CN108355671A - 一种中温催化脱硝蓄热一体化莫来石质陶瓷材料 - Google Patents
一种中温催化脱硝蓄热一体化莫来石质陶瓷材料 Download PDFInfo
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 32
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 11
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000008117 stearic acid Substances 0.000 claims abstract description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 5
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- 241001408630 Chloroclystis Species 0.000 description 2
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- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本发明公开了一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,属于催化技术领域;该陶瓷材料主要由以下组分:堇青石35~40份,莫来石70~80份、三氧化钨5~10份、SiO25~8份、蒙脱石10~15份、木浆棉2~3份、玻璃纤维4~5份、氯化聚乙烯3~6份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物3~5份、羟丙基甲基纤维素3~6份、邻苯二甲酸酯2~3份、单乙醇胺2~3份、硬脂酸1~3份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成。
Description
技术领域
本发明涉及一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,本发明制备的脱硝催化剂,具备良好的机械强度、抗酸腐蚀能力、抗热震性能,可适应于燃煤锅炉、火电机组的空预器中,以取代空预器中换热原件考登钢,兼具良好的换热性能、脱硝活性和较宽的温度窗口。
背景技术
近年来,能源及与之相关的环境成为全世界各国最为关注的热点。我国由于人均能源资源短缺,环境容量有限,生态脆弱,将极大的制约我国的可持续发展。国内GDP 每年高速发展,能源消耗急骤增加,环境、生态日益恶化。节能降耗成为解决能源问题的一大主攻方向。据统计,国内的工业部门能源消耗量占全国能源总量的70%。其中工业窑炉是我国耗能大户,约占全国总能耗的25%,能源利用率低是造成工业炉耗能大的主要原因之一。
与发达国家的工业炉相比,国内的工业窑炉平均热效率要低20%左右,浪费的能源相当于2亿吨标准煤,可见工业窑炉节能潜力是十分巨大的。
目前工业窑炉中的空气预热器中所用的换热原件材质为考登钢,考登钢具有机械强度高、不易破损、换热速率快、热容大等优点,但是在使用过程中,考登钢表面的搪瓷易脱落,钢材裸漏以后非常容易被硫酸氢铵或结露而成的硫酸腐蚀,尤其是全国燃煤电厂在全面实施超低排放之后。为使脱硝处理后的氮氧化物浓度达到超低排放标准,目前,主流的降低NOx排放方法是,增加一层催化剂,这样会导致系统阻力、空气预热器阻力提高,SO2向SO3的转化率上升,气溶胶排放增加,导致氨逃逸增大、腐蚀及堵塞现象增加等。
空气预热器在使用过程中,换热元件缓慢转动,温度较高的烟气和冷空气交替流经换热元件,进行周期性的换热。在一个换热周期内,换热元件的温度周期性变化,选用稀土元素Ce、La作为活性组分,具有较宽的脱硝活性温度区间。
传统的钒钛系脱硝催化剂,活性温度窗口较窄(320~400℃),运行过程中易受SO2中毒,低温下活性较低,且易产生硫铵,堵塞催化剂孔及空预器及下游设备,造成系统压降较大,增加引风机的用电成本等不利因素。
