CN116297672A - Device and method for detecting sulfate radical content in phosphoric acid extracted by wet method - Google Patents
Device and method for detecting sulfate radical content in phosphoric acid extracted by wet methodDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及试剂含量自动测量技术领域，具体而言，涉及一种湿法萃取磷酸中硫酸根含量的检测装置和方法。The invention relates to the technical field of automatic measurement of reagent content, in particular to a device and method for detecting sulfate content in phosphoric acid by wet extraction.
背景技术Background technique
目前，国内外“836”高浓度大型磷肥生产装置萃取反应槽内料浆中硫酸根(SO42-)含量的分析测量，都采用人工取样、人工分析的方法提供测量结果。分析测量周期为1～4小时不等，普遍存在着分析测量周期长、分析结果不稳定、费时费力等各种因素，严重制约了工艺生产的稳定运行和原材料消耗控制、能耗控制。伴随着磷矿资源、硫磺资源的贫化程度不断加剧，磷化工装置的精细生产、智能化控制越来越重要，越来越迫切。At present, the analysis and measurement of sulfate radical (SO42-) content in the extraction reaction tank of the "836" high-concentration large-scale phosphate fertilizer production plant at home and abroad all use manual sampling and manual analysis to provide measurement results. The analysis and measurement period ranges from 1 to 4 hours. There are various factors such as long analysis and measurement period, unstable analysis results, time-consuming and laborious, etc., which seriously restrict the stable operation of process production and the control of raw material consumption and energy consumption. With the increasing depletion of phosphate rock resources and sulfur resources, the fine production and intelligent control of phosphorus chemical equipment are becoming more and more important and urgent.
发明内容Contents of the invention
有鉴于此，本发明提出了一种湿法萃取磷酸中硫酸根含量的检测装置和方法，以实现工业化生产中硫酸根(SO42-)的在线自动检测，避免了人工操作误差，提高了准确度和效率。In view of this, the present invention proposes a detection device and method for sulfate radical content in phosphoric acid by wet extraction, so as to realize the online automatic detection of sulfate radical (SO42-) in industrialized production, avoid manual operation error, and improve accuracy and efficiency.
本发明的目的在于提供一种湿法萃取磷酸中硫酸根含量的检测装置，包括恒温单元、检测单元、转换单元、清洗单元、标液单元、空调单元、PLC控制单元及控制柜；所述恒温单元用于基于设定的恒温值对样液进行恒温；所述检测单元用于检测化学反应所造成的所述检测装置内的温度变化，并将所述温度变换转换为电信号，传输至所述转换单元；所述转换单元用于将所述电信号转换为标准信号，并将所述标准信号传输至所述PLC控制单元；所述清洗单元用于清洗和吹净残留样液；所述标液单元用于存放稀释溶液和反应溶液；所述空调单元用于保持所述控制柜内恒温，消除环境温度变化对所述检测装置的干扰；所述PLC控制单元用于控制所述恒温单元、所述检测单元、所述转换单元、所述清洗单元、所述标液单元和所述空调单元，以实现对所述样液进行硫酸根含量的检测；所述控制柜用于集成所述恒温单元、所述检测单元、所述转换单元、所述清洗单元、所述标液单元、所述空调单元及所述PLC控制单元。The object of the present invention is to provide a detection device for sulfate radical content in wet extraction phosphoric acid, comprising constant temperature unit, detection unit, conversion unit, cleaning unit, standard liquid unit, air conditioning unit, PLC control unit and control cabinet; The unit is used to keep the temperature of the sample liquid constant based on the set constant temperature value; the detection unit is used to detect the temperature change in the detection device caused by the chemical reaction, convert the temperature change into an electrical signal, and transmit it to the The conversion unit; the conversion unit is used to convert the electrical signal into a standard signal, and transmit the standard signal to the PLC control unit; the cleaning unit is used to clean and blow off the residual sample liquid; the The standard solution unit is used to store the dilution solution and the reaction solution; the air-conditioning unit is used to maintain a constant temperature in the control cabinet to eliminate the interference of ambient temperature changes on the detection device; the PLC control unit is used to control the constant temperature unit , the detection unit, the conversion unit, the cleaning unit, the standard liquid unit and the air conditioning unit, so as to detect the sulfate content of the sample liquid; the control cabinet is used to integrate the The constant temperature unit, the detection unit, the conversion unit, the cleaning unit, the standard liquid unit, the air conditioning unit and the PLC control unit.
