CN112759397A - 稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法 - Google Patents
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Abstract
本发明涉及高性能陶瓷材料领域,具体为稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法。以氧化稀土粉、碳化硼粉和石墨粉为原料制备稀土二硼二碳粉体,将适量配比的原料粉经物理机械方法混合6~12小时,烘干、过筛后装入石墨坩埚,然后放入通有高纯氩气的烧结炉内进行烧结,升温速率5~20℃/分钟,烧结温度1800~2200℃、保温1~8小时。将制备的稀土二硼二碳粉体过500目筛,室温下与去离子水混合,即可制备氢气氧气和烃类等成分丰富的混合气体:氢气和氧气为主要成分,烃类包括甲烷、乙烷、乙烯、乙炔、丙烷、丙烯和丁烯等,甚至还含少量的一氧化碳和二氧化碳。该材料与水反应过程及气体产物在能源、化工、机械等行业具有潜在应用价值。
Description
技术领域
本发明涉及高性能陶瓷材料领域,具体为一种稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法。
背景技术
REB2C2材料具有层状晶体结构,可以描述为RE片层与B2C2片层在c轴方向上交替堆垛而成。目前,对REB2C2材料,除了研究其晶体结构外,主要集中在磁性能和电性能方面,而关于REB2C2材料的化学活性和力学性能研究较少。文献1:Journal of Inorganic andNuclear Chemistry 1967,29:375-382中SmithP.K.等人用电弧熔炼法制备了GdB2C2材料,并以此为例研究了REB2C2相的鉴别与表征以及RE-B-C体系中各种相之间的关系。文献2:ScriptaMaterialia2016,124:86-89中Zhao G.R.等制备的YB2C2材料具有典型的片层状结构、优异的抗损伤容限性和良好的可加工性。文献3:Ceramics International 2019,45(2):1857-1867中Bao W.Z.等人利用“第一性原理”计算了REB2C2材料的结构、弹性各向异性和热导率等。
文献4:Journal of the Less-Common Metals 1991,170:191-198中Mccolm I.J.等人研究发现稀土二碳(REC2)材料与H2O反应可产生H2、C2H6、C2H4、C2H2、和C4H6等烃类。此外,电解水制备H2和O2的技术早已为人们所熟知并加以利用。然而,能与水反应同时产生H2、O2、和CH4、C2H6、C2H4、C2H2、C3H8、C3H6、C4H8等烃类的材料尚未见报道,尤其反应在室温下即可进行,且反应过程中不需额外提供能量。
发明内容
本发明的目的在于提供一种稀土二硼二碳(REB2C2)材料与水反应制备氢、氧和烃类等混合气体的方法,其意义在于REB2C2材料在室温下与水反应同时产生H2、O2、和CH4、C2H6、C2H4、C2H2、C3H8、C3H6、C4H8等烃类,且整个过程中不需要额外提供能量。
本发明的技术方案是:
一种稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,稀土二硼二碳(REB2C2)材料与水(H2O)反应,室温下制备混合气体,混合气体的主要成分为氢气(H2)、氧气(O2),还包括甲烷(CH4)、乙烷(C2H6)、乙烯(C2H4)、乙炔(C2H2)、丙烷(C3H8)、丙烯(C3H6)和丁烯(C4H8),以及一氧化碳(CO)和二氧化碳(CO2)。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,REB2C2材料中的“稀土”RE是指:钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥之一或两种以上。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,REB2C2材料的制备方法,具体步骤如下:
(1)原料组成及成分范围:
原料由稀土氧化物粉RE2O3、碳化硼粉B4C和石墨粉C组成,其中RE2O3:B4C:C的摩尔比为(0.7~1.1):(0.8~1.1):(5.5~6.5);
(2)制备工艺:
首先将稀土氧化物粉、碳化硼粉和石墨粉按配比称重,经物理机械方法混合6~12小时;在通有高纯氩气的烧结炉内进行烧结,升温速率为5~20℃/分钟,烧结温度为1800~2200℃,烧结时间为1~8小时,合成的材料为单相的稀土二硼二碳REB2C2材料粉体。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,将制备的REB2C2材料粉体过500目筛,室温下与水反应制备氢、氧和烃类混合气体。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,H2O是指“去离子水”。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,REB2C2材料与H2O反应的环境为室温。
所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,混合气体中各种成分的体积含量:H2为50~80%,O2为10~40%,CH4为2~15%,C2H6、C2H4、C2H2、C3H8、C3H6、C4H8、CO和CO2为0.01~0.5%。
