CN117362068B - 一种铝电解用尖晶石基多孔保温盖板的制备方法 - Google Patents
一种铝电解用尖晶石基多孔保温盖板的制备方法 Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 75
- 239000011029 spinel Substances 0.000 title claims abstract description 75
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000002131 composite material Substances 0.000 claims abstract description 61
- 239000004088 foaming agent Substances 0.000 claims abstract description 61
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000012745 toughening agent Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 9
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
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- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及一种铝电解用尖晶石基多孔保温盖板的制备方法，属于新型复合材料技术领域。制备硅酸盐‑碳酸盐‑纤维复合发泡剂；制备复合增韧剂；以尖晶石基材料作为原料，将尖晶石基材料、硅酸盐‑碳酸盐‑纤维复合发泡剂和复合增韧剂按照质量比为5‑7：2：1‑3混合均匀得到混合料，混合料放入定制模具中，在压力为10MPa‑200MPa，温度为1200℃‑1470℃，保温2‑6h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。发明所制备的铝电解用尖晶石基多孔保温盖板所具备耐腐蚀、多孔保温性能优越同时质量较轻、抗压抗震性能优越、高韧性等性能。
Description
技术领域
本发明涉及一种铝电解用尖晶石基多孔保温盖板的制备方法，属于新型复合材料技术领域。
背景技术
目前铝电解槽所用的保温盖板主要其保温性能差、抗震抗压性能差，盖板的料易脱落在电解质中污染电解质，导致后期耗费大量的人力物力去清理电解质中的杂质；同时质量较重所以操作难度较大，在更换阳极过程中会造成大量的热量损失，我们应当节约能耗、降低能源损失，因此传统的用铝电解保温料性能有明显缺陷，所带来的经济效益不高。
针对上述中的传统材料，传统铝电解用保温料存在以下缺陷：传统的铝电解用保温材，1：其料容易脱落，更换阳极过程中要将掉落在电解质中的散料清理，其操作难度大，且时间较长，热量散失严重；2：其保温料粉末易破碎掉入电解质中会很大程度上对电解质造成污染，所以增加了后期清理电解质的工作量。3：传统铝电解保温装置使得劳动强度大幅增加的同时也使得大量能量的损耗，不利于节能减排低碳量的排放。
因此制备一种耐腐蚀、多孔保温且质轻、韧性好、抗震抗压性能优越的铝电解用多孔保温盖板方可解决以上缺陷。
发明内容
针对传统的铝电解用保温盖板耐腐蚀性能差、抗压抗震性能不好、换极操作难度大，散失热量巨大，易破碎等缺陷，本发明提供一种铝电解用尖晶石基多孔保温盖板的制备方法。本发明目的之一在于提高保温盖板的耐腐蚀性能；目的之二在于提高尖晶石基材料的多孔性使其质轻以提高其保温性能；目的之三在于提高所制备保温板的韧性以及抗震抗压强度高使其不易断裂；目的之四所用烧结成型一体化技术可以使得其操作简便，提高其生产效益，创造更大的经济效益。
本发明所使用的原料为尖晶石基材料，其包括镁铝尖晶石、镍铁尖晶石、锌铬尖晶石等尖晶石基材料等，因其本身具有耐腐蚀，高抗压抗震性能，优异的机械性能。这种尖晶石基材料拥有如此优越的性能，再将其经行发泡、增韧、烧结成型处理可以更大程度提高其耐腐蚀，抗压抗震，保温等性能以制备铝电解用尖晶石基多孔保温盖板。
本发明通过以下技术方案实现。
一种铝电解用尖晶石基多孔保温盖板的制备方法，其包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石基材料、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为5-7：2：1-3混合均匀得到混合料，混合料放入定制模具中，在压力为10MPa-200MPa，温度为1200℃-1470℃，保温2-6h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。
所述S1中硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐、碳酸盐和纤维按照质量百分比为80％-90％：5％-12％：4％-8％混合均匀得到混合发泡剂物料；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.2KHZ-20.8KHZ、功率为400W-1500W，同时以500r/min磁力搅拌，超声和磁力搅拌2h-6h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5-10℃/min的升温速率，升温至温度为200℃-280℃，在通入惰性气体条件下烧结2h-8h得到硅酸盐-碳酸盐-纤维复合发泡剂。
所述S2中复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为2-8：1g/mL混合均匀，然后在微波场为2200MHZ-3200MHZ、波长32-70cm，温度为140℃-280℃下微波处理160min-200min，处理完成后得到复合增韧剂。
