WO2020062377A1 - 一种涉硫石化设备腐蚀自燃预测方法 - Google Patents

一种涉硫石化设备腐蚀自燃预测方法 Download PDF

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WO2020062377A1
WO2020062377A1 PCT/CN2018/111767 CN2018111767W WO2020062377A1 WO 2020062377 A1 WO2020062377 A1 WO 2020062377A1 CN 2018111767 W CN2018111767 W CN 2018111767W WO 2020062377 A1 WO2020062377 A1 WO 2020062377A1
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sulfur
spontaneous combustion
gas
predicting
petrochemical equipment
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PCT/CN2018/111767
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English (en)
French (fr)
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王志荣
沈硕勋
赵声萍
蒋军成
赵雪娥
窦站
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南京工业大学
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Priority to US16/958,753 priority Critical patent/US11428654B2/en
Publication of WO2020062377A1 publication Critical patent/WO2020062377A1/zh

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/02—Investigating or analyzing materials by the use of thermal means by investigating changes of state or changes of phase; by investigating sintering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/04—Corrosion probes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • G01N31/224—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for investigating presence of dangerous gases
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0042—SO2 or SO3
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0062—General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method or the display, e.g. intermittent measurement or digital display
    • G01N33/0063—General constructional details of gas analysers, e.g. portable test equipment concerning the measuring method or the display, e.g. intermittent measurement or digital display using a threshold to release an alarm or displaying means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4075—Limiting deterioration of equipment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D35/00—Controlling engines, dependent on conditions exterior or interior to engines, not otherwise provided for
    • F02D35/02—Controlling engines, dependent on conditions exterior or interior to engines, not otherwise provided for on interior conditions
    • F02D35/025—Controlling engines, dependent on conditions exterior or interior to engines, not otherwise provided for on interior conditions by determining temperatures inside the cylinder, e.g. combustion temperatures
    • G—PHYSICS
    • G08—SIGNALLING
    • G08B—SIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B21/00—Alarms responsive to a single specified undesired or abnormal condition and not otherwise provided for
    • G08B21/02—Alarms for ensuring the safety of persons
    • G08B21/12—Alarms for ensuring the safety of persons responsive to undesired emission of substances, e.g. pollution alarms
    • G08B21/16—Combustible gas alarms
    • G—PHYSICS
    • G08—SIGNALLING
    • G08B—SIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B21/00—Alarms responsive to a single specified undesired or abnormal condition and not otherwise provided for
    • G08B21/18—Status alarms
    • G08B21/182—Level alarms, e.g. alarms responsive to variables exceeding a threshold

