氫(qing)(qing)(qing)能(neng)(neng)(neng)(neng)是(shi)(shi)一種二次能(neng)(neng)(neng)(neng)源,必(bi)須通過(guo)化(hua)(hua)(hua)(hua)學(xue)過(guo)程由(you)存在于化(hua)(hua)(hua)(hua)合(he)物中(zhong)的(de)(de)氫(qing)(qing)(qing)元(yuan)素轉化(hua)(hua)(hua)(hua)而來。中(zhong)國(guo)是(shi)(shi)氫(qing)(qing)(qing)氣(H2)生產(chan)大(da)國(guo),2021年我(wo)國(guo)氫(qing)(qing)(qing)氣總產(chan)量(liang)超過(guo)3000萬t。當(dang)前(qian)我(wo)國(guo)H2主要用于化(hua)(hua)(hua)(hua)工(gong)領域,其(qi)(qi)(qi)中(zhong)化(hua)(hua)(hua)(hua)石(shi)燃(ran)料生產(chan)的(de)(de)H2占了將近80%,而電(dian)解水及其(qi)(qi)(qi)他綠色制(zhi)氫(qing)(qing)(qing)技(ji)(ji)術(shu)所制(zhi)H2總量(liang)不足1%。現階段,我(wo)國(guo)能(neng)(neng)(neng)(neng)源央(yang)企紛紛將構建(jian)氫(qing)(qing)(qing)能(neng)(neng)(neng)(neng)供給(gei)體系作(zuo)為(wei)重要的(de)(de)發展方向。國(guo)家(jia)電(dian)投、中(zhong)國(guo)石(shi)油及中(zhong)國(guo)石(shi)化(hua)(hua)(hua)(hua)等(deng)國(guo)家(jia)能(neng)(neng)(neng)(neng)源巨頭,結合(he)自身優勢(shi)選擇不同的(de)(de)技(ji)(ji)術(shu)路線,相(xiang)繼(ji)著手在國(guo)內(nei)布局氫(qing)(qing)(qing)能(neng)(neng)(neng)(neng)生產(chan)和供給(gei),中(zhong)船重工(gong)及部分民企制(zhi)氫(qing)(qing)(qing)技(ji)(ji)術(shu)和設備已具備商業化(hua)(hua)(hua)(hua)推廣條件(jian)。除此之外,我(wo)國(guo)企業及科研院所也在積極探索其(qi)(qi)(qi)他新型制(zhi)氫(qing)(qing)(qing)技(ji)(ji)術(shu)或(huo)低(di)價制(zhi)氫(qing)(qing)(qing)技(ji)(ji)術(shu),但距其(qi)(qi)(qi)產(chan)業化(hua)(hua)(hua)(hua)應用還(huan)有相(xiang)當(dang)長的(de)(de)一段路要走(zou)。
1傳統制氫技術體系概況
在傳統制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)方(fang)法中,煤與天然(ran)氣(qi)重整等化(hua)(hua)石能(neng)(neng)(neng)源(yuan)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)是現今工業制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)的(de)(de)(de)主(zhu)流。當前化(hua)(hua)石能(neng)(neng)(neng)源(yuan)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)工藝(yi)成(cheng)熟(shu),可用(yong)于(yu)(yu)大(da)規模(mo)工業生(sheng)產,且原料價格相對低廉,但氫(qing)(qing)(qing)(qing)(qing)(qing)氣(qi)制(zhi)(zhi)(zhi)(zhi)備過(guo)程中會排放(fang)(fang)大(da)量(liang)CO2和污(wu)染(ran)(ran)物。工業副(fu)產氫(qing)(qing)(qing)(qing)(qing)(qing)則集(ji)(ji)中分布(bu)于(yu)(yu)化(hua)(hua)工、冶(ye)金等領域,其(qi)中煤氣(qi)化(hua)(hua)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)(圖1)規模(mo)較大(da),技(ji)術相對成(cheng)熟(shu),且成(cheng)本低廉,但卻面臨污(wu)染(ran)(ran)大(da)、制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)純度低等瓶頸。氯堿副(fu)產制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)因其(qi)經(jing)濟、操作(zuo)簡單、純度高等特點,擁有較好(hao)的(de)(de)(de)應用(yong)潛能(neng)(neng)(neng),但也存(cun)在產氫(qing)(qing)(qing)(qing)(qing)(qing)量(liang)小(xiao)且產能(neng)(neng)(neng)分散(san)的(de)(de)(de)問(wen)題。