JP5373695B2 - Sulfur online analyzer - Google Patents
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- JP5373695B2 JP5373695B2 JP2010107055A JP2010107055A JP5373695B2 JP 5373695 B2 JP5373695 B2 JP 5373695B2 JP 2010107055 A JP2010107055 A JP 2010107055A JP 2010107055 A JP2010107055 A JP 2010107055A JP 5373695 B2 JP5373695 B2 JP 5373695B2
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本発明は、自動サンプリング装置により硫黄含有有機試料を採取し、前記試料を加熱炉において酸素含有ガスの存在下で燃焼分解し、当該燃焼分解ガス中の二酸化硫黄の蛍光強度を紫外蛍光検出器により検出する硫黄オンライン分析装置に関する。 In the present invention, a sulfur-containing organic sample is collected by an automatic sampling device, the sample is combusted and decomposed in the presence of an oxygen-containing gas in a heating furnace, and the fluorescence intensity of sulfur dioxide in the combustion-decomposed gas is detected by an ultraviolet fluorescence detector. The present invention relates to a sulfur online analyzer for detection.
ガソリンや軽油などに含まれる硫黄の分析方法の一つとして、酸素で試料を燃焼分解し、燃焼排ガスに紫外線を照射すると共に、放出される蛍光の強度から燃焼排ガス中の二酸化硫黄の含有量を測定するいわゆる紫外蛍光測定法が知られている。上記の分析方法は、例えば、沸点が２５〜４００℃の留分で、室温における動粘度が０.２〜１０mm2/sのナフサ、自動車ガソリン、灯油、軽油中の硫黄の含有量が、３〜５００ppmを越える試料の分析に採用されている（非特許文献１）。 As one of the methods for analyzing sulfur contained in gasoline, light oil, etc., the sample is burned and decomposed with oxygen, the exhaust gas is irradiated with ultraviolet rays, and the sulfur dioxide content in the exhaust gas is determined from the intensity of the emitted fluorescence. A so-called ultraviolet fluorescence measurement method for measuring is known. The above analysis method is, for example, a fraction having a boiling point of 25 to 400 ° C. and a kinematic viscosity at room temperature of 0.2 to 10 mm 2 / s, naphtha, automobile gasoline, kerosene, and diesel oil containing 3 sulfur. It is employed for analysis of samples exceeding ˜500 ppm (Non-patent Document 1).
石油精製プロセスにおいては、日常の運転管理のために、上記分析方法を応用して、これに自動サンプリング装置を設けた、例えば図１に概略を示したような硫黄オンライン分析装置が用いられている。
図１において、石油精製プロセスからの試料は、常時、採取管１から自動サンプリングバルブ２に導入され、非測定時は排出管３から排出されている。測定時には、自動サンプリングバルブ２の切り替えにより、所定量（１.２μL程度）の試料がミキシングチャンバー４に導入され、空気などの酸素含有ガス５と混合されて、１１００℃程度に加熱された加熱炉６に導入され、燃焼分解される。ここで、試料中の硫黄化合物は二酸化硫黄に、炭化水素は二酸化炭素や水などの燃焼分解ガスとなり、測定セル７に導入される。紫外線ランプ８から発光された紫外線がミラーアセンブリ９を介して、この測定セル７において、燃焼分解ガスに照射されると、二酸化硫黄は蛍光を発する。この蛍光発光の強度を光電子増倍管１０で測定し、演算制御器１１で処理して、硫黄濃度を表示する。なお、紫外線ランプ８を正常にコントロールするために光検出器１２が設けられている。
In the oil refining process, for the daily operation management, a sulfur on-line analyzer as schematically shown in FIG. 1, for example, is used in which the above analysis method is applied and an automatic sampling device is provided. .
In FIG. 1, a sample from an oil refining process is always introduced from an extraction pipe 1 into an automatic sampling valve 2 and discharged from an exhaust pipe 3 when not measured. At the time of measurement, by switching the automatic sampling valve 2, a predetermined amount (about 1.2 μL) of sample is introduced into the mixing chamber 4, mixed with an oxygen-containing gas 5 such as air, and heated to about 1100 ° C. 6 is burned and decomposed. Here, the sulfur compound in the sample is converted into sulfur dioxide, and the hydrocarbon is converted into a combustion cracked gas such as carbon dioxide or water and introduced into the measurement cell 7. When the ultraviolet light emitted from the ultraviolet lamp 8 is irradiated to the combustion decomposition gas in the measurement cell 7 through the mirror assembly 9, the sulfur dioxide emits fluorescence. The intensity of the fluorescence emission is measured by the photomultiplier tube 10 and processed by the arithmetic controller 11 to display the sulfur concentration. A photodetector 12 is provided to control the ultraviolet lamp 8 normally.
