JP2007112923A - Method for reducing viscosity of heavy oil - Google Patents

Method for reducing viscosity of heavy oil Download PDF

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JP2007112923A
JP2007112923A JP2005306844A JP2005306844A JP2007112923A JP 2007112923 A JP2007112923 A JP 2007112923A JP 2005306844 A JP2005306844 A JP 2005306844A JP 2005306844 A JP2005306844 A JP 2005306844A JP 2007112923 A JP2007112923 A JP 2007112923A
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heavy oil
viscosity
oil
reducing
organic compound
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JP4982069B2 (en
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Yoshitoshi Sekiguchi
善利 関口
Toshio Hama
利雄 濱
Hideo Suzuki
秀男 鈴木
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Hitachi Zosen Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for reducing the viscosity of heavy oil, by which the viscosity of extra heavy oil can be reduced in milder semi-critical region conditions than extra critical states. <P>SOLUTION: This method for reducing the viscosity of the heavy oil is characterized by subjecting extra heavy oil to a hydrothermal treatment in a semi-critical region of 300 to 374°C. The method for reducing the viscosity of the heavy oil is also characterized by adding a hydrogen-imparting organic compound to extra heavy oil, adding zinc chloride or iron chloride as a catalyst, and then hydrocracking the extra heavy oil under reaction conditions comprising a temperature of 150 to 300°C and a pressure of 0.1 to 50 kgf/cm<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、超重質油（オイルサンド、重質原油、減圧残渣油、ヘビーオイル等）の粘度をC重油なみの粘度に低減する方法に関する。   The present invention relates to a method for reducing the viscosity of super heavy oil (oil sand, heavy crude oil, vacuum residue oil, heavy oil, etc.) to a viscosity similar to C heavy oil.

超重質油（オイルサンド、重質原油、減圧残渣油、ヘビーオイル等）は、世界的に埋蔵量が多く、石油に次ぐ貴重な炭化水素源としてその開発が進められている。   Ultra-heavy oil (oil sand, heavy crude oil, vacuum residue oil, heavy oil, etc.) has a large reserve in the world and is being developed as a valuable hydrocarbon source after oil.

しかしながら、超重質油は、数万センチポイズ以上の高粘性を有しており、そのままでは流動させることは難しく、また、流動性を向上させるために水素化精製法、熱分解法、接触分解法、溶剤抽出法等の改質、精製が試みられているが、いずれの方法を用いても、８０〜８００ｃＰ（５０℃における粘度、以下、粘度を示す場合、特に断らない限り５０℃での粘度を表す）の粘度を有するＣ重油並みの粘度まで低粘度化するには至っていない。   However, superheavy oil has a high viscosity of tens of thousands of centipoise and is difficult to flow as it is, and in order to improve fluidity, hydrorefining, thermal cracking, catalytic cracking, Modifications and purifications such as the solvent extraction method have been attempted, but no matter which method is used, 80 to 800 cP (viscosity at 50 ° C., hereinafter, the viscosity at 50 ° C. unless otherwise indicated) It has not yet been reduced to a viscosity equivalent to that of C heavy oil having a viscosity of

特許文献１には、少なくとも一部が液相状態にある水分を超臨界状態として得られる超臨界水（液相超臨界水）を用いて石油アルファルトに対して処理を加えると、２８０ｃＰの粘度に低粘度化されることが開示されている。   In Patent Document 1, when a process is applied to petroleum alfalt using supercritical water (liquid phase supercritical water) obtained by making water at least partially in a liquid phase state into a supercritical state, a viscosity of 280 cP is obtained. It is disclosed that the viscosity is reduced.

しかし、特許文献１の方法では、超臨界状態という非常に厳しい条件に高粘度重質油を付すことが必要であり、より緩和な条件の元で超重質油の低粘度化を行うことが望まれる。
特開２００４−３３７８１５号公報 However, in the method of Patent Document 1, it is necessary to apply a high-viscosity heavy oil to a very severe condition of a supercritical state, and it is desirable to reduce the viscosity of the super-heavy oil under more relaxed conditions. It is.
JP 2004-337815 A

本発明は、上記事情に鑑みてなされたものであり、超臨界状態よりも緩和な亜臨界域条件で超重質油の粘度を低減することができる方法を提供することを目的とする。   The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method capable of reducing the viscosity of superheavy oil under subcritical conditions that are more relaxed than the supercritical state.

