CN113087504A - 一种高导热致密硅砖及其制备方法 - Google Patents
一种高导热致密硅砖及其制备方法 Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 258
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 95
- 239000011449 brick Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000004576 sand Substances 0.000 claims abstract description 26
- 229910002026 crystalline silica Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000000571 coke Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 239000002910 solid waste Substances 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229920005610 lignin Polymers 0.000 claims description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 17
- 230000009471 action Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000010453 quartz Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种高导热致密硅砖及其制备方法，所述硅砖可选自包括以质量分数计的如下组分：50％～60％的结晶硅砂、5％～15％的熟硅砂、5％～15％的高纯石英玻璃、15％～25％的结晶硅石粉、3％～6％的硅微粉、2％～5％的硅基质、外加0％～0.5％的促烧结剂、3.2％～4％的矿化剂、0.5％～1％的粘结剂、1％～2％的塑化剂。通过上述材料的混合作用及烧结过程的控制，制备出气孔率低、体密大、导热率高的硅砖制品，大大提高硅砖的使用寿命，且提高焦炉和热风炉的工作效率，并有助于节能环保。
Description
技术领域
本发明涉及硅砖制备技术领域，尤其涉及一种高导热致密硅砖及其制备方法。
背景技术
硅砖因其优良的性价比，常常作为焦炉、热风炉用的主要材料，常规的考量硅砖的参数有气孔率、体密、耐压强度、荷重、蠕变率及热膨胀。实际上硅砖的使用寿命或者使用性能主要取决于其致密程度和矿相组成，而硅质材料在石英充分转化的情况下，其导热率和强度也很重要，导热率越高，传热效率越高，可以有效降低焦炉的焦化时间，同时也可以缩短热风炉的送风时间，因此高导热材料是焦炉和热风炉节能的关键所在。对硅砖而言，材料气孔率越低、材料越致密、强度越高、导热率越大，其使用寿命和节能效果都会提高；同时矿相组成中鳞石英含量越高，材料的体积稳定性越好，使用寿命越长、导热率越大、节能效果越好。气孔率与材料的堆积密度关系密切，矿化剂和烧结密切相关，烧结同时影响气孔率和矿相组成。在生产过程中通常在硅砖中添加矿化剂，矿化剂促进烧结中液相的产生从而促进石英的转化，但硅砖中的石英相在多个温度段都有晶型转变，并伴随不同程度的体积膨胀，因此矿化剂的选用和硅砖的烧结过程都非常重要。目前市场上常见的焦炉和热风炉用硅砖气孔率为22～24％，体密为1.75～1.85g/cm3，对导热率没有明确的要求，其使用寿命一般。因此本申请提供一种气孔率低、体密大、导热率高的硅砖制品，显著提高硅砖的使用寿命，且提高焦炉和热风炉的工作效率，并有助于节能环保。
发明内容
为解决现有技术的不足，提高焦炉和热风炉用硅砖的导热率和致密性，本发明提出一种高导热致密硅砖及其制备方法。
为实现以上目的，本发明所采用的技术方案包括：