化(hua)(hua)石能(neng)(neng)(neng)源(yuan)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)具有較高的(de)(de)(de)碳(tan)排量(liang),其(qi)中煤制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)碳(tan)排量(liang)最高,制(zhi)(zhi)(zhi)(zhi)取1kg H2的(de)(de)(de)碳(tan)排量(liang)超(chao)過(guo)20kg CO2。目前我國電(dian)(dian)力大(da)部分來(lai)自火電(dian)(dian),因此碳(tan)排放(fang)(fang)很高,甚至超(chao)過(guo)煤制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)。近年來(lai),隨著(zhu)化(hua)(hua)石能(neng)(neng)(neng)源(yuan)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing)耦合碳(tan)捕集(ji)(ji)技(ji)術的(de)(de)(de)發展和完(wan)善,碳(tan)排放(fang)(fang)強度會大(da)幅度下(xia)降,但仍高于(yu)(yu)可再生(sheng)能(neng)(neng)(neng)源(yuan)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)(qing)(qing),且帶(dai)來(lai)較高的(de)(de)(de)碳(tan)捕集(ji)(ji)成(cheng)本。
2先進綠色制氫關鍵技術研究進展
2.1電解水制氫技術
現階段,常用的電(dian)(dian)解(jie)水(shui)制(zhi)氫技術包(bao)括(kuo)堿性(xing)電(dian)(dian)解(jie)水(shui)制(zhi)氫、質(zhi)子交換(huan)膜(mo)電(dian)(dian)解(jie)水(shui)制(zhi)氫及固(gu)體氧(yang)化物電(dian)(dian)解(jie)水(shui)制(zhi)氫三大類(lei)。
2.1.1堿(jian)性(xing)電解水制(zhi)氫
堿(jian)性電(dian)解(jie)水(AWE)制氫裝置(zhi)由(you)電(dian)解(jie)槽(cao)與(yu)輔助系統構(gou)成(cheng),以KOH為電(dian)解(jie)液、多孔(kong)膜為隔膜,在直流(liu)電(dian)的(de)(de)(de)刺激(ji)下(xia)將H2O分(fen)解(jie)為H2和(he)O2。堿(jian)性電(dian)解(jie)水制氫的(de)(de)(de)優(you)點是不需(xu)(xu)要貴金屬(shu)作為催化劑,成(cheng)本相對較(jiao)(jiao)低(di),裝備(bei)技術成(cheng)熟(shu),產(chan)品(pin)耐久性好,服(fu)役(yi)壽命(ming)可達30年。缺點在于所需(xu)(xu)的(de)(de)(de)隔膜較(jiao)(jiao)厚,電(dian)阻較(jiao)(jiao)大(da),制氫的(de)(de)(de)工作電(dian)流(liu)低(di),設備(bei)體積大(da)等。此外,由(you)于多孔(kong)膜透氣(qi)(qi)性強,需(xu)(xu)有效保證電(dian)解(jie)槽(cao)兩側的(de)(de)(de)壓(ya)力(li)平衡(heng)。更重要的(de)(de)(de)是,堿(jian)性電(dian)解(jie)液會與(yu)空氣(qi)(qi)中的(de)(de)(de)CO2反應,形成(cheng)難容性的(de)(de)(de)碳酸鹽(如K2CO3、Na2CO3等)。
2.1.2質子交換膜電解水制(zhi)氫
質(zhi)(zhi)(zhi)子交換(huan)(huan)膜(PEM)電(dian)解(jie)(jie)水(shui)(shui)制(zhi)氫采用的(de)質(zhi)(zhi)(zhi)子交換(huan)(huan)膜很薄、電(dian)阻較小,可(ke)在(zai)高效率前(qian)提(ti)下承受較大(da)的(de)電(dian)流(liu),因此設(she)備(bei)體積(ji)和占地面積(ji)都遠(yuan)小于堿(jian)性電(dian)解(jie)(jie)水(shui)(shui)設(she)備(bei)。同時由于PEM電(dian)解(jie)(jie)水(shui)(shui)采用不(bu)透氣的(de)膜,可(ke)承受更大(da)的(de)壓力(li),無(wu)需兩(liang)側嚴格的(de)壓力(li)控制(zhi),可(ke)做(zuo)到快速(su)啟停,功率調節的(de)幅度和響應(ying)速(su)度也遠(yuan)高于堿(jian)性電(dian)解(jie)(jie)水(shui)(shui)。