The Development of Ozone Technology in China after 2000
Research on Ozone Generation Technology in China after 2000
Wang Fang and others in the 309th Hospital of the People’s Liberation Army studied the effect of peptone on the germicidal efficacy of the ozone water, turning out that organics in water could destroy ozone and reduce its sterilization effect.
According to the years of research on ceramic chips, Ni Guonian and Sui Ying of Beijing Institute of Technology drafted "Performance Testing and Acceptance Standards for Ceramic Chips in Surface Discharge" in 2000, and improved the nickel plating process of tungsten electrodes for surface discharge ceramic chips in 2003.
Around 2000, enterprises represented by Zhejiang Jinhua Light Instrument and Yantai Baite Environmental Protection Technology Co., Ltd. gradually developed into well-known manufacturers of electrolytic ozone generators and high-concentration ozone generators at home and abroad.
Chen Junsheng in Shanghai Guanghui Institute of Ozone Development developed photon ozone generators on the basis of years of research on ozone generation by the photoelectric effect and carried out the experiments of "photon ozone" for fungicide and water discoloration.
Seizing the opportunity of GMP certification in our pharmaceutical industry, multitudes of enterprises including Zhenjiang Kanger, Jiangsu Chengcheng, and Anqiu Azon Max developed the "built-in" and "external" ozone generators for the central air-conditioning to sterilize the air in the pharmaceutical workshop, promoting the application of ozone in this field nationwide.
In 2000, Wei Xingyi, Liu Yongdi, and others in Shanghai East China University of Science and Technology conducted the research on ozonation pretreatment to improve the biodegradability of manganese wastewater in order to solve the wastewater of a chemical plant in Jiangsu Province. In the next year, they conducted a study on the treatment of cuprous cyanide wastewater with the ozone oxidation method in a chemical plant in Shanghai.
In 2001, two companies, Qingdao Yihai Breeding Center for Fine Breed Fish and Jinzhou Dalin Aquaculture Co., Ltd., respectively cooperated with Qingdao Guolin Industrial Co., Ltd. to study the seawater treatment for industrial ozone farming. In this process, the two enterprises adopted the 500g/h and 200g per hour air source ozone generators separately for the purpose of recycling. The similar experimental studies were carried out through the cooperation between Qingdao Lanka Biotechnology Co., Ltd. and Qingdao Zhongtong Ozone Technology Co., Ltd. in the following year.
In May 2003, Qingdao Guolin Industrial Co., Ltd. cooperated with Shandong Quanlin Packaging Co., Ltd. to conducted the research on the effect of ozone pretreatment for the composite process of the dairy product packaging film and developed it successfully in December of the same year after more than half a year of small-scale and pilot-scale tests. In February 2004, the 1kg/h oxygen-enriched ozone generator specially developed by Qingdao Guolin Industrial Co., Ltd. was put into production and use, which can adjust the flow freely in the case of constant ozone concentration. As the first domestic project applying ozone to the composite process of the films, it blazed the trail in the field of the ozone application in China.
In 2003, Zhang Zhiren of the General Engineering Design Institute of PLA General Armament Department carried out research on ozone purification and treatment for rocket propellant wastewater, achieving a breakthrough. In the ensuing year, Zhang Tong of the institute cooperated with Qingdao Guolin Industrial Co., Ltd. to apply ozone treatment technology to explosive wastewater containing trinitrotoluene.
During the SARS epidemic in May and June 2003, professor Li Zelin, director of the Viral Pharmacology Laboratory in Beijing University of Technology, conducted the experiment on inactivating the SARS virus with ozone in the and BSL-3 Laboratory showing the inactivation rate of SARS virus inoculated with green monkey kidney cells was as high as 99.22%, which was the first successful one worldwide applying ozone to inactivate the SARS virus. Subsequently, the State Environmental Protection Administration issued the Technical Plan for Emergency Treatment of Sewage Contaminated by SARS Virus, in which ozone was regarded as one of its recommended disinfectants.
