Analysis on the dangers and countermeasures of refining high sulfur crude oil

1 Introduction The crude oil workshop of Changling Branch is responsible for the supply of raw material oil for each production unit. With the increase of sulfur content in the crude oil processed by the branch, the phenomenon that the content of hydrogen sulfide in the tanks outside the tank is seriously exceeded. At the same time, a series of technical reform measures, such as wax oil hydrogenation and blending crude benzene, which are implemented by the branch to maximize the benefits, also make the time and frequency of storing high H 2 S feedstock in the tank area more and more. Therefore, the probability of occurrence of hydrogen sulfide poisoning accidents in the tank area also increases, and the corresponding prevention and control measures for the risk of high-sulfur crude oil is necessary to ensure the safe production of the tank area. 2 H 2 S hazard analysis The hydrogen sulfide produced by high-sulfur crude oil in one processing and subsequent processing process is not only corrosive to catalytic cracking, hydrocracking, catalytic reforming, hydrorefining, coking, visbreaking and other equipment, but also for storage and transportation. The corrosion of the facility cannot be ignored. The gas phase corrosion of light oil, dirty oil and liquid hydrocarbon systems in storage and transportation facilities is most prominent during processing. The hydrogen sulfide produced by various sulfides in the hydrodesulfurization reaction is mainly characterized by gas phase corrosion. Hydrogen sulfide is in contact with equipment to form metal sulfides, which are usually iron sulfide. At room temperature, iron sulfide is in contact with oxygen in the air, and an oxidative exothermic reaction occurs, causing a spontaneous combustion accident. For example , on February 20, 1998, a 2000m 3 coking gasoline tank in a petrochemical plant of a petrochemical plant was in the process of feeding, and a tank fire occurred due to spontaneous combustion of iron sulfide in the inner wall of the tank. On April 12, 1998, a 10,000 m 3 sulfur-containing sewage tank of a petrochemical plant's sewage stripping unit was suddenly fired due to spontaneous combustion of iron sulfide on the inner wall, which was caused by corrosion of hydrogen sulfide on the tank. The corrosion of various equipment in the crude oil workshop is also very serious, such as: 506#, 507#, 508#, 620#, 624#, 611#, 612#, 701#, 803#, 805#, 806# and other oils. The tank tops of the tanks have been corroded and perforated, and they cannot be completely deactivated due to production needs, which puts more stringent requirements on the metering safety of the workshop. There are 5 tanks in the workshop and there are 54 oil tanks. There are some problems in the metering instruments in the tank area. Some measuring instruments are old and aging and have no accessories. Some measuring instruments often fail, and the maintenance power can not keep up, resulting in These tanks must be manually inspected; some meters have large errors, which leads to inaccurate measurement, so the gauge must also be used. In recent years, due to the increase in the sulfur content of the crude oil refined by the branch, the number of hydrogen sulfide content exceeding the standard in each tank area has been greatly increased. The data displayed on the hydrogen sulfide alarm has sometimes reached 100 mg/m 3 or more, which greatly exceeds the national regulations. The workplace should not exceed the standard of 10mg/m 3 , especially the large classes such as Wuyi, Liuyi and Qiqi. At the same time, due to the operation of the I-set device to the later stage, the number of unplanned shutdowns has increased significantly, and the time and frequency of high-containing H 2 S feedstock oil generated by unplanned shutdowns in each tank area are increasing; plus coking wax oil hydrogenation and blending The implementation of a synergistic process such as refining crude benzene may lead to an increase in the S content in the oil in the tank area, which may easily cause various accidents. For example, in 1996 and 1994, there were two serious accidents in which there was a serious excess of hydrogen sulfide in the tank area, and the operator violated the regulations and caused hydrogen sulfide poisoning. 3 control measures According to the actual situation of each position in the workshop and the experience of the external control, the countermeasures for controlling the H 2 S hazard were formulated . See Table 1 for details. Table 1 Control H 2 S Hazard Countermeasures Table 3.1 Conducting safety awareness education so that everyone can achieve “I have a sense of safety” ( 1) Use the lessons of blood to carry out safety awareness education, make full use of the pre-class and post-class meetings, and the time of safety activities to communicate the recent accident information inside and outside the factory to each employee and conduct study and discussion, analyze and discuss these accidents. What rules and regulations are violated by the local authorities? What lessons should be learned in the future? What are the gaps in my work? ( 2) Organize safety publicity activities, make full use of publicity tools such as blackboard newspapers, radio and television, etc. to carry out safety education, and make safe production alarm bells. ( 3) In order to implement the spirit of safe production in a timely manner, we have taken a series of measures in security activities. Concentrate the safety activities that were originally dispersed in the team to the workshop. It is stipulated that each safety activity must be headed by a technician. There must be a workshop leader to participate, otherwise it will be considered invalid. At the same time, the workshop requires safety activities for the workshop every other week. week. During the week from Monday to Friday, every day, the white shifters in the workshops went to the workshop meeting room to organize safety activities. They consciously signed the safety activity sign-in form, effectively preventing the excessive concentration of safety activities and the phenomenon of false recordings. Participants will be punished according to the relevant provisions of the economic responsibility system of the workshop, so that the safety activities can be truly implemented in time, personnel and content. ( 4) Seriously do a good job in the three-level safety education of new workers. For those who have been away from the post for more than three months, they must resume their education. Only after passing the examination can they return to production. 