Definitions

  • the invention relates to the technical field of safety prediction methods, in particular to a method for predicting the spontaneous combustion of sulfur-related petrochemical equipment.
  • Crude oil has been mined for more than a hundred years. At present, the world ’s crude oil consumption is increasing. Traditional light and low-sulfur crude oil production in North Africa is rapidly decreasing. Asian low-density and low-sulfur crude oil is also decreasing. Weight and sulfur content are also increasing. In the future, the quality of world crude oil will tend to be heavy and sulfur-containing.
  • the corrosion of oil storage tanks by active sulfur present in sulfur-containing oils on active sulfur in oils belongs to low-temperature sulfur corrosion.
  • H 2 S in active sulfur has no corrosive effect on the inner wall of the storage tank under a low-temperature and dry environment, but will exhibit strong corrosiveness in the presence of water.
  • the effect of the anticorrosive layer on the inner wall surface of the tank wall decreases, resulting in chemical and electrochemical corrosion of the wall surface, resulting in a mixture mainly composed of FeS.
  • H 2 S in the active sulfur further corroded the tank wall, slowly forming a sac-like or layered substance, which was composed of a sulfur iron compound, a rust-like compound, elemental sulfur, and a small amount of water and oil droplets.
  • Elemental sulfur and other flammable sulfur iron oxide solid particles constitute a flammable substance on the inner wall of the storage tank.
  • the tops of atmospheric pressure reduction, catalytic cracking, coking and other devices in the refinery and their condensation cooling systems, as well as the tops of wastewater stripping towers, air cooling of sulfurization and dehydrogenation reactors, etc. are opened and cleaned after shutdown During the inspection and maintenance, the phenomenon of oxidation and self-heating of sulfur iron compounds will occur frequently.
  • the corrosion products of previous scientific research are mostly single corrosion products, which cannot effectively simulate the sulfide and iron compounds generated in the sulphur-related petrochemical equipment under actual conditions.
  • Temperature measurement method The temperature sensor is installed inside the device. Because it is a point contact, the prediction range is small, and the workload of installation and maintenance is large, especially the temperature sensor's probe and lead are vulnerable to damage; the iconic gas detection method is set. If the quantitative index is too high, there is a certain hysteresis. In the case of fast oxidation reaction, the prediction of the spontaneous combustion in the equipment is not timely enough; the manual inspection workload is large and the interval is long, and continuous real-time detection cannot be performed.
  • the invention provides a method for predicting the spontaneous combustion of sulfur-related petrochemical equipment to solve the technical problems that the prediction range in the prior art is relatively small, the workload of installation and maintenance is large, and the situation of spontaneous combustion of corrosion in the equipment is not timely enough.
  • the technical solution of the present invention is as follows: a method for predicting the spontaneous combustion of sulfur-related petrochemical equipment, including the step of predicting a dual index system; Steps for detecting the generated SO 2 gas;
  • the steps for temperature monitoring are:
  • thermocouple connected to the outer wall of the sulfur-related petrochemical equipment, and the temperature measurement value is displayed by a temperature measuring instrument and the temperature rise data is transmitted to the temperature parameter data processing equipment;
  • the temperature parameter data processing device compares the temperature rise situation data in the sulfur-related petrochemical equipment with the temperature rise critical index to determine whether the alarm is turned on, and transmits a signal to the DCS central control system if the alarm needs to be turned on;
  • the DCS central control system turns on the alarm after receiving the alarm signal
  • the step of detecting the SO 2 gas generated by spontaneous combustion includes:
  • the wireless SO 2 gas detector connected to the sulfur-related petrochemical equipment is used to detect the SO 2 gas concentration in the sulfur-related petrochemical equipment, and the sulfurization degree in the equipment is determined based on the SO 2 gas concentration, and the sulfurization degree data is transmitted to Gas concentration parameter data processing equipment;
  • the gas concentration parameter data processing device compares the sulfurization degree data inside the sulfur-related petrochemical equipment with the critical value of the fitting formula corresponding to the sulfuration degree to determine whether the alarm is turned on, and transmits a signal to the case where the alarm needs to be turned on.
  • DCS central control system