而且现有稀土基催化剂不具有蓄热功能,并且耐磨性差,活性温度范围窄,强度低,使用寿命短;使得应用范围受到极大局限,因此,我们迫切需要研究一种新型催化剂,以替代上述产品。
发明内容
本发明提供一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,以解决上述技术问题。
为解决上述技术问题,本发明方案采用的技术方案是:一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,其特征在于该陶瓷材料主要由以下组分:堇青石35~40份,莫来石70~80份、三氧化钨5~10份、SiO25~8份、蒙脱石10~15份、木浆棉2~3份、玻璃纤维4~5份、氯化聚乙烯3~6份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物3~5份、羟丙基甲基纤维素3~6份、邻苯二甲酸酯2~3份、单乙醇胺2~3份、硬脂酸1~3份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成;
所述催化浆料主要由以下组分构成:氧化铝5~8份、硝酸铁5~10份、硝酸锰5~15份、莫来石5~10份、磷酸二氢铵5~10份、聚二甲基硅氧烷0.5~2份、硬脂酸铝6~10份;硝酸钇3~5份、偏钨酸铵5~8份、硝酸铈5~8份,硝酸镧2~4份、钛酸酯偶联剂3份。
一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,其制备方法包括以下步骤:
(1)泥料捏合:
i)称取堇青石,莫来石、三氧化钨、SiO2、蒙脱石、硬脂酸、单乙醇胺、邻苯二甲酸酯、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物混合,加入去离子水和20%氨水,搅拌捏合20min左右,通过捏合及调节添加的去离子水、氨水调节泥料指标,泥料捏合(i)泥料水分目标值38~45%,pH目标值7.8~9.4;
ii)添加20%氨水0.5~1.5份,盖上搅拌机顶盖,边搅拌边加热升温至95℃以上,然后打开顶盖,蒸发浓缩泥料水分至泥料呈颗粒状,所述泥料水分目标值25~28%,pH目标值7.8~8.5;
iii)边搅拌边依次添加木浆棉,玻璃纤维,添加20%氨水,搅拌15min左右,所述泥料水分目标值29~34%,pH目标值8.1~9.2;
iv)依次添加氯化聚乙烯、羟丙基甲基纤维素,搅拌10min以上,所述泥料水分目标值28~32%,pH目标值8.1~9.0;
(2)陈腐:将混炼好的泥料,用保鲜膜密封保存,陈腐,陈腐3-4h;
(3)预过滤挤出:将陈腐好的泥料,在预过滤挤出机上,挤出力塑性1700~2200N,过滤挤出成泥条;
(4)成型挤出:在前端装有SCR成型模具的真空挤出机上进行挤出成型,得到催化剂湿坯;
(5)干燥-煅烧:将步骤(4)得到的催化剂湿坯,转移至铝合金托盘上,用带保温棉的玻璃钢材质的盒盖包装好,干燥温度为90℃,干燥周期5h;将干燥后的催化剂坯料送入窑炉进行煅烧,煅烧温度1100~1200℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为18~22h,得到蜂窝陶瓷坯体;
(6)上浆-干燥:称取氧化铝、硝酸铁、硝酸锰、莫来石、磷酸二氢铵、聚二甲基硅氧烷、硬脂酸铝、硝酸钇、偏钨酸铵、硝酸铈、硝酸镧、钛酸酯偶联剂,在70~95℃溶于含有1.2~3.5份草酸的水溶液,浆液比1:3,加升温至80℃并保温,用超声波震荡搅拌1~2小时,制成催化浆料;将步骤5所得蜂窝陶瓷坯体放入催化浆料池内,裹上催化浆料后放入干燥炉,干燥温度为70℃,干燥周期20~30分钟,刮除蜂窝陶瓷坯体外侧的催化浆料并清理干净后,重新放入干燥炉,干燥温度为90℃,干燥周期1h;
(7)煅烧:将步骤(6)得到的蜂窝陶瓷坯体,送入窑炉内进行煅烧,煅烧温度550℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为7~9h,得到中温蜂窝陶瓷。
作为优选,所述步骤(3)预过滤挤出,滤网采用网孔规格为1.0x4mm 或0.8x3mm的不锈钢滤网。