水は、温度３７４℃、圧力２２ＭＰａに達すると、液体でも気体でもない状態となる。この温度および圧力は臨界点と呼ばれ、この臨界点以上の状態は超臨界域、臨界点よりやや低い温度である状態は亜臨界域と呼ばれている。本発明は、このような臨界点に到達していない亜臨界域の状態の水で水熱反応を行うことにより超重質油を低粘度化することができることを見出し、これにより本発明に至った。   When the temperature reaches a temperature of 374 ° C. and a pressure of 22 MPa, the water becomes neither liquid nor gas. This temperature and pressure is called a critical point, a state above this critical point is called a supercritical region, and a state slightly lower than the critical point is called a subcritical region. The present invention has found that it is possible to lower the viscosity of superheavy oil by carrying out a hydrothermal reaction with water in a subcritical region that has not reached the critical point, thereby reaching the present invention. .

すなわち、本発明の重質油の粘度低減方法は、超重質油を３００〜３７４℃の亜臨界域の水熱処理に付すことにより、該超重質油を分解することを特徴とする。   That is, the method for reducing the viscosity of heavy oil according to the present invention is characterized by decomposing the super heavy oil by subjecting the super heavy oil to hydrothermal treatment in a subcritical region of 300 to 374 ° C.

また、本発明は、水素を供与することができる有機化合物の存在下に、特定の触媒を添加して超重質油の処理を行えば、超臨界域と呼ばれる過酷な条件を用いなくても超重質油を低粘度化することができることを見出し、これにより本発明に至った。   In addition, the present invention can be applied to the treatment of superheavy oil by adding a specific catalyst in the presence of an organic compound capable of donating hydrogen, even without using a harsh condition called a supercritical region. It has been found that the viscosity of the quality oil can be reduced, and this has led to the present invention.

すなわち、本発明の超重質油の粘度低減方法は、超重質油に水素供与性有機化合物を加え、触媒として塩化亜鉛または塩化鉄を添加し、温度１５０〜３００℃、圧力０．１〜５０ｋｇｆ／ｃｍ２の反応条件下に、該超重質油を水素分解することによりこれを低粘度化することを特徴とする。 That is, the method for reducing the viscosity of super heavy oil according to the present invention comprises adding a hydrogen-donating organic compound to super heavy oil, adding zinc chloride or iron chloride as a catalyst, temperature of 150 to 300 ° C., pressure of 0.1 to 50 kgf / Under the reaction conditions of cm 2 , the ultra-heavy oil is hydrocracked to reduce its viscosity.

上記方法において、水素供与性有機化合物は、水素を供与することができるものであれば、あらゆるものでも用いてよく、例えば、炭化水素、アルコール、エーテル、油脂、脂肪酸および植物由来の高分子物質が挙げられる。さらに、植物由来の高分子物質としては、木質、バイオマス等が挙げられる。   In the above method, any hydrogen-donating organic compound may be used as long as it can donate hydrogen. For example, hydrocarbons, alcohols, ethers, oils and fats, fatty acids, and plant-derived polymer substances may be used. Can be mentioned. Furthermore, examples of plant-derived polymer substances include wood and biomass.

この水素供与性有機化合物の添加量は、超重質油、水素性有機化合物および触媒を合わせた全重量の２０％以上である必要がある。水素性有機化合物が２０重量％に満たない場合には、超重質油を十分に水素化することができないからである。触媒は、超重質油量に対して３〜５％程度であることが好ましい。   The amount of the hydrogen-donating organic compound added needs to be 20% or more of the total weight of the super heavy oil, the hydrogenous organic compound and the catalyst. This is because when the hydrogenous organic compound is less than 20% by weight, the superheavy oil cannot be sufficiently hydrogenated. The catalyst is preferably about 3 to 5% with respect to the amount of superheavy oil.

また、水をさらに加えてもよい。   Further, water may be further added.

また、本発明の重質油は、上記いずれか１つに記載の方法を用いることにより低粘度化された重質油である。   Further, the heavy oil of the present invention is a heavy oil whose viscosity has been reduced by using any one of the methods described above.

