本文選題：氫氣純化 + 氫氣回收　； 參考：《北京有色金屬研究總院》2015年碩士論文

【摘要】：金屬氫化物具有“易于雜質(zhì)氣體反應(yīng)”性質(zhì),可作為純化材料用于吸附H2中的雜質(zhì)氣體；金屬氫化物具有“可逆吸放氫”性質(zhì),可作為回收材料用于回收混合氣體中H2。材料的結(jié)構(gòu)及形貌分別采用XRD及SEM進(jìn)行表征,金屬氫化物的吸氫動(dòng)力學(xué)及熱力學(xué)參數(shù)選用“儲(chǔ)氫性能測(cè)試裝置”進(jìn)行測(cè)試并計(jì)算,雜質(zhì)氣體濃度采用GC進(jìn)行測(cè)定,材料的表面狀態(tài)采用XPS進(jìn)行分析。首先通過(guò)測(cè)試Zr基金屬氫化物的吸氫PCT及動(dòng)力學(xué)曲線,計(jì)算出金屬氫化物的吸氫焓變、熵變及動(dòng)力學(xué)激活能。隨后分別對(duì)“Zr基氫氣純化材料”與兩類雜質(zhì)氣體N2、O2及CH4、C02吸附作用規(guī)律進(jìn)行了研究,包括吸附效率、吸附容量及吸附產(chǎn)物。測(cè)試了不同溫度下材料的吸附N2及O2效率,結(jié)果表明純化后H2(He)中N2及02濃度均低于0.500 ppm,材料吸附N2及02效率高。通過(guò)測(cè)試材料吸附N2及02穿透曲線,獲得了材料的吸附N2及02容量；并發(fā)現(xiàn)材料純化H2中02時(shí),02濃度上升前,氣體中先出現(xiàn)H20。對(duì)吸附N2及O2穿透前后,材料表面進(jìn)行了XPS分析,明確材料吸附N2產(chǎn)物為ZrN及TiN,吸附O2產(chǎn)物為Zr及Ti的氧化物和氫氧化物。材料吸附CH4及CO2效率受溫度影響大,溫度低,吸附效率低；材料吸附CO2,會(huì)與H反應(yīng)生成副產(chǎn)物CH4。材料吸附CH4及CO2,低溫降低C原子擴(kuò)散速度,使得C原子聚集在材料表面；在材料的催化作用下,表面聚集C原子與H2反應(yīng)生成CH4,導(dǎo)致CH4濃度上升,吸附效率下降。通過(guò)測(cè)試材料吸附CH4及C02穿透曲線,獲得了材料的吸附CH4及CO2容量。對(duì)吸附CO2穿透前后的材料表面進(jìn)行了XPS分析,明確了材料吸附CO2產(chǎn)物所形成的碳化物為TiC。在“Zr基氫氣純化材料”與雜質(zhì)氣體吸附作用規(guī)律的研究基礎(chǔ)之上,進(jìn)行了N2及02對(duì)“Zr基氫氣回收材料”吸氫過(guò)程影響的研究。測(cè)試了回收材料的吸純氫動(dòng)力學(xué)曲線,對(duì)其進(jìn)行動(dòng)力學(xué)模型擬合,判定材料吸氫控速步驟為“形成氫化物”過(guò)程。當(dāng)H2中含有一定量N2,材料吸氫控速步驟為“化學(xué)吸附”過(guò)程,動(dòng)力學(xué)曲線與Elovich經(jīng)驗(yàn)公式相吻合。當(dāng)H2中含有一定量02,材料的吸氫過(guò)程可分為快速吸氫段和緩慢吸氫段。快速吸氫段,材料表面活性高,吸氫控速步驟為“形成氫化物”過(guò)程,動(dòng)力學(xué)激活能要高于材料吸純氫。緩慢吸氫段,材料表面活性低,吸氫控速步驟為“化學(xué)吸附”過(guò)程,符合“氧化模型”。H2中同時(shí)存在N2及O2時(shí),材料吸氫動(dòng)力學(xué)符合“氧化模型’N2及O：改變回收材料的吸氫過(guò)程,對(duì)材料具有毒化效果。為提高材料的抗N2及02毒化能力,對(duì)材料進(jìn)行了化學(xué)鍍Pd表面改性處理。隨后測(cè)試了材料經(jīng)化學(xué)鍍Pd后,在含N2及02混合氫氣中的吸氫動(dòng)力學(xué)曲線,結(jié)果表明化學(xué)鍍Pd能提高材料的抗毒化能力。最后優(yōu)化了化學(xué)鍍Pd方法,在化學(xué)鍍Pd前對(duì)材料進(jìn)行了預(yù)處理。使用優(yōu)化后的化學(xué)鍍Pd方法對(duì)材料進(jìn)行表面改性,改性后材料在含N2及O2混合氫氣中的吸氫動(dòng)力學(xué)性能優(yōu)異,動(dòng)力學(xué)符合二維擴(kuò)散模型,Pd膜是一層隔絕02和N2的選擇性滲氫膜。
[Abstract]:Metal hydride has the nature of "easy to react with impurity gas" and can be used as a purified material to adsorb impurity gases in H2. Metal hydrides have the properties of "reversible absorption of hydrogen". The structure and morphology of H2. materials used in the recovery of mixed gases can be characterized by XRD and SEM, and hydrogen absorption of metal hydride. The mechanical and thermodynamic parameters are tested and calculated with the "testing device for hydrogen storage performance". The concentration of impurity gas is measured by GC. The surface state of the material is analyzed by XPS. First, the hydrogen absorption enthalpy, entropy change and kinetic activation of the metal hydride are calculated by testing the hydrogen absorption PCT and the kinetic curve of the Zr based metal hydride. The adsorption of "Zr based hydrogen purification material" and two kinds of impurity gas N2, O2 and CH4, C02, respectively, including adsorption efficiency, adsorption capacity and adsorption products. The adsorption of N2 and O2 efficiency at different temperatures were tested. The results showed that the concentration of N2 and 02 in H2 (He) was lower than 0.500 ppm, and the material adsorbed N2 and 02. The absorption of N2 and the 02 penetration curve of the material is high. The adsorption of N2 and 02 capacity of the material is obtained by the adsorption of the material. It is found that before the 02 concentration of the material is purified H2, the H20. is first appeared in the gas before and after the adsorption of N2 and O2, and the surface of the material is analyzed by