當前(qian)國外PEM制(zhi)氫技(ji)術已較為成熟,進入市(shi)場化(hua)(hua)應(ying)用早期。普頓(dun)、西門子、ITM Power等代表性企(qi)業已相(xiang)繼分布(bu)了兆瓦級PEN電(dian)解(jie)(jie)水(shui)(shui)系統產(chan)品,大(da)力(li)推動(dong)了其規模化(hua)(hua)應(ying)用。中國PEM制(zhi)氫產(chan)業發展相(xiang)對(dui)滯后,雖部分企(qi)業已形成具(ju)有較高自主化(hua)(hua)程(cheng)度的(de)制(zhi)氫樣機,但還(huan)存在(zai)質(zhi)(zhi)(zhi)子交換(huan)(huan)膜等關鍵材(cai)料(liao)的(de)“卡脖子”問題(ti)。后續應(ying)加大(da)力(li)度攻關低成本催化(hua)(hua)劑和氣體擴(kuo)散層等關鍵技(ji)術,提(ti)升關鍵設(she)備(bei)的(de)效率與壽命。
2.1.3固體氧化物(wu)電解(jie)水制氫
固(gu)體(ti)氧化(hua)物(SOEC)電(dian)解(jie)(jie)水(shui)制(zhi)氫(qing)(qing)(qing)是一(yi)(yi)種高(gao)溫電(dian)解(jie)(jie)水(shui)技術(shu)(shu),操作溫度為(wei)700~1000℃,其結構由(you)多孔的氫(qing)(qing)(qing)電(dian)極、氧電(dian)極和一(yi)(yi)層致密的固(gu)體(ti)電(dian)解(jie)(jie)質組成。由(you)于其工(gong)作溫度高(gao),能(neng)(neng)夠大(da)大(da)增加反應的動(dong)力,同時可大(da)幅降低(di)電(dian)能(neng)(neng)消(xiao)耗。在某(mou)些特定(ding)場合,如高(gao)溫氣(qi)冷堆(dui)、太陽能(neng)(neng)集熱等(deng),SOEC電(dian)解(jie)(jie)水(shui)制(zhi)氫(qing)(qing)(qing)技術(shu)(shu)有較大(da)的發揮空間。SOEC電(dian)解(jie)(jie)水(shui)制(zhi)氫(qing)(qing)(qing)技術(shu)(shu)在電(dian)耗等(deng)方面具有不小(xiao)優勢(shi),但仍存在使用溫度高(gao)、投入大(da)、啟停慢(man)、循環壽(shou)命低(di)等(deng)技術(shu)(shu)壁壘,尚處于室內驗證階段(duan),未實(shi)現(xian)市(shi)場化(hua)推廣(guang)。目前除固(gu)體(ti)氧化(hua)物電(dian)解(jie)(jie)水(shui)外,AWE和PEM制(zhi)氫(qing)(qing)(qing)都已獲得(de)規(gui)模化(hua)應用。
2.2太陽能分解水制氫技(ji)術
目前,已存(cun)在的太陽能(neng)分解(jie)水制(zhi)(zhi)氫涵蓋(gai)光(guang)催化法制(zhi)(zhi)氫、光(guang)電化學(xue)法制(zhi)(zhi)氫及固(gu)光(guang)熱分解(jie)法制(zhi)(zhi)氫三大類。
2.2.1光催化(hua)法制(zhi)氫(qing)
光(guang)催(cui)(cui)化(hua)(hua)制(zhi)氫的(de)(de)原理是(shi)利(li)用(yong)光(guang)催(cui)(cui)化(hua)(hua)劑(ji)的(de)(de)吸光(guang)特(te)性(xing),實現光(guang)解(jie)水反應(ying)(ying)。光(guang)催(cui)(cui)化(hua)(hua)劑(ji)在(zai)光(guang)照的(de)(de)作用(yong)下可產生(sheng)一定數量的(de)(de)光(guang)生(sheng)電(dian)子(zi)和(he)空穴,可將吸附在(zai)催(cui)(cui)化(hua)(hua)劑(ji)表面的(de)(de)H2O分子(zi)還原為H2(圖2)。光(guang)導(dao)體材(cai)料(liao)應(ying)(ying)具備的(de)(de)特(te)殊(shu)性(xing)能應(ying)(ying)涵蓋:①太陽光(guang)響(xiang)應(ying)(ying)范(fan)圍廣;②電(dian)子(zi)和(he)空穴分離(li)效率高(gao);③合(he)(he)適的(de)(de)表面反應(ying)(ying)活性(xing)位;④耐久性(xing)強等。光(guang)催(cui)(cui)化(hua)(hua)制(zhi)氫具有光(guang)催(cui)(cui)化(hua)(hua)材(cai)料(liao)易(yi)(yi)得(de)、制(zhi)氫系統簡便、成本低(di)等優勢,具有廣闊(kuo)的(de)(de)應(ying)(ying)用(yong)前景。但(dan)光(guang)催(cui)(cui)化(hua)(hua)劑(ji)現階段(duan)還處(chu)于示范(fan)研發階段(duan),普遍(bian)存在(zai)制(zhi)氫效率低(di)、光(guang)激電(dian)子(zi)-空穴對易(yi)(yi)復(fu)合(he)(he)等難題(ti),與商(shang)業化(hua)(hua)應(ying)(ying)用(yong)仍有較大(da)距離(li)。
