JP5508837B2 - Heavy oil component analysis method - Google Patents
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本発明は、重質油の成分分析方法に関し、詳しくは、分子量が大きくかつ極めて多種類の有機化合物の混合物であるため詳細分析が困難な重質油の成分分析方法に関するものである。 The present invention relates to a component analysis method for heavy oil, and more particularly to a component analysis method for heavy oil that has a large molecular weight and is extremely difficult to analyze because it is a mixture of various organic compounds.
原油を精製して得られる重質油は、それ自体を有効に利用するとともに、さらにその品質を高めて利用し、またそれを分解処理して新たな原料として活用される。
例えば、原油を常圧蒸留して得られる重油は、水素化脱硫処理により硫黄分を低減した重油とすることによって大気汚染を低減する品質の高い重油として利用され、また、重質油を接触分解処理などの分解処理により低級炭化水素とし、その低級炭化水素を燃料油や石油化学原料として利用されることが多い。
しかし、重質油などの分子量が大きく、硫黄などのヘテロ元素を多く含む炭化水素について水素化脱硫処理や接触分解処理などを行うには、選択された触媒を用い、高温、高圧の過酷な条件下で脱硫反応や分解反応を実施することが要求されため、多大なエネルギーやコストが費やされている。
したがって、それらの反応効率を一層高める研究開発が要求され、触媒の改良とともに原料である重質油の化学成分や化学構造と反応効率との関係を詳細に追跡することが必要となってくる。
Heavy oil obtained by refining crude oil effectively uses itself, and further improves its quality and uses it as a new raw material by decomposing it.
For example, heavy oil obtained by atmospheric distillation of crude oil is used as high-quality heavy oil that reduces air pollution by reducing the sulfur content by hydrodesulfurization, and catalytic cracking of heavy oil In many cases, the lower hydrocarbon is converted into a lower hydrocarbon by a decomposition treatment such as a treatment, and the lower hydrocarbon is used as a fuel oil or petrochemical raw material.
However, hydrodesulfurization treatment and catalytic cracking treatment of hydrocarbons with large molecular weight such as heavy oil and rich in heteroelements such as sulfur are performed using harsh conditions at high temperature and high pressure using the selected catalyst. Under the circumstances, it is required to carry out desulfurization reaction and decomposition reaction, and thus enormous energy and cost are spent.
Therefore, research and development to further increase the reaction efficiency is required, and it is necessary to closely track the relationship between the chemical components and chemical structure of heavy oil as a raw material and the reaction efficiency as well as the improvement of the catalyst.
ところが、重質油についての化学構造の分析方法は、重質油が分子量が大きく、かつ複雑な化学構造を有する分子が極めて多種類存在するため、それらの具体的な化学成分や化学構造は殆ど解明されていないのが現状である。
例えば、従来の重質油の分析法としては、「ＡＰＩ」などの一般性状以外の化学構造に関しては、飽和分、芳香族分、レジン分及びアスファルテン分の４つの化学構造のタイプに分離し、各留分について、ＮＭＲ法などを用いて平均構造を求める方法が知られている（例えば、非特許文献１、２参照）。したがって、この方法では、重質油の大まかな組成の特徴についての情報を得られるものの、実際に存在する具体的な化学成分や化学構造を知ることができない。
その結果、従来の重質油の分析方法で得られた知見に基づいて、脱硫反応や、分解反応に用いる触媒や反応効率に影響を与える重質油の因子を把握することができなく、その分野の研究の発展を阻害することとなっていた。
このようなことから、分析が困難な重質油について、その化学成分や化学構造をより詳細に知ることができる成分分析方法が求められていた。
However, the analysis method of the chemical structure of heavy oil has almost all of its specific chemical components and chemical structures because heavy oil has a large molecular weight and a very large number of molecules having a complicated chemical structure. The current situation has not been elucidated.
For example, as a conventional heavy oil analysis method, chemical structures other than general properties such as “API” are separated into four chemical structure types of saturated, aromatic, resin and asphaltenes, For each fraction, a method for obtaining an average structure using an NMR method or the like is known (for example, see Non-Patent Documents 1 and 2). Therefore, although this method can obtain information on the characteristics of the rough composition of heavy oil, it cannot know the actual chemical components and chemical structures that actually exist.
As a result, based on the knowledge obtained by the conventional heavy oil analysis method, it is impossible to grasp the desulfurization reaction, the catalyst used in the decomposition reaction, and the factors of heavy oil that affect the reaction efficiency. It was to hinder the development of research in the field.
For these reasons, there has been a demand for a component analysis method that can know in detail the chemical components and chemical structures of heavy oils that are difficult to analyze.
本発明は、このような状況下で、従来困難とされる重質油の化学成分をより詳細に知ることができる成分分析方法を提供することを目的とするものである。 An object of the present invention is to provide a component analysis method capable of knowing in detail the chemical components of heavy oil, which has been conventionally difficult, under such circumstances.
本発明者は、鋭意研究を重ねた結果、重質油に特定の前処理を施し、芳香族分を環数別に分離した上で、特定の分析手法を行うことによって、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
［１］（ａ）以下の（１）〜（３）の工程を有して、重質油を飽和分、環数別芳香族分、極性化合物及び多環芳香族分の各フラクションに分離する前処理を行い、次いで（ｂ）前処理によって得られた各フラクションについて（ｂ−１）得率を求め、（ｂ−２）下記（２）及び（３）で得た飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分のフラクションの中の少なくとも１つのフラクションについて、
(i) 元素分析、(ii) 1 Ｈ−ＮＭＲ分析、(iii) 質量分析、及び(iv) 紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）のいずれか１以上の分析を実施し、その分析結果に基づいて構造解析を行い、該構造解析方法が、以下の（５）〜（９）の工程を含むものであることを特徴とする重質油の成分分析方法。
（１）重質油をｎ−パラフィンに可溶なマルテン分とそれ以外のフラクションに分離する第１工程、
（２）上記（１）で分離したマルテン分をカラムクロマトグラフィーを用いて飽和分、１環芳香族分、２環芳香族分、３環以上の芳香族分、極性化合物、及び多環芳香族分の各フラクションに分離する第２工程、
（３）上記（２）で得た３環以上の芳香族分フラクションを分取液体クロマトグラフィーを用いて、さらに３環芳香族分、４環芳香族分、及び５環以上の芳香族分の各フラクションに分離する第３工程、
（５）上記（２）及び（３）で得たフラクションについて元素分析を行う第５工程、
（６）上記（２）及び（３）で得たフラクションについて 1 Ｈ−ＮＭＲ分析を行う第６工程、
（７）上記（２）及び（３）で得たフラクションについて質量分析を行い、個々の成分の分子量とフラクションの数平均分子量を求める第７工程、
（８）上記（５）の元素分析値と上記（６）の 1 Ｈ−ＮＭＲ積算値と（７）の数平均分子量から、各フラクションの平均構造を特定する第８工程、及び
（９）上記（８）から得られた各フラクションの平均構造と、上記（７）から得られた各フラクションの質量分析結果より、上記（２）及び（３）の各フラクションで得たフラクション中の個々の分子の構造を推定し、必要に応じて定量する第９工程
［２］前記（５）〜（７）の工程に加えて、紫外可視分光分析を行う工程を有する、上記［１］に記載の重質油の成分分析方法、
［３］（ａ）以下の（１）〜（４）の工程を有して、重質油を飽和分、環数別芳香族分、極性化合物及び多環芳香族分の各フラクションに分離する前処理を行い、次いで（ｂ）前処理によって得られた各フラクションについて（ｂ−１）得率を求め、及び／又は（ｂ−２）構造解析を行うことを特徴とする重質油の成分分析方法。
（１）重質油をｎ−パラフィンに可溶なマルテン分とそれ以外のフラクションに分離する第１工程、
（２）上記（１）で分離したマルテン分をカラムクロマトグラフィーを用いて飽和分、１環芳香族分、２環芳香族分、３環以上の芳香族分、極性化合物、及び多環芳香族分の各フラクションに分離する第２工程
（３）上記（２）で得た３環以上の芳香族分フラクションを分取液体クロマトグラフィーを用いて、さらに３環芳香族分、４環芳香族分、及び５環以上の芳香族分の各フラクションに分離する第３工程、及び、
（４）上記（３）工程で得られた４環芳香族分フラクションを、分取液体クロマトグラフィーを用いて、さらにＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分のフラクションに分離する第４工程
［４］（ｂ）の構造解析方法が、上記（２）及び（３）で得た飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分、もしくは、さらに上記（４）で得たＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分のフラクション中の少なくとも１つのフラクションについて、
(i) 元素分析、(ii) 1Ｈ−ＮＭＲ分析、(iii) 質量分析、及び(iv) 紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）のいずれか１以上の分析を実施し、その分析結果に基づいて行う方法である上記 [３]に記載の重質油の成分分析方法、
［５］（ｂ）の構造解析方法が、以下の（５）〜（９）の工程を含むものである上記［４］に記載の重質油の成分分析方法、
