CN111530449A - 一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺 - Google Patents

一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺 Download PDF

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CN111530449A
CN111530449A CN202010518416.8A CN202010518416A CN111530449A CN 111530449 A CN111530449 A CN 111530449A CN 202010518416 A CN202010518416 A CN 202010518416A CN 111530449 A CN111530449 A CN 111530449A
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parts
catalyst
titanium dioxide
temperature
low
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CN111530449B (zh
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张涛
刘安阳
罗春云
任英杰
张深根
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Jiangsu Longjing Kejie Environmental Protection Technology Co ltd
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Jiangsu Longjing Kejie Environmental Protection Technology Co ltd
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Priority to CN202010518416.8A priority Critical patent/CN111530449B/zh
Publication of CN111530449A publication Critical patent/CN111530449A/zh
Priority to US17/606,758 priority patent/US11478783B2/en
Priority to PCT/CN2021/085652 priority patent/WO2021248998A1/zh
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Abstract

本发明公开了一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺。该催化剂由以下重量份的原料制备而成：煅烧二氧化钛30‑60份、生二氧化钛30‑50份、勃姆石3‑5份、熔融硅微粉2‑4份、粘结剂0.5‑2份、润滑剂0.5‑2份、钒钼复合氧化物5‑10份和水150‑200份；所述钒钼复合氧化物由偏钒酸铵和钼酸铵溶解在草酸溶液中，喷雾干燥得到。本发明催化剂的制备工艺简单，成本低廉，且制备的壁流式除尘低温脱硝催化剂除尘效率高、低温160‑200℃脱硝活性高，寿命长，成本低，用于玻璃、焦化、垃圾焚烧等行业半/干法脱硫后的除尘低温脱硝一体化项目。

