Domestic chlorohydrin method of producing propylene oxide accounted for how many

Chlorohydrin method has a long history of production and has been industrialized for more than 60 years, represented by the chlorohydrin method of DowChemical Company in the United States. The main process of chlorohydrin method is propylene chlorohydrinization, lime milk saponification and product refining, which is characterized by mature production process, flexible operation load, good selectivity, the purity of raw material propylene is not high, so as to improve the safety of the production, and less investment in construction. Due to low investment in fixed assets and low product cost, its products have strong cost competitiveness. Today, about 40% of the world's propylene oxide production capacity is chlorohydrin method. The disadvantage of chlorohydrin method is that it consumes a lot of water and produces a large amount of waste water and waste residue. Each production of 1t of epichlorohydrin produces 40~50t of saponification waste water containing chlorides and more than 2t of waste residue, and the waste water has the characteristics of "five highs" with high temperature, high pH, high chlorine content, high COD content and high suspended matter content, which is difficult to be processed. At the same time, chlorohydrin method also consumes a lot of chlorine and lime raw materials with high energy consumption, while chlorine and calcium are discharged in wastewater and waste residue, and hypochlorous acid generated in the process of production has serious corrosion on equipment. China's propylene oxide production began in the 1960s, the use of self-developed chlorohydrin process route. the late 1980s and early 1990s, China has introduced Japan's Asahi Nitrite, Mitsui East Pressure Company, Showa Denko and the United States of America Dow chlorohydrin technology, Jinhua Chemical, Shandong Binhua, Sinopec Shanghai Gaoqiao petrochemicals, Tianjin Dagu Chemical and other enterprises of the propylene oxide plant was completed and put into operation! After that, they have achieved better economic benefits and improved the production level. Nowadays, except for the 250,000t/a propylene oxide plant of CNOOC Shell which adopts *** oxidation method, 80% of the existing domestic propylene oxide production capacity uses chlorohydrin method. The *** oxidation method, also known as Hakon method, includes 2 kinds of isobutane *** oxidation method and ethylbenzene *** oxidation method, respectively, by isobutane or ethylbenzene and propylene *** oxidation reaction, generating tertiary butanol or styrene, and at the same time co-producing propylene oxide. The *** oxidation method was developed by the Oakland Company in the United States, and is now owned by the Lyondell (also translated as Lyondell) Company in the United States. The *** oxidation method overcomes the shortcomings of the chlorohydrin method, such as large corrosion, sewage, etc., and has the advantages of low product cost (co-product cost sharing) and less environmental pollution. Since its industrialization in 1969, it has developed rapidly worldwide, and today, *** oxidation method of propylene oxide production capacity has accounted for about 55% of the world's total production capacity. The disadvantages of *** oxidation method are long process flow, many varieties of raw materials, high purity requirements of propylene, process operation under high pressure, equipment materials are mostly made of alloy steel, high cost of equipment and large construction investment. At the same time, propylene oxide in the production of *** oxidation method, just a co-product of a small yield, per ton of propylene oxide to co-produce 2.2 ~ 2.5t styrene or 2.3t tert-butanol, raw material sources and product sales mutual constraints are larger, must be properly resolved, only propylene oxide and co-products market demand match to show the advantages of the process. In addition, *** oxidation method of sewage containing COD is also relatively high, treatment costs account for about 10% of the total investment. Domestic propylene oxide production has been using the chlorohydrin process, and in March 2006, with the commissioning of the 250,000t/year propylene oxide plant of China Sea Shell, the pattern of propylene oxide production has changed to a certain extent. China Sea Shell project is now the largest propylene oxide plant in China, and the only propylene oxide plant using propylene oxide/styrene*** oxidation cogeneration process. It is expected that by the end of 2009, the 280,000t/a*** oxidized propylene oxide production unit in Zhenhai, a joint venture between Lyondell and Sinopec, will be completed and put into operation. Hydrogen peroxide direct oxidation method (HPPO method) is a new process of epoxidation of propylene from hydrogen peroxide (hydrogen peroxide) catalyzed epoxidation of propylene to make propylene oxide, the production process generates only propylene oxide and water, the process is simple, the product yield is high, there is no other co-products, basically no pollution, belongs to the environmentally friendly cleaner production system. Nowadays, the hydrogen peroxide true oxidation process is developed and industrialized by Evonik Industries (formerly Degussa) in cooperation with Uhde, Dow Chemical and BASF. 2001, Evonik Industries and Uhde constructed a pilot plant in Frankfurt, Germany, to test the optimal catalysts and to determine the critical parameters, and started the design of the technology for industrialization. In 2003, Evonik launched a commercialized process package for the technology. In May 2006, SKC, a South Korean producer of propylene oxide and polyester film, purchased the patents from Evonik and Wood and started to build the world's first hydrogen peroxide propylene oxide plant in Ulsan, South Korea, with a production scale of 100,000 t/a, which was put into operation in July 2008 with good production and operation. The plant has been put into operation in July 2008 and is running well. Evonik Industries is negotiating with Sibur, a subsidiary of Russian gas oligarch Gazprom, to build a combined hydrogen peroxide and propylene oxide production unit in Russia. 