进一步的，所述检测单元包括测量池、搅拌器、检测探针、搅拌器电机、电磁阀及管道；所述测量池用于所述样液和所述反应溶液进行所述化学反应；所述搅拌器用于搅拌所述测量池中的溶液，使所述样液和所述反应溶液充分反应；所述检测探针用于探测所述化学反应造成的温度变化；所述搅拌器电机用于带动所述搅拌器搅拌所述测量池内的溶液；所述电磁阀用于控制所述反应溶液、所述稀释溶液和所述样液注入所述测量池；所述管道用于注入或排出溶液。Further, the detection unit includes a measuring cell, an agitator, a detection probe, an agitator motor, a solenoid valve, and a pipeline; the measuring cell is used for the chemical reaction between the sample liquid and the reaction solution; the The stirrer is used to stir the solution in the measuring cell, so that the sample liquid and the reaction solution fully react; the detection probe is used to detect the temperature change caused by the chemical reaction; the stirrer motor is used to drive The agitator stirs the solution in the measuring cell; the solenoid valve is used to control the injection of the reaction solution, the dilution solution and the sample liquid into the measuring cell; the pipeline is used to inject or discharge the solution.
进一步的，所述测量池包括U形腔体和盖板；所述U形腔体和盖板通过法兰密封；所述盖板上设置有多个供所述管道插入的通孔，以注入所述反应溶液、所述稀释溶液和所述样液；所述盖板上还设置有供搅拌器通过的通孔和供所述检测探针探测温度的通孔；所述U形腔体的底部设置有排液管道；以排出U形腔体内的溶液。Further, the measuring pool includes a U-shaped cavity and a cover plate; the U-shaped cavity and the cover plate are sealed by flanges; the cover plate is provided with a plurality of through holes for the pipeline to be inserted into to inject The reaction solution, the dilution solution and the sample solution; the cover plate is also provided with a through hole for the agitator to pass through and a through hole for the detection probe to detect the temperature; the U-shaped cavity A drain pipe is provided at the bottom to discharge the solution in the U-shaped cavity.
进一步的，所述检测探针包括探针电阻、温度补偿电阻、调零可变电阻、调量程可变电阻、第一电阻、第二电阻、第三电阻和直流电源；所述探针电阻、所述温度补偿电阻、所述第三电阻、所述调零可变电阻和所述第二电阻依次收尾相连；在所述探针电阻和所述温度补偿电阻之间的通路上设置第一检测点；在所述调零可变电阻和所述第三电阻之间的通路上设置第二检测点；所述第一检测点和所述第二检测点用于输出检测信号；所述调量程可变电阻的一端通过所述第一电阻与所述直流电源的正极相连，另一端直接与所述直流电源的负极相连；所述调量程可变电阻的滑动端与所述探针电阻和所述第二电阻的之间的通路相连；所述温度补偿电阻和所述第三电阻之间的通路与所述直流电源的负极相连。Further, the detection probe includes a probe resistance, a temperature compensation resistance, a zero-adjustment variable resistance, a range-adjustment variable resistance, a first resistance, a second resistance, a third resistance and a DC power supply; the probe resistance, The temperature compensation resistor, the third resistor, the zero-adjustment variable resistor and the second resistor are sequentially connected to each other; a first detection device is set on the path between the probe resistor and the temperature compensation resistor point; a second detection point is set on the path between the zero-adjusting variable resistance and the third resistance; the first detection point and the second detection point are used to output detection signals; the range adjustment One end of the variable resistor is connected to the positive pole of the DC power supply through the first resistor, and the other end is directly connected to the negative pole of the DC power supply; the sliding end of the range-adjusting variable resistor is connected to the probe resistance and the The path between the second resistor is connected; the path between the temperature compensation resistor and the third resistor is connected to the negative pole of the DC power supply.
进一步的，所述控制柜为内、外双层不锈钢防护结构；所述转换单元由金属盒子封装后放置在所述控制柜内；所述转换单元的接地点与电力电源的接地线连接；所述检测单元的接地点与独立接地桩连接。Further, the control cabinet is an inner and outer double-layer stainless steel protective structure; the conversion unit is packaged in a metal box and placed in the control cabinet; the ground point of the conversion unit is connected to the ground wire of the power supply; the The grounding point of the detection unit is connected to an independent grounding stake.
