本文選題：膜反應(yīng)器 + 膜分離��； 參考：《華南理工大學(xué)》2016年博士論文

【摘要】：膜反應(yīng)器將反應(yīng)和分離過程耦合在一起同時(shí)進(jìn)行,有利于實(shí)現(xiàn)過程強(qiáng)化,是實(shí)現(xiàn)綠色高效生產(chǎn)的關(guān)鍵技術(shù)之一。對(duì)于小規(guī)模天然氣制氫,荷蘭的Kuipers教授研究團(tuán)隊(duì)提出了一個(gè)天然氣自熱重整雙膜反應(yīng)系統(tǒng)的概念:整個(gè)反應(yīng)系統(tǒng)分為兩個(gè)區(qū)域,頂部的鈀膜反應(yīng)器部分和底部的鈣鈦礦膜反應(yīng)器部分。鈀膜可以分離產(chǎn)物氫氣,促使反應(yīng)向生成氫氣的理想方向進(jìn)行。鈣鈦礦膜從空氣中分離純氧,燃燒部分甲烷,為反應(yīng)體系提供熱量,避免了昂貴的空分裝置。通過調(diào)整進(jìn)料比,能夠?qū)崿F(xiàn)整個(gè)反應(yīng)系統(tǒng)的自熱平衡操作,具有較高能效。由于鈣鈦礦透氧膜穩(wěn)定性和密封技術(shù)的限制,Kuipers教授課題組主要對(duì)頂部的鈀膜反應(yīng)器部分開展了實(shí)驗(yàn)和模擬研究。本論文實(shí)現(xiàn)了鈣鈦礦膜組件的密封,對(duì)鈣鈦礦膜反應(yīng)器部分進(jìn)行了相關(guān)實(shí)驗(yàn)和模擬研究。鈣鈦礦膜與連接組件的密封技術(shù)是實(shí)現(xiàn)雙膜反應(yīng)系統(tǒng)整合的關(guān)鍵技術(shù)之一。本研究使用相轉(zhuǎn)化紡絲法制備BaCo_(0.4)Fe_(0.4)Zr_(0.2)O_(3-δ)(BCFZ)毛細(xì)透氧膜管,使用金漿和玻璃膠經(jīng)過高溫加熱成功密封BCFZ膜管和Al2O3連接組件。密封后的膜組件仍然有很高的O2選擇性和透氧量,透過的N2體積分?jǐn)?shù)低于0.71%。研究操作條件對(duì)不同類型透氧膜組件透氧性能的影響,升高溫度,增大壓力,增大吹掃氣量,均有利于提高透氧量。構(gòu)建了BCFZ毛細(xì)膜管的一維透氧模型,對(duì)膜管透氧量進(jìn)行了理論模擬,通過比較實(shí)驗(yàn)值與理論計(jì)算值,對(duì)透氧模型進(jìn)行了驗(yàn)證。質(zhì)量傳遞會(huì)影響各個(gè)組分的濃度分布,進(jìn)而影響反應(yīng)的最終結(jié)果,考察質(zhì)量傳遞過程的速控步驟可以合理優(yōu)化操作參數(shù)。對(duì)雙膜反應(yīng)系統(tǒng)中的鈣鈦礦膜反應(yīng)器部分,建立兩個(gè)三相模型,研究O2在透氧膜、氣泡相、云相、乳化相之間不同的質(zhì)量傳遞路徑對(duì)反應(yīng)結(jié)果的影響,考察三相之間的質(zhì)量傳遞是否充分�；谀芰科胶�,計(jì)算自熱重整操作條件下實(shí)現(xiàn)一定反應(yīng)器溫度所需要的氧碳比,所需的氧碳比隨反應(yīng)器溫度的升高而增大,隨著壓力的升高而減小。研究操作條件對(duì)反應(yīng)結(jié)果的影響,隨著溫度的升高,CH4轉(zhuǎn)化率增加,CO選擇性升高。增大表觀氣速,H_2產(chǎn)量增加但CH4轉(zhuǎn)化率降低。對(duì)于鈀膜反應(yīng)器部分,反應(yīng)和氫氣分離同時(shí)進(jìn)行,研究操作參數(shù)對(duì)鈀膜組件透氫性能的影響,能有效提高反應(yīng)系統(tǒng)的產(chǎn)能。本論文設(shè)計(jì)了一種平板狀鈀銀復(fù)合膜組件,研究了不同的操作條件下鈀膜組件的透氫性能。針對(duì)鈀膜在制備和使用過程中容易形成缺陷的問題,基于金屬擴(kuò)散原理,研究了一種易操作,針對(duì)于毫米尺寸鈀膜缺陷的修復(fù)方法,并對(duì)修復(fù)后膜組件的H_2選擇性和透氫量進(jìn)行了考察。引入修復(fù)因子來比較鈀膜組件修復(fù)前后總透氫量的改變,無吹掃氣時(shí),修復(fù)因子主要與膜本身性質(zhì)有關(guān)。當(dāng)存在吹掃氣時(shí),計(jì)算修復(fù)因子還需要考慮膜兩側(cè)的氣體流動(dòng)狀態(tài)。對(duì)雙膜反應(yīng)系統(tǒng)定量分析時(shí),當(dāng)目標(biāo)產(chǎn)氫量確定,需要估算用于分離氫氣的鈀膜面積,這就需要先對(duì)鈀膜組件的透氫量進(jìn)行理論研究。透氫量不僅與膜本身的透過能力有關(guān),同時(shí)還要考慮膜兩側(cè)的氣體流動(dòng)狀態(tài),當(dāng)氫氣分壓不是恒定的,Sieverts’Law就不能直接用于透氫量的計(jì)算。根據(jù)氣體的基本流動(dòng)狀態(tài),構(gòu)建了鈀膜透氫的理想模型。引入膜透能力的概念,分析各個(gè)模型中理論產(chǎn)氫量和膜透能力的關(guān)系。當(dāng)目標(biāo)產(chǎn)氫量一定,選擇合適的模型,可估算所需的膜透能力,當(dāng)膜透能力一定,也可估算理論產(chǎn)氫量。比較發(fā)現(xiàn),與全混流相比,平推流狀態(tài)更有利于氫氣透過。氫氣產(chǎn)量并不隨著膜透能力的增加而線性增加,首次提出并定義了經(jīng)濟(jì)膜透能力的概念,通過典型案例,分析了經(jīng)濟(jì)膜透能力的計(jì)算方法,有利于實(shí)現(xiàn)合理的投資回收。
[Abstract]:The membrane reactor is one of the key technologies for realizing green and efficient production by coupling reaction and separation process together. It is one of the key technologies for realizing green and efficient production. For small scale natural gas hydrogen production, the research team of Professor Kuipers of Holland proposed a concept of natural gas autothermal reformer double film reaction system: the whole reaction system is divided into two The palladium membrane reactor section at the top and the perovskite membrane reactor at the bottom. The palladium membrane can separate the product hydrogen and promote the reaction to the ideal direction of hydrogen generation. The perovskite membrane separate pure oxygen from the air and burn some methane to provide heat for the reaction system, avoiding the expensive air separation unit. By adjusting the feed ratio, Because of the stability of the perovskite oxygen permeable membrane and the limitation of sealing technology, the research group of Professor Kuipers carried out experimental and simulated research on the palladium membrane reactor at the top of the perovskite membrane reactor. The sealing technology of the perovskite membrane and the connecting component is one of the key technologies to realize the integration of the double membrane reaction system. This study uses the phase transformation spinning method to prepare BaCo_ (0.4) Fe_ (0.4) Zr_ (0.2) O_ (3- delta) (BCFZ) capillary permeable membrane tube, and successfully seal the BCFZ membrane tube through high temperature heating with gold pulp and glass glue. Al2O3 connection components. The sealed membrane components still have high O2 selectivity and oxygen permeability. The volume fraction of N2 through the influence of the operating conditions on the oxygen permeability of different types of