（５）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて元素分析を行う第５工程、
（６）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて1Ｈ−ＮＭＲ分析を行う第６工程
（７）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて質量分析を行い、個々の成分の分子量とフラクションの数平均分子量を求める第７工程、
（８）上記（５）の元素分析値と上記（６）の1Ｈ−ＮＭＲスペクトル面積積分値と（７）の数平均分子量から、各フラクションの平均構造を特定する第８工程、及び
（９）上記（８）から得られた各フラクションの平均構造と、上記（７）から得られた各フラクションの質量分析結果より、上記（２）及び（３）の各フラクション、もしくは、さらに上記（４）で得たフラクション中の個々の分子の構造を推定し、必要に応じて定量する第９工、
[６]前記（５）〜（７）の工程に加えて、紫外可視分光分析を行う工程を有する、上記［５］に記載の重質油の成分分析方法、
を提供するものである。
As a result of intensive research, the present inventor can achieve the object by performing a specific pretreatment on heavy oil, separating aromatic components by number of rings, and performing a specific analysis method. I found out. The present invention has been completed based on such findings.
That is, the present invention
[1] (a) Having the following steps (1) to (3), the heavy oil is separated into each fraction of saturated, aromatic by ring, polar compound and polycyclic aromatic. (B-1) Obtain the yield of each fraction obtained by the pretreatment (b) , and ( b-2) the saturated component obtained in (2) and (3) below, At least one of the fractions of the family, the 2-ring aromatics, the 3-rings aromatics, the 4-rings aromatics, the 5-rings or more aromatics, the polar compounds and the polycyclics aromatics,
performing any one or more of (i) elemental analysis, (ii) 1 H-NMR analysis, (iii) mass spectrometry, and (iv) ultraviolet-visible spectroscopy (UV-Vis), There line a structural analysis based on its analysis, the structural analysis method, the following (5) the method of component analysis of heavy oil, characterized in that comprising the steps of - (9).
(1) a first step of separating heavy oil into n-paraffin-soluble marten and other fractions;
(2) Saturation, 1-ring aromatics, 2-rings aromatics, 3-rings or more aromatics, polar compounds, and polycyclic aromatics using column chromatography A second step of separating each fraction of minutes,
(3) Using the preparative liquid chromatography, the fractions of three or more aromatic rings obtained in (2) above are further divided into three ring aromatics, four ring aromatics, and five or more ring aromatics. A third step of separating each fraction;
(5) a fifth step of performing elemental analysis on the fraction obtained in (2) and (3) above,
(6) A sixth step in which 1 H-NMR analysis is performed on the fractions obtained in (2) and (3) above ,
(7) A seventh step of performing mass spectrometry on the fractions obtained in (2) and (3) above to determine the molecular weight of each component and the number average molecular weight of the fractions;
(8) an eighth step of specifying the average structure of each fraction from the elemental analysis value of (5) above, the 1 H-NMR integrated value of (6) above and the number average molecular weight of (7);
(9) From the average structure of each fraction obtained from the above (8) and the mass analysis result of each fraction obtained from the above (7), among the fractions obtained from the above (2) and (3) Ninth step of estimating the structure of individual molecules and quantifying as necessary
[2] In addition to the steps (5) to (7), the component analysis method for heavy oil according to the above [1], including a step of performing UV-visible spectroscopic analysis,
[3] (a) Having the following steps (1) to (4) to separate heavy oil into fractions of saturated components, aromatic components by number of rings, polar compounds and polycyclic aromatic components. A heavy oil component characterized by performing pretreatment and then (b) obtaining (b-1) the yield of each fraction obtained by pretreatment and / or (b-2) conducting structural analysis Analysis method.
(1) a first step of separating heavy oil into n-paraffin-soluble marten and other fractions;
(2) Saturation, 1-ring aromatics, 2-rings aromatics, 3-rings or more aromatics, polar compounds, and polycyclic aromatics using column chromatography 2nd process of separating into fractions of minutes
(3) Using the preparative liquid chromatography, the fractions of three or more aromatic rings obtained in (2) above are further divided into three ring aromatics, four ring aromatics, and five or more ring aromatics. A third step of separating each fraction; and
(4) The 4-ring aromatic fraction obtained in the above step (3) is further separated into a Peri-type 4-ring aromatic fraction and a Cat-type 4-ring aromatic fraction using preparative liquid chromatography. The structure analysis method of the fourth step [4] (b) is the saturated, monocyclic aromatic, bicyclic aromatic, tricyclic aromatic or tetracyclic aromatic obtained in (2) and (3) above. At least in the fraction of the aromatic group of 5 or more rings, the polar compound and the polycyclic aromatic group, or the Peri type 4 ring aromatic part and the Cat type 4 ring aromatic part obtained in the above (4) For one fraction,
performing any one or more of (i) elemental analysis, (ii) 1 H-NMR analysis, (iii) mass spectrometry, and (iv) ultraviolet-visible spectroscopy (UV-Vis), the method of component analysis of heavy oil according to the above SL is a method of performing, based on the analysis results [3],
[5] The heavy oil component analysis method according to the above [4], wherein the structural analysis method of (b) includes the following steps (5) to (9):
(5) Fifth step of performing elemental analysis on the fraction obtained in (2) and (3) above or (4) above,
(6) Sixth step of performing 1 H-NMR analysis on the fraction obtained in the above (2) and (3) or (4) above (7) (2) and (3) above, or further above The seventh step of performing mass spectrometry on the fraction obtained in (4) to determine the molecular weight of each component and the number average molecular weight of the fraction,
(8) The eighth step of specifying the average structure of each fraction from the elemental analysis value of (5) above, the 1 H-NMR spectrum area integral value of (6) above and the number average molecular weight of (7), and (9 ) From the average structure of each fraction obtained from the above (8) and the mass analysis result of each fraction obtained from the above (7), each of the above fractions (2) and (3) or the above (4) 9) to estimate the structure of individual molecules in the fraction obtained in step) and quantify them as necessary.