  • the DCS central control system turns on the alarm after receiving the alarm signal.
  • thermocouple described in step A in the pair temperature monitoring step is an externally armored thermocouple.
  • the temperature rise critical index ⁇ Ts in the temperature monitoring step is calculated as follows:
  • ⁇ T s is the critical temperature rise for predicting the spontaneous combustion of sulfur-related petrochemical equipment, and the unit of measurement is °C;
  • ⁇ T max is the maximum temperature rise that may be reached during the initial period of oxidation when a sulfur-fired petrochemical equipment spontaneously ignites under the research conditions.
  • the unit of measurement is °C.
  • the critical index of ambient temperature rise ⁇ T s is 30 ° C.
  • corresponding cooling and cooling pre-control measures are taken for the equipment.
  • the critical value y s of the fitting formula corresponding to the degree of sulfurization in the step of detecting the SO 2 gas generated by spontaneous combustion is calculated as follows:
  • y s is the critical SO 2 gas concentration for predicting the spontaneous combustion of fires involving sulfur petrochemical equipment, and the unit of measurement is mg / ⁇ L;
  • y max is the maximum concentration of SO 2 gas under the research conditions, and the measurement unit is mg / ⁇ L.
  • the corrosion conditions generated during the spontaneous combustion of the sulfur-related petrochemical equipment include mild sulfurization and deep sulfurization.
  • cure and depth of cure can be calculated from the formula SO 2 Quantitative Relationship between concentration and time t y autoignition by:
  • y is the concentration of SO 2 gas, and the unit of measurement is mg / ⁇ L;
  • t is the reaction time, and the unit of measurement is min;
  • the SO 2 gas when the SO 2 gas is generated within 150 s after the start of the oxidation spontaneous combustion reaction, it is determined that the corrosion that occurs in the equipment is deep sulfurization; when the SO 2 gas is generated after the start of the oxidization spontaneous reaction, it is determined that the corrosion that occurs in the equipment is mild. vulcanization.
  • the present invention has the following beneficial effects:
  • the present invention has high accuracy. Using the quantitative relationship formula fitting the spontaneous combustion of corrosion products, it is possible to more accurately calculate the time.
  • the labor cost of the present invention is low, and it is not necessary to perform on-site gas detection in the form of manual detection, which reduces the cost and ensures detection accuracy.
  • the method of the present invention is simple to operate, and the prediction method uses the form of automatic detection of equipment detection and running programs, without requiring additional operations by the operator, ensuring detection accuracy and avoiding accidents caused by human errors.
  • the online real-time detection, real-time feedback of the monitoring results of the armored thermocouple and SO 2 gas detector ensure that the equipment is always under monitoring, and can promptly issue alarms and provide early warning.
  • FIG. 1 is a schematic structural diagram of the present invention for predicting the spontaneous combustion of sulfur-related petrochemical equipment.
  • FIG. 2 is a prediction flowchart of the method of the present invention.
  • 1-sulfur-related petrochemical equipment 2-thermocouple, 3-temperature measuring instrument, 4-temperature parameter data processing equipment, 5-DCS central control system, 6-gas concentration parameter data processing equipment, 7-wireless SO 2 Gas detector.
  • thermocouple According to the size of the floating roof tank, the porcelain sleeve with armored thermocouple is welded to the outer wall of the sulphur petrochemical equipment and the top of the gas phase space, which is easy to contact with the air to cause corrosion.
  • the thermocouple time constant is 15s.
  • the thermocouple is cold-terminated with a compensation wire, the other end of the compensation wire is connected with a temperature measuring instrument, and the temperature measuring instrument is connected with a temperature data processing device.
  • the starting time of the feedback reaction of the temperature measuring instrument is combined with the appearance time of the SO 2 gas detected by the wireless SO 2 gas detector to analyze and determine the degree of sulfuration of the corrosives in the floating roof tank.
  • the quantitative relationship between SO 2 concentration and time is fitted to the formula to obtain the maximum concentration of SO 2 gas y max and the critical value of the critical SO 2 gas concentration.
  • the SO 2 concentration in the device is detected in real time by the wireless SO 2 gas detector, and the SO 2 concentration value is fed back every 10 s by the gas detector. If the concentration reaches the SO 2 gas early warning concentration of the spontaneous fire, the time (tys) of the SO 2 gas concentration in the storage tank to reach the critical concentration is fed back to the DCS system.