2001, Dow Chemical purchased laboratory technology from EniChem for the production of propylene oxide using hydrogen peroxide as an oxidizing agent, which also included a pilot plant in Italy. 2003, Dow Chemical and BASF started cooperation. Dow Chemical and BASF began to cooperate in the development and commercialization of hydrogen peroxide technology. 2006, Dow Chemical and BASF Corporation*** jointly announced the construction of 300,000t/a hydrogen peroxide propylene oxide plant in Antwerp, Belgium, which is scheduled to be completed and put into operation in early 2009. 2008, June, Dow Chemical and Thailand's SiamCement Group (SCG) joint venture established In June 2008, Dow Chemical and Thailand's SiamCement Group (SCG) joint venture SCG-DOW Group in Thailand's epichlorohydrin plant to start construction, the use of Dow and BASF jointly developed hydrogen peroxide process, the capacity of 390,000t / a, the project is expected to be put into operation in 2011. Dow Chemical also plans to start construction of 380,000t/a hydrogen peroxide propylene oxide project in 2010 in Switzerland. Dalian Institute of Chemical Physics (DICP) of China is also engaged in the research of hydrogen peroxide technology. 2002, DICP signed a pilot cooperation contract with Sinopec, and in the first half of 2005, DICP's "reaction-controlled phase-transfer-catalyzed propylene oxidation to propylene oxide pilot study" passed the technical appraisal organized by Sinopec. 2008, August, DICP's "reaction-controlled phase-transfer-catalyzed propylene oxidation to propylene oxide pilot study" passed the technical appraisal organized by Sinopec. In August 2008, the technology of propylene oxide production by direct oxidation of propylene oxide with hydrogen peroxide developed by DIC passed the appraisal organized by Liaoning Provincial Science and Technology Department. China's propylene oxide production began in the 1960s, the initial production scale and production technology level is relatively low. 80's, China has introduced AsahiGlass, MitsuiToatsu, ShowaDenko and other more advanced production technology to promote the development of domestic propylene oxide technology. 2000 years after the development of China's epichlorohydrin industry entered a rapid growth stage. 2004 is the first year of China's epichlorohydrin industry development. After 2000, the development of China's propylene oxide industry has entered a rapid growth stage. 2004 is the most rapid development of China's polyether industry in 2005 by the domestic and foreign macro-economy, the supply of raw materials and other factors affecting the growth rate of the polyether industry is slightly reduced. In terms of product structure, the actual growth of hard foam polyether industry in 2005 was not much, and the soft foam polyether industry developed faster in the second half of 2005.2006 is a very important year in the history of China's PO development. First of all, many sets of new and expanded equipments were put into production, and the supply and demand relationship was gradually moving towards balance from the tight situation; secondly, the market price was slightly down from the high level in the past years; and the profit of the producers was obviously reduced. Finally, the downstream derivatives of the demand market from the suppression in 2005 released PO and its derivatives demand in 2006, the total amount of rapid growth. At present, there are more than 30 polyether polyol manufacturers in China, with a production capacity of 1.135 million tons in 2005, of which nearly 20 are above 10,000 tons in scale. The main manufacturers are Shanghai Gaoqiao Petrochemical Company Polyurethane Division, China Shell, Jiangsu Zhongshan Chemical Co., Ltd, Tianjin Petrochemical Company Polyurethane Department, Jinhua Chemical Group Company, Shandong Dongda Chemical Industry Group Company, Fujian Meizhouwan Chlor-alkali Industry Co. According to the analysis of the development of polyurethane industry, in the next few years, the annual growth of China's polyether polyol consumption demand is expected to remain at more than 10%. 2008 China's polyethylene polyol global production of PO in the three methods of chlorohydrin and *** oxidation method is still the dominant position of these two processes will co-exist for a long period of time *** oxidation method of production process in the short term without absolute advantage of the elimination of the chlorohydrin method process. Most of the enterprises in our country are using the chlorohydrin method now by increasing technological transformation, especially the use of biochemical treatment technology to better solve the sewage problem of the process in our country still has room for development. Direct oxidation method of hydrogen peroxide oxidation to produce PO process is beginning to industrialize direct oxidation method of oxygen direct oxidation method is still in the conceptual test stage. Industrial production units for PO by direct oxidation may not appear in China. With the transfer of the center of the world polyurethane industry to mainland China will greatly promote the development of China's polyurethane industry, while the promotion of building energy-saving policies, the continuous development of the automotive furniture industry makes the polyurethane industry to maintain good growth, thereby stimulating the development of the PO industry. Therefore, in the raw material advantages of large petrochemical enterprises can build *** oxidation method production unit is recommended to expand the scale. Production of propylene oxide enterprise capacity