CN111472866B - 一种抑制压燃式发动机内氮氧化物的抑制剂 - Google Patents
一种抑制压燃式发动机内氮氧化物的抑制剂 Download PDFInfo
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- CN111472866B CN111472866B CN202010303965.3A CN202010303965A CN111472866B CN 111472866 B CN111472866 B CN 111472866B CN 202010303965 A CN202010303965 A CN 202010303965A CN 111472866 B CN111472866 B CN 111472866B
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 22
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- 239000012964 benzotriazole Substances 0.000 claims 1
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- 238000003916 acid precipitation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
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- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/105—General auxiliary catalysts, e.g. upstream or downstream of the main catalyst
- F01N3/108—Auxiliary reduction catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
- F01N3/2066—Selective catalytic reduction [SCR]
- F01N3/2073—Selective catalytic reduction [SCR] with means for generating a reducing substance from the exhaust gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种抑制压燃式发动机内氮氧化物的抑制剂,所述抑制剂按重量百分比计,包括以下组分:多氮化合物40~30%;尿素或三聚氰胺30~40%;乙二醇20%;助溶剂10%;其中,所述多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物。本发明提供的氮氧化物抑制剂中多氮化合物与尿素或三聚氰胺复配,能够在燃烧过程中起到高效阻止氮氧化和高效催化氮还原的功能,两者相互促进,加大彼此的功能,更加有效地减少了燃烧引起的氮氧化物排放。大大提高了尿素SCR系统在应用时NOx的转化效率,能够很好解决排气管路产生沉积物及氨泄漏等问题。
Description
技术领域
本发明属于一种氮氧化物抑制剂,具体涉及一种抑制压燃式发动机内氮氧化物的抑制剂。
背景技术
人类生命活动(如汽油和柴油等燃料燃烧)导致出现了大气污染,产生了大量的氮氧化物(NOx),大气中的氮氧化物能够与空气中的水结合最终转化为硝酸和硝酸盐,从而形成酸雨或者光化学烟雾,对人体健康和生态系统造成极大的危害,我国一直致力于解决酸雨对人类和生态环境造成的危害。NOx的主要成分是NO,NO还会造成人体中枢神经系统障碍,可导致高铁血红蛋白败血症、肺纤维化、牙齿酸蚀症。NO不稳定,在空气中很快转变为NO2,可与血液中血红蛋白结合,破坏血液的输氧作用,危害人体健康。此外,NO还是臭氧分解的催化剂,对高空的臭氧保护层具有破坏作用。随着人们对环境问题的日益重视,世界各国都对NOx的排放和治理提出了更高的要求。因此,有关NOx废气处理的研究具有十分重要的研究意义和应用前景,也一直是摆在我们面前的一个难题。
