01项目简介
随着我国社会经济的发展，工业化、城市化进程步伐不断加快，环境保护，城市可持续发展成为人们共同关注的问题，由此带来的大气污染物的治理问题也越来越受到重视。甲醛是室内最严重的污染物之一，具有非常高的毒性，高居我国有毒化学品优先控制名单上的第二位，是日常起居中危害人们健康的一大杀手。挥发性有机物(VOCs)作为重点的大气污染物之一，是形成复合型大气污染、二次有机气溶胶(SOA)的主要元凶，严重影响大气能见度，形成光化学烟雾、酸雨等，其中芳香族VOCs包括BTX(苯、甲苯和邻二甲苯)、氯苯等，对人类具有高毒性和致癌、致畸作用。
催化氧化技术是公认的比较理想的消除甲醛及VOCs的方法，利用催化氧化反应可以在室温下将甲醛转化为无毒的CO2和H2O；在较低温度下将工业尾气中的VOCs处理至排放标准以下。催化氧化技术的优点是：相对成本低、处理废气效率高、处理量大、处理完全、不存在吸附饱和以及没有二次污染等问题，对低浓度和高浓度甲醛的处理都特别有效，是最有应用前景的废气处理技术。截止目前，课题组针对甲醛及VOCs催化氧化项目的研究工作已经陆续开展了六年，在相关领域也取得了众多突破性的研究成果。相关研究内容已申请多项中国发明专利对知识产权进行了有效保护。
02项目特色
目前已开发出具有完全自主知识产权的室温甲醛催化氧化关键技术。目前与相关企业正在合作，在空气净化器和车载空气滤网中加装除甲醛催化剂后，可以实现室内和车内甲醛和VOCs气体的完全脱除。在国际上首次实现了室温催化氧化除甲醛催化剂的商品化生产和应用。也正在与相关制药企业合作，在尾气处理时加装催化氧化装置，实现工厂尾气的彻底净化。
03市场应用前景
甲醛的广泛使用以及其毒性和挥发性，已成为建筑材料和气密性建筑中最常见的有害室内空气污染物之一。随着人们环保意识的增强，越来越多的商家看到了空气净化的商机，目前市面上有很多甲醛净化器在销售，很多商家宣称自己的净化器对甲醛的去除率达到了99%以上，然而权威检测机构对市面上的这些净化器调查的结果却发现多数声称具有除甲醛功能的产品都有功能夸大之嫌，即使产品有一定效果，也只是起到很弱的辅助作用。该项目催化剂在兼顾性能和成本的情况下，在国际上率先实现了真正的催化氧化消除甲醛，其应用前景非常广泛。
近些年随着我国工业快速发展，尾气的污染问题越发严重，工业废气污染治理迫在眉睫。各种废气弥漫在天空的时候，我们所需的空气质量也在下降，呼吸上新鲜空气，是我们生而为人最基础的需求。目前多数企业采用活性炭吸附或者蓄热燃烧处理工业尾气，能耗高，投入大，本课题组开发的催化氧化技术能在较低温度下将VOCs充分净化，能耗低，安全系数高，是最具潜力的VOCs处理方式之一。随着技术研究的日益成熟，催化氧化法去除VOCs应用领域越发广阔。
04应用技术成果
通过实际27m3标准玻璃实验舱的测试得到以下结论：从市场上购买的四种除甲醛催化剂，在测试的1小时内都无法将甲醛降低到国家标准值以下。而南开大学研发的除甲醛催化剂效果显著，在10分钟左右就能让甲醛浓度大幅下降；12分钟就能将甲醛降低到国家标准值以下，1小时内几乎将甲醛完全消除。
聚氯乙烯根据生产过程中原料来源和生产工艺路线的不同，主要可以分为乙炔法和乙烯法两类。乙烯法工艺路线包括以石油乙烯为原料的乙烯氧氯化法生产1，2-二氯乙烷（EDC），EDC裂解氯乙烯单体（VCM）进而聚合成聚氯乙烯（PVC）；以及国内少量通过进口1，2-二氯乙烷（EDC）、氯乙烯单体（VCM）生产聚氯氯乙烯（PVC）。乙炔法聚氯乙烯是指以电石为原料与水反应生成乙炔，乙炔与氯化氢在汞触媒作用下生成氯乙烯单体，再通过聚合生成聚氯乙烯的生产方法。在我国由于特殊的能源及资源结构，乙炔法聚氯乙烯的生产占据绝对主导地位并在可预见的时期内难以撼动。
乙炔法氯乙烯生产中几乎全部使用汞触媒，该触媒系以活性炭为载体，浸渍吸附10～12%左右的氯化汞制备而成的。触媒并不参加反应，但由于汞升华及触媒中毒等原因会引起触媒活性下降，下降到一定程度以后，触媒就要被更换，失活的汞触媒成为废汞触媒。乙炔法聚氯乙烯行业已成为中国汞用量最大的行业。尽管在后续的含汞废物收集处理方面企业已采取了有效的防控措施，如采用活性炭吸附蒸发的汞，将废弃汞触媒送有资质的企业回收处理，对含汞废酸进行集中收集处理，对含汞废水进行循环利用等等，但生产过程中仍有一定量的汞排放进入环境。因此，有效解决乙炔法聚氯乙烯行业汞消耗量大及汞排放造成的汞污染问题，是行业企业面临的来自环境保护方面的严峻考验。
为了解决上述问题，开发出新型的无汞触媒取代当前使用的含汞触媒是最终解决方案。
目前，汞污染作为一个新的全球环境问题受到国际社会的高度重视。联合国环境规划署（UNEP）正在研究制定限制汞流通和实施汞削减的国际公约。随着国际方面对制定具有法律约束力的国际文书的呼声越来越高，我国坚持自愿性立场所面临的国际压力也越来越大。为积极应对汞对乙炔法聚氯乙烯行业发展带来的巨大挑战，确保我国乙炔法聚氯乙烯和氯碱产业的安全发展，中国政府有关部门积极应对，有序推进汞减排。2009底，国家工信部、石油和化学工业协会、中国氯碱工业协会、中国化工环保协会共同起草了《关于加强聚氯乙烯行业汞污染防治的指导意见》。
该意见提出了聚氯乙烯行业汞污染防治的工作目标：2012 年，实现我国电石法聚氯乙烯行业低汞触媒普及率达到50%，并全部合理回收废汞触媒；到2015 年，全行业全部使用低汞触媒，废汞触媒回收率达到100%。由此可见，面对国内外多重压力，尽快开发出能够彻底替代高汞触媒的新型高效低汞触媒已经迫在眉睫，低汞触媒取代高汞触媒已经进行到实质阶段。在此情况下，南开大学课题组在多年技术储备及开发无汞触媒的基础上，与国内重要PVC生产企业合作，工业放大制备的低汞触媒由合作单位PVC生产企业进行了工业试用，至今触媒使用时间已超过8000小时，目前仍在使用中。触媒表现出极高的催化活性，催化剂性能全面达到国家HG/T
4192-2011 氯乙烯合成用低汞触媒化工行业标准要求。
该项技术已获得多项国家发明专利授权。
English version:
Polyvinyl chloride (PVC) can be divided into acetylene method and ethylene method according to the source of raw materials and production process. The ethylene method means ethylene oxychlorination using petroleum ethylene as raw material to produce 1,2-dichloroethane (EDC). EDC cracks vinyl chloride monomer (VCM) and polymerizes it into polyvinyl chloride (PVC). However, this method is rarely used domesticly due to import restrictions. Acetylene method refers to the reaction between calcium carbide and water to produce acetylene, acetylene and hydrogen chloride to generate vinyl chloride monomer under the action of mercury catalyst, and then to produce PVC through polymerization. Because of the special energy and resource structure in China, the production of PVC by acetylene process occupies an absolute dominant position and is difficult to be shaken in the short term.