上述のような硫黄オンライン分析装置は、サンプリング部１３、燃焼分解部１４、検出部１５に、それぞれ区切られたボックス内に一体として収納され、燃焼分解部１４は、加熱炉６に熱を付与するためにエアーオーブンとなっており、通常、自動サンプリングバルブ２表面は、その輻射熱によって、１５０℃程度に予熱されている。 The sulfur on-line analyzer as described above is housed in the sampling unit 13 , the combustion decomposition unit 14 , and the detection unit 15 as a single unit in each partitioned box, and the combustion decomposition unit 14 applies heat to the heating furnace 6. Therefore, the surface of the automatic sampling valve 2 is preheated to about 150 ° C. by the radiant heat.
上記硫黄オンライン分析装置は、長時間測定し続けていると分析誤差が生じるという課題があり、本発明は、かかる課題を解決するものである。 The sulfur online analyzer has a problem that an analysis error occurs if measurement is continued for a long time, and the present invention solves such a problem.
本発明者は、上記課題を解決するために、鋭意検討を加えた結果、自動サンプリングバルブで、試料の熱分解が生じ、自動サンプリングバルブの採取孔に微量の熱分解重合物が付着し、試料採取量が１.２μL程度と僅かなため、採取量に変動を与え、分析誤差が生じていること、及び自動サンプリングバルブの温度を３５℃以下にすることにより、自動サンプリングバルブで熱分解重合物の付着を抑え、長期に亘って安定して硫黄濃度を測定できることを見出し、本発明に想到した。 As a result of diligent investigations to solve the above problems, the present inventors have resulted in thermal decomposition of the sample with the automatic sampling valve, and a small amount of pyrolysis polymer adheres to the sampling hole of the automatic sampling valve. Since the sampled amount is as small as about 1.2μL, the sampled amount varies, and there is an analytical error. By setting the temperature of the automatic sampling valve to 35 ° C or less, the pyrolysis polymer is obtained with the automatic sampling valve. The inventors have found that the sulfur concentration can be measured stably over a long period of time, and the present invention has been conceived.
すなわち、本発明は、自動サンプリングバルブにより硫黄含有有機試料を採取し、前記試料を加熱炉で酸素含有ガスの存在下に燃焼分解し、当該燃焼分解ガス中の二酸化硫黄の蛍光強度を紫外蛍光検出器により検出する硫黄オンライン分析装置において、前記自動サンプリングバルブの温度を３５℃以下に保持するものである。なお、前記有機硫黄含有試料はガソリン又はナフサであることが好ましい。 That is, the present invention collects a sulfur-containing organic sample with an automatic sampling valve, burns and decomposes the sample in the presence of an oxygen-containing gas in a heating furnace, and detects the fluorescence intensity of sulfur dioxide in the combustion-decomposed gas by ultraviolet fluorescence detection. In the sulfur on-line analyzer detected by a vessel, the temperature of the automatic sampling valve is maintained at 35 ° C. or lower. The organic sulfur-containing sample is preferably gasoline or naphtha.
本発明は、自動サンプリングバルブでの熱分解重合物の付着を抑え、長期に亘って安定して硫黄濃度を測定でき、分析誤差を非常に小さくできるという効果を奏する。 The present invention has the effect of suppressing the adhesion of the pyrolysis polymer in the automatic sampling valve, allowing the sulfur concentration to be measured stably over a long period of time, and reducing the analysis error.
以下、本発明の実施形態について、詳細に説明する。
本発明の硫黄オンライン分析装置は、自動サンプリングバルブにより試料を採取し、前記試料を加熱炉で酸素含有ガスの存在下に燃焼分解し、当該燃焼分解ガス中の二酸化硫黄の蛍光強度を紫外蛍光検出器により検出するものであれば、特に制限するものではなく、一般に市販されている硫黄オンライン分析装置に適用できる。
なお、自動サンプリングバルブとしては、市販のスライダー式バルブやロータリー式バルブなどが好適に用いられる。
Hereinafter, embodiments of the present invention will be described in detail.
The sulfur online analyzer of the present invention collects a sample by an automatic sampling valve, burns and decomposes the sample in the presence of an oxygen-containing gas in a heating furnace, and detects the fluorescence intensity of sulfur dioxide in the combustion cracked gas by ultraviolet fluorescence detection. If it detects with a detector, it will not restrict | limit in particular, It can apply to the sulfur online analyzer generally marketed.