一种高导热致密硅砖，其特征在于，可选自包括以质量分数计的如下组分：50％～60％的结晶硅砂、5％～15％的熟硅砂、5％～15％的高纯石英玻璃、15％～25％的结晶硅石粉、3％～6％的硅微粉、2％～5％的硅基质、外加0％～0.5％的促烧结剂、3.2％～4％的矿化剂、0.5％～1％的粘结剂、1％～2％的塑化剂。
进一步地，所述硅基质包括金属硅、碳化硅或氮化硅且所述金属硅、碳化硅或氮化硅的质量纯度不低于98％。
进一步地，所述3.2％～4％的矿化剂包括2％～4％的固废粉、1％～2％的氯化钙和0.2％～0.6％的铁鳞粉。
进一步地，所述固废粉粒度小于等于0.038mm，所述铁鳞粉粒度小于等于0.088mm且Fe3O4含量不低于90％。
进一步地，所述固废粉包括以质量分数计的如下组分：0％～3％的SO3、30％～35％的CaF2、60％～65％的CaO、0.4％～0.6％的R2O、0％～1％的MgO、0.2％～0.4％的Al2O3、0.15％～0.3％的Fe2O3。
进一步地，所述促烧结剂包括硼酸，所述硼酸的粒度小于等于0.09mm。
进一步地，所述粘结剂包括膨润土，所述膨润土的粒度小于等于0.045mm。
进一步地，所述塑化剂包括木质素。
进一步地，所述结晶硅砂粒度小于等于2.5mm且SiO2含量不低于98.5％，所述熟硅砂粒度小于等于1mm且SiO2含量不低于94.5％，所述高纯石英玻璃粒度小于等于3mm且SiO2含量不低于99％，所述结晶硅石粉粒度小于等于0.074mm，所述硅微粉粒度小于等于0.002mm且SiO2含量不低于96％，所述硅基质粒度小于等于0.074mm。
进一步地，所述硅砖应用于焦炉或热风炉。
本发明还涉及一种如上所述的高导热致密硅砖的制备方法，包括原料混合、压制成型、干燥、烧结、降温冷却的工艺过程，所述干燥工艺温度区间为80～120℃，所述烧结工艺为在1420～1440℃的温度区间内保温20～25h。
本发明的有益效果为：
采用本发明所述的一种高导热致密硅砖，包括加入结晶硅砂、熟硅砂、高纯石英玻璃、结晶硅石粉、硅微粉、硅基质、促烧结剂、矿化剂、粘结剂、塑化剂等材料。其中硅微粉的加入，可以填充气孔，促进材料的致密化；硅基质在烧结过程中部分氧化生成无定形二氧化硅，起到封闭和填充气孔的作用，显著降低显气孔率；这些材料的混合加入，可以促进泥料的流动性，降低泥料内部本身的摩擦力，也有助于降低显气孔率；塑化剂有效促进泥料的塑性，受压状态下更容易致密化；矿化剂粒度细、分散均匀，可以促进石英的转化，促进材料的致密化，同时矿化剂在低温下即可生成液相，有效促进石英转化、减少内部应力。上述材料的混合作用及烧结过程的控制，制备出气孔率低、体密大、导热率高的硅砖制品，大大提高硅砖的使用寿命，且提高焦炉和热风炉的工作效率，并有助于节能环保。
具体实施方式
本申请的硅砖利用自产的固废粉、氯化钙和铁鳞粉作为矿化剂，固废粉中含有多种成分、粒度较细，在硅砖的烧结过程中早期促使液相在较低温度下生成，进而促使磷石英的转化；氯化钙在700℃以上即成液相，不降低高温性能；铁鳞的加入也可以促进磷石英的生成；同时硼酸的加入在180℃左右变成液相，有效缓解应力，避免低温体积变化产生应力而导致基体疏松和裂纹产生，且硼酸的沸点极低，在高温时不发挥任何副作用。三种矿化剂在烧结过程的不同的温度段都有液相产生。矿化剂和石英的作用下，产生液相，然后在高温下逐步转化成磷石英和方石英，因此液相的粘度、烧成曲线和高温时间对硅砖的烧结过程至关重要，液相进入到硅石颗粒中干转化产生的裂隙中，从而促使生成更多的磷石英，液相的烧结使晶粒拉紧拉进，保证硅制品致密强度更高，导热率自然更高。
硅砖气孔率难以优化降低的原因之一就是石英转化过程中体积膨胀过大，高纯的玻璃相的加入有助于减少石英转化过程中的体积效应，增加致密度；高导热材料的加入有助于强化烧结过程；硅微粉的加入可增加致密度；同时考虑石英的转化规律，采用慢升温、快降温的烧成制度，在多种措施的综合作用下，使硅砖制品的气孔率降低到18％以下，导热率提高至2.45w/mk以上。
为了更清楚的理解本发明的内容，将结合实施例详细说明。