In acetylene method, mercury containing catalyst is used widely, which is prepared with activated carbon as the carrier and loaded with about 10 - 12% mercury chloride. The catalyst does not participate in the reaction, but its activity will decrease for mercury sublimation and poisoning, and finally becomes a waste mercury catalyst. At present, the production of PVC by acetylene method is the industry with the largest mercury consumption in China. Even if enterprises have taken effective measures to deal with mercury-containing wastes, such as using activated carbon to adsorb evaporated mercury, sending waste mercury catalysts to relevant enterprises for recycling, centralized treatment of mercury-containing waste acids recycling of mercury-containing wastewater and so on. A certain amount of mercury is still discharged into the environment during the whole process. As a result, it is a severe test for the industry to effectively solve the problem of high mercury consumption and mercury pollution in acetylene method.
Nowadays, mercury pollution has drawn great attention from the international community. The United Nations Environment Programme (UNEP) is working on an international convention to restrict the flow and implement reductions in mercury. With more and more international calls for the development of a legally binding international instrument, China's insistence on the voluntary position is facing increasing international pressure. In order to actively respond to international restrictions on mercury and ensure the safe development of China's acetylene production PVC and chlor-alkali industries, the relevant departments of the Chinese government actively respond and promote the reduction of mercury emissions in an orderly manner. At the end of 2009, the Ministry of Industry and Information Technology, the Petroleum and Chemical Industry Association, the China Chlor-Alkali Industry Association and the China Chemical Industry Environmental Protection Association jointly drafted the document, 《Guidance on Strengthening the Prevention and Control of Mercury Pollution in the PVC industry》.
The document put forward the work objectives of mercury pollution prevention and control in the PVC industry: in 2012, the utilization rate of low mercury catalysts reached 50%, and all of them should be reasonably recycled; by 2015, the entire industries used low mercury catalysts with a recovery rate of 100%.Obviously, in the face of multiple pressures at home and abroad, it is urgent to develop a new low mercury catalyst that can completely replace the high mercury catalyst. Under this circumstance, the research team of Nankai University, relying on years of technical reserve and mercury-free catalyst research, has cooperated with important domestic PVC manufacturers to develop low-mercury catalysts that have been used in industrial trials. So far, the catalyst has been used for more than 8,000 hours and is still in use. The catalyst shows extremely high catalytic activity, and the catalyst performance fully meets the requirements of national standards: HG/T 4192-2011, for low mercury catalyst in PVC industry.
The technology has been applied for national invention patent.
