200920835 九、發明說明 【發明所屬之技術領域】 本發明係關於烴油之氫化精製方法，更詳言之，係關 於使用含有重質烴油及特定之烴油的原料油，且有效率氫 化精製該重質烴油之烴油之氫化精製方法。 【先前技術】 以往，原油的精製處理方法，一般，將原油常壓蒸飽 分離出各餾分後，將分離的各餾分分別進行脫硫的方法。 但是，此方法爲精油設備的基數多，且步驟煩雜，加上因 爲重複製品的冷卻、加熱，故具有能量效率差等之問題， 不一定可令人滿足，追求新形式之原油處理方法。由此類 觀點而言，近年嘗試將原油或除去石腦油餾分的原油一倂 處理。例如，提案（1 )將原油中之石腦油餾分蒸餾分離 後，將除去石腦油餾分之殘油一倂氫化脫硫處理，其次蒸 餾分離各製品之方法（專利文獻1 )、（ 2 )將原油中之石 腦油餾分蒸餾分離後，將除去石腦油餾分之殘油一倂氫化 脫硫處理，其次，以高壓分離槽將輕質餾分和重質餾分予 以分離，並將所得之輕質餾分氫化精製之方法（專利文獻 2 )等。如此，發現對於含有二種以上餾分之原料油進行 氫化處理，則具有圖謀令氫化精製處理效率化之可能性。 又，提案將重質油稀釋，將先前困難之重質油的脫硫 處理及脫金屬處理予以改良的方法。例如，專利文獻3爲 揭示將殘油與具有特定沸點之稀釋劑摻混，並且於特定條 -5- 200920835 件下進行脫硫及脫金屬方法，如此令脫硫速度及/或脫金 屬速度上升，且有效降低氫化處理殘油中之硫及/或金屬 含量。 如上述，於氫化精製處理中，使用含有二種以上餾分 之原料油的技術、和稀釋重質油的技術中非常重要爲提高 效率，但由環境問題和節省能量化的觀點而言，進一步進 行氫化精製處理之效率化乃爲必要之狀況。又，就達成省 能量化之方面，專利文獻3之技術並非必定有效。即，作 爲摻混重質油的低沸點稀釋劑，可爲使用輕油、餾出油等 ’通常，彼等比重質油可在更短時間且溫和之條件下進行 精製處理，故在原油之精製處理全體中殘留節省能量化之 課題。 如此，雖然改良先前技術和開發新的精製處理方法爲 必要之狀況，但上述先前技術中使用二種以上原料油之技 術和稀釋重質油之技術中的詳細混合效果仍爲未知，改良 先前技術和開發新的精製處理方法乃爲困難之狀況。 專利文獻1 :特開平3-294390號公報 專利文獻2:特開平4-224890號公報 專利文獻3 :特開平4-239094號公報 【發明內容】 (發明所欲解決之課題） 本發明爲於此類狀況下完成者，以提供於含有重質油 之煙油之氫化精製中，提高重質油之氫化精製的效率，達 -6 - 200920835 成精製油的增產、高品質精製油之製造及氫化精製條件之 溫和化之烴油之氫化精製方法爲其目的。 (解決課題之手段） 以往，於氫化脫硫反應中，已知於重質烴油與輕質烴 油的處理速度上有差別，一般重質烴油的處理比輕質烴油 的處理效率非常差。因此，若於重質烴油中混合輕質烴油 並且進行氫化脫硫處理，則輕質烴油於反應裝置入口附近 令反應終了，並於其後作用爲惰性的稀釋劑。其結果，即 使經由輕質烴油的混合以增加L H S V，亦無法令重質油所 相關的脫硫率降低，可有效進行脫硫處理（於本說明書中 ，將該效果稱爲稀釋效果）。但是，因爲此等輕質烴油比 重質油可在較短時間且溫和的條件下進行精製處理，故此 方法殘留原油之精製處理全體之省能量化的課題。本發明 者等人致力硏究之結果，發現對重質烴油添加特定的輕質 烴油，並以特定之方法處理，則可表現出與上述稀釋效果 不同之效果，可更有效率地氫化精製，並且達到完成本發 明。即，本發明爲提供以下（1 )〜（1 0 )所示之方法。 (1 ) 一種烴油之氫化精製方法，其爲氫化精製烴油 之方法，其特徵爲使用重質烴油與具有增加氫溶解濃度的 效果之烴油的混合物作爲氫化精製的原料，於該混合物中 混合氫後，於進行氫化精製的反應塔中通過油者、 (2 )如上述（1 )中記載之烴油之氫化精製方法，其 中重質烴油與具有增加氫溶解濃度的效果之烴油的混合物 -7- 200920835 中之氫溶解濃度爲，可溶解於該重質烴油之氫濃度的1.1 倍以上、 (3 )如上述（1 )中記載之烴油之氫化精製方法，其 中重質烴油爲1種或2種以上選自減壓渣油、減壓輕油、 常壓渣油、蒸餘原油、原油、脫瀝青油（deasphalted oil )、液態煤油、油沙油及瀝青頁岩油之組合、 (4 )如上述（1 )中記載之烴油之氫化精製方法，其 中具有增加氫溶解濃度的效果之烴油爲，反應塔內之條件 下該全量或一部份存在於液相中者、 (5 )如上述（1 )中記載之烴油之氫化精製方法，其 中增加氫溶解濃度的效果係以反應塔內的氫之氣液平衡爲 準而推算出、 (6 )如上述（1 )中記載之烴油之氫化精製方法，其 中將具有增加氫溶解濃度的效果之烴油，進一步作爲急冷 油供給於反應塔內、 (7 )如上述（1 )中記載之烴油之氫化精製方法，其 中具有增加氫溶解濃度的效果之烴油係爲1種或2種以上 選自直餾燈油餾分、直餾輕質輕油餾分、直餾重質輕油餾 分、由FCC裝置所得之分解油及焦化裝置所得之熱分解油 的組合、 (8 )如上述（1 )中記載之烴油之氫化精製方法，其 中氫化精製爲1種或2種以上選自氫化脫金屬處理、氫化 脫硫處理、氫化分解處理、氫化脫氮處理及氫化脫芳香族 處理之處理、 -8- 200920835 (9 )如上述（1 )中記載之烴油之氫化精製方法，其 中氫化精製的條件爲，反應溫度300〜450 °C ’氫氣分壓 5.1 〜25.3MPa ( G)、氫 / 油比 200 〜2000Nm3/kl、 LHSV0.05 〜1 Oh]、 (1 0 )如上述（1 )中記載之烴油之氫化精製方法， 其中氫化精製的條件爲’反應溫度3 3 0〜4 3 0 °c，氫氣分壓 10.1 〜20.3MPa ( G)、氫 / 油比 500 〜1000Nm3/kl、 LHSV0.1 〜1 .Oh·1。 (發明之效果） 若根據本發明，則提供於含有重質油之烴油之氫化精 製處理中，更加提高重質油之氫化精製的效率’可達成精 製油之增產、高品質精製油之製造及氫化精製條件之溫和 化之烴油的氫化精製方法。該氫化精製方法爲於重質烴油 中加入特定之輕質烴油，並以特定條件處理，經由此等特 定化則可彌補輕質烴油不得不以長時間且嚴苛之條件精製 的缺點，可圖謀原油之精製處理全體的省能量化。 【實施方式】 本發明之烴油之氫化精製方法爲於含有重質烴油及具 有增加氫溶解濃度的效果之烴油的原料油中，混合氫，並 將該混合氫的原料油於反應塔中通過油，進行氫化精製處 理。 上述重質烴油可使用一種或二種以上選自減壓渣油、 -9- 200920835 減壓輕油、常壓渣油、蒸餾原油、原油、脫瀝青油、液態 煤油、油沙油、瀝青頁豈油之組合。於反應塔內未形成液 相之重質烴油難以取得本發明之效果，故必須選擇適切的 重質油或設定反應條件。又，本發明達成先前困難之重質 烴油之氫化精製的效率提高，故重質烴油中之瀝青質（於 本說明書中，所謂瀝青質，係意指對於重質油以正庚烷萃 取處理時之正庚烷不溶解部分）的含量爲2質量％以上爲 佳，且以4質量％以上爲更佳。雖然即使使用未滿2質量 %之重質烴油所得之精製油的性狀並無問題，但此等重質 烴油即使未應用本發明亦較容易引起氫化反應，故就費用 效果方面、和省能量化方面而言爲不佳。又，關於上限並 無特別限制，但於裝置運作上，以未滿1 5質量％爲佳。又 ，由同樣之理由較佳使用含有1 〇質量ppm以上之釩、鎳 ’ 0.1質量％以上之硫分者。 重質烴油爲視需要施以前處理爲佳。例如，重質烴油 中之鹽分濃度高時’施以脫鹽處理，令氯化鈉10質量 ppm以下爲佳。又’固形成分多時，以1 Ομπι左右之濾紙 處理爲佳。 於本說明書中’使用具有增加氫溶解濃度效果之烴油 。另外，本說明書中所謂具有增加氫溶解濃度效果之烴油 ，係指平均沸點爲100°C以上，密度爲0.70〜0.95g/ml之 範圍，以溶解於重質烴油之氫濃度爲基準時，於相同條件 (溫度、壓力）下具有提高原料油之氫溶解濃度效果之烴 油。若平均沸點爲低於l〇〇°C、密度爲低於0.70g/m卜則 -10- 200920835 於液相中存在的比例顯著降低，具有令提高氫濃度之效果 降低的傾向。密度超過0.95g/ml的烴油具有缺乏提高氫溶 解濃度之效果的傾向。具體而言可列舉直餾燈油餾分、直 餾輕質輕油餾分、直餾重質輕油餾分，由FCC裝置所得之 分解油、焦化裝置所得之熱分解油等。其可單獨或組合使 用二種以上。又，亦可使用石油系以外之烴。一般而言， 比原料油之重質烴油，沸點更低的輕質烴等，具有提高反 應塔內之液相溶存氫濃度之效果。但是，若過度供給沸點 過低之輕質烴，則於反應塔內幾乎完全存在於氣相中，故 導致氣相之氫分壓降低，有時不表現出增加氫溶解濃度的 效果。 上述具有增加氫溶解濃度之效果的烴油，於反應塔內 之溫度、壓力條件下，其全量或其一部份必須爲液相。如 此，可提高氫化精製處理的效率。較佳使用於反應塔內之 溫度、壓力下，相對於全量於液相中的存在比例爲1 〇%以 上、較佳爲20%以上之烴油。 具有增加氫溶解濃度效果之烴油與重質油共同進行氫 化精製處理下，經由與前述稀釋效果不同之作用，可進一 步提高氫化精製處理之效率。於本發明中，重質烴油與具 有增加氫溶解濃度效果之烴油之混合物中的氫溶解濃度， 爲該重質烴油中溶解之氫濃度的1 .1倍以上爲佳。低於 1.1倍時，輕質烴油等之具有增加氫溶解濃度效果的烴油 因爲不得不以長時間且嚴苛條件下精製之缺點，易在原油 精製處理全體的省能量化和費用方面發生問題。又’根據 -11 - 200920835 上述理由，更佳於氫溶解濃度提高至1 . 1 5倍以上，再佳 爲1.2倍以上之條件下，供給輕質烴油爲佳。 於本發明中，具有增加氫溶解濃度效果的烴油，可使 用能推算反應塔內之氫溶解濃度及氫之氣液平衡的工具加 以選擇。以下，說明使用 Pro/II ( ver6.01 ) ( Inbensis200920835 IX. INSTRUCTIONS OF THE INVENTION [Technical Fields of the Invention] The present invention relates to a method for hydrotreating a hydrocarbon oil, and more particularly to the use of a feedstock oil containing a heavy hydrocarbon oil and a specific hydrocarbon oil, and efficient hydrogenation refining A method for hydrotreating a hydrocarbon oil of the heavy hydrocarbon oil. [Prior Art] Conventionally, a method for purifying crude oil is generally a method in which each of the separated fractions is subjected to desulfurization after the crude oil is saturated under normal pressure to separate the fractions. However, this method has many bases for essential oil equipment, and the steps are cumbersome, and the problem of poor energy efficiency due to cooling and heating of the duplicated product is not necessarily satisfactory, and a new form of crude oil processing method is pursued. From this point of view, in recent years, attempts have been made to treat crude oil or crude oil from which naphtha fractions are removed. For example, in the proposal (1), the naphtha fraction in the crude oil is distilled and separated, and the residual oil of the naphtha fraction is removed, followed by hydrodesulfurization, and the method of separating and separating each product (Patent Document 1), (2) After distilling and separating the naphtha fraction in the crude oil, the residual oil of the naphtha fraction is removed for hydrodesulfurization treatment, and second, the light fraction and the heavy fraction are separated by a high pressure separation tank, and the obtained light is obtained. A method for hydrotreating a fraction (Patent Document 2). As described above, it has been found that the hydrogenation treatment of the feedstock oil containing two or more fractions has the possibility of improving the efficiency of the hydrorefining treatment. In addition, it is proposed to dilute heavy oil and improve the desulfurization treatment and demetallization treatment of previously difficult heavy oil. For example, Patent Document 3 discloses that a residual oil is blended with a diluent having a specific boiling point, and a desulfurization and demetallization method is carried out under a specific strip-5-200920835, so that the desulfurization speed and/or the demetallization speed increase. And effectively reducing the sulfur and/or metal content in the hydrotreated residual oil. As described above, in the hydrorefining treatment, it is very important to use a technique of using a feedstock oil containing two or more fractions and a technique of diluting a heavy oil to improve the efficiency, but further from the viewpoint of environmental problems and energy saving. The efficiency of the hydrorefining treatment is a necessary condition. Further, the technique of Patent Document 3 is not necessarily effective in terms of achieving energy saving in the province. That is, as a low-boiling point diluent for blending heavy oil, it is possible to use light oil, distillate oil, etc. 