CN107344068A - 光催化氧化与光催化曝气集成的烟气海水脱硫脱硝工艺 - Google Patents
光催化氧化与光催化曝气集成的烟气海水脱硫脱硝工艺 Download PDFInfo
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Abstract
本发明公开了一种光催化氧化与光催化曝气集成的烟气海水脱硫脱硝工艺,包括以下三个子工艺模块:烟气与海水通过射流反应器混合、光催化氧化海水脱硫脱硝和光催化降解COD与多环芳烃(PHAs)模块,三个工艺模块相互串联,组合使用,达到同时海水烟气脱硫脱硝与废海水处理的一体化目的。本发明的优点:由于实现了烟气同时海水脱硫脱硝,使整个光催化海水脱硫脱硝吸收塔与曝气池的体积大大缩小,更有利于船舶上有限面积的设备安装与技术推广使用。只需光催化剂,天然海水就可实现烟气的同时脱硫脱硝一体化与废海水的曝气达标排放,降低了空气曝气量和新鲜海水的掺混量,从而显著降低工程造价,具有广阔的应用前景。
Description
技术领域
本发明涉及一种烟气海水脱硫脱硝技术,特别涉及一种利用海水对燃煤电厂、远洋船舶、军舰和海上平台柴油机烟气同时脱硫脱硝的新工艺。
背景技术
海水脱硫技术始于上世纪70年代,并很快在欧洲、美洲、亚洲等沿海电厂推广应用。众所周知,天然海水中含有大量的可溶性盐,通常呈碱性,自然碱度为1.2~2.5mmol/L,具有天然的酸碱缓冲能力及吸收SO2的能力,这是海水直接用于烟气脱硫的理论依据。
海水脱硫过程的核心是烟气与海水的接触传质,该过程在气液接触传质设备中进行。填料塔是以塔内的填料作为气液两相间接触构件的传质设备,具备分离效率高、阻力小、通量大、操作弹性大等特点,在气液初始分布良好的情况下几乎无放大效应。
传统的海水脱硫工艺通常采用的是散堆聚丙烯填料或陶瓷填料,相对来讲,聚丙烯填料易老化,浸润性差,寿命短,单重量轻;而改性催化陶瓷规整填料具有比表面积大,空隙率高,浸润性好,压降小,通量大,寿命长,操作液气比和温度弹性大等特点。另外,陶瓷填料具有表面易改性、耐高温、耐海水腐蚀、不易堵塞、抗冻性能好、水热老化性能稳定和维护费用低等优点。李春虎等人在国家“863”课题资助下,也发明了多种海水脱硫高效填料(用于海水脱硫的陶瓷规整催化填料的制备方法,ZL200910308778.8;用于海水脱硫的塑料规整催化填料的制备方法,ZL200910308741.5)与海水脱硫工艺(一种利用海水脱除烟气中二氧化硫的工艺,ZL 200910310771.X)。这些海水脱硫填料和工艺技术发明,使海水脱硫中的海水的喷淋量、填料抗海水腐蚀、寿命以及脱硫后的废酸性海水曝气量等指标大幅提升,但该技术仍然无法实现海水脱硝。
另一方面,海水脱硫技术也逐步移植到船舶和海上平台柴油机烟气脱硫中,船舶烟气中含有大量的大气污染物,其中占绝大多数的为SO2、NOx和颗粒物。其中SO2、NOx对人类健康、动植物、农作物、生态环境以及国民经济的危害也逐渐为人们所熟知。数据显示,2010年全国内河船舶气体排放的污染物中仅氮氧化物(NOx)就高达81万吨,而在船舶聚集的沿海港口地区,各类船舶气体排放的污染物更是可观,以成为港口大气污染和雾霾的主要元凶。。面对日趋严峻的状况国内外对船舶烟气的排放标准也日益严格。根据国际防止船舶造成污染公约(MARPOL)附则VI技术规则修正案,最为严格的船舶尾气中SO2、NOx的排放要求已于近几年陆续生效。因此,我国相关部门近些年一直在寻找有效的解决方法,争取尽快达到国际要求。
目前,国际上对于船舶烟气脱硫研究的公司和技术种类较多,包括,欧洲、美国等的Marine Exhaust