聚氯乙烯根据生产过程中原料来源和生产工艺路线的不同，主要可以分为乙炔法和乙烯法两类。乙烯法工艺路线包括以石油乙烯为原料的乙烯氧氯化法生产1，2-二氯乙烷（EDC），EDC裂解氯乙烯单体（VCM）进而聚合成聚氯乙烯（PVC）；以及国内少量通过进口1，2-二氯乙烷（EDC）、氯乙烯单体（VCM）生产聚氯氯乙烯（PVC）。乙炔法聚氯乙烯是指以电石为原料与水反应生成乙炔，乙炔与氯化氢在汞触媒作用下生成氯乙烯单体，再通过聚合生成聚氯乙烯的生产方法。在我国由于特殊的能源及资源结构，乙炔法聚氯乙烯的生产占据绝对主导地位并在可预见的时期内难以撼动。
乙炔法氯乙烯生产中几乎全部使用汞触媒，该触媒系以活性炭为载体，浸渍吸附10～12%左右的氯化汞制备而成的。触媒并不参加反应，但由于汞升华及触媒中毒等原因会引起触媒活性下降，下降到一定程度以后，触媒就要被更换，失活的汞触媒成为废汞触媒。乙炔法聚氯乙烯行业已成为中国汞用量最大的行业。尽管在后续的含汞废物收集处理方面企业已采取了有效的防控措施，如采用活性炭吸附蒸发的汞，将废弃汞触媒送有资质的企业回收处理，对含汞废酸进行集中收集处理，对含汞废水进行循环利用等等，但生产过程中仍有一定量的汞排放进入环境。因此，有效解决乙炔法聚氯乙烯行业汞消耗量大及汞排放造成的汞污染问题，是行业企业面临的来自环境保护方面的严峻考验。
为了解决上述问题，开发出新型的无汞触媒取代当前使用的含汞触媒是最终解决方案。
目前，汞污染作为一个新的全球环境问题受到国际社会的高度重视。联合国环境规划署（UNEP）正在研究制定限制汞流通和实施汞削减的国际公约。随着国际方面对制定具有法律约束力的国际文书的呼声越来越高，我国坚持自愿性立场所面临的国际压力也越来越大。为积极应对汞对乙炔法聚氯乙烯行业发展带来的巨大挑战，确保我国乙炔法聚氯乙烯和氯碱产业的安全发展，中国政府有关部门积极应对，有序推进汞减排。2009底，国家工信部、石油和化学工业协会、中国氯碱工业协会、中国化工环保协会共同起草了《关于加强聚氯乙烯行业汞污染防治的指导意见》。
该意见提出了聚氯乙烯行业汞污染防治的工作目标：2012 年，实现我国电石法聚氯乙烯行业低汞触媒普及率达到50%，并全部合理回收废汞触媒；到2015 年，全行业全部使用低汞触媒，废汞触媒回收率达到100%。由此可见，面对国内外多重压力，尽快开发出能够彻底替代高汞触媒的新型高效低汞触媒已经迫在眉睫，低汞触媒取代高汞触媒已经进行到实质阶段。在此情况下，南开大学课题组在多年技术储备及开发无汞触媒的基础上，与国内重要PVC生产企业合作，工业放大制备的低汞触媒由合作单位PVC生产企业进行了工业试用，至今触媒使用时间已超过8000小时，目前仍在使用中。触媒表现出极高的催化活性，催化剂性能全面达到国家HG/T
4192-2011 氯乙烯合成用低汞触媒化工行业标准要求。
该项技术已申请国家发明专利。
English version:
Polyvinyl chloride (PVC) can be divided into acetylene method and ethylene method according to the source of raw materials and production process. The ethylene method means ethylene oxychlorination using petroleum ethylene as raw material to produce 1,2-dichloroethane (EDC). EDC cracks vinyl chloride monomer (VCM) and polymerizes it into polyvinyl chloride (PVC). However, this method is rarely used domesticly due to import restrictions. Acetylene method refers to the reaction between calcium carbide and water to produce acetylene, acetylene and hydrogen chloride to generate vinyl chloride monomer under the action of mercury catalyst, and then to produce PVC through polymerization. Because of the special energy and resource structure in China, the production of PVC by acetylene process occupies an absolute dominant position and is difficult to be shaken in the short term.
In acetylene method, mercury containing catalyst is used widely, which is prepared with activated carbon as the carrier and loaded with about 10 - 12% mercury chloride. The catalyst does not participate in the reaction, but its activity will decrease for mercury sublimation and poisoning, and finally becomes a waste mercury catalyst. At present, the production of PVC by acetylene method is the industry with the largest mercury consumption in China. Even if enterprises have taken effective measures to deal with mercury-containing wastes, such as using activated carbon to adsorb evaporated mercury, sending waste mercury catalysts to relevant enterprises for recycling, centralized treatment of mercury-containing waste acids recycling of mercury-containing wastewater and so on. A certain amount of mercury is still discharged into the environment during the whole process. As a result, it is a severe test for the industry to effectively solve the problem of high mercury consumption and mercury pollution in acetylene method.
Nowadays, mercury pollution has drawn great attention from the international community. The United Nations Environment Programme (UNEP) is working on an international convention to restrict the flow and implement reductions in mercury. With more and more international calls for the development of a legally binding international instrument, China's insistence on the voluntary position is facing increasing international pressure. In order to actively respond to international restrictions on mercury and ensure the safe development of China's acetylene production PVC and chlor-alkali industries, the relevant departments of the Chinese government actively respond and promote the reduction of mercury emissions in an orderly manner. At the end of 2009, the Ministry of Industry and Information Technology, the Petroleum and Chemical Industry Association, the China Chlor-Alkali Industry Association and the China Chemical Industry Environmental Protection Association jointly drafted the document, 《Guidance on Strengthening the Prevention and Control of Mercury Pollution in the PVC industry》.
The document put forward the work objectives of mercury pollution prevention and control in the PVC industry: in 2012, the utilization rate of low mercury catalysts reached 50%, and all of them should be reasonably recycled; by 2015, the entire industries used low mercury catalysts with a recovery rate of 100%.Obviously, in the face of multiple pressures at home and abroad, it is urgent to develop a new low mercury catalyst that can completely replace the high mercury catalyst. Under this circumstance, the research team of Nankai University, relying on years of technical reserve and mercury-free catalyst research, has cooperated with important domestic PVC manufacturers to develop low-mercury catalysts that have been used in industrial trials. So far, the catalyst has been used for more than 8,000 hours and is still in use. The catalyst shows extremely high catalytic activity, and the catalyst performance fully meets the requirements of national standards: HG/T 4192-2011, for low mercury catalyst in PVC industry.
The technology has been applied for national invention patent.