本发明的目的在于提供一种湿法萃取磷酸中硫酸根含量的检测方法，包括：基于设定的恒温值对样液进行恒温，得到恒温样液；取第一预设量的所述恒温样液送入测量池；基于所述样液的浓度，取第二预设量的稀释液送入所述测量池，并搅拌；向所述测量池内均匀注射反应溶液进行化学反应；获取所述化学反应的起始温度和终止温度，基于所述起始温度和所述终止温度，确定反应热；基于所述反应热，确定所述样液中的硫酸根含量；清洗和吹净残留的所述样液；结束本次检测，并等待下一检测指令。The object of the present invention is to provide a method for detecting the content of sulfate radicals in phosphoric acid by wet extraction, comprising: performing constant temperature on the sample liquid based on a set constant temperature value to obtain a constant temperature sample liquid; taking the first preset amount of the constant temperature sample The liquid is sent into the measurement pool; based on the concentration of the sample liquid, a second preset amount of diluent is taken and sent into the measurement pool, and stirred; the reaction solution is evenly injected into the measurement pool for chemical reaction; the chemical reaction is obtained The starting temperature and the ending temperature of the reaction, based on the starting temperature and the ending temperature, determine the heat of reaction; based on the heat of reaction, determine the sulfate content in the sample liquid; clean and blow off the residual Sample liquid; end this test and wait for the next test command.
进一步的，所述获取所述化学反应的起始温度和终止温度，包括：确定所述化学反应造成的温度变化随时间的变化曲线；基于微分算法，判断温度的变化趋势，确定拐点；基于所述拐点确定反应起始点和反应终止点；将在所述起始点获取的温度作为所述起始温度；将在所述终止点获取的温度作为所述终止温度。Further, the acquisition of the start temperature and end temperature of the chemical reaction includes: determining the change curve of the temperature change over time caused by the chemical reaction; judging the change trend of the temperature based on the differential algorithm, and determining the inflection point; The inflection point determines the reaction start point and the reaction end point; the temperature obtained at the start point is used as the start temperature; the temperature obtained at the end point is used as the end temperature.
进一步的，所述基于所述反应热，确定所述样液中的硫酸根含量，包括：获取所述反应起始点和反应终止点之间的温度变化曲线；获取所述反应起始点的温度；基于所述温度变化曲线和所述起始点的温度所围成的面积，确定所述样品中硫酸根的含量；其中，基于面积确定硫酸根的含量的表达式为：Further, the determination of the sulfate content in the sample liquid based on the heat of reaction includes: obtaining the temperature change curve between the reaction start point and the reaction end point; obtaining the temperature of the reaction start point; Based on the area surrounded by the temperature change curve and the temperature of the starting point, determine the content of sulfate in the sample; wherein, the expression for determining the content of sulfate based on the area is:
其中，S表示硫酸根的含量，t0表示所述反应起始点，t1表示所述反应终止点；f(t)表示温度变化曲线，g(t)表示常量函数，所述常量为所述反应起始点的温度。Wherein, S represents the content of sulfate radical, and t0 represents described reaction initiation point, and t1 represents described reaction termination point; f (t) represents temperature variation curve, and g (t) represents constant function, and described constant is described The temperature at the starting point of the reaction.
进一步的，所述清洗和吹净残留的所述样液，包括：用气水混合液清洗残留有所述样液的单元和管道；用压缩空气将清洗后的所述单元和管道吹净，为下一次进样提供洁净的检测条件；将清洗水返回生产系统进行处理。Further, the cleaning and blowing off of the residual sample liquid include: cleaning the unit and pipeline with the residual sample liquid with an air-water mixture; blowing off the cleaned unit and pipeline with compressed air, Provide clean detection conditions for the next injection; return the wash water to the production system for processing.
进一步的，所述基于所述反应热，确定所述样液中的硫酸根含量的表达式为：Further, the expression for determining the sulfate content in the sample liquid based on the heat of reaction is:
A＝K×(T2-T1)＝K×ΔTA=K×(T2 -T1 )=K×ΔT
其中，K为检测常数，T1为所述起始温度，T2为所述终止温度，ΔT为所述化学反应温升。Wherein, K is a detection constant,T1 is the start temperature,T2 is the end temperature, and ΔT is the temperature rise of the chemical reaction.
本发明实施例的技术方案至少具有如下优点和有益效果：The technical solutions of the embodiments of the present invention have at least the following advantages and beneficial effects:
本发明中的一些实施例可以实现湿法萃取磷酸溶液中硫酸根(SO42-)含量的在线自动检测和检测结果的自动显示、存贮、传输，为大型湿法磷酸装置稳定运行、精益生产和原材料消耗控制、能耗控制提供关键技术支持，推进装置自动化、智能化控制水平提升。解决了湿法磷酸工业生产装置自动化控制的行业技术难题。Some embodiments of the present invention can realize the online automatic detection of the sulfate group (SO42-) content in the phosphoric acid solution by wet extraction and the automatic display, storage and transmission of the detection results, providing a stable operation, lean production and Raw material consumption control and energy consumption control provide key technical support to promote equipment automation and intelligent control. Solved the industrial technical problems of automatic control of wet-process phosphoric acid industrial production equipment.