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Abstract

一种涉硫石化设备腐蚀自燃预测方法，包括双指标体系预测的步骤；所述双指标体系预测的步骤，包括对温度监测的步骤和对自燃生成的SO 2气体检测的步骤；运用拟合腐蚀产物自燃产生的定量关系公式，能较为精确的计算出发生自燃的时间；人工成本较低，不必使用人工检测的形式进行现场气体检测，降低成本的同时还确保了检测精度。

Description

一种涉硫石化设备腐蚀自燃预测方法 技术领域
本发明涉及安全预测方法技术领域，具体涉及一种涉硫石化设备腐蚀自燃预测方法。
背景技术
原油开采至今已有百余年，当下世界原油消耗量不断增加，位于北非地区传统的轻质低硫原油出产率快速下降，亚洲低密度、低硫原油同时进一步减少，而波斯湾地区生产的原油重量和含硫量也在不断升高。今后，世界原油质量将趋向于重质化、含硫化。
含硫油品中存在的活性硫对油品中存在的活性硫对油品储罐的腐蚀属于低温硫腐蚀。活性硫中的H 2S处于低温干燥的环境下对储罐内壁没有腐蚀作用，但在有水的条件下会呈现出极强的腐蚀性。随着储罐服役时间的增加，罐壁内壁表面防腐层作用降低，导致壁面发生化学和电化学腐蚀，生成以FeS为主的混合物。随之，活性硫中的H 2S进一步腐蚀罐壁，缓慢形成囊状或者层状物质，该物质由硫铁化合物、铁锈类化合物、单质硫以及少量的水分和油滴组成，其中油滴、单质硫及其它可燃性硫铁氧化物固体颗粒构成了储罐内壁上的可燃物质。特殊地，炼油厂内常减压、催化裂化、焦化等装置的塔顶及其冷凝冷却系统，以及污水气提塔塔顶，加硫脱氢反应器空冷等部位，装置、设备停车后打开清洗、检测与维修期间硫铁化合物氧化自热现象均会频繁发生。
当有大量空气进入设备内部气相空间时，一方面硫铁化物快速氧化放出大量热，设备内壁上形成的囊状或层状物质阻碍了热量扩散，致导热量积聚而形成自燃，并引起可燃物质燃烧；另一方面，大量空气与油品挥发或气化出来的气体形成火灾、爆炸环境、热量积聚形成的自燃以及可燃物质的燃烧极易造成火灾、爆炸事故。
目前，石化工业中设备腐蚀自燃预测的几种方法都存在着一定的缺陷：先前科研研究的腐蚀产物多为单一腐蚀物无法有效模拟实际情况下涉硫石化设备内所生成的硫铁化物。测温法安装温度传感器在设备内部，由于是点接触，预测范围较小，安装、维护的工作量大，特别是温度传感的探头、引线极易遭受到破坏；标志性气体检测法设定的指标定量若过高的话，存在一定的滞后性，在氧化反应速度快的情况下，对设备内腐蚀自燃的情况预测不够及时；人工检测工作量大、间隔时间长，不能连续实时检测。
发明内容
本发明提供了一种涉硫石化设备腐蚀自燃预测方法，以解决现有技术中预测范围较小，安 装、维护的工作量大，对设备内腐蚀自燃的情况预测不够及时的技术问题。
为了解决上述技术问题，本发明的技术方案如下：一种涉硫石化设备腐蚀自燃预测方法，包括双指标体系预测的步骤；所述双指标体系预测的步骤，包括对温度监测的步骤和对自燃生成的SO 2气体检测的步骤；
所述对温度监测步骤为：
A.通过连接在涉硫石化设备外壁的热电偶进行实时温度测量，并且温度测量值通过测温仪表进行显示并且将温升情况数据传递至温度参数数据处理设备；
B.所述温度参数数据处理设备将涉硫石化设备内的温升情况数据与温升临界指标比对从而判断是否开启警报，在需要开启警报的情况下传送信号至DCS中控系统；
C.所述DCS中控系统接到报警信号后开启警报；
所述对自燃生成的SO 2气体检测的步骤包括：
A.通过连接在涉硫石化设备上的无线SO 2气体检测仪对涉硫石化设备内的SO 2气体浓度进行检测，并且根据SO 2气体浓度判定设备内的硫化程度，将硫化程度数据传递至气体浓度参数数据处理设备；
B.选用对应硫化程度的拟合公式的临界值；
C.所述气体浓度参数数据处理设备将涉硫石化设备内部的硫化程度数据和对应硫化程度的拟合公式的临界值进行比对从而判断是否开启警报，在需要开启警报的情况下传送信号至DCS中控系统；
D.所述DCS中控系统接到报警信号后开启警报。
优选的，所述对温度监测步骤中的步骤A中所述的热电偶为外部铠装热电偶。
优选的，所述对温度监测步骤中的温升临界指标△Ts的计算方式如下：
ΔT s＝C sΔT max
式中，△T s为预测涉硫石化设备自燃火灾的临界温升，计量单位为℃；
C s为安全控制系数，在大空间建筑中采用Cs＝0.2～0.8，本预警方法优选C s＝0.5；