3.2 Conduct operational knowledge and safety knowledge education for employees, so that I will (understand) safe skills and operational skills. ( 1) Closely combine safety education with post training, focusing on the improvement of post safety technology, improving the staff's post operation skills, and the ability to prevent and handle accidents. ( 2) Hold a fire and gas prevention knowledge class and ask all operators to participate. Conduct safety competitions, training, such as post anti-accident exercises, fire and gas defense knowledge contests, on-site fire fighting, first aid and other activities to improve the self-protection ability of employees. ( 3) Strengthen the training of employees on the use of protective equipment such as air breathing apparatus to ensure that every employee will use it. ( 4) Organize employees to learn the hazards and rescue measures of H2S. ( 5) Organizing employees to study the “Measures for Safety in Measurement”. To perform a metering operation, you must do the following: 1 It is strictly forbidden to carry firelights or put on spiked shoes. 2 The metering staff should stand in the upwind position when making measurement measurements on the tank; 3 illuminating lamps shall be equipped with explosion-proof luminaires, which shall leave the metering hole when the flashlight is turned on and off at night; 4 The metering hole should be lined with aluminum or lead pad, and the metering hole cover should be lightly stepped; 5 When measuring rain or snow, you should be very careful to prevent slipping or falling accidents; 6 The metering staff should eliminate the static electricity carried by the human body before the tank is placed on the tank. The speed of the ruler and the lower ruler should not be too fast. 3.3 Strengthen the staff's rules and regulations and legal education, and impose strict penalties on those who violate the rules and disciplines, so that everyone can achieve "I want to be safe." ( 1) In safety education, we pay special attention to explaining that safety rules and regulations are a supplement to national laws. Violation of regulations is illegal. Those who violate the rules are victims. If they violate the law, they will be sanctioned by law, so that everyone can know and understand the law. Obey the law and obey the rules. ( 2) Inspection and assessment of strict safety rules and regulations. The pre-holiday safety inspection, daily safety inspection, and seasonal safety inspection were carried out. The inspection situation was linked to the economic responsibility system; the inspection system was implemented once a month for small inspections, once a week for HSE inspections, and once for safety inspections of the team. The workshop will report the problems of each inspection to the whole workshop, and rectify the problems found within a time limit, and formulate preventive measures for rectification at a time, so that the employees can understand the hidden dangers in their posts. ( 3) Increase the propaganda of the dangers of hydrogen sulfide, formulate the “Procedures for the Treatment of Hydrogen Sulfide Poisoning Accidents” and print the “Dangers of Hydrogen Sulfide with Different Concentrations on the Human Body” to the relevant posts, and organize the employees to study seriously. Efforts will be made to improve employees' awareness of the dangers of hydrogen sulfide. They do not conduct random checks on a regular basis, impose strict penalties on employees who cannot answer them, and set up warning signs for “no cans” at important locations. The procedures for handling hydrogen sulfide poisoning accidents are shown in Table 2. The harms of different concentrations of hydrogen sulfide to human body are shown in Table 3. Table 2 Hydrogen sulfide poisoning accident handling procedures Table 3 harm to human body by different concentrations of hydrogen sulfide 3.4 Formulate relevant regulations for the period of hydrogen sulfide exceeding the standard and the cans of the cans to ensure the personal safety of the metering personnel In order to ensure the personal safety of the upper cans, the workshop has specially formulated the relevant safety production regulations for preventing H2S poisoning in the hydrogen sulfide super standard period in the tank area according to the actual situation of each post , and requires the operators and workshops of the post. Managers strictly follow the prescribed requirements to carry out related operations. For example, according to the actual situation of Wuyi, Liuyi, Qiyi and Torch positions, the workshop has timely formulated the “Safety Measures for Preventing H2S Poisoning in Wuyi”, “Safety Measures for Prevention of H2S Poisoning in Liuyi”, and “H2S Poisoning Prevention in Seven Miles”. "Safety measures" and "Torch 1 # gas cabinet film disease operation safety regulations", and organized staff to learn. According to the actual situation of the operation of the dangerous tank, the workshop has also formulated the regulations for the cans on the dangerous tanks, and the operators are required to strictly follow the regulations. According to the situation that the concentration of hydrogen sulfide in the crude benzene gas phase exceeds 4000 mg /m3, the safety department of the crude benzene unloading and storage (provisional) is formulated with the superior safety department, and the seven-inch operator is strictly enforced. In this safety regulation, not only the safety measures for unloading crude benzene and storing crude benzene are specified, but also the hazards and first aid measures of benzene are introduced, and employees are organized to study. 3.5 Governing safety hazards such as dangerous tanks In recent years, with the strong support of the relevant departments at the higher level, we have managed 506#, 507#, 624#, 611#, 612#, 803#, 805#, 806# eight dangerous tanks, The hidden dangers were treated, and the 515# gas-liquid separation container and related automatic control system were used, and the 620# and 701# two dangerous tanks were suspended in time. Due to the implementation of these measures, the intrinsic safety level of the workshop personnel and equipment has been improved, and the production safety of refining high-sulfur crude oil has been guaranteed. 4 legacy issues Although the intrinsic safety level of workshop personnel and equipment has been improved to some extent, due to factors such as funds, the following problems also exist, waiting to be resolved in future work: ( 1) There are still 620# and 701# two dangerous tanks that have not been treated. ( 2) The equipment in the tank area is seriously corroded, and a large number of atmospheric pressure storage tanks have not been inspected. ( 3) 1# gas cabinet membrane with disease operation, at any time may cause a large number of high-H2S-containing gas leakage accidents caused by tearing of the membrane.

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