本发明中的一些实施例可以有效替代分析人员，提高分析效率。缩短测量周期，消除人为干扰因素。分析结果准确性高，重复性好。Some embodiments of the present invention can effectively replace analysts and improve analysis efficiency. Shorten the measurement cycle and eliminate human interference factors. The analysis results have high accuracy and good repeatability.
附图说明Description of drawings
图1为本发明一些实施例提供的一种湿法萃取磷酸中硫酸根含量的检测装置的示例性示意图；Fig. 1 is an exemplary schematic diagram of a detection device for sulfate content in a kind of wet extraction phosphoric acid provided by some embodiments of the present invention;
图2为本发明一些实施例提供的检测单元的示例性示意图；Fig. 2 is an exemplary schematic diagram of a detection unit provided by some embodiments of the present invention;
图3为本发明一些实施例提供的检测探针的示例性示意图；Fig. 3 is an exemplary schematic diagram of detection probes provided by some embodiments of the present invention;
图4为本发明一些实施例提供的一种湿法萃取磷酸中硫酸根含量的检测方法的示例性流程图。Fig. 4 is an exemplary flowchart of a method for detecting sulfate content in phosphoric acid by wet extraction provided by some embodiments of the present invention.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。通常在此处附图中描述和示出的本发明实施例的组件可以以各种不同的配置来布置和设计。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. The components of the embodiments of the invention generally described and illustrated in the figures herein may be arranged and designed in a variety of different configurations.
图1为本发明一些实施例提供的一种湿法萃取磷酸中硫酸根含量的检测装置的示例性示意图。如图1所示，检测装置包括恒温单元1、检测单元2、转换单元3、清洗单元4、标液单元5、空调单元6、PLC控制单元7及控制柜8。Fig. 1 is an exemplary schematic diagram of a detection device for sulfate content in phosphoric acid in wet extraction provided by some embodiments of the present invention. As shown in FIG. 1 , the detection device includes a
恒温单元1用于基于设定的恒温值对样液进行恒温。The
恒温值可以根据实验需要确定，误差0.5℃。The constant temperature value can be determined according to the needs of the experiment, with an error of 0.5°C.
检测单元2用于检测化学反应所造成的检测装置内的温度变化，并将温度变换转换为电信号，传输至转换单元3。关于检测单元的更多内容，参见图2及其相关描述。The
转换单元3用于将电信号转换为标准信号，并将标准信号传输至PLC控制单元7。The conversion unit 3 is used to convert the electrical signal into a standard signal, and transmit the standard signal to the PLC control unit 7 .
清洗单元4用于清洗和吹净残留样液。The
标液单元5用于存放稀释溶液和反应溶液。The standard solution unit 5 is used to store the dilution solution and the reaction solution.
稀释溶液可以是指用于稀释样液的溶液。例如，纯水。反应溶液可以是指与硫酸根进行化学反应放热的溶液。例如，浓度为20～28％的氯化钡溶液。The diluting solution may refer to a solution used to dilute the sample liquid. For example, pure water. The reaction solution may refer to a solution that undergoes a chemical reaction with sulfate to produce heat. For example, a barium chloride solution with a concentration of 20-28%.
空调单元6用于保持控制柜内恒温，消除环境温度变化对检测装置的干扰。The
PLC控制单元7用于控制恒温单元1、检测单元2、转换单元3、清洗单元4、标液单元5和空调单元6，以实现对样液进行硫酸根含量的检测。PLC控制单元7可以确定恒温值和检测系统的环境温度，并指示恒温单元1对样液进行恒温；PLC控制单元7还可以控制样液、稀释溶液和反应溶液的加入，自动进行化学反应，并进行测量，在测量完成后接收检测数据，对检测数据进行分析，得到样液中硫酸根含量，最后，PLC控制单元7还控制清洗单元4清洗残留样液。The PLC control unit 7 is used to control the
在一些实施例中，PLC控制单元7为在线自动检测系统的控制中枢，包括PLC系统硬件(包括PLC控制器、存在器、触膜屏、IO/DO卡件、UPS电源、控制柜等)和实现此技术方案专门开发的控制程序及相关软件。In some embodiments, the PLC control unit 7 is the control center of the online automatic detection system, including PLC system hardware (including PLC controller, presence device, touch film screen, IO/DO card, UPS power supply, control cabinet, etc.) and Realize the control program and related software specially developed for this technical solution.