should be a minimum of 100,000t / a above. If the supply of raw materials and transportation is sufficient to build 200,000-300,000t / a large device. Domestic consumption of propylene oxide for polyether polyol accounts for 85% of the total consumption, occupying a dominant position, and PG/DMC accounts for 8%. In the future consumption of propylene oxide, polyether is still dominant, and the proportion of it has increased. The downstream demand for propylene oxide is mainly supported by the polyether industry. Polyether polyol, as the main raw material of polyurethane industry, the application of polyether polyol is mainly concentrated in four fields, such as furniture, automobile, construction and industrial insulation, etc., and the dosage occupies more than 2/3 of the total dosage of polyurethane. starting from the 1980s, the consumption of furniture and mattresses grows rapidly, and the demand for flexible polyurethane foam increases significantly, and after the 1990s, the consumption of polyurethane in the industries of automobiles, construction and household electrical appliances grows rapidly, and the domestic consumption of polyurethane increases steadily. After the 1990s, the consumption of polyurethane for industrial use such as automobile, construction and household appliances increased rapidly, and the domestic consumption of polyurethane increased steadily. From the perspective of domestic polyurethane consumption structure, furniture, household appliances and automobiles are the main consumption areas. In the field of construction, the domestic is the use of EPS products, polyurethane demand is relatively low, but the future environmental protection and energy saving requirements are getting higher and higher, which will bring a constant development momentum to the polyurethane industry, thus pulling the growth of demand for propylene oxide. Based on the rapid growth in demand for polyurethane is expected, the polyether industry has entered a rapid expansion phase, and the next two years during the polyether project has been completed or will be completed numerous, such as Shaoxing Hengfeng 100,000 tons of new production capacity, Jurong Ningwu 100,000 tons of new production capacity, etc. In 2012, the polyether production capacity will be more than 2 million tons. The rapid growth of polyether industry, propylene oxide consumption will also increase significantly. In the next two years, the new capacity of polyether 1 million tons of calculation, the production of 1 ton of polyether needs about 0.75 tons of propylene oxide, so only the polyether industry in 2010-2012 on the demand for propylene oxide will increase by about 70-80 million tons of propylene oxide, the demand for propylene oxide will have a greater growth. First, the main problems existing in the market of propylene oxide products with the development of China's fine chemical industry and polyurethane industry, propylene oxide products market prospects are increasingly broad, but at present, China's production of propylene oxide is used in all the chlorohydrin method of production process, the process exists on the equipment corrosion is serious, resulting in serious pollution of the environment containing calcium chloride wastewater, and other shortcomings. China's large-scale production of propylene oxide device to the introduction of technology-based, Japan's Asahi Glass Company technology, Japan's Mitsui East Pressure Company technology, Japan's Showa Denko technology and the U.S. Dow Chemical Company technology, the domestic technology to the Petrochemical Corporation to organize the main research technology. As a traditional production process, chlorohydrin method has been gradually phased out in foreign production due to its high emission of "three wastes", and the reason why there is no big breakthrough in the production capacity of propylene oxide by chlorohydrin method in China has an important relationship with this. The wastewater and waste residue produced by this production process are not easy to be treated and cannot adapt to the increasingly strict environmental standards. Especially in the treatment of waste residue, due to the high salt content of the waste residue, there are not many ways to utilize the waste residue in accordance with the standard. Most of the manufacturers use methods such as piling up and burying, which will inevitably cause serious pollution to the surrounding environment and groundwater, and bring great potential danger to the future environmental management. If the chlorohydrin process is used to produce propylene oxide, and if the problems of wastewater and waste residue cannot be solved effectively, the larger the capacity of the enterprise's production unit, the larger its burden of environmental protection; and the higher the production volume, the deeper the harm to the environment. Therefore, relevant experts believe that the technology of chlorohydrin production of propylene oxide is not mature enough. It is recognized that the more mature technology was introduced about 50 years ago and is not adapted to the current environmental requirements. Therefore, environmental protection has become the primary factor restricting the development of propylene oxide industry. Cracking the environmental problems in the development of propylene oxide industry has become the goal of the current technical research. In addition to the improvement of the original production process, how to realize the recycling of wastewater and waste residue will be related to the development of the whole propylene oxide industry, once this key factor is cracked, it will bring new opportunities for the industry. China's propylene oxide industry has made great progress, but compared with the advanced level of foreign countries and domestic downstream industries, there is still a big gap, the future should be clean process, device scale, application