JPH06100540B2 - Analysis method of arsenic in petroleum fraction - Google Patents
Analysis method of arsenic in petroleum fractionInfo
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- JPH06100540B2 JPH06100540B2 JP61095681A JP9568186A JPH06100540B2 JP H06100540 B2 JPH06100540 B2 JP H06100540B2 JP 61095681 A JP61095681 A JP 61095681A JP 9568186 A JP9568186 A JP 9568186A JP H06100540 B2 JPH06100540 B2 JP H06100540B2
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- arsenic
- petroleum fraction
- hydride
- oxide
- petroleum
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Description
【発明の詳細な説明】 発明の技術分野 本発明は、石油留分中の砒素の分析方法に関し、さらに
詳しくは、特にナフサなどの軟質石油留分中の砒素を正
確にかつ迅速に定量分析するための方法に関する。Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for analyzing arsenic in petroleum fractions, and more particularly to an accurate and rapid quantitative analysis of arsenic in soft petroleum fractions such as naphtha. For how to.
発明の技術的背景ならびにその問題点 直留ナフサ、灯油、接触分解などによって生成する留分
などの石油留分からエチレン、重合体などの石油化学原
料あるいは石油化学製品を触媒を用いて製造する際に、
石油留分中に砒素（As）が含まれていると、触媒の砒素
により被毒されて触媒活性が急激に低下したり、あるい
は石油留分の熱分解の際にコーキングが促進されてしま
うなどの悪影響が生じてしまう。特に触媒としてPt、Pd
などの貴金属触媒を用いた場合には、砒素は微量であっ
ても触媒に著しい悪影響を及ぼしてしまう。このため、
直留ナフサなどの石油留分から砒素を所定量以下まで除
去することが強く望まれている。Technical background of the invention and its problems When producing petrochemical raw materials or petrochemical products such as ethylene and polymers from petroleum fractions such as straight-run naphtha, kerosene, and fractions produced by catalytic cracking using catalysts ,
If the petroleum fraction contains arsenic (As), it will be poisoned by the arsenic of the catalyst and the catalytic activity will drop sharply, or coking will be promoted during the thermal decomposition of the petroleum fraction. Will have an adverse effect. Especially as a catalyst Pt, Pd
When a noble metal catalyst such as the above is used, even if the amount of arsenic is very small, it has a significant adverse effect on the catalyst. For this reason,
It is strongly desired to remove arsenic to a predetermined amount or less from petroleum fractions such as straight-run naphtha.
このようにナフサなどの石油留分中の砒素を所定量以下
まで除去することが望まれているが、そのためには石油
留分中に砒素がどの程度含有されているかを正確かつ迅
速に把握する必要がある。As described above, it is desired to remove arsenic in petroleum fractions such as naphtha to a predetermined amount or less. To this end, it is necessary to accurately and quickly grasp how much arsenic is contained in petroleum fractions. There is a need.
従来石油留分中の砒素を定量分析するには、以下のよう
な方法が行なわれていた。すなわち砒素が含まれた石油
留分を、硫酸含有シリカゲルカラムに通過させて砒素を
カラムに吸着させ、次いでこのカラムに硫酸、硝酸、あ
るいは過塩素酸を加えて吸着された砒素を溶出させた
後、塩酸酸性下でヨウ化カリウム、塩化スズ（II）また
は亜鉛を加えてアルシンとし、このアルシンガスをジエ
チルジチオカルバミン酸銀のピリジン溶液に吸収させ、
このピリジン溶液の吸光度から砒素を定量していた。ま
た、砒素が含まれた石油留分を、酸水素炎で燃焼させて
砒素を水酸化ナトリウムに吸収させ、次いでこの溶液に
ついてジエチルジチオカルバミン酸銀吸光光度分析法に
て定量していた。さらには、砒素が含まれた石油留分
に、硫酸と過酸化水素水とを加え、砒素有機物を分解し
た後砒素を水相に抽出し、この溶液についてジチオカル
バミン酸銀吸光光度分析法にて定量していた。また別の
方法としては、砒素が含まれた石油留分をボンベ内で酸
素を助燃剤として燃焼させた後、硝酸マグネシウム−硝
酸溶液に砒素を吸収させた後、黒鉛炉原子吸光法で定量
していた。あるいはまた、砒素が含まれた石油留分をウ
ィックボルト酸水素炎で燃焼した後過酸化水素水に吸収
させ、次いで硝酸マグネシウムを加えた後濃縮乾固さ
せ、これに１％硝酸水溶液を加えた後原子吸光法で定量
していた。Conventionally, the following method has been used to quantitatively analyze arsenic in petroleum fractions. That is, the petroleum fraction containing arsenic is passed through a silica gel column containing sulfuric acid to adsorb arsenic to the column, and then sulfuric acid, nitric acid, or perchloric acid is added to this column to elute the adsorbed arsenic. , Potassium iodide, tin (II) chloride or zinc was added under acidic condition of hydrochloric acid to give arsine, and this arsine gas was absorbed into a solution of silver diethyldithiocarbamate in pyridine,