XPS, and the adsorption N2 products are ZrN and TiN, and the adsorption O2 product is the oxidation of Zr and the oxidation. Materials and hydroxides. The material adsorbed CH4 and CO2 efficiency greatly influenced by temperature, low temperature and low adsorption efficiency. The material adsorbed CO2, which will react with H to form a by-product CH4. material to adsorb CH4 and CO2, lower the C atom diffusion speed, and make C atoms gather on the surface of the material. Under the catalysis of the material, the surface aggregation C atom and H2 reaction generates CH4. The adsorption efficiency of CH4 increased and the adsorption efficiency decreased. The adsorption of CH4 and CO2 capacity of the material was obtained through the adsorption of CH4 and C02 through the test materials. The XPS analysis of the surface of the material before and after the adsorption of CO2 was analyzed. It was clear that the carbide formed by the adsorption of CO2 products was TiC. in the "Zr based hydrogen purification material" and the adsorption of impurities. On the basis of the study of the action law, the influence of N2 and 02 on the hydrogen absorption process of "Zr based hydrogen recovery material" was studied. The kinetic curve of the hydrogen absorption of the recycled material was tested. The kinetic model was fitted to it. The process of hydrogen absorption and control was determined as a "hydride generation" process. When a certain amount of N2 was contained in H2, the rate of hydrogen absorption and control of the material was found. In the process of "chemical adsorption", the kinetic curve coincides with the empirical formula of Elovich. When a certain amount of 02 is contained in H2, the hydrogen absorption process of the material can be divided into a fast hydrogen absorption section and a slow hydrogen absorption section. The rapid hydrogen absorption section, the high surface activity of the material, the process of hydrogen absorption and control speed is "hydrogenated" process, and the kinetic activation energy is higher than the material absorption. Hydrogen. Slow hydrogen absorption section, the material surface activity is low, the process of hydrogen absorption and control is "chemical adsorption" process. When N2 and O2 exist in the "oxidation model".H2, the hydrogen absorption kinetics of the material conforms to the "oxidation model" N2 and O: to change the hydrogen absorption process of the recycled material and to be toxic to the material. To improve the anti N2 and 02 toxicity of the material, The surface modification of electroless Pd was carried out. After electroless Pd, the kinetics curve of hydrogen absorption in N2 and 02 mixed hydrogen was tested. The results showed that the electroless plating Pd could improve the anti toxic ability of the material. Finally, the electroless plating Pd method was optimized and the material was pretreated before the Electroless plating of Pd. The optimized chemistry was used. Plating Pd method for surface modification of materials, modified materials containing N2 and O2 mixed hydrogen in hydrogen absorption kinetics performance, kinetics of a two-dimensional diffusion model of Pd membrane is a layer 02 N2 and selective isolation of hydrogen permeation membrane.
【學(xué)位授予單位】：北京有色金屬研究總院
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ116.2;O647.3

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 曾力丁;朱冬生;王春華;謝振;;氫氣中氧氣的鈀催化去除[J];華南理工大學(xué)學(xué)報(bào)(自然科學(xué)版);2008年11期

，

本文編號(hào)：2045371