Description

一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺
技术领域
本发明涉及催化剂制备技术领域，尤其涉及一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺。
背景技术
氮氧化物(NOx)是主要大气污染物之一，是形成酸雨、雾霾和光化学烟雾的主要原因。我国每年NOx排放量高达2400万吨，因酸雨污染造成的损失超过3000亿元/年。粉尘也是大气的主要污染物之一，尤其是PM10以下的微细颗粒物，粉尘排放量达到1500万吨/年。随着国家环保政策要求越来越严格，玻璃、焦化、垃圾焚烧等行业二氧化硫、氮氧化物、粉尘排放指标越来越严格。由于上述行业的烟温较低，为了保证温度较低(一般低于200℃)时，氮氧化物脱硝效率及催化剂寿命，会在前端采用半/干法脱硫，保证SO2含量低于50mg/Nm3。但目前烟气处理技术还存在一些问题，如：烟气除尘、脱硝等都是单独进行开发的，形成了各自的技术体系和工艺流程，制成专门的控制设备。为了除去烟气中的粉尘和其他的有害污染物，都采用至少两套以上独立的烟气净化系统，烟气净化系统存在占地面积大，投资成本高，烟气阻力大，投资及运行成本高，企业的负担大，经济性差等问题，特别是有些粉尘等含量较低的烟气脱硝，因此，开发除尘和低温脱硝一体化的催化剂具有重要意义。
然而，已知现有较多除尘脱硝一体化的催化剂都是采用滤筒或者滤袋上涂覆脱硝活性物质，虽然采用以上方法制备的过滤器取得一定效果，但是存在催化剂在陶瓷过滤器中内分散不均匀、磨损严重、负载量高、除尘低温脱硝效率低等缺点。
发明内容
基于现有技术中存在的上述不足，本发明的目的在于提供一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺。
本发明所述具烟气壁流式除尘低温脱硝蜂窝式催化剂，是以煅烧二氧化钛、生二氧化钛、勃姆石、熔融硅微粉、粘结剂糊精、润滑剂机油、活性组分钒钼复合氧化物混合制成泥团；经挤出形成蜂窝型湿坯，交叉封孔形成壁流式的除尘过滤单元，经高温烧结热处理得到催化剂。
本发明催化剂的制备工艺简单，成本低廉，且制备的壁流式除尘低温脱硝催化剂除尘效率高、低温160-200℃脱硝活性高，寿命长，成本低，用于玻璃、焦化、垃圾焚烧等行业半/干法脱硫后的除尘低温脱硝一体化项目。
本发明的第一方面在于提供一种烟气壁流式除尘低温脱硝蜂窝式催化剂，由以下重量份的原料制备而成：
煅烧二氧化钛30-60份、生二氧化钛30-50份、勃姆石3-5份、熔融硅微粉2-4份、粘结剂0.5-2份、润滑剂0.5-2份、钒钼复合氧化物5-10份和水150-200份；
所述钒钼复合氧化物由偏钒酸铵和钼酸铵溶解在草酸溶液中，喷雾干燥得到。
本发明的催化剂中，活性物质为钒钼复合氧化物，载体为两种不同比表面积的二氧化钛，即煅烧二氧化钛和生二氧化钛。勃姆石粒度d50≤3-4μm，熔融硅微粉粒度d50≤2-3μm，增强催化剂机械强度和耐磨性。
在本发明的一些实施方式中，所述粘结剂为糊精，比一般胶黏剂成本便宜，原材料易得。
在本发明的一些实施方式中，所述润滑剂为机油，比商用的硬脂酸、油酸等便宜。
在本发明的一些实施方式中，所述煅烧二氧化钛的平均粒度为2.5-3.5μm，比表面积为250-350m2/g，所述生二氧化钛的平均粒度为4.5-5.5μm，比表面积为130-150m2/g。
2种不同粒度和比表面积组合的质量比1：1.1-2得到的壁流式除尘低温脱硝蜂窝式催化剂孔径控制在15-20μm，除尘效率最高达到95％以上。
在本发明的一些实施方式中，制备所述组分钒钼复合氧化物的偏钒酸铵和钼酸铵的摩尔比为1：(1-3)。
活性组分原料中，主要起催化作用的偏钒酸铵量，钼酸铵量起助催化剂的作用。偏钒酸和钼酸铵的组合，确定了偏钒酸保证最少量的基础上，保证低温脱硝效率最大。
在本发明的一些实施方式中，所述糊精由面粉和水混合成浆后经熟化而成。
本发明的第二方面在于提供第一方面所述的烟气壁流式除尘低温脱硝蜂窝式催化剂的制备工艺，包括以下步骤：
S1，将煅烧二氧化钛、生二氧化钛与勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，搅拌混合；
S2，将面粉和水，混合成浆，熟化成糊精；
S3，将S1步骤的得到的混合物和S2步骤得到的糊精，搅拌混合，得到泥料；
S4，将所述泥料进行混炼和筛制；
S5，将S4步骤处理过的泥料用蜂窝模具挤出成型，形成蜂窝型陶瓷素坯；经干燥，叉孔封堵；
S6，高温烧结，制得所需的催化剂。
在本发明的一些实施方式中，所述熟化的温度为65-100℃。
在本发明的一些实施方式中，所述蜂窝型陶瓷素坯的截面尺寸为(130-170mm)×(130-170mm)。
在本发明的一些实施方式中，所述高温烧结为，以＜3℃/分钟的速度加温到200-300℃保温6-12小时；然后将温度升到450-500℃保温4-12小时，随炉冷却到室温出窑。
与现有技术相比本发明具有以下有益效果：
(1)本发明采用2种不同粒径级、煅烧和生的二氧化钛、不同比表面积使的制备的壁流式除尘低温脱硝催化剂孔壁上形成及其丰富的孔大小和分布，有利于烟气除尘和低温脱硝和烟气充分接触，实现高的除尘率和脱硝效率。
(2)采用挤出成型制备的壁流式除尘低温催化剂，比现有涂覆式催化剂活性物质分布高，耐磨性强。
(3)本发明催化剂脱硝温度低、性价比优良，采用世界通用的的方法，其制备方法原料丰富，成本低廉，成型容易，烧结工艺合理。
(4)具有十分广泛的应用，用于玻璃、焦化、垃圾焚烧等行业半/干法脱硫后的除尘低温脱硝一体化项目。
附图说明
图1为本发明的烟气壁流式除尘低温脱硝蜂窝式催化剂的使用时的一种烟气流向示意图；
图2为本发明的烟气壁流式除尘低温脱硝蜂窝式催化剂的一种实施方式的结构示意图。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
除非特别指出，以下实施例和对比例为平行试验，采用同样的处理步骤和参数。技术路线为：原料混合制成泥团；经挤出成型蜂窝型湿坯，交叉封孔形成壁流式的除尘过滤单元，经高温烧结热处理得到孔径在15-20μm的催化剂。其中，煅烧二氧化钛的平均粒度为3μm，生二氧化钛的平均粒度为5μm；勃姆石粒度d50≤3-4μm，熔融硅微粉粒度d50≤2-3μm。糊精的制浆过程中，面粉和水的比例为每100ml中加入30g面粉，制备糊精的水不计在泥料制备原料的水中。
本发明的壁流式除尘低温脱硝蜂窝式催化剂，外部结构如图2所示，使用时待处理的烟气按图1所示的方向进行除尘和低温脱硝。带有粉尘和氮氧化物的烟气与NH3气体混合均匀，然后从蜂窝式催化剂一端进入，经过该入口端上未被封闭的孔的相邻孔侧壁，利用侧壁过滤除去烟尘，延长烟气在其中的停留时间，在壁面上的活性物质催化剂作用，低温下在NH3将氮氧化物还原为氮气和水。除尘可以通过定期脉冲空气反吹除去，收集回收粉尘，保证除尘和低温脱硝持续进行。
实施例1
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：煅烧二氧化钛50份、生二氧化钛30份、勃姆石5份、熔融硅微粉4份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物8份和200份水。
其中，所述煅烧二氧化钛比表面积为250m2/g，生二氧化钛比表面积为150m2/g。活性组分钒钼复合氧化物是由每0.1mol的偏钒酸铵和每0.1mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)取煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)取面粉和水在常温下混合成浆，在65℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌3小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到200℃保温12小时；然后将温度升到450℃保温12小时，随炉冷却到室温出窑，制得所需的催化剂。
实施例2
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：煅烧二氧化钛40份、生二氧化钛49份、勃姆石3份，熔融硅微粉2份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物份5份和150份水；
