农业工程学报
農業工程學報
농업공정학보
2014年
9期
183-191
,共9页
李雁斌%徐莹%马隆龙%陈冠益%王铁军%张琦
李雁斌%徐瑩%馬隆龍%陳冠益%王鐵軍%張琦
리안빈%서형%마륭룡%진관익%왕철군%장기
生物质%燃料%催化剂%生物油%加氢%原位加氢%加氢酯化%分段加氢
生物質%燃料%催化劑%生物油%加氫%原位加氫%加氫酯化%分段加氫
생물질%연료%최화제%생물유%가경%원위가경%가경지화%분단가경
biomass%fuels%catalysts%bio-oil%hydroprocessing%in-situ hydrogenation%hydrogenation-esterification%multi-stage hydrogenation
该文针对近年来生物油加氢精制方面的研究进行了探讨,介绍了加氢精制原理,总结了国内外生物油加氢精制工艺研究取得的进展,包括催化剂性能,反应机理和工艺路线的创新与研究。详细说明了分段加氢、加氢酯化、原位加氢等工艺流程的创新和缺点;传统加氢催化剂:如NiMo、CoMo催化剂,以及Ru、Pt、Pd、Rh等贵金属催化剂,在加氢工艺中的特点,前者价格便宜但效果较差,失活现象更严重;后者具有更强的反应活性,但价格昂贵且须在反应后回收。同时,该文对模型化合物、生物油部分相以及生物油真实体系的加氢试验分别进行了详述。最后,针对目前研究中遇到的无法长时间连续运行,成本过高工艺复杂以及缺乏合适催化剂等问题,预测了该技术未来加强催化剂抗结焦能力和低温活性,简化工艺流程并降低成本的研究方向。
該文針對近年來生物油加氫精製方麵的研究進行瞭探討,介紹瞭加氫精製原理,總結瞭國內外生物油加氫精製工藝研究取得的進展,包括催化劑性能,反應機理和工藝路線的創新與研究。詳細說明瞭分段加氫、加氫酯化、原位加氫等工藝流程的創新和缺點;傳統加氫催化劑:如NiMo、CoMo催化劑,以及Ru、Pt、Pd、Rh等貴金屬催化劑,在加氫工藝中的特點,前者價格便宜但效果較差,失活現象更嚴重;後者具有更彊的反應活性,但價格昂貴且鬚在反應後迴收。同時,該文對模型化閤物、生物油部分相以及生物油真實體繫的加氫試驗分彆進行瞭詳述。最後,針對目前研究中遇到的無法長時間連續運行,成本過高工藝複雜以及缺乏閤適催化劑等問題,預測瞭該技術未來加彊催化劑抗結焦能力和低溫活性,簡化工藝流程併降低成本的研究方嚮。
해문침대근년래생물유가경정제방면적연구진행료탐토,개소료가경정제원리,총결료국내외생물유가경정제공예연구취득적진전,포괄최화제성능,반응궤리화공예로선적창신여연구。상세설명료분단가경、가경지화、원위가경등공예류정적창신화결점;전통가경최화제:여NiMo、CoMo최화제,이급Ru、Pt、Pd、Rh등귀금속최화제,재가경공예중적특점,전자개격편의단효과교차,실활현상경엄중;후자구유경강적반응활성,단개격앙귀차수재반응후회수。동시,해문대모형화합물、생물유부분상이급생물유진실체계적가경시험분별진행료상술。최후,침대목전연구중우도적무법장시간련속운행,성본과고공예복잡이급결핍합괄최화제등문제,예측료해기술미래가강최화제항결초능력화저온활성,간화공예류정병강저성본적연구방향。
This paper reviews catalytic the hydrotreatment upgrading technology of biomass-derive d oil. It provides an overview of the reaction mechanism and the condition of the operation, then summarizes the process of bio-oil hydrogenation at home and abroad. Detailed comparison of various technological processes such as multi-stage hydrogenation, hydrogenation-esterification, in-situ hydrogenation, etc. are made. Multi-stage hydrogenation, which separates the hydroprocessing into two stages (mild hydrotreating and deep hydrotreating), can improve the selectivity of products, moreover avoiding an economic penalty by using less hydrogen. Hydrogenation-esterification combines hydrogenation and esterfication to establish a new upgrading method. Through the method, unstable compounds of biomass-derived oil can be converted more effectively. In-situ hydrogenation, which leads to reducing the cost and enhancing the safety, uses other reagents as resources of hydrogen, simultaneously generating hydrogen and hydrotreating in one reaction system to replace transporting hydrogen from outside. The reasonable optimization of the process routes benefits improving product quality. Research in this area is expected to become a main research direction for bio-oil hydrotreatment. Experimental data were collected about various model compounds including cresol, phenol, guaiacol, acetone, aldehyde, etc. and bio-oil from the literature in the field of this study. Also, a test is reviewed about a range of catalysts including the conventional and novel types of supported noble metal and transition metal catalytic materials and their performance in bio-oil hydroprocessing. Conventional catalysts, such as NiMo and CoMo, have economic advantages; the reaction using noble metal catalysts have better reactivity; amorphous catalysts have both advantages of these two types of catalysts, but amorphous catalysts have terrible thermal stability, and can only be used below 473 K; then, zeolite catalysts and mesoporous catalysts exhibit magnificent effects on reducing oxygen content and moisture content in bio-oil, but still can’t avoid coking in the reaction. Unfortunately, researchers have not found any catalyst's hydrothermal stability good enough to improve the effect of reaction continuously (more than seven days), Deactivation and coking of catalysts are still main problems. Obviously, further study is required to prepare these catalysts which have better durability. Finally, this article gives information about the problems which researchers may meet, including equipment plugging, catalyst deactivation, and high operation costs etc., and predicts that the future research directions of this technology is to optimize the hydrogenation process, and to develop new types of composite catalysts which exhibit excellent activity at low temperature and anti-coking performance. The technology development is still on the way but can play a significant role in supplying increasingly expensive petroleum.