[6] In addition to the steps (5) to (7), the component analysis method for heavy oil according to the above [5], including a step of performing UV-visible spectroscopic analysis,
Is to provide.
本発明によれば、従来困難とされる重質油中の成分をより詳細に知ることができる成分分析方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the component analysis method which can know in detail the component in the heavy oil considered conventionally difficult can be provided.
本発明は、（ａ）重質油を飽和分等の各フラクションに分離する前処理を行い、次いで（ｂ）前記前処理によって得られた各フラクションについて（ｂ−１）得率を求め、及び／又は（ｂ−２）構造解析を行うことを特徴とする重質油の成分分析方法である。
本発明における「重質油」は、沸点が４００℃以上の留分を含む石油留分をいい、例えば、常圧残油（ＡＲ）、脱硫残油（ＤＳＡＲ）、重質油流動接触分解残油（ＣＬＯ）、ビチューメン、減圧軽油（ＶＧＯ）、および減圧残油（ＶＲ）などが含まれる。
以下、（ａ）の前処理方法及び（ｂ）の（ｂ−１）得率の測定、（ｂ−２）構造解析方法について説明する。
The present invention performs (a) pretreatment for separating heavy oil into each fraction such as a saturated component, and then (b) obtains (b-1) the yield of each fraction obtained by the pretreatment, and (B-2) A heavy oil component analysis method characterized in that structural analysis is performed.
The “heavy oil” in the present invention refers to a petroleum fraction containing a fraction having a boiling point of 400 ° C. or higher. For example, atmospheric residue (AR), desulfurized residue (DSAR), heavy oil fluid catalytic cracking residue. Oil (CLO), bitumen, vacuum gas oil (VGO), vacuum residue (VR), and the like are included.
Hereinafter, the pretreatment method (a), the measurement of the yield (b-1) of (b), and the structural analysis method (b-2) will be described.
〔（ａ）の前処理方法〕
前処理工程（ａ）においては、重質油を飽和分、環数別芳香族分、極性化合物及び多環芳香族分の各フラクションに分離する。
このような前処理、特に、芳香族分については環数別フラクションに分離する前処理を施すことによって、続く（ｂ）の各フラクション得率及び構造解析においてより詳細な成分分析や組成分析を可能にする効果をもたらす。
上記「環数別フラクション」の環数としては、少なくとも１〜５環まで分離することが好ましい。一般的な重質油（ＡＲ等）中に存在する芳香族化合物は、１〜５環のものが主成分だからである。
[Pretreatment method of (a)]
In the pretreatment step (a), heavy oil is separated into fractions of saturated components, aromatic components by number of rings, polar compounds, and polycyclic aromatic components.
By performing such pretreatment, especially for the aromatic component, pretreatment that separates into fractions by number of rings, more detailed component analysis and composition analysis are possible in each fraction yield and structure analysis of (b). The effect is made.
The number of rings in the “fraction by number of rings” is preferably separated into at least 1 to 5 rings. This is because aromatic compounds present in general heavy oils (such as AR) are mainly composed of 1 to 5 rings.
本発明における（ａ）の前処理工程は、以下の（１）〜（３）、もしくは（１）〜（４）の工程で行うことができる。
（１）重質油をｎ−パラフィンに可溶なマルテン分とそれ以外のフラクションに分離する第１工程、
前記第１工程では、重質油中のマルテン分を溶剤抽出し、それ以外のアスファルテン分などを除去する、いわゆる溶剤脱歴工程である。
当該第１工程で使用する溶剤としては、ｎ−ヘプタンを用いることが望ましい。
具体的な分離操作については、特に制限はなく、従来公知の方法でその後の分析に使用するマルテン分を分離すればよい。例えば、ソックスレー抽出器や不溶解分試験装置を用いて分離することができる。
The pretreatment step (a) in the present invention can be performed by the following steps (1) to (3) or (1) to (4).
(1) a first step of separating heavy oil into n-paraffin-soluble marten and other fractions;
The first step is a so-called solvent history step in which the marten content in the heavy oil is extracted with a solvent and the other asphaltenes are removed.
It is desirable to use n-heptane as the solvent used in the first step.
The specific separation operation is not particularly limited, and the martens component used for the subsequent analysis may be separated by a conventionally known method. For example, it can be separated using a Soxhlet extractor or an insoluble matter tester.
（２）上記（１）で分離したマルテン分をカラムクロマトグラフィーを用いて飽和分、１環芳香族分、２環芳香族分、３環以上の芳香族分、極性化合物、及び多環芳香族分の各フラクションに分離する第２工程
当該第２工程では、上記（１）で分離したマルテン分をいわゆる構造タイプ別に分離する工程である。
この工程におけるカラムクロマトグラフィーによる分離方法は、特に制限はないが、例えば、充填剤として、アルミナゲルとシリカゲルの二種類のゲルを下から順番に充填して用い、展開溶剤として、ヘプタン、トルエン、エタノール、及びクロロホルムを用いて行うことが好ましい。これらの展開溶剤は、通常この順序でカラムに投入して行う。これによって上記構造タイプ別分離が可能である。
(2) Saturation, 1-ring aromatics, 2-rings aromatics, 3-rings or more aromatics, polar compounds, and polycyclic aromatics using column chromatography 2nd process which isolate | separates into each fraction of minutes In the said 2nd process, it is the process of isolate | separating the marten part isolate | separated by said (1) according to what is called structure type.
The separation method by column chromatography in this step is not particularly limited. For example, as a filler, two types of gels, alumina gel and silica gel, are used in order from the bottom, and as a developing solvent, heptane, toluene, It is preferable to carry out using ethanol and chloroform. These developing solvents are usually added to the column in this order. As a result, the structure type separation is possible.
（３）上記（２）で得た３環以上の芳香族分を含むフラクションを分取液体クロマトグラフィー（ＬＣ）を用いて、さらに３環芳香族分、４環芳香族分、及び５環以上の芳香族分の各フラクションに分離する第３工程、
当該第３工程では、上記（２）で得た３環以上の芳香族分を含むフラクションをさらに詳細に、芳香族分の各フラクションに分離する。
このように芳香族分の環数別分離を（２）と（３）の二工程で行うことにより、環数３，４および５の芳香族分を高精度に分離することができる。
分取液体クロマトグラフィー（ＬＣ）による分離の具体的方法としては、特に制限はないが、例えば、カラムにはＮＨ2カラムを用い、移動相溶媒として、ｎ−ヘキサンを用いて行う方法が好適である。
(3) Using a preparative liquid chromatography (LC), the fraction containing an aromatic component of 3 or more rings obtained in (2) above is further divided into 3 ring aromatics, 4 ring aromatics, and 5 or more rings. A third step of separating each aromatic fraction of
In the said 3rd process, the fraction containing the aromatic component of 3 or more rings obtained by said (2) is isolate | separated into each aromatic fraction further in detail.
As described above, by separating the aromatic components according to the number of rings in two steps (2) and (3), the aromatic components having the number of
A specific method for separation by preparative liquid chromatography (LC) is not particularly limited, but for example, a method using an NH 2 column as a column and n-hexane as a mobile phase solvent is preferable. is there.