oxygen membrane components is lower than that of 0.71%.. The increase of temperature, pressure and the increase of blowing gas are beneficial to the increase of oxygen permeation. The one dimension oxygen permeation of BCFZ capillary tube is constructed. The oxygen permeability of the membrane tube was simulated by the model. The oxygen permeable model was verified by comparing the experimental values and theoretical values. The mass transfer will affect the concentration distribution of each component, and then influence the final result of the reaction. The speed control steps of the mass transfer process can be optimized to optimize the operating parameters. In the perovskite membrane reactor, two three phase models are established to study the effect of different mass transfer paths between the oxygen permeable membrane, bubble phase, cloud phase and emulsified phase on the reaction results, to investigate whether the mass transfer between the three phases is sufficient. Based on the energy balance, the oxygen required for the realization of the temperature of a certain reactor under the conditions of self heating reforming operation is calculated. The ratio of carbon to carbon is increased with the increase of the reactor temperature, and decreases with the increase of pressure. The effect of the operating conditions on the reaction results, as the temperature increases, the conversion of CH4 increases, and the CO selectivity increases. The apparent gas velocity increases, the production of H_2 increases but the conversion of CH4 decreases. For the palladium membrane reactor, reaction and hydrogen separation are also increased. At the same time, the study of the effect of operating parameters on the hydrogen permeability of palladium membrane components can effectively improve the capacity of the reaction system. A flat palladium and silver composite membrane module was designed in this paper. The hydrogen permeation performance of palladium membrane components under different operating conditions was studied. In the principle of metal diffusion, a method of repairing the defect of palladium membrane in millimeter size is studied, and the H_2 selectivity and hydrogen permeation of the repaired membrane module are investigated. The repair factor is introduced to compare the change of the total hydrogen permeability of the palladium membrane module before and after the repair. The repair factor is mainly related to the property of the membrane itself. It is necessary to estimate the area of the palladium membrane for the separation of hydrogen when the target hydrogen production is determined. It is necessary to study the hydrogen permeation of the palladium membrane module first. The hydrogen permeation capacity is not only related to the permeability of the membrane itself, but also the hydrogen permeation capacity of the membrane. At the same time, the flow state of the gas on both sides of the membrane must be considered. When the hydrogen partial pressure is not constant, Sieverts' Law can not be directly used for the calculation of the hydrogen permeable amount. Based on the basic flow state of the gas, an ideal model for the hydrogen permeation of the palladium membrane is constructed. The concept of the membrane permeability is introduced and the relationship between the theoretical hydrogen production and the membrane permeability in each model is analyzed. When the target hydrogen production is certain, the appropriate model can be selected to estimate the required membrane permeability. When the membrane permeability is certain, the theoretical hydrogen production can be estimated. Compared with the total flow, the state of the flat push flow is more beneficial to the hydrogen permeation. The hydrogen production does not increase linearly with the increase of the membrane permeability. The first proposed and defined economic membrane permeability. Through the typical cases, the calculation method of economic membrane permeability is analyzed, which is conducive to achieving a reasonable investment recovery.

【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TQ028.8

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相關(guān)期刊論文 前10條

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本文編號(hào)：1867772