In addition, as an automatic sampling valve, a commercially available slider type valve, a rotary type valve, etc. are used suitably.
本発明の測定対象である硫黄含有有機試料としては、硫黄を含有する有機化合物があれば、特に支障はないが、石油精製プロセスにおける中間生成物及び最終製品などで、ＬＰＧ、ガソリン、ナフサ、灯油、軽油などが好適である。特には、沸点が２５〜２２０℃、硫黄濃度が０.５〜２０ppm、臭素価が２０〜３５gBr2/100gのガソリン、ナフサが好ましい。 As the sulfur-containing organic sample to be measured in the present invention, there is no particular problem as long as there is an organic compound containing sulfur, but it is an intermediate product and final product in the petroleum refining process, such as LPG, gasoline, naphtha, kerosene. Gas oil and the like are preferred. In particular, the boiling point of 25-220 ° C., the sulfur concentration is 0.5 to 20, gasoline bromine number 20~35gBr 2 / 100g, naphtha are preferred.
本発明においては、自動サンプリングバルブを３５℃以下に保持するものである。３５℃を超える温度では熱分解重合物の付着を十分に抑制できない。好ましくは３０℃以下、より好ましくは１０〜３０℃に保持する。 In the present invention, the automatic sampling valve is maintained at 35 ° C. or lower. If the temperature exceeds 35 ° C., adhesion of the pyrolytic polymer cannot be sufficiently suppressed. Preferably it is 30 degrees C or less, More preferably, it maintains at 10-30 degreeC.
また、自動サンプリングバルブを上記温度に保持する方法としては、燃焼分解部からの輻射熱を断熱層を設けて断熱する方法、例えば自動サンプリングバルブと燃焼分解部との間に断熱部材として断熱板を設ける方法でも良いが、この方法では、一般的に５０℃程度までしか下げることができない。このため、さらに冷却により所定温度に保持することが好ましい。 In addition, as a method of maintaining the automatic sampling valve at the above temperature, a method of insulating the radiant heat from the combustion decomposition portion by providing a heat insulating layer, for example, providing a heat insulating plate as a heat insulating member between the automatic sampling valve and the combustion decomposition portion. Although a method may be used, this method can generally lower the temperature only to about 50 ° C. For this reason, it is preferable to hold | maintain to predetermined temperature by further cooling.
この冷却方法としては、自動サンプリングバルブの表面に冷却管を巻きつけ、冷却水などの冷却剤を流す方法や、圧縮空気により空気を暖冷させるボルテックスチューブを用いて、その冷気を自動サンプリングバルブの表面に噴出させる方法などを用いることができる。特には、後者のボルテックスチューブによる冷却が簡便で好ましい。なお、この自動サンプリングバルブの温度は、その表面温度を測定し、冷却剤の流量或いは圧縮空気の供給圧をコントロールして、一定温度になるように制御しても良いが、多くは、冷却剤の流量や供給圧を一度決定すれば、特に制御しなくても所定の温度に保持できる。 As a cooling method, a cooling pipe is wound around the surface of the automatic sampling valve and a coolant such as cooling water is flown, or a vortex tube that heats and cools the air using compressed air is used. A method of ejecting to the surface can be used. In particular, cooling by the latter vortex tube is simple and preferable. The temperature of the automatic sampling valve may be controlled to be a constant temperature by measuring the surface temperature and controlling the flow rate of the coolant or the supply pressure of the compressed air. Once the flow rate and supply pressure are determined, they can be maintained at a predetermined temperature without any particular control.
以下、本発明を実施例、比較例により詳細に説明するが、本発明はこれらにより限定して解釈されるものではない。
（加熱による重合確認試験）
沸点９１.５〜２０７℃、硫黄濃度２０ppm、臭素価２６gBr2/100gの脱硫重質ガソリン留分の２００mlを、#１５０研磨紙で湿式研磨後、脱水乾燥処理した金属試験片（炭素鋼SS400、サイズ２５×２５×６mm）と共に、耐圧ガラスオートクレーブの５００mlガラス容器に入れ、２５℃、５０℃、１５０℃で、７日間加熱した。加熱終了後に、金属試験片に析出した重合物の重量及び試料をろ過して、金属試験上と試料中に生成した重合物を０.４５μmの樹脂フッルターを用いて減圧ろ過し、ヘキサン不溶解分を重合物量として測定した。また、試料中に生成したガム分（不揮発性残渣分）の測定は、ＪＩＳ Ｋ２２６１に規定された方法で測定した。この結果を表１に示した。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is limited to these and is not interpreted.
