原油及車(chē)用燃油中硫分析測(cè)試儀

XRF熒光測(cè)硫儀Compass-4294光譜儀

1. 背景與簡(jiǎn)介

過(guò)去幾年國(guó)內(nèi)多個(gè)重點(diǎn)城市出現(xiàn)嚴(yán)重的霧霾天氣，引發(fā)了市場(chǎng)對(duì)中國(guó)油品質(zhì)量的廣泛質(zhì)疑。隨著國(guó)家對(duì)環(huán)境保護(hù)的重視和民眾對(duì)公共健康意識(shí)的提高，對(duì)降低車(chē)用燃油、船用和鍋爐用燃油、航空煤油中的硫含量提出了更高的要求。石油產(chǎn)品中的多種硫化物是導(dǎo)致空氣污染的重要因素;而在PM2.5監(jiān)測(cè)中，硫化物也是一個(gè)組成部分。加強(qiáng)對(duì)石油產(chǎn)品中含硫量的嚴(yán)格控制，空氣中PM2.5微顆粒的濃度會(huì)相應(yīng)降低。

對(duì)車(chē)用燃油中硫含量控制，是減少城市空氣污染的主要舉措之一。國(guó)家自2011年7月1日開(kāi)始實(shí)施輕型汽油車(chē)排放的國(guó)IV標(biāo)準(zhǔn)，并將于2014年1月1日在國(guó)內(nèi)實(shí)施相應(yīng)的國(guó)IV標(biāo)號(hào)汽油。目前，北京、上海、廣州等大城市已經(jīng)在使用國(guó)IV標(biāo)號(hào)汽油，并開(kāi)始著手準(zhǔn)備使用國(guó)V標(biāo)號(hào)的汽油。國(guó)V標(biāo)號(hào)的汽油硫含量小于10mg/kg。

能量色散型X射線熒光光譜儀已經(jīng)被廣泛的應(yīng)用于石油煉化企業(yè)、產(chǎn)品質(zhì)量監(jiān)察、環(huán)境監(jiān)測(cè)監(jiān)察和檢測(cè)公司分析實(shí)驗(yàn)室，做為油品中硫含量的快速分析工具

本應(yīng)用方案展示了能量色散X射線熒光光譜法Compass4294測(cè)定石油產(chǎn)品中硫含量.結(jié)果表明,該方法不僅快速,簡(jiǎn)便,而且準(zhǔn)確度和精密度較好.適用于測(cè)定包括石腦油,中間餾分漬,燃料油,渣油,潤(rùn)滑油基礎(chǔ)油和無(wú)鉛汽油在內(nèi)的碳?xì)浠衔镏械牧蚝?/span>.濃度范圍從2ppm到5w%

2. 儀器參數(shù)

為硫分析設(shè)定了工廠優(yōu)化的測(cè)試條件。客戶無(wú)需標(biāo)定設(shè)備即可即時(shí)現(xiàn)場(chǎng)檢測(cè)樣品。

該技術(shù)可實(shí)現(xiàn)低檢測(cè)限和高精度，而無(wú)需消耗氦氣，真空泵。也無(wú)需復(fù)雜而耗時(shí)的化學(xué)樣品制備。只需將樣品放入樣品杯中，即可上機(jī)測(cè)試，整個(gè)測(cè)試過(guò)程*無(wú)損，測(cè)試時(shí)間僅需130秒，且結(jié)果準(zhǔn)確。

3. 準(zhǔn)確性研究

為了研究Compass 4294的準(zhǔn)確性，對(duì)市售的含50 ppm硫的燃油參考材料進(jìn)行了十次測(cè)量。

連續(xù)進(jìn)行20次50 ppm的測(cè)試，測(cè)試值顯示在下面的報(bào)告中。

> 50 ppm硫的測(cè)試性能

4. 精密度研究

為了研究Compass 4294的精度，分析了兩個(gè)含硫量分別為0.1％和1％的標(biāo)準(zhǔn)原油樣品。下面顯示的結(jié)果表明，指南針4294可對(duì)各種石油樣品進(jìn)行精確測(cè)量。

XRF設(shè)備的另一個(gè)重要參數(shù)是分析的可重復(fù)性。

> 0.1％和1％硫的測(cè)試性能

5.測(cè)試程序和校準(zhǔn)演示

一系列進(jìn)口石油標(biāo)準(zhǔn)品已在工廠用于標(biāo)定EDXRF熒光光譜儀Compass4294。客戶可以運(yùn)行樣品測(cè)試，而無(wú)需在現(xiàn)場(chǎng)進(jìn)行任何進(jìn)一步的校準(zhǔn)過(guò)程。

只需執(zhí)行四個(gè)步驟即可進(jìn)行測(cè)量。如下圖所示，了解如何準(zhǔn)備和放置樣品進(jìn)行分析的圖片

1-1，準(zhǔn)備樣品杯。用6 um聚酯薄膜薄膜在分析側(cè)將樣品杯蓋好。在保護(hù)測(cè)試窗口平臺(tái)上還預(yù)先設(shè)置了相同的聚酯薄膜，以避免任何意外樣品泄漏到分析儀中。

