Epoxy resin reactive diluent series of products is a variety of varieties of multi-purpose fine chemical products, widely used in various fields of national economy and national defense industry.Foreign 50 to 60 years of last century has developed a series of epoxy resin reactive diluent, Mainly allyl, butyl, octyl, C12-14 alkyl monoglycidyl ether, ethylene glycol, butanediol and other polyglycidyl ether series, the number of dozens of species as much. Domestic late , 90s of last century began to attach importance to the application of epoxy resin thinner research and industrial development, although there are several varieties available, but the variety is incomplete, compared with foreign quality gap.Nanjing Forestry University Professor Zhu Xinbao through industry-university cooperation, Formed an innovative team, aimed at the market demand, based on independent innovation, which lasted more than ten years and achieved the first result of the domestic product performance reached the international advanced level, and replaced the import and export volume and create significant environmental benefits and economic benefits And social benefits.
A good team must have an outstanding leader, team leader, doctoral tutor Professor Zhu Xinbao has long been engaged in chemical (chemical) professional teaching and research work, focusing on the development of fine derivatives of epoxy compounds, respectively, on the second Glycol monoether and its ester series, glycol ethers advanced solvent series, end-capped polyether series, epoxy reactive diluent series of advanced solvents and reactive monomer cleansing technology were studied in depth. A number of production and research base, respectively, the establishment of Jiangsu Province, alcohol Engineering Research Center, Anhui Province, epoxy resin and additives Engineering Research Center; completed more than 20 new products and new technology achievements, the output value of about 50 Over 100 billion yuan of profits and taxes; published over 50 scientific papers, edited a textbook; declared 41 Chinese invention patents (20 have been authorized); completed 18 provincial scientific and technological achievements appraisal, by PetroChina Chemical Industry Association Scientific and Technological Progress Award three, one third prize, Liang Xi Forestry Science and Technology Award three prize 1, Jiangsu Province Science and Technology Progress Award 1, Anhui Science and Technology Progress 2 3, a third prize, Huangshan Municipal Science and Technology Cooperation Award 1.
Professor Zhu Xinbao attaches great importance to the transformation of scientific and technological achievements, with the strong support of schools and colleges, give play to the advantages of scientific research, establish close cooperative relations with enterprises, and promote the transformation of scientific and technological achievements.He takes research and development achievements of epoxy reactive diluent production technology and Anhui Yuan Yuan Science and Technology Co., Ltd. to carry out production and research cooperation, the scientific research strengths and tertiary institutions, facilities, equipment, engineering technology and capital advantages fully integrated through concerted efforts, continuous innovation, continuous improvement in the same time, Anhui Xin Yuan Technology Co., Ltd. also developed from a small micro-enterprise into the largest manufacturer of epoxy resin active diluent, and has been identified as high-tech enterprises and national Torch Plan high-tech enterprises.
Epoxy resin reactive diluent is a low molecular epoxy compound containing epoxy groups, with low viscosity and good flexibility and other characteristics, they can participate in the curing reaction of epoxy resin, a cured epoxy crosslinking structure as part of the network, Can promote the flow of epoxy resin, reduce the shrinkage of cured products, improve the toughness of the cured material, mainly used for epoxy potting materials, casting materials, impregnating materials, adhesives and coatings viscosity, etc., a wide range of applications, it is important Of the fine chemical products.However, the traditional process of production of such products heavier pollution.Ju professor led the technology development team, in accordance with the concept of circular economy, with green manufacturing as the development goal, developed a two-step synthesis of cleaner production technology, to achieve the epoxy Resin-based active diluent production technology of major technological innovations. They use a special process, the product clean production process, so that basically no pollutant emissions, to the protection of the environment and ecology have a very beneficial impact on the environment in line with today's social requirements, in line with National industrial policy-oriented.Advanced technology and application of new technology and continuous development of new products, not only changed the domestic epoxy Resin reactive diluent single species, product quality and low level of technology, high-end products to be imported from abroad the status quo, but also to fill our country in the environmentally friendly high-end epoxy resin thinner on the industrialization of the product.
Among them, C12-14 alkyl glycidyl ether, one of the important varieties of active diluent for epoxy resin, is an important achievement of the cooperation between Professor Zhu Xinbao and Anhui Xinyuan Science and Technology Co., Ltd. C12-14 alkyl glycidyl ether has high boiling point and irritation Low toxicity, with a lively epoxy group can participate in the curing reaction, effectively improve the performance of the operation and products, in addition to play a dilution effect can also increase the flexibility of the cured product, is the traditional butyl glycidyl ether ideal Substitutes abroad C12-14 alkyl glycidyl ether using the process is C12-14 alcohol and epichlorohydrin in a homogeneous liquid Lewis acid catalyst for ring-opening reaction to generate C12-14 alkyl chlorohydrin ether intermediate Body; chlorohydrin ether intermediate and low concentration caustic soda closed loop reaction, the reaction product was separated into saturated brine, refined C12-14 alkyl glycidyl ether. The process of ring-opening reaction using homogeneous Lewis acid catalyst has many disadvantages , Such as: when the feed contact with the air 'smoke', harmful to the operator; met with water sensitive, inactivation, high moisture content of raw materials; serious corrosion of production equipment, etc. At the same time, closed-loop The reaction produces saturated brine. The reaction product is separated and diluted with water for biochemical treatment. Although the discharge can reach the standard, the COD of the saturated brine is about 30000 mg / L, the biochemical treatment load is large, and the amount of dilution water is large, which is not conducive to energy saving and emission reduction.