Solutions、Hamworthy Krystallon、Ecospec、Advanced Cleanup
Technologies、DuPont、Wartsila、Green Tech Marine、Alfa
Laval Aalborg、Rolls-Royce Marine、MAN Diesel & Turbo和Wartsila等十多家;国内,则有中国海洋大学、大连海事大学和上海海洋大学等。但对于船舶烟气同时脱硫脱硝的技术开发与研究则较少。
同时,多数船舶公司对于船舶尾气的脱硫脱硝处理只是简单的将陆地上已发展成熟的海水脱硫技术(碱法或镁法脱硫)与SCR脱硝整体搬移至船舶上。这种做法虽能达到净化烟气的目的,但其占地面积大、船舶需携带危险化学品、海外港口补给困难、存在二次污染等问题又使其应用受到了一定限制。因而开发出更适合应用于船舶的烟气净化技术逐渐提上日程。
海水脱硫是海水直接利用领域的重要研究课题与技术开发方向,具有极其重要的科研及经济价值。中国海洋大学李春虎教授课题组在已有的多项海水脱硫专利和研究成果的基础上, 发明了多种光催化剂,使传统的海水脱硫技术跃变为同时脱硫脱硝。这项烟气光催化海水净化技术,具有反应条件温和、能耗低、二次污染少等优点。这项技术主要是利用半导体TiO2、BiVO4和g-C3N4等的光敏感性,当这些材料暴露在超过其带隙能以上的光照时,其价带上的电子被激发,超过禁带,进入导带,同时在价带上产生相应的空穴,这些空穴具有很强的得电子能力,可将烟气中的水变成羟基自由基,光生电子把吸附的氧气变成超氧自由基,羟基自由基和超氧自由基有很强的氧化性,可夺取SO2、NOx体系中的电子,使其被活化氧化为高价态的氧化物SO3和NO2。而高价态的SO3和NO2极易被碱性海水吸收脱除,并排入大海。
发明内容
本发明的目的是提供一种占地面积小,工程造价低,安全高效的适用于船舶的光催化氧化与光催化曝气集成的海水脱硫脱硝工艺。
本发明利用光催化陶瓷填料催化剂使烟气中的SO2和NOx被催化氧化成SO3和NO2,从源头上降低进入曝气池的亚硫酸根和亚硝酸根含量,同时在曝气池内也放置光催化陶瓷催化剂,进一步将脱硫后废海水中的COD和多环芳烃降解,从而可显著降低曝气池的面积和体积,降低空气曝气量和新鲜海水的掺混量,从而显著降低工程造价。
本发明包括以下三个子工艺模块:烟气与海水通过射流反应器混合、光催化氧化海水脱硫脱硝和光催化降解COD与多环芳烃(PHAs)模块,三个工艺模块相互串联,组合使用,达到同时海水烟气脱硫脱硝与废海水处理的一体化目的。
本发明具体的工艺流程如下:
(1)船舶柴油发动机排出的烟气与新鲜海水经射流反应器混合后将烟气温度从380-450℃降低到70-90℃,同时脱除烟气中的固体颗粒和部分SO2(第一个工艺模块);
(2)经过射流反应器洗涤降温后的烟气被从底部送入内装光催化剂的光催化氧化海水脱硫脱硝吸收塔,用新鲜海水自塔顶喷淋洗涤以除去烟气中的SO2和NO2;同时,通过光催化将大部分SO2氧化成SO3, NO氧化成NO2;经光催化氧化海水脱硫脱硝吸收塔完成脱硫脱硝一体化处理后的洁净烟气通过烟囱排放(第二个工艺模块);
(3)经过射流反应器洗涤烟气后的废海水与从吸收塔底部排放的废海水同时汇入曝气池,经陶瓷板过滤截留水中的固体颗粒,过滤后的废海水在曝气的条件下经光催化剂光催化氧化降解COD和部分多环芳烃后,达到排放标准,直接排入大海或与新鲜海水掺混后使混合海水的pH值大于等于6.8后,排入大海;所述陶瓷板截留后的固体颗粒压缩成滤饼储存(第三个工艺模块)。
所述光催化氧化海水脱硫脱硝吸收塔为内装筛板、光催化剂和光源的圆型或方形塔。