本申请采用50％～60％的结晶硅砂、5％～15％的焦炉或热风炉产生的废砖熟硅砂、5％～15％的高纯石英玻璃做骨料；15％～25％的结晶硅石粉、3％～6％的硅微粉、2％～5％的硅基质做基质，添加0％～0.5％的硼酸作为促烧结剂，添加2％～4％我司自产的固废粉、1％～2％的氯化钙、0.2％～0.6％的铁磷粉作为矿化剂，促进石英的转化；添加0.5％～1％的涂料行业用钙基膨润土作为粘结剂，添加1％～2％的木质素作为塑化剂，加入水将上述原料混合均匀、压制成型，成型压力不小于400吨，成型后干燥，然后在1420～1440℃的烧成温度下保温20～25h小时即可。其中硅微粉可以填充气孔，促进材料的致密化；固废粒度很细，分散均匀，可以存进石英的转化，结构更均匀、更致密；添加金属硅、碳化硅等硅基质，在烧结过程中部分氧化生成无定形二氧化硅，达到封闭气孔和填充气孔作用，显著降低显气孔率；这些材料的混合加入，可以促进泥料的流动性，降低泥料内部本身的摩擦力，也有助于降低显气孔率；木质素作为塑化剂有效促进泥料的塑性，受压状态下更容易致密化；同时硼酸和氯化钙在低温下即可生成液相，有效促进石英转化、减少内部应力。上述材料的混合作用及烧结过程的控制，制备出气孔率低、体密大、导热率高的硅砖制品，提高焦炉和热风炉的工作效率，并有助于节能环保。
实施例1
一种高导热致密硅砖，选自包括以质量分数计的如下组分：56％的结晶硅砂、12％的废砖熟硅砂、8％的高纯石英玻璃、21％的结晶硅石粉、3％的硅微粉、外加0.2％的硼酸、2.3％的固废粉、1％的氯化钙、0.5％的铁鳞粉、0.5％的膨润土、2％的木质素。其中所述结晶硅砂粒度小于等于2.5mm且SiO2含量不低于98.5％，所述废砖熟硅砂粒度小于等于1mm且SiO2含量不低于94.5％，所述高纯石英玻璃粒度小于等于3mm且SiO2含量不低于99％，所述结晶硅石粉粒度小于等于0.074mm，所述硅微粉粒度小于等于0.002mm且SiO2含量不低于96％，所述硼酸粒度小于等于0.09mm，所述固废粉粒度小于等于0.038mm，所述铁鳞粉粒度小于等于0.088mm且Fe3O4含量不低于90％，所述膨润土粒度小于等于0.045mm。
优选的，上述高导热致密硅砖的制备方法包括原料混合、压制成型、干燥、烧结、降温冷却的工艺过程，所述干燥工艺温度区间为80～120℃，所述烧结工艺为在1430℃的温度下保温20～25h。
实施例2
一种高导热致密硅砖，选自包括以质量分数计的如下组分：54％的结晶硅砂、12％的废砖熟硅砂、10％的高纯石英玻璃、17％的结晶硅石粉、5％的硅微粉、2％的碳化硅、外加0.2％的硼酸、2.5％的固废粉、1％的氯化钙、0.5％的铁鳞粉、0.5％的膨润土、2％的木质素。其中所述结晶硅砂粒度小于等于2.5mm且SiO2含量不低于98.5％，所述废砖熟硅砂粒度小于等于1mm且SiO2含量不低于94.5％，所述高纯石英玻璃粒度小于等于3mm且SiO2含量不低于99％，所述结晶硅石粉粒度小于等于0.074mm，所述硅微粉粒度小于等于0.002mm且SiO2含量不低于96％，所述碳化硅粒度小于等于0.074mm且质量含量不低于98％，所述硼酸粒度小于等于0.09mm，所述固废粉粒度小于等于0.038mm，所述铁鳞粉粒度小于等于0.088mm且Fe3O4含量不低于90％，所述膨润土粒度小于等于0.045mm。
优选的，上述高导热致密硅砖的制备方法包括原料混合、压制成型、干燥、烧结、降温冷却的工艺过程，所述干燥工艺温度区间为80～120℃，所述烧结工艺为在1430℃的温度下保温20～25h。
实施例3
一种高导热致密硅砖，选自包括以质量分数计的如下组分：50％的结晶硅砂、12％的废砖熟硅砂、14％的高纯石英玻璃、16％的结晶硅石粉、6％的硅微粉、2％的金属硅、外加0.3％的硼酸、2.7％的固废粉、1％的氯化钙、0.5％的铁鳞粉、0.5％的膨润土、2％的木质素。其中所述结晶硅砂粒度小于等于2.5mm且SiO2含量不低于98.5％，所述废砖熟硅砂粒度小于等于1mm且SiO2含量不低于94.5％，所述高纯石英玻璃粒度小于等于3mm且SiO2含量不低于99％，所述结晶硅石粉粒度小于等于0.074mm，所述硅微粉粒度小于等于0.002mm且SiO2含量不低于96％，所述金属硅粒度小于等于0.074mm且质量含量不低于98％，所述硼酸粒度小于等于0.09mm，所述固废粉粒度小于等于0.038mm，所述铁鳞粉粒度小于等于0.088mm且Fe3O4含量不低于90％，所述膨润土粒度小于等于0.045mm。