所述S3中尖晶石基材料包括镁铝尖晶石、镍铁尖晶石或锌铬尖晶石尖的晶石基材料。
上述制备得到铝电解用尖晶石基多孔保温盖板为内部多孔结构。
上述S3中制备得到的铝电解用尖晶石基多孔保温盖板将进一步制备得到用于铝电解盖板尺寸大小的保温盖板。
本发明的有益效果是：
（1）本发明通过选用尖晶石基材料如镁铝尖晶石、镍铁尖晶石、锌铬尖晶石等尖晶石基材料本身具有很好的耐腐蚀性能。
（2）本发明制备硅酸盐-碳酸盐-纤维复合发泡剂可以有效地使得尖晶石基形成多孔状提高孔隙率使得材料的保温性能优越同时增加其抗震抗压强度；其次在微波水热的条件下用硅烷耦合剂改性的纤维可以很好的改性纤维以增强增韧剂的性能，同时提高增韧剂的粘度，可以使得增韧剂很好地附着在目标材料上。
（3）本发明所使用的烧结成型一体化技术可以将已制备的物料放入可以增温增压的模具中进行烧结成型一体化技术可以得到理想的成品，使得操作过程简便，实现智能化烧结成型，最大程度上提高其成产效率，减少在生产合成过程中时间和经济的损耗以及减少人工劳动成本。
（4）本发明所制备的铝电解用尖晶石基多孔保温盖板所具备耐腐蚀、多孔保温性能优越同时质量较轻、抗压抗震性能优越、高韧性等性能。使得铝电解过程中减少能量的损耗，以及具有很好的耐腐蚀性能所以降低了原材料的损耗。最大程度增加了铝电解过程中的经济效益，最大程度上实现了节能减排以及降低碳的排放量。
附图说明
图1是本发明本发明实施例1制备得到的铝电解槽用多孔保温盖板和对比例1制备得到的保温盖板的粒度分布的测试图，其中（a）为对比例1制备得到的多孔保温盖板，（b）为实施例1制备得到的铝电解槽多孔保温盖板；
图2是本发明实施例1制备得到的铝电解槽用多孔保温盖板实物图。
具体实施方式
下面结合附图和具体实施方式，对本发明作进一步说明。
实施例1
将铝电解用尖晶石基多孔保温盖板的制备方法，其包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐（硅酸钠）、碳酸盐（碳酸钠）和纤维（聚丙烯腈预氧化纤维）按照质量百分比为80％：12％：8％混合均匀得到混合发泡剂物料；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.4KHZ、功率为800W，同时以500r/min磁力搅拌，超声和磁力搅拌2h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5℃/min的升温速率，升温至温度为200℃-240℃，在通入惰性气体（氩气，氩气通入量为2L/min）条件下烧结4h得到硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为6：1g/mL混合均匀，然后在微波场为2450MHZ、波长32cm，温度为160℃下微波处理180min，处理完成后得到复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石基材料(镁铝尖晶石，尺寸为50cm×60cm的镁铝尖晶石)、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为7：2：1混合均匀得到混合料，混合料放入定制模具中，在压力为180MPa，温度为1470℃，保温2h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。
本发明制备得到的铝电解用尖晶石基多孔保温盖板为内部多孔结构，其粒度分布的测试图如图1（b）所示，本发明制备得到的铝电解用尖晶石基多孔保温盖板实物图如图2所示。
铝电解用尖晶石基多孔保温盖板质量仅为未使用复合发泡剂所制备的保温盖板的的16%，抗压强度是320MPa，弹性模量是70GPa。
对比实施例1
省略实施例1中的S1，其他步骤不变
S2、制备复合增韧剂；复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为6：1g/mL混合均匀，然后在微波场为2450MHZ、波长32cm，温度为160℃下微波水热处理180min，处理完成后得到复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石基材料(镁铝尖晶石，尺寸为50cm×60cm的镁铝尖晶石)和S2制备复合增韧剂按照质量比为9：1混合均匀得到混合料，混合料放入定制模具中，在压力为180MPa，温度为1470℃，保温2h，进行烧结成型一体化，得到保温盖板。
本对比实施例1制备得到的保温盖板内部也有孔，其粒度分布的测试图如图1（a）所示。
实施例1和对比实施例1的粒径分布图如图一说明此尖晶石材料（镁铝尖晶石材料）都有很好的孔隙率，高比表面积。图1（b）是经硅酸钠-碳酸钠-纤维复合发泡剂的作用，可以直白地表现出此材料更加多孔，表面积更大，经发泡剂作用其孔径在10nm、18nm、23nm、40nm均有分布其均属于介孔，同时也有少量的大孔，如150nm也有少量的分布，其进一步说明经硅酸钠-碳酸钠-纤维的发泡作用使得材料拥有更加复杂的孔径分布，同样此材料的多孔性能也使得保温性能更加优越。
实施例2
将铝电解用尖晶石基多孔保温盖板的制备方法，其包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐（硅酸钠）、碳酸盐（碳酸钠）和纤维（聚丙烯腈预氧化纤维）按照质量百分比为90％：6％：4％混合均匀得到混合发泡剂物料；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.2KHZ、功率为600W，同时以500r/min磁力搅拌，超声和磁力搅拌2h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5℃/min的升温速率，升温至温度为220℃-260℃，在通入惰性气体（氮气，氮气通入量为2L/min）条件下烧结4h得到硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为4：1g/mL混合均匀，然后在微波场为2780MHZ、波长40cm，温度为200℃下微波处理160min，处理完成后得到复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石材料(镍铁尖晶石材料，尺寸为50cm×60cm的镍铁尖晶石)、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为5：2：3混合均匀得到混合料，混合料放入定制模具中，在压力为90MPa，温度为1200℃，保温6h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。