△T max为研究工况下，涉硫石化设备发生自燃火灾时，在氧化初始期可能达到的最大温升，计量单位为℃。
更优选的，环境温升临界指标△T s取30℃，在设备内温升超过30℃时，则对该设备采取相应的冷却降温预控措施。
优选的，所述对自燃生成的SO 2气体检测的步骤中对应硫化程度的拟合公式的临界值y s 的计算方式如下：
y s＝C sy max
式中，y s为预测涉硫石化设备自燃火灾的临界SO 2气体浓度，计量单位为mg/μL；
C s为安全控制系数，在大空间建筑中采用C s＝0.2～0.8；
y max为研究工况下SO 2气体的最大浓度，计量单位为mg/μL。
优选的，所述涉硫石化设备腐蚀自燃中产生的腐蚀情况包括轻度硫化和深度硫化。
更优选的，对于轻度硫化和深度硫化情况下可通过如下的自燃生成SO 2浓度y与时间t的定量关系公式进行计算：
1)轻度硫化：
Figure PCTCN2018111767-appb-000001
2)深度硫化：
Figure PCTCN2018111767-appb-000002
其中，y为SO 2气体浓度，计量单位为mg/μL；
t为反应时间，计量单位为min；
对SO 2浓度y与时间t定量关系拟合公式两边求一阶导数，令dy/dt＝0，可求得SO 2气体浓度y达到最大值时的对应时间t max，把t max代入拟合公式则可得到SO 2气体的最大浓度y max。
对深度硫化产物其自燃火灾的SO 2气体预警浓度宜取y s＝0.017mg/μL；对轻度硫化产物的自燃火灾SO 2气体预警浓度宜取y s＝0.012mg/μL。
更优选的，在氧化自燃反应开始后150s内产生SO 2气体时，判定设备内发生的腐蚀为深度硫化；在氧化自燃反应开始150s之后产生SO 2气体时，判定设备内发生的腐蚀为轻度硫化。
本发明作为针对涉硫石化设备腐蚀自燃的一种预测方法，具有以下有益效果：
现有技术大部分自燃火灾监测指标的选取不恰当，对于设备内自燃情况预测不准确，本发明精确度高，运用拟合腐蚀产物自燃产生的定量关系公式，能较为精确的计算出发生自燃的时间。一方面，本发明的人工成本较低，不必使用人工检测的形式进行现场气体检测，降低成本的同时还确保了检测精度。另一方面，本发明的方法操作简单，预测方法使用设备检测和运行程序自动化处理的形式，无需操作人员进行额外操作，确保了检测精度，避免了人员失误产生的事故。最后，在线实时检测，铠装热电偶和SO 2气体检测仪实时反馈监测结果，保障设备一 直处于监控之下，能够及时的发出警报，进行预警。
附图说明
图1是本发明用于涉硫石化设备腐蚀自燃预测的结构示意图。
图2是本发明方法的预测流程图。
图中，1-涉硫石化设备，2-热电偶，3-测温仪表，4-温度参数数据处理设备，5-DCS中控系统，6-气体浓度参数数据处理设备，7-无线SO 2气体检测仪。
具体实施方式
下面结合附图和具体实例对本发明的技术方案作进一步的说明。
实施例1
如图1和图2所示，本实施例的具体实施步骤为：
1、根据浮顶罐尺寸将装有铠装热电偶的瓷套管焊接在涉硫石化设备底部以及气相空间顶部等器壁内部易与空气接触发生腐蚀部位对应的外壁，热电偶时间常数为15s，热电偶冷端接补偿导线，补偿导线另一端接测温仪表，将测温仪表与温度数据处理设备相连接。
2、在温度数据处理设备处设置好温度临界值△T s＝30℃，通过热电偶获得设备腐蚀自燃部位的实时温度，当任意一处热电偶所测温度超过临界值△T s＝30℃时，将温升温度到达临界时间(t△T s)反馈至DCS系统处进行下一步处理。
3、发生腐蚀自燃后，测温仪表反馈反应开始起始时间，结合无线SO 2气体检测仪检测的SO 2气体出现时间，分析判定得到浮顶罐内腐蚀物的硫化程度，选用对应硫化程度的SO 2浓度与时间的定量关系拟合公式，得到SO 2气体的最大浓度y max及临界SO 2气体浓度临界值。同时，通过无线SO 2气体检测仪实时检测设备内SO 2浓度，气体检测仪每10s反馈一次SO 2浓度数值。若浓度到达自燃火灾的SO 2气体预警浓度时，将储罐SO 2气体浓度达到临界浓度的时间(tys)反馈至DCS系统。
4、当温升达到临界温升的时间(t△T s)和SO 2气体浓度达到临界浓度的时间(tys)其中任一或两者反馈到DCS系统中时，DCS控制界面即发出浮顶罐内发生腐蚀自燃的事故预警警报，对操作人员进行事故预警。
以上所述，仅是本发明的实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效方法的变化，均属于本发明技术方案的保护范围内。