Processor Wang Zhansheng from the Department of Environment and Engineering, Tsinghua University, has further studied the advanced treatment technology for drinking water—ozone + biological activated carbon technology for many years, pointing out the direction for the advanced treatment process of running water in China in the future.
In 2001, research on non-glass discharges was carried out in Qingdao Guolin Industrial Co., Ltd. and other enterprises. After more than a year, Qingdao Guolin Industrial Co., Ltd. successfully developed the key technologies required for the manufacture of large ozone generators such as DTA non-glass discharges, high voltage fuses, thyristor medium frequency power supplies, and intermediate frequency transformers. Moreover, products including “GL-CF-G004A-type ozone food sterilizers” and “dual-cooling high-frequency zone generators” through independent development were appraised as “National Key New Products”.
In October 2002, Qingdao Guolin Industrial Co., Ltd. developed the 3kg per hour air source medium frequency ozone generator, which was regarded as one of the largest domestic equipment on ozone output per unit at that time, as well as the first large medium frequency ozone generator. In November, the two pieces of equipment of this kind, 16-22mg/L ozone concentration and less than 18kw·h/kgO3 power consumption, were put into use in Hangzhou Youbang Flavor and Fragrance Co., Ltd. With the steady operation, the power consumption of the host and air source equipment of the two ozone generators was greatly reduced compared with several power frequency ones in this company after more than a year of operation verification. In February 2004, the company ordered two more 4kg per hour air source medium frequency ozone generators, which were put into operation in August. two 5kg per hour air source medium frequency ozone generators were produced in Qingdao Guolin Industrial Co., Ltd. for Sichuan Yibin Jianzhong Perfumery Company, which were put into operation in May 2004.
In 2003, Liu Yong of Jinan Sankang Ozone Technology Company conducted the experiments and research on ceramic dielectric materials. In the micro gap tubular ceramic ozone discharge chamber developed by him, matched with the corresponding IGBT power supply, the oxygen source ozone concentration can reach as high as 122mg/L. Ma Tian, Yang Jinlong, and others in the Department of Materials Science and Engineering, Tsinghua University also carried out the relevant experiments in the same period.
At the end of 2003, obtaining the project approval from the Ministry of Construction, Qingdao Guolin Industrial Co., Ltd. developed the 20kg per hour air source medium frequency ozone generator, which was mainly applied to the water supply industry with the increasing demand for ozone to replace imported counterparts. In July 2004, the product was tested successfully.
In July 2004, the application of 2 2kg/h ozone generators produced by Qingdao Guolin Industrial Co., Ltd. to Lijin Water Supply Company signified the beginning of large domestic ozone equipment entering into the water supply industry.
In 2005, with professor Li Hanzhong as the first director, the Ozone Speciality Committee of China Federation of Industrial Economies was formally established and was not disbanded until the consecutive four years.
In 2008, the first domestic“50kg/h large ozone generator” with 127.6mg/l ozone concentration and 53.7kg/h ozone output, produced by Qingdao Guolin Industrial Co., Ltd, passed the evaluation of the sci-tech achievement of the Ministry of Construction. It was consistently recognized as ”the national key new product” by ministries and commissions including the Ministry of Science and Technology and State Environmental Protection Administration, and was listed as “industrial promotion plan projects of Ministry of Construction”.
In 2009, the industrial standard CJ/T322-2010 ”Ozone Generator for Water Treatment” was formulated through Qingdao Guolin Industrial Co., Ltd. cooperating with the Department of Environmental Science and Engineering of Tsinghua University, Ozone Speciality Committee of China Federation of Industrial Economics, Qingdao Engineering Research Center for Ozone Application, Tongfang Co., Ltd. Water Engineering Company, Jiangsu Kanger Ozone Co., Ltd., Fujian Newland Environmental Protection Technology Co., Ltd. and Jinan Sankang Environmental Protection Technology Co., Ltd.
In the next year, Jiangsu Kanger Ozone Co., Ltd. independently developed the 20kg per hour high-frequency ozone generator with an enamel tube. The experts of the Department of Housing and Urban-Rural Development identified the product’s technology to reach the international advanced level with 153.0mg/l ozone concentration, 22.0kg/l ozone output, and 9.0kWh/kg power consumption.