所述光催化氧化海水脱硫脱硝吸收塔内的光催化剂与光源灯通过筛板交替放置。
所述光源为紫外灯、日光灯、汞灯、无极灯或LED光源。
所述光催化剂,是以规整陶瓷为载体,由氮化碳(g-C3N4)、光活性催化剂TiO2、氧化石墨烯组成;其中,所述氮化碳(g-C3N4)为人工合成的可见光催化剂;所述的光活性催化剂TiO2为纳米剂TiO2;所述的氧化石墨烯为以石墨为原料由各种方法制备的石墨烯,经氧化得来。
所述光催化氧化海水脱硫脱硝吸收塔内的光催化氧化海水脱硫脱硝工艺参数为温度50-140℃,压力为常压。
所述曝气池内光催化降解脱硫后的酸性废海水COD和多环芳烃的工艺参数为温度常温-40℃,空气曝气,pH为1.0-7.0。
本发明的优点:由于实现了烟气同时海水脱硫脱硝,使整个光催化海水脱硫脱硝吸收塔与曝气池的体积大大缩小,更有利于船舶上有限面积的设备安装与技术推广使用。只需光催化剂,天然海水就可实现烟气的同时脱硫脱硝一体化与废海水的曝气达标排放,降低了空气曝气量和新鲜海水的掺混量,从而显著降低工程造价,具有广阔的应用前景。
附图说明
图1是本发明的工艺流程图。
1. 舰船柴油机;2. 海水-烟气射流反应器;3. 射流用海水泵;4. 光催化氧化海水脱硫脱硝吸收塔;5. 填料型光催化剂;6. 紫外灯;7. 烟囱;8. 一段塔脱硫脱硝海水泵;9. 二段塔脱硫脱硝海水泵;10. 曝气池;11. 混合池;12. 日光灯13. 光催化剂填料;14. 曝气池海水稀释泵;15. 曝气鼓风机。
具体实施方式
下面结合附图并通过具体实施例来详细说明本发明。
实施例
1
:
如图1所示,本发明所用主要装置包括:射流反应器2、光催化氧化海水脱硫脱硝吸收塔4与曝气池10,其中,射流反应器2不锈钢制成的文丘里管。光催化氧化海水脱硫脱硝吸收塔4内径1996 x 1996mm,高度98400mm(2 x 492mm)的方形塔组成。内装有筛板,筛板上放置陶瓷规整填料光催化剂,光催化剂上面再放置紫外灯形成一个光催化海水吸收塔板单元,重复这个规整填料型光催化剂与紫外灯组合的单元,直到塔顶,也可在塔内自下往上由紫外灯、筛板和陶瓷规整填料型光催化脱硫脱硝剂组成一个光催化海水吸收塔板单元,重复这个组合到塔顶或混装组合。内装9.0m3涂覆TiO2的规整陶瓷填料光催化剂。为便于观察塔内流体流动状态及填料装填状况,塔体设计有压力和温度测量口。海水由吸收塔上部经喷头喷淋至规整陶瓷填料型光催化剂上,内置H型350W紫外灯或可见光源或LED灯,曝气池为长x宽x高分别为3000 x 3000 x 1200mm聚四氟乙烯制成,内置350W的H型紫外灯与陶瓷光催化剂,并用微型空压机曝气,空气曝气量为250m3/h左右;2x1270KW荷兰SULZER公司生产的SULZER S20舰船柴油机,其产生的进塔烟气流量为16000m3/h,SO2进气压力0.12MPa,模拟烟气SO2含量约为1800mg/m3,NO含量约为800mg/m3,还有12%的O2和8%的水蒸气。海水光催化脱硫脱硝塔操作温度60℃的条件下,改变海水喷流量,测定了四个不同的海水流量下的光催化脱硫脱硝塔出口烟气的光催化脱硫率和脱硝率。其中,脱硫海水的碱度为2.28。测得的光催化海水脱硫率和脱硝率如下表 1所示。
表1 60℃和350W紫外灯下光催化氧化海水脱硫率和脱硝率
序号 | 射流海水量 /m3/h | 海水喷淋量/m3/h | SO2 脱除率/% | 脱硝率/% |
1 | 15 | 150 | 99.0 | 85 |
2 | 15 | 120 | 98.1 | 82 |
3 | 15 | 100 | 97.8 | 78 |
4 | 15 | 90 | 94.5 | 74 |
