CN-122017113-A - Crude oil organic chlorine content detection method and system based on ion chromatography and intelligent optimization system

CN122017113ACN 122017113 ACN122017113 ACN 122017113ACN-122017113-A

Abstract

The invention discloses a crude oil organochlorine content detection method and system based on an ion chromatography and intelligent optimization system, and aims to solve the problems of inaccurate detection, low efficiency and poor suitability in the prior art. The system comprises an automatic sample pretreatment module, an intelligent ion chromatography module and a central control and data processing AI platform, so that full-flow automation is realized. The detection flow comprises sample introduction, scheme calling, automatic pretreatment, intelligent chromatographic analysis, AI diagnosis calibration and report early warning. The parameters are precisely matched through a crude oil type-special scheme, and the multi-matrix crude oil such as light, heavy, high wax and the like is adapted. The detection report with the two-dimension code can be generated rapidly, the supervision requirements of customs are deeply met, the detection efficiency and reliability are improved, and the practical application value is realized.

Inventors

Gao Sunqiong
Gao Sunhui
LI ZHENGZHANG
HUANG SHENGNAN

Assignees

海口海关技术中心

Dates

Publication Date: 20260512
Application Date: 20251223

Claims (10)

1. The crude oil organochlorine content detecting system based on ion chromatography and intelligent optimization system is characterized by comprising: An automatic sample pretreatment module, an intelligent ion chromatography module and a central control and data processing AI platform; the automatic sample pretreatment module is connected with the intelligent ion chromatography module through a flow path; the central control and data processing AI platform is electrically connected with the automatic sample pretreatment module and the intelligent ion chromatographic analysis module; the automatic sample pretreatment module comprises a precise weighing and diluting unit, an online extraction and separation unit, an online combustion/high-temperature hydrolysis unit and an absorption liquid quantitative collection unit which are sequentially connected; the intelligent ion chromatographic analysis module comprises an intelligent sample injector, an online purifying and protecting column system, a chromatographic pump, a column incubator, a conductivity detector and an intelligent condition recommending unit; the central control and data processing AI platform comprises a system main control unit, a data acquisition and processing unit, an AI intelligent diagnosis and calibration unit and a result report and risk early warning unit.
2. The crude oil organochlorine content detection system based on the ion chromatography and intelligent optimization system according to claim 1, wherein the on-line extraction and separation unit comprises a constant temperature oscillator, a high-speed centrifuge and a phase separation membrane, and the on-line combustion/hydrolysis unit comprises a programmed temperature combustion furnace and a multi-path gas flow controller.
3. The crude oil organochlorine content detection system based on ion chromatography and intelligent optimization system of claim 1, wherein the intelligent condition recommendation unit is built-in with a combination model, and input parameters of the combination model comprise crude oil density, viscosity and hydrocarbon ratio.
4. The system for detecting the organic chlorine content of crude oil based on the ion chromatography and intelligent optimization system according to claim 1, wherein the AI intelligent diagnosis and calibration unit comprises a preset tolerance range for judging chromatographic peak tailing factors, symmetry, retention time drift and standard sample recovery rate.
5. The crude oil organochlorine content detection system based on ion chromatography and intelligent optimization system according to claim 3, wherein the model of the intelligent condition recommendation unit is provided with a periodic update program, and model parameters thereof are automatically updated according to newly input sample data and corresponding analysis result feedback.
6. A method for detecting the organic chlorine content of crude oil based on an ion chromatography and intelligent optimization system, which is characterized by adopting the detection system as claimed in any one of claims 1-5 and comprising the following steps: s1, sample introduction, namely placing a crude oil sample into a system and correlating the crude oil sample with declaration information; S2, scheme calling, wherein the system calls a detection scheme according to the sample information; S3, automatic pretreatment, namely performing automatic sample pretreatment by a system to obtain a liquid to be tested; s4, intelligent chromatographic analysis, wherein the system executes ion chromatographic analysis based on recommended analysis conditions and collects data; s5, AI diagnosis calibration and report early warning, wherein the system performs diagnosis verification on the analysis process and the result to generate a report.
7. The method for detecting the organic chlorine content of crude oil based on the ion chromatography and intelligent optimization system according to claim 6, wherein the step S3 comprises: (1) Precisely weighing and diluting, namely automatically weighing a crude oil sample, and adding dimethyl sulfoxide-toluene mixed solvent for dissolution; (2) On-line extraction and separation, namely adding ultrapure water for extraction, and removing a water phase through centrifugation and membrane separation; (3) On-line high-temperature hydrolysis, namely, carrying out high-temperature hydrolysis on the separated organic phase; (4) And collecting the absorption liquid, namely absorbing the hydrolysate by using the alkaline hydrogen peroxide absorption liquid to obtain the liquid to be detected.
8. The method for detecting the organic chlorine content of crude oil based on the ion chromatography and intelligent optimization system according to claim 6, wherein in the step S4, the type of analytical column or the elution gradient recommended by the system is different for different types of crude oil.
9. The method for detecting the organic chlorine content of crude oil based on the ion chromatography and the intelligent optimization system according to claim 6, wherein in the step S5, when any diagnostic index exceeds a preset tolerance range, the system triggers a rechecking or maintenance instruction.
10. The method for detecting the organic chlorine content of the crude oil based on the ion chromatography and the intelligent optimization system according to claim 9 is characterized in that the step S5 further comprises the steps of comparing a detection result with a preset limit value, generating an electronic detection report, uploading the electronic detection report to a database, and sending early warning information to a designated supervision terminal by the system when the detection result exceeds the standard or the data is abnormal.

