天然氣現(xiàn)場制氫新工藝的研究-中國氣體分離設(shè)備商務(wù)網(wǎng)

1、天然氣現(xiàn)場制氫新工藝的研討學(xué)生 汪叢偉導(dǎo)師 王樹東 研討員Friday, April 01, 2022內(nèi)容綱要天然氣現(xiàn)場制氫的意義及優(yōu)勢天然氣現(xiàn)場制氫的新工藝總結(jié)與展望研討背景分散站制氫規(guī)模集中制氫ON-BOARD FUEL PROCESSING GO/NO-GO DECISION DOE DECISION TEAM COMMITTEE REPORT , August 2004車載制氫設(shè)備投資大氫氣儲運(yùn)、分配困難啟動時(shí)間(10min)啟動能量(7MJ/50kw天然氣現(xiàn)場制氫優(yōu)勢原燃料比較充足天然氣水合物天然氣清潔,能量密度大供應(yīng)方便(完善的輸運(yùn)管道)制氫本錢低，是目前最廉價(jià)的制氫方式之一天然氣

2、水蒸汽轉(zhuǎn)化CO高溫變換CO低溫變換CO甲烷化CO2脫除H2分別天然氣水蒸汽重整制氫大規(guī)模US$3.665/kg H2天然氣水蒸汽重整制氫(小規(guī)模)US$ 12 /kg H2目前天然氣水蒸汽規(guī)模制氫與現(xiàn)場制氫的本錢比較高本錢高本錢現(xiàn)有天然氣水蒸汽重整工藝用于現(xiàn)場制氫是極其昂貴的，開發(fā)現(xiàn)場制氫新工藝與新技術(shù)已成為當(dāng)務(wù)之急 ！重點(diǎn)：1. 產(chǎn)氫,純化一體化,技術(shù)集成,縮短工藝流程; 2.安裝投資小,消費(fèi)本錢低;天然氣水蒸汽重整CH4+H2O=CO+3H2， H298K= 206kJ/mol CH4+2H2O=CO2+3H2， H298K= 165kJ/mol CH4+2O2=CO2+2H2O，H298

3、K= -804 kJ/mol天然氣自熱重整CH4+0.5O2=CO+2H2， H298K=-36 kJ/mol CH4+H2O=CO+3H2， H298K=206kJ/molCH4+2H2O=CO2+3H2， H298K=165kJ/mol天然氣現(xiàn)場制氫的技術(shù)道路產(chǎn)氫純度高，分別相對易，但能效相對不高能量效率高，但分別能耗相對較大天然氣現(xiàn)場制氫新工藝集成換熱式(反響耦合循環(huán)利用熱流：壁式反響器，兩段式反響器，多層套筒式反響器降低傳熱傳質(zhì)阻力：板式反響器，微通道反響器凈化純化式制備高純度H2 ：膜反響器降低CO排放：雙層催化劑無CO反響器 壁式反響器Theophilos Ioannides, X

4、enophon E. Verykios, Development of a novel heat-integrated wall reactor for the partial oxidation of methane to synthesis gas, Catalysis Today 46 (1998) 71-81University of Patras, Greece反響器由陶瓷管組成，陶瓷管內(nèi)外表堆積熄滅催化劑層，外外表堆積重整催化劑層原料從里面的管子進(jìn)入后被外層的出口氣體預(yù)熱，在反響區(qū)發(fā)生反響，放出的熱量經(jīng)過管壁傳到外層，在那里發(fā)生吸熱的重整反響。循環(huán)利用熱流 兩段式重整反響器Frau

5、nhofer Institute ，Germany 甲烷和水作為冷料通入換熱器中與熄滅尾氣換熱，被加熱至450600進(jìn)入一次重整器中進(jìn)展重整反響熱量來自熄滅尾氣的對流換熱進(jìn)入二次重整，熱量來自陶瓷熄滅器的直接熱輻射Vogel, B., G. Schaumberg, A. Schuler, 1998, .Hydrogen Generation Technologies for PEM Fuel Cells,. 1998 Fuel Cell Seminar Abstracts, November 16-19, 1998, Palm Springs, CA, pp. 364-367.循環(huán)利用熱流 多