'Generally, these viscosified oils can be refined in a shorter time and under mild conditions, so in crude oil The problem of energy saving in the entire purification process remains. Thus, although it is necessary to improve the prior art and develop a new refining treatment method, the detailed mixing effect in the technique of using two or more raw material oils and the technique of diluting heavy oil in the above prior art is still unknown, and the prior art is improved. And the development of new refining methods is a difficult situation. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. Under the condition of the class, in the hydrorefining of the heavy oil-containing soot oil, the efficiency of hydrogenation of heavy oil is improved, and the production of refined oil is increased, and the production and hydrogenation of high-quality refined oil are up to -6 - 200920835 A hydrorefining method for the mildening of a hydrocarbon oil under refining conditions is an object thereof. (Means for Solving the Problem) In the past, in the hydrodesulfurization reaction, it is known that there is a difference in the processing speed between the heavy hydrocarbon oil and the light hydrocarbon oil. Generally, the treatment of the heavy hydrocarbon oil is very efficient than the treatment of the light hydrocarbon oil. difference. Therefore, if a light hydrocarbon oil is mixed with a heavy hydrocarbon oil and subjected to a hydrodesulfurization treatment, the light hydrocarbon oil is allowed to terminate near the inlet of the reaction apparatus, and thereafter acts as an inert diluent. As a result, even if L H S V is increased by mixing with a light hydrocarbon oil, the desulfurization rate associated with the heavy oil cannot be lowered, and the desulfurization treatment can be effectively performed (this effect is referred to as a dilution effect in the present specification). However, since these light hydrocarbon oils can be purified in a shorter time and under mild conditions than the heavy oils, this method leaves the problem of energy saving of the entire purification process of the crude oil. As a result of intensive research, the present inventors have found that adding a specific light hydrocarbon oil to a heavy hydrocarbon oil and treating it by a specific method can exhibit an effect different from the above dilution effect, and can be hydrogenated more efficiently. Refined and achieved the completion of the present invention. That is, the present invention provides the methods shown in the following (1) to (1 0). (1) A method for hydrotreating a hydrocarbon oil, which is a method for hydrotreating a hydrocarbon oil, characterized in that a mixture of a heavy hydrocarbon oil and a hydrocarbon oil having an effect of increasing a hydrogen dissolution concentration is used as a raw material for hydrorefining, in the mixture After the hydrogen is mixed, the oil is passed through to the reaction column for hydrorefining, and (2) the method for hydrotreating the hydrocarbon oil according to the above (1), wherein the heavy hydrocarbon oil and the hydrocarbon having an effect of increasing the dissolved concentration of hydrogen The hydrogen-dissolving concentration of the oil-containing mixture -7-200920835 is 1.1 times or more of the hydrogen concentration of the heavy hydrocarbon oil. (3) The method for hydrotreating a hydrocarbon oil according to the above (1), wherein The hydrocarbon oil is one or more selected from the group consisting of vacuum residue, vacuum gas oil, atmospheric residue, steam crude oil, crude oil, deasphalted oil, liquid kerosene, oil sand oil and asphalt shale. (4) The method for hydrotreating a hydrocarbon oil according to the above (1), wherein the hydrocarbon oil having an effect of increasing a hydrogen dissolution concentration is the whole amount or a part of the liquid in the reaction column. In the middle, (5) as above (1 The method for hydrotreating a hydrocarbon oil according to the above, wherein the effect of increasing the hydrogen dissolution concentration is calculated based on the gas-liquid equilibrium of hydrogen in the reaction column, and (6) hydrogenation of the hydrocarbon oil as described in the above (1) In a purification method, a hydrocarbon oil having an effect of increasing a hydrogen solubility concentration is further supplied as a quenching oil to a reaction column, and (7) a method for hydrotreating a hydrocarbon oil according to the above (1), wherein the hydrogen concentration is increased. The hydrocarbon oil of the effect is one or two or more kinds selected from the group consisting of a straight-run lamp oil fraction, a straight-run light gas oil fraction, a straight-run heavy light oil fraction, a decomposition oil obtained by an FCC device, and a thermal decomposition obtained by a coking unit. (8) The method for hydrotreating a hydrocarbon oil according to the above (1), wherein the hydrotreating is one or more selected from the group consisting of hydrodemetallization, hydrodesulfurization, hydrodecomposition, and hydrogenation. Nitrogen treatment and hydrodearomatization treatment, -8-200920835 (9) The method for hydrotreating a hydrocarbon oil according to the above (1), wherein the hydrogenation purification condition is a reaction temperature of 300 to 450 ° C. Pressure 5.1 ~ 25.3 MPa (G), hydrogen/oil ratio 200 to 2000 Nm3/kl, LHSV 0.05 to 1 Oh], (1 0) The method for hydrotreating a hydrocarbon oil according to the above (1), wherein the condition of the hydrorefining is ' The reaction temperature is 3 3 0 to 4 3 0 °c, the partial pressure of hydrogen is 10.1 to 20.3 MPa (G), the ratio of hydrogen to oil is 500 to 1000 Nm3/kl, and LHSV is 0.1 to 1.Oh·1. (Effect of the Invention) According to the present invention, in the hydrorefining treatment of a hydrocarbon oil containing a heavy oil, the efficiency of hydrorefining of heavy oil can be further improved, and the production of a refined oil can be increased, and the production of a high-quality refined oil can be achieved. And a method for hydrotreating a mildly hydrolyzed hydrocarbon oil under hydrorefining conditions. The hydrorefining method is to add a specific light hydrocarbon oil to a heavy hydrocarbon oil and treat it under specific conditions, and the specificization can compensate for the disadvantage that the light hydrocarbon oil has to be refined under long-term and severe conditions. In the process of refining the crude oil, it is possible to save energy. [Embodiment] The method for hydrotreating a hydrocarbon oil according to the present invention is to mix hydrogen in a feedstock oil containing a heavy hydrocarbon oil and a hydrocarbon oil having an effect of increasing a hydrogen dissolved concentration, and to mix the mixed feedstock oil in the reaction tower. The oil is refining by oil. The above heavy hydrocarbon oil may be used in one or more selected from the group consisting of vacuum residue, -9-200920835 vacuum gas oil, atmospheric residue, distilled crude oil, crude oil, deasphalted oil, liquid kerosene, oil sand oil, asphalt. Page 岂 oil combination. It is difficult to obtain the effect of