01项目简介
南开大学李伟课题组世界首创植物油二代生物航煤催化剂及催化工艺技术，致力于生产由蓖麻油、棕榈油、亚麻芥油、转基因植物油、废弃脂肪酸等油脂加氢制备系列生物燃料，包括车用汽油、航空汽油、航空煤油、车用柴油及船用燃料等。
02 项目特色
南开大学自主开发的“生物航煤”，具有自主知识产权，授权十几项中国专利、两项美国等发明专利，产品符合3号喷气燃料、ASTM D7566等国内外相关标准，冰点低于零下60 ℃，磨痕直径0.5WSD/mm，烟点大于50mm，不含硫、磷、重金属、芳烃及杂质，燃烧无黑烟，能有效减少发动机腐蚀和磨损，大幅降低PM2.5污染，实现全生命周期二氧化碳零排放，比传统石化航油具有更好的清洁性、燃烧性、润滑性和低温流动性，对航空业节省燃油、减排降霾有重要作用，是现阶段绿色航空燃料的首选，更是我们抓住“碳战”机遇、引领全球生物燃料发展的先锋。
03市场应用前景
2021年3月15日习近平主持召开中央财经委员会第九次会议，强调推动平台经济规范健康持续发展，把碳达峰、碳中和纳入生态文明建设整体布局。可再生能源（生物燃料）被列入十四五规划国家重点研发技术指南，生物航煤的应用大势所趋。据国际民航组织（ICAO）预测，到2025年全球生物航煤需要5000万吨，2035年全球生物航煤需要1.35亿吨，2045年需要1.58亿吨。对于中国来说，未来中国航空燃油的30%（约1200万吨）要打上“生物质标签”，如果按“50%生物质航油：50%化石航油”掺混，需要600万吨“纯”生物质航油，总产值达数千亿元，市场前景广阔。
04应用技术成果
本项目组已自主开发出具国际领先水平的植物油生物航煤加氢催化剂，以天津蓖能科技有限公司为载体平台进行产业化工业放大，并成功完成了中试2000小时稳定性试验。产品样品经中石化石科院、解放军空军油料所等权威机构检测，全项达标，对比石油基航煤和一代生物燃料具有更加优异的燃烧性，低温流动性，抗腐蚀性，氧化安定性等。本项目拥有十三项中国授权发明专利，两项美国授权发明专利，另外还有十几项中国、东南亚、欧洲专利正在申请，形成了完整体系的专利保护群，从催化剂、工艺以及应用等各个方面拥有完整的专利布局。目前正在建设万吨生物航煤示范生产装置，完成中国首台套和适航认证，未来建设50万吨/年、100万吨/年的生物基燃料项目，以南开大学的技术优势引领地方经产业技术，带动地方经济发展，形成绿色循环的可持续性产业链，未来将以更好的经济效益和社会效益回报社会。
非晶态合金加氢催化剂项目是我组近年来开展的重大项目之一，自1998年正式立项以来，在国家“十五”科技攻关及天津市科委重大攻关项目支持下，前后共投入近五百万元的研发经费，数十位博、硕士生进行了全面、系统、深入的持续性研究，发表文章40余篇，申请国内外专利20余项，并通过了天津市科委主持下的成果鉴定，鉴定等级为：国际领先。近年来，经过不懈努力，并且在化工生产行业诸多合作企业的大力配合下，终于在2007年成功实现催化剂工业化生产，建成了100吨/年的催化剂生产装置。并在部分加氢生产企业中进行了应用，开创了世界范围内化学法生产非晶态合金催化剂的先河，与国内闵恩泽的物理法制备非晶态合金催化剂形成了优势互补，共同为全球化工加氢行业镍系催化剂的更新换代作出了贡献。目前该催化剂正处于全面推广阶段，诚挚欢迎业内有识之士来电来函洽谈合作事宜。
非晶态合金催化剂简介：
非晶态合金是一类原子排列具有长程无序短程有序特点的材料，其具有优良的物理、化学和力学性能，已成为一种技术潜力很大的新型材料。非晶态合金作为催化剂的研究自二十世纪八十年代以来一直是催化学科研究的热点问题之一，大量研究成果见诸于报道，但由于种种原因，其工业化进程一直比较缓慢，我组在充分把握当前科研前沿的基础上，时刻以非晶态合金催化剂的产业化为根本目标，不断开拓创新，开发出了粉末诱导化学镀法制备负载型非晶态合金催化剂的新方法，进而成功实现了催化剂生产的工业化，并在多个加氢领域中得到应用及试用。如，葡萄糖类加氢，硝基苯类加氢，烯烃，炔烃类加氢，肟基类加氢，腈类加氢等等。与常规的加氢催化剂骨架镍相比，非晶态合金催化剂具有安全不着火，绿色环保，活性高，成本低等优点，受到广大用户一致好评。
English version:
The amorphous alloy hydrogenation catalyst project is one of the major projects of our team in recent years. Since the formal establishment of the project in 1998, with the support of the national "Tenth Five-Year" scientific and technological research and the projects of the Tianjin Municipal Science and Technology Commission, a total of nearly 5 million yuan has been invested. During this period, dozens of PhD and master students conducted comprehensive, systematic and in-depth research, published more than 40 articles, and applied for more than 20 patents at home and abroad. The project passed the achievement appraisal of Tianjin Science and Technology Commission, and the appraisal level is: international leading. In recent years, our group successfully accomplished the industrial production of catalysts in 2007, and built a catalyst production facility. of 100 tons per year through unremitting efforts and the cooperation with many enterprises in the chemical industry. Hydrogenation catalysts have been applied in some enterprises, creating a precedent for the chemical production of amorphous alloy catalysts worldwide. At the same time, it is complementary to the amorphous alloy catalysts prepared by Min Enze's physical method in China and contributes to the upgrading of nickel-based catalysts in the global chemical hydrogenation industry. At present, the catalyst is in the stage of comprehensive promotion. Our group sincerely welcomes industry insiders to discuss cooperation matters.