（４）本発明においては、前記３工程で分離された４環芳香族分を、さらに、分取液体クロマトグラフィーによって、ピレンタイプのＰｅｒｉ型４環芳香族分とクリセン、ベンゾアントラセンタイプのＣａｔａ型４環芳香族分に分離する第４工程を有することが好ましい。
この場合におけるカラムは、ＮＨ2カラムを用い、分離には、移動相溶としてｎ−ヘキサンを用いて行う方法が好適である。従って、分取クロマトグラフィーによる分離工程において、ＮＨ2カラムを用い、移動相溶媒としてｎ−ヘキサンを用いる場合、Ｐｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分は前記（３）の工程で同時に分離することができる。
以上１〜３の工程、もしくは1〜４の工程によって、飽和分、１〜４環の各芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分、もしくはさらにＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分を分離することができ、（ａ）の前処理が完了する。
(4) In the present invention, the tetracyclic aromatic component separated in the above-mentioned three steps is further subjected to preparative liquid chromatographic analysis using a pyrene type Peri type tetracyclic aromatic component and chrysene, benzoanthracene type Cata type. It is preferable to have the 4th process isolate | separated into a 4-ring aromatic part.
In this case, an NH 2 column is used as the column, and n-hexane is preferably used as the mobile phase for separation. Accordingly, in the separation step by preparative chromatography, when an NH 2 column is used and n-hexane is used as the mobile phase solvent, the Peri type tetracyclic aromatic component and the Cat type tetracyclic aromatic component are the same as those in the step (3). Can be separated at the same time.
According to the above steps 1 to 3 or 1-4, the saturated component, each aromatic component of 1 to 4 rings, the aromatic component of 5 or more rings, the polar compound and the polycyclic aromatic component, or further Peri type 4 The ring aromatic component and the Cat type 4 ring aromatic component can be separated, and the pretreatment of (a) is completed.
〔（ｂ）（ｂ−１）の得率〕
前処理で得た各フラクション、及び好ましくは第１工程で分離したアスファルテン分を含めてそれぞれの得率を測定する。
得られた得率の測定結果は、例えば、重質油の反応の前後における全フラクションの得率を対比することにより重質油の反応による成分変化を確認することに利用できる。したがって、反応に関与する重質油の因子を見出すことができる。
[Yield of (b) (b-1)]
The respective yields are measured including each fraction obtained in the pretreatment, and preferably the asphaltenes separated in the first step.
The measurement result of the obtained yield can be used, for example, to confirm the component change due to the reaction of the heavy oil by comparing the yield of all fractions before and after the reaction of the heavy oil. Therefore, the heavy oil factor involved in the reaction can be found.
〔（ｂ）（ｂ−２）の構造解析〕
（ｂ）の構造解析工程においては、前記各フラクションの成分分析を行う。
本発明における（ｂ）の構造解析工程は、（２）及び（３）で得た飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分、もしくは、さらに上記（３）または（４）で得たＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分のフラクションの中の少なくとも１つのフラクションについて、
(i) 元素分析、(ii) 1Ｈ−ＮＭＲ分析、(iii) 質量分析、及び(iv) 紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）のいずれか１以上の分析を実施し、その分析結果に基づいて行う方法である。
上記(i)〜(iv)の分析は、全てのフラクションの分析に必ずしも全ての分析を用いる必要は無く、例えば、飽和分の分析には、(i) 元素分析、(ii) 1Ｈ−ＮＭＲ分析、及び(iii) 質量分析で成分分析が可能であり、芳香族分の分析では、芳香族の骨格を正確に判別で切る点で（iv) 紫外可視分光分析が必要な場合が多い。
[Structural analysis of (b) and (b-2)]
In the structural analysis step (b), component analysis of each fraction is performed.
In the structure analysis step (b) in the present invention, the saturated content, the 1-ring aromatic content, the 2-ring aromatic content, the 3-ring aromatic content, the 4-ring aromatic content, 5) obtained in (2) and (3) Among the fractions of aromatic components above ring, polar compounds and polycyclic aromatic components, or the fractions of Peri type 4-ring aromatics and Cat type 4-ring aromatics obtained in (3) or (4) above For at least one fraction
performing any one or more of (i) elemental analysis, (ii) 1 H-NMR analysis, (iii) mass spectrometry, and (iv) ultraviolet-visible spectroscopy (UV-Vis), This method is based on the analysis result.
In the analyzes (i) to (iv), it is not always necessary to use all analyzes for analysis of all fractions. For example, (i) elemental analysis and (ii) 1 H-NMR are used for analysis of saturated components. Analysis and (iii) Mass analysis can be used for component analysis, and aromatic analysis often requires (iv) UV-visible spectroscopic analysis in that the aromatic skeleton can be accurately discriminated.
本発明における、（ｂ）の構造解析工程は、以下の（５）〜（９）の工程で行うことが好ましい。但し、（５）〜（７）の行程の順序は、任意に変更することができる。
（５）上記（２）及び（３）で得た飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分の各フラクション、もしくは、さらに上記（３）または（４）で得たＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分について元素分析することにより各フラクションの組成式を求める第４工程、なお、Ｃ、Ｈ、Ｎ、Ｓなどの元素分析方法は、特に制限はなく、公知の方法で行えばよい。
In the present invention, the structural analysis step (b) is preferably performed in the following steps (5) to (9). However, the order of the steps (5) to (7) can be arbitrarily changed.
(5) Saturated, 1-ring aromatic, 2-ring aromatic, 3-ring aromatic, 4-ring aromatic, 5 or more aromatics, polar, obtained in (2) and (3) above Composition of each fraction by elemental analysis of each fraction of compound and polycyclic aromatic component, or Peri type 4-ring aromatic component and Cat type 4-ring aromatic component obtained in (3) or (4) above The fourth step for obtaining the formula, and the elemental analysis method such as C, H, N, and S is not particularly limited, and may be performed by a known method.
（６）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて1Ｈ−ＮＭＲ分析を行う第６工程、
1Ｈ−ＮＭＲの測定は、特に制限はなく公知の方法で行えばよい。1Ｈ−ＮＭＲにおいては、例えば、化学シフトのデータから、置換基の鎖長、置換基の数などを求めることができる。
（７）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて質量分析を行い、個々の成分の分子量とフラクションの数平均分子量を求める第７工程、
（８）上記（５）の元素分析値と上記（６）の1Ｈ−ＮＭＲ積算値と（７）の数平均分子量から、各フラクションの平均構造を特定する第８工程、
具体的には、Ｊ．Ｋ．Ｂｒｏｗｎ，Ｗ．Ｒ．Ｌａｄｎｅｒ ａｎｄ Ｎ．Ｓｈｅｐｐａｒｄ，Ｆｕｅｌ，３９，７９，８７（１９６０）．に則って行う。
（９）上記（８）から得られた各フラクションの平均構造と、上記（７）から得られた各フラクションの質量分析結果より、上記（２）及び（３）の各フラクション、もしくは、さらに上記（４）で得たフラクション中の個々の分子の構造を推定し、必要に応じて定量する第９工程、
である。
また、この場合、前記（５）〜（８）の工程に加えて、さらに紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）を行う工程を有することが好ましい。これによって、芳香族化合物の芳香族の骨格を特定することが容易になる。
(6) A sixth step in which 1 H-NMR analysis is performed on the fraction obtained in (2) and (3) above or (4) above,
The measurement of 1 H-NMR is not particularly limited and may be performed by a known method. In 1 H-NMR, for example, the chain length of a substituent, the number of substituents, and the like can be determined from chemical shift data.