2.2.2光(guang)電(dian)化學法制氫
光電(dian)化學(xue)(PEC)制(zhi)(zhi)(zhi)氫在(zai)分解水(shui)過程中,可產(chan)生大量的(de)(de)載流子,可實(shi)(shi)現強(qiang)光條件(jian)下和強(qiang)電(dian)解質中的(de)(de)長(chang)期(qi)耐(nai)久性(xing)(xing)。迄今為止,已研發的(de)(de)PEC制(zhi)(zhi)(zhi)氫光電(dian)極(ji)材料包括(kuo):GaAs、InGaN、MoS2及金屬硒化物(wu)等。MoS2因具備(bei)經濟(ji)、合成流程簡易及良好的(de)(de)光電(dian)效(xiao)應等特性(xing)(xing),制(zhi)(zhi)(zhi)氫效(xiao)果最好。經大量實(shi)(shi)踐證明,經改性(xing)(xing)后的(de)(de)MoS2材料制(zhi)(zhi)(zhi)氫性(xing)(xing)能(neng)更優,通過引入高(gao)性(xing)(xing)能(neng)碳材料,能(neng)夠大幅增加(jia)MoS2表(biao)面(mian)的(de)(de)活(huo)性(xing)(xing)位(wei)點(dian),同時顯著改善其電(dian)學(xue)性(xing)(xing)能(neng)。
2.2.3光熱分解法制(zhi)氫(qing)
早在(zai)(zai)1971年(nian),Ford等便率先報道了直(zhi)接(jie)光(guang)(guang)熱分解(jie)制(zhi)氫(qing)(qing)(qing)工(gong)藝(yi),其主(zhu)要原理為(wei):在(zai)(zai)光(guang)(guang)照下(xia)(xia)使系(xi)統(tong)溫度(du)達到2000K以(yi)上,一(yi)步到位直(zhi)接(jie)獲取H2和(he)O2,最后再利(li)用分離(li)裝置獲取純氫(qing)(qing)(qing)。因此(ci),光(guang)(guang)熱分解(jie)制(zhi)氫(qing)(qing)(qing)(TWSC)的(de)核心在(zai)(zai)于(yu)良好(hao)的(de)抗溫材料和(he)有(you)效(xiao)的(de)氣(qi)體分離(li)設施。為(wei)顯著改善(shan)TWSC制(zhi)氫(qing)(qing)(qing)的(de)功效(xiao)和(he)純度(du),研究人員提出了上百種太陽能熱化學制(zhi)氫(qing)(qing)(qing)方法,包(bao)括HyS、Cu-Cl及S-I等TWSC制(zhi)氫(qing)(qing)(qing)技術。而Cu-Cl制(zhi)氫(qing)(qing)(qing)因其產氫(qing)(qing)(qing)純度(du)高(gao)、污染小(xiao)、節約等優(you)勢,已(yi)成為(wei)當下(xia)(xia)TWSC制(zhi)氫(qing)(qing)(qing)的(de)主(zhu)流。Pal等于(yu)21世紀(ji)初(chu)建立了Cu-Cl制(zhi)氫(qing)(qing)(qing)模型,并成功應用于(yu)全(quan)年(nian)光(guang)(guang)照充足(zu)的(de)Algeria地區,現場結果顯示,該模型的(de)太陽能利(li)用效(xiao)率高(gao)達93%,年(nian)制(zhi)氫(qing)(qing)(qing)量突(tu)破82 t/a。
2.3生物質制(zhi)氫技(ji)術
目前,生物(wu)質制氫技術主要包(bao)括熱化學法和生物(wu)法兩大類。
2.3.1熱化學法制氫
當下主(zhu)流的(de)熱(re)(re)化(hua)(hua)(hua)學制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)技(ji)術有生(sheng)物(wu)質(zhi)催化(hua)(hua)(hua)氣化(hua)(hua)(hua)、生(sheng)物(wu)質(zhi)重整(zheng)及生(sheng)物(wu)質(zhi)熱(re)(re)解制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)等,其工(gong)藝流程如(ru)圖3所示(shi)。生(sheng)物(wu)質(zhi)催化(hua)(hua)(hua)氣化(hua)(hua)(hua)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)的(de)研究重點是提(ti)高產(chan)物(wu)中的(de)H2純度(du),由(you)于氣化(hua)(hua)(hua)過(guo)程中還產(chan)生(sheng)H2S、HCl、堿金屬等微量雜質(zhi),反應器中需加(jia)入吸(xi)附劑加(jia)以處理。