the present invention in the heavy hydrocarbon oil in which the liquid phase is not formed in the reaction column, so it is necessary to select a suitable heavy oil or set the reaction conditions. Moreover, the present invention achieves an increase in the efficiency of hydrorefining of heavy hydrocarbon oils which have previously been difficult, and therefore asphaltenes in heavy hydrocarbon oils (in the present specification, the so-called asphaltenes means that the heavy oil is extracted with n-heptane. The content of the n-heptane insoluble portion at the time of the treatment is preferably 2% by mass or more, and more preferably 4% by mass or more. Although the properties of the refined oil obtained by using the heavy hydrocarbon oil of less than 2% by mass are not problematic, such heavy hydrocarbon oils are more likely to cause a hydrogenation reaction even if the present invention is not applied, so that the cost effect and the province are In terms of energy, it is not good. Further, the upper limit is not particularly limited, but it is preferably less than 15 mass% in terms of device operation. Further, for the same reason, it is preferable to use a sulfur component containing vanadium or nickel 0.001 mass% or more of 1 〇 mass ppm or more. Heavy hydrocarbon oils are preferably treated as needed. For example, when the salt concentration in the heavy hydrocarbon oil is high, desalting treatment is preferably carried out so that sodium chloride is preferably 10 ppm by mass or less. Further, when the solid content is large, it is preferably treated with a filter paper of about 1 Ομπι. In the present specification, a hydrocarbon oil having an effect of increasing the hydrogen dissolution concentration is used. In addition, the hydrocarbon oil having an effect of increasing the hydrogen solubility concentration in the present specification means an average boiling point of 100 ° C or more and a density of 0.70 to 0.95 g/ml, and is based on the hydrogen concentration of the heavy hydrocarbon oil. A hydrocarbon oil having the effect of increasing the hydrogen solubility concentration of the feedstock oil under the same conditions (temperature, pressure). When the average boiling point is less than 10 ° C and the density is less than 0.70 g / m, the ratio of the presence of the liquid in the liquid phase is significantly lowered, and the effect of increasing the hydrogen concentration tends to be lowered. A hydrocarbon oil having a density of more than 0.95 g/ml has a tendency to have an effect of increasing the concentration of hydrogen dissolved. Specific examples thereof include a straight-run lamp oil fraction, a linear light oil fraction, a straight-run heavy light oil fraction, a decomposition oil obtained from an FCC unit, and a thermal decomposition oil obtained by a coking unit. They may be used alone or in combination of two or more. Further, hydrocarbons other than the petroleum system can also be used. In general, a heavy hydrocarbon oil having a lower boiling point than a heavy hydrocarbon oil of a feedstock oil has an effect of increasing the concentration of dissolved hydrogen in the liquid phase in the reaction column. However, if the light hydrocarbon having a too low boiling point is excessively supplied, it is almost completely present in the gas phase in the reaction column, so that the hydrogen partial pressure in the gas phase is lowered, and the effect of increasing the hydrogen dissolution concentration may not be exhibited. The above hydrocarbon oil having an effect of increasing the concentration of hydrogen dissolved, in the temperature and pressure conditions in the reaction column, the entire amount or a part thereof must be a liquid phase. Thus, the efficiency of the hydrorefining treatment can be improved. It is preferably used in a hydrocarbon oil having a ratio of more than 1% by weight, preferably 20% or more, based on the total amount in the liquid phase at a temperature and a pressure in the reaction column. The hydrocarbon oil having the effect of increasing the hydrogen dissolution concentration is subjected to a hydrogenation refining treatment together with the heavy oil, and the efficiency of the hydrorefining treatment can be further improved by the action different from the aforementioned dilution effect. In the present invention, the hydrogen dissolution concentration in the mixture of the heavy hydrocarbon oil and the hydrocarbon oil having an effect of increasing the hydrogen dissolution concentration is preferably 1.1 times or more of the dissolved hydrogen concentration in the heavy hydrocarbon oil. When it is less than 1.1 times, a hydrocarbon oil having an effect of increasing the hydrogen solubility concentration such as a light hydrocarbon oil is disadvantageous in that it has to be refined under a long time and under severe conditions, and it is easy to cause energy saving and cost in the entire crude oil purification treatment. problem. Further, according to the above reasons, it is more preferable to supply a light hydrocarbon oil under the condition that the hydrogen dissolution concentration is increased to 1.5 times or more, and more preferably 1.2 times or more. In the present invention, a hydrocarbon oil having an effect of increasing the hydrogen dissolution concentration can be selected by a tool capable of estimating the hydrogen dissolution concentration in the reaction column and the gas-liquid equilibrium of hydrogen. The following is a description of the use of Pro/II ( ver6.01 ) ( Inbensis
System Incorporate 公司製 Process Simulator)作爲其具 體例之情形。 (1 )由PFD步驟單元選擇混合器和其下游的沖洗器 〇 (2 )於混合器的入口流體選擇氫，輸入氫的供給速 度。 (3 )將混合器之另一者的入口流體種類選擇石油（ Petroleum Assay)，輸入供給之重質烴油的供給速度、重 質烴油之密度（g/cm3 )、蒸餾性狀。 (4 )輸入沖洗器之分離條件的溫度和壓力。 (5 )由一般式中，選出SRK式（SRK01 )作爲使用 之熱力學數據。 〔SRK式爲於石油精製領域之步驟模擬器中最標準使 用之熱力學式之一〕 (6 )根據使用步驟模擬器之計算，將沖洗器出口液 相部之氫質量流量，重複除以沖洗器出口液相部合計之質 量流量，求出氫的含量（wt% )。如此’則可推算出單獨 供給重質烴油時之反應塔入口之液相的氫溶解濃度。 以上述相同方法’將（3 )之混合器的入口流體’除 -12- 200920835 了重質烴油，加上輸入輕質烴油的供給速度、輕質烴油的 密度、蒸餾性狀，進行同樣之計算。經由比較，則可把握 以某條件供給輕質烴油時之反應塔內液相部之氫溶解濃度 的變化。以上爲反應塔入口的推算方法。 反應塔出口爲輸入實際進行反應時之關於（2)爲斷 氣（off-gas )的組成和速度、關於（3 )爲精製油之密度 和蒸餾性狀及精製油回收速度。熱力學式其他亦有PR式 和GS式，若比較3式，則混合通過輕質油時之液相之氫 溶解濃度的增加比例爲顯示出相同傾向。又，反應塔出口 之組成爲未知時，僅以反應塔入口條件亦可推算。 又，使用上述之步驟模擬器，可推算重質烴油及具有 增加氫溶解濃度效果之烴油的最適混合比。更且，以增加 氫溶解濃度效果爲基準決定反應條件，則可輕易控制反應 ’可圖謀令氫化精製反應省能量化。 以下’具體說明烴油的氫化精製處理。於本發明之氫 化精製處理中，於進行氫化精製之反應塔中通過油之前， 於原料油（烴油）中混合氫。較佳爲將重質烴油與輕質烴 油等之具有增加氫溶解濃度效果的烴油混合，作成原料油 後’將該原料油升壓並且以熱交換器之餘熱中混合氫，再 將該 '混合高壓氫之原料油以加熱爐加熱至反應溫度爲止， ΐέ丨共，铪Μ反應塔。若於原料油之升壓和熱交換步驟以前混 合氮’則必須在氣液混相下升壓及熱交換，易令升壓和加 % @率降低。又，若於原料油通過加熱爐後與氫混合，則 具有令氫溶解時間不足的可能性。 -13- 200920835 氫化精製之條件可列舉例如’反應溫度 氫分壓 5.1〜25.3MPa(G)、氫/油比 200-LHSVO.05^10111^1，和反應溫度 3 3 0〜430 10.1 〜20.3MPa ( G )、氫 / 油比 500 〜 LHS VO. 1 〜1 .Ohr·1。 上述氫化精製處理可列舉氫化脫金屬處 處理、氫化分解處理、氫化脫氮處理及氫化 ，且本發明之方法無特別限制且可於上述氫 ，且於二種以上之氫化處理中應用亦可。連 氫化處理時，其順序並無特別限制，但以最 金屬處理爲佳，通常，首先進行氫化脫金屬 行氫化脫氮處理、氫化分解處理等，最後進 理。又，根據目的進行氫化脫硫處理後，進 分解處理等亦可。又，於此等氫化處理中， 裝置的型式並無特別限制，例如，可使用固 、流動床、沸騰床、流漿床等。又，將具有 度效果之烴油於反應塔內以急冷油型式供給 於上述氫化脫金屬處理中，將混合氫之 升溫後，以一塔或數塔之反應塔進行。 氫化脫金屬處理所使用之觸媒爲於氧化 、二氧化矽-氧化鋁或沸石等之多孔質無機 礦物等之載體，擔持屬於周期表第8、9及 選出至少一種之活性金屬、及屬於周期表第 選出至少一種之助觸媒金屬爲佳。上述活性 300〜450〇C、 -20 00Nm3/kl、 t 、氫分壓 1 000Nm3/kl 、 理、氫化脫硫 脫芳香族處理 化處理中應用 續進行上述之 初進行氫化脫 處理，其次進 行氫化脫硫處 一步進行氫化 所使用之反應 定床、移動床 增加氫溶解濃 亦可。 