(7) The seventh step of performing mass spectrometry on the fractions obtained in (2) and (3) above or (4) above to determine the molecular weight of each component and the number average molecular weight of the fractions,
(8) The eighth step of specifying the average structure of each fraction from the elemental analysis value of (5) above, the 1 H-NMR integrated value of (6) above and the number average molecular weight of (7);
Specifically, J. et al. K. Brown, W.M. R. Ladner and N.M. Sheppard, Fuel, 39, 79, 87 (1960). Follow the procedure.
(9) From the average structure of each fraction obtained from the above (8) and the mass analysis result of each fraction obtained from the above (7), each fraction of the above (2) and (3), or further above A ninth step in which the structure of each molecule in the fraction obtained in (4) is estimated and quantified as necessary;
It is.
In this case, in addition to the steps (5) to (8), it is preferable to further include a step of performing ultraviolet-visible spectroscopy (UV-Vis). This makes it easy to specify the aromatic skeleton of the aromatic compound.
例えば、芳香族分について、個々の成分の分子構造を推定する方法について説明すると以下のようになる。
まず、元素分析の結果及び質量分析で得られた質量数から成分の組成式を同定する。また、紫外・可視分光法（ＵＶ−Ｖｉｓ）により、芳香族化合物の主骨格を決定する。
例えば、第４工程で分離した４環ｐｅｒｉ型芳香族を含むフラクションの場合について説明する。
対象成分の質量分析により質量数が３９２．２５、組成式はＣ30Ｈ32で、ＵＶ−Ｖｉｓ分析により、主骨格がピレン構造であることが確認された。
ここで、ピレンは不飽和数１２であり、成分の組成式の不飽和数が１５であるから主骨格の不飽和数を引いた残りの不飽和数３をナフテン環数によるものとする。すなわち、ピレン骨格にナフテン環３つを持つ主骨格を持つものと同定できる。
ここでナフテン環はすべて６員環とし、構造を決定する。これらの主骨格の炭素数が２６となるから対象成分の組成式のＣ30から差し引いたものが側鎖による炭素数となる。よって質量分析により質量数が３９２．２５の化合物はピレン＋３環ナフテンを主骨格とする側鎖の炭素数３の化合物と同定することができる。
また、定量する場合は、例えば、水素炎イオン化検出器（ＦＩＤ）を有するＧＣ−ＭＳで定量すればよい。
このようにして、他の環数の芳香族フラクションの個々の成分の分子構造を決定し、必要に応じて定量することができる。
For example, a method for estimating the molecular structure of each component for the aromatic component will be described as follows.
First, the composition formula of a component is identified from the result of elemental analysis and the mass number obtained by mass spectrometry. The main skeleton of the aromatic compound is determined by ultraviolet / visible spectroscopy (UV-Vis).
For example, the case of a fraction containing a 4-ring peri-type aromatic separated in the fourth step will be described.
Mass number by mass spectrometry of the target component is 392.25, the composition formula is C 30 H 32, by UV-Vis analysis, the main skeleton was confirmed to be pyrene structure.
Here, since pyrene has an unsaturated number of 12 and the unsaturated number in the composition formula of the component is 15, the remaining unsaturated number 3 obtained by subtracting the unsaturated number of the main skeleton is determined by the naphthene ring number. That is, it can be identified as having a main skeleton having three naphthene rings in the pyrene skeleton.
Here, all the naphthene rings are 6-membered rings, and the structure is determined. Since the carbon number of these main skeletons is 26, the value obtained by subtracting from C 30 in the composition formula of the target component is the carbon number due to the side chain. Therefore, a compound having a mass number of 392.25 can be identified as a compound having 3 carbon atoms in the side chain having pyrene + tricyclic naphthene as a main skeleton by mass spectrometry.
Moreover, what is necessary is just to quantify by GC-MS which has a flame ionization detector (FID), for example, when quantifying.
In this way, the molecular structure of the individual components of other ring aromatic fractions can be determined and quantified as necessary.
上記のとおり、本発明（ａ）の前処理を行い重質油を飽和分、環数別芳香族分、極性化合物及び多環芳香族分の各フラクション、もしくは、さらに上記（３）または（４）で得たＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分に分離し、次いで（ｂ−１）の各フラクションの得率を測定する成分分析によって、すなわち得率（得率分布）から従来にない有効な情報がえられる。また、本発明（ａ）の前処理を行い、次いで（ｂ−２）の構造解析を行うことによって、重質油中に存在する化合物の構造を特定し、また定量することができる。さらに本発明（ａ）の前処理を行い、次いで（ｂ−１）の各フラクションの得率を求め、さらに（ｂ−２）の構造解析を行うことによって、重質油の成分と構造を詳細に明らかにすることができる。 As described above, the pretreatment of the present invention (a) is performed, and the heavy oil is saturated, aromatics by number of rings, each fraction of polar compounds and polycyclic aromatics, or further the above (3) or (4 The Peri-type 4-ring aromatic component and the Cat-type 4-ring aromatic component obtained in (1) above were separated, and then analyzed by component analysis to measure the yield of each fraction of (b-1), that is, yield (yield distribution) Therefore, useful information that is not available in the past can be obtained. Moreover, the structure of the compound which exists in heavy oil can be specified and quantified by performing the pre-processing of this invention (a) and then performing the structural analysis of (b-2). Furthermore, the pretreatment of the present invention (a) is carried out, then the yield of each fraction of (b-1) is obtained, and further the structural analysis of (b-2) is performed, whereby the components and structure of heavy oil are detailed. Can be revealed.
本発明の実施例をさらに説明するが、本発明はこれらの例によって何ら限定されるものではない。
〔実施例１〕
重質油として、常圧残油（ＡＲ）とそれを脱硫し、さらに接触分解処理して生成した接触分解残油（ＣＬＯ）を、本発明に用いる前処理方法（第１〜３工程）によって得られた飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分の各フラクション、並びに、第１工程でマルテン分と分離したアスファルテン分の各フラクションについて、それぞれの得率を求めた。結果を図１及び図２に示す。また、用いた常圧残油（ＡＲ）及び接触分解残油（ＣＬＯ）の性状を表−１に示す。
なお、前処理方法の第１〜３工程は以下の方法で行った。
＜第１工程：マルテン分の分離＞
容量５００ｍＬの三角フラスコに試料（重質油）を７ｇはかりとり、ｎ−ヘプタンを２２０ｍＬ加え、空気冷却管をつけてｎ−ヘプタン不溶解分試験器で混合物を１時間還流煮沸した。
還流煮沸後、放置冷却し、ろ紙を用いてアスファルテン分を分離し、マルテン分を含むフラクションを得た。
Examples of the present invention will be further described, but the present invention is not limited to these examples.
[Example 1]
As heavy oil, atmospheric residual oil (AR) and catalytic cracking residual oil (CLO) produced by desulfurization and further catalytic cracking are used according to the pretreatment method (first to third steps) used in the present invention. Fractions of the obtained saturated component, one-ring aromatic component, two-ring aromatic component, three-ring aromatic component, four-ring aromatic component, five-ring or more aromatic component, polar compound and polycyclic aromatic component, And each yield was calculated | required about each fraction of the asphaltene part isolate | separated from the marten part in the 1st process. The results are shown in FIGS. The properties of the atmospheric residue (AR) and catalytic cracking residue (CLO) used are shown in Table 1.