Arsenic was quantified from the absorbance of this pyridine solution. Further, a petroleum fraction containing arsenic was burned with an oxyhydrogen flame to absorb arsenic into sodium hydroxide, and then this solution was quantified by silver diethyldithiocarbamate absorptiometry. Furthermore, sulfuric acid and hydrogen peroxide solution were added to a petroleum fraction containing arsenic to decompose organic compounds of arsenic and then arsenic was extracted into an aqueous phase, and this solution was quantified by silver dithiocarbamate spectrophotometry. Was. As another method, a petroleum fraction containing arsenic is burned in a cylinder using oxygen as a combustion enhancer, and then magnesium nitrate-nitric acid solution is allowed to absorb arsenic, followed by quantitative determination by graphite furnace atomic absorption spectrometry. Was there. Alternatively, a petroleum fraction containing arsenic is burned with a wick bolt hydrogen hydrogen flame, absorbed in hydrogen peroxide water, then magnesium nitrate is added and the mixture is concentrated to dryness, and a 1% nitric acid aqueous solution is added thereto. It was quantified by the post atomic absorption method.
ところが、上記の方法ではいずれも砒素の定量に２日程
度もの長時間を要し、しかも分析精度も必ずしも満足が
いくものではないという問題点があった。また砒素の定
量分析に際して酸水素炎を用いる場合には、分析に熟練
を要するとともに爆発範囲のガスを扱うため危険が伴な
うという問題点もあった。However, each of the above methods has a problem in that it takes a long time of about 2 days to quantify arsenic, and the analysis accuracy is not always satisfactory. Further, when an oxyhydrogen flame is used in the quantitative analysis of arsenic, there is a problem that analysis is required and that gas in the explosion range is handled, which is dangerous.
発明の目的 本発明は、上記のような従来技術に伴なう問題点を解決
しようとするものであって、ナフサなどの石油留分中の
砒素を、長時間を要することなく迅速にしかも正確に、
その上安全に定量分析しうるような石油留分中の砒素の
分析方法を提供することを目的としている。OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and to remove arsenic in a petroleum fraction such as naphtha quickly and accurately without requiring a long time. To
Moreover, it is an object of the present invention to provide a method for analyzing arsenic in petroleum fractions, which enables safe quantitative analysis.
発明の概要 本発明に係る石油留分中の砒素の分析方法は、有機砒素
化合物を含有する石油留分に酸化剤および酸を加えて、
前記有機砒素化合物を砒素酸化物として水相に移行さ
せ、次いで得られた砒素酸化物を水相で還元して砒素水
素化物とし、この砒素水素化物を加熱して砒素原子とし
て原子吸光法により定量することを特徴としている。SUMMARY OF THE INVENTION The method for analyzing arsenic in a petroleum fraction according to the present invention comprises adding an oxidizing agent and an acid to a petroleum fraction containing an organic arsenic compound,
The organic arsenic compound is transferred to the aqueous phase as arsenic oxide, and then the obtained arsenic oxide is reduced in the aqueous phase to form arsenic hydride. The arsenic hydride is heated and arsenic atoms are quantified by atomic absorption spectrometry. It is characterized by doing.
本発明に係る石油留分中の砒素の分析方法によれば、石
油留分中に含まれる有機砒素化合物を酸化して砒素酸化
物とし、次いで還元して砒素水素化物とした後原子吸光
法により定量しているので、極めて短時間で砒素を精度
ならびに再現性よく定量分析することができ、その上酸
水素炎などを用いていないため安全性は極めて高い。し
かも極めて微量の砒素をも分析することができる。According to the method for analyzing arsenic in a petroleum fraction according to the present invention, an organic arsenic compound contained in a petroleum fraction is oxidized into an arsenic oxide, and then reduced into an arsenic hydride by an atomic absorption method. Since it is quantified, arsenic can be quantitatively analyzed with high accuracy and reproducibility in an extremely short time, and safety is extremely high because oxyhydrogen flame is not used. Moreover, even a very small amount of arsenic can be analyzed.