Introduction of amorphous alloy catalyst:
Amorphous alloys are a class of materials with long-range disordered and short-range ordered atomic arrangements, which shows excellent physical, chemical and mechanical properties. Amorphous alloys as catalysts have been one of the hot topics in the field of catalysis since the 1980s.
Neverthless, industrialization has been slow for a variety of reasons. On the basis of fully grasping the current scientific frontiers, our team has developed a new method for preparing supported amorphous alloy catalysts by powder-induced electroless plating method to industrialize amorphous alloy catalysts. This method has been applied in multiple hydrogenation fields, such as hydrogenation of glucose, nitrobenzene, alkene, alkyne, oxime, nitrile and so on.
Amorphous alloy catalysts have the advantages of safety, non-flammability, environmental protection, high activity, and low cost, compared with conventional nickel-based catalysts. Therefore, the catalysts have been well received by the majority of users.
二甲醚亦称甲醚，英文名称为：Dimethyl ether; Methyl ether(简称DME)。二甲醚的用途很广，主要用于医药、染料、农药的生产以及化工生产中的萃取剂、烷基化剂和卤化剂等，是一个非常重要的化工原料。
使用对环境无害的制冷剂取代氟利昂已势在必行，自喷式日用化学品(如气溶胶喷发胶等)所用的气雾推进剂氯氟烃行将被淘汰。由于二甲醚的性质与氟利昂很相似，国际上已大量采用其作为氟利昂的替代品，它作为气雾剂可用于定型发胶、摩丝、空气清新剂、杀虫剂、汽车喷漆、涂膜和抛光剂、防锈剂、萃取剂，高浓度二甲醚可用于麻醉剂。作为化工原料，二甲醚羰基化可制醋酸甲酯、醋酐；作为甲基化剂用于制备农药、染料和医药，也可以用作溶剂。燃料级二甲醚可用作城市煤气(调峰)、汽车燃料、二甲醚液化气及配制醇--醚燃料。二甲醚在西欧各国已是民用气溶胶制品中必不可少的氟氯烃替代物，单其一项的用量就达1.5万吨／年。我国对二甲醚产品的需求量也在不断增加。近来发现，少量二甲醚即可以将液化石油气中难以挥发利用的C5、C6组分与易挥发组分C3、C4均匀混合，从而充分利用全部液化石油气，彻底解决民用气残留液问题。
南开大学研制的NK-40新型催化剂，低温、高空速的反应条件下，甲醇转化率高，二甲醚的选择性达到100%。新的二甲醚工艺技术与国内其它的气相法工艺相比，由于反应温度大大降低，从而大幅度降低设备投资，更节省能量消耗，反应产物二甲醚纯度非常高，将可直接用于硫酸二甲酯生产并可直接用于液化石油气的添加剂，具有先进性和良好的推广应用前景。该项目获得了天津市科委重大攻关项目支持。
由于二甲醚是一种绿色化学产品，用于硫酸二甲酯生产中可以解决原工艺中的腐蚀和污染问题并节省投资；用于液化石油气中可解决大量废气的利用，因此，新工艺技术具有良好的经济和社会效益。
English Version:
Dimethyl ether is a very important chemical raw material, mainly used in the production of medicines, dyes and pesticides, as well as extractants, alkylating agents and halogenating agents in the chemical industry. People are studying environmentally friendly refrigerants to replace Freon, and the aerosol propellant chlorofluorocarbons used in self-spraying household chemicals such as aerosol hairsprays will be eliminated. Due to the similar properties to Freon, a large amount of dimethyl ether has been adopted internationally as a substitute for Freon. Fuel grade dimethyl ether can be used as urban gas (peak-regulating), automobile fuel, liquid dimethyl ether gas and alcohol-ether fuel. Dimethyl ether is already an indispensable HCFC substitute in civil aerosol products in Western European countries, with the consumption of one item alone reaching 15000 tons per year. China's demand for dimethyl ether products is also increasing. Recently, it has been found that a small amount of dimethyl ether can uniformly mix C5 and C6 components that are difficult to use in liquefied petroleum gas with volatile components C3 and C4, so as to make full use of all liquefied petroleum gas and completely solve the problem of residual liquid in civil gas.
The new NK-40 catalyst developed by Nankai University has a high methanol conversion rate and a dimethyl ether selectivity of 100% under low temperature and high space velocity. Compared with other domestic gas phase process, the new dimethyl ether process reduces the reaction temperature greatly, thereby reducing the equipment investment. High-purity dimethyl ether can be directly used in the production of dimethyl sulfate, which has a good application prospect. The project has received strong support from Tianjin Science and Technology Commission.
N，N-二甲基苯胺（DMA）主要用于三苯甲基甲烷类染料生产，还可作为溶剂、炸药、医药等原料，也用于生产碱性嫩黄素O；碱性紫5BN、碱性艳兰RB、阳离子红2BL等，也用于生产碱性染料中间体四甲基米氏酮等。我国生产的DMA除供国内消费外，每年有一定量出口。DMA的主要消费部门是染料工业和香料工业。由于近年来碱性嫩黄、碱性紫等品种销路趋好，DMA消费有所上升。
在香料工业中，DMA主要用于香兰素生产中。香兰素广泛用做定香剂、变味剂和调和剂的主要原料，也是有机合成原料和某些医药中间体。随着人民生活水平的提高，对食品的需求已从温饱型向营养型、高档次转化，从简单化向高、精细发展，因而香兰素在国内用量会逐年增加。此外，香兰素出口前景良好。由此可见，DMA在香料工业中呈上升趋势。
南开大学针对国内DMA生产工艺的落后现状，经多年开发研究，成功地开发了常压、气相、连续合成DMA的新工艺。该新工艺克服了现行液相法的全部缺点，成为目前国内第一个汽相法生产DMA的技术,该成果获得天津市2006年度技术发明二等奖。
与液相法比较，气相法具有如下优势：
（1） 工艺流程短，设备投资与操作费用大大降低。
（2） 苯胺生成二甲基苯胺接近完全转化。
（3） 气相法副产物少。
（4） 原料消耗小。
（5） 气相法全仪表操作，节省人力。
（6） 气相法不用酸催化剂，无污染。而国内液相法，以浓硫酸为催化剂，污染严重，解决污染需较大投资。
（7） 气相法产品质量好，外观为无色-苍黄色。
English version:
N,N-Dimethylaniline (DMA) is mainly used for the production of trityl methane dyes, the production of alkaline flavin O, basic violet 5BN, alkali Sex brilliant blue RB, cationic red 2BL, the production of basic dye intermediate tetramethyl Michler's ketone. and can also be used as raw materials for solvents, explosives, medicines. Except for domestic consumption, DMA produced in my country has a certain amount of export every year. In recent years, sales of various downstream products have increased, and DMA consumption has also increased.
