最新天然氣現(xiàn)場制氫新工藝的研究

1、內容綱要 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 總結與展望研究背景分散站制氫規(guī)模集中制氫on-board fuel processing go/no-go decision doe decision team committee report , august 2004車載制氫設備投資大設備投資大氫氣儲運、分配困難氫氣儲運、分配困難啟動時間啟動時間(10min)啟動能量啟動能量(7mj/50kw）原燃料供給方便(完善的輸運管道)天然氣水天然氣水蒸汽轉化蒸汽轉化co高溫變高溫變換換co低溫變低溫變換換co甲甲烷化烷化co2脫除脫除h2分分離離天然氣水蒸天然氣水蒸汽重整制氫汽重整制氫

2、（大規(guī)模）（大規(guī)模）us$us$3.665/kg h/kg h2 2天然氣水蒸天然氣水蒸汽重整制氫汽重整制氫( (小規(guī)模小規(guī)模) )us$ us$ 12 /kg h/kg h2 2目前天然氣水蒸汽規(guī)模制氫與現(xiàn)場制氫的成本比較目前天然氣水蒸汽規(guī)模制氫與現(xiàn)場制氫的成本比較高成本高成本高成本高成本現(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，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已成為當務之急開發(fā)現(xiàn)場制氫新工藝與新技術已成為當務之急 ！重點：重點：1. 產氫產氫,純化一體化純化一體化,技術集成技術集成,縮短工藝流程縮短工藝流程; 2.裝置投資小裝置投資小,生

3、產成本低生產成本低;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，h298k= -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)場制氫的技術路線產氫純度高，分離相對易，但能效相對不高產氫純度高，分離相對易，但能效相對不高能量效率高，但分離能耗相對較大能量效率高，但分

4、離能耗相對較大天然氣現(xiàn)場制氫新工藝集成換熱式(反應耦合）循環(huán)利用熱流：壁式反應器，兩段式反應器，多層套筒式反應器降低傳熱傳質阻力：板式反應器，微通道反應器凈化純化式制備高純度h2 ：膜反應器降低co排放：雙層催化劑無co反應器 壁式反應器theophilos ioannides, xenophon e. verykios, development of a novel heat-integrated wall reactor for the partial oxidation of methane to synthesis gas, catalysis today 46 (1998) 71-8

5、1university of patras, greece反應器由陶瓷管組成，陶瓷管內表面沉積燃燒催化劑層，外表面沉積重整催化劑層反應器由陶瓷管組成，陶瓷管內表面沉積燃燒催化劑層，外表面沉積重整催化劑層原料從里面的管子進入后被外層的出口氣體預熱，在反應區(qū)發(fā)生反應，放出的熱量通原料從里面的管子進入后被外層的出口氣體預熱，在反應區(qū)發(fā)生反應，放出的熱量通過管壁傳到外層，在那里發(fā)生吸熱的重整反應。過管壁傳到外層，在那里發(fā)生吸熱的重整反應。循環(huán)利用熱流循環(huán)利用熱流 兩段式重整反應器fraunhofer institute ，germany 甲烷和水作為冷料通入換熱器中與燃甲烷和水作為冷料通入換熱器中與燃

6、燒尾氣換熱，被加熱至燒尾氣換熱，被加熱至450600進入一次重整器中進行重整反應（熱進入一次重整器中進行重整反應（熱量來自燃燒尾氣的對流換熱）量來自燃燒尾氣的對流換熱）進入二次重整，熱量來自陶瓷燃燒器進入二次重整，熱量來自陶瓷燃燒器的直接熱輻射的直接熱輻射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,

7、 pp. 364-367.循環(huán)利用熱流循環(huán)利用熱流 多層套筒式重整反應器a novel steam reforming reactor for fuel cell distributed power generation, california energy commission, may 2000存在問題：傳熱阻力較大存在問題：傳熱阻力較大 系統(tǒng)較龐大系統(tǒng)較龐大循環(huán)利用熱流循環(huán)利用熱流 板式反應器催化劑層板的厚度很薄催化劑層板的厚度很薄, ,大大提高了反應器的結構緊湊性大大提高了反應器的結構緊湊性, ,降低了傳熱與傳質阻力降低了傳熱與傳質阻力板式反應器的效率比傳統(tǒng)水蒸汽重整器高一個數(shù)量級，而

8、體積和催化劑重量低板式反應器的效率比傳統(tǒng)水蒸汽重整器高一個數(shù)量級，而體積和催化劑重量低2 2個數(shù)量級個數(shù)量級板式反應器的換熱效率提高。壁面和氣相截面溫度分布更均勻板式反應器的換熱效率提高。壁面和氣相截面溫度分布更均勻m. zanir, a. gavriilidis, catalytic combustion assisted methane steam reforming ina catalytic plate reactor, chemical engineering science 58 (2003) 3947 3960存在問題：催化劑涂覆困難存在問題：催化劑涂覆困難 降低傳熱傳質阻力降低

9、傳熱傳質阻力 微通道反應器 picture of a velocys manufacturing scale-up microchannel reactor (pacific northwest national laboratory)微通道可把傳熱傳質速率提高微通道可把傳熱傳質速率提高12個數(shù)量級個數(shù)量級由于過程強化降低了操作成本由于過程強化降低了操作成本均勻布氧，先部分氧化后完全燃燒為原料預熱和重整供熱均勻布氧，先部分氧化后完全燃燒為原料預熱和重整供熱a.y. tonkovicha, s. perrya, w.a. rogers, microchannel process technolo

10、gy for compact methane steam reforming, chemical engineering science 59 (2004) 4819 4824存在問題：存在問題： 反應器加工成本高反應器加工成本高 通道阻力降大通道阻力降大降低傳熱傳質阻力降低傳熱傳質阻力 集成化膜反應器yu-ming lin, min-hon rei, process development for generating high purity hydrogenby using supported palladium membrane reactor as steam reformer, in

11、ternational journal of hydrogen energy 25 (2000) 211219ch4存在問題：鈀膜具有氫脆現(xiàn)象，如何增強穩(wěn)定性？存在問題：鈀膜具有氫脆現(xiàn)象，如何增強穩(wěn)定性？凈化純化式凈化純化式 兩層催化劑無co水蒸氣制氫反應器vladimir galvita a, kai sundmacher, hydrogen production from methane by steam reforming in a periodically operated two-layer catalytic reactor, applied catalysis a: genera

12、l 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：催化劑表面沉積碳，實際應用存在問題：催化劑表面沉積碳，實際應用?凈化純化式凈化純化式 總結與展望將重整制氫,供熱,純化一體化,實現(xiàn)過程強化、系統(tǒng)高度集成是降低制

13、氫成本的出路集成換熱式(熱量耦合）凈化純化式（降低成本）現(xiàn)場制氫新工藝要真正走向實際應用，還需切實解決自身的關鍵技術，揚長避短參考文獻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

14、 gas, 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

15、fuel 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

16、 from 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(續(xù))8. yu m l, min h r, process development fo

17、r generating 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, hy