其中，所述煅烧二氧化钛比表面积为350m2/g，生二氧化钛比表面积为150m2/g。活性组分钒钼复合氧化物是由每0.15mol的偏钒酸铵和每0.45mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)取煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在100℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌1小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到300℃保温6小时；然后将温度升到500℃保温4小时，随炉冷却到室温出窑，制得所需的催化剂。
实施例3
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：煅烧二氧化钛45份、生二氧化钛40份、勃姆石4份，熔融硅微粉4份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物7份和180份水。
其中，所述煅烧二氧化钛比表面积为300m2/g，生二氧化钛比表面积为140m2/g。活性组分钒钼复合氧化物是由每0.1mol的偏钒酸铵和每0.2mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)取煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在90℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌2小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到300℃保温8小时；然后将温度升到480℃℃保温8小时，随炉冷却到室温出窑，制得所需的催化剂。
实施例4
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：煅烧二氧化钛48份、生二氧化钛42份、勃姆石3份，熔融硅微粉2份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物5份和170份水。
其中，所述煅烧二氧化钛比表面积为328m2/g，生二氧化钛比表面积为130m2/g。活性组分钒钼复合氧化物是由每0.15mol的偏钒酸铵和每0.15mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)取煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在100℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌3小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到200℃保温12小时；然后将温度升到500℃温8小时，随炉冷却到室温出窑，制得所需的催化剂。
实施例5
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：煅烧二氧化钛44份、生二氧化钛40份、勃姆石3份，熔融硅微粉2份、粘结剂糊精0.5份、润滑剂机油0.5份、活性组分钒钼复合氧化物8份和190份水。
其中，所述煅烧二氧化钛比表面积为320m2/g，生二氧化钛比表面积为130m2/g。活性组分钒钼复合氧化物是由每0.1mol的偏钒酸铵和每0.3mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)取煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在90℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌2小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到250℃保10小时；然后将温度升到500℃保温12小时，随炉冷却到室温出窑，制得所需的催化剂。
对比例1
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：以煅烧二氧化钛80份、勃姆石5份，熔融硅微粉4份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物8份和200份水。
其中，所述煅烧二氧化钛比表面积为250m2/g。活性组分钒钼复合氧化物是由每0.1mol的偏钒酸铵和每0.1mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)将煅烧二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在65℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌3小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到200℃保温12小时；然后将温度升到450℃保温12小时，随炉冷却到室温出窑，制得所需的催化剂。
对比例2
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：以煅烧二氧化钛50份、生二氧化钛30份、勃姆石5份，熔融硅微粉4份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分偏钒酸铵4份，钼酸铵4份和200份水。
其中，所述煅烧二氧化钛比表面积为250m2/g，生二氧化钛比表面积为150m2/g。
(2)将煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油和偏钒酸铵、钼酸铵、水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在65℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌3小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到200℃保温12小时；然后将温度升到450℃保温12小时，随炉冷却到室温出窑，制得所需的催化剂。
对比例3
一种烟气壁流式除尘低温脱硝蜂窝式催化剂制备工艺，步骤如下：
(1)按重量份数配比称量各组份：以商业生产用二氧化钛80份、勃姆石5份，熔融硅微粉4份、粘结剂糊精1.5份、润滑剂机油1.5份、活性组分钒钼复合氧化物8份和200份水。
其中，所述商业生产用二氧化钛为100m2/g。活性组分钒钼复合氧化物是由每0.1mol的偏钒酸铵和每0.1mol的钼酸铵溶解在1L草酸溶液中，喷雾干燥得到。
(2)将煅烧二氧化钛、生二氧化钛；加入勃姆石、熔融硅微粉、机油、钒钼复合氧化物和水，在搅拌机内充分搅拌混合均匀，待用；
(3)将面粉和水在常温下混合成浆，在65℃下熟化成糊精；
(4)将糊精和步骤(2)的所得物在搅拌机内混合，搅拌3小时；
(5)对泥料进行混炼和筛制，使泥料充分均匀；
(6)用蜂窝模具挤出成型，形成截面150mm×150mm蜂窝型陶瓷素坯；经室温干燥，叉孔封堵；
(7)以＜3℃/分钟的速度加温到200℃保温12小时；然后将温度升到450℃保温12小时，随炉冷却到室温出窑，制得所需的催化剂。
壁流式除尘低温脱硝蜂窝式催化剂性能测试实验：
取实施例1-5及对比例1-3制备的催化剂，在固定床反应器中除尘设备上检测除尘效率测试，粉煤灰为灰尘介质。
低温测试条件为：NO 500mg/Nm3，NH3 500Nm3，O2 5％，SO2 100mg/Nm3，5％H2O，N2为平衡气，AV 6.5m/h，催化剂25×25孔，长度500mm。
分别在160℃、180℃、200℃温度下检测进出口NOX的浓度，采用MRU烟气分析仪进行检测。
表1不同催化剂的除尘脱硝性能检测结果
Figure BDA0002530989900000091
从上表1可以看出，与对比例1、3相比，实施例1-5的烟气壁流式除尘低温脱硝蜂窝式催化剂除尘率高、低温脱硝效率高，说明了本发明选择250-350m2/g和130-150m2/g两种粒径的二氧化钛作为载体，优于单独使用250m2/g和100m2/g粒径的二氧化钛作为载体。
与对比例2相比，实施例1-5的烟气壁流式除尘低温脱硝蜂窝式催化剂除尘率高、低温脱硝效率高，说明了本发明选择偏钒酸铵和钼酸铵混合溶解在草酸溶液中，喷雾干燥得到钒钼复合氧化物作为活性物质，优于活性组分偏钒酸铵和钼酸铵直接加入到二氧化钛中，单独起作用。
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。
以上对本发明优选的具体实施方式和实施例作了详细说明，但是本发明并不限于上述实施方式和实施例，在本领域技术人员所具备的知识范围内，还可以在不脱离本发明构思的前提下作出各种变化。