作为优选,所述步骤(4)成型挤出,挤出机控制条件为,挤出压力7MPa,挤出温度<35℃,真空度-0.094MPa左右。
本发明原料易得、成本较低,并且在中温环境下的脱硝率极高,反应条件温和,对环境无任何污染。本发明先经过高温烧制蜂窝陶瓷胚体,再将蜂窝陶瓷坯体上浆,最后经过中温烧制而成。这种工艺能明显提高了催化剂抗烧结能力,提高催化剂温度的均匀性,改善催化性能,有利于提高催化剂热稳定性,同时,由于蜂窝陶瓷胚体高温烧制,结构强度大,使用时,可以多层叠放,大大增强蜂窝陶瓷载体的蓄热功能。本发明可广泛应用于燃煤锅炉、火电机组等的空预器中,以取代原空预器中换热原件考登钢,兼具良好的换热性能、脱硝活性和较宽的温度窗口,可以节省能源、提高能源利用效率,降低了污染排放,实为一项利国利民的新技术。
具体实施方式
为了便于理解本发明,下面将实施例对本发明进行更全面的描述。但是本发明可以以不同的形式来实现,并不限于本文所描述的实施例。相反的,提供这些实施例的目的是使对本发明的公开内容更加透彻全面。
实施例1
一种中温催化脱硝蓄热一体化莫来石质陶瓷材料主要由以下组分:堇青石35份,莫来石80份、三氧化钨5份、SiO28份、蒙脱石10份、木浆棉2份、玻璃纤维4份、氯化聚乙烯3份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物5份、羟丙基甲基纤维素3份、邻苯二甲酸酯3份、单乙醇胺2份、硬脂酸3份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成。
所述催化浆料主要由以下组分构成:氧化铝5份、硝酸铁10份、硝酸锰15份、莫来石5份、磷酸二氢铵5份、聚二甲基硅氧烷2份、硬脂酸铝10份、硝酸钇5份、偏钨酸铵8份、硝酸铈5份、硝酸镧4份、钛酸酯偶联剂3份。
其制备方法包括以下步骤:
(1)泥料捏合:
i)按量称取堇青石,莫来石、三氧化钨、SiO2、蒙脱石、硬脂酸、单乙醇胺、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物,邻苯二甲酸酯,加入去离子水混合,添加20%氨水调节泥料pH,所述去离子水:粉料重量比为1:(0.4~0.6),搅拌捏合20min左右,通过捏合及调节添加的去离子水、氨水调节泥料指标,泥料捏合(i)泥料水分目标值38~45%,pH目标值7.8~9.4;
ii)添加20%氨水,盖上搅拌机顶盖,边搅拌边加热升温至95℃以上,然后打开顶盖,蒸发浓缩泥料水分至泥料呈颗粒状,所述泥料水分目标值25~28%,pH目标值7.8~8.5;
iii)边搅拌边依次添加木浆棉,玻璃纤维,添加20%氨水,搅拌15min左右,所述泥料水分目标值29~34%,pH目标值8.1~9.2;
iv)依次添加氯化聚乙烯、羟丙基甲基纤维素,搅拌10min以上,所述泥料水分目标值28~32%,pH目标值8.1~9.0;
(2)陈腐:将混炼好的泥料,用保鲜膜密封保存,陈腐,陈腐4h;
(3)预过滤挤出:将陈腐好的泥料,在预过滤挤出机上,挤出力塑性1700~2200N,滤网采用网孔规格为1.0x4mm 或0.8x3mm的不锈钢滤网,过滤挤出成泥条;
(4)成型挤出:在前端装有SCR成型模具的真空挤出机上进行挤出成型,挤出机控制条件为,挤出压力7MPa,挤出温度<35℃,真空度-0.094MPa左右,得到催化剂湿坯;
(5)干燥-煅烧:将步骤(4)得到的催化剂湿坯,转移至铝合金托盘上,用带保温棉的玻璃钢材质的盒盖包装好,干燥温度为90℃,干燥周期5h;将干燥后的催化剂坯料送入窑炉进行煅烧,煅烧温度1100~1200℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为18h,得到蜂窝陶瓷坯体;
(6)上浆-干燥:称取氧化铝、硝酸铁、硝酸锰、莫来石、磷酸二氢铵、聚二甲基硅氧烷、硬脂酸铝、硝酸钇、偏钨酸铵、硝酸铈,硝酸镧、钛酸酯偶联剂,在70℃溶于含有1.2份草酸的水溶液,浆液比1:3,加升温至80℃并保温,用超声波震荡搅拌1小时,制成催化浆料;将步骤5所得蜂窝陶瓷坯体放入催化浆料池内,裹上催化浆料后放入干燥炉,干燥温度为70℃,干燥周期20分钟,刮除蜂窝陶瓷坯体外侧的催化浆料并清理干净后,重新放入干燥炉,干燥温度为90℃,干燥周期1h;