控制柜8用于集成恒温单元1、检测单元2、转换单元3、清洗单元4、标液单元5、空调单元6及PLC控制单元7。The
在一些实施例中，控制柜8为内、外双层不锈钢防护结构；转换单元3由金属盒子封装后放置在控制柜内；转换单元3的接地点与电力电源的接地线连接；检测单元2的接地点与独立接地桩连接。In some embodiments, the
由于检测范围窄，精度要求高，检测时受介质温度，环境温度变化干扰大，且测量时间短(小于80s)，因此，检测信息容易错失或被干扰信号淹没。本发明中的一些实施例通过恒温单元对样液进行恒温、将多个单元集成到控制柜内，并设置空调单元维持控制柜内的温度，并对转换单元和检测装置分别设置接地措施，防止了静电、电磁干扰等的干扰，提高了检测结果的精确度。Due to the narrow detection range and high precision requirements, the detection is greatly disturbed by the change of medium temperature and ambient temperature, and the measurement time is short (less than 80s). Therefore, the detection information is easy to be missed or overwhelmed by interference signals. In some embodiments of the present invention, the constant temperature unit is used to keep the temperature of the sample liquid constant, multiple units are integrated into the control cabinet, and the air conditioning unit is set to maintain the temperature in the control cabinet, and the conversion unit and the detection device are respectively provided with grounding measures to prevent It eliminates the interference of static electricity and electromagnetic interference, and improves the accuracy of the test results.
图2为本发明一些实施例提供的检测单元的示例性示意图。如图2所示，检测单元包括测量池25、搅拌器24、检测探针23、搅拌器电机22、电磁阀21及管道。Fig. 2 is an exemplary schematic diagram of a detection unit provided by some embodiments of the present invention. As shown in FIG. 2 , the detection unit includes a
测量池25用于样液和反应溶液进行化学反应。测量池25包括U形腔体和盖板；U形腔体和盖板通过法兰密封；盖板上设置有多个供管道插入的通孔，以注入反应溶液、稀释溶液和样液；盖板上还设置有供搅拌器24通过的通孔和供检测探针23探测温度的通孔；U形腔体的底部设置有排液管道；以排出U形腔体内的溶液。测量池的容积在50～1000ml。例如，50～100ml。又例如，120ml。The
搅拌器24用于搅拌测量池25中的溶液，使样液和反应溶液充分反应。搅拌器通过盖板上的通孔与测量池内的溶液接触，以搅拌溶液。The
检测探针23用于探测化学反应造成的温度变化。检测探针通过盖板上的通孔与测量池内的溶液接触，以获取温度变化。在一些实施例中，检测探针23的外径小于4mm。通过单臂直流电桥将温度信号转换为电信号。关于检测探针的更多内容，参见图3及其相关描述。The
搅拌器电机22用于带动搅拌器24搅拌测量池内的溶液。The
电磁阀21用于控制反应溶液、稀释溶液和样液注入测量池25。在测量池25的排液管道上也设置有电池阀，用于将反应完成后的溶液和清洗水排出。The
反应溶液、稀释溶液和样液通过不同的管道注入所述测量池。通过在相应的管道上设置电池阀，以控制对应溶液的通断。在一些实施例中，通入稀释溶液和样液的管道的后部分可以连通，以稀释样液。在另一些实施例中，也可以先通入稀释溶液和样液，通过搅拌器搅拌均匀后，通入反应溶液进行反应。The reaction solution, dilution solution and sample liquid are injected into the measuring cell through different pipes. By setting the battery valve on the corresponding pipeline to control the on-off of the corresponding solution. In some embodiments, the rear part of the pipeline leading to the dilution solution and the sample liquid can be connected to dilute the sample liquid. In some other embodiments, the dilute solution and the sample liquid may also be introduced first, and after being uniformly stirred by a stirrer, the reaction solution may be introduced to carry out the reaction.
管道用于注入或排出溶液。Pipes are used to inject or drain solutions.