In the perfume industry, DMA is mainly used in the production of vanillin. Vanillin is widely used as the main raw material for flavoring agents, flavor-changing agents and blending agents, as well as organic synthetic raw materials and certain pharmaceutical intermediates. With the improvement of living standard, people's demand for food has been transformed from subsistence to nutrition and high-grade, thus the domestic consumption of vanillin will increase year by year. At the same time, the export prospect of vanillin is broad. It can be seen that DMA is on the rise in the spice industry.
In response to the backward status of the domestic DMA production process, Nankai University has successfully developed a new process of atmospheric pressure, gas phase and continuous synthesis of DMA after years of development and research. This new technology overcomes all the shortcomings of the current liquid phase method and becomes the first domestic technology to produce DMA by vapor phase method. This achievement won the second prize of Tianjin 2006 Technical Invention.
The gas phase method has the following advantages, compared with the liquid phase method:
(1) Short process flow, low costs of equipment investment and operating;
(2) Conversion and selectivity rate close to 100%;
(3) Less by-products;
(4) Low raw material consumption;
(5) Full instrument operation to save manpower;
(6) No acid catalyst such as sulfuric acid, no pollution;
(7) Good product quality, colorless appearance-pale yellow.
甲基异丁基酮（MIBK）是一种重要的溶剂，其应用范围广泛，需求量与日俱增。据多方面资料报道，目前我国每年需求MIBK约3.2-3.7万吨。但长期以来，由于合成MIBK的催化剂和工艺技术上的原因，目前在国内没有生产能力，长期依赖进口，是一个长线缺口产品。
南开大学经过近三年的基础研究，克服了一系列技术上的难点，研制、开发成功新型催化剂和新的工艺路线，并进行了工业催化剂的放大与制备，并在放大装置上完成了年产100吨规模中试试验，获得了批量合格产品，其技术指标达到了生产要求，为设计并实现工业生产提供了依据。该新催化剂和联产二异丁基酮（DIBK）新工艺技术为国内外首创，该产品填补了国内生产空白，具有重大经济效益和社会效益。
与其它生产工艺比较，新生产工艺技术有以下几大优势：
1、 生产中为常压操作、反应温度低，所以较之其它生产工艺系统安全性高。
2、 工艺流程短，大大降低了设备投资和生产成本。
3、 催化剂活性和选择性高，抗中毒能力强，稳定性好。
4、 连续性生产，可大幅度提高产品产量。
5、 产品收率高，并联产高附加值产物。
6、 精馏后所得各组分产品纯度高，质量好。
Methyl isobutyl ketone (MIBK) is an important solvent with wide application and increasing demand. At present, China's annual demand for MIBK is about 32-37,000 tons. However, domestic MIBK cannot be produced independently, and keeps a long-term dependence on imports due to catalysts and technological reasons.
Nankai University has overcome a series of technical difficulties, successfully developed new catalysts and new process routes, and completed a pilot test of an annual output of 100 tons on the amplification device after nearly three years of basic research. The technical index has reached the production requirement. The new catalyst and the new process technology of diisobutyl ketone (DIBK) are the first domestic and international, and have significant economic and social benefits. There are significant economic and social benefits.
New technology has the following advantages:
(1) Low pressure, low temperature, high safety;
(2) Short process flow, low costs of equipment investment and operating;
(3) High activity and selectivity, strong anti-poisoning ability, good stability;
(4) Continuous production to increase product output;
(5) High product yield and high value-added products in parallel;
(6) High purity of components obtained after rectification.
γ-丁内酯是一种用途极其广泛的重要化工原料，尤其近几年国内外需求量呈上升趋势。现阶段合成γ-丁内酯主要有1,4-丁二醇脱氢法和顺酐加氢法。顺酐加氢法虽然原料成本较低，但由于原料对反应器有严重的腐蚀，并且氢气耗量大，产物损失较多，生产效率低，所以已经逐渐被生产厂家淘汰。1,4-丁二醇脱氢法，为目前较为先进的生产方法，但生产中仍需引入氢气，所以氢源问题限制了一部分企业的生产，并造成设备造价提高。我组经多年的研究开发，成功研制出了高效专用工业催化剂，即在非临氢状态下合成γ-丁内酯，在高空速、较低的反应温度条件下，原料转化率99.5%以上，产物γ-丁内酯收率在98%以上，催化剂寿命长，其设备投资、生产成本、生产效率大大优于其它生产方法。
g-butyllactone is a widely used
chemical raw material, with a increasing demand at home and abroad in recent
years. Synthesis of g-butyllactone
mainly includes dehydrogenation of 1, 4-butanediol and hydrogenation of maleic
anhydride. The feedstock of maleic anhydride hydrogenation method seriously
corrodes the reactor, as well as large hydrogen consumption and low production
efficiency. As a consequence, the method
has been gradually eliminated by the industry. The 1,4-butanediol
dehydrogenation method is a relatively advanced production method, whereas some
enterprises cannot afford it depending on hydrogen source problems and
equipment cost issues. Our team successfully developed a highly efficient
industrial catalyst after years of research, which was able to synthesize g-butyllactone in a non-hydrogen state. The conversion rate was over
99.5% and the yield of product γ-butyrolactone was over 98% under the
conditions of high space velocity and low reaction temperature. Our catalyst
has a long service life, low investment cost and high production efficiency,
far superior to other production methods.