of fine direction. Second, three major bottlenecks in the domestic market of propylene oxide products "Eleventh Five-Year Plan" is China's epichlorohydrin industry boom, the quality of the double rise of five years. During this period, China has become the world's largest producer and seller of propylene oxide, with the production capacity reaching 1.545 million tons in 2010 and the output 1.4376 million tons. The quality of products of large and medium-sized enterprises has generally improved, and they can be used in the manufacture of high-quality electronic products and aerospace products. However, there are also some problems worth reflecting on. Looking forward to the "Twelfth Five-Year Plan", propylene oxide industry in consolidating and expanding the results at the same time, will strive to break through the following bottlenecks. First of all, China has become the world's largest producer and seller of the industry, certainly "Made in China" is the result of the booming development, but there are foreign enterprises to transfer the basic epichlorohydrin products, specializing in adding the influence of epichlorohydrin products. Additive resin production is not only zero-pollution, but also better product performance and higher prices. At present, China's epichlorohydrin product enterprises are still basically based on basic epichlorohydrin products, market competition is white-hot, profit margins are shrinking, and structural adjustment of the industry has been stagnant for a long time. And foreign manufacturers precisely take advantage of this time, to China as the basic supply base of propylene oxide products, and constantly expand the production capacity of additive resins. This not only avoids the environmental risks, but also earns a big profit. Therefore, how to reduce the pollution in the production process of basic resin, open up the market of additive resins, and improve the added value of products is an important issue facing the whole industry. Secondly, the systematic construction to be put on the agenda. Multinational companies are no longer a single supply of resin products, but according to customer demand, the preparation of a good mixture to provide systematic services, this mixture includes resin, curing agent, diluent, additives and so on. This can form a product chain advantage, consolidate the market, but also fully expand the profit margin. Specialized development of product varieties targeted, specialized performance, can better adapt to customer needs, so the level of profitability is higher, customer loyalty is also higher. Again, for the domestic epoxy resin production capacity development is too fast, the basic curing agent device development is too slow, insufficient supporting capacity of the status quo, should pay attention to epoxy resins, curing agents, additives, raw materials, coordinated supporting the development of special epoxy resin research and development, at the same time to strengthen the exchange of information, to avoid blindly or repeatedly on the project. China's demand for propylene oxide products is still developing rapidly, and it is predicted that the consumption will soon reach 2.756 million tons by 2020. The low utilization rate of some devices is largely related to the unreasonable product structure in China. Therefore, China can no longer rush to grab the same runway and engage in vicious competition as before. To consider the development level from the variety, quality and process level and other aspects. First, the future development of propylene oxide analysis in the production of raw material propylene prices, propylene oxide prices finally began to rise sharply, however, in the case of rising market conditions, the production of propylene oxide enterprises are still struggling to get by, the loss of money is still the first major element they always need to worry about. The production cost of propylene oxide is directly affected by the price trend of propylene, after the international high oil price era, the price of propylene is also rising, however, sensitive to the ups and downs of oil prices also affects the price of propylene, after the price of propylene began to fall, the price of propylene oxide lack of strong support for the price of the demand appears to be the bottom of the gas is not enough. Although, from the point of view of manufacturers, even after raising the market price of propylene oxide, still burdened with the burden of loss, but, after the raw material prices began to fall, although the manufacturers still said that the intention to maintain high prices, but whether the downstream buyers can understand and accept is not known. Propylene oxide price increases naturally drive the polyether price quotations in the red, and propylene oxide quotations are the same, the downstream demand is still weak so that the high price of the market is not optimistic. In fact, the production enterprises unilaterally because of the pressure of production costs and lead to the high market price of the product, and can not fully explain the optimism of the product market, when the time is the helplessness of the production enterprises. China's polyether consumption of 73% for the manufacture of flexible foam (soft foam) material, the rest of the more for the production of hard foam, while about 50% of the polyether in developed countries is used in the construction industry. Due to the rapid growth of coatings, adhesives, sealants, elastomers and other products in the market, polyether in the field will make a big difference. With the development of China's automobile industry, the demand for polyether in automotive polyurethane parts is increasing rapidly. Therefore, the gradual diversification of polyether consumption structure has become one of the important factors for the industry to develop in depth. There is an urgent need to expand the application field