在进行工作时，先取固定量的样液(如，硫酸H2SO4)、稀释液(如，纯水)加入测量池，测量池的热容量可视为恒定值(如，120m l)。再向测量池中注射反应溶液(如，氯化钡BaCl2)。样液与反应溶液发生放热化学反应，化学反应释放出的反应热使测量系统的温度由T1上升到T2。由于检测时间很短暂(实验中，检测时间为10～80S)，可忽略测量系统散热因素的影响。因此，通过准确检测出测量系统温度变化值(ΔT＝T2-T1)，可以计算出化学反应释放出的反应热量Q值。When working, first take a fixed amount of sample liquid (eg, sulfuric acid H2 SO4 ) and diluent (eg, pure water) and add it to the measuring cell, and the heat capacity of the measuring cell can be regarded as a constant value (eg, 120ml). A reaction solution (for example, barium chloride BaCl2 ) is then injected into the measuring cell. The sample liquid and the reaction solution have an exothermic chemical reaction, and the reaction heat released by the chemical reaction makes the temperature of the measurement system rise from T1 to T2. Because the detection time is very short (in the experiment, the detection time is 10 ~ 80S), the influence of heat dissipation factors of the measurement system can be ignored. Therefore, by accurately detecting the temperature change value of the measurement system (ΔT=T2 −T1 ), the reaction heat Q value released by the chemical reaction can be calculated.
图3为本发明一些实施例提供的检测探针的示例性示意图。如图3所示，检测探针包括探针电阻Rt、温度补偿电阻Rb、调零可变电阻Wz、调量程可变电阻Ws、第一电阻R1、第二电阻R2、第三电阻R3和直流电源E。Fig. 3 is an exemplary schematic diagram of detection probes provided by some embodiments of the present invention. As shown in Figure 3, the detection probe includes probe resistance Rt, temperature compensation resistance Rb, zero adjustment variable resistance Wz, range adjustment variable resistance Ws, first resistance R1, second resistance R2, third resistance R3 and DC Power E.
探针电阻Rt、温度补偿电阻Rb、第三电阻R3、调零可变电阻Wz和第二电阻R2依次收尾相连。在探针电阻Rt和温度补偿电阻Rb之间的通路上设置第一检测点。在调零可变电阻Wz和第三电阻R3之间的通路上设置第二检测点；第一检测点和第二检测点用于输出检测信号Vab。调量程可变电阻Ws的一端通过第一电阻R1与直流电源E的正极相连，另一端直接与直流电源E的负极相连；调量程可变电阻Ws的滑动端与探针电阻Rt和第二电阻R2的之间的通路相连。温度补偿电阻Rb和第三电阻R3之间的通路与直流电源E的负极相连。The probe resistor Rt, the temperature compensation resistor Rb, the third resistor R3, the zero-adjusting variable resistor Wz and the second resistor R2 are sequentially connected to each other. A first detection point is set on the path between the probe resistance Rt and the temperature compensation resistance Rb. A second detection point is set on the path between the zero-adjusting variable resistor Wz and the third resistor R3; the first detection point and the second detection point are used to output a detection signal Vab. One end of the range-adjusting variable resistor Ws is connected to the positive pole of the DC power supply E through the first resistor R1, and the other end is directly connected to the negative pole of the DC power supply E; the sliding end of the range-adjusting variable resistor Ws is connected to the probe resistor Rt and the second resistor The pathway between R2 is connected. The path between the temperature compensation resistor Rb and the third resistor R3 is connected to the negative pole of the DC power supply E.
探针电阻Rt选择封装Pt100、Pt1000、Pt10、Pt800、Pt500铂电阻或Cu50、Cu100、Cu10等铜电阻或镍Ni120、Ni500、Ni1000等镍电阻，以及PTC或NTC半导体热敏电阻，并选择单只或双只热电阻方式进行封装。示例性地，探针电阻Rt选用Pt100单只或双只封装，探针材质可选304、316、316L或310S材质。The probe resistor Rt can be packaged with Pt100, Pt1000, Pt10, Pt800, Pt500 platinum resistors or Cu50, Cu100, Cu10 and other copper resistors or nickel Ni120, Ni500, Ni1000 and other nickel resistors, as well as PTC or NTC semiconductor thermistors, and choose a single Or package with two thermal resistances. Exemplarily, the probe resistor Rt is packaged in single or double Pt100, and the material of the probe can be 304, 316, 316L or 310S.
本说明书中的一些实施例通过在接探针电阻Rt的电桥桥臂的相邻桥臂上接入完全相同的温度补偿电阻Rb，使得可以抵消桥路的不平衡电压。In some embodiments of this specification, an identical temperature compensation resistor Rb is connected to the adjacent bridge arm of the bridge arm connected to the probe resistor Rt, so that the unbalanced voltage of the bridge circuit can be offset.