从表1可以看出,随着海水喷淋量的减少,脱硫率和脱硝率均有所下降。
实施例
2
:
装置和工艺流程同实施例1,光催化剂改为装填改性后的TiO2涂覆陶瓷填料光催化剂,该光催化剂为涂覆g-C3N4与石墨烯的9m3规整陶瓷填料型光催化剂,并安装400W的H型紫外灯,通入光催化海水吸收塔内的模拟烟气为含有1000mg/m3的SO2、800mg/m3的NO、12%的O2和8%的水蒸气,其余为N2平衡的混合气,实验温度为60-90℃。射流海水量13m3/h,海水喷淋量120m3/h,从喷淋塔流出的废海水进入曝气池,曝气池内的pH经测量为1.0-1.5左右,COD约500-1000mg/L。经光催化降解COD和海水稀释后,最终实验结果如表2。
表2 不同温度下和400W紫外灯下光催化氧化海水脱硫率、脱硝率和COD降解率
塔内温度/℃ | SO2脱除率/% | NO脱除率/% | COD脱除率/% | 曝气池处理前pH值 | 曝气池海水稀释后pH值 |
60 | 99.0 | 88.2 | 80.1 | 1.1 | 6.8 |
70 | 98.4 | 87.9 | 82.2 | 1.0 | 6.9 |
80 | 98.0 | 85.8 | 82.4 | 1.3 | 6.9 |
90 | 97.1 | 85.6 | 82.1 | 1.4 | 6.9 |
从表2可以看出,提高射流海水和喷淋海水流量,该新型工艺不仅实现了海水同时脱硫脱硝,而且经海水稀释后还可达标处理脱硫后的酸性废海水。
Claims (7)
1.一种光催化氧化与光催化曝气集成的烟气海水脱硫脱硝工艺,其特征在于包括以下步骤:
(1)船舶柴油发动机排出的烟气与新鲜海水经射流反应器混合后将烟气温度从380-450℃降低到70-90℃,同时脱除烟气中的固体颗粒和部分SO2;
(2)经过射流反应器洗涤降温后的烟气被从底部送入内装光催化剂的光催化氧化海水脱硫脱硝吸收塔,用新鲜海水自塔顶喷淋洗涤以除去烟气中的SO2和NO2;同时,通过光催化将大部分SO2氧化成SO3, NO氧化成NO2;经光催化氧化海水脱硫脱硝吸收塔完成脱硫脱硝一体化处理后的洁净烟气通过烟囱排放;
(3)经过射流反应器洗涤烟气后的废海水与从吸收塔底部排放的废海水同时汇入曝气池,经陶瓷板过滤截留水中的固体颗粒,过滤后的废海水在曝气的条件下经光催化剂光催化氧化降解COD和部分多环芳烃后,达到排放标准,直接排入大海或与新鲜海水掺混后使混合海水的pH值大于等于6.8后,排入大海;所述陶瓷板截留后的固体颗粒压缩成滤饼储存。
2.根据权利要求1所述的烟气海水脱硫脱硝工艺,其特征在于所述光催化氧化海水脱硫脱硝吸收塔为内装筛板、光催化剂和光源的圆型或方形塔。
3.根据权利要求2所述的烟气海水脱硫脱硝工艺,其特征在于所述光催化氧化海水脱硫脱硝吸收塔内的光催化剂与光源灯通过筛板交替放置。
4.根据权利要求2所述的烟气海水脱硫脱硝工艺,其特征在于所述光源为紫外灯、日光灯、汞灯、无极灯或LED光源。
5.根据权利要求1所述的烟气海水脱硫脱硝工艺,其特征在于所述光催化剂,是以规整陶瓷为载体,由氮化碳、光活性催化剂TiO2、氧化石墨烯组成。
6.根据权利要求1所述的烟气海水脱硫脱硝工艺,其特征在于所述光催化氧化海水脱硫脱硝吸收塔内的光催化氧化海水脱硫脱硝工艺参数为温度50-140℃,压力为常压。
7.根据权利要求1所述的烟气海水脱硫脱硝工艺,其特征在于所述曝气池内光催化降解脱硫后的酸性废海水COD和多环芳烃的工艺参数为温度常温-40℃,空气曝气,pH为1.0-7.0。
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