Series of catalysts and technology for hydrogen production from hydrocarbon feedstock by steam reforming

The Research Institute of Qilu Branch of China Petroleum and Chemical Corporation has won the 2006 National Science and Technology Progress Award for the series catalyst and application technology project of hydrogen production from hydrocarbon feedstock steam conversion Hydrogen is an indispensable raw material for refining and chemical enterprises to improve crude oil processing depth, produce clean fuel and produce synthetic ammonia, and it is also a raw material for many fine chemical production processes At present, the steam reforming method with hydrocarbon as raw material is a basic industrial hydrogen production method with wide application and high efficiency The process is as follows: the raw material of hydrocarbon is purified, steam is added, mixed and preheated, and water vapor (and CO2) is generated in the variable temperature conversion catalyst bed at 500 ℃ - 850 ℃ The crude syngas containing H2, Co, CO2 and a small amount of CH4 is generated After transformation and decarbonization, methanation or PSA purification, high-purity industrial hydrogen and carbonyl synthesis with different H2 / CO ratio are produced respectively Qi The key technology of this process is to apply it to the steam reforming catalyst in the variable temperature bed of 500 ℃ - 850 ℃ Because 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, which requires the conversion catalyst to have high and stable conversion activity, excellent mechanical strength and erosion resistance When hydrocarbon is used as raw material, the conversion catalyst must also have good anti coking performance, anti poisoning performance and regeneration performance Therefore, it is very difficult to develop hydrocarbon steam reforming catalyst The Research Institute of Sinopec Qilu Branch, with the support of relevant ministries and commissions of the state and Sinopec, has successfully developed a series of hydrocarbon steam conversion catalysts and application technologies from natural gas as raw material to naphtha with dry point of 210 ℃ through continuous development, research and promotion for 30 years, and has obtained more than 10 inventions The series catalysts and application technologies have reached the international level Advanced level It has replaced 7 brands of catalysts from 4 well-known foreign companies, realized the complete localization of hydrocarbon steam reforming catalysts, with a market share of more than 95%, and achieved remarkable economic and social benefits The preliminary development work of the project is aimed at the large-scale ammonia synthesis plant with naphtha as raw material The purpose is to introduce the domestic catalyst On this basis, a series of catalysts are developed for different raw materials, different processes, different conditions and different scale of process requirements The catalysts include Z409 / Z405G for heavy naphtha conversion, Z402 / Z405G for light naphtha conversion, Z417 / Z418 for naphtha and refinery gas conversion, z412 / z413 and z416 for natural gas conversion, QZ201 / QZ202 for second stage conversion and autothermal conversion, and pre conversion of naphtha for large-scale hydrogen production Chemical catalyst Z501, catalyst z502 suitable for pre conversion of natural gas and catalyst Z503 suitable for pre conversion of refinery gas form a series of hydrocarbon steam conversion catalysts to meet the current demand for hydrogen production and synthesis gas manufacturing A series of successfully developed conversion catalysts have been widely used in industrial units, with more than 60 users Good application results have been achieved in both imported units and domestic units Their performance is superior to that of foreign similar catalysts, and new records of operation cycle and output have been created It plays an increasingly important role in the fields of oil refining, petrochemical industry, chemical fertilizer, methanol and carbonyl syngas Since 1990s, with the rapid development of petroleum refining and petrochemical industry in China, the demand for hydrogen is increasing Domestic refineries began to build a large number of hydrogen production units with refinery gas, LPG, light naphtha and other hydrocarbons as raw materials, and are developing towards large-scale, energy-saving and efficient direction In recent years, China has put forward higher standards for the production of clean fuels In addition, the price of crude oil has increased significantly, which requires further improvement of crude oil processing depth Therefore, a large number of various hydrotreating processes are used in the refining process, resulting in an increased demand for hydrogen There are nearly 30 sets of hydrogen production units under design and construction in China With the rapid increase of hydrogen production units and the increasing scale of units, the raw materials for hydrogen production are becoming more and more diversified and inferior, which puts forward higher requirements for the series of hydrocarbon steam reforming catalysts and their application technologies At the same time, in order to save energy and reduce consumption, the process requirements of "three high and one low", i.e high conversion inlet / outlet temperature, high airspeed, high heat flux and low water / carbon ratio, are put forward for the industrial unit that uses hydrocarbon as raw material for steam conversion to produce H2 and Co Combined with the development and application of new processes for hydrogen production and syngas production in recent years, and in line with the development and change trend of domestic hydrogen production raw materials, new series catalysts with high activity and low bed resistance, which are suitable for the conversion of cheap hydrocarbon raw materials such as refinery gas and large-scale hydrogen production, are successively developed, and are suitable for the processes and catalysts for the production of carbonyl syngas with different CO content It has played an important role in promoting the technological progress of hydrogen production and syngas production in China The Research Institute of Qilu Company not only developed a series of hydrocarbon steam reforming catalysts, but also improved the use technology of catalysts According to the different process characteristics, different raw materials, different converter types and design conditions of each user's production unit, reasonable catalyst combination and Zui's best use process conditions can be recommended, and on-site technical services can be provided to timely solve the catalyst poisoning, carbon deposition and other accidents caused by the fluctuation of process conditions in the production process, and Zui can solve the problems for users to a large extent In addition, according to the production requirements of methanol synthesis gas and carbonyl synthesis gas, the method of adding different content of CO2 into the converter inlet is studied and developed, and the water carbon ratio and outlet temperature are adjusted accordingly to produce synthesis gas with high CO content and the synthesis gas with proper H2 / CO ratio can be produced in a controllable way The promotion and application of a series of hydrocarbon steam reforming catalysts have replaced all the imported products of all brands and promoted the overall progress of hydrogen production and synthesis gas technology in China It creates conditions for clean fuel production, improving crude oil processing utilization ratio and making full use of limited resources Due to the increase of catalyst activity, the increase of raw material applicability, the decrease of bed resistance and the prolongation of service life, the energy consumption and material consumption of the production unit are reduced, the production cost is reduced, and the production efficiency is obviously improved In addition, in view of the relative shortage of petroleum resources and the relative abundance of coal resources in China, the "coal to oil" technology of direct and indirect coal hydrogenation liquefaction will have a great development The relatively cheap hydrogen source has a positive practical significance for the promotion and implementation of coal hydrogenation liquefaction technology, the realization of energy structure upgrading and the realization of technology leapfrogging Mainly completed by Hao Shuren, Cheng Yuchun, Yin Changxue, Gao Jianguo, Shi Fangzhu, Zhong Daowen, Niu Chunde, Liang Weizhong, Wang Xiaoxin, Zhang Guoliang, Wan Shouyu, Mao Pengsheng, Li Zhenhua, Tan Yongfang, Li Shiqin Hao Cunren, Professor engineer, deputy chief engineer of Research Institute of Qilu Branch, Secretary General of Sinopec light oil hydrogen production technical liaison station Young and middle-aged experts with outstanding contributions from the Ministry of personnel of the people's Republic of China Project leader of series catalyst and application technology for hydrogen production from hydrocarbon feedstock steam conversion.