原料烴油加壓 銘、二氧化砂 氧化物、天然 1 〇族之金屬中 6族之金屬中 金屬之含量爲 -14 - 200920835 以氫化脫金屬觸媒全量爲基準，以金屬氧化物型式較佳爲 2〜8質量％、更佳爲2〜4質量％，上述助觸媒金屬之含量爲 以氫化脫金屬觸媒全量爲基準，以金屬氧化物型式較佳爲 0.5〜5質量％、更佳爲1〜5質量％。具體而言，作爲活性金 屬之屬於周期表第8、9及10族之金屬以鎳、鈷及铑爲更 佳，作爲助觸媒之屬於周期表第6族之金屬以鉬及鎢爲更 佳。氫化脫金屬觸媒量爲根據原料烴油中之金屬濃度而使 用任意之份量，但相對於全處理步驟所用之觸媒全量使用 1 〇 ~ 5 0體積％爲佳。 氫化脫金屬處理之較佳的反應條件爲反應溫度 3 00~45 0 °C、更佳爲 3 3 0〜43 0 °C，氫分壓 5〜25MPa ( G )、 更佳爲 10~20MPa(G)，氫 / 油比 200〜2,000Nm3/kl、更佳 爲 50O~l，OOONm3/kl、L H S V (液時空間速度）0 · 1 ~2 0 hr—1 、更佳爲0.2〜2hr-1。氫分壓、氫/油比若低於上述範圍， 則反應效率易降低，若超過上述範圍，則經濟性易降低。 又，LHSV若低於上述範圍，則經濟性易降低，若超過上 述範圍，則反應效率易降低。 上述氫化脫硫處理通常爲於氫化脫金屬處理等之氫化 處理後進行。因此，於必須控制反應溫度之情形中’經由 熱交換器、氫氣急冷和油急冷控制反應溫度爲佳。氫化脫 硫處理爲以一塔或數塔之反應塔進行。 氫化脫硫處理所使用之觸媒，可使用通常之重質油用 之氫化脫硫觸媒，可列舉於氧化鋁、二氧化矽、二氧化 石夕-氧化銘、沸石或其混合物之載體等，擔持屬於周期表 -15- 200920835 第5、6、8、9及10族之金屬中選出至少一種所得之觸媒 。載體之平均細孔徑爲8nm以上爲佳，且擔持金屬量爲以 氫化脫硫觸媒全量爲基礎，以氧化物爲3〜3 0質量％爲佳。 氫化脫金屬處理之較佳的反應條件爲反應溫度 300 〜450 〇C、更佳爲 330~430 〇C，氫分壓 5~25MPa(G)、 更佳爲10〜20MPa(G)，氫/油比2 0 0〜2，0 0 0 N m3/k 1、更佳 爲 5 00~l，000Nm3/kl、LHSV (液時空間速度）0.1 〜2011Γ-1 、更佳爲0.2〜2111-1。反應溫度、氫分壓、氫/油比若低於 上述範圍，則反應效率易降低，若超過上述範圍，則經濟 性易降低。又，LHSV若低於上述範圍，則經濟性易降低 ，若超過上述範圍，則反應效率易降低。 上述氫化分解處理通常爲於氫化脫金屬處理等之氫化 處理後進行。因此，於必須控制反應溫度之情形中，經由 熱交換器、氫氣急冷和油急冷控制反應溫度爲佳。氫化分 解處理爲以一塔或數塔之反應塔進行。 氫化分解處理所使用之觸媒，以含鐵銘矽酸鹽與氧化 鋁混合之載體，擔持作爲氫化活性金屬之屬於周期表第6 、8、9及10族之金屬中選出至少一種爲佳。屬於周期表 第6族之金屬以鎢、鉬爲佳。組合數種金屬時，由氫化活 性高，且劣化少之方面而言，以鎳-鉬、鈷-鉬、鎳-鎢、 鎳-鈷-鉬之組合爲適當。 氫化分解處理之較佳的反應條件爲反應溫度3 0 0〜4 5 0 °C、更佳爲380〜4 20 °C，氫分壓5〜25MPa(G)、更佳爲 10〜20MPa ( G )，氫 / 油比 200〜2，000Nm3/kl、更佳爲 -16- 200920835 500~l，000Nm3/kl、LHSV (液時空間速度）0.〗〜20hr 1、更 佳爲0.2〜21^-1。反應溫度、氫分壓、氫/油比若低於上述 範圍，則反應效率易降低，若超過上述範圍’則經濟性易 降低。又，L H S V若低於上述範圍’則經濟性易降低’右 超過上述範圍，則反應效率易降低。 上述氫化脫氮處理爲在氫化分解處理減壓輕油時’於 其前進行爲佳，且以一塔或數塔之反應塔進行。氮化脫氮 處理可應用先前公知之方法，例如可使用特開2003_ 049 1 7 5號記載之方法。 於上述氫化脫芳香族處理中，由實施前述氫化精製處 理之精製油中，於取得潤滑油基材之目的下，以一塔或數 塔之反應塔進行。氫化脫芳香族處理之較佳的反應條件爲 反應溫度 300〜45 0 °C 、更佳爲 3 80〜420 °C ’氫分壓 10〜25MPa ( G )、更佳爲 1 5 ~2 3 MP a ( G )，氫 /油比 200〜2,000Nm3/kl、L H S V (液時空間速度）〇 · 1 〜2 0 h r _1、更 佳爲0.2〜Zhr·1。反應溫度、氫分壓、氫/油比若低於上述 範圍，則反應效率易降低，若超過上述範圍，則經濟性易 降低。又，LHSV若低於上述範圍，則經濟性易降低，若 超過上述範圍，則反應效率易降低。 上述氫化精製處理之油爲根據常法導入分離步驟，並 且以複數之分離槽處理，分離成氣體部分和液體部分。其 中’氣體部分爲在除去硫化氣、氨等進彳了提局氮純度之處 理等之後，與新供給的氣體共同於反應步驟中再循環。分 離步驟所得之液體部分被導入稱爲汽提器的常壓分離塔， -17- 200920835 除去脫硫處理所附隨的硫化氫，並由精製油中分離出輕質 的餾分。 圖1〜圖4中示出使用本發明之烴油之氫化精製方法例 。圖1爲示出於常壓渣油和減壓渣油之直接脫硫裝置中， 混合通過輕質烴油的方法（方法1 )。圖2爲示出方法i 之精製方法中，將輕質烴油進一步使用作爲急冷油的方法 (方法2)。圖3爲示出於常壓渣油和減壓渣油之氫化分 解裝置中，混合通過輕質烴油的方法（方法3 )。圖4爲 不出於減壓渣油之氫化分解裝置中，混合通過輕質烴油的 方法（方法4)。此處’並不需要底部循環油。該方法若 除去氫化分解步驟，則就其原樣可應用於減壓輕油脫硫裝 置，所謂之間接脫硫裝置中混合通過輕質烴油的案例。 實施例 根據實施例進一步具體說明本發明，但本發明並非被 此些例所限定。 使用作爲原料油之重質烴油的性狀示於表1，其他烴 油（混合用油）的性狀示於表2及表3。另外，表中之測 定値爲根據下述之測定法求出。 (表1及表2 ) 密度：JIS K2249 硫分：JIS K2 5 4 1 氮分：JIS K2609 -18- 200920835 鈀分： JPI 5S-10 ， 11 鎳分： JPI 5S-10 ， 11 殘留碳分：JIS K2270 動黏度 ：JIS K2283 (表3 ) 比重： ASTM D2598 動黏度 ：JIS K2283 蒸氣壓 [表1] ：ASTM D1267 第1表 重質烴油A 重質烴油B 重質烴油c Arabian Hebe 常壓渣油 Arabian Hebe 減壓輕油 Arabian Hebe 減壓輕油 密度 (g/ml) 0.9873 0.9171 1.0409 硫分 (wt%) 4.41 2.94 5.54 氮分 (wtppm) 2500 740 3760 鈀分 (wtppm) 84 0.5 152 鎳分 (wtppm) 27 0·5> 50 正庚烷不溶解部分（wt%) 7.89 - - 殘留碳分 (wt%) 14.1 0.33 25.2 IBP 340 348 479 5% 362 360 527 10% 380 370 548 20% 418 388 576 30X 457 406 601 蒸餾性狀（°c) 40X 499 425 630 50% 543 442 661 60% 589 460 688 70% 648 478 - 80% - 498 - 90% - 522 - -19- 200920835 [表2] 第2表 混合用油A 混合用油B 混合用油c 混合用油D 混合用油Ε Arabian Hebe 直餾燈油 Arabian Hebe 直餾輕質輕油 Arabian Hebe 脫硫輕油 R-FCC裝置 輕質循環油 Delad 焦化裝置 焦化輕油 密度 0.7922 0.8554 0.8339 0.9370 0.8496 硫分 (wtppm) 2410 13000 10 22000 22300 氮分 (wtppm) 1> 120 1> 830 440 動黏度 (mm Vs、30¾) 1.358 6.393 4.858 4.377 4.618 1環芳香族 （voiw 16.7 14 16.9 21.2 19 2環芳香族 （v〇m) 0.9 9.7 2 38.1 22 3環芳香族 （v〇W 0.1> 2.5 0.1 11.5 4 IBP 125 200 138 203 125 5% 160 247 215 234 160 10% 167 265 238 243 175 20% 176 281 262 256 198 30S 185 293 279 264 218 40% 195 304 290 273 236 50X 201 313 300 2B4 262 蒸餾性狀(¾) 60K 210 323 311 297 267 70% 218 334 322 311 283 80% 224 346 336 328 29θ BG% 234 363 354 34β 314 95% 238 37Θ 370 362 323 97% 240 380 376 365 330 EP 248 385 380 370 354 〔表3〕 第3表 混合用油F 直餾正丁烷 比重 (60/60F) 0.5847 動黏度 (mm2/s、20。〇 0.299 蒸氣壓 (kg/cm2 ' 37.8°〇 3.9 平均分子量 — 58 氫化精製處理所使用之觸媒性狀示於表4 °另外’氫 化脫硫觸媒（觸媒B )之氧化鋁-B 〇 r i a載體及氫化分解觸 媒（觸媒C )之含鐵蒸烘沸石爲分別根據特開平06_ 3 1 9 9 9 4號公報之實施例1、特開平0 2 - 2 8 9 4 1 9號公報之實 施例1調製。 -20- 200920835System Incorporate Process Simulator) is a specific case. (1) The mixer is selected by the PFD step unit and the irrigator downstream thereof 〇 (2) Hydrogen is selected at the inlet fluid of the mixer, and the supply rate of hydrogen is input. (3) The petroleum inlet of the other type of the mixer is selected, and the supply rate of the heavy hydrocarbon oil to be supplied, the density (g/cm3) of the heavy hydrocarbon oil, and the distillation property are input. (4) Enter the temperature and pressure of the separation conditions of the flusher. (5) From the general formula, SRK type (SRK01) is selected as the thermodynamic data for use. [SRK type is one of the most standard thermodynamics used in the step simulator of the petroleum refining field] (6) According to the calculation of the use step simulator, the hydrogen mass flow rate of the liquid phase portion of the flusher outlet is repeatedly divided by the flusher The total mass flow rate of the liquid phase portion was exported, and the hydrogen content (wt%) was determined. Thus, the hydrogen dissolution concentration of the liquid phase at the inlet of the reaction column when the heavy hydrocarbon oil is supplied alone can be derived. In the same manner as described above, 'the inlet fluid of the mixer of (3)' is divided by -12-200920835, and the heavy hydrocarbon oil is added, and the supply speed of the input light hydrocarbon oil, the density of the light hydrocarbon oil, and the distillation property are performed. Calculation. By comparison, it is possible to grasp the change in the hydrogen dissolution concentration in the liquid phase portion in the reaction column when the light hydrocarbon oil is supplied under a certain condition. The above is the calculation method of the inlet of the reaction tower. The reaction tower outlet is the composition and speed of (2) off-gas when the reaction is actually carried out, and (3) the density and distillation property of the refined oil and the recovery rate of the refined oil. Other thermodynamic formulas include the PR type and the GS type. When the type 3 is compared, the ratio of the hydrogen concentration of the liquid phase in the case of mixing with a light oil exhibits the same tendency. Further, when the composition of the outlet of the reaction column is unknown, it can be estimated only by the inlet conditions of the reaction column. Further, by using the above-described step simulator, the optimum mixing ratio of the heavy hydrocarbon oil and the hydrocarbon oil having the effect of increasing the hydrogen dissolution concentration can be estimated. Further, by determining the reaction conditions based on the effect of increasing the hydrogen dissolution concentration, the reaction can be easily controlled to save energy in the hydrorefining reaction. Hereinafter, the hydrorefining treatment of the hydrocarbon oil will be specifically described. In the hydrogenation treatment of the present invention, hydrogen is mixed in the feedstock