本发明的设计思想是:将硼/碳热还原法制备的REB2C2材料,室温下与H2O混合生成H2、O2和C2H2等基础气体;同时,H2与C2H2经过一系列聚合反应生成CH4、C2H6、C2H4、C3H8、C3H6和C4H8等烃类;此外,反应生成的活泼氧原子[O]和碳原子[C]结合生成CO和CO2。
本发明的优点及有益效果是:
1.本发明REB2C2材料与H2O反应,产生的混合气体成分丰富:除主要成分H2和O2外,还包括CH4、C2H6、C2H4、C2H2、C3H8、C3H6和C4H8等烃类,甚至还有少量的CO和CO2。
2.本发明REB2C2材料与H2O反应的条件温和,室温下即可进行,且不需要额外提供能量。
3.本发明材料与水的反应过程及生成的气体产物在能源、化工、机械等行业具有潜在应用价值。
附图说明
图1为YbB2C2粉体的XRD衍射图。图中,横坐标2θ代表衍射角(degrees),纵坐标Intensity代表相对强度(arb.units)
图2为YbB2C2粉体扫描电镜图片。
图3为15.00克(g)YbB2C2粉体与500毫升(mL)H2O反应的动力学曲线。
图4为YB2C2粉体的XRD衍射图。图中,横坐标2θ代表衍射角(degrees),纵坐标Intensity代表相对强度(arb.units)
图5为YB2C2粉体扫描电镜图片。
图6为9.25克(g)YB2C2粉体与500(mL)H2O反应的动力学曲线。
具体实施方式
在具体实施过程中,本发明以氧化稀土(RE2O3)粉、碳化硼(B4C)粉和石墨(C)粉为原料制备REB2C2粉体,将适量配比的原料粉经物理机械方法混合6~12小时(h),烘干、过筛后装入石墨坩埚,然后放入通有高纯氩气(Ar)的烧结炉内进行烧结,升温速率5~20℃/分钟,烧结温度1800℃~2200℃、保温1~8h。将制备的REB2C2粉体过500目筛,室温下与去离子水(H2O)混合,即可制备氢气(H2)氧气(O2)和烃类等成分丰富的混合气体:H2和O2为主要成分,烃类包括甲烷(CH4)、乙烷(C2H6)、乙烯(C2H4)、乙炔(C2H2)、丙烷(C3H8)、丙烯(C3H6)和丁烯(C4H8)等,甚至还含少量的一氧化碳(CO)和二氧化碳(CO2),且随着反应的进行,混合气体的组成和含量略有变化。
其中,REB2C2材料的制备方法为硼/碳热还原,具体制备方法可参照已申请的专利“硼/碳热还原法制备三元稀土二硼二碳陶瓷粉体的方法,公开号107814570A”。
另外,REB2C2材料中的“稀土”(RE)是指:钪(Sc)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)和镥(Lu)等17种元素。
下面,通过实施例进一步详述本发明。
实施例1
本实施例中,将300目的Yb2O3粉49.24g、200目的B4C粉7.88g和200目的C粉12.88g装入氮化硅球磨罐中以无水乙醇球磨6h,60℃烘干24h,过100目筛,随后装入石墨坩埚中,将石墨坩埚烧结炉中进行烧结,升温速率为20℃/分钟,升至1800℃时保温8h,整个烧结过程在高纯氩气(氩气体积纯度在99.999%以上)保护下进行。如图1所示,将获得的反应产物进行XRD分析,可以发现制备材料为YbB2C2相。如图2所示,从扫描电镜照片可以发现,制备的粉体具有典型的片层结构。将烧结后的样品过500目筛,取15.00g样品与500mL H2O混合,约29h后反应趋于停止,其反应动力学曲线见图3;取50.00g样品与500mL H2O混合,收集不同阶段气体并用气相色谱仪分析,得氢、氧和烃类混合气体的成分及相对含量见表1。
表1为50.00g的YbB2C2粉体与500mL的H2O反应生成混合气体的成分及含量
由图3的动力学曲线可以看出,反应过程可分为“准备期”(0~2h)、“初始期”(2~11.9h)、“平衡期”(11.9~29.3h)和“末期”(29.3h以后)。其中,“准备期”是由于反应动力学过程测试方法所致,测试方法为“集气排水法”,只有当产生的气体达到一定量(即气压达到一定值)才能将溶剂瓶中的水压出,具体表现为曲线中的台阶段;“初始期”实际为反应的第一阶段,反应开始时YbB2C2粉体与H2O接触面积大,反应速度快;“平衡期”为实际反应的第二阶段,随着反应的进行,YbB2C2粉体表面一方面生成胶状的黏膜不利于反应的进行,另一方面反应生成的气泡不断冲破黏膜,露出新的表面促进反应的进行,两者共同作用趋于平衡;“末期”为实际反应的第三阶段,随着反应的进行,YbB2C2粉体逐渐减少,表面生成胶状的黏膜越来越致密,而产生气泡冲破黏膜的能力越来越弱,反应速度越来越慢,最后趋于停止。
由表1的混合气体成分及含量可以看出:混合气体主要为H2(50~80%),其次是O2(10~40%),再次是CH4(2~15%);随着反应进行,H2和C2H2呈减少趋势,而O2呈增加趋势;H2和C2H2生成量多时,其聚合生成CH4、C2H6、C2H4、C3H8、C3H6和C4H8等烃类的能力越强,表现为种类多、生成量多;O2生成量多时,意味着活泼的氧原子[O]也越多,随着[O]增多,它与活泼碳原子[C]依次生成CO和CO2。
实施例2
本实施例中,将200目的Y2O3粉28.80g、200目的B4C粉8.05g和200目的C粉13.15g装入氮化硅球磨罐中以无水乙醇球磨12h,60℃烘干24h,过100目筛,随后装入石墨坩埚中,将石墨坩埚烧结炉中进行烧结,升温速率为5℃/分钟,升至2200℃时保温1h,整个烧结过程在高纯氩气(氩气体积纯度在99.999%以上)保护下进行。如图4所示,将获得的反应产物进行XRD分析,可以发现制备材料为YB2C2相。如图5所示,从扫描电镜照片可以发现,制备的粉体具有典型的片层结构。将烧结后的样品过500目筛,取9.25g样品与500mL H2O混合,约37h后反应明显变慢,随后逐渐趋于停止,其反应动力学曲线见图6;取30.83g样品与500mL H2O混合,收集不同阶段气体并用气相色谱仪分析,得氢、氧和烃类混合气体的成分及相对含量见表2。