1-2，通常將來(lái)自每種標(biāo)準(zhǔn)品的3-5毫升油倒入分析儀的杯子中直至加注線。

1-3，將樣品杯放在指南針XRF樣品裝載器上，它*適合樣品杯尺寸。

1-4，單擊“開(kāi)始"按鈕以運(yùn)行分析。結(jié)果將在130秒后顯示。

使用一組已知硫濃度的市售重質(zhì)燃油標(biāo)準(zhǔn)品來(lái)進(jìn)行校準(zhǔn)。

下面的圖2-2顯示了百分比水平下高濃度范圍的油中硫的相關(guān)曲線。

用線性函數(shù)近似該數(shù)據(jù)。 R2是確定系數(shù)。理想的相關(guān)性的R2值為1。

5. 結(jié)論

本應(yīng)用案例介紹了一種新型分析儀表Compass4294 ---X射線熒光光譜儀在原油及汽車(chē)用油中硫量監(jiān)測(cè)的應(yīng)用。它是基于能量色散 X 射線熒光光譜的測(cè)量原理,進(jìn)行原油中硫含量測(cè)定的,與傳統(tǒng)色譜法相比,在實(shí)際應(yīng)用中具有簡(jiǎn)便、準(zhǔn)確、快捷的特點(diǎn)

用能量色散X射線熒光光譜儀Compass4294代替?zhèn)鹘y(tǒng)的燈硫法 (GB/T380 - 88)和管硫法 (GB/T387- 90 )測(cè)定石油產(chǎn)品硫含量 ,取得了與傳統(tǒng)方法相一致的分析準(zhǔn)確性和重復(fù)性.該方法具有快速,經(jīng)濟(jì)等優(yōu)點(diǎn) ,是一種比較理想的測(cè)定石油產(chǎn)品中硫含量的光譜儀

Sulfur-in-oil Analyzer Compass 4294 Application Note- Sulfur

1. Background and Introduction

 Fuels & oils monitoring- Compass 4294 XRF

For ships operating outside designated Emission Control Areas, IMO has set a limit for sulphur in fuel oil used on board ships of 0.50% m/m (mass by mass) from 1 January 2020. This will significantly reduce the amount of sulphur oxide emanating from ships and should have major health and environmental benefits for the world, particularly for populations living close to ports and coasts.

Since 1 January 2015, the sulphur limit for fuel oil used by ships operating in Emission Control Areas (ECAs) designated by IMO for the control of sulphur oxides (SOX) has been 0.10% m/m.

The powerful Energy Dispersive X-ray Fluorescence (EDXRF) Compass 4294 serial Sulfur analyzer of ESI Instrument are capable of more sensitive and precise analysis than can be expected from a laboratory class analyzer. This application note demonstrate the Compass 4294 test performance of sulfur in different oil and fuel samples.

2. Instrument parameter

Factory optimized test conditions are set for sulfur analysis. This industry leading

technology enabling low detection limits and high precision without the need for consumable helium gas, a vacuum pump, or extensive sample preparation.

4. Test procedure and Calibration demonstration

A serial of commercial available oil standards were used to calibrate the EDXRF spectrometer at factory. Customer can run the sample test without any further calibration process on-site.

Only four steps are needed to make the measurement. See pictures of how to prepare and put the sample for analysis as below picture

1-1, Prepare the sample cup. The cup was closed on the analytical side with a 6 um thin Mylar film. The same Mylar was also preset on the protection test window platform to avoid any accident sample leak into the analyzer.

1-2, Typically 3-5 ml oil from each standard was poured into the analyzer’s cups up to the fill line.

1-3, Put the sample cup on the compass XRF sample loader, which is perfectly fit wit the sample cup dimension.

1-4, Click the ‘start’ button to run analysis. Results will be shown after 130 seconds.

>A set of commercially available heavy fuel oil standards with know sulfur concentrations were used to setup the calibration.

Figures 2-2 below shows the correlation curves sulfur in oil for high concentration ranges in percentage level.

This data was approximated with linear function. R2 is the coefficient of determination. An ideal correlation would have an R2 value of 1.

The red points are sulfur standards: Blank, 0.01%, 0.075%, 0.1%, 0.5%, 2% and 5%. The perfect R2 value(0.999921) demonstrate the good linear with wide concentrate range of sulfur.

Figures 2-3 below shows the correlation curves sulfur in oil for low concentration ranges in ppm level.

The red points are sulfur standards: Blank, 5ppm, 10ppm, 30ppm and 100ppm. The perfect R2 value(0.999664) demonstrate the good linear and high sensitivity for the low sulfur concentration analysis.

5．Conclusion

Sulfur analysis using ASTM D4294 and ISO 8754 continues to be an important measurement for refinery and independent laboratories around the world. Global regulation trends toward lower sulfur fuels demonstrate the need for a rapid and precise analysis solution. Based on the test results obtained above, it is proved that the Compass 4294 is capable of measuring sulfur in oil or fuel samples complying with the most strict standard.

On board fuel oil management is an important element of preventing operational issues and sulphur non-compliance.Improper handling of fuel oil on board may lead to non-compliance with MARPOL requirements,even if the fuel oil received was compliant. With it’s compact and portable design, Compass 4294 becomes essential tool to do on board oil quality control for sulfur.