oil (hydrocarbon oil) before passing through the oil in the reaction column for hydrorefining. Preferably, the heavy hydrocarbon oil is mixed with a hydrocarbon oil having a effect of increasing the hydrogen dissolution concentration, such as a light hydrocarbon oil, and after the feedstock oil is formed, the feedstock oil is pressurized and hydrogen is mixed in the heat of the heat exchanger, and then The raw material oil of the mixed high-pressure hydrogen is heated to a reaction temperature in a heating furnace, and the reaction tower is ruthenium. If the nitrogen is mixed before the pressure-up and heat exchange steps of the feedstock, it is necessary to increase the pressure and heat exchange in the gas-liquid mixed phase, which tends to lower the pressure increase and the %@ rate. Further, if the raw material oil is mixed with hydrogen after passing through the heating furnace, there is a possibility that the hydrogen dissolution time is insufficient. -13- 200920835 The conditions of the hydrorefining may, for example, be 'reaction temperature hydrogen partial pressure 5.1 to 25.3 MPa (G), hydrogen/oil ratio 200-LHSVO.05^10111^1, and reaction temperature 3 3 0 to 430 10.1 to 20.3 MPa (G), hydrogen/oil ratio 500 ~ LHS VO. 1 ~1 .Ohr·1. The hydrotreating treatment may be a hydrodemetallization treatment, a hydrodecomposition treatment, a hydrodenitrogenation treatment or a hydrogenation, and the method of the present invention is not particularly limited and may be applied to the above hydrogen or in two or more hydrogenation treatments. In the case of the hydrotreatment, the order is not particularly limited, but it is preferably the most metal treatment. Usually, the hydrodemetallization treatment, the hydrodecomposition treatment, and the like are first carried out, and finally, the treatment is carried out. Further, after the hydrodesulfurization treatment is carried out according to the purpose, it may be subjected to decomposition treatment or the like. Further, in the hydrogenation treatment, the type of the apparatus is not particularly limited, and for example, a solid, a fluidized bed, a fluidized bed, a slurry bed or the like can be used. Further, the hydrocarbon oil having a degree of effect is supplied to the above-mentioned hydrodemetallization treatment in a quenching oil type in a reaction column, and the mixed hydrogen is heated, and then it is carried out in a reaction column of one column or several columns. The catalyst used in the hydrodemetallization treatment is a carrier of a porous inorganic mineral such as oxidation, cerium oxide-alumina or zeolite, and is active in at least one of the active metals belonging to the eighth and ninth periodic tables, and It is preferred that at least one of the promoter metals is selected in the periodic table. The above-mentioned activities of 300~450〇C, -20 00Nm3/kl, t, hydrogen partial pressure of 1 000Nm3/kl, and the use of hydrogenation, desulfurization and dearomatization treatment, continue the above-mentioned hydrogenation treatment, and then hydrogenation In the desulfurization step, the reaction is carried out in a single step, and the moving bed is increased in hydrogen concentration. The content of the metal in the metal of the 6-group metal of the raw material hydrocarbon oil, the oxidized sand oxide, and the natural lanthanide metal is -14 - 200920835. The metal oxide type is preferably based on the total amount of the hydrogenation demetallization catalyst. 2 to 8 mass%, more preferably 2 to 4 mass%, the content of the above-mentioned promoter metal is based on the total amount of the hydrogenation demetallization catalyst, and the metal oxide type is preferably 0.5 to 5% by mass, more preferably It is 1 to 5 mass%. Specifically, as the active metal, the metals belonging to Groups 8, 9 and 10 of the periodic table are preferably nickel, cobalt and rhenium, and the metal belonging to Group 6 of the periodic table as the promoter is preferably molybdenum and tungsten. . The amount of the hydrodemetallization catalyst is any amount depending on the metal concentration in the raw material hydrocarbon oil, but it is preferably used in an amount of from 1 〇 to 50% by volume based on the total amount of the catalyst used in the entire treatment step. The preferred reaction conditions for the hydrodemetallization treatment are a reaction temperature of 300 to 45 ° C, more preferably 3 3 0 to 43 ° C, a hydrogen partial pressure of 5 to 25 MPa (G), more preferably 10 to 20 MPa ( G), hydrogen/oil ratio 200~2,000Nm3/kl, more preferably 50O~l, OOONm3/kl, LHSV (liquid space velocity) 0 · 1 ~ 2 0 hr-1, more preferably 0.2~2hr-1 . When the hydrogen partial pressure and the hydrogen/oil ratio are less than the above range, the reaction efficiency is liable to lower, and if it exceeds the above range, the economical efficiency is liable to lower. Further, when the LHSV is less than the above range, the economic efficiency is liable to lower, and if it exceeds the above range, the reaction efficiency is liable to lower. The above hydrodesulfurization treatment is usually carried out after hydrogenation treatment such as hydrodemetallization treatment. Therefore, it is preferred to control the reaction temperature via a heat exchanger, hydrogen quenching, and oil quenching in the case where the reaction temperature must be controlled. The hydrodesulfurization treatment is carried out in a reaction column of one column or several columns. The catalyst used in the hydrodesulfurization treatment may be a hydrogenation desulfurization catalyst for a conventional heavy oil, and may be exemplified by alumina, cerium oxide, cerium oxide, cerium oxide or a mixture thereof. At least one of the metals obtained from Groups 5, 6, 8, 9 and 10 of the Periodic Table -15-200920835 is selected. The average pore diameter of the carrier is preferably 8 nm or more, and the amount of the supported metal is preferably from 3 to 30% by mass based on the total amount of the hydrogenation desulfurization catalyst. The preferred reaction conditions for the hydrodemetallization treatment are a reaction temperature of 300 to 450 〇C, more preferably 330 to 430 〇C, a hydrogen partial pressure of 5 to 25 MPa (G), more preferably 10 to 20 MPa (G), and hydrogen/ Oil ratio 2 0 0~2, 0 0 0 N m3/k 1, more preferably 5 00~l,000Nm3/kl, LHSV (liquid hourly space velocity) 0.1 to 2011Γ-1, more preferably 0.2~2111-1 . When the reaction temperature, the hydrogen partial pressure, and the hydrogen/oil ratio are less than the above range, the reaction efficiency is liable to lower, and if it exceeds the above range, the economy is liable to lower. Further, when the LHSV is less than the above range, the economic efficiency is liable to lower, and if it exceeds the above range, the reaction efficiency is liable to lower. The above hydrogenation decomposition treatment is usually carried out after a hydrogenation treatment such as a hydrodemetallization treatment. Therefore, in the case where the reaction temperature must be controlled, it is preferred to control the reaction temperature via a heat exchanger, hydrogen quenching, and