表2为30.83g的YB2C2粉体与500mL的H2O反应生成混合气体的成分及含量
由图6的动力学曲线可以看出,与YbB2C2粉体类似,YB2C2粉体与H2O反应过程也可分为“准备期”(0~1.5h)、“初始期”(1.5~21.7h)、“平衡期”(21.7~37.4h)和“末期”(37.4h以后)。其中,各个时期的含义也同YbB2C2粉体与H2O反应过程基本相同,不同之处在于:YbB2C2粉体与H2O反应的“初始期”较短(不足12h),“平衡期”稍长(约18h);而YB2C2粉体与H2O反应的“初始期”较长(约22h),“平衡期”稍短(约16h)。YB2C2粉体与H2O反应的“初始期”较长的原因可能是其比表面积较大。
由表2的混合气体成分及含量可以看出:混合气体主要为H2(50~80%),其次是O2(15~40%),再次是CH4(4~8%);与YbB2C2粉体和H2O反应不同,随着反应进行,H2呈增加趋势,而O2和C2H2呈减少趋势;尽管H2较多,但由于C2H2生成量不足,其聚合生成CH4、C2H6、C2H4、C3H8、C3H6和C4H8等烃类的能力不足;“初始期”O2生成量较多,活泼的氧原子[O]也较多,它与活泼碳原子[C]便能生成CO和CO2。
Claims (7)
1.一种稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,稀土二硼二碳(REB2C2)材料与水(H2O)反应,室温下制备混合气体,混合气体的主要成分为氢气(H2)、氧气(O2),还包括甲烷(CH4)、乙烷(C2H6)、乙烯(C2H4)、乙炔(C2H2)、丙烷(C3H8)、丙烯(C3H6)和丁烯(C4H8),以及一氧化碳(CO)和二氧化碳(CO2)。
2.按照权利要求1所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,REB2C2材料中的“稀土”RE是指:钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱和镥之一或两种以上。
3.按照权利要求1所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,REB2C2材料的制备方法,具体步骤如下:
(1)原料组成及成分范围:
原料由稀土氧化物粉RE2O3、碳化硼粉B4C和石墨粉C组成,其中RE2O3:B4C:C的摩尔比为(0.7~1.1):(0.8~1.1):(5.5~6.5);
(2)制备工艺:
首先将稀土氧化物粉、碳化硼粉和石墨粉按配比称重,经物理机械方法混合6~12小时;在通有高纯氩气的烧结炉内进行烧结,升温速率为5~20℃/分钟,烧结温度为1800~2200℃,烧结时间为1~8小时,合成的材料为单相的稀土二硼二碳REB2C2材料粉体。
4.按照权利要求3所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,将制备的REB2C2材料粉体过500目筛,室温下与水反应制备氢、氧和烃类混合气体。
5.按照权利要求1所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,H2O是指“去离子水”。
6.按照权利要求1所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,REB2C2材料与H2O反应的环境为室温。
7.按照权利要求1所述的稀土二硼二碳材料与水反应制备氢、氧和烃类混合气体的方法,其特征在于,混合气体中各种成分的体积含量:H2为50~80%,O2为10~40%,CH4为2~15%,C2H6、C2H4、C2H2、C3H8、C3H6、C4H8、CO和CO2为0.01~0.5%。
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CN114606426A (zh) * | 2022-03-14 | 2022-06-10 | 宁波杭州湾新材料研究院 | 新型中高熵材料增强金属基复合材料及其制备方法与应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES273293A1 (es) * | 1960-12-29 | 1962-04-16 | Exxon Research Engineering Co | Un procedimiento para la producciën de una mezcla de hidrëgeno y nitrëgeno |
US6207104B1 (en) * | 1998-09-29 | 2001-03-27 | Agency Of Industrial Science & Technology | Ternary hydrogen storage alloy and process for production thereof |
WO2003058644A2 (en) * | 2001-10-11 | 2003-07-17 | Arizona Board Of Regents | Superhard dielectric compounds and methods of preparation |