(7)煅烧:将步骤(6)得到的蜂窝陶瓷坯体,送入窑炉内进行煅烧,煅烧温度550℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为9h,得到中温蜂窝陶瓷。所得产品几何尺寸为150x150x(500~1250)mm,孔径为5~8mm,内壁厚0.7~1.2mm,几何比表面积为360~700m2/m3。
实施例2
一种中温催化脱硝蓄热一体化莫来石质陶瓷材料主要由以下组分:堇青石38份,莫来石75份、三氧化钨7份、SiO26份、蒙脱石14份、木浆棉3份、玻璃纤维5份、氯化聚乙烯5份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物4份、羟丙基甲基纤维素5份、邻苯二甲酸酯2份、单乙醇胺3份、硬脂酸2份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成。
所述催化浆料主要由以下组分构成:氧化铝6份、硝酸铁8份、硝酸锰10份、莫来石9份、磷酸二氢铵8份、聚二甲基硅氧烷1.3份、硬脂酸铝7份、硝酸钇4份、偏钨酸铵7份、硝酸铈6份、硝酸镧3份、钛酸酯偶联剂3份。
其制备方法包括以下步骤:
(1)泥料捏合:
i)按量称取堇青石,莫来石、三氧化钨、SiO2、蒙脱石、硬脂酸、单乙醇胺、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物,邻苯二甲酸酯,加入去离子水混合,添加20%氨水调节泥料pH,所述去离子水:粉料重量比为1:(0.4~0.6),搅拌捏合20min左右,通过捏合及调节添加的去离子水、氨水调节泥料指标,泥料捏合(i)泥料水分目标值38~45%,pH目标值7.8~9.4;
ii)添加20%氨水,盖上搅拌机顶盖,边搅拌边加热升温至95℃以上,然后打开顶盖,蒸发浓缩泥料水分至泥料呈颗粒状,所述泥料水分目标值25~28%,pH目标值7.8~8.5;
iii)边搅拌边依次添加木浆棉3份,玻璃纤维5份,添加20%氨水,搅拌15min左右,所述泥料水分目标值29~34%,pH目标值8.1~9.2;
iv)依次添加氯化聚乙烯5份、羟丙基甲基纤维素5份,搅拌10min以上,所述泥料水分目标值28~32%,pH目标值8.1~9.0;
(2)陈腐:将混炼好的泥料,用保鲜膜密封保存,陈腐,陈腐3h;
(3)预过滤挤出:将陈腐好的泥料,在预过滤挤出机上,挤出力塑性1700~2200N,滤网采用网孔规格为1.0x4mm 或0.8x3mm的不锈钢滤网,过滤挤出成泥条;
(4)成型挤出:在前端装有SCR成型模具的真空挤出机上进行挤出成型,挤出机控制条件为,挤出压力7MPa,挤出温度<35℃,真空度-0.094MPa左右,得到催化剂湿坯;
(5)干燥-煅烧:将步骤(4)得到的催化剂湿坯,转移至铝合金托盘上,用带保温棉的玻璃钢材质的盒盖包装好,干燥温度为90℃,干燥周期5h;将干燥后的催化剂坯料送入窑炉进行煅烧,煅烧温度1100~1200℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为21h,得到蜂窝陶瓷坯体;
(6)上浆-干燥:称取氧化铝、硝酸铁、硝酸锰、莫来石、磷酸二氢铵、聚二甲基硅氧烷、硬脂酸铝、硝酸钇、偏钨酸铵、硝酸铈、硝酸镧、钛酸酯偶联剂,在85℃溶于含有2.2份草酸的水溶液,浆液比1:3,加升温至80℃并保温,用超声波震荡搅拌1.5小时,制成催化浆料;将步骤5所得蜂窝陶瓷坯体放入催化浆料池内,裹上催化浆料后放入干燥炉,干燥温度为70℃,干燥周期25分钟,刮除蜂窝陶瓷坯体外侧的催化浆料并清理干净后,重新放入干燥炉,干燥温度为90℃,干燥周期1h;
(7)煅烧:将步骤(6)得到的蜂窝陶瓷坯体,送入窑炉内进行煅烧,煅烧温度550℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为8h,得到中温蜂窝陶瓷。所得产品几何尺寸为150x150x(500~1250)mm,孔径为5~8mm,内壁厚0.7~1.2mm,几何比表面积为360~700m2/m3。
实施例3