生(sheng)物(wu)油重整(zheng)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)最早由(you)美國NREL于1997年(nian)(nian)報(bao)道,其通過(guo)生(sheng)物(wu)質(zhi)熱(re)(re)裂解獲得生(sheng)物(wu)油,再結合水蒸氣重整(zheng)進而實現制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)。經過(guo)多年(nian)(nian)的(de)創新(xin)和(he)發(fa)展(zhan),已成(cheng)為(wei)一(yi)項舉足輕重的(de)制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)技(ji)術。與前者相比,生(sheng)物(wu)質(zhi)熱(re)(re)解制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)發(fa)展(zhan)至今(jin),技(ji)術成(cheng)熟度(du)已相對(dui)成(cheng)熟,當前全(quan)世界已有多套商業(ye)化(hua)(hua)(hua)運作的(de)生(sheng)物(wu)質(zhi)熱(re)(re)解裝(zhuang)置。與其他制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)技(ji)術相比,熱(re)(re)化(hua)(hua)(hua)學制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)優(you)勢顯著(zhu),但也存在一(yi)定的(de)技(ji)術瓶頸,如(ru)熱(re)(re)化(hua)(hua)(hua)學制(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)成(cheng)本高,混(hun)合產(chan)物(wu)中氫(qing)(qing)含(han)量低,含(han)有大量的(de)CO、H2S及焦油等雜質(zhi)。這(zhe)些雜質(zhi)均會對(dui)燃料(liao)電池產(chan)生(sheng)一(yi)定的(de)損(sun)害,因此混(hun)合產(chan)物(wu)適(shi)合作為(wei)燃料(liao)或工(gong)業(ye)原料(liao),不適(shi)合于燃料(liao)電池等高純氫(qing)(qing)應用場景(jing)。
2.3.2生(sheng)物法(fa)制(zhi)氫(qing)
生物(wu)法制氫(qing)(qing)(qing)體系(xi)包括(kuo)暗(an)厭(yan)(yan)氧(yang)菌發(fa)酵(jiao)、光(guang)(guang)(guang)(guang)合(he)(he)生物(wu)及其耦合(he)(he)制氫(qing)(qing)(qing)等。暗(an)厭(yan)(yan)氧(yang)菌發(fa)酵(jiao)制氫(qing)(qing)(qing)是(shi)通過厭(yan)(yan)氧(yang)細菌在(zai)氫(qing)(qing)(qing)化酶(mei)的(de)作(zuo)用下實現有(you)機物(wu)分解(jie)(jie)從而獲取H2,此(ci)過程可(ke)實現無光(guang)(guang)(guang)(guang)能(neng)(neng)產氫(qing)(qing)(qing)。光(guang)(guang)(guang)(guang)合(he)(he)生物(wu)制氫(qing)(qing)(qing)則是(shi)以(yi)光(guang)(guang)(guang)(guang)能(neng)(neng)為(wei)反應條件,利于(yu)微藻等光(guang)(guang)(guang)(guang)合(he)(he)微生物(wu)分解(jie)(jie)水(shui)產氫(qing)(qing)(qing)。該(gai)技(ji)(ji)術制氫(qing)(qing)(qing)利用的(de)能(neng)(neng)源既(ji)有(you)生物(wu)能(neng)(neng)也有(you)光(guang)(guang)(guang)(guang)能(neng)(neng),因此(ci)光(guang)(guang)(guang)(guang)發(fa)酵(jiao)制氫(qing)(qing)(qing)效率一般高于(yu)暗(an)發(fa)酵(jiao)。光(guang)(guang)(guang)(guang)合(he)(he)-發(fa)酵(jiao)耦合(he)(he)技(ji)(ji)術可(ke)兼(jian)具暗(an)發(fa)酵(jiao)與光(guang)(guang)(guang)(guang)合(he)(he)生物(wu)制氫(qing)(qing)(qing)的(de)優勢(shi),不僅能(neng)(neng)夠(gou)在(zai)一定(ding)程度上減少光(guang)(guang)(guang)(guang)能(neng)(neng)需(xu)求(qiu),同時可(ke)大幅增加(jia)H2的(de)產量(liang),是(shi)生物(wu)法制氫(qing)(qing)(qing)的(de)主要發(fa)展方向(xiang)。