In addition, the 1st-3rd process of the pre-processing method was performed with the following method.
<First step: separation of martensite minute>
7 g of a sample (heavy oil) was weighed into a 500 mL Erlenmeyer flask, 220 mL of n-heptane was added, an air cooling tube was attached, and the mixture was reflux-boiled for 1 hour using an n-heptane insoluble fraction tester.
After boiling at reflux, the mixture was allowed to cool, and the asphaltene content was separated using filter paper to obtain a fraction containing the marten content.
＜第２工程：マルテン分のカラムクロマトグラフィーによる分離＞
第１工程で得たマルテン分を以下の条件のカラムクロマトグラフィーで分離した。
（１）カラムクロマトグラフィーのカラム条件
カラム：１５ｍｍ×６００ｍｍ（ゲル充填部分、ガラス製）
ゲル：シリカゲル４０ｇ＋アルミナゲル５０ｇ（活性化後）
シリカゲル：Ｆｕｊｉ Ｓｉｌｙｓｉａ製、Ｃｈｒｏｍａｔｏ Ｇｅｌ Ｇｒａｄｅ ９２３ＡＲ
アルミナゲル：ＭＰ ＢｉｏｍｅｄｉｃａＬｓ製、ＭＰ Ａｌｕｍｉｎａ，Ａｃｔｉｖａｔｅｄ，Ｎｅｕｔｒａｌ，Ｓｕｐｅｒ Ｉ
活性化条件：シリカゲル２５０℃×２０ｈ、アルミナゲル４００℃×２０ｈ、０．２ｋｇ／ｃｍ2（Ｎ2ガス）加圧
試料量：１．５ｇ（マルテン）
溶媒：ｎ−ヘプタン（和光純薬工業株式会社、１級）、トルエン（和光純薬工業株式会社、１級）、エタノール（純正化学株式会社、特級）、クロロホルム（和光純薬工業株式会社、特級）
<Second step: separation by column chromatography maltene fraction>
The marten content obtained in the first step was separated by column chromatography under the following conditions.
(1) Column conditions for column chromatography Column: 15 mm × 600 mm (gel packed part, glass)
Gel: 40 g of silica gel + 50 g of alumina gel (after activation)
Silica gel: manufactured by Fuji Silysia, Chromato Gel Grade 923AR
Alumina gel: MP Biomedica Ls, MP Alumina, Activated, Neutral, Super I
Activation conditions: Silica gel 250 ° C. × 20 h, Alumina gel 400 ° C. × 20 h, 0.2 kg / cm 2 (N 2 gas) pressurization Sample amount: 1.5 g (Marten)
Solvent: n-heptane (Wako Pure Chemical Industries, Ltd., Grade 1), Toluene (Wako Pure Chemical Industries, Ltd., Grade 1), Ethanol (Pure Chemical Co., Ltd., Special Grade), Chloroform (Wako Pure Chemical Industries, Ltd., Special Grade) )
（２）分離方法
以下の溶媒を順次カラムに投入し、溶出溶液を分取した。
（ｉ） ｎ−ヘプタン２００ｍＬ
溶出した試料溶液２５０ｍＬまでを飽和分（Ｆｒ．Ｓａ）としてカットする。
(ii) ｎ−ヘプタン９５％、トルエン５％混合溶媒２５０ｍＬ
溶出した試料溶液２００ｍＬまでを１環芳香族分（Ｆｒ．１Ａ）としてカットする。
(iii) ｎ−ヘプタン９０％、トルエン１０％混合溶媒２５０ｍＬ
溶出した試料溶液２００ｍＬまでをカットし、２環芳香族分（Ｆｒ．２Ａ）とする。
（iv）トルエン２５０ｍＬ
溶出した試料溶液３００ｍＬをカットし、３環以上芳香族分（Ｆｒ．３Ａ＋）とする。
（ｖ） エタノール２５０ ｍＬ
２３０ｍＬをカットし、極性化合物（Ｆｒ．Ｐｏ）とする。
（vi） クロロホルム１００ｍＬ
（vii）エタノール１００ｍＬ
（viii）もう一度（vi)、(vii)を繰り返す。
(vi)、(vii)、(viii)は全て1つのフラクションとして分取し、多環芳香族分（Ｆｒ．ＰＡ）とする。
(2) Separation method The following solvents were sequentially added to the column to separate the elution solution.
(I) n-heptane 200 mL
Cut up to 250 mL of the eluted sample solution as a saturated component (Fr.Sa).
(ii) n-heptane 95%,
Cut up to 200 mL of the eluted sample solution as a 1-ring aromatic component (Fr. 1A).
(iii) n-heptane 90%,
Cut up to 200 mL of the eluted sample solution to obtain a bicyclic aromatic component (Fr. 2A).
(Iv) Toluene 250 mL
The eluted sample solution (300 mL) is cut to obtain an aromatic component (Fr.3A +) having 3 or more rings.
(V) Ethanol 250 mL
Cut 230 mL to make a polar compound (Fr.Po).
(Vi) Chloroform 100mL
(Vii) Ethanol 100mL
(Viii) Repeat (vi) and (vii) once again.
(vi), (vii), and (viii) are all fractionated as one fraction and used as a polycyclic aromatic component (Fr. PA).
＜第３工程：分取液体クロマトグラフィーによる分離＞
第２工程で得られた３環以上芳香族分を含むフラクションを以下の条件でさらに分離した。
（１）分析装置：
高速液体クロマトグラム装置、島津製作所１０Ａシリーズ
カラム：ＹＭＣ−Ｐａｃｋ ＮＨ2（２０ｍｍＩＤ×２５０ｍｍ、１０μｍ）
（２）測定条件
移動相：ｎ−ヘキサン（ＨＰＬＣグレード）
カラム温度：４０℃
検出器：ＵＶ（２５４ｎｍ）
流速：９．９９９ｍＬ／ｍｉｎ
試料注入量：１００μＬ（オートサンプラー、ループ：１００μＬ）
<Third Step: separation by preparative liquid chromatography>
The fraction containing 3 or more ring aromatics obtained in the second step was further separated under the following conditions.
(1) Analyzer:
High-speed liquid chromatogram apparatus, Shimadzu Corporation 10A Series Column: YMC-Pack NH 2 (20 mm ID × 250 mm, 10 μm)
(2) Measurement conditions Mobile phase: n-hexane (HPLC grade)
Column temperature: 40 ° C
Detector: UV (254 nm)
Flow rate: 9.999 mL / min
Sample injection volume: 100 μL (autosampler, loop: 100 μL)
〔比較例１〕
前処理方法を従来法により、飽和分、芳香族分、レジン分、及びアスファルテンの各フラクションに分離し、各フラクションの得率を求めた。結果を図３及び図４に示す。
なお、従来法の分離方法は、石油学会規格、ＪＰＩ−５Ｓ−２２−８３にのっとって分離する方法である。
[Comparative Example 1]
The pretreatment method was separated into fractions of a saturated component, an aromatic component, a resin component, and an asphaltene by a conventional method, and the yield of each fraction was determined. The results are shown in FIGS.
The conventional separation method is a separation method in accordance with the Petroleum Institute Standard, JPI-5S-22-83.