発明の具体的説明 以下本発明に係る石油留分中の砒素の分析方法につい
て、具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The method for analyzing arsenic in a petroleum fraction according to the present invention will be specifically described below.
石油留分 本発明において、石油留分中の砒素が定量分析される
が、このような石油留分としては、原油から直接留出さ
れた直留ナフサ、灯油、軽油、減圧留出物などの留分、
あるいはエチレンプラント、コーカー、ビスブレーカー
など熱処理によって生成された軽質留分、さらには流動
接触分解処理などによって生成された軽質留分などが広
く用いられる。また本発明では、石油留分としてコンデ
ンセート（NGL）などのような比較的軽質な留分あるい
は液化石油ガスも用いることができる。Petroleum fraction In the present invention, arsenic in a petroleum fraction is quantitatively analyzed. Examples of such a petroleum fraction include straight-run naphtha directly distilled from crude oil, kerosene, gas oil, and vacuum distillate. Fraction,
Alternatively, a light fraction produced by heat treatment such as an ethylene plant, a coker, a bisbreaker, and a light fraction produced by fluid catalytic cracking treatment are widely used. In the present invention, a relatively light fraction such as condensate (NGL) or liquefied petroleum gas can also be used as a petroleum fraction.
このような石油留分中には、砒素は、通常はRnAsH
3-n（式中Ｒはアルキル、フェニル基などであり、ｎは
0,1,2,3である）で表わされるような水素化物あるいは
有機化合物の形態で含有されている。このような砒素化
合物としては、具体的にアルシン、モノメチルアルシ
ン、ジメチルアルシン、トリメチルアルシン、トリブチ
ルアルシン、トリフェニルアルシンなどが挙げられる。
またハロゲン化された砒素化合物たとえばジメチルクロ
ルアルシンあるいは酸化された砒素化合物たとえばトリ
メチルアルシンオキシドなどの形態で、砒素が石油留分
中に含まれていることもありうる。In such petroleum fractions, arsenic is usually found in R n AsH
3-n (wherein R is an alkyl group, a phenyl group, etc., and n is
0,1,2,3) and is contained in the form of a hydride or an organic compound. Specific examples of such an arsenic compound include arsine, monomethylarsine, dimethylarsine, trimethylarsine, tributylarsine, and triphenylarsine.
It is also possible that arsenic is contained in the petroleum fraction in the form of a halogenated arsenic compound such as dimethyl chlorarsine or an oxidized arsenic compound such as trimethyl arsine oxide.
このような砒素は、石油留分の種類によって異なるが、
一般に石油留分中に数ppb（重量）から数百ppb（重量）
で含まれていることが多い。Such arsenic varies depending on the type of petroleum fraction,
Generally several ppb (weight) to several hundred ppb (weight) in petroleum fraction
Often included in.
分析操作 石油留分中に含まれた有機砒素化合物は、その蒸気圧が
比較的高く加熱によって揮散しやすいため、砒素の分析
に際しては前処理が必要となる。Analytical procedure The organic arsenic compound contained in the petroleum fraction has a relatively high vapor pressure and is easily volatilized by heating. Therefore, pretreatment is required for arsenic analysis.
まず有機砒素化合物を含有する石油留分に酸化剤および
酸を加えて、有機砒素化合物を酸化するとともに分解し
て砒素酸化物とし、この砒素酸化物を水相に抽出する。First, an oxidizing agent and an acid are added to a petroleum fraction containing an organic arsenic compound to oxidize and decompose the organic arsenic compound into arsenic oxide, and the arsenic oxide is extracted into an aqueous phase.
このような酸化剤としては、過酸化水素、重クロム酸カ
リウム、シュウ酸カリウム、過マンガン酸カリウム、硝
酸、あるいは有機過酸化物などが用いられる。As such an oxidizing agent, hydrogen peroxide, potassium dichromate, potassium oxalate, potassium permanganate, nitric acid, or organic peroxide is used.