2.4核能制氫技術
核能到氫(qing)(qing)(qing)(qing)能的(de)(de)轉化有(you)多種(zhong)途徑,可(ke)(ke)以(yi)(yi)利用(yong)(yong)(yong)核能發(fa)電(dian)進(jin)(jin)行電(dian)解(jie)水制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing),也可(ke)(ke)利用(yong)(yong)(yong)核反(fan)(fan)(fan)應(ying)(ying)堆(dui)產生(sheng)的(de)(de)熱(re)來制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)。核能發(fa)電(dian)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)與普通電(dian)解(jie)水制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)技術相同,而利用(yong)(yong)(yong)核反(fan)(fan)(fan)應(ying)(ying)堆(dui)發(fa)熱(re)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)是(shi)未來應(ying)(ying)用(yong)(yong)(yong)前景廣闊的(de)(de)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)技術,其制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)原(yuan)理見圖(tu)4。甲(jia)烷(wan)蒸汽重(zhong)整(zheng)(SMR)是(shi)工業上(shang)主要的(de)(de)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)方法(fa),利用(yong)(yong)(yong)核反(fan)(fan)(fan)應(ying)(ying)堆(dui)產生(sheng)的(de)(de)熱(re)作為(wei)蒸汽重(zhong)整(zheng)的(de)(de)熱(re)源時,可(ke)(ke)顯著降(jiang)低過程(cheng)所需甲(jia)烷(wan)氣(qi)(qi)量和成(cheng)本。但(dan)該技術仍屬于化石能源制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing),會產生(sheng)大量的(de)(de)溫(wen)室(shi)氣(qi)(qi)體,不利于推動碳中和進(jin)(jin)程(cheng)。高溫(wen)電(dian)解(jie)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)是(shi)以(yi)(yi)核反(fan)(fan)(fan)應(ying)(ying)堆(dui)產生(sheng)的(de)(de)高溫(wen)蒸汽為(wei)原(yuan)料,電(dian)耗可(ke)(ke)降(jiang)至(zhi)2.8kWh/m3,遠低于傳(chuan)統制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing),但(dan)目前仍面臨技術不夠成(cheng)熟和高成(cheng)本等壁(bi)壘。而熱(re)化學循環分解(jie)水制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing)則是(shi)利用(yong)(yong)(yong)核反(fan)(fan)(fan)應(ying)(ying)的(de)(de)產熱(re)直接制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)(qing),由(you)于反(fan)(fan)(fan)應(ying)(ying)需在2500℃以(yi)(yi)上(shang)的(de)(de)高溫(wen)下進(jin)(jin)行,難以(yi)(yi)實際應(ying)(ying)用(yong)(yong)(yong),如何利用(yong)(yong)(yong)熱(re)循環將(jiang)反(fan)(fan)(fan)應(ying)(ying)溫(wen)度控(kong)制(zhi)(zhi)(zhi)(zhi)(zhi)在適合的(de)(de)范圍內是(shi)未來該領(ling)域的(de)(de)主攻方向(xiang)。
2.5海水制氫技術
