2O：0.47％、H2O：23.29％。Bentonite: Analysis value: Al 2 O 3 : 16.54%, FeO: 0.26%, SiO 2 : 50.95%, Fe 2 O 3 : 1.36%, MgO: 4.65%, CaO: 2.26%, K 2 O: 0.47%, H 2 O: 23.29%.
硅铁灰：SiO2：96.66％。Ferrosilicon ash: SiO 2 : 96.66%.
下述实施例中所用提钒尾渣的的化学成分为：Cr2O3＝2.24％、TFe＝32.8％、TiO2＝12.90％、V2O5＝2.08％、MnO＝7.84％、SiO2＝14.40％、Al2O3＝3.20、CaO＝2.50、MgO＝3.57％、Na2O＝5.26％、S＝0.05％。钒钛磁铁矿选钛矿尾渣的化学组成为：TiO2＝4.16％、Fe＝7.89％、S＝0.04％、SiO2＝45.61％、CaO＝10.89％、MgO＝8.12％，其余为22.84％。还原剂煤粉的成分为：固定碳＝86％、灰分＝10.2％、挥发物＝5.3％。本发明实施例中，所述提钒尾渣的粒度为0.165-0.417mm，所述碳质还原剂的粒度为0.25～0.05mm，所述铁粉的粒度为0.063～0.125mm。The chemical composition of vanadium extraction tailings used in the following examples is: Cr2O3 = 2.24%, TFe=32.8%, TiO2 =12.90%, V2O5 =2.08%, MnO =7.84%, SiO2 =14.40%, Al 2 O 3 =3.20, CaO=2.50, MgO=3.57%, Na 2 O=5.26%, S=0.05%. The chemical composition of vanadium titanomagnetite titanium ore tailings is: TiO 2 =4.16%, Fe=7.89%, S=0.04%, SiO 2 =45.61%, CaO=10.89%, MgO=8.12%, and the rest is 22.84% %. The composition of the reducing agent coal powder is: fixed carbon = 86%, ash = 10.2%, volatile matter = 5.3%. In the embodiment of the present invention, the particle size of the vanadium extraction tailings is 0.165-0.417mm, the particle size of the carbonaceous reducing agent is 0.25-0.05mm, and the particle size of the iron powder is 0.063-0.125mm.
实施例1Example 1
提钒尾渣还原磁选处理：称量1000g提钒尾渣、105g石墨粉、加入浓度为1.87mol/L的碳酸钠溶液200ml混合均匀；然后将这种混合料压制成球团；在100℃下干燥12小时后取干燥后的球团在管式炉内，1220℃、氮气气氛下保温4h，得到金属化率为88.3％；还原球团破碎为粒度是0.165mm粉末在磁感强度为55mT下次选得到还原铁粉和非磁性物质。Reduction magnetic separation treatment of vanadium extraction tailings: Weigh 1000g of vanadium extraction tailings, 105g of graphite powder, add 200ml of sodium carbonate solution with a concentration of 1.87mol/L and mix evenly; then press this mixture into pellets; After drying under high temperature for 12 hours, take the dried pellets and put them in a tube furnace at 1220°C under a nitrogen atmosphere for 4 hours to obtain a metallization rate of 88.3%; the reduced pellets are broken into powders with a particle size of 0.165mm at a magnetic induction of 55mT The next time you choose reduced iron powder and non-magnetic substances.
选钛尾矿在1100℃下煅烧10min，破碎到粒度为0.198mm。The titanium-selected tailings were calcined at 1100°C for 10 minutes and crushed to a particle size of 0.198mm.