(Polymerization confirmation test by heating)
Boiling point 91.5 to 207 ° C., the sulfur concentration 20 ppm, a bromine number 26gBr 2 / 100g of desulfurization heavy gasoline fraction 200 ml, after the wet grinding with # 150 abrasive paper, dehydrated and dried treated metal specimens (carbon steel SS400, Together with a size 25 × 25 × 6 mm) and placed in a pressure-resistant glass autoclave 500 ml glass container and heated at 25 ° C., 50 ° C. and 150 ° C. for 7 days. After heating, the weight of the polymer deposited on the metal test piece and the sample are filtered, and the polymer formed on the metal test and in the sample is filtered under reduced pressure using a 0.45 μm resin filter to dissolve the hexane insoluble matter. Was measured as the amount of polymer. Moreover, the measurement of the gum part (nonvolatile residue part) produced | generated in the sample was measured by the method prescribed | regulated to JISK2261. The results are shown in Table 1.
ガソリン脱硫プロセスの脱硫重質ガソリン留分中の硫黄濃度を測定するために設置した図１に示したような硫黄オンライン分析装置を用いて、硫黄濃度を測定すると同時に試料を採取して試験室で、ＪＩＳ Ｋ２５４１、同Ｋ２６０５及びＫ２２５４に規定された方法により硫黄濃度、臭素価及び留出温度（初留点と終点）を測定した。
測定は、硫黄オンライン分析装置に何もしていない状態で、自動サンプリングバルブの表面が１５０℃の場合、自動サンプリングバルブの燃焼分解部側に断熱板を設けた状態で、同表面温度を５０℃にした場合、これにさらにボルテックスチューブ（トラスコ中山株式会社製エアージェット；AJ-C）を設置して自動サンプリングバルブの表面温度を２５℃に冷却した場合について、それぞれ４ヶ月間測定を行った。試験開始直後と開始１か月後毎の硫黄濃度、臭素価及び留出温度の測定結果を表２に示した。
Using a sulfur online analyzer as shown in Fig. 1 installed to measure the sulfur concentration in the desulfurized heavy gasoline fraction of the gasoline desulfurization process, a sample was taken at the same time as measuring the sulfur concentration. The sulfur concentration, bromine number, and distillation temperature (initial boiling point and end point) were measured by the methods specified in JIS K2541, K2605 and K2254.
When the surface of the automatic sampling valve is 150 ° C with nothing in the sulfur online analyzer, the surface temperature is set to 50 ° C with a heat insulating plate provided on the combustion decomposition part side of the automatic sampling valve. In this case, a vortex tube (air jet manufactured by TRUSCO NAKAYAMA Co., Ltd .; AJ-C) was further installed, and the surface temperature of the automatic sampling valve was cooled to 25 ° C., and measurement was performed for 4 months. Table 2 shows the measurement results of the sulfur concentration, bromine number, and distillation temperature immediately after the start of the test and every month after the start of the test.
上記結果から、自動サンプリングバルブの温度を３５℃以下にすることにより、長期に亘って、硫黄濃度を精度よく測定できることが分かる。 From the above results, it can be seen that the sulfur concentration can be accurately measured over a long period of time by setting the temperature of the automatic sampling valve to 35 ° C. or lower.
本発明は、石油精製プロセスにおける各種留分の硫黄濃度をオンラインで、長期に亘って、継続的に測定するために利用できる。 The present invention can be used to continuously measure the sulfur concentration of various fractions in an oil refining process online, over a long period of time.
１ 採取管
２ 自動サンプリングバルブ
４ ミキシングチャンバー
６ 加熱炉
７ 測定セル７
８ 紫外線ランプ
１０ 光電子増倍管
1 sampling tube 2 automatic sampling valve 4 mixing chamber 6 heating furnace 7 measuring cell 7
8 UV lamp 10 Photomultiplier tube
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| KR101579011B1 (en) | 2011-08-12 | 2015-12-18 | 제이에프이 스틸 가부시키가이샤 | Molten steel desulfurization method, molten steel secondary refining method, and molten steel manufacturing method |
| JP5177263B2 (en) | 2011-08-12 | 2013-04-03 | Ｊｆｅスチール株式会社 | Hot metal desulfurization method |
| WO2013044229A1 (en) * | 2011-09-23 | 2013-03-28 | Lucas Milhaupt, Inc. | Luminescent braze preforms |
| JP6089445B2 (en) * | 2012-05-17 | 2017-03-08 | 株式会社島津製作所 | Component analysis apparatus and component analysis method |
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| CN105651750B (en) * | 2016-01-26 | 2018-09-25 | 张继勇 | The online analysis of total sulfur control system of Ultraluminescence and method |
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