In 2011, independently developing the 20kg/h ozone generator, Jinan Sankang Environmental Protection Technology Co., Ltd. was regarded as the third domestic enterprises capable of manufacturing this kind of equipment.
In 2011, Qingdao Guolin Industrial Co., Ltd. and Fujian Newland Environmental Protection Technology Co., Ltd. respectively undertook the subject of “development and industrialization of large ozone generator equipment with non-glass material” and “development and industrialization of large ozone generator equipment with glass discharge tube” under the theme of “Research and Demonstration of Drinking Water Security Technology System”, one of the major national science and technology projects on water pollution control and treatment.
In 2011, Zhang Kuanzhao of Beijing Qianrun Kaiyuan Environmental Protection Technology Co., Ltd. further optimized the design of a plate-type ozone generator to achieve the discharge of the ground electrode structurally and spread the ceramic technology on the surface on a large scale. After the optimization, the maximum ozone output of a single plate-type ozone generator module can reach 1.2kg, and the maximum ozone output of combination can be up to 50kg. Later, the ozone generation system was used in the treatment of printing and dyeing wastewater, and also began to be used in the fields of water supply, chemical wastewater, and municipal wastewater on a small scale.
In November 2011, at the report meeting on the results of the water project of Fujian Newland Environmental Protection Technology Co., Ltd., a total of eleven experts led by professor Wang Zhansheng agreed that 130kg/h large ozone generators developed by this company reached the international advanced level with the maximum concentration of 296.3mg/L, the rated operating concentration of 154mg/L, the power consumption of 7.38kWh/kg and water temperature of 24.8℃, two sets of which have been successfully applied to the De-NOx project of Shaanxi Pucheng Clean Energy Chemical Co., Ltd. in 2012.
In 2011, Fujian Newland Environmental Protection Technology Co., Ltd. undertook the alternative investment project of resource conservation and environmental protection of the National Development and Reform Commission under the central budget—” the industrialization of large ozone generator devices and its application on the treatment of high-concentration organic wastewater(2011C0055)”.
In June 2012, passing the evaluation of the sci-tech achievement of the Science and Technology Development Promotion Center Ministry of Housing and Urban-Rural Development, “the development of large (120kg/h) ozone generator” project studied by Qingdao Guolin Industrial Co., Ltd. was considered to reach the international advanced level on the performance index with 121.2kg/h ozone output and 6.8kWh/kgO3 power consumption under the condition of cooling water temperature of 25℃ and ozone concentration of 150.2mg/L.
In 2012, Fujian Newland Environmental Protection Technology Co., Ltd. Undertook the national major sci-tech achievements transformation project of “Development and Industrialization of High-performance Large Ozone Generator of over 100kg/h”.
Jiangsu Kanger Ozone Co., Ltd. cooperated with Sumitomo Precision Industry Co., Ltd. in ozone technology from 2012 to 2013.
In 2013, Newland Environmental Protection Technology Co., Ltd undertook the national key special project for industrial revitalization and technological transformation—” Production Project for Large Ozone Generator Equipment with glass discharge tube”.
In 2014, Beijing Jinda Wanxiang Environmental Protection Technology Co., Ltd. was established to develop and design modular plate ozone generators, for which the ozone output of a single module unit can reach 2.5kg/h, and the maximum ozone output of combination can be up to 150kg/h. Among them, 150kg/h plate ozone generation system has been used in the De-NOx project. Moreover, the company established and put into operation a production line with an annual output of 10,000kg of plate ozone generators. This kind of ozone generators began to move towards large-scale production and was applied to the fields including the advanced treatment for water supply and De-NOx projects.
In 2016, Qingdao Guolin Industrial Co., Ltd. undertook the topic of “Co-absorption Technology based on Pre-ozonation” in the national key R&D plan of“Integrated Control Technology Engineering Demonstration Project of Coal-fired Pollutants(SO2,NOx,PM)”.