取磁选尾渣100g、钒钛磁铁矿选钛矿尾渣50g、昔格达土10g，将这三种固体料混合均匀；在球磨机内球磨8h；得到的球磨混合料的粒度为0.045mm将球磨混合料用压制的方法成型，将成型坯在1000℃烧结0.5小时，再将烧结坯粉碎至0.074mm，得到黑色陶瓷材料末，测量黑瓷阳光吸收率为0.85。Take 100g of magnetic separation tailings, 50g of vanadium-titanium-magnetite titanium-separation tailings, and 10g of Xigeda soil, and mix these three solid materials evenly; ball mill in a ball mill for 8 hours; the particle size of the obtained ball mill mixture is 0.045mm The ball mill mixture was molded by pressing, and the molded body was sintered at 1000°C for 0.5 hours, and then the sintered body was crushed to 0.074mm to obtain black ceramic material powder. The measured solar absorption rate of black porcelain was 0.85.
实施例2Example 2
提钒尾渣还原磁选处理：称量1000g提钒尾渣、105g石墨粉、加入浓度为1.87mol/L的碳酸钠溶液200ml混合均匀；然后将这种混合料压制成球团；在100℃下干燥12小时后取干燥后的球团在在管式炉内，1220℃、氩气气氛下保温4h，得到金属化率为88.3％。还原球团破碎为粒度是0.165mm粉末在磁感强度为55mT下次选得到还原铁粉和非磁性物质。Reduction magnetic separation treatment of vanadium extraction tailings: Weigh 1000g of vanadium extraction tailings, 105g of graphite powder, add 200ml of sodium carbonate solution with a concentration of 1.87mol/L and mix evenly; then press this mixture into pellets; After drying under high temperature for 12 hours, the dried pellets were kept in a tube furnace at 1220° C. under an argon atmosphere for 4 hours to obtain a metallization rate of 88.3%. The reduced pellets are crushed into powders with a particle size of 0.165 mm and the magnetic induction intensity is 55 mT for next selection to obtain reduced iron powder and non-magnetic substances.
选钛尾矿在1100℃下煅烧10min，破碎到粒度为0.198mm。The titanium-selected tailings were calcined at 1100°C for 10 minutes and crushed to a particle size of 0.198mm.
取磁选尾渣200g、钒钛磁铁矿选钛矿尾渣50g、昔格达土10g，将这三种固体料混合均匀。在球磨机内球磨10h；将球磨混合料用压制的方法成型，将成型坯在1075℃烧结1小时，再将烧结坯粉碎至0.074mm，得到黑色陶瓷材料末，测量黑瓷阳光吸收率为0.85。Take 200g of magnetic separation tailings, 50g of vanadium-titanium magnetite titanium ore tailings, and 10g of Xigeda soil, and mix these three solid materials evenly. Ball milled in a ball mill for 10 hours; the ball-milled mixture was formed by pressing, and the molded body was sintered at 1075°C for 1 hour, and then the sintered body was crushed to 0.074mm to obtain a black ceramic material powder. The measured black porcelain sunlight absorption rate was 0.85.
实施例3Example 3
提钒尾渣还原磁选处理：称量1000g提钒尾渣、150g煤粉、加入浓度为1.87mol/L的碳酸钠溶液200ml混合均匀、加入CaO含量为66.45％的熟石灰75.25g、20g铁粉；然后将这种混合料压制成球团，在100℃下干燥12小时，取干燥后的球团置于坩锅内，球团周围充填煤粉后放入马弗炉内，在1150℃保温3h，得到金属化率为86.3％；还原球团破碎为粒度是0.165mm粉末在磁感强度65mT下次选得到还原铁粉和非磁性物质。Reduction magnetic separation treatment of vanadium extraction tailings: Weigh 1000g of vanadium extraction tailings, 150g of coal powder, add 200ml of sodium carbonate solution with a concentration of 1.87mol/L and mix evenly, add 75.25g of slaked lime with a CaO content of 66.45%, and 20g of iron powder ; Then press this mixture into pellets, dry at 100°C for 12 hours, take the dried pellets and place them in a crucible, fill the pellets with coal powder and put them in a muffle furnace, and keep warm at 1150°C After 3 hours, the metallization rate was 86.3%. The reduced pellets were crushed into powders with a particle size of 0.165 mm, and the reduced iron powder and non-magnetic substances were obtained by the next election at a magnetic induction intensity of 65 mT.