Claims (8)

  1. 一种涉硫石化设备腐蚀自燃预测方法，其特征在于：包括双指标体系预测的步骤；所述双指标体系预测的步骤，包括对温度监测的步骤和对自燃生成的SO 2气体检测的步骤；
    所述对温度监测步骤为：
    A.通过连接在涉硫石化设备(1)外壁的热电偶(2)进行实时温度测量，并且温度测量值通过测温仪表(3)进行显示并且将温升情况数据传递至温度参数数据处理设备(4)；
    B.所述温度参数数据处理设备(4)将涉硫石化设备(1)内的温升情况数据与温升临界指标比对从而判断是否开启警报，在需要开启警报的情况下传送信号至DCS中控系统(5)；
    C.所述DCS中控系统(5)接到报警信号后开启警报；
    所述对自燃生成的SO 2气体检测的步骤包括：
    A.通过连接在涉硫石化设备(1)上的无线SO 2气体检测仪(7)对涉硫石化设备(1)内的SO 2气体浓度进行检测，并且根据SO 2气体浓度判定设备内的硫化程度，将硫化程度数据传递至气体浓度参数数据处理设备(6)；
    B.选用对应硫化程度的拟合公式的临界值；
    C.所述气体浓度参数数据处理设备(6)将涉硫石化设备(1)内部的硫化程度数据和对应硫化程度的拟合公式的临界值进行比对从而判断是否开启警报，在需要开启警报的情况下传送信号至DCS中控系统(5)；
    D.所述DCS中控系统(5)接到报警信号后开启警报。
  2. 根据权利要求1所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：所述对温度监测步骤中的步骤A中所述的热电偶(2)为外部铠装热电偶(2)。
  3. 根据权利要求1所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：所述对温度监测步骤中的温升临界指标△Ts的计算方式如下：
    ΔT s＝C sΔT max
    式中，△T s为预测涉硫石化设备(1)自燃火灾的临界温升，计量单位为℃；
    C s为安全控制系数，在大空间建筑中采用Cs＝0.2～0.8，本预警方法优选C s＝0.5；
    △T max为研究工况下，涉硫石化设备(1)发生自燃火灾时，在氧化初始期可能达到的最大温升，计量单位为℃。
  4. 根据权利要求3所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：环境温升临界指标△T s取30℃，在涉硫石化设备(1)内温升超过30℃时，则对该设备采取相应的冷却降温 预控措施。
  5. 根据权利要求1所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：所述对自燃生成的SO 2气体检测的步骤中对应硫化程度的拟合公式的临界值y s的计算方式如下：
    y s＝C sy max
    式中，y s为预测涉硫石化设备(1)自燃火灾的临界SO 2气体浓度，计量单位为mg/μL；
    C s为安全控制系数，在大空间建筑中采用C s＝0.2～0.8；
    y max为研究工况下SO 2气体的最大浓度，计量单位为mg/μL。
  6. 根据权利要求1所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：所述涉硫石化设备(1)腐蚀自燃中产生的腐蚀情况包括轻度硫化和深度硫化。
  7. 根据权利要5或6所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：对于轻度硫化和深度硫化情况下可通过如下的自燃生成SO 2浓度y与时间t的定量关系公式进行计算：
    1)轻度硫化：y＝-3×10 -9t 5+2×10 -7t 4-3×10 -6t 3
    -0.0002t 2+0.0055t-0.0101
    2)深度硫化：y＝-5×10 -7t 4+4×10 -5t 3
    -0.0012t 2+0.0129t-0.0125
    其中，y为SO 2气体浓度，计量单位为mg/μL；
    t为反应时间，计量单位为min；
    对SO 2浓度y与时间t定量关系拟合公式两边求一阶导数，令dy/dt＝0，可求得SO 2气体浓度y达到最大值时的对应时间t max，把t max代入拟合公式则可得到SO 2气体的最大浓度y max。
    对深度硫化产物其自燃火灾的SO 2气体预警浓度宜取y s＝0.017mg/μL；对轻度硫化产物的自燃火灾SO 2气体预警浓度宜取y s＝0.012mg/μL。
  8. 根据权利要求6所述的涉硫石化设备腐蚀自燃预测方法，其特征在于：在氧化自燃反应开始后150s内产生SO2气体时，判定设备内发生的腐蚀为深度硫化；在氧化自燃反应开始150s之后产生SO2气体时，判定设备内发生的腐蚀为轻度硫化。
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