Description

Crude oil organic chlorine content detection method and system based on ion chromatography and intelligent optimization system Technical Field The invention relates to the technical field of analytical chemistry, in particular to an ion chromatography intelligent system and method for rapidly, accurately and automatically detecting the content of organic chlorine in crude oil under supervision scenes such as customs. Background In the macro view of global energy trade, crude oil is taken as industrial blood, and the quality safety of the crude oil is the first defense line for guaranteeing the stable operation of a refining industry chain. Among them, the content of organic chlorine is a critical but easily neglected invisible index. The chlorine elements hidden in crude oil in the form of complex compounds are converted into hydrogen chloride with extremely high corrosiveness in the subsequent high-temperature and high-pressure refining process, and the hydrogen chloride is like a latent catalyst killer and a latent equipment corrosive agent, so that the production safety is seriously threatened, expensive equipment is damaged, and the quality of the finished oil is deteriorated. Therefore, the method for screening the content of the organic chlorine in the imported crude oil is one of the core responsibilities of national customs to fulfill technical barrier supervision and maintain the safety of the national industry. However, in the face of crude oil cargo with various sources, which is flowing in a rough way every day, the customs laboratory is involved in a technical dilemma of 'inaccurate and unsmooth' detection and a manpower-intensive work puddle for a long time. Three main stream detection technologies commonly relied on in the industry at present expose short plates which are difficult to overcome when the requirements of high throughput, high aging and high accuracy of the port are met. First, the principle of detection is considered as microcoulomb method (according to GB/T18612-2011) of classical method, but the detection works as if it is a tedious chemical experiment "ceremony". The skilled person must perform at least six fine steps of extraction, washing, purification, transfer, etc. in hand, and the whole process is highly dependent on the skill and experience of the operator. Individual samples take more than two hours from processing to outputting results. During peak-to-peak traffic, the sample bottles are piled up in the laboratory, and technicians need to repeat these fine operations continuously and in high tension, which not only is labor intensive, but also the risk of human error is superimposed. More seriously, the method has limited anti-interference capability on complex matrixes in crude oil, and when the method is applied to heavy, high-sulfur and high-asphaltene crude oil, the result can deviate from a true value seriously due to incomplete pretreatment, and the detection of hysteresis and possible misalignment definitely buried hidden danger for high-risk oil products to flow into domestic markets. Second, X-ray fluorescence spectroscopy (according to SH/T0842-2017) has been considered desirable for acceleration due to its rapid, non-destructive surface advantage. The instrument is irradiated for a few minutes to obtain the total chlorine data. However, the fatal defect is that only forests can be seen, and woods cannot be seen, and organic chlorine and inorganic chlorine cannot be distinguished. The chlorine source in crude oil is complex, and may be derived from either brine (inorganic chloride) remaining during production or primary or secondary organic chloride. For refineries, inorganic chlorine can be removed by a simple electric desalting process, the harm is not great, and the true 'basic' is organic chlorine. X-ray fluorescence combines the two methods, the provided total chlorine data has limited reference value, and the inferred distinction error of organic chlorine/inorganic chlorine can reach more than 30 percent according to industry evaluation. The customs supervision can not realize accurate striking, and misjudgment can be caused by either putting the "problem oil" with the exceeding organic chlorine or withholding the actual safe "qualified oil" due to the high total chlorine, so that unnecessary trade disputes are caused. Furthermore, the existing ion chromatography has the capability of accurately quantifying chloride ions in principle, and seems to see the dawn. However, once applied to a crude oil matrix of varying composition, it suffers from "water and soil disuse". It is difficult to compromise fixed chromatographic conditions (e.g., eluent concentration, flow rate, column temperature) with light sand light oil from the middle east, heavy Ma Ruiyou from south america, or high acid oil from africa. Different densities, viscosities, hydrocarbon compositions can lead to chloride peaks with drift in retention time, tailing of peak shape, or reduced deg