选钛尾矿在1100℃下煅烧10min，破碎到粒度为0.198mm。The titanium-selected tailings were calcined at 1100°C for 10 minutes and crushed to a particle size of 0.198mm.
取磁选尾渣200g、钒钛磁铁矿选钛矿尾渣50g、昔格达土10g、硅灰10g，将这四种固体料混合均匀；在球磨机内球磨8h；将球磨混合料用压制的方法成型，得到的球磨混合料的粒度为0.045mm将成型坯在1000℃烧结0.5小时，再将烧结坯粉碎至0.074mm，得到黑色陶瓷材料末，测量黑瓷阳光吸收率为0.85。Take 200g of magnetic separation tailings, 50g of vanadium-titanium-magnetite titanium-separation tailings, 10g of Xigeda soil, and 10g of silica fume, and mix these four solid materials evenly; ball mill in a ball mill for 8 hours; The particle size of the obtained ball mill mixture is 0.045mm. Sinter the compact at 1000°C for 0.5 hour, and then crush the sintered compact to 0.074mm to obtain black ceramic material powder. The measured black porcelain sunlight absorption rate is 0.85.
实施例4Example 4
提钒尾渣还原磁选处理：称量1000g提钒尾渣、150g煤粉、加入浓度为1.87mol/L的碳酸钠溶液200ml混合均匀、加入CaO含量为66.45％的熟石灰75.245g、20g铁粉；然后将这种混合料压制成球团；在100℃下干燥12小时，取干燥后的球团置于坩锅内，球团周围充填石墨粉后放入马弗炉内，在马弗炉内1150℃保温3h，得到金属化率为86.3％；还原球团破碎为粒度是0.165mm粉末在磁感强度65mT下次选得到还原铁粉和非磁性物质。Reduction magnetic separation treatment of vanadium extraction tailings: Weigh 1000g of vanadium extraction tailings, 150g of coal powder, add 200ml of sodium carbonate solution with a concentration of 1.87mol/L and mix evenly, add 75.245g of slaked lime with a CaO content of 66.45%, and 20g of iron powder Then press this mixture into pellets; dry at 100°C for 12 hours, take the dried pellets and place them in a crucible, fill graphite powder around the pellets and put them into a muffle furnace. Insulated at 1150°C for 3 hours, the metallization rate was 86.3%; the reduced pellets were crushed into powders with a particle size of 0.165mm, and the reduced iron powder and non-magnetic substances were obtained by the next election at a magnetic induction intensity of 65mT.
选钛尾矿在1100℃下煅烧10min，破碎到粒度为0.198mm。The titanium-selected tailings were calcined at 1100°C for 10 minutes and crushed to a particle size of 0.198mm.
取磁选尾渣300g、钒钛磁铁矿选钛矿尾渣50g、昔格达土10g、硅灰10g，将这四种固体料混合均匀；在球磨机内球磨10h，得到的球磨混合料的粒度为0.038mm将球磨混合料用压制的方法成型，将成型坯在1100℃烧结0.5小时，再将烧结坯粉碎至0.074mm，得到黑色陶瓷材料末，测量黑瓷阳光吸收率为0.87。Get magnetic separation tailings 300g, vanadium-titanium-magnetite titanium ore tailings 50g, Xigeda soil 10g, silica fume 10g, these four kinds of solid materials are mixed uniformly; Ball milling 10h in ball mill, the ball mill mixture obtained The ball mill mixture with a particle size of 0.038mm is molded by pressing, and the molded body is sintered at 1100°C for 0.5 hours, and then the sintered body is crushed to 0.074mm to obtain a black ceramic material powder. The measured solar absorption rate of black porcelain is 0.87.
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