CN116239379B - 一种Ce-Cr-Fe共掺钙钛锆石陶瓷固化体及其制备方法和应用 - Google Patents
一种Ce-Cr-Fe共掺钙钛锆石陶瓷固化体及其制备方法和应用 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 229910052845 zircon Inorganic materials 0.000 title claims abstract description 47
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910019589 Cr—Fe Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011651 chromium Substances 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 16
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Abstract
本发明属于高放射性固态核废料固化处理技术领域，公开了一种Ce‑Cr‑Fe共掺钙钛锆石陶瓷固化体及其制备方法和应用。所述共掺钙钛锆石型陶瓷固化体的化学式为Ca1‑xCexZrTi2‑ 2xCrxFexO7，其中x＝0.05～0.35。本发明是将钛酸钙、二氧化钛、氧化锆、氧化铈、铁粉和铬粉混合、球磨、干燥、成型后，将陶坯在650～900℃煅烧，再升温至1200～1400℃进行烧结，制得Ce‑Cr‑Fe共掺的钙钛锆石陶瓷固化体。本发明制备的钙钛锆石陶瓷固化体主要相为钙钛锆石，避免了相分离，致密度高，化学性质稳定，核素浸出率低，适合长期深层地质存储。
Description
技术领域
本发明属于高放射性核废物处理技术领域，更具体地，涉及一种Ce-Cr-Fe共掺钙钛锆石陶瓷固化体及其制备方法和应用。
背景技术
核能作为一种高密度的清洁能源，在全球迅速发展，在核燃料循环的整个过程中，开采、转换、燃料制造、放射性制药工业、核电厂、燃料循环配套设施、研究以及开发活动均会产生放射性废物。作为核能终端裂变堆和后处理产生的高放射性废物，包含半衰期长（钚239半衰期为24100年）、放射性强（α/ β 粒子和 γ 射线）、毒性高（钚摄入半致死量为0.089 毫克）的锕系元素和裂变元素。同时，反应堆与后处理里的不锈钢结构部件中的铁、铬元素，通常与α 废物和高放射性核废物共存，钢制结构与锕系元素等高放射性核废物的分离成本高、化学去污工艺复杂、二次废液产生量大，因此，协同安全处理与处置高放射性核废物与不锈钢构件，使其与土水系统和生物圈实现充分、可靠和长期的隔离，在核设施退役和乏燃料后处理运行中有着非常重要的现实意义。由于核素半衰期较长、毒性高、放射性强，在实验过程中通常采用氧化铈模拟高放射性废物中氧化钚。
钙钛锆石（CaZrTi2O7）作为一种固化高放射性废物的宿主相，可在Al、Fe、Cr等元素作为电荷补偿元素的情况下，实现固化多种核素（钚、镎、铀等）。其中Al、Fe、Cr及模拟核素均以氧化物形式掺杂得到钙钛锆石固化体，在2020发表的文献Influence of TransitionMetal Charge Compensation Species on Phase Assemblage inZirconolite Ceramicsfor Pu Immobilisation中报道，通过固态反应烧结，以Cr2O3和CeO2掺杂形成的Cr-Ce共掺钙钛锆石陶瓷固化体（Ca1-xCexZrTi2-2xCr2xO7）具有较高的气孔率；以Fe2O3、CeO2掺杂形成的Fe-Ce共掺钙钛锆石陶瓷固化体（Ca1-xCexZrTi2-2xFe2xO7）生成较多钙钛矿杂质相（当掺杂量为x=0.35时，钙钛矿含量为3.46±0.60 wt.%），其中钙钛矿会降降低钙钛锆石的抗浸出性能。两者均不能很好的实现放射性废物固化体的长期深地存储。到目前为止，Fe和Cr元素仅作为电荷补偿元素，且以氧化物的形式单独参与核废料固化，未涉及到因核废料污染的不锈钢（主要成分为铁、铬）的固化问题，同时其不锈钢与高放射性核废物分离工艺复杂、成本高。
发明内容
为了解决现有技术中存在的缺点和不足之处，本发明首要目的在于提供一种Ce-Cr-Fe共掺钙钛锆石型陶瓷固化体。
本发明的另一目的在于提供上述Ce-Cr-Fe共掺钙钛锆石型陶瓷的制备方法。为了更好的贴合实际核废料及其污染的不锈钢处理情况，同时实现简化工艺，降低成本，本发明将核废料污染的不锈钢破碎后与核废料协同固化的理念，以铈元素模拟钚核素，金属铁和铬模拟不锈钢，通过固态反应烧结制备Ce-Cr-Fe共掺钙钛锆石固化体。