oil quenching. The hydrogenation decomposition treatment is carried out in a reaction column of one column or several columns. The catalyst used in the hydrocracking treatment is preferably a carrier containing iron sulphate and alumina, and at least one selected from the group consisting of metals belonging to Groups 6, 8, 9 and 10 of the periodic table as the hydrogenation-active metal. . The metals belonging to Group 6 of the periodic table are preferably tungsten or molybdenum. When a plurality of metals are combined, a combination of nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, and nickel-cobalt-molybdenum is suitable in view of high hydrogenation activity and little deterioration. The preferred reaction conditions for the hydrocracking treatment are a reaction temperature of from 300 to 4,500 ° C, more preferably from 380 to 4, 20 ° C, and a partial pressure of hydrogen of from 5 to 25 MPa (G), more preferably from 10 to 20 MPa (G). ), hydrogen/oil ratio 200~2,000Nm3/kl, more preferably -16-200920835 500~l,000Nm3/kl, LHSV (liquid hour space velocity) 0. 〗 〜 20hr 1, more preferably 0.2~21^ -1. When the reaction temperature, the hydrogen partial pressure, and the hydrogen/oil ratio are less than the above range, the reaction efficiency is liable to lower, and if it exceeds the above range, the economical efficiency is liable to lower. Further, if L H S V is less than the above range, the economical efficiency is liable to decrease. When the right is outside the above range, the reaction efficiency is liable to lower. The above hydrodenitrogenation treatment is carried out in the case of hydrogenation decomposition treatment of decompressed light oil, and is carried out in a reaction tower of one column or several columns. The nitriding and denitrification treatment can be carried out by a conventionally known method, and for example, the method described in JP-A-2003-049 175 can be used. In the above-described hydrodearomatization treatment, the purified oil subjected to the above-described hydrorefining treatment is carried out in the reaction column of one column or several columns for the purpose of obtaining a lubricating oil base material. The preferred reaction conditions for the hydrodearomatization treatment are a reaction temperature of 300 to 45 ° C, more preferably 380 to 420 ° C, a hydrogen partial pressure of 10 to 25 MPa (G), more preferably 15 to 2 3 MP. a ( G ), hydrogen/oil ratio 200 to 2,000 Nm 3 /kl, LHSV (liquid hour space velocity) 〇·1 to 2 0 hr _1, more preferably 0.2 to Zhr·1. When the reaction temperature, the hydrogen partial pressure, and the hydrogen/oil ratio are less than the above range, the reaction efficiency is liable to lower, and if it exceeds the above range, the economical efficiency is liable to lower. Further, when the LHSV is less than the above range, the economic efficiency is liable to lower, and if it exceeds the above range, the reaction efficiency is liable to lower. The oil for the hydrorefining treatment is introduced into a separation step according to a usual method, and is treated in a plurality of separation tanks to be separated into a gas portion and a liquid portion. The 'gas portion' is recycled in the reaction step together with the newly supplied gas after removing the sulfide gas, ammonia, etc., and extracting the nitrogen purity. The liquid portion obtained in the separation step is introduced into an atmospheric separation column called a stripper, -17-200920835, and the hydrogen sulfide attached to the desulfurization treatment is removed, and the light fraction is separated from the refined oil. An example of a hydrotreating method using the hydrocarbon oil of the present invention is shown in Figs. 1 to 4 . Fig. 1 is a view showing a method of mixing light hydrocarbon oil in a direct desulfurization apparatus for atmospheric residue and vacuum residue (method 1). Fig. 2 is a view showing a method of further using a light hydrocarbon oil as a quenching oil in the method of purifying the method i (method 2). Fig. 3 is a view showing a method of mixing light hydrocarbon oil in a hydrogenation decomposition apparatus of an atmospheric residue and a vacuum residue (method 3). Fig. 4 is a method of mixing light hydrocarbon oil (method 4) in a hydrogenation decomposition apparatus which is not used for vacuum residue. Here, the bottom circulation oil is not required. If the method removes the hydrocracking step, it can be applied to the decompressed light oil desulfurization apparatus as it is, and the case where the interfacial desulfurization apparatus is mixed with the light hydrocarbon oil. EXAMPLES The present invention will be further specifically described based on examples, but the present invention is not limited by such examples. The properties of the heavy hydrocarbon oil used as the stock oil are shown in Table 1, and the properties of the other hydrocarbon oils (mixed oil) are shown in Table 2 and Table 3. In addition, the measurement enthalpy in the table is obtained by the following measurement method. (Tables 1 and 2) Density: JIS K2249 Sulfur: JIS K2 5 4 1 Nitrogen: JIS K2609 -18- 200920835 Palladium: JPI 5S-10 , 11 Nickel: JPI 5S-10 , 11 Residual carbon: JIS K2270 Dynamic viscosity: JIS K2283 (Table 3) Specific gravity: ASTM D2598 Dynamic viscosity: JIS K2283 Vapor pressure [Table 1]: ASTM D1267 Table 1 Heavy hydrocarbon oil A Heavy hydrocarbon oil B Heavy hydrocarbon oil c Arabian Hebe Arabian Hebe Vacuum Light Oil Arabian Hebe Vacuum Light Oil Density (g/ml) 0.9873 0.9171 1.0409 Sulfur (wt%) 4.41 2.94 5.54 Nitrogen (wtppm) 2500 740 3760 Palladium (wtppm) 84 0.5 152 Nickel Minutes (wtppm) 27 0·5> 50 n-heptane insoluble fraction (wt%) 7.89 - - residual carbon (wt%) 14.1 0.33 25.2 IBP 340 348 479 5% 362 360 527 10% 380 370 548 20% 418 388 576 30X 457 406 601 Distillation (°c) 40X 499 425 630 50% 543 442 661 60% 589 460 688 70% 648 478 - 80% - 498 - 90% - 522 - -19- 200920835 [Table 2] 2 mixing oil A mixing oil B mixing oil c mixing oil D mixing oil Ε Arabian Hebe straightening lamp oil Arabian Hebe straight light weight Light oil Arabian Hebe desulfurized light oil R-FCC unit Light cycle oil Delad coking unit Coking light oil density 0.7922 0.8554 0.8339 0.9370 0.8496 Sulfur content (wtppm) 2410 13000 10 22000 22300 Nitrogen (wtppm) 1> 120 1> 830 440 Dynamic viscosity (mm Vs, 303⁄4) 1.358 6.393 4.858 4.377 4.618 1 ring aromatic (voiw 16.7 14 16.9 21.2 19 2 ring aromatic (v〇m) 0.9 9.7 2 38.1 22 3 ring aromatic (v〇W 0.1> 2.5 0.1 11.5 4 IBP 125 200 138 203 125 5% 160 247 215 234 160 10% 167 265 238 243 175 20% 176 281 262 256 198 30S 185 293 279 264 218 40% 195 304 290 273 236 50X 201 313 300 2B4 262 Distillation Attributes (3⁄4) 60K 210 323 311 297 267 70% 218 334 322 311 283 80% 224 346 336 328 29θ BG% 234 363 354 34β 314 95% 238 37Θ 370 362 323 97% 240 380 376 365 330 EP 248 385 380 370 354 [Table 3] Table 3 Mixture Oil F Straight-run n-butane specific gravity (60/60F) 0.5847 Dynamic viscosity (mm2/s, 20. 〇0.299 Vapour pressure (kg/cm2 '37.8°〇3.9 Average molecular weight—58 The catalytic properties used in the hydrotreating treatment are shown in Table 4 ° Additional 'Hydrogenation Desulfurization Catalyst (Catalyst B) Alumina-B 〇ria The iron-containing steam-dried zeolite of the carrier and the hydrogenation-decomposing catalyst (catalyst C) is disclosed in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. Example 1 Modulation -20- 200920835