US20100050597A1 (en) * | 2007-03-22 | 2010-03-04 | Peugeot Citroen Automobiles S.A. | Low temperature urea injection method |
US20110257356A1 (en) * | 2008-02-27 | 2011-10-20 | The Trustees Of The University Of Pennsylvania | Synthesis of Poly-(P-Aryleneethynylene)s in Neat Water Under Aerobic Conditions |
CN107814570A (zh) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | 硼∕碳热还原法制备三元稀土二硼二碳陶瓷粉体的方法 |
CN109385528A (zh) * | 2018-11-01 | 2019-02-26 | 华南理工大学 | 一种废永磁体中稀土的回收方法 |
-
2019
- 2019-11-06 CN CN201911074600.1A patent/CN112759397B/zh not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES273293A1 (es) * | 1960-12-29 | 1962-04-16 | Exxon Research Engineering Co | Un procedimiento para la producciën de una mezcla de hidrëgeno y nitrëgeno |
US6207104B1 (en) * | 1998-09-29 | 2001-03-27 | Agency Of Industrial Science & Technology | Ternary hydrogen storage alloy and process for production thereof |
DE69917178D1 (de) * | 1998-09-29 | 2004-06-17 | Agency Ind Science Techn | Ternäre Wasserstoffspeichernde Legierung und Verfahren zu deren Herstellung |
WO2003058644A2 (en) * | 2001-10-11 | 2003-07-17 | Arizona Board Of Regents | Superhard dielectric compounds and methods of preparation |
US20100050597A1 (en) * | 2007-03-22 | 2010-03-04 | Peugeot Citroen Automobiles S.A. | Low temperature urea injection method |
US20110257356A1 (en) * | 2008-02-27 | 2011-10-20 | The Trustees Of The University Of Pennsylvania | Synthesis of Poly-(P-Aryleneethynylene)s in Neat Water Under Aerobic Conditions |
CN107814570A (zh) * | 2016-09-12 | 2018-03-20 | 中国科学院金属研究所 | 硼∕碳热还原法制备三元稀土二硼二碳陶瓷粉体的方法 |
CN109385528A (zh) * | 2018-11-01 | 2019-02-26 | 华南理工大学 | 一种废永磁体中稀土的回收方法 |
Non-Patent Citations (6)
Title |
---|
BAUER. J.: "New rare-earth borocarbides", 《AIP CONFERENCE PROCEEDINGS》 * |
I. J. MCCOLM ET AL.: "Hydrolysis of lanthanide dicarbides: rates of reaction with water", 《JOURNAL OF THE LESS-COMMON METALS》 * |
P. KENT SMITH ET AL.: "High temperature rare earth-boron-carbon studies-Ⅲ LnB2C2 and the ternary phase diagram", 《JOURNAL OF INORGANIC AND NUCLEAR CHEMISTRY》 * |
李治辉: "几种新型层状REB2C2陶瓷的制备与性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
王广昌等: "十二氢十硼双二乙基硫醚络合物新合成法的研究", 《化学学报》 * |
郭瑞松等: "《工程结构陶瓷》", 30 September 2002, 天津大学出版社 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114606426A (zh) * | 2022-03-14 | 2022-06-10 | 宁波杭州湾新材料研究院 | 新型中高熵材料增强金属基复合材料及其制备方法与应用 |
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