本发明的再一目的在于提供上述Ce-Cr-Fe共掺钙钛锆石型陶瓷的应用。
本发明的目的通过下述技术方案来实现：
一种Ce-Cr-Fe共掺钙钛锆石型陶瓷固化体，所述共掺钙钛锆石型陶瓷固化体的化学式为Ca1-xCexZrTi2-2xCrxFexO7，其中x=0.05~0.35。
优选地，所述共掺钙钛锆石型陶瓷固化体是将钛酸钙、二氧化钛、氧化锆、氧化铈、铁粉和铬粉混合，加入溶剂和氧化锆磨球进行球磨混合，干燥后过筛得到混合粉体；再将混合粉体进行干压成型成陶坯，将陶坯在650~900℃煅烧，再升温至1200~1400℃进行烧结，随后降至室温制得。
优选地，所述铁粉的粒径为10~200μm；所述铬粉的粒径为10~200μm；所述钛酸钙、二氧化钛、氧化锆、氧化铈的粒径均为20nm~10μm。
优选地，所述溶剂为无水乙醇或丙酮。
优选地，所述干压成型的压力为30~40MPa。
所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体的制备方法，包括以下具体步骤：
S1. 将钛酸钙、二氧化钛、氧化锆、氧化铈、铁粉和铬粉混合，加入溶剂和氧化锆磨球进行球磨混合，干燥后过筛，得到混合粉体；
S2. 将混合粉体在30~40MPa进行干压成型，制得陶坯；
S3. 将陶坯于马弗炉升温至650~900℃保温；然后升温至1200~1400℃保温，再降温至室温，制得Ce-Cr-Fe共掺钙钛锆石陶瓷固化体。
优选地，步骤S1中所述球磨的转速为200~300r/min，所述球磨的时间为12~24h，所述过筛的孔径为100~200目。
优选地，步骤S1中所述升温和降温的速率均为5~10℃/min；升温至650~900℃保温的时间为5~10，升温至1200~1400℃保温的时间为10~24h。所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体在处理高放废物领域中的应用。
与现有技术相比，本发明具有以下有益效果：
1. 本发明以铈元素模拟钚核素，金属铁和铬模拟不锈钢，通过固态反应烧结制备Ce-Cr-Fe共掺钙钛锆石固化体，实现了Ce、Cr、Fe元素同时固溶到钙钛锆石中，对放射性核素及核素污染的不锈钢的协同模拟固化。
2. 本发明相比于Ce-Fe共掺钙钛锆石陶瓷固化体的主要相为钙钛锆石，避免了相分离，生成的有害相钙钛矿有所减少，相比于Ce-Cr共掺钙钛锆石陶瓷固化体中的气孔率有所减少，具有更加优良的抗浸出性能。
3. 本发明制备的钙钛锆陶瓷石固化体主要相为钙钛锆石，避免了相分离，以金属单质Cr和Fe为原料，更贴合实际地实现对核废料污染的不锈钢的模拟固化，简化了工艺，降低了成本工艺，致密度高(98%以上），化学性质稳定，热稳定性好，核素浸出率低，适合长期深层地质存储。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
将x=0.5时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应的钛酸钙、二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）和铬粉（50μm）进行混合，将其加入无水乙醇和氧化锆球中，在行星球磨机球磨以转速300r/min球磨4h，干燥后将混合粉体30MPa干压成陶坯，然后放如马弗炉中以5℃/min速率升温至800℃煅烧并保温5h，再以5℃/min的速率升温至1400℃并保温10h，随后以5℃/min速率降至室温，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为99.58%，钙钛锆石含量为99.565±0.1 wt.%，含微氧化锆、氧化铈，无有害相钙钛矿，核素浸出率为5.068±0.1×10-6g·m-2·d-1。由此可知，核素浸出率较低，说明该共掺钙钛锆石固化体的化学性质稳定，热稳定性好。
实施例2
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.1时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为99.32%，钙钛锆石含量为99.488±0.1 wt.%，含微氧化锆，无有害相钙钛矿，核素浸出率为4.896±0.1×10-6g·m-2·d-1。
实施例3
