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Zhou Yonghong, deputy director of the Forest Products Chemical Industry Research Institute of the Chinese Academy of Forestry, pointed out that after the completion of the project, the production of polyurethane (PU) intermediates is expected to replace poisonous and harmful petrochemical raw materials by woody oils, waste oils, and rosin on a large scale. Polyurethane industry technology upgrades to improve the level of clean production technology.
Abundant natural oil resources At present, the vast majority of raw materials and intermediates used in PU production come from petroleum, coal, natural gas and other mineral resources, and are mostly toxic and hazardous chemicals such as phthalic anhydride, phthalic acid, and propylene oxide. According to Zhou Yonghong, at present, the price of rosin is about 7,000 yuan per ton, oil is more than 6,000 yuan per ton, and the price of waste oil is about 4,000 yuan/ton, while the price of propylene oxide is as high as 15,000 yuan per ton, and phthalic anhydride is also more than 10,000 yuan per ton. Compared with polyester and polyether polyols produced from petrochemical raw materials, polyester polyols produced from natural oils and fats have obvious advantages in terms of cost, performance and environmental protection. Changing the route of raw material production has become a major issue for the sustainable development of the polyurethane industry.
China has abundant natural oil resources, among which, the annual recoverable amount of turpentine is over 2 million tons, and the current turpentine output is about 800,000 tons per year, ranking the first in the world. Rosin and turpentine processed from turpentine are important chemical raw materials.
At the same time, China also has superior conditions for the development of other woody oils and fats. It is estimated that by 2015, China's woody oil production will exceed 10 million tons. In addition, China produces about 5 million tons of waste oil, such as fats and oils, and urban waste oil, which are produced annually. Therefore, the use of inexpensive natural oils such as rosin, woody fats and waste oils to replace or partially replace expensive petrochemicals such as phthalic anhydride, phthalic acid and propylene oxide to produce polyurethane materials will have good ecological performance and Strong market competitiveness.
The technical bottleneck has been overcome Although it is very feasible from the perspective of natural resources to produce polyurethane materials, there are still technical difficulties in actual implementation.
According to reports, the production of oil-based polyols mainly uses the double bonds in the molecular chain of vegetable oils for epoxidation, and is then made by hydroxylation. Due to the difficulty in separation of the vegetable oil molecules and epoxides from the unpaired bond, the use of the raw materials for the hydroxylation reaction together has a great influence on the product performance, and therefore cannot replace more petroleum-based polyesters and polyether polyols in parts by mass. In addition, during the synthetic process of oil-based polyether polyols, liquid acid-base catalysts and hydrogen peroxide and other epoxidizing reagents are still used, causing serious pollution in the production process.
The only forestry chemical industry research institute of the Chinese Academy of Forestry that specializes in the chemical processing and utilization of forestry biomass resources has been conducting studies on rosin polyester polyols and rigid polyurethane foams since the 1990s. They optimized and improved the production process, product performance, and polyurethane compatibility of rosin polyester polyols and foams to form a unique process technology. In 2004, they first achieved the simultaneous production of dimer in the production of biodiesel. Increased the economy of biodiesel.
As dimer can replace phthalic anhydride, phthalic acid, etc., as the main raw material for producing polyester polyols, the researchers conducted a systematic study on the preparation of polyester polyols by the transesterification of dimers and established an annual output of 500 Tons of oil-based polyester polyol pilot production line. According to reports, the performance index of polyurethane products produced from natural oils and fats has reached the level of petrochemical products.
On the basis of industrial demonstration, the Institute of Forest Products and Chemical Industry Co., Ltd. and Jiangsu Liqiang Chemical Co., Ltd. jointly undertook the national major industrialization technology development project of the National Development and Reform Commission in 2007—establishing an annual output of 50,000 tons of rosin and oil-based polyester multivariate. Alcohol continuous production demonstration line. Through technological innovation, researchers have developed and designed pipeline reactors with special structures so that reaction products such as dimerization and transesterification of oil products can be quickly mixed and dispersed, and the reaction speed of reactants can be improved and energy consumption can be saved. The device achieves continuous production of grease-based polyester polyols. Their self-developed green catalyst has accelerated the reaction rate of dimerization, transesterification and rosin diene addition and dehydration esterification of oil products, improved the safety of operation, and reduced the environmental pollution caused by the catalyst.
During the implementation of the project, researchers also overcame the fatal shortcomings of "poor storage stability" of polyester composites. Researchers adjusted the proportion of non-polar and polar parts of the rosin polyester molecules so that the rosin polyester polyol has good miscibility with other components of the polyurethane, and the prepared compound can be stored stably for a long time.
According to Zhou Yonghong, the ultimate goal of the project is to establish a continuous high-efficiency production device for polyester polyols with high fats and oils, so that the product performance can reach the petrochemical route level, and the cost is lower than the petrochemical route, and the independent intellectual property rights are formed. According to the requirements of the project plan, an annual output of 50,000 tons of rosin and oil-based polyester polyol devices will be put into operation within the year.
Polyurethane Industry Pathfinder Renewable Resources
As oil prices continue to soar, the prices of raw materials for the production of polyester and polyether polyols are also rising rapidly. As a renewable resource, natural oils and fats are used as raw materials to produce polyurethane intermediates, and the cost advantages have begun to show. To this end, the National Development and Reform Commission will develop an annual production capacity of 50,000 tons of rosin-based and oil-based polyester polyols, and will be included in the 2007 national major industrialization technology development project, which has now entered the installation phase.