我国最近几年城市雾霾天气频发,严重影响城市生活秩序和人体健康,2014年1月4日,国家首次将雾霾天气纳入自然灾情进行通报,而氮氧化物、二氧化硫和可吸入颗粒物是雾霾的三大主要组成成分,目前我国对雾霾的治理手段尚处在深入研究阶段。
我国现有的产业现状和能源结构决定了氮氧化物的排放量一直居高不下,制造业、电力行业和交通运输业是中国氮氧化物的主要排放源,其中交通运输业氮氧化物排放量呈现逐年增长趋势,而电力行业如火力发电厂等作为我国的燃煤大户,其通过煤炭的直接燃烧产生了我国70%的氮氧化物排放量。2010年中国氮氧化物的排放量约是2000年的两倍;到2020年中国氮氧化物排放量超过15Mt。人类生产活动对生态环境已造成了极大的破坏,大气中氮氧化物污染物已对人类健康产生了严重的威胁,我国目前正面临着严峻的氮氧化物减排形势。
2018年10月26日,我国颁布实施了最新修订后的《中华人民共和国大气污染防治法》,其中重点强调了对氮氧化物的排放控制,规定燃煤电厂和其他燃煤单位应当采用清洁生产工艺,配套建设脱硝装置,或者采取技术改造等其他控制大气污染物排放的措施。钢铁、建材、有色金属、石油、化工等企业生产过程中排放氮氧化物的,应当采用清洁生产工艺,配套建设脱硝装置,或者采取技术改造等其他控制大气污染物排放的措施。国家鼓励上述单位采用先进的脱硝协同控制的技术和装置,减少大气污染物的排放。
随着我国压燃机排放法规愈加严格,法规中压燃机氮氧化物(NOx)排放限值越来越低,国-Ⅳ法规NOx限值为3.5g/(KW·H),国-Ⅴ标准中这一限值直接降至2.0g/(KW·H)。为了减少机动车尾气中NOx的排放量,人们展开了大量的研究,目前主要集中在对氮氧化物的催化还原研究。涉及NOx催化还原的催化剂的研究工作已有大量文献报道,例如使用含贵金属Pt、Rh、Pd的三效尾气催化剂,可以有效地将汽车尾气中76%的NOx转化,但无法在富氧条件下将NOx还原成N2,限制了其使用。80年代开始研究者采用NH3作为还原剂应用于燃煤锅炉中NOx的催化还原,初期认为在富氧条件下只有以NH3为还原剂才能将NOx转化为N2,直到1990年,Iwamoto小组和Held小组分别独立报道了有氧存在条件下Cu-ZSM-5分子筛催化剂上用烃类还原NO反应的催化过程,开辟了NOx催化还原的新途径。Gervasini和Wogerbaner也分别以C2H4和C3H6作为还原剂,对铂族贵金属催化剂催化还原NOx进行了详细研究,用烃类取代NH3作为还原剂,显示出极大的优越性。近年来使用乙醇催化还原NOx也是一个极具发展前景的研究课题,我国也有很多学者在NOx催化转化领域也做了很多有意义的研究工作,如包信和院士课题组研究了银催化剂用于氮氧化物的还原和分解,贺泓课题组研究了Ag/Al2O3、Ag-Pd/Al2O3催化剂选择性催化还原NOx,李雪辉课题组探索了以Cr-Mn复合氧化物催化剂用NH3催化还原NOx,杨栋课题组探索了以In/金属硫酸盐/TiO2催化剂用NH3催化还原NOx,童志权等研究了SO2对Mn-Cu-Ce/TiO2催化性能的影响,全燮制备了蜂窝状金属丝网的Pd/CeZr/TiO2/Al2O3催化剂用于还原NOx,万颖研究了O2在Cu-Al-MCM-41上NO的选择性还原作用,刘振宇利用V2O5/TiO2催化剂研究NH3催化还原NO过程的吸附与活化,李哲课题组利用ZSM-5型分子筛制备Mo-ZSM-5催化剂以用于NO催化反应机理的研究,李彩亭课题组也制备了分子筛型催化剂CuMn-ZSM-5和Ce2Fe/ACF催化剂并研究其对NO的催化活性,胡将军等人研究了CeO2-CoO/ACF低温SCR烟气的脱氮性能。上述催化剂的研究虽然取得了丰富的研究成果,却仍然存在稳定性差、催化活性温度范围窄、活性易受氧气和水等其他成分的影响以及价格昂贵等多方面问题。
目前解决压燃机中NOx排放的主要手段是采用优化缸内燃烧,并在压燃机排气系统加装选择性催化还原(selective catalystreduction,SCR)系统。SCR系统通常向排气管中喷射尿素,经过热解水解后,以氨作为还原剂在SCR催化剂表面将柴油机排气中的NOx还原为N2和水。但是尿素SCR系统也存在一些应用问题,如NOx低温转化效率低下,排气管路产生沉积物及氨泄漏等。
对于如何更高效稳定的除去废气中的NOx,如何有效减少大气污染物中氮氧化物的排放量,实现电力燃煤等企业生产活动中的高效脱硝,成为我国环境治理方面正面临的一个严峻考验,目前仍在进行大量的研究。
发明内容
本发明的目的就是为了解决机动车尾气氮氧化物的排放问题,而提供一种抑制压燃式发动机内氮氧化物的抑制剂,本发明的抑制剂特别适合发动机的减排,能够大大减少机动车尾气中排放的氮氧化物,具备清洁环保的特点。
