China Petrochemical Co., Ltd. Qilu Branch Research Institute has undertaken the 2006 National Science and Technology Progress Award for the series of catalysts and application technology for steam conversion of hydrocarbon raw materials.
Hydrogen is an indispensable raw material for refining and chemical companies to improve the depth of crude oil processing, produce clean fuel and produce synthetic ammonia. It is also the raw material for many fine chemical production processes.
At present, the steam reforming method using hydrocarbons as a raw material is a basic industrial hydrogen production method using a wide range of zui and high efficiency. The process is: the hydrocarbon raw material is purified, steamed, mixed and preheated, and enters a temperature-transformed catalyst bed of about 500 ° C to 850 ° C to generate a steam (and CO 2 ) catalytic conversion reaction to form H 2 , CO, The crude syngas of CO2 and a small amount of CH4 is converted and decarburized, methanated or PSA purified to produce high purity industrial hydrogen and carbonyl synthesis gas with different H2/CO ratios, respectively.
The key technology of this process is applied to steam reforming catalysts in a variable temperature bed from 500 °C to 850 °C. Since the conversion reaction is carried out under high temperature, high pressure and high water vapor (and CO2) partial pressure, it is a strong endothermic reaction process, and the conversion catalyst is required to have high and stable conversion activity, excellent mechanical strength and erosion resistance. When a higher hydrocarbon is used as a raw material, the conversion catalyst must also have good carbon deposition resistance, poisoning resistance and regeneration performance. Therefore, the development of hydrocarbon steam reforming catalysts is highly technically difficult.
With the support of relevant state ministries and commissions and Sinopec, Sinopec Qilu Branch has developed and researched and promoted it continuously for 30 years, from natural gas as raw material to naphtha with 210°C dry point. The series of hydrocarbon steam reforming catalysts and using technologies have won more than 10 invention patents, and the series of catalysts and using technologies have reached the international advanced level. It replaced 7 brand-name catalysts of 4 well-known foreign companies, and realized the complete localization of hydrocarbon steam reforming catalysts. The market share was over 95%, and significant economic and social benefits were achieved.
The preliminary development of the project is aimed at large-scale ammonia plant using naphtha as raw material. The purpose of this project is to introduce the localization of catalysts. Based on this, the development of different raw materials, different processes, different conditions and different scales has been developed. Series catalysts. These include catalyst Z409/Z405G for heavy naphtha conversion, catalyst Z402/Z405G for light naphtha conversion, catalyst Z417/Z418 for light hydrocarbon conversion such as naphtha and refinery gas, suitable for natural gas conversion. Catalysts Z412/Z413 and Z416, catalyst QZ201/QZ202 suitable for two-stage conversion and autothermal conversion, naphtha pre-conversion catalyst Z501 suitable for energy-saving large-scale hydrogen production, catalyst Z502 suitable for natural gas pre-conversion and suitable for refining The catalyst Z503, which is pre-converted by the plant gas, forms a series of hydrocarbon steam reforming catalysts, which meets the needs of all current hydrogen production and syngas production. The successful development of series of conversion catalysts has been widely applied to industrial installations, with more than 60 users. It has achieved good application results in both imported and domestic equipment, and its performance is superior to that of foreign similar catalysts, constantly creating operating cycles and A new record of production. It plays an increasingly important role in refining, petrochemical, fertilizer, methanol and oxo gas.
Since the 1990s, China's petroleum refining and petrochemicals have developed rapidly, and the demand for hydrogen is increasing. Various refineries in China have begun to build a large number of hydrogen production facilities using high-grade hydrocarbons such as refinery gas, LPG, and light naphtha, and are developing toward large-scale, energy-saving, and high-efficiency. In recent years, China has put forward higher standards for the production of clean fuels. In addition, the price of crude oil has risen sharply, and it is required to further increase the depth of crude oil processing. Therefore, the refining process uses a large number of various hydrotreating processes, resulting in an increase in the demand for hydrogen. Big. There are nearly 30 sets of hydrogen production devices being designed and constructed in China. The hydrogen production equipment is rapidly increasing, the scale of the equipment is getting larger and larger, and the hydrogen production raw materials are increasingly diversified and inferior. The requirements for serialized hydrocarbon steam reforming catalysts and using technologies are put forward. At the same time, in order to save energy and reduce consumption, an industrial device for producing H2 and CO by steam conversion from hydrocarbons is proposed, and “three highs and one lowâ€, that is, high conversion inlet/outlet temperature, high space velocity, high heat flux and low water carbon are proposed. More than the process requirements. In combination with the development and application of new hydrogen production and syngas processes in recent years, and adapting to the development trend of domestic hydrogen production materials, the new development has been successfully applied to the conversion of low-cost hydrocarbon raw materials such as refinery gas and the high activity and low use of large-scale hydrogen production. Bed resistance series catalyst, suitable for the production process and catalyst of carbonyl synthesis gas with different CO content. It has played an important role in promoting the scientific and technological progress of China's hydrogen production and syngas production technology.