of polyether industry, is an effective method to fundamentally change the situation of polyether market demand. As for propylene oxide, changes in the production process will be the direction of future development. Currently domestic enterprises to produce propylene oxide production of environmental issues arising from social issues, but also the cost of enterprise issues, the promotion of advanced technology will be the solution to the high cost of production of propylene oxide, pollution is a serious problem of the fundamental way. 2008 BASF and Dow Chemical is located in Antwerp, Belgium, direct oxidation of hydrogen peroxide production of propylene oxide device will be put into operation, South Korea's SKC will be put into operation using the technology device. BASF and Dow are planning to start production of propylene oxide by direct oxidation of hydrogen peroxide in Antwerp, Belgium in 2008. BASF and Dow Chemical plan to build further hydrogen peroxide direct oxidation epichlorohydrin plants in Asia and the United States in 2009-2010, and Lyondell plans to build a new project in China, and several other companies have projects planned for China in 2008-2010. In the past ten years, the domestic demand for propylene oxide in the downstream derivatives of the strong pull of rapid growth, from only 785,000 tons of consumption in 2006 to 1,546,000 tons in 2011, an increase of 1-2 times more than the average annual growth rate of up to 15.03%. Among them, the total consumption of polyether polyol industry reached 550,000 tons, accounting for 84.9% of the total consumption, which is much higher than the global average. With the rapid development of China's polyurethane industry, a large number of new domestic polyether polyol plant, expansion, polyether polyol self-sufficiency rate increased year by year, to 2011, the self-sufficiency rate has reached more than 90%, for the demand for epichlorohydrin has also greatly increased. Thus, in fact, whether it is propylene oxide or polyether market, the development prospects are still broad, just in the process of development, encountered twists and turns need to be effective means to solve the rescue of propylene oxide and polyether market, relying solely on price increases is not a long-term solution to reverse the loss situation, or the need for meta-road of development. Second, the future direction of technological development of the propylene oxide industry to follow the principle of sustainable development, the protection of the human living environment of the virtuous cycle, the production of propylene oxide appeared a variety of new processes, such as the direct oxidation of the aforementioned, Lunmus chlorohydrin method, double oxidation, biological a fermentation method, peracetic acid method, electrochemical chlorohydrin method, etc., the best of which is the direct oxidation of hydrogen oxide method. Theoretically, the redox potential of H202 is higher than that of propylene oxide, and it can be used to oxidize propylene directly to make propylene oxide.The mass fraction of active oxygen in H202 is much higher than that of other peroxides, amounting to 47%. Its reduction product is only water, clean and pollution-free, is the ideal oxidizing wattle. Therefore, some people have long wanted to use H202 to oxidize propylene to produce propylene oxide, but due to the reason of catalysts are unsuccessful. When Ts I 1 catalyst was developed, this idea finally became a reality. Under the condition of pressure 0.4MPa and temperature close to room temperature, with methanol aqueous solution as solvent, propylene and H202 were directly reacted to produce propylene oxide, and the conversion rate of H202 reached more than 98%, and the selectivity of propylene conversion to propylene oxide was more than 97%. Recently, the process is still in the development stage, and the main research focuses on the influence of various factors on catalyst performance and cost. It can be foreseen that the future trend of propylene oxide production is large-scale and harmless, but in the short term, the technical conditions are not yet able to achieve the goal of harmlessness, especially for our country, and there is also a problem of affordability in our country. Combined with this actual situation, the domestic propylene oxide industry in this field to be more reasonable, rapid development, but also minimize the pollution of the environment, it is imperative to increase the treatment of propylene oxide wastewater, so we have this topic is very meaningful. Third, the overall industry 12th Five-Year Plan and forecast - the overall goal to improve the existing devices of energy saving, consumption reduction, environmental protection level, strengthen the introduction of new processes HPPO and improve the new process of key technologies of independent development capabilities; increase the integration of the industry, improve the overall HSE level of the PO industry; through the inter-industry exchanges, Communication, to create a favorable atmosphere for the development of the industry, and effectively promote the rapid and healthy development of the industry. --The main task is to continuously improve the energy saving and consumption reduction level of the existing installations and energy recovery and reutilization under the condition of ensuring the production scale. At present, China's propylene oxide production units, in addition to two sets of PO/SM devices, the rest are still chlorohydrin process. Chlorohydrin process inherent in some environmental issues such as serious corrosion of equipment, wastewater, sludge pollution has been bound to the continued development of the process. Especially at home and abroad to promote environmental protection, low-carbon environment, to improve the chlorohydrin process of energy saving, consumption reduction, environmental protection level has to be put on the agenda.