为了实现上述目的,本发明提供了一种抑制压燃式发动机内氮氧化物的抑制剂,所述抑制剂按重量百分比计,包括以下组分:
多氮化合物40~30%;
尿素或三聚氰胺30~40%;
乙二醇20%;
助溶剂10%;
其中,所述多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物。
本发明提供的氮氧化物抑制剂,其中选择尿素或三聚氰胺与多氮化合物复配组成氮氧化物抑制剂,应用于发动机中能够起到很好的脱硝作用,大大减少了机动车尾气的氮氧化物排放量。尿素作为催化还原系统的主要物质,能够提供氨作为还原剂在SCR催化剂表面将柴油机排气中的NOx还原为N2和水,但是其也存在NOx低温转化效率低下,排气管路产生沉积物及氨泄漏等缺陷。而采用多氮化合物进行复配,能够很好解决这一缺陷。
尿素为无色或白色针状或棒状结晶体,为白色略带微红色固体颗粒,无臭无味,含氮量约为46.67%,密度1.335g/cm3,熔点132.7℃,溶于水和醇。其化学性质呈弱碱性,可与酸作用生成盐,有水解作用;在高温下可进行缩合反应,生成缩二脲、缩三脲和三聚氰酸;加热至160℃时分解,产生氨气同时变为异氰酸。因为在人尿中含有这种物质,所以取名尿素,是固体氮肥中含氮量最高的。而SCR系统中就是利用尿素经过热解水解后,能够释放出氨作为还原剂在SCR催化剂表面将柴油机排气中的NOx还原为N2和水,但是目前转化效率较低。
另外作为可替换的高含氮组合物三聚氰胺,其是一种含氮杂环有机物,分子式为C3H6N6,相对分子量:126.15,其分子结构如下:
三聚氰胺是性状为纯白色单斜棱晶体,不可燃,无味,低毒,密度1.573g/cm3(16℃),含氧量为68%,常压下的熔点为354℃,急剧加热则分解;快速加热升华,升华温度300℃。在水中溶解度随温度升高而增大,在20℃时,约为3.3g/L,溶于热水,可溶于多元醇等。其化学性质呈弱碱性(pH值=8),与盐酸、硫酸、硝酸、乙酸、草酸等都能形成三聚氰胺盐,在中性或微碱性情况下与甲醛缩合而成各种羟甲基三聚氰胺,但在微酸性(pH值5.5~6.5)中与羟甲基的衍生物进行缩聚反应而生成树脂产物。三聚氰胺是含氮最高的杂环有机化合物,和尿素具有相同的分子功能团—NH2,两者的物理性质相似,在燃烧过程中同样能够提供NH3源,实现氮氧化物的还原转化。
在体系内存在尿素或三聚氰胺的情况下,本发明创造性地以一种多氮化合物进行复配,所述多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物。该多氮化合物的氮含量较高,能够对催化还原过程起来促进作用,同时还能对氧化起到抑制作用。二者复配后可以在燃烧过程中对氮氧化物的产生起到很好的阻止作用同时还能促使产生的氮氧化物发生还原作用。这种体系的复配不仅本身不能氧化,而且对氧化有抑制作用,特别是在快速加热升华状态下对燃烧中间态的氮气和氧气,具有较高的阻止氧化能力。尿素或三聚氰胺在燃烧过程中,将快速高效分解为氨气、水和二氧化碳,其中氨气(NH3)作为还原剂,在尾气催化还原器的作用下能够促使氮氧化物(NOx)变成氮气(N2)与水(H2O)。
本发明的复配组合物能够起到互相补充和互相促进的作用,使空气在燃烧过程中氮气和氧气受到阻止氧化和还原氮气的作用。而乙二醇和增溶剂的添加可以将多氮化合物与尿素或三聚氰胺很好进行溶解,使各原料保证稳定的液体状态,更好的发挥复配组分的作用。
由于氮氧化物产生于燃烧过程而非燃料本身的组份,以发动机为代表的燃烧系统的氮氧化物排放问题的解决主要集中于燃烧之后的处理。本抑制剂配方从燃料的改性过程出发,将液态的氮氧化物抑制剂掺入液态燃料之中,通过燃烧器中的燃煤过程使其达到减少氮氧化物排放的目的。且所选择的溶剂和增溶剂均具有较高的闪点,可以用于汽油和柴油的添加。增溶剂的添加具有高效的油、醇、醚的亲合作用,使抑制剂能与汽油组份和柴油组份完全互溶,克服了应用上的困难。
进一步的是,所述邻苯二胺的纯度为99.5%以上。
进一步的是,所述亚硝酸钠的纯度为99%以上。
进一步的是,所述邻苯二胺与亚硝酸钠的摩尔比为1:1.2~1.5。
进一步的是,所述酸为浓硫酸,其质量分数为98%,所述酸的用量为邻苯二胺摩尔量的2.5倍。
进一步的是,所述重氮化和酯化反应的温度为75~82℃。
进一步的是,所述重氮化反应过程中缓慢将原料投入反应釜中。