図１によれば、常圧残油を本発明の方法でフラクション分離して得られた各フラクションの得率は、極性化合物と多環芳香族が比較的多い。これに対し図２の、前記常圧残油を脱硫し、さらに水素化分解して得られた接触分解残油の各フラクションの得率は、３環芳香族分、４環芳香族分、５環以上の芳香族分及び、極性化合物の得率が高いことが分る。
一方、図３、４によれば、従来法で前処理した各フラクションの得率は、常圧残油と接触分解残油の各フラクションの得率とに明確な差異は認められない。
したがって、本願発明の成分分析方法が重質油の反応機構解明に有効な情報を得ることができ、従来法による成分分析方法では有効な情報が得られないことが分る。
According to FIG. 1, the yield of each fraction obtained by fractionating atmospheric residual oil by the method of the present invention is relatively large for polar compounds and polycyclic aromatics. On the other hand, the yield of each fraction of the catalytic cracking residue obtained by desulfurizing and hydrocracking the atmospheric residual oil in FIG. It can be seen that the yield of aromatic components over the ring and polar compounds is high.
On the other hand, according to FIGS. 3 and 4, there is no clear difference between the yields of the fractions pretreated by the conventional method and the yields of the fractions of atmospheric residual oil and catalytic cracked residual oil.
Therefore, it can be seen that the component analysis method of the present invention can obtain information effective for elucidating the reaction mechanism of heavy oil, and that the component analysis method according to the conventional method cannot provide effective information.
〔実施例２〕
実施例１で用いた表1に示す性状を有する接触分解残油（ＣＬＯ）を、本発明に用いる前処理方法を行い、飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分、極性化合物及び多環芳香族分の各フラクションを得、それぞれについて構造解析を行った。
構造解析の方法は、元素分析、1Ｈ−ＮＭＲ分析、質量分析、及び紫外可視分光分析であり、それぞれ以下の装置で測定し解析し、定量した。
解析方法は、各フラクションについて明細書に記載した方法で行った。次いでそれらの結果をまとめて、３次元グラフにまとめた。結果は図５に示した。
[Example 2]
The catalytic cracking residual oil (CLO) having the properties shown in Table 1 used in Example 1 is subjected to a pretreatment method used in the present invention, and is subjected to a saturated content, a 1-ring aromatic content, a 2-ring aromatic content, a 3-ring aroma Fractions of 4 groups, 4 ring aromatics, 5 or more rings, polar compounds and polycyclic aromatics were obtained, and structural analysis was performed on each of them.
The structural analysis methods were elemental analysis, 1 H-NMR analysis, mass spectrometry, and ultraviolet-visible spectroscopic analysis, which were measured, analyzed, and quantified by the following apparatuses, respectively.
The analysis method was performed by the method described in the specification for each fraction. The results were then combined into a three-dimensional graph. The results are shown in FIG.
なお、図５のＸ軸は、左から順に、飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、５環以上の芳香族分の各フラクション群を示し、Ｙ軸（奥行き）は、各成分の炭素数、Ｚ軸（高さ）は、定量値を示す。
なお、分析には下記の装置を用いた。
（１）元素分析
窒素：化学発光法、
硫黄分：紫外蛍光法
炭素、水素：ＣＨＮコーダー法
（２）1Ｈ−ＮＭＲ分析
日本電子株式会社製 ＧＳＸ−４００（1Ｈ：４００ＭＨｚ）
（３）質量分析
ＭｉｃｒｏＭａｓｓ製 ＧＣＴ、イオン化法：電解脱離法（ＦＤ）
（４）紫外可視分光分析
ＵＶ−Ｖｉｓ装置：島津製作所製 自記分光光度計ＵＶ−３１００ＰＣ
ＬＣ／ＵＶ−Ｖｉｓ：Shimadzu Prominence series UFLC system
In addition, the X-axis of FIG. 5 is each fraction from a saturated part, a 1 ring aromatic part, a 2 ring aromatic part, a 3 ring aromatic part, a 4 ring aromatic part, a 5 ring or more aromatic part in order from the left. A group is shown, the Y-axis (depth) indicates the number of carbon atoms of each component, and the Z-axis (height) indicates a quantitative value.
In addition, the following apparatus was used for the analysis.
(1) Elemental analysis Nitrogen: chemiluminescence method,
Sulfur content: UV fluorescence method Carbon, hydrogen: CHN coder method (2) 1 H-NMR analysis GSX-400 ( 1 H: 400 MHz) manufactured by JEOL Ltd.
(3) mass spectrometry MicroMass made GCT, ionization method: electrolytic desorption (FD)
(4) UV-Vis spectroscopic analysis UV-Vis apparatus: Shimadzu Corporation self-recording spectrophotometer UV-3100PC
LC / UV-Vis: Shimadzu Prominence series UFLC system
〔実施例３〕
実施例２で得られた接触分解残油（ＣＬＯ）の飽和分のフラクションについて、実施例２と同様の構造解析を行って、３次元グラフにまとめた。結果を図６に示した。
Example 3
The fractions of the saturated portion of the catalytic cracking residual oil (CLO) obtained in Example 2 were subjected to the same structural analysis as in Example 2 and summarized into a three-dimensional graph. The results are shown in FIG.
図５によれば、本発明の方法で前処理した成分分析方法では、飽和分、１環芳香族分、２環芳香族分、３環芳香族分、４環芳香族分、および５環芳香族分の個々の成分が詳細に特定でき、同時にそれらの定量ができることが分る。さらに、図６により、各フラクション群についてより詳細な化合物の同定が可能であることが分かり、従って、本発明の方法により重質油中の個々の成分について同定および定量ができることが分かる。 According to FIG. 5, in the component analysis method pretreated by the method of the present invention, the saturated component, the one-ring aromatic component, the two-ring aromatic component, the three-ring aromatic component, the four-ring aromatic component, and the five-ring aromatic component are used. It can be seen that the individual components of the family can be identified in detail and at the same time their quantification is possible. Furthermore, it can be seen from FIG. 6 that it is possible to identify more detailed compounds for each fraction group, and thus it is possible to identify and quantify individual components in heavy oil by the method of the present invention.
本発明によれば、従来困難とされる重質油中の成分をより詳細に知ることができる成分分析方法を提供することができる。その結果、得られた重質油の詳細な成分の情報に基づいて重質油の分解、改質反などの反応性に関与する因子を究明する研究に利用することができ、また重質油のさらなる有効活用に利用することもできる。 ADVANTAGE OF THE INVENTION According to this invention, the component analysis method which can know in detail the component in the heavy oil considered conventionally difficult can be provided. As a result, it can be used for research to determine factors involved in reactivity such as decomposition and reforming reaction of heavy oil based on the detailed component information of the obtained heavy oil. It can also be used for further effective utilization.