酸化剤としては過酸化水素水を用いる場合には、その濃
度は10〜30重量％程度であることが望ましい。When hydrogen peroxide solution is used as the oxidizing agent, its concentration is preferably about 10 to 30% by weight.
また酸として、硫酸、塩酸、硝酸などが用いられる。As the acid, sulfuric acid, hydrochloric acid, nitric acid or the like is used.
この添加される酸は、50重量％以上の高濃度のものであ
ることが望ましい。It is desirable that the added acid has a high concentration of 50% by weight or more.
石油留分中の有機砒素化合物を酸化分解して砒素酸化物
とするに際して、石油留分中にまず上記の酸化物たとえ
ば過酸化水素水を加え、次いで得られた混合物に酸化剤
と酸との混合物たとえば過酸化水素水と硫酸との混合物
を加えることが好ましいが、石油留分中の直接酸化物と
酸との混合物を加えることもできる。When the organic arsenic compound in the petroleum fraction is oxidatively decomposed to form an arsenic oxide, the above oxide such as hydrogen peroxide water is first added to the petroleum fraction, and then the resulting mixture of oxidant and acid is added. It is preferred to add a mixture, for example a mixture of aqueous hydrogen peroxide and sulfuric acid, but it is also possible to add a mixture of direct oxides and acids in the petroleum fraction.
このようにして石油留分中の有機砒素化合物を酸化分解
すると、有機砒素化合物が次式に示されるようにして砒
素酸化物となるであろう。When the organic arsenic compound in the petroleum fraction is oxidatively decomposed in this manner, the organic arsenic compound will be an arsenic oxide as shown by the following formula.
砒素定量分析が行なわれる際に用いられる石油留分の試
料量は、砒素の含有量に応じて大きく変化しうるが、一
般に５〜100ml程度である。たとえば石油留分中に砒素
が500wtppb含有されている場合には5mlの試料量で充分
であるが、100wtppbである場合には20〜25ml、20〜50wt
ppbである場合には30〜50ml、２〜10wtppbである場合に
は100ml程度の試料量が用いられる。 The sample amount of the petroleum fraction used when the arsenic quantitative analysis is performed can vary greatly depending on the arsenic content, but is generally about 5 to 100 ml. For example, if the petroleum fraction contains 500 wtppb of arsenic, a sample volume of 5 ml is sufficient, but if it is 100 wtppb, 20-25 ml, 20-50 wt.
In the case of ppb, a sample amount of 30 to 50 ml is used, and in the case of 2 to 10 wtppb, a sample amount of about 100 ml is used.
上記のような石油留分中に含まれる有機砒素化合物の酸
化分解に際して、あるいは酸化分解後に反応系を還流温
度に加熱することが好ましく、このように加熱すること
によって、試料中の炭化水素が分解されたりあるいは蒸
発除去されたりして、得られる砒素酸化物は水相に移行
する。この際反応系にもし過剰の酸化剤たとえば過酸化
水素が存在しても、これらは分解される。なお後述する
原子吸光分析時に、過酸化水素などの酸化剤が水相に残
存していると、砒素の定量分析に悪影響が生ずるために
好ましくない。During the oxidative decomposition of the organic arsenic compound contained in the petroleum fraction as described above, or after the oxidative decomposition, it is preferable to heat the reaction system to the reflux temperature. By heating in this manner, the hydrocarbons in the sample are decomposed. The resulting arsenic oxide is transferred to the aqueous phase by being removed or evaporated. At this time, if an excess of oxidizing agent such as hydrogen peroxide is present in the reaction system, these are decomposed. It should be noted that it is not preferable that an oxidizing agent such as hydrogen peroxide remains in the aqueous phase at the time of atomic absorption analysis, which will be described later, because it adversely affects the quantitative analysis of arsenic.
このような加熱中に石油留分の一部が炭化する場合があ
るが、このような石油留分の場合には過酸化水素などの
酸化剤を多めに用いて炭化した石油留分を分解して除去
すればよい。A part of the petroleum fraction may be carbonized during such heating, but in the case of such a petroleum fraction, the carbonized petroleum fraction is decomposed by using a large amount of an oxidizing agent such as hydrogen peroxide. And remove it.
次に、上記のようにして酸化して得られた砒素酸化物を
還元して砒素水素化物とする。砒素酸化物の砒素水素化
物への還元は、次式のように進行すると考えられる。Next, the arsenic oxide obtained by oxidation as described above is reduced to arsenic hydride. It is considered that the reduction of arsenic oxide to arsenic hydride proceeds according to the following equation.