进一步的是,所述助溶剂为乙醇胺与正丁醇的混合物。这两种助溶剂均具有很高的闪点。
与现有技术相比,本发明的有益效果如下:
本发明提供的氮氧化物抑制剂,含高氮组合物三聚氰胺或尿素以及一种多氮化合物,该多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化和酯化反应而得的产物。二者复配能够在燃烧过程中起到高效阻止氮氧化和高效催化氮还原的功能,两者相互促进,加大彼此的功能,更加有效地减少了燃烧引起的氮氧化物排放。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例对本发明进行具体描述,有必要指出的是,以下实施例仅仅用于对本发明进行解释和说明,并不用于限定本发明。本领域技术人员根据上述发明内容所做出的一些非本质的改进和调整,仍属于本发明的保护范围。
实施例1
一种氮氧化物抑制剂,其原料配方组分按照如下表1组成:
表1
其中助溶剂为乙醇胺与正丁醇按体积比1:1的混合物。
多氮化合物的制备方法如下:
在反应釜中先加入由邻苯二胺(99.5%)与98%浓硫酸配成的悬浮液(邻苯二胺与浓硫酸的摩尔比为1:2.5),搅拌均匀,控制瓶内温度为75~82℃,然后经漏斗缓慢滴加由亚硝酸钠(99%)与水制成的溶液,并使之剧烈机械搅拌,滴加时间为1.5h(邻苯二胺的用量为亚硝酸钠摩尔量的1.2~1.5倍),滴加完毕后继续搅拌反应20min,将所得沉淀物趁冷抽滤,并依次用工业乙醇和乙醚洗涤后,真空干燥一段时间,得到产物,产率90%以上。
制备过程中涉及的主要反应式如下(酯化反应为副反应,产物很少,可忽略):
对比例1
一种氮氧化物抑制剂,是将多氮化合物组分去除,抑制剂中三聚氰胺、乙二醇和助溶剂的配比为70:20:10。
对比例2
一种氮氧化物抑制剂,是将多氮化合物组分去除,抑制剂中尿素、乙二醇和助溶剂的配比为70:20:10。
对比例3
一种氮氧化物抑制剂,是将多氮化合物组分去除,抑制剂中尿素、三聚氰胺、乙二醇和助溶剂的配比为40:30:20:10。
实验例1
将表1中的各氮氧化物抑制剂(抑制剂1-5)和对比例1-3中的抑制剂分别用于发动机的燃烧脱硝试验,将抑制剂1-5分别添加到发动机燃烧室内进行燃烧,测试发动机在2400r/min负荷特性对应工况点的排放性能,发动机型号选用DK4A型科研用柴油机。抑制剂用量占车用燃料总重量的3‰,车用燃料选用0#柴油,对发动机尾气排放口的氮氧化物排放量进行实时监测,并与未添加抑制剂的试验进行对比。以抑制剂用量为3‰计,试验测得添加抑制剂后尾气中氮氧化物排放量的变化如表2所示:
表2
从表2可以看出,添加本发明的抑制剂后,柴油车尾气中氮氧化物的排放量均得到了较大幅度的下降。
Claims (4)
1.一种抑制压燃式发动机内氮氧化物的抑制剂,其特征在于,所述抑制剂按重量百分比计,包括以下组分:
多氮化合物30~40%;
尿素或三聚氰胺30~40%;
乙二醇20%;
助溶剂10%;
其中,所述多氮化合物为邻苯二胺和亚硝酸钠在酸性条件下发生重氮化反应而得到的苯并三氮唑产物,所述邻苯二胺与亚硝酸钠的摩尔比为1 .2~1 .5:1,所述酸为浓硫酸,其质量分数为98%,浓硫酸的用量为邻苯二胺摩尔量的2.5倍,所述重氮化反应的温度为75~82℃;所述助溶剂为乙醇胺与正丁醇按体积比1:1的混合物。
2.根据权利要求1所述的抑制压燃式发动机内氮氧化物的抑制剂,其特征在于,所述邻苯二胺的纯度为99.5%以上。
3.根据权利要求1所述的抑制压燃式发动机内氮氧化物的抑制剂,其特征在于,所述亚硝酸钠的纯度为99%以上。
4.根据权利要求1所述的抑制压燃式发动机内氮氧化物的抑制剂,其特征在于,反应过程中缓慢将原料投入反应釜中。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103949154A (zh) * | 2014-05-08 | 2014-07-30 | 夏光甫 | 汽车尾气排放净化处理液 |
CN106085673A (zh) * | 2016-06-30 | 2016-11-09 | 蓝星沈阳轻工机械设计研究所 | 一种环保型汽车发动机内部清洗剂 |
CN106674140A (zh) * | 2015-11-09 | 2017-05-17 | 宁夏际华环境安全科技有限公司 | 一种苯并三氮唑生产工艺 |
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