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.15时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为99.09%，钙钛锆石含量为99.396±0.1 wt.%，含微氧化锆，无有害相钙钛矿，核素浸出率为5.153±0.1×10-6g·m-2·d-1。
实施例4
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.2时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为98.78%，钙钛锆石含量为99.281±0.1 wt.%，钙钛矿含量为0.39±0.1 wt.%，含微量氧化锆，核素浸出率为6.256±0.1×10-6g·m-2·d-1。
实施例5
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.25时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为98.82%，钙钛锆石含量为98.96±0.1 wt.%，钙钛矿含量为0.69±0.1 wt.%，含微量氧化锆，核素浸出率为6.563±0.1×10-6g·m-2·d-1。
实施例6
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.3时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为98.78%，钙钛锆石含量为98.73±0.1 wt.%，钙钛矿含量为1.02±0.1 wt.%，含微量氧化锆，核素浸出率为6.991±0.1×10-6g·m-2·d-1。
实施例7
与实施例1不同在于：将二氧化钛（50nm）、氧化锆、氧化铈、铁粉（50μm）、铬粉（50μm）原料按x=0.35时，化学式Ca1-xCexZrTi2-2xCrxFexO7对应原料进行混合，制得Ce-Cr-Fe共掺钙钛锆石固化体。
该钙钛锆石陶瓷固化体致密度为98.53%，钙钛锆石含量为98.59±0.1 wt.%，钙钛矿含量为1.39±0.1 wt.%，含微量氧化锆，核素浸出率为7.263±0.1×10-6g·m-2·d-1。
本发明的钙钛锆石陶瓷固化体以钙钛锆石为主相，致密度高，核素浸出率较低，说明该共掺钙钛锆石固化体的化学性质稳定，热稳定性好。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内 。
Claims (5)
1.一种Ce-Cr-Fe共掺钙钛锆石陶瓷固化体，其特征在于，所述共掺钙钛锆石陶瓷固化体的化学式为Ca1-xCexZrTi2-2xCrxFexO7，其中x=0.05~0.35；
所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体的制备方法，包括以下具体步骤：
S1. 将钛酸钙、二氧化钛、氧化锆、氧化铈、铁粉和铬粉混合，加入溶剂和氧化锆磨球进行球磨混合，干燥后过筛，得到混合粉体；
S2. 将混合粉体在30~40MPa进行干压成型，制得陶坯；
S3. 将陶坯于马弗炉升温至650~900℃保温；然后升温至1200~1400℃保温，再降温至室温，制得Ce-Cr-Fe共掺钙钛锆石陶瓷固化体；所述升温和降温的速率均为5~10℃/min；升温至650~900℃保温的时间为5~10h，升温至1200~1400℃保温的时间为10~24h。
2.根据权利要求1所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体，其特征在于，步骤S1中所述铁粉的粒径为10~200μm；所述铬粉的粒径为10~200μm；所述钛酸钙、二氧化钛、氧化锆、氧化铈的粒径均为20nm~10μm。
3.根据权利要求1所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体，其特征在于，步骤S1中所述溶剂为无水乙醇或丙酮。
4.根据权利要求1所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体，其特征在于，步骤S1中所述球磨的转速为200~300r/min，所述球磨的时间为12~24h，所述过筛的孔径为100~200目。
5.权利要求1-4任一项所述的Ce-Cr-Fe共掺钙钛锆石陶瓷固化体在处理高放射性废物领域中的应用。
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