探针电阻Rt插入检测池内，一起安装于检测箱内。温度补偿电阻Rb也安装于检测箱内。当检测箱内温度发生变化时，探针电阻Rt和温度补偿电阻Rb都能检测到，产生的桥路不平衡电压正好相互抵消。这样就不影响桥路的最终输出的检测信号Vab，达到了温度补偿的作用。The probe resistance Rt is inserted into the detection pool and installed together in the detection box. The temperature compensation resistor Rb is also installed in the detection box. When the temperature in the detection box changes, both the probe resistance Rt and the temperature compensation resistance Rb can be detected, and the resulting unbalanced voltage of the bridge just cancels each other out. In this way, the final output detection signal Vab of the bridge circuit is not affected, and the function of temperature compensation is achieved.
图4为本发明一些实施例提供的一种湿法萃取磷酸中硫酸根含量的检测方法的示例性流程图。如图4所示，检测方法的流程可以包括以下内容：Fig. 4 is an exemplary flowchart of a method for detecting sulfate content in phosphoric acid by wet extraction provided by some embodiments of the present invention. As shown in Figure 4, the flow of the detection method may include the following:
步骤410，基于设定的恒温值对样液进行恒温，得到恒温样液。In
例如，通过PLC控制单元设定恒温值，恒温单元执行恒温指令，对样液进行恒温。样液可以是指含硫酸根的溶液，例如，溶液中硫酸根含量为10～40mg/mL的溶液(按SO3计算)。当然，溶液中硫酸根含量也可以为其他值，包括但不限于20～60mg/mL、30～80mg/mL、40～100mg/mL、50～120mg/mL(按SO3计算)等。For example, the constant temperature value is set by the PLC control unit, and the constant temperature unit executes the constant temperature command to keep the temperature of the sample liquid constant. The sample solution may refer to a solution containing sulfate, for example, a solution with a sulfate content of 10-40 mg/mL (calculated as SO3 ). Of course, the sulfate content in the solution can also be other values, including but not limited to 20-60 mg/mL, 30-80 mg/mL, 40-100 mg/mL, 50-120 mg/mL (calculated asSO3 ) and the like.
在一些实施例中，采用间歇式在线自动取样过滤方式对样液取样，以最大限度减少检测装置中单元及管路与样液的接触时间，延长单元及管路的使用周期。In some embodiments, the sample liquid is sampled by intermittent on-line automatic sampling and filtration, so as to minimize the contact time between the units and pipelines in the detection device and the sample liquid, and prolong the service life of the units and pipelines.
步骤420，取第一预设量的恒温样液送入测量池。
第一预设量可以是指固定量的恒温样液的量。第一预设量可以根据实验具体设置，并由PLC控制单元下发。例如，第一预设量可以为30ml。The first preset amount may refer to a fixed amount of constant temperature sample liquid. The first preset amount can be specifically set according to the experiment and issued by the PLC control unit. For example, the first preset volume may be 30ml.
步骤430，基于样液的浓度，取第二预设量的稀释液送入测量池，并搅拌。
例如，当样液中硫酸含量＜30mg/mL(按SO3计算)时，不加稀释液；当样液中硫酸含量≥30mg/mL(按SO3计算)时，加入20～50稀释液。For example, when the sulfuric acid content in the sample solution is <30mg/mL (calculated asSO3 ), no diluent is added; when the sulfuric acid content in the sample solution is ≥30mg/mL (calculated asSO3 ), add 20-50 diluent.
步骤440，向测量池内均匀注射反应溶液进行化学反应。
反应溶液可以是指与硫酸根进行化学反应会放热的溶液。例如，氯化钡溶液。The reaction solution may refer to a solution that undergoes a chemical reaction with sulfate radicals, exothermic. For example, barium chloride solution.
步骤450，获取化学反应的起始温度和终止温度，基于起始温度和终止温度，确定反应热。
化学反应释放出的反应热会使检测装置的温度由T1上升到T2。由于检测时间很短暂(实验中，检测时间为10～80S)，可忽略测量系统散热因素的影响。因此，可以得到检测装置的温度变化值ΔT＝T2-T1。The reaction heat released by the chemical reaction will raise the temperature of the detection device from T1 to T2 . Because the detection time is very short (in the experiment, the detection time is 10 ~ 80S), the influence of heat dissipation factors of the measurement system can be ignored. Therefore, the temperature change value ΔT=T2 −T1 of the detection device can be obtained.