As2O5→（As2O3）→AsH3 砒素酸化物の砒素水素化物への還元は、反応系中に水素
化ホウ素ナトリウムを添加することによって行なわれる
ことが好ましい。水素化ホウ素ナトリウムは、水溶液の
形態で反応系に添加されることが好ましく、この際水溶
液中には塩酸などの酸が添加されて酸性とされているこ
とが好ましい。水素化ホウ素ナトリウム水溶液の濃度
は、１〜５重量％程度であることが好ましい。また、こ
の水素化ホウ素ナトリウムは、還元すべき砒素酸化物に
対して過剰量で用いられる。As 2 O 5 → (As 2 O 3 ) → AsH 3 The reduction of arsenic oxide to arsenic hydride is preferably carried out by adding sodium borohydride to the reaction system. Sodium borohydride is preferably added to the reaction system in the form of an aqueous solution, and it is preferable that the aqueous solution is acidified by adding an acid such as hydrochloric acid. The concentration of the sodium borohydride aqueous solution is preferably about 1 to 5% by weight. Further, this sodium borohydride is used in an excessive amount with respect to the arsenic oxide to be reduced.
上記のような砒素酸化物の水素化ホウ素ナトリウムによ
る還元に際して、反応系にヨウ化カリウムを共存させる
ことにより、酸化砒素（Ｖ）の酸化砒素（III）への還
元が促進され、砒素の分析の感度が向上する。このよう
なヨウ化カリウムは、反応系に0.1〜10重量％好ましく
は、0.5〜５重量％の量で存在することが好ましい。When sodium borohydride is used to reduce arsenic oxide as described above, the presence of potassium iodide in the reaction system promotes the reduction of arsenic oxide (V) to arsenic oxide (III), and the analysis of arsenic is performed. The sensitivity is improved. Such potassium iodide is preferably present in the reaction system in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
このようにして石油留分中の有機砒素化合物を砒素水素
化物（AsH3）とした後、この砒素水素化物を加熱して砒
素原子とし、この砒素原子を原子吸光分析法により定量
分析する。In this way, after the organic arsenic compound in the petroleum fraction is converted to arsenic hydride (AsH 3 ), the arsenic hydride is heated to arsenic atoms, and the arsenic atoms are quantitatively analyzed by atomic absorption spectrometry.
砒素水素化物を加熱して砒素原子とするには、砒素水素
化物を市販されている水素化物原子化装置を用いて砒素
水素化物の加熱原子化法における従来公知の条件たとえ
ば約800〜1100℃程度の温度に加熱すればよい。また得
られた砒素原子の原子吸光分析による定量は、市販の原
子吸光装置を用いて行なえばよく、この際の条件などに
ついては、砒素の原子吸光分析法における従来公知の条
件を採用しうる。In order to heat arsenic hydride into arsenic atoms, the arsenic hydride can be heated by using a commercially available hydride atomizer, which is a conventionally known condition in the heating atomization method of arsenic hydride, for example, about 800 to 1100 ° C. It may be heated to the temperature of. Further, the quantification of the obtained arsenic atom by atomic absorption spectrometry may be carried out by using a commercially available atomic absorption spectrometer, and regarding the conditions at this time, the conventionally known conditions in the atomic absorption spectrometry of arsenic can be adopted.
発明の効果 本発明に係る石油留分中の砒素の分析方法によれば、石
油留分中に含まれる有機砒素化合物を酸化して砒素酸化
物として水相に移行させ、次いで得られた砒素酸化物を
水相で還元して砒素水素化物とした後原子吸光法により
定量しているので、極めて短時間で砒素を精度ならびに
再現性よく定量分析することができ、その上酸水素炎な
どを用いていないため安全性は極めて高い。しかも極め
て微量の砒素をも分析することができる。Effects of the Invention According to the method for analyzing arsenic in petroleum fractions according to the present invention, the organic arsenic compound contained in the petroleum fraction is oxidized to be transferred to the aqueous phase as arsenic oxide, and then the obtained arsenic oxide is obtained. Since the substance is reduced in the aqueous phase to form arsenic hydride and then quantified by the atomic absorption method, arsenic can be quantitatively analyzed with high accuracy and reproducibility in a very short time. Not very safe. Moreover, even a very small amount of arsenic can be analyzed.