The Qilu Branch Research Institute not only developed a series of hydrocarbon steam reforming catalysts, but also improved the catalyst use technology. According to the different process characteristics, different raw material types, different types of reformer and design conditions of each user's production equipment, it is recommended to use reasonable catalyst combination and Zuijia's use of process conditions, and provide on-site technical services to timely solve the production process due to process conditions. Due to fluctuations in catalyst poisoning, carbon deposits and other accidents, Zui has largely solved problems for users. In addition, for the production requirements of methanol synthesis gas and oxo-syngas, research and development of the conversion furnace inlet with different levels of CO2, and adjust the water-carbon ratio and outlet temperature to produce high-CO content syngas, controllable Syngas with a suitable H2/CO ratio is produced.
The promotion and application of series of hydrocarbon steam reforming catalysts have replaced all imported products, which has promoted the comprehensive progress of China's hydrogen production and syngas technology. It has created conditions for China's clean fuel production, improving the utilization rate of crude oil processing, and making full use of limited resources. As the activity of the catalyst is improved, the applicability of the raw material is enhanced, the resistance of the bed is decreased, and the service life is prolonged, the energy consumption and material consumption of the production device are lowered, the production cost is lowered, and the production efficiency is remarkably improved. In addition, in view of the relative shortage of petroleum resources and the relatively abundant coal resources in China, the “coal to oil†of coal hydro-hydrogenation direct liquefaction and indirect liquefaction technology will have great development, and the relatively cheap hydrogen source for coal hydro-liquefaction technology. Promoting implementation, achieving energy structure upgrading and upgrading, and achieving technological leapfrog have positive practical significance.
The main accomplishers are Hao Shuren, Cheng Yuchun, Yin Changxue, Gao Jianguo, Shi Fangzhu, Wen Daowen, Niu Chunde, Liang Weizhong, Wang Xiaoxin, Zhang Guoliang, Wan Shouyu, Mao Pengsheng, Li Zhenhua, Tan Yongfang, Li Shiqin. Hao Muren, professor-level senior engineer, deputy chief engineer of Qilu Branch Research Institute, secretary-general of Sinopec Light Oil Hydrogen Technology Technical Contact Station. Young and middle-aged experts with outstanding contributions from the Ministry of Personnel. The person in charge of the series of catalysts for the steam conversion of hydrocarbon feedstocks and the use of technology.
Hydrogen is an indispensable raw material for refining and chemical companies to improve the depth of crude oil processing, produce clean fuel and produce synthetic ammonia. It is also the raw material for many fine chemical production processes.
At present, the steam reforming method using hydrocarbons as a raw material is a basic industrial hydrogen production method using a wide range of zui and high efficiency. The process is: the hydrocarbon raw material is purified, steamed, mixed and preheated, and enters a temperature-transformed catalyst bed of about 500 ° C to 850 ° C to generate a steam (and CO 2 ) catalytic conversion reaction to form H 2 , CO, The crude syngas of CO2 and a small amount of CH4 is converted and decarburized, methanated or PSA purified to produce high purity industrial hydrogen and carbonyl synthesis gas with different H2/CO ratios, respectively.
The key technology of this process is applied to steam reforming catalysts in a variable temperature bed from 500 °C to 850 °C. Since the conversion reaction is carried out under high temperature, high pressure and high water vapor (and CO2) partial pressure, it is a strong endothermic reaction process, and the conversion catalyst is required to have high and stable conversion activity, excellent mechanical strength and erosion resistance. When a higher hydrocarbon is used as a raw material, the conversion catalyst must also have good carbon deposition resistance, poisoning resistance and regeneration performance. Therefore, the development of hydrocarbon steam reforming catalysts is highly technically difficult.
With the support of relevant state ministries and commissions and Sinopec, Sinopec Qilu Branch has developed and researched and promoted it continuously for 30 years, from natural gas as raw material to naphtha with 210°C dry point. The series of hydrocarbon steam reforming catalysts and using technologies have won more than 10 invention patents, and the series of catalysts and using technologies have reached the international advanced level. It replaced 7 brand-name catalysts of 4 well-known foreign companies, and realized the complete localization of hydrocarbon steam reforming catalysts. The market share was over 95%, and significant economic and social benefits were achieved.