Claims (10)

1.一种烟气壁流式除尘低温脱硝蜂窝式催化剂，由泥料成型后经高温烧结而成，所述泥料包括以下重量份的各原料：
煅烧二氧化钛30-60份、生二氧化钛30-50份、勃姆石3-5份、熔融硅微粉2-4份、粘结剂0.5-2份、润滑剂0.5-2份、钒钼复合氧化物5-10份和水150-200份；
所述钒钼复合氧化物由偏钒酸铵和钼酸铵溶解在草酸溶液中，喷雾干燥得到。
2.根据权利要求1所述的催化剂，其特征在于，所述粘结剂为糊精。
3.根据权利要求1或2所述的催化剂，其特征在于，所述润滑剂为机油。
4.根据权利要求1-3任一所述的催化剂，其特征在于，所述煅烧二氧化钛的平均粒度为2.5-3.5μm，比表面积为250-350m2/g，所述生二氧化钛的平均粒度为4.5-5.5μm，比表面积为130-150m2/g。
5.根据权利要求1-4任一所述的催化剂，其特征在于，制备所述组分钒钼复合氧化物的偏钒酸铵和钼酸铵的摩尔比为1：(1-3)。
6.根据权利要求1-5任一所述的催化剂，其特征在于，所述糊精由面粉和水混合成浆后经熟化而成。
7.一种根据权利要求1-6任一所述的催化剂的制备工艺，包括以下步骤：
S1，将煅烧二氧化钛、生二氧化钛、勃姆石、熔融硅微粉、润滑剂、钒钼复合氧化物和水，搅拌混合；
S2，将面粉和水，混合成浆，熟化成糊精；
S3，将S1步骤的得到的混合物和S2步骤得到的糊精，搅拌混合，得到泥料；
S4，将所述泥料进行混炼和筛制；
S5，将S4步骤处理过的泥料用蜂窝模具挤出成型，形成蜂窝型陶瓷素坯；经干燥，叉孔封堵；
S6，高温烧结，制得所需的催化剂。
8.根据权利要求7所述的制备工艺，其特征在于，所述熟化的温度为65-100℃。
9.根据权利要求7或8所述的制备工艺，其特征在于，所述蜂窝型陶瓷素坯的截面尺寸为(130-170mm)×(130-170mm)。
10.根据权利要求7-9任一所述的制备工艺，其特征在于，所述高温烧结为，以＜3℃/分钟的速度加温到200-300℃保温6-12小时；然后将温度升到450-500℃保温4-12小时，随炉冷却到室温出窑。
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