In 2017, Qingdao Guolin Industrial Co., Ltd. undertook the sub-topic ”Evaluation, Verification, and Standardization of Integrated Equipment R&D on Large Ozone Generator ”of national major special science and technology projects for the control and treatment of water pollution—“Evaluation and Standardization of Key Materials and Equipment for Urban Water Supply Systems". In the same year, the company, together with the School of Environment of Tsinghua University, Shandong urban water supply and drainage quality monitoring Center and other units, drafted the national standard “Technical Requirement of Ozone Generator For Water Treatment”, for which the approval process has been completed so far.
In 2018, Fujian Newland Environmental Protection Technology Co., Ltd. Won the second prize of National Science and Technology Award” Water Quality Safety Guarantee Technology and Application for Urban Centralized Reclaimed Water Systems”, in which major innovative achievements included breakthroughs in ozone/UV/chlorine disinfection technology, and manufacturing technology of large ozone generators and high-flow UV disinfection equipment, and the realization of high-standard disinfection of large reclaimed water systems.
In February 2018, Incorporated into Fujian Longjing Environmental Protection Co., Ltd.(stock code: 600338), Newland Environmental Protection Technology Co., Ltd. served as the first domestic manufacturer of ozone generators and ultraviolet disinfection products to be included in the operation of the listed company.
In November 2018, with professor Wei Linsheng as the first director, Ozone Professional Committee was established, affiliated with the China Association of Machinery Industry for Environmental Protection(CAMIE).
In June 2019, Qingdao Guolin Industrial Co., Ltd., with its initial public offering successfully, was listed on the Shenzhen Stock Exchange GEM(stock code: 300786), becoming the first listed company worldwide which mainly focused on ozone technology research and ozone equipment manufacturing.
Since 2005, scientific research institutions, represented by professor Wei Linsheng of School of Resource Environmental & Chemical Engineering, Nanchang University, and professor Wang Zhihua of Institute of Thermal Energy, Zhejiang University, have conducted in-depth research on the mechanism of ozone, including characteristics of reaction kinetics, streamer propagation, energy conversion, and heat transfer, as well as new discharge forms such as mixed discharge and pulse discharge, and have made fruitful achievements, thus laying the solid foundation for further improving the technical indicators of ozone generators.
This stage also witnessed the development of a batch of ozone analyzer manufacturers including Qingdao Langke Electronics Co., Ltd, and Zibo Zhipu Automation Technology Co., Ltd. However, in the light of performance indicators, there was still a great disparity with foreign brands.
- Research on Ozone ApplicationTechnology in China after 2000
After 2000, ozone was widely applied in the fields of drinking water treatment, sewage treatment, pulp bleaching, intermediate synthesis, textile decoloration, perfume synthesis, waste tire treatment, disease treatment, storage, and transportation, etc, and it especially gained rapid growth in the fields of water treatment and De-NOx.
Processor Wang Zhansheng from the Department of Environment and Engineering, Tsinghua University, has further studied the advanced treatment technology for drinking water—ozone + biological activated carbon technology for many years, pointing out the direction for the advanced treatment process of running water in China in the future. After 2000, the ozone-granular activated carbon (ozone-gac) process was adopted in water supply companies in Jiangsu, Shanghai, Shenzhen, Guangzhou, Hangzhou, Jiaxing, Changzhou, Tongxiang, and other places, as the application of ozone-activated carbon technology for advanced treatment of drinking water has reached an unprecedented scale in the water supply industry in China. In 2008, Qingdao Guolin Industrial Co., Ltd. won the bid for the 20kg/h ozone system of the Third Water Plant of Kunshan Water Supply Company, breaking the monopoly of imported ozone equipment in the field of municipal water supply. Since then, domestic ozone generators began its entry into the field of water supply treatment, and have occupied nearly half of the market in this industry. Qingdao Guolin Industrial Co., Ltd, and Newland Environmental Protection Technology Co., Ltd. performed well in this regard.