实施例3
将铝电解用尖晶石基多孔保温盖板的制备方法，其包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐（硅酸钠）、碳酸盐（碳酸钠）和纤维（聚丙烯腈预氧化纤维）按照质量百分比为82％：12％：6％混合均匀得到混合发泡剂物料；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.6KHZ、功率为1500W，同时以500r/min磁力搅拌，超声和磁力搅拌6h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5℃/min的升温速率，升温至温度为240℃-280℃，在通入惰性气体（氮气，氮气通入量为2L/min）条件下烧结8h得到硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为2：1g/mL混合均匀，然后在微波场为3200MHZ、波长60cm，温度为190℃下微波处理170min，处理完成后得到复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石材料(锌铬尖晶石材料，尺寸为50cm×60cm的锌铬尖晶石)、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为6：2：2混合均匀得到混合料，混合料放入定制模具中，在压力为40MPa，温度为1300℃，保温2h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。
实施例4
将铝电解用尖晶石基多孔保温盖板的制备方法，其包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐（硅酸钠）、碳酸盐（碳酸钠）和纤维（聚丙烯腈预氧化纤维）按照质量百分比为88％：8％：4％混合均匀得到混合发泡剂物料；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.8KHZ、功率为1400W，同时以500r/min磁力搅拌，超声和磁力搅拌5h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5℃/min的升温速率，升温至温度为230℃-270℃，在通入惰性气体（氩气，氩气通入量为2L/min）条件下烧结7h得到硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为8：1g/mL混合均匀，然后在微波场为3000MHZ、波长70cm，温度为240℃下微波水热处理190min，处理完成后得到复合增韧剂；
S3、以尖晶石基材料作为原料，将尖晶石材料(镁铝尖晶石材料，尺寸为50cm×60cm的镁铝尖晶石)、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为7：2：1混合均匀得到混合料，混合料放入定制模具中，在压力为140MPa，温度为1400℃，保温5h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板。
以上结合附图对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (2)
1.一种铝电解用尖晶石基多孔保温盖板的制备方法，其特征在于包括以下步骤：
S1、制备硅酸盐-碳酸盐-纤维复合发泡剂；
S2、制备复合增韧剂；
S3、以尖晶石材料作为原料，将尖晶石材料、S1制备得到的硅酸盐-碳酸盐-纤维复合发泡剂和S2制备复合增韧剂按照质量比为5-7：2：1-3混合均匀得到混合料，混合料放入定制模具中，在压力为10MPa-200MPa，温度为1200℃-1470℃，保温2-6h，进行烧结成型一体化，得到铝电解用尖晶石基多孔保温盖板；
所述S1中硅酸盐-碳酸盐-纤维复合发泡剂的制备方法为：
S1.1、将硅酸盐、碳酸盐和纤维按照质量百分比为80％-90％：5％-12％：4％-8％混合均匀得到混合发泡剂物料；所述混合发泡剂物料中纤维为聚丙烯腈预氧化纤维；
S1.2、将S1.1中的混合发泡剂物料，在超声频率为20.2KHZ-20.8KHZ、功率为400W-1500W，同时以500r/min磁力搅拌，超声和磁力搅拌2h-6h，得到超声处理发泡剂物料；
S1.3、将S1.2中的超声处理发泡剂物料，以5-10℃/min的升温速率，升温至温度为200℃-280℃，在通入惰性气体条件下烧结2h-8h得到硅酸盐-碳酸盐-纤维复合发泡剂；
所述S2中复合增韧剂的制备方法为：将纤维和硅烷偶联剂按照固液比为2-8：1g/mL混合均匀，然后在微波场为2200MHZ-3200MHZ、波长32-70cm，温度为140℃-280℃下微波处理160min-200min，处理完成后得到复合增韧剂。
2.根据权利要求1所述的铝电解用尖晶石基多孔保温盖板的制备方法，其特征在于：所述S3中尖晶石材料包括镁铝尖晶石、镍铁尖晶石或锌铬尖晶石。
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