一种中温催化脱硝蓄热一体化莫来石质陶瓷材料主要由以下组分:堇青石40份,莫来石70份、三氧化钨10份、SiO25份、蒙脱石15份、木浆棉3份、玻璃纤维5份、氯化聚乙烯6份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物3份、羟丙基甲基纤维素6份、邻苯二甲酸酯2份、单乙醇胺2份、硬脂酸1份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成。
所述催化浆料主要由以下组分构成:氧化铝8份、硝酸铁5份、硝酸锰5份、莫来石10份、磷酸二氢铵10份、聚二甲基硅氧烷0.5份、硬脂酸铝6份、硝酸钇3份、偏钨酸铵5份、硝酸铈8份,硝酸镧2份、钛酸酯偶联剂3份。
其制备方法包括以下步骤:
(1)泥料捏合:
i)按量称取堇青石,莫来石、三氧化钨、SiO2、蒙脱石、硬脂酸、单乙醇胺、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物,邻苯二甲酸酯,加入去离子水混合,添加20%氨水调节泥料pH,所述去离子水:粉料重量比为1:(0.4~0.6),搅拌捏合20min左右,通过捏合及调节添加的去离子水、氨水调节泥料指标,泥料捏合(i)泥料水分目标值38~45%,pH目标值7.8~9.4;
ii)添加20%氨水,盖上搅拌机顶盖,边搅拌边加热升温至95℃以上,然后打开顶盖,蒸发浓缩泥料水分至泥料呈颗粒状,所述泥料水分目标值25~28%,pH目标值7.8~8.5;
iii)边搅拌边依次添加木浆棉3份,玻璃纤维5份,添加20%氨水,搅拌15min左右,所述泥料水分目标值29~34%,pH目标值8.1~9.2;
iv)依次添加氯化聚乙烯6份、羟丙基甲基纤维素3份,搅拌10min以上,所述泥料水分目标值28~32%,pH目标值8.1~9.0;
(2)陈腐:将混炼好的泥料,用保鲜膜密封保存,陈腐,陈腐3h;
(3)预过滤挤出:将陈腐好的泥料,在预过滤挤出机上,挤出力塑性1700~2200N,滤网采用网孔规格为1.0x4mm 或0.8x3mm的不锈钢滤网,过滤挤出成泥条;
(4)成型挤出:在前端装有SCR成型模具的真空挤出机上进行挤出成型,挤出机控制条件为,挤出压力7MPa,挤出温度<35℃,真空度-0.094MPa左右,得到催化剂湿坯;
(5)干燥-煅烧:将步骤(4)得到的催化剂湿坯,转移至铝合金托盘上,用带保温棉的玻璃钢材质的盒盖包装好,干燥温度为90℃,干燥周期5h;将干燥后的催化剂坯料送入窑炉进行煅烧,煅烧温度1100~1200℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为22h,得到蜂窝陶瓷坯体;
(6)上浆-干燥:称取氧化铝、硝酸铁、硝酸锰、莫来石、磷酸二氢铵、聚二甲基硅氧烷、硬脂酸铝、硝酸钇、偏钨酸铵、硝酸铈,硝酸镧、钛酸酯偶联剂,在95℃溶于含有1.2~3.5份草酸的水溶液,浆液比1:3,加升温至80℃并保温,用超声波震荡搅拌2小时,制成催化浆料;将步骤5所得蜂窝陶瓷坯体放入催化浆料池内,裹上催化浆料后放入干燥炉,干燥温度为70℃,干燥周期30分钟,刮除蜂窝陶瓷坯体外侧的催化浆料并清理干净后,重新放入干燥炉,干燥温度为90℃,干燥周期1h;
(7)煅烧:将步骤(6)得到的蜂窝陶瓷坯体,送入窑炉内进行煅烧,煅烧温度550℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为7h,得到中温蜂窝陶瓷。所得产品几何尺寸为150x150x(500~1250)mm,孔径为5~8mm,内壁厚0.7~1.2mm,几何比表面积为360~700m2/m3。
将本发明实施例1-3所得产品与从市场上买到的其他公司产品进行对比,得到以下检测指标:
将本发明实施例1-3所得产品与从市场上买到的其他公司产品进行对比,得到以下检测指标:
经测试,本发明催化剂的抗压强度轴向为 35~40MPa,耐磨损5.2~5.5cm3,催化剂的使用寿命在5~6年,具有较高的强度和导热系数,因此具有广泛的社会和经济价值。
最后,应当指出,以上具体实施方式仅是本发明较有代表性的例子。显然,本发明不限于上述具体实施方式,还可以有许多变形。凡是依据本发明的技术实质对以上具体实施方式所作的任何简单修改、等同变化与修饰,均应认为属于本发明的保护范围。