The preliminary development of the project is aimed at large-scale ammonia plant using naphtha as raw material. The purpose of this project is to introduce the localization of catalysts. Based on this, the development of different raw materials, different processes, different conditions and different scales has been developed. Series catalysts. These include catalyst Z409/Z405G for heavy naphtha conversion, catalyst Z402/Z405G for light naphtha conversion, catalyst Z417/Z418 for light hydrocarbon conversion such as naphtha and refinery gas, suitable for natural gas conversion. Catalysts Z412/Z413 and Z416, catalyst QZ201/QZ202 suitable for two-stage conversion and autothermal conversion, naphtha pre-conversion catalyst Z501 suitable for energy-saving large-scale hydrogen production, catalyst Z502 suitable for natural gas pre-conversion and suitable for refining The catalyst Z503, which is pre-converted by the plant gas, forms a series of hydrocarbon steam reforming catalysts, which meets the needs of all current hydrogen production and syngas production. The successful development of series of conversion catalysts has been widely applied to industrial installations, with more than 60 users. It has achieved good application results in both imported and domestic equipment, and its performance is superior to that of foreign similar catalysts, constantly creating operating cycles and A new record of production. It plays an increasingly important role in refining, petrochemical, fertilizer, methanol and oxo gas.
Since the 1990s, China's petroleum refining and petrochemicals have developed rapidly, and the demand for hydrogen is increasing. Various refineries in China have begun to build a large number of hydrogen production facilities using high-grade hydrocarbons such as refinery gas, LPG, and light naphtha, and are developing toward large-scale, energy-saving, and high-efficiency. In recent years, China has put forward higher standards for the production of clean fuels. In addition, the price of crude oil has risen sharply, and it is required to further increase the depth of crude oil processing. Therefore, the refining process uses a large number of various hydrotreating processes, resulting in an increase in the demand for hydrogen. Big. There are nearly 30 sets of hydrogen production devices being designed and constructed in China. The hydrogen production equipment is rapidly increasing, the scale of the equipment is getting larger and larger, and the hydrogen production raw materials are increasingly diversified and inferior. The requirements for serialized hydrocarbon steam reforming catalysts and using technologies are put forward. At the same time, in order to save energy and reduce consumption, an industrial device for producing H2 and CO by steam conversion from hydrocarbons is proposed, and “three highs and one lowâ€, that is, high conversion inlet/outlet temperature, high space velocity, high heat flux and low water carbon are proposed. More than the process requirements. In combination with the development and application of new hydrogen production and syngas processes in recent years, and adapting to the development trend of domestic hydrogen production materials, the new development has been successfully applied to the conversion of low-cost hydrocarbon raw materials such as refinery gas and the high activity and low use of large-scale hydrogen production. Bed resistance series catalyst, suitable for the production process and catalyst of carbonyl synthesis gas with different CO content. It has played an important role in promoting the scientific and technological progress of China's hydrogen production and syngas production technology.
The Qilu Branch Research Institute not only developed a series of hydrocarbon steam reforming catalysts, but also improved the catalyst use technology. According to the different process characteristics, different raw material types, different types of reformer and design conditions of each user's production equipment, it is recommended to use reasonable catalyst combination and Zuijia's use of process conditions, and provide on-site technical services to timely solve the production process due to process conditions. Due to fluctuations in catalyst poisoning, carbon deposits and other accidents, Zui has largely solved problems for users. In addition, for the production requirements of methanol synthesis gas and oxo-syngas, research and development of the conversion furnace inlet with different levels of CO2, and adjust the water-carbon ratio and outlet temperature to produce high-CO content syngas, controllable Syngas with a suitable H2/CO ratio is produced.
The promotion and application of series of hydrocarbon steam reforming catalysts have replaced all imported products, which has promoted the comprehensive progress of China's hydrogen production and syngas technology. It has created conditions for China's clean fuel production, improving the utilization rate of crude oil processing, and making full use of limited resources. As the activity of the catalyst is improved, the applicability of the raw material is enhanced, the resistance of the bed is decreased, and the service life is prolonged, the energy consumption and material consumption of the production device are lowered, the production cost is lowered, and the production efficiency is remarkably improved. In addition, in view of the relative shortage of petroleum resources and the relatively abundant coal resources in China, the “coal to oil†of coal hydro-hydrogenation direct liquefaction and indirect liquefaction technology will have great development, and the relatively cheap hydrogen source for coal hydro-liquefaction technology. Promoting implementation, achieving energy structure upgrading and upgrading, and achieving technological leapfrog have positive practical significance.
The main accomplishers are Hao Shuren, Cheng Yuchun, Yin Changxue, Gao Jianguo, Shi Fangzhu, Wen Daowen, Niu Chunde, Liang Weizhong, Wang Xiaoxin, Zhang Guoliang, Wan Shouyu, Mao Pengsheng, Li Zhenhua, Tan Yongfang, Li Shiqin. Hao Muren, professor-level senior engineer, deputy chief engineer of Qilu Branch Research Institute, secretary-general of Sinopec Light Oil Hydrogen Technology Technical Contact Station. Young and middle-aged experts with outstanding contributions from the Ministry of Personnel. The person in charge of the series of catalysts for the steam conversion of hydrocarbon feedstocks and the use of technology.
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