二嗪磷又名二嗪农、地亚农，是一种广谱、高效有机磷杀虫杀螨剂，二嗪磷毒性较低，具有高效、低毒、低残留等特点。它对鳞翅目、同翅目等多种害虫均有较好的防治效果，适用于防治棉、水稻、小麦、蔬菜、花卉等作物的多种害虫及螨类，亦可拌种防治作物的地下害虫。
作为甲胺磷替代品种, 我国限于原料供应、价格等原因之前一直未能投产。作为农产品出口大国，异丁腈是合成农药二嗪磷的基础原料, 一直依赖进口,导致二嗪磷生产成本过高, 成为二嗪磷工业生产的技术瓶颈, 制约了它的发展。南开大学推出的异丁腈用催化剂技术, 采用气相法连续生产异丁腈新型催化反应工艺与工程技术，生产的异丁腈纯度高，可直接用于合成二嗪磷。该项技术突破了传统工艺难关, 大大降低了二嗪磷的生产成本,并已在千吨级规模工业装置上放大成功,这项新技术填补了我国异丁腈生产的空白并已获得国家发明专利。新型催化剂的研制成功,为我国大力发展二嗪磷新型农药创造了条件。该技术获得天津市2006年度技术发明二等奖。
Diazinon is a broad-spectrum organophosphorus insecticide with high
efficiency, low toxicity and low residue. It has a good control effect on a
variety of pests such as lepidoptera and homoptera, and is suitable for crops
such as cotton, rice, wheat, vegetables, flowers and so on.
China is a big exporter of agricultural products, where diazine
phosphorus is very important. Isobutyronitrile as its raw material was
dependent on import, leading to high production cost of diazinon. Nankai
University developed a new catalytic reaction process and engineering
technology, using gas phase method to continuously produce isobutyronitrile. This
method has high purity and can be directly used to synthesize diazine phosphorus.
This new technology has greatly reduced the production cost of diazine
phosphorus, and has been successfully scaled up in kiloton scale industrial
devices. Meanwhile, the national invention patent and the second prize of 2006
technology invention in Tianjin were obtained.
正丁腈是有机合成及医药中间体的关键原料。此前该产品的合成工艺为国内生产空白，没有成熟的合成工艺及工业催化剂。经过多年研究，南开大学推出的正丁腈用催化剂技术, 采用气相法连续生产正丁腈新型催化反应工艺与工程技术，生产的正丁腈纯度高，可满足产品出口的各项指标要求。
N-butyronitrile is a key raw material for organic synthesis and
pharmaceutical intermediates. Prior to this, no domestic company had made this
product, and there was no mature synthesis process or industrial catalyst.
After years of research, Nankai University has developed a new type of
catalytic reaction process and engineering technology, using the gas phase
method to continuously produce n-butyronitrile. This method has high purity of
n-butyronitrile, which can meet the requirements of various indicators for
product export.
高纯纳米氧化铝粉体是由我组经过长期的研究与开发，采用特殊工艺制备的高纯、高分散的纳米氧化铝粉体。该粉体不经过任何特殊的物理及化学处理便可分散于分散相中，形成稳定、均一的分散体系。
LNK-I型
应用领域：涂料，如彩色喷墨打印介质用的无机颜料，能够赋予彩色喷墨打印介质高光高吸墨的优良特质。
性能指标
化学组成：AlOOH·xH2O
颜色：白色
晶体结构：勃姆石，又名一水软铝石（英文名称Boehmite）
物理性质:
|
晶粒大小(nm)
|
20~30
|
|
比表面(m2/g)
|
＞100
|
|
孔容(cm3/g)
|
＞0.4
|
|
水中分散度(%)
|
＞95
|
|
Al2O3含量(%)
|
≥80
|
LNK-II型
应用领域：催化剂载体，作为催化剂载体使用，能够使活性组分负载均匀且高分散，提高催化剂的选择性和活性。
LNK-III型
应用领域：陶瓷材料添加剂，提高陶瓷抗冲击性：与其它粉体配合使用，可提高陶瓷晶界滑移能力，从而降低陶瓷脆性。且与常规陶瓷粉体相比较，由于其极高的表面能可以在相对较低的温度进行烧结。
Our team successfully prepared nano-alumina powder with high purity
and high dispersion by using special process. The powder can be dispersed in
the dispersed phase without any special physical and chemical treatment,
forming a stable and uniform dispersion system. There are three types of nano
alumina powder.
1. LNK-I
LNK-I can be used as a coating, such as inorganic pigments for color
inkjet printing, which can give high gloss and high ink absorption
characteristics.
2. LNK-II
LNK-II is considered to be a catalyst carrier, which can make the
active component load uniform and highly dispersed, and improve the selectivity
and activity of the catalyst.
3. LNK-III
LNK-III can be used as a ceramic additive to improve the impact
resistance of ceramics. When used in conjunction with other powders, it can
improve the ceramic grain boundary slip ability, thereby reducing the ceramic
brittleness. And compared with conventional ceramic powder, it can be sintered
at a relatively low temperature due to its extremely high surface energy.