由于海(hai)(hai)(hai)(hai)(hai)水(shui)的(de)(de)成分(fen)復雜(za)且缺乏(fa)行之有效(xiao)的(de)(de)催(cui)化(hua)(hua)(hua)劑,直(zhi)接電(dian)解(jie)海(hai)(hai)(hai)(hai)(hai)水(shui)會導致(zhi)制(zhi)(zhi)(zhi)取(qu)H2時副反應競爭、催(cui)化(hua)(hua)(hua)劑失活(huo)、隔(ge)膜堵塞等問題。基于此,諸多專家和學(xue)者提出了不(bu)同的(de)(de)間接海(hai)(hai)(hai)(hai)(hai)水(shui)制(zhi)(zhi)(zhi)氫(qing)(qing)技術(shu)。有研究者采用固(gu)體(ti)氧化(hua)(hua)(hua)物電(dian)解(jie)技術(shu)對(dui)海(hai)(hai)(hai)(hai)(hai)水(shui)進(jin)行電(dian)解(jie),將海(hai)(hai)(hai)(hai)(hai)水(shui)首先(xian)轉化(hua)(hua)(hua)為高溫水(shui)蒸氣再電(dian)解(jie),大(da)部分(fen)海(hai)(hai)(hai)(hai)(hai)水(shui)中的(de)(de)雜(za)質不(bu)會接觸到電(dian)解(jie)裝(zhuang)置,因此電(dian)解(jie)效(xiao)率相(xiang)對(dui)較(jiao)好(hao),但由于固(gu)體(ti)氧化(hua)(hua)(hua)物電(dian)解(jie)技術(shu)發展滯后,且經濟(ji)性差(cha),在(zai)全(quan)球(qiu)范圍內的(de)(de)活(huo)躍(yue)度相(xiang)對(dui)較(jiao)低(di)。海(hai)(hai)(hai)(hai)(hai)水(shui)淡化(hua)(hua)(hua)-電(dian)解(jie)制(zhi)(zhi)(zhi)氫(qing)(qing)是現今海(hai)(hai)(hai)(hai)(hai)水(shui)制(zhi)(zhi)(zhi)氫(qing)(qing)技術(shu)的(de)(de)主流(liu),其先(xian)通(tong)過處理技術(shu)將海(hai)(hai)(hai)(hai)(hai)水(shui)進(jin)行淡化(hua)(hua)(hua),在(zai)結合(he)成熟的(de)(de)淡水(shui)制(zhi)(zhi)(zhi)氫(qing)(qing)技術(shu)來制(zhi)(zhi)(zhi)取(qu)H2。從多方面考(kao)慮,海(hai)(hai)(hai)(hai)(hai)水(shui)淡化(hua)(hua)(hua)制(zhi)(zhi)(zhi)氫(qing)(qing)都具備明顯優勢,但由于受相(xiang)關技術(shu)條件的(de)(de)限(xian)制(zhi)(zhi)(zhi),該技術(shu)尚處于實(shi)驗室階(jie)段,與實(shi)際應用還有很(hen)長的(de)(de)距離。
3評價與對策
3.1不同(tong)綠(lv)色(se)制(zhi)氫(qing)技術(shu)特點對比
近年來世界各(ge)國對電解水制(zhi)氫、生物質(zhi)制(zhi)氫及(ji)核(he)能制(zhi)氫等工藝(yi)進行了(le)大量研究,綠(lv)色(se)制(zhi)氫方(fang)法正(zheng)朝著(zhu)多樣化(hua)方(fang)向發(fa)展(zhan),各(ge)種新型制(zhi)氫技術(shu)蔚然成(cheng)風,在(zai)推動全球(qiu)氫能資源(yuan)的(de)利(li)用(yong)中扮演著(zhu)重要的(de)角色(se),不同綠(lv)色(se)制(zhi)氫技術(shu)在(zai)適(shi)用(yong)條件(jian)、應用(yong)效果及(ji)成(cheng)本投入(ru)等方(fang)面(mian)不盡相(xiang)同,其各(ge)自(zi)工藝(yi)特點(dian)如表1所示。
3.2綠色制氫(qing)產業化面臨的(de)挑戰(zhan)
新型綠(lv)色(se)制(zhi)(zhi)(zhi)氫(qing)技術(shu)雖(sui)在(zai)諸多方面都體(ti)現出一定的(de)優勢,但由于相(xiang)(xiang)關技術(shu)條件的(de)局限性(xing)(xing),在(zai)應用(yong)過程(cheng)(cheng)中勢必會有(you)不少實際問題存在(zai)。(1)首(shou)先是(shi)制(zhi)(zhi)(zhi)氫(qing)裝備及技術(shu)方面,國內雖(sui)已有(you)相(xiang)(xiang)關企業(ye)(ye)開展相(xiang)(xiang)應的(de)技術(shu)研(yan)發,但均處于小批(pi)量試制(zhi)(zhi)(zhi)階(jie)段,尚未(wei)形成(cheng)成(cheng)熟(shu)的(de)制(zhi)(zhi)(zhi)氫(qing)工藝生產(chan)線,相(xiang)(xiang)關核心(xin)技術(shu)成(cheng)熟(shu)度(du)(du)低,系統設備國產(chan)化(hua)程(cheng)(cheng)度(du)(du)不高(gao)。