本発明の重質油の低粘度化方法によると、過酷な超臨界状態にすることなく、より緩和な亜臨界域条件で超重質油の粘度を低減することができ、得られた低粘度化された重質油は、バーナー燃料として利用することができる。   According to the method for reducing the viscosity of heavy oil of the present invention, the viscosity of the superheavy oil can be reduced under more relaxed subcritical conditions without being in a severe supercritical state. The resulting heavy oil can be used as a burner fuel.

以下、本発明の超重質油の低粘度化方法について具体的な実施例により説明する。   Hereinafter, the method for reducing the viscosity of super heavy oil of the present invention will be described with reference to specific examples.

（実施例）
図１に示す低粘度化プロセスに従い本発明の方法を実施した。所定量の高粘度の超重質油をチタン製の容器を有する亜臨界装置に投入し、さらに、水または各水素供与性有機化合物、塩化亜鉛または塩化鉄である触媒を所定量加えた。また、亜臨界装置には、コーキング防止剤であるチャーを２５ｇ加えた。超重質油の重量、水または水素供与製有機化合物の重量および水素供与製有機化合物の種類、触媒量およびその種類、反応温度および圧力は、下記の各実施例ごとに異なっているが、反応時間は各実施例および比較例の全てについて０．５時間である。表１に超重質油の性状を示し、表２〜４に実施例１〜１３および比較例１〜２の添加物量および種類、反応条件を示した。なお、表中の触媒の欄において、Ａは塩化亜鉛、Ｂは塩化鉄を示す。

Figure 2007112923
(Example)
The method of the present invention was carried out according to the viscosity reduction process shown in FIG. A predetermined amount of high-viscosity superheavy oil was put into a subcritical apparatus having a titanium container, and a predetermined amount of water or a catalyst that was each hydrogen-donating organic compound, zinc chloride, or iron chloride was added. In addition, 25 g of char as an anti-coking agent was added to the subcritical apparatus. The weight of the super heavy oil, the weight of water or the organic compound made from hydrogen donation, the kind of the organic compound made from hydrogen donation, the amount of the catalyst and the kind thereof, the reaction temperature and the pressure are different for each of the following examples, but the reaction time Is 0.5 hour for all examples and comparative examples. Table 1 shows the properties of the superheavy oil, and Tables 2 to 4 show the amounts and types of the additives and the reaction conditions of Examples 1 to 13 and Comparative Examples 1 and 2. In the catalyst column in the table, A represents zinc chloride and B represents iron chloride.
Figure 2007112923

Figure 2007112923
Figure 2007112923

Figure 2007112923
Figure 2007112923

Figure 2007112923
Figure 2007112923

上記各実施例１〜１３および比較例１〜２により得られた重質油の粘度を下記表５に示す。表５に示す通り、実施例１〜１３により得られた重質油の粘度は、Ｃ重油並（８０〜８００ｃＰ＠５０℃）の粘度を有していた。また、得られた各重質油の発熱量は１６，０００〜３２，０００ｋｇＪ／ｋｇであり、十分バーナー用燃料として利用できるものであった。比較例１および２はいずれも、Ｃ重油並の粘度まで低粘度化することができなかった。

Figure 2007112923
The viscosities of the heavy oils obtained in Examples 1 to 13 and Comparative Examples 1 and 2 are shown in Table 5 below. As shown in Table 5, the heavy oils obtained in Examples 1 to 13 had the same viscosity as heavy oil C (80 to 800 cP @ 50 ° C.). Moreover, the calorific value of each obtained heavy oil was 16,000-32,000 kgJ / kg, and it could fully be utilized as a fuel for burners. In both Comparative Examples 1 and 2, the viscosity could not be lowered to the same level as that of C heavy oil.
Figure 2007112923

本発明の方法を示すフローシートである。It is a flow sheet which shows the method of this invention.