In view of the shortcomings of environmental pollution in the production process of C12-14 alkyl glycidyl ether, the project team of "key technologies and industrialization of C12-14 alkyl glycidyl ether cleaner production process" started with natural C12-14 fatty alcohol Raw materials, developed with independent intellectual property rights C12-14 alkyl glycidyl ether two-step green production technology, and the achievement of industrialization of technological achievements.
'C12-14 alkyl glycidyl ether cleaner production process of key technologies and industrialization' project by the Nanjing Forestry University and Anhui Xinyuan Science and Technology Co., Ltd. to undertake the completion of the main people are Zhu Xinbao, Cheng Zhenshuo, Zhu Kai, Wang Fang, Zhou Zi, Yang Yun, Li big money, including 2 professors, 1 associate professor, 2 doctors, 2 engineers.
First, the overall idea of product development
The natural C12-14 fatty alcohol was used as raw material to develop the green technology of C12-14 alkyl glycidyl ether.Firstly, the production technology of C12-14 alkyl glycidyl ether was studied by two-step process, High activity and good selectivity of solid Lewis acid catalyst, C12-14 alcohol and epichlorohydrin ring-opening catalytic reaction to improve the C12-14 alkyl chlorohydrin intermediate selectivity; and then with more than 40% high concentration of hydrogen The sodium hydroxide is subjected to a ring-closing reaction under the action of a phase transfer catalyst to obtain a crude product of C12-14 alkyl glycidyl ether, which is refined by washing with water, vacuum distillation of a low boil and the like to obtain a C12-14 alkyl glycidyl ether product. The salt is extracted and washed several times by saturated brine, and can be refined into industrial salt. The saturated salt water is recovered by the heat pump evaporation technology to realize the green production of C12-14 alkyl glycidyl ether.
Second, the formation of the main innovation
1. Developed a new type of solid Lewis acid catalyst with high selectivity for ring-opening epichlorohydrin.The new solid Lewis acid catalyst has good selectivity and convenient feeding, overcomes the toxicity of the commonly used liquid Lewis acid catalyst, Live, corrosive and other issues.
The closed-loop reaction and low-cost by-product salt recovery process of organic combination, developed a high concentration of alkali closed-loop reaction, the solid salt refining key process equipment.Selected low toxicity quaternary ammonium phase transfer catalyst, high reactivity; using 40% The above NaOH is closed-loop, the by-product solid NaCl is more and the saturated brine is less. The high solids salt content mixer of the closed-loop reactor is designed to facilitate the closed-loop reaction smoothly. The saturated brine extraction and separation system of the reaction product and the solid salt is designed, The reaction product is conveniently separated in a closed-loop reaction vessel. A solid salt and brine salt recovery system are designed to recover industrial-grade NaCl at a low cost.
3. Developed the technology of saturated salt water heat pump evaporation and organic matter recovery and utilization.The organic content of saturated brine is about 3%, accumulates in the process of heat pump evaporation and concentration, and regularly discharges the concentrated liquid containing 30% of organic matter and about 50% of water, The other is salt.The organic substance is rich in hydroxyl (570mgKOH / g), using one-step process, with epichlorohydrin, sodium hydroxide reaction, refined to prepare epoxy compounds can be used as anti-corrosion coating.
4. Developed a higher salinity wastewater biological treatment system.The salt content of the salt water in the production process is 5000 ~ 6000mg / L, the project team has developed a salt-tolerant species with independent intellectual property rights and salt-tolerant species culture and feeding System, before sending to the recycling economy sewage treatment system, through the anaerobic, aerobic and other biochemical treatment, the wastewater COD is less than 150 mg / L.
Third, application promotion and benefit situation
Based on the innovative small-scale research process, the project team took the pilot plant of 600t / a glycidyl ether as the expansion test platform to conduct the expansion test of the cleaner production technology and established the 3000t / a C12-14 alkyl glycidyl ether Production line.At the same time continue to industrialization of key technologies of cleaner production and then innovation, during which the production process is stable, high product quality, sales revenue by the end of 2016 to 872 million yuan, profits and taxes 128 million yuan. C12-14 alkyl glycidyl ether products can replace imported , Eased the urgent need for high-end active diluent products in our country, led and promoted the development of high-end and environmentally friendly products in the fields of coatings, electronic chemicals and adhesives. The products were exported to Southeast Asia and Western Europe And the United States, has won the praise of foreign customers.
This project is based on the national policy-oriented, aimed at the market demand, through the cooperation of industry, universities and research, the achievements made by independent innovation.The cleaner production technology for the domestic initiative, the product performance reached the international advanced level, replacing the import and export.Using high concentrations of hydrogen Sodium oxide raw material by-product solid extraction of salt refining, heat pump technology evaporation of saturated brine recovery by-product salt, with a lower cost to eliminate the impact of by-product salt on the environment, to achieve a cleaner production, with significant environmental benefits, economic benefits and Social benefits.
Professor Zhu Xinbao, on behalf of Nanjing Forestry University, has conducted close cooperation among industry, universities and research institutes with a number of enterprises. The continuous realization of the transformation of scientific and technological achievements and the promotion of industrial innovation have far-reaching significance for the rapid development of the active diluent industry in China.