以下本発明を実施例により説明するが、本発明はこれら
実施例に限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１ 有機砒素化合物を実質的に全く含まないライトナフサ10
0mlに、有機砒素化合物としてトリフェニルアルシンを2
0wtppb添加し、このライトナフサに31％過酸化水素20ml
および18Nの硫酸30mlを加え、砒素を酸化するとともに
分解して砒素酸化物とするとともに、ナフサ中の炭化水
素を除去した。さらにこの反応混合物を水の還流温度に
約10分加熱して、残留する過剰な過酸化水素を分解し
た。Example 1 Light naphtha 10 containing substantially no organic arsenic compound
To 0 ml, add 2 phenylarsine as an organic arsenic compound.
Add 0 wtppb and add 20% of 31% hydrogen peroxide to this light naphtha.
And 30 ml of 18N sulfuric acid were added to oxidize and decompose arsenic to arsenic oxide, and to remove hydrocarbons in naphtha. The reaction mixture was further heated to the reflux temperature of water for about 10 minutes to decompose the residual excess hydrogen peroxide.
このようにして得られた砒素酸化物を含む水溶液に、40
重量％のヨウ化カリウム水溶液を5ml添加し、約30分間
放置した。その後この水溶液および同容量の２重量％の
水素化ホウ素ナトリウム水溶液をおのおの水素化物発生
装置（日本ジャーレルアッシュ製HYD−１）に導入し、
砒素酸化物を水素化砒素（AsH3）に還元した。The aqueous solution containing the arsenic oxide thus obtained was added with 40
5 ml of a weight% potassium iodide aqueous solution was added, and the mixture was allowed to stand for about 30 minutes. After that, this aqueous solution and the same volume of 2% by weight sodium borohydride aqueous solution were introduced into each hydride generator (HYD-1 manufactured by Jarre Ash Co., Ltd.),
Arsenic oxide was reduced to arsenic hydride (AsH 3 ).
このようにして得られた水素化砒素AsH3を市販の水素化
物原子化装置（日本ジャーレルアッシュ製HYD−２）に
導き、原子化炉温度1000℃で水素化砒素を分解して砒素
原子とした。このようにして得られた砒素原子を市販の
原子吸光装置（日本ジャーレルアッシュ製AA−8200）に
導き、193.7nmにおける原子吸光光度計の吸光度から砒
素の定量を行なった。The thus-obtained arsenic hydride AsH 3 was introduced into a commercially available hydride atomizer (HYD-2 manufactured by Jarrel Ash, Japan), and the arsenic hydride was decomposed at a reactor temperature of 1000 ° C. to form arsenic atoms. did. The arsenic atom thus obtained was introduced into a commercially available atomic absorption spectrometer (AA-8200 manufactured by Jarre Ash Co., Ltd.), and arsenic was quantified from the absorbance of an atomic absorption spectrophotometer at 193.7 nm.
上記のような砒素の定量分析操作は、約２時間で完了し
た。The arsenic quantitative analysis operation as described above was completed in about 2 hours.
この操作を20回操作して、分析精度および再現性を調べ
た。This operation was repeated 20 times to examine the analytical accuracy and reproducibility.
結果を表１に示す。The results are shown in Table 1.
これらの結果から、砒素の定量分布の再現性は、非常に
良好であり、分析精度も良好であることがわかる。 From these results, it is understood that the reproducibility of the quantitative distribution of arsenic is very good and the analysis accuracy is also good.
実施例２ 表２に示すような種々の濃度で有機砒素化合物を各種の
石油留分100mlを用いて、実施例１と同様にして石油留
分中の砒素濃度を分析した。Example 2 The arsenic concentration in the petroleum fraction was analyzed in the same manner as in Example 1 using 100 ml of various petroleum fractions containing various organic arsenic compounds as shown in Table 2.
結果を表２に示す。The results are shown in Table 2.
比較例１ 実施例２で用いたのと同一の各種石油留分100mlを酸水
素炎で燃焼し、燃焼室の壁面に付着した砒素を塩酸で洗
浄した後過酸化水素水に吸収させた。ついでこの溶液に
硝酸マグネシウムを添加した後、濃縮乾固させ、これに
１％硝酸水溶液を加えた。得られた溶液を原子吸光光度
計に導き、砒素の定量を行なった。Comparative Example 1 100 ml of the same various petroleum fractions used in Example 2 were burned with an oxyhydrogen flame, arsenic adhering to the wall of the combustion chamber was washed with hydrochloric acid and then absorbed in hydrogen peroxide solution. Then, magnesium nitrate was added to this solution, which was then concentrated to dryness, and a 1% nitric acid aqueous solution was added thereto. The obtained solution was introduced into an atomic absorption spectrophotometer to quantify arsenic.