At present, the water plants using ozone-biological activated carbon advanced treatment processes have accomplished over 20 million m3/d of water treatment and equipped with more than 3000kg/h ozone generators. In the case where the deterioration of water quality has not been significantly improved, the improvement of drinking water quality standards will vigorously promote the application of O3 - GAC advanced treatment and optimization process which will gradually become the dominant advanced treatment technology for drinking water. If calculated according to the estimated water consumption of 94.9 million m3 in 2020, adding 3mg/L of ozone per cubic meter and 30% reserve, a total of 42,000 kg/h of ozone generators will be required.
In addition, the application of ozone is also a flashpoint in wastewater which is difficult to be treated, including high-concentration industrial wastewater and landfill leachate, and related studies are being carried out. Since 2008, 10kg/h ozone generators developed by Qingdao Guolin Industrial Co., Ltd. have been exported for the chemical oxidation project of Turkey MELTEM Company and 2 6.5kg/h ozone generators for the gold mine wastewater treatment project of Ghana P2W Company. As we can see, the domestic large and medium-sized ozone generators began to be applied to foreign water treatment projects.
De-NOx was regarded as one of the measures to control haze which has increasingly captured people’s attention in recent years. Regarding the treatment process for De-NOx, ozone attracted more attention on industries related to environmental protection compared with other oxidation methods. The ozone treatment process for De-NOx in the low temperature played a vital role in promoting the rapid growth of domestic ozone generators, driving the market demand for this kind of equipment and the technological innovation of large domestic ozone generators. Professor Wang Zhihua of Zhejiang University first proposed ozone denitration in China, and carried out a lot of basic research and applied research, as well as engineering applications. In 2018, the technology won the second prize of Zhejiang Province Technical Invention "Integrated Removal Technology of Multiple Pollutants in Flue Gas of Active Molecular Ozone Oxidation Combustion".
In 2010, PetroChina Sichuan Petrochemical Co., Ltd. introduced LoTOx low-temperature oxidation denitrification process from America and adopted three sets of 57kg/h ozone systems from Qingdao Guolin Industrial Co., Ltd. in flue gas treatment projects of its 2.5 million ton/year heavy oil fluid catalytic cracking unit. Since then, ozone oxidation denitrification technology has been used in large domestic De-NOx projects and gradually extended into the De-NOx treatment in many fields including coal-fired boilers, sintering machines in steel mills, roasters, and coke ovens. In the meantime, the domestic ozone generators market has expanded rapidly with the successful promotion application from enterprises including Qingdao Guolin Industrial Co., Ltd., Newland Environmental Protection Technology Co., Ltd, and Jinan Sankang Ozone Technology Company for 100-kilogram ozone generator products in this field. By the end of 2018, ozone denitrification at low temperature had driven the domestic demand for tens of thousands of kilograms of ozone output. Since 2015, ozone denitrification technology has also entered into the overseas market, and Newland Environmental Protection Technology Co., Ltd. won the bidding for the ozone denitrification project of the Atyrau refinery in Kazakhstan. Not only did The application of ozone generators in this field make tremendous contributions on the domestic flue gas treatment, but it also set the solid foundation for realizing the leap of domestic ozone equipment from quantitative changes to qualitative changes, thus making domestic ozone equipment manufacturers a bigger voice in the largest international ozone application market so far.
Conclusion
China has witnessed six to seven decades of development in ozone technology. The major performance indicators of ozone equipment have reached the international advanced level. At the time when our country pays the increasing attention to environmental protection, ozone technology is in the stage of rapid growth and is bound to embrace the greater development with the broader prospect. Furthermore, the international ozone market is also expanded year by year with the rise of developing countries. With excellent product quality, remarkable advantages in cost and services, China’s ozone equipment enjoys the greater competitiveness driven by National Belt and Road Initiative Policy, and will also create a wider international market. In the years to come, ozone technology in China will experience the development process that is from bigger to stronger, in which the major performance indicators of ozone equipment will reach and even catch up with the international leading level, as well as expand the scale of the occupation of international high-end markets.
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Translated by Qin Zeyu, Tianjin University
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