Claims (6)

超重質油を３００〜３７４℃の亜臨界域の水熱処理に付すことにより、該超重質油を分解することを特徴とする重質油の粘度低減方法。   A method for reducing the viscosity of a heavy oil, comprising subjecting the super heavy oil to hydrothermal treatment in a subcritical region at 300 to 374 ° C to decompose the super heavy oil. 超重質油に水素供与性有機化合物を加え、触媒として塩化亜鉛または塩化鉄を添加し、温度１５０〜３００℃、圧力０．１〜５０ｋｇｆ／ｃｍ２の反応条件下に、該超重質油を水素分解することによりこれを低粘度化することを特徴とする重質油の粘度低減方法。 A hydrogen-donating organic compound is added to ultraheavy oil, zinc chloride or iron chloride is added as a catalyst, and the ultraheavy oil is hydrogenated under reaction conditions of a temperature of 150 to 300 ° C. and a pressure of 0.1 to 50 kgf / cm 2. A method for reducing the viscosity of heavy oil, characterized in that the viscosity is reduced by decomposing. 水素供与性有機化合物は、炭化水素、アルコール、エーテル、油脂、脂肪酸、および植物由来の高分子物質からなる群から選択される少なくとも一つである、請求項２に記載の方法。   The method according to claim 2, wherein the hydrogen-donating organic compound is at least one selected from the group consisting of hydrocarbons, alcohols, ethers, fats and oils, fatty acids, and plant-derived polymer substances. 植物由来の高分子物質は木質またはバイオマスである、請求項３に記載の方法。   4. The method according to claim 3, wherein the plant-derived polymer substance is woody or biomass. 水をさらに加える、請求項２〜４のいずれか１つに記載の方法。   The method according to any one of claims 2 to 4, wherein water is further added. 請求項１〜５のいずれか１つに記載の方法を用いることにより低粘度化された重質油。   A heavy oil having a reduced viscosity by using the method according to any one of claims 1 to 5.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009242467A (en) * 2008-03-28 2009-10-22 Japan Energy Corp Method for cracking hydrocarbon oil
JP2010174144A (en) * 2009-01-29 2010-08-12 Japan Energy Corp Process for producing light hydrocarbon oil
JP2010174140A (en) * 2009-01-29 2010-08-12 Japan Energy Corp Process for producing light hydrocarbon oil
JP2012525388A (en) * 2009-04-28 2012-10-22 ユニバーシティ オブ サザン カリフォルニア Efficient and environmentally friendly processing of heavy oils into methanol and derived products
CN103173240A (en) * 2011-12-22 2013-06-26 北京低碳清洁能源研究所 Viscosity breaking improver and co-viscosity breaking process of coal tar or biomass oil and heavy oil containing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS573886A (en) * 1980-06-09 1982-01-09 Mitsubishi Chem Ind Ltd Method for converting petroleum heavy hydrocarbon oil into light oil
JPS6166792A (en) * 1984-09-10 1986-04-05 モ−ビル　オイル　コ−ポレ−ション Rivet braking method
JPH06279763A (en) * 1993-03-30 1994-10-04 Heiji Enomoto Reforming of heavy oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS573886A (en) * 1980-06-09 1982-01-09 Mitsubishi Chem Ind Ltd Method for converting petroleum heavy hydrocarbon oil into light oil
JPS6166792A (en) * 1984-09-10 1986-04-05 モ−ビル　オイル　コ−ポレ−ション Rivet braking method
JPH06279763A (en) * 1993-03-30 1994-10-04 Heiji Enomoto Reforming of heavy oil

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009242467A (en) * 2008-03-28 2009-10-22 Japan Energy Corp Method for cracking hydrocarbon oil
JP2010174144A (en) * 2009-01-29 2010-08-12 Japan Energy Corp Process for producing light hydrocarbon oil
JP2010174140A (en) * 2009-01-29 2010-08-12 Japan Energy Corp Process for producing light hydrocarbon oil
JP2012525388A (en) * 2009-04-28 2012-10-22 ユニバーシティ オブ サザン カリフォルニア Efficient and environmentally friendly processing of heavy oils into methanol and derived products
CN103173240A (en) * 2011-12-22 2013-06-26 北京低碳清洁能源研究所 Viscosity breaking improver and co-viscosity breaking process of coal tar or biomass oil and heavy oil containing same
CN103173240B (en) * 2011-12-22 2015-05-20 北京低碳清洁能源研究所 Co-visbreaking process of coal tar and/or biomass oil and heavy oil

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