結果を表２に示す。The results are shown in Table 2.
このような砒素の定量分析操作には、約１日半〜２日必
要であった。About one and a half to two days were required for such an arsenic quantitative analysis operation.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 橋本 尚武 神奈川県横浜市港北区下田町５丁目21番24 号 (56)参考文献 特開 昭56−22953（ＪＰ，Ａ) 特開 昭59−119244（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naotake Hashimoto 5-21-24 Shimoda-cho, Kohoku-ku, Yokohama-shi, Kanagawa (56) References JP-A-56-22953 (JP, A) JP-A-59-119244 (JP, A)
Claims (4)
剤および酸を加えて、前記有機砒素化合物を砒素酸化物
として水相に移行させ、次いで得られた砒素酸化物を水
相で還元して砒素水素化物とし、この砒素水素化物を加
熱して砒素原子として原子吸光法により定量することを
特徴とする石油留分中の砒素の分析方法。1. An oxidizer and an acid are added to a petroleum fraction containing an organic arsenic compound to transfer the organic arsenic compound as an arsenic oxide to an aqueous phase, and then the obtained arsenic oxide is reduced in the aqueous phase. An arsenic hydride in a petroleum fraction is characterized by heating the arsenic hydride to determine the amount of arsenic atoms by atomic absorption spectrometry.
る特許請求の範囲第１項に記載の方法。2. The method according to claim 1, wherein the oxidizing agent is hydrogen peroxide and the acid is sulfuric acid.
際に、水素化ホウ素ナトリウムが用いられる特許請求の
範囲第１項に記載の方法。3. The method according to claim 1, wherein sodium borohydride is used in reducing arsenic oxide to arsenic hydride.
り還元して砒素水素化物とする際に、反応系にヨウ化カ
リウムが共存せしめられている特許請求の範囲第３項に
記載の方法。4. The method according to claim 3, wherein when the arsenic oxide is reduced with sodium borohydride to form an arsenic hydride, potassium iodide is allowed to coexist in the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61095681A JPH06100540B2 (en) | 1986-04-23 | 1986-04-23 | Analysis method of arsenic in petroleum fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61095681A JPH06100540B2 (en) | 1986-04-23 | 1986-04-23 | Analysis method of arsenic in petroleum fraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62250338A JPS62250338A (en) | 1987-10-31 |
| JPH06100540B2 true JPH06100540B2 (en) | 1994-12-12 |
Family
ID=14144240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61095681A Expired - Lifetime JPH06100540B2 (en) | 1986-04-23 | 1986-04-23 | Analysis method of arsenic in petroleum fraction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06100540B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196853A (en) * | 2013-04-15 | 2013-07-10 | 贵州百灵企业集团制药股份有限公司 | Method for detecting arsenic salt of Huanglian Shangqing tablets |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4602070B2 (en) * | 2004-12-24 | 2010-12-22 | 株式会社島津製作所 | Sample pretreatment method for arsenic analysis by chemical form |
| CN103196851A (en) * | 2013-03-27 | 2013-07-10 | 广西中烟工业有限责任公司 | Measuring method of arsenic content of glyceryl triacetate |
| CN114609320B (en) * | 2022-03-08 | 2024-04-09 | 苏州恒润商品检验有限公司 | Cold atomic fluorescence analysis method for trace arsenic in petroleum pyrolysis gas phase product |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5622953A (en) * | 1979-07-31 | 1981-03-04 | Shimadzu Corp | Analyzer for phosphorus and arsenic compound |
| JPS59119244A (en) * | 1982-12-25 | 1984-07-10 | Nippon Jiyaareru H Kk | Hydride generator |
-
1986
- 1986-04-23 JP JP61095681A patent/JPH06100540B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196853A (en) * | 2013-04-15 | 2013-07-10 | 贵州百灵企业集团制药股份有限公司 | Method for detecting arsenic salt of Huanglian Shangqing tablets |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62250338A (en) | 1987-10-31 |
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