6、層套筒式重整反響器A novel steam reforming reactor for fuel cell distributed power generation, California Energy Commission, May 2000存在問題：傳熱阻力較大 系統(tǒng)較龐大循環(huán)利用熱流 板式反響器催化劑層板的厚度很薄,大大提高了反響器的構(gòu)造緊湊性,降低了傳熱與傳質(zhì)阻力板式反響器的效率比傳統(tǒng)水蒸汽重整器高一個(gè)數(shù)量級，而體積和催化劑分量低2個(gè)數(shù)量級板式反響器的換熱效率提高。壁面和氣相截面溫度分布更均勻M. Zanir, A. Gavriilidis, Catalytic combustion

7、 assisted methane steam reforming ina catalytic plate reactor, Chemical Engineering Science 58 (2003) 3947 3960存在問題：催化劑涂覆困難 降低傳熱傳質(zhì)阻力 微通道反響器 Picture of a Velocys manufacturing scale-up microchannel reactor (Pacific Northwest National Laboratory)微通道可把傳熱傳質(zhì)速率提高12個(gè)數(shù)量級由于過程強(qiáng)化降低了操作本錢均勻布氧，先部分氧化后完全熄滅為原料預(yù)熱和重整供

8、熱A.Y. Tonkovicha, S. Perrya, W.A. Rogers, Microchannel process technology for compact methane steam reforming, Chemical Engineering Science 59 (2004) 4819 4824存在問題： 反響器加工本錢高 通道阻力降大降低傳熱傳質(zhì)阻力 集成化膜反響器Yu-Ming Lin, Min-Hon Rei, Process development for generating high purity hydrogenby using supported pall

9、adium membrane reactor as steam Reformer, International Journal of Hydrogen Energy 25 (2000) 211219CH4存在問題：鈀膜具有氫脆景象，如何加強(qiáng)穩(wěn)定性？凈化純化式 兩層催化劑無CO水蒸氣制氫反響器Vladimir Galvita a, Kai Sundmacher, Hydrogen production from methane by steam reforming in a periodically operated two-layer catalytic reactor, Applied Ca

10、talysis A: General 289 (2005) 121127Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, GermanyStep 1:ReductionPt-CeO2-ZrO2Fe3O4-CeO2-ZrO2CH4CO+H2H2O+CO2H2H2OH2O+H2Pt-Ce2O3-ZrO2Fe-Ce2O3-ZrO2Step 2:Re-oxidation存在問題：催化劑外表堆積碳，實(shí)踐運(yùn)用?凈化純化式 總結(jié)與展望將重整制氫,供熱,純化一體化,實(shí)現(xiàn)過程強(qiáng)化、系統(tǒng)高度集成是降低制氫本錢的出路

11、集成換熱式(熱量耦合凈化純化式降低本錢現(xiàn)場制氫新工藝要真正走向?qū)嵺`運(yùn)用，還需真實(shí)處理本身的關(guān)鍵技術(shù)，揚(yáng)長避短謝謝大家! 參考文獻(xiàn)1.ON-BOARD FUEL PROCESSING GO/NO-GO DECISION, DOE DECISION TEAM COMMITTEE REPORT , August 20042.Theophilos I, Xenophon E. Verykios, Development of a novel heat-integrated wall reactor for the partial oxidation of methane to synthesis ga

12、s, Catalysis Today 46 (1998) 71-813.M. Zanir, A. Gavriilidis, Catalytic combustion assisted methane steam reforming in a catalytic plate reactor, Chemical Engineering Science 58 (2003) 3947 39604.Vogel, B., G. Schaumberg, A. Schuler, and A. Henizel, 1998, .Hydrogen GenerationTechnologies for PEM Fue

13、l Cells,. 1998 Fuel Cell Seminar Abstracts, November 16-19, 1998,Palm Springs, CA, pp. 364-367.5. A.Y. Tonkovicha, S. Perrya,W.A. Rogersa, Microchannel process technology for compact methane steam reforming, Chemical Engineering Science 59 (2004) 4819 48246. Vladimir G, Kai S, Hydrogen production fr

14、om methane by steam reforming in a periodically operated two-layer catalytic reactor, Applied Catalysis A: General 289 (2005) 1211277.A novel steam reforming reactor for fuel cell distributed power generation, California Energy Commission, May 2000參考文獻(xiàn)(續(xù))8. Yu M L, Min H R, Process development for g

15、enerating high purity hydrogen by using supported palladium membrane reactor as steam Reformer, International Journal of Hydrogen Energy 25 (2000) 211-219 9. S Lin, Y Chen, C Lee, Dynamic modeling and control structure design of an experimental fuel processor, International Journal of Hydrogen Energy (in press)10.Sheldon Lee, Daniel V. A, Shabbir A, Hydrogen from natural gas: part Iautothermal reforming in an integrated fuel processor, Internationa