Performance indicators:
|
Chemical components
|
AlOOH·xH2O
|
|
Color
|
White
|
|
Crystal structure
|
Boehmite
|
|
Grain size (nm)
|
20 - 30
|
|
Specific surface area (m2/g)
|
> 100
|
|
Pore volume (cm3/g)
|
> 0.4
|
|
Dispersion in water (%)
|
> 95
|
|
Al2O3 content (%)
|
> 80
|
ZSM-5 分子筛在国内外已有广泛的用途，是石油化工、精细化工等行业多种催化剂的母体。柴油临氢降凝催化剂，固定床催化裂化催化剂和低烃烷基化、异构化，甲醇气相合成二甲醚以及脱腊降凝催化剂都是以ZSM-5分子筛为母体经过改性制成的。在流动床催化裂化反应FCC 催化剂添加 ZSM-5 分子筛对提高汽油辛烷值，增加气体的烯烃含量有明显效果。
我组采用新型高压水热晶化合成法制备的硅铝分子筛ZSM-5，具有工艺简单、无污染、质量稳定、水热稳定性高等优点。
性能指标：
|
|
|
|
硅铝比(Si02/Al203)
|
|
|
Na2O(%)
|
|
|
比表面(m2/g)
|
|
|
水分(%)
|
|
|
（正己烷）吸附量(%)
|
|
|
结晶度(%)
|
|
|
颗粒度(nm)
|
|
ZSM-5 molecular sieve is widely used in petrochemical and fine
chemical industries at home and abroad. Diesel hydrodehydration catalysts,
fixed-bed catalytic cracking catalysts and low hydrocarbon alkylation and
isomerization, methanol gas-phase synthesis of dimethyl ether and dewaxing
decondensation catalysts are all modified by ZSM-5 molecular sieve. In FCC
catalytic cracking reaction, ZSM-5 molecular sieve has a significant effect on
increasing gasoline octane number and increasing the olefin content of the gas.
Our team adopt a new method of synthesizing ZSM-5 through high-pressure
hydrothermal crystallization, which had the advantages of simple process, no
pollution, stable quality, high hydrothermal stability and so on.
Performance indicators:
|
Product
Performance indicators
|
ZSM-5 molecular sieve
|
|
Si/Al ratio
|
50
|
|
Na2O (%)
|
< 0.04
|
|
Specific surface area (m2/g)
|
> 340
|
|
Water content (%)
|
< 7
|
|
(N-hexane) Adsorption capacity (%)
|
> 9.5
|
|
Crystallinity (%)
|
> 108
|
|
Graininess (nm)
|
± 200
|
SAPO-34晶体结构类似菱沸石型，属于小孔沸石，具有特殊的吸水性能和质子酸性，可用作吸附剂、催化剂和催化剂载体。例如，低碳烯烃的转化、汽车尾气净化催化剂的载体、MTO反应等。
该项目已获得国家发明专利授权。
The crystal structure of SAPO-34 is similar to chabazite type, which
belongs to small pore zeolite. It can be used as adsorbent, catalyst and
catalyst carrier with special water absorption properties and protonic acidity.
SAPO-34 can be used in many fields, such as the conversion of low carbon
olefin, vehicle exhaust purification catalyst carrier, MTO reaction and so on.
This
project has obtained the national invention patent authorization.
MCM-41分子筛属于一维孔道体系结构，其孔径均匀,具有高比表面积 和大吸附容量的特点，比沸石和磷铝酸盐等微孔材料更有利于有机分子的快速扩散,这使得它能为大分子尤其是石油化工过程中重油有机分子进行择型反应提供无可比拟的有利空间和有效酸性活性中心，可根据需要调节孔径和酸性浓度、强度，这类分子筛在渣油催化裂化、重油加氢、润滑油加氢、烷基化、烯烃聚合、CO2 - CH4的分离等酸催化领域和石油化工的分离过程中具有相当大的潜在价值。
该产品及相关技术已获得国家发明专利授权。
MCM-41 molecular sieve is a one-dimensional channel system structure
with uniform pore size, high specific surface area and large adsorption
capacity. Based on the above advantages, it is more conducive to the rapid
diffusion of organic molecules than microporous materials such as zeolite and
phosphoaluminate. As a result, it is more conducive for large molecules,
especially heavy oil organic molecules in petrochemical industry to participate
in the reaction, depending on excellent space and suitable acid center for type
selection reaction. Researchers can adjust the pore size and acid concentration
and strength as needed. This type of molecular sieve has considerable potential
value in the catalytic field of residual oil catalytic cracking, heavy oil
hydrogenation, lubricating oil hydrogenation, alkylation, olefin
polymerization, CO2-CH4 separation and the separation
process of petrochemical industry.
This project has obtained the national invention patent
authorization.
课题组经过长期合作研究，成功推出一种新型固体超强酸催化剂，该种催化剂可广泛用于醇酸酯化、烃类裂解、重整、异构化、烯烃水合、烯烃聚合、芳烃烷基化、芳烃酰基化等石油化工和精细化工过程。与液体酸（如浓硫酸）催化剂相比，固体超强酸催化剂酸强度更高，可达浓硫酸的100倍以上，而且克服了液体酸催化剂在使用上的缺点。具有容易与液相反应体系分离、不腐蚀设备、后处理简单、无污染、选择性高等特点，且可在较高温度范围内使用，扩大了热力学上可能进行的酸催化反应的应用范围。
Our team successfully launched a new solid
superacid catalyst, which can be widely used in alcohol esterification,
hydrocarbon cracking, reforming, isomerization, olefin hydration, olefin
polymerization, aromatic alkylation, aromatic acylation and other petrochemical
and fine chemical processes. Compared with liquid acid (such as concentrated
sulfuric acid) catalysts, solid superacid catalyst has higher acid strength,
which can reach more than 100 times that of concentrated sulfuric acid. It has
the characteristics of easy separation from the liquid phase reaction system,
non-corrosive equipment, simple post-processing, no pollution, high
selectivity, etc. The solid superacid catalyst can be used in a higher
temperature range, expanding the application range of thermodynamic
acid-catalyzed reactions.