在一些实施例中，获取化学反应的起始温度和终止温度，包括：In some embodiments, obtaining the starting temperature and ending temperature of the chemical reaction includes:
确定化学反应造成的温度变化随时间的变化曲线。其中，可以通过检测探针定时获取反应温度(例如，200ms获取一次)，基于连续获取的反应温度，确定变化曲线。Determine the temperature change versus time profile for a chemical reaction. Wherein, the reaction temperature can be acquired regularly (for example, once every 200 ms) through the detection probe, and the change curve can be determined based on the continuously acquired reaction temperature.
基于微分算法，判断温度的变化趋势，确定拐点。例如，可以对温度变化曲线进行求导，确定拐点。Based on the differential algorithm, the temperature trend is judged and the inflection point is determined. For example, the temperature variation curve can be derived to determine the inflection point.
基于拐点确定反应起始点和反应终止点。例如，可以将导数最大的点作为反应起始点，将导数为0的点作为反应终止点。在一些实施例中，反应起始点也可以是变化曲线的起点。The reaction start point and the reaction end point are determined based on the inflection point. For example, the point where the derivative is the largest can be used as the starting point of the reaction, and the point where the derivative is 0 can be used as the ending point of the reaction. In some embodiments, the starting point of the reaction can also be the starting point of the change curve.
将在起始点获取的温度作为起始温度；将在终止点获取的温度作为终止温度。The temperature obtained at the start point was taken as the start temperature; the temperature obtained at the end point was taken as the end temperature.
在检测过程中，检测探针监测测量池内的混合溶液的温度，经转换单元转换为4～20mADC标准信号送至PLC控制单元进行运算处理。PLC控制单元通过反应热Q值自动计算出硫酸(H2SO4)含量。During the detection process, the detection probe monitors the temperature of the mixed solution in the measurement pool, and the conversion unit converts it into a 4-20mADC standard signal and sends it to the PLC control unit for calculation and processing. The PLC control unit automatically calculates the sulfuric acid (H2 SO4 ) content through the reaction heat Q value.
步骤460，基于反应热，确定样液中的硫酸根含量。
在一些实施例中，基于反应热，确定样液中的硫酸根含量，包括：In some embodiments, determining the sulfate content in the sample liquid based on the heat of reaction includes:
获取反应起始点和反应终止点之间的温度变化曲线；Obtain the temperature change curve between the reaction start point and the reaction end point;
获取反应起始点的温度；Obtain the temperature at the starting point of the reaction;
基于温度变化曲线和起始点的温度所围成的面积，确定样品中硫酸根的含量；其中，基于面积确定硫酸根的含量的表达式为：Based on the area enclosed by the temperature curve and the temperature of the starting point, determine the content of sulfate radicals in the sample; wherein, the expression for determining the content of sulfate radicals based on the area is:
其中，S表示硫酸根的含量，t0表示反应起始点，t1表示反应终止点；f(t)表示温度变化曲线，g(t)表示常量函数，常量为所述反应起始点的温度。Wherein, S represents the content of sulfate radical, t0 represents the reaction starting point, t1 represents the reaction termination point; f (t) represents the temperature change curve, g (t) represents the constant function, and constant is the temperature of described reaction starting point.
在另一些实施例中，基于反应热，确定样液中的硫酸根含量的表达式为：In other embodiments, based on the heat of reaction, the expression for determining the sulfate content in the sample liquid is:
A＝K×(T2-T1)＝K×ΔTA=K×(T2 -T1 )=K×ΔT
其中，K为检测常数，可以通过查表得到，T1为起始温度，T2为终止温度，ΔT为化学反应温升。Among them, K is the detection constant, which can be obtained by looking up the table, T1 is the starting temperature, T2 is the ending temperature, and ΔT is the temperature rise of the chemical reaction.
步骤470，清洗和吹净残留的样液。清洗单元对恒温单元、检测单元等接触到样液的设备、管道自动进行清洗和吹净。
在一些实施例中，清洗和吹净残留的样液，包括：In some embodiments, cleaning and blowing off residual sample liquid includes:
用气水混合液清洗残留有样液的单元和管道；Use air-water mixture to clean the unit and pipeline with residual sample liquid;
用压缩空气将清洗后的单元和管道吹净，为下一次进样提供洁净的检测条件；其中，气水混合液压力和压缩空气压力被控制在-0.02～-0.05MPa。Blow out the cleaned unit and pipeline with compressed air to provide clean detection conditions for the next sample injection; among them, the pressure of the gas-water mixture and the pressure of compressed air are controlled at -0.02 ~ -0.05MPa.
将清洗水返回生产系统进行处理，避免对环境造成污染。Return the cleaning water to the production system for treatment to avoid pollution to the environment.
步骤480，结束本次检测，并等待下一检测指令。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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