(2)其次是(shi)經濟性(xing)(xing)方面,高(gao)投入成(cheng)本(ben)仍是(shi)限制(zhi)(zhi)(zhi)部分綠(lv)色(se)制(zhi)(zhi)(zhi)氫(qing)技術(shu)發展的(de)最大因素,加之多數制(zhi)(zhi)(zhi)氫(qing)工藝需(xu)添加后續(xu)的(de)氫(qing)提純(chun)技術(shu),以獲(huo)取(qu)高(gao)純(chun)度(du)(du)H2,如何有(you)效降低制(zhi)(zhi)(zhi)氫(qing)成(cheng)本(ben)是(shi)未(wei)來制(zhi)(zhi)(zhi)氫(qing)領域的(de)主要發展方向(xiang)。(3)最后是(shi)標(biao)(biao)準(zhun)體(ti)系方面,當前(qian)中國制(zhi)(zhi)(zhi)氫(qing)產(chan)業(ye)(ye)單一、分散,關鍵技術(shu)指標(biao)(biao)多有(you)缺(que)少,強制(zhi)(zhi)(zhi)性(xing)(xing)國家標(biao)(biao)準(zhun)較少,已難(nan)以適應制(zhi)(zhi)(zhi)氫(qing)產(chan)業(ye)(ye)標(biao)(biao)準(zhun)化(hua)的(de)需(xu)求。
3.3推動制(zhi)氫產(chan)業有(you)序(xu)發(fa)展的(de)策略
加(jia)強對(dui)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)核心技術(shu)的(de)研發力度,最優化(hua)提(ti)升制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)技術(shu)效率的(de)同時,有效改善光催(cui)化(hua)劑、反(fan)應(ying)器等(deng)關鍵(jian)材(cai)料(liao)的(de)耐(nai)久(jiu)性,進(jin)而(er)實(shi)現H2產(chan)(chan)量的(de)最大(da)化(hua)。聚焦(jiao)低(di)(di)成本(ben)催(cui)化(hua)劑、氣(qi)體擴散層等(deng)關鍵(jian)技術(shu)的(de)提(ti)升,提(ti)高制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)裝置效率和壽(shou)命的(de)同時,加(jia)快實(shi)現低(di)(di)成本(ben)化(hua)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)、產(chan)(chan)氫(qing)(qing)(qing)及(ji)提(ti)純(chun),最大(da)化(hua)實(shi)現降本(ben)增效。打破傳統制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)標(biao)準化(hua)工作模(mo)式(shi),建立系統完整的(de)制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)工藝產(chan)(chan)業鏈,盡快彌補制(zhi)(zhi)(zhi)(zhi)(zhi)氫(qing)(qing)(qing)標(biao)準化(hua)工作與技術(shu)發展間的(de)短(duan)板,縮小與美(mei)日等(deng)國成熟(shu)標(biao)準體系的(de)差距。
4展望
新型綠(lv)色制(zhi)(zhi)氫(qing)雖(sui)然在(zai)眾多(duo)方面都具備顯著的(de)優(you)勢,但由于受能耗、成(cheng)本等方面的(de)限(xian)制(zhi)(zhi),部分(fen)技(ji)術(shu)尚未在(zai)實(shi)際生產中(zhong)得以應用(yong),要想真正實(shi)現綠(lv)色低碳制(zhi)(zhi)氫(qing)并(bing)非易事。建(jian)議從不同(tong)角(jiao)度出發,多(duo)管齊下,共同(tong)推(tui)動(dong)(dong)我國綠(lv)色制(zhi)(zhi)氫(qing)產業(ye)的(de)有(you)序發展。其一:增強(qiang)國際合(he)(he)作,結合(he)(he)我國綠(lv)色制(zhi)(zhi)氫(qing)產業(ye)現狀,積極開(kai)展適合(he)(he)本國國情(qing)的(de)變革性(xing)制(zhi)(zhi)氫(qing)技(ji)術(shu)的(de)研發。其二:深度學科(ke)交叉,集成(cheng)反應動(dong)(dong)力(li)學、熱力(li)學、氣體分(fen)離及材(cai)料耐(nai)久性(xing)等多(duo)門學科(ke),賦予制(zhi)(zhi)氫(qing)工(gong)藝(yi)目標(biao)性(xing)和高效性(xing)。其三:理論實(shi)踐并(bing)舉,加強(qiang)先進制(zhi)(zhi)氫(qing)技(ji)術(shu)的(de)實(shi)用(yong)性(xing)評價和經濟可行(xing)性(xing)分(fen)析,室內驗(yan)證、市場實(shi)踐兩(liang)手(shou)抓(zhua),為推(tui)動(dong)(dong)中(zhong)國綠(lv)色制(zhi)(zhi)氫(qing)工(gong)藝(yi)規模化應用(yong)提供有(you)力(li)支撐。