Claims (4)
1.一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,其特征在于该陶瓷材料主要由以下组分:该脱硝催化剂主要由以下组分:堇青石35~40份,莫来石70~80份、三氧化钨5~10份、SiO25~8份、蒙脱石10~15份、木浆棉2~3份、玻璃纤维4~5份、氯化聚乙烯3~6份、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物3~5份、羟丙基甲基纤维素3~6份、邻苯二甲酸酯2~3份、单乙醇胺2~3份、硬脂酸1~3份经过泥料捏合,陈腐,挤出成型、干燥与煅烧、浸渍催化浆料、再次干燥与煅烧工序制备而成;
所述催化浆料主要由以下组分构成:氧化铝5~8份、硝酸铁5~10份、硝酸锰5~15份、莫来石5~10份、磷酸二氢铵5~10份、聚二甲基硅氧烷0.5~2份、硬脂酸铝6~10份;硝酸钇3~5份、偏钨酸铵5~8份、硝酸铈5~8份,硝酸镧2~4份、钛酸酯偶联剂3份。
2.根据权利要求1所述的一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,其特征在于其制备方法包括以下步骤:
(1)泥料捏合:
i)称取堇青石,莫来石、三氧化钨、SiO2、蒙脱石、硬脂酸、单乙醇胺、邻苯二甲酸酯、甲基丙烯酸甲酯—丁二烯—苯乙烯三元共聚物混合,加入去离子水和20%氨水,搅拌捏合20min左右,通过捏合及调节添加的去离子水、氨水调节泥料指标,泥料捏合(i)泥料水分目标值38~45%,pH目标值7.8~9.4;
ii)添加20%氨水0.5~1.5份,盖上搅拌机顶盖,边搅拌边加热升温至95℃以上,然后打开顶盖,蒸发浓缩泥料水分至泥料呈颗粒状,所述泥料水分目标值25~28%,pH目标值7.8~8.5;
iii)边搅拌边依次添加木浆棉,玻璃纤维,添加20%氨水,搅拌15min左右,所述泥料水分目标值29~34%,pH目标值8.1~9.2;
iv)依次添加氯化聚乙烯、羟丙基甲基纤维素,搅拌10min以上,所述泥料水分目标值28~32%,pH目标值8.1~9.0;
(2)陈腐:将混炼好的泥料,用保鲜膜密封保存,陈腐,陈腐3-4h;
(3)预过滤挤出:将陈腐好的泥料,在预过滤挤出机上,挤出力塑性1700~2200N,过滤挤出成泥条;
(4)成型挤出:在前端装有SCR成型模具的真空挤出机上进行挤出成型,得到催化剂湿坯;
(5)干燥-煅烧:将步骤(4)得到的催化剂湿坯,转移至铝合金托盘上,用带保温棉的玻璃钢材质的盒盖包装好,干燥温度为90℃,干燥周期5h;将干燥后的催化剂坯料送入窑炉进行煅烧,煅烧温度1100~1200℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为18~22h,得到蜂窝陶瓷坯体;
(6)上浆-干燥:称取氧化铝、硝酸铁、硝酸锰、莫来石、磷酸二氢铵、聚二甲基硅氧烷、硬脂酸铝、硝酸钇、偏钨酸铵、硝酸铈、硝酸镧、钛酸酯偶联剂,在70~95℃溶于含有1.2~3.5份草酸的水溶液,浆液比1:3,加升温至80℃并保温,用超声波震荡搅拌1~2小时,制成催化浆料;将步骤5所得蜂窝陶瓷坯体放入催化浆料池内,裹上催化浆料后放入干燥炉,干燥温度为70℃,干燥周期20~30分钟,刮除蜂窝陶瓷坯体外侧的催化浆料并清理干净后,重新放入干燥炉,干燥温度为90℃,干燥周期1h;
(7)煅烧:将步骤(6)得到的蜂窝陶瓷坯体,送入窑炉内进行煅烧,煅烧温度550℃,煅烧过程中,控制温度从100℃起,按100℃/小时梯度递增,煅烧时间为7~9h,得到中温蜂窝陶瓷。
3. 根据权利要求2所述的一种中温催化脱硝蓄热一体化莫来石质陶瓷材料,其特征在于:步骤(3)预过滤挤出,滤网采用网孔规格为1.0x4mm 或0.8x3mm的不锈钢滤网。
4.根据权利要求2所述的中温催化脱硝蓄热一体化莫来石质陶瓷材料,其特征在于:步骤(4)成型挤出,挤出机控制条件为,挤出压力7MPa,挤出温度<35℃,真空度-0.094MPa左右。
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