Claims (6)
(i) 元素分析、(ii) 1 Ｈ−ＮＭＲ分析、(iii) 質量分析、及び(iv) 紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）のいずれか１以上の分析を実施し、その分析結果に基づいて構造解析を行い、該構造解析方法が、以下の（５）〜（９）の工程を含むものであることを特徴とする重質油の成分分析方法。
（１）重質油をｎ−パラフィンに可溶なマルテン分とそれ以外のフラクションに分離する第１工程、
（２）上記（１）で分離したマルテン分をカラムクロマトグラフィーを用いて飽和分、１環芳香族分、２環芳香族分、３環以上の芳香族分、極性化合物、及び多環芳香族分の各フラクションに分離する第２工程、
（３）上記（２）で得た３環以上の芳香族分フラクションを分取液体クロマトグラフィーを用いて、さらに３環芳香族分、４環芳香族分、及び５環以上の芳香族分の各フラクションに分離する第３工程、
（５）上記（２）及び（３）で得たフラクションについて元素分析を行う第５工程、
（６）上記（２）及び（３）で得たフラクションについて 1 Ｈ−ＮＭＲ分析を行う第６工程、
（７）上記（２）及び（３）で得たフラクションについて質量分析を行い、個々の成分の分子量とフラクションの数平均分子量を求める第７工程、
（８）上記（５）の元素分析値と上記（６）の 1 Ｈ−ＮＭＲ積算値と（７）の数平均分子量から、各フラクションの平均構造を特定する第８工程、及び
（９）上記（８）から得られた各フラクションの平均構造と、上記（７）から得られた各フラクションの質量分析結果より、上記（２）及び（３）の各フラクションで得たフラクション中の個々の分子の構造を推定し、必要に応じて定量する第９工程 (A) Pretreatment for separating heavy oil into fractions of saturated components, aromatic components by number of rings, polar compounds and polycyclic aromatic components , comprising the following steps (1) to (3): And then (b) obtaining the fraction (b-1) for each fraction obtained by the pretreatment , ( b-2) the saturated content, the 1-ring aromatic content obtained in (2) and (3) below, At least one of the fractions of 2-ring aromatics, 3-rings aromatics, 4-rings aromatics, 5-rings or more aromatics, polar compounds and polycyclic aromatics,
performing any one or more of (i) elemental analysis, (ii) 1 H-NMR analysis, (iii) mass spectrometry, and (iv) ultraviolet-visible spectroscopy (UV-Vis), There line a structural analysis based on the analysis result, the structural analysis method, the following (5) the method of component analysis of heavy oil, characterized in that comprising the steps of - (9).
(1) a first step of separating heavy oil into n-paraffin-soluble marten and other fractions;
(2) Saturation, 1-ring aromatics, 2-rings aromatics, 3-rings or more aromatics, polar compounds, and polycyclic aromatics using column chromatography A second step of separating each fraction of minutes,
(3) Using the preparative liquid chromatography, the fractions of three or more aromatic rings obtained in (2) above are further divided into three ring aromatics, four ring aromatics, and five or more ring aromatics. A third step of separating each fraction;
(5) a fifth step of performing elemental analysis on the fraction obtained in (2) and (3) above,
(6) A sixth step in which 1 H-NMR analysis is performed on the fractions obtained in (2) and (3) above ,
(7) A seventh step of performing mass spectrometry on the fractions obtained in (2) and (3) above to determine the molecular weight of each component and the number average molecular weight of the fractions;
(8) an eighth step of specifying the average structure of each fraction from the elemental analysis value of (5) above, the 1 H-NMR integrated value of (6) above and the number average molecular weight of (7);
(9) From the average structure of each fraction obtained from the above (8) and the mass analysis result of each fraction obtained from the above (7), among the fractions obtained from the above (2) and (3) Ninth step of estimating the structure of individual molecules and quantifying as necessary
（１）重質油をｎ−パラフィンに可溶なマルテン分とそれ以外のフラクションに分離する第１工程、
（２）上記（１）で分離したマルテン分をカラムクロマトグラフィーを用いて飽和分、１環芳香族分、２環芳香族分、３環以上の芳香族分、極性化合物、及び多環芳香族分の各フラクションに分離する第２工程
（３）上記（２）で得た３環以上の芳香族分フラクションを分取液体クロマトグラフィーを用いて、さらに３環芳香族分、４環芳香族分、及び５環以上の芳香族分の各フラクションに分離する第３工程、及び、
（４）上記（３）工程で得られた４環芳香族分フラクションを、分取液体クロマトグラフィーを用いて、さらにＰｅｒｉ型４環芳香族分とＣａｔａ型４環芳香族分のフラクションに分離する第４工程 (A) Pretreatment for separating heavy oil into fractions of saturated components, aromatic components by number of rings, polar compounds and polycyclic aromatic components , comprising the following steps (1) to (4): A component analysis method for heavy oil, characterized in that (b-1) obtaining rate and / or (b-2) structural analysis is performed on each fraction obtained by pretreatment (b).
(1) a first step of separating heavy oil into n-paraffin-soluble marten and other fractions;
(2) Saturation, 1-ring aromatics, 2-rings aromatics, 3-rings or more aromatics, polar compounds, and polycyclic aromatics using column chromatography 2nd process of separating into fractions of minutes
(3) Using the preparative liquid chromatography, the fractions of three or more aromatic rings obtained in (2) above are further divided into three ring aromatics, four ring aromatics, and five or more ring aromatics. A third step of separating each fraction; and
(4) The 4-ring aromatic fraction obtained in the above step (3) is further separated into a Peri-type 4-ring aromatic fraction and a Cat-type 4-ring aromatic fraction using preparative liquid chromatography. Fourth step
(i) 元素分析、(ii) 1Ｈ−ＮＭＲ分析、(iii) 質量分析、及び(iv) 紫外可視分光分析（ultraviolet-visible spectroscopy：ＵＶ−Ｖｉｓ）のいずれか１以上の分析を実施し、その分析結果に基づいて行う方法である請求項３に記載の重質油の成分分析方法。 The structural analysis method of (b) is the saturated, 1-ring aromatic, 2-ring aromatic, 3-ring aromatic, 4-ring aromatic, 5 or more rings obtained in (2) and (3) above. Or at least one fraction of the peri-type 4-ring aromatic part and the Cat-type 4-ring aromatic part obtained in (4) above,
performing any one or more of (i) elemental analysis, (ii) 1 H-NMR analysis, (iii) mass spectrometry, and (iv) ultraviolet-visible spectroscopy (UV-Vis), The heavy oil component analysis method according to claim 3, wherein the method is performed based on the analysis result.
（５）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて元素分析を行う第５工程、
（６）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて1Ｈ−ＮＭＲ分析を行う第６工程
（７）上記（２）及び（３）、もしくは、さらに上記（４）で得たフラクションについて質量分析を行い、個々の成分の分子量とフラクションの数平均分子量を求める第７工程、
（８）上記（５）の元素分析値と上記（６）の1Ｈ−ＮＭＲ積算値と（７）の数平均分子量から、各フラクションの平均構造を特定する第８工程、及び
（９）上記（８）から得られた各フラクションの平均構造と、上記（７）から得られた各フラクションの質量分析結果より、上記（２）及び（３）の各フラクション、もしくは、さらに上記（４）で得たフラクション中の個々の分子の構造を推定し、必要に応じて定量する第９工程、 The heavy oil component analysis method according to claim 4, wherein the structural analysis method (b) includes the following steps (5) to (9).
(5) Fifth step of performing elemental analysis on the fraction obtained in (2) and (3) above or (4) above,
(6) Sixth step of performing 1 H-NMR analysis on the fraction obtained in the above (2) and (3) or (4) above (7) (2) and (3) above, or further above The seventh step of performing mass spectrometry on the fraction obtained in (4) to determine the molecular weight of each component and the number average molecular weight of the fraction,
(8) The eighth step of specifying the average structure of each fraction from the elemental analysis value of (5) above, the 1 H-NMR integrated value of (6) above and the number average molecular weight of (7), and (9) above From the average structure of each fraction obtained from (8) and the mass analysis result of each fraction obtained from (7) above, each fraction of (2) and (3) above, or further above (4) A ninth step in which the structure of individual molecules in the obtained fraction is estimated and quantified as necessary;
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