优选的，上述高导热致密硅砖的制备方法包括原料混合、压制成型、干燥、烧结、降温冷却的工艺过程，所述干燥工艺温度区间为80～120℃，所述烧结工艺为在1430℃的温度下保温20～25h。
上述实施例1至3得到的硅砖产品，产品质地均匀、质量良好，而且与现有的硅砖相比，显著降低了硅砖的显气孔率、增大了耐压强度且极大地提高了导热率，使硅砖性能远远优于市面上的硅砖制品，大大提高硅砖的使用寿命，且提高了焦炉和热风炉工作效率的同时，并有助于节能环保。所述硅砖产品的理化检测结果如表1所示。
表1一种高导热致密硅砖的性能指标
以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换等都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (10)
1.一种高导热致密硅砖，其特征在于，可选自包括以质量分数计的如下组分：50％～60％的结晶硅砂、5％～15％的熟硅砂、5％～15％的高纯石英玻璃、15％～25％的结晶硅石粉、3％～6％的硅微粉、2％～5％的硅基质、外加0％～0.5％的促烧结剂、3.2％～4％的矿化剂、0.5％～1％的粘结剂、1％～2％的塑化剂。
2.如权利要求1所述的硅砖，其特征在于，所述硅基质包括金属硅、碳化硅或氮化硅且所述金属硅、碳化硅或氮化硅的质量纯度不低于98％。
3.如权利要求1所述的硅砖，其特征在于，所述3.2％～4％的矿化剂包括2％～4％的固废粉、1％～2％的氯化钙和0.2％～0.6％的铁鳞粉。
4.如权利要求3所述的硅砖，其特征在于，所述固废粉粒度小于等于0.038mm，所述铁鳞粉粒度小于等于0.088mm且Fe3O4含量不低于90％。
5.如权利要求1所述的硅砖，其特征在于，所述促烧结剂包括硼酸，所述硼酸的粒度小于等于0.09mm。
6.如权利要求1所述的硅砖，其特征在于，所述粘结剂包括膨润土，所述膨润土的粒度小于等于0.045mm。
7.如权利要求1所述的硅砖，其特征在于，所述塑化剂包括木质素。
8.如权利要求1至7任一项所述的硅砖，其特征在于，所述结晶硅砂粒度小于等于2.5mm且SiO2含量不低于98.5％，所述熟硅砂粒度小于等于1mm且SiO2含量不低于94.5％，所述高纯石英玻璃粒度小于等于3mm且SiO2含量不低于99％，所述结晶硅石粉粒度小于等于0.074mm，所述硅微粉粒度小于等于0.002mm且SiO2含量不低于96％，所述硅基质粒度小于等于0.074mm。
9.如权利要求8所述的硅砖，其特征在于，所述硅砖应用于焦炉或热风炉。
10.一种如权利要求1至9任一项所述的高导热致密硅砖的制备方法，其特征在于，包括原料混合、压制成型、干燥、烧结、降温冷却的工艺过程，所述干燥工艺温度区间为80～120℃，所述烧结工艺为在1420～1440℃的温度区间内保温20～25h。
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| CN115849923A (zh) * | 2022-12-22 | 2023-03-28 | 郑州通达耐材有限责任公司 | 超高导热焦炉硅砖及制作工艺 |
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| CN115849923A (zh) * | 2022-12-22 | 2023-03-28 | 郑州通达耐材有限责任公司 | 超高导热焦炉硅砖及制作工艺 |
| CN115894055A (zh) * | 2022-12-22 | 2023-04-04 | 郑州通达耐材有限责任公司 | 高耐磨焦炉硅砖及制作工艺 |
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