第4表 觸媒A 觸媒B 觸媒C 氫化脫金屬觸媒 氫化脫硫觸媒 氫化分解觸媒 擔體 氧化鋁 100 90 35 (Wt%對擔體） Boria — 10 含鐵鋁矽酸鹽 — 65 活性金屬 氧化鎳 2.3 一 (Wt0/o對觸媒） 氧化鉬 8.3 14 10 氧化鈷 — 3.7 4 比表面積(m2/g) 143 228 445 物性 細孔容積(ml/g) 0.76 0.71 0.62 平均細孔徑(A) 190 124 -—'— , 158 〔實施例1〕 如表5所示般’將觸媒A25毫升和觸媒B75毫升以此 順序充塡至反應管並進行氫化精製反應。於該反應中，將 表1所示之Arabian Hebe常壓渣油（重質烴油A )以 LHSV0.21h 供給，问時供給表2所不之Arabian Hebe直 餾燈油（混合用油A)，並將全體的LHSV調整至0.315 1Γ1。又，氫分壓 13_2MPa(G)，氫 / 油比 800Nm3/kl、反 應溫度爲維持3 8 (TC。另外，氫爲在該反應溫度升溫後， 於反應管中通過油之前的階段中混合。通過油1 5 〇 〇小時 令活性安定後，取得精製油。將此精製油以1 5段蒸餾裝 置根據 ASTM D2892-84所規定之方法予以分餾，取得各 餾分。精製油中之沸點3 43。(：以上之常壓渣油（以343 °C + 餾分表示）中的分解率、硫分、金屬分示於表5° -21 - 200920835 〔實施例2〜10〕 除了將使用之原料油及反應條件如表5記載般變更以 外，同實施例1進行氫化精製處理。另外，於實施例1 〇 中，反應溫度於氫化脫金屬區和氫化脫硫區調整爲3 80 °C ，於氫化分解區調整爲400 °C。 〔比較例1〜5〕 除了將使用之烴油及反應條件如表6記載般變更以外 ，同實施例1進行氫化精製處理。另外，於比較例5中， 反應溫度於氫化脫金屬區和氫化脫硫區調整爲3 8 0 °C，於 氫化分解區調整爲400°C。 -22- 200920835 實施例 1 ο < m E E E U> Ο N M TO寸 < om 3B0 (400) 132 | i 0.2S7 I 72.6 0^00 46.$ 1 26.2 | 79.4 18.2 0.113 0.172 0.143 [ 〇> m οι A25ml B75ml 380 13^ 800 0.287 72Λ I 0.209 Ll6.5 ais 0_1> 93.5 1013 0.175 0.187 0.181 CO o IS in in n h» <0 380 13.2 1 0.315 66.2 0^09 CO CD 1.00 36.0 B1‘9 0.087 | 0.175 | 0.131 卜 < UJ A25ml B75ml ο St 13.2 800 0.305 68.4 0.209 16.5 0.40 1 31<9 909 475 0.113 | 0.168 0.141 €〇 < a A25ml 1 B75ml s to 13.2 § 0.297 70.2 丨 0.200 I 16.5 9 d 31.9 | 90.9 | 412 1 1 0.115 | 0.16β | 0.141 to < o A25ml B75mt s n \Z2 i | 0.296 | 70.4 0·20β 16.4 3 32Λ Ί Θ0.8 \ | 46.7 1 0.114 | 0.167 0.140 < m u> u> C4 N <{D o s m 1 | 0^19 | 47.9 0·209 1 2ΜΊ 0.30 eo | 93^ 1 | 65.B 1 0.157 | OJ229 1 0.193 CO < m A25ml B75ml s c〇 l 13^Ί 800 0.364 57·3 | 0.209 | 18.2 a35 5 ea | 92.1 | 55.1 0.130 αΐ95 αιβ3 «Μ < ο A25ml B75ml 〇 13^ i | 0Λ87 I 72.6 0.209 10.4 a4〇 31.6 1 91.0 「47.8 1 0.113 Γ〇.172 1 0.143 一 < < A25ml B75m) o s 13J2 1 | a3i5 | 9β·2 0209 16.5 0.38 30.0 91^ 4Θ.6 0.108 0.186 0.147 重質油 混合用油 觸媒 JJ踔 m 1=^ 氫分屋（MP·。） S "Ϊ a m \ X 原料油全體之LHSV (hr-，〉 原料油中之343°C+餾分含量（ν<Λ> 343°C/+餾分之LHSV (hr·1) ! 分解率（容量基準％) 硫分（wt94) 金屬分(V+Nl) (wtppm) | 脫硫率（Wt96) s Η U 轵 m 1w/l 腾 m μ m 渥 I 反應塔入口液相中之氫含量（Wt%) I _ •Ν 廿 紫 □ S 珑 m η 氫含量(入口與出□平均値）（w«6> 1 g Ϊ S 反應條件 φ 班键 1ι 以Pro/II之計算値 -23- 200920835 §m 比較例 m < 1 A2Sml C33ml B42ml 380 (400) 13.2 i 0210 99.3 0.209 42.1 1.08 32.0 75.5 14.6 0.090 0.143 0.117 ffi 1 ΈΈ \〇 IO M卜 <ω ο 00 co | 135 1 0.209 100.0 0.209 15.0 0.22 0.1> 92.5 1 87.7 0.152 0.164 0.158 CO 〇 1 EE U) 10 CM N 1 ί 380 1_ 13.2 i 0.209 100.0 I 0^09 | s CM CO 75.0 广 1 0.060 0.061 0.061 CM < U. A25ml B75ml 380 ι_ \Z2 i 0.315 66.2 0209 14.0 0.50 39.0 88.7 37.1 1 0.087 0.138 | 0.113 - < 1 U> 10 <m r i 380 1 1_ 13.2 i 0.210 99.3 0209 14.4 0.48 38.1 89.1 38.8 0.090 0.142 0.116 重質油 混合用油 觸媒 gs m 氫分壓（MPeG) "e 5 £. 思 \ 原料油全體之LHSV (hr*') 原料油中之343°C+餾分含量（voHO 343°C+餾分之LHSV (hr一，） 分解率(容量基準％) 硫分（wt%) 1 _-___1 金屬分(V+Ni) (wtppm) 脫硫率（wt%) 脫硫反應速度定數(二次反應）（hr—) 反應塔入α液相中之氫含量（wt%) 反應塔出口液相中之氫含量（wt%) 氫含量(入口與出口平均値）（Wt%〉 ί Ά e Ξ 1 s 反應條件 iif hioO 以Pro/II之計算値 -24- 200920835 表5及表6中所謂343 °C +餾分之LHSV，爲於實驗中 於原料油之液空時速度（LHSV)相乘以原料油中之343 °C +餾分的容量基準含量，表示供給至反應塔之343它+餾分 的實質LHSV。又，本發明並非單純根據稀釋效果令氫化 精製處理效率化，而爲根據增加氫溶解濃度之效果以圖謀 重質油餾分之氫化精製處理的效率化，故在評價中，注目 精製油中之沸點爲343 °C以上之餾分所含的硫分等。3 43 °C +餾分的脫硫率爲根據下列計算式求出。 3 43 t +餾分的脫硫率（％ )4th catalyst A catalyst B catalyst C hydrogenation demetallization catalyst hydrogenation desulfurization catalyst hydrogenation decomposition catalyst carrier alumina 100 90 35 (Wt% to support) Boria — 10 65 Active metal nickel oxide 2.3 I (Wt0/o to catalyst) Molybdenum oxide 8.3 14 10 Cobalt oxide - 3.7 4 Specific surface area (m2/g) 143 228 445 Physical pore volume (ml/g) 0.76 0.71 0.62 Average pore diameter (A) 190 124 - - '-, 158 [Example 1] As shown in Table 5, 25 ml of a catalyst A and 75 ml of a catalyst B were charged in this order to a reaction tube to carry out a hydrorefining reaction. In this reaction, the Arabian Hebe atmospheric residue (heavy hydrocarbon oil A) shown in Table 1 was supplied at LHSV0.21h, and when supplied, the Arabian Hebe straight-run lamp oil (mixing oil A) of Table 2 was supplied. And adjust the overall LHSV to 0.315 1Γ1. Further, the hydrogen partial pressure is 13-2 MPa (G), the hydrogen/oil ratio is 800 Nm 3 /kl, and the reaction temperature is maintained at 3 8 (TC. Further, hydrogen is mixed at a stage before the oil is passed through the reaction tube after the temperature is raised at the reaction temperature. After the oil was stabilized by the oil for 15 hours, the refined oil was obtained, and the refined oil was fractionally distilled in a 15 minute distillation apparatus according to the method specified in ASTM D2892-84 to obtain each fraction. The boiling point of the refined oil was 3 43 . (The decomposition rate, sulfur content, and metal content in the above atmospheric residue (expressed as 343 ° C + fraction) are shown in Table 5 ° -21 - 200920835 [Examples 2 to 10] except the raw material oil to be used and The reaction conditions were changed as described in Table 5, and the hydrotreating treatment was carried out in the same manner as in Example 1. Further, in Example 1, the reaction temperature was adjusted to 3 80 ° C in the hydrodemetallization zone and the hydrodesulfurization zone, and hydrogenation decomposition was carried out. The area was adjusted to 400 ° C. [Comparative Examples 1 to 5] Hydrogenation purification treatment was carried out in the same manner as in Example 1 except that the hydrocarbon oil to be used and the reaction conditions were changed as described in Table 6. Further, in Comparative Example 5, the reaction temperature was In the hydrodemetallization zone and the hydrodesulfurization zone The whole is 380 ° C, and is adjusted to 400 ° C in the hydrogenation decomposition zone. -22- 200920835 Example 1 ο < m EEE U> Ο NM TO inch < om 3B0 (400) 132 | i 0.2S7 I 72.6 0^00 46.$ 1 26.2 | 79.4 18.2 0.113 0.172 0.143 [ 〇> m οι A25ml B75ml 380 13^ 800 0.287 72Λ I 0.209 Ll6.5 ais 0_1> 93.5 1013 0.175 0.187 0.181 CO o IS in in nh» < 0 380 13.2 1 0.315 66.2 0^09 CO CD 1.00 36.0 B1'9 0.087 | 0.175 | 0.131 卜<UJ A25ml B75ml ο St 13.2 800 0.305 68.4 0.209 16.5 0.40 1 31<9 909 475 0.113 | 0.168 0.141 €〇< a A25ml 1 B75ml s to 13.2 § 0.297 70.2 丨0.200 I 16.5 9 d 31.9 | 90.9 | 412 1 1 0.115 | 0.16β | 0.141 to < o A25ml B75mt sn \Z2 i | 0.296 | 70.4 0·20β 16.4 3 32Λ Ί Θ0.8 \ | 46.7 1 0.114 | 0.167 0.140 < m u>u> C4 N <{D osm 1 | 0^19 | 47.9 0·209 1 2ΜΊ 0.30 eo | 93^ 1 | 65.B 1 0.157 | OJ229 1 0.193 CO < m A25ml B75ml sc〇l 13^Ί 800 0.364 57·3 | 0.209 | 18.2 a35 5 ea | 92.1 | 55.1 0.130 αΐ95 αιβ3 «Μ < ο A25ml B75ml 〇13^ i | 0Λ87 I 72.6 0.209 10.4 a4〇31.6 1 91.0 "47.8 1 0.113 Γ〇.172 1 0.143 a << A25ml B75m) os 13J2 1 | a3i5 | 9β·2 0209 16.5 0.38 30.0 91^ 4Θ. 6 0.108 0.186 0.147 Heavy oil mixed oil catalyst JJ踔m 1=^ Hydrogen partition (MP·. ) S "Ϊ am \ X LHSV of the whole stock oil (hr-,〉 343 °C + fraction content in the stock oil (ν <Λ> 343 °C / + LHSV of the fraction (hr·1) ! Decomposition rate (capacity Base %) Sulfur (wt94) Metals (V+Nl) (wtppm) | Desulfurization rate (Wt96) s Η U 轵m 1w/l 腾 m μ m 渥I Hydrogen content in the liquid phase of the inlet of the reaction column (Wt %) I _ •Ν 廿紫□ S 珑m η Hydrogen content (inlet and out 値 average 値) (w«6> 1 g Ϊ S Reaction condition φ Ban key 1ι Calculated by Pro/II 値-23- 200920835 § m Comparative Example m < 1 A2Sml C33ml B42ml 380 (400) 13.2 i 0210 99.3 0.209 42.1 1.08 32.0 75.5 14.6 0.090 0.143 0.117 ffi 1 ΈΈ \〇IO M b<ω ο 00 co | 135 1 0.209 100.0 0.209 15.0 0.22 0.1 > 92.5 1 87.7 0.152 0.164 0.158 CO 〇1 EE U) 10 CM N 1 ί 380 1_ 13.2 i 0.209 100.0 I 0^09 | s CM CO 75.0 广 1 0.060 0.061 0.061 CM < U. A25ml B75ml 380 ι_ \Z2 i 0.315 66.2 0209 14.0 0.50 39.0 88.7 37.1 1 0.087 0.138 | 0.113 - < 1 U> 10 <mri 380 1 1_ 13.2 i 0.210 99.3 0209 14.4 0.48 38.1 89.1 38.8 0.090 0.142 0.1 16 Heavy oil mixed oil catalyst gs m Hydrogen partial pressure (MPeG) "e 5 £. Think \ Raw material oil LHSV (hr*') 343 ° C + fraction content in raw oil (voHO 343 ° C + fraction LHSV (hr a,) decomposition rate (capacity basis %) sulfur content (wt%) 1 _-___1 metal fraction (V+Ni) (wtppm) desulfurization rate (wt%) desulfurization reaction rate constant (secondary Reaction) (hr—) Hydrogen content of the reaction column in the α liquid phase (wt%) Hydrogen content in the liquid phase of the reaction column outlet (wt%) Hydrogen content (inlet and outlet average 値) (Wt%> ί Ά e Ξ 1 s Reaction conditions iif hioO Calculated by Pro/II 値-24- 200920835 The LHSV of the so-called 343 °C + fraction in Tables 5 and 6 is multiplied by the liquid hour velocity (LHSV) of the feedstock oil in the experiment. The capacity-based content of the 343 ° C + fraction in the feedstock oil indicates the substantial LHSV of the + fraction supplied to the reaction column. Further, the present invention does not reduce the efficiency of the hydrotreating treatment simply by the dilution effect, but also optimizes the efficiency of the hydrorefining treatment of the heavy oil fraction according to the effect of increasing the hydrogen dissolution concentration. Therefore, in the evaluation, the boiling point of the refined oil is noted. It is a sulfur content contained in a fraction of 343 ° C or higher. The desulfurization rate of the 3 43 ° C + fraction was determined according to the following calculation formula. Desulfurization rate of 3 43 t + fraction (%)
=(原料油3 43 °C+餾分的硫分-精製油3 43 °C+餾分的 硫分）/原料油343 °C+餾分的硫分xlOO 又，將脫硫反應假定爲反應次數2次，根據下式，求 出表觀的反應速度常數。 表觀的反應速度常數 =(343 °C +餾分的LHSV ) / (原料油3 43 °C +餾分的硫 分 ％/ 1 00 ) X ( 343 t： +餾分的脫硫率 ％/1〇〇 ) / ( 1-( 343 °C+餾分的脫硫率％/1〇〇)) 反應塔之入口與出口中的氣相、液相組成爲如前述， 使用 Pro/II ( ver6.0 1 ) ( Invensis System Incorporate 公司 製 Process Simulator)推算。 推算結果示於表5及表6。 -25- 200920835 U9 卜 〇· <0 〇 〇 1 1 1 1 S 1^; 00 1 〇' I 1 t 1 CO *·» S 卜 S CNJ 1 1 1 1 CSI to 5 κ CO IO 〇 - ο s o’ δ T-· <2 <0 ύ 〇 d 1 1 1 1 揭 IK 〇 5 d S S g lf> N ψ» 5 σ» S 5 m 5 r- 1 ΙΟ ΙΟ — CO 5 S ro ΙΟ S3 csi 卜 i «S rj S O Μ (〇 — «s rj Si csa ;· ΙΟ o 5 卜 s Ol 5i 7 寸 S 5 <〇. S 〇> 1 «D «R Ο jj CO 3 o' s o 5 ff οι 5 5 60 每 r«* S d δ R i (D 5 IA 〇 产 βο s □ a m □ K _ m -a- 装 按 截 1¾ § U η U « IfVI 撕 懺 1¾ m 3 •M 鹏 Μ m m m 谥 a hi 龌 寂 i 瑙 \ 辑 m 5 _ <f〇 相 仕 m U § U 丑 \ 闺 Κ S 截 η m in£l 脚 m 1¾ i 崧 \ m 闺 5 3 實施例及比較例之結果整理於表7。 -26 - 200920835 實施例1爲相比於比較例1，反應塔液相中之氫含量 爲更高28%。又，實際的LHSV爲1 .5倍，故無關於不利 之條件，提高343 °C+餾分的反應速度。因此，可達成更 有效率的氫化精製處理。又，由實施例與比較例之比’可 知反應塔液相中之氫含量爲與343 °C +餾分的反應速度相 關。又，同樣之傾向亦於實施例2〜10中察見。 另一方面，於使用不具有增加氫溶解濃度效果之直餾 正丁烷的比較例2中，無法進行有效率的氫化精製處理。 產業上之可利用性 若根據本發明，則提供於含有重質油之烴油的氫化精 製處理中，可提高重質油之氫化精製的效率，可達成精製 油之增產、高品質精製油之製造及氫化精製條件之溫和化 之烴油的氫化精製方法。根據該氫化精製方法則可圖謀原 油之精製處理全體中的省能量化。 【圖式簡單說明】 圖1爲實施本發明之步驟槪略圖之一。 圖2爲實施本發明之步驟槪略圖之一。 圖3爲實施本發明之步驟槪略圖之一。 圖4爲實施本發明之步驟槪略圖之一。 【主要元件符號說明】 1 :氫化脫金屬步驟 -27- 200920835 2 :氣化脫硫步驟 3 :分離精製步驟 4 :氫化分解步驟 5 :氫化脫氮步驟 6 :底油再循環 7 :氫再循環 8 -氣急冷 9 :油急冷 1 1 :重質烴油 1 2 =具有增加氫溶解濃度效果的烴油 13 :氫 1 4 :精製重質烴油 1 5 :精製輕質烴油 -28-= (raw oil 3 43 ° C + fraction of sulfur - refined oil 3 43 ° C + fraction of sulfur) / feedstock oil 343 ° C + fraction of sulfur x lOO Again, the desulfurization reaction is assumed to be the number of reactions 2 times, according to Formula, the apparent reaction rate constant is obtained. Apparent reaction rate constant = (343 °C + LHSV of the fraction) / (raw oil 3 43 °C + fraction of sulfur % / 1 00 ) X ( 343 t: desulfurization rate of the fraction % / 1 〇〇 / ( 1-( 343 °C + fraction desulfurization rate % / 1 〇〇)) The gas phase and liquid phase in the inlet and outlet of the reaction column are as described above, using Pro/II ( ver6.0 1 ) ( Invensis System Incorporate Process Simulator). The calculation results are shown in Tables 5 and 6. -25- 200920835 U9 〇··lt;0 〇〇1 1 1 1 S 1^; 00 1 〇' I 1 t 1 CO *·» S 卜 S CNJ 1 1 1 1 CSI to 5 κ CO IO 〇- ο s o' δ T-· <2 <0 ύ 〇d 1 1 1 1 IK 〇5 d SS g lf> N ψ» 5 σ» S 5 m 5 r- 1 ΙΟ ΙΟ — CO 5 S ro ΙΟ S3 csi 卜i «S rj SO Μ (〇— «s rj Si csa ;· ΙΟ o 5 卜 Ol 5i 7 inch S 5 <〇. S 〇> 1 «D «R Ο jj CO 3 o' so 5 ff οι 5 5 60 per r«* S d δ R i (D 5 IA ββο s □ am □ K _ m -a- 装 截 13⁄4 § U η U « IfVI 忏 13⁄4 m 3 •M 鹏Μ mmm 谥a hi 龌 i \ 辑 辑 辑 5 5 5 5 5 U U U U U U U in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in The results are summarized in Table 7. -26 - 200920835 Example 1 is that the hydrogen content in the liquid phase of the reaction column is 28% higher than that of Comparative Example 1. Further, the actual LHSV is 1.5 times, so there is no relevant Unfavorable conditions increase the reaction rate of the 343 ° C + fraction. Therefore, a more efficient hydrorefining treatment can be achieved. From the ratio of the example to the comparative example, it is understood that the hydrogen content in the liquid phase of the reaction column is related to the reaction rate of the 343 ° C + fraction. Further, the same tendency is also observed in Examples 2 to 10. In Comparative Example 2 using straight-run n-butane which does not have an effect of increasing the hydrogen solubility concentration, efficient hydrogenation purification treatment cannot be performed. Industrial Applicability According to the present invention, it is provided in a product containing heavy oil. In the hydrorefining treatment of the hydrocarbon oil, the efficiency of hydrogenation purification of the heavy oil can be improved, and a hydrogenation purification method of the hydrocarbon oil can be achieved by the production of the refined oil, the production of the high-quality refined oil, and the mildening of the hydrogenation purification conditions. The purification method can exemplify the energy saving in the whole process of refining the crude oil. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the steps of the present invention. Fig. 2 is a schematic diagram showing the steps of the present invention. One of the steps of the present invention is shown in the drawings. Fig. 4 is a schematic diagram showing the steps of the present invention. [Main component symbol description] 1 : Hydrogenation demetallization step -27- 200920835 2 : Gasification desulfurization step 3 : separation and purification step 4 : hydrogenation decomposition step 5 : hydrodenitrogenation step 6 : bottom oil recycle 7 : hydrogen recycle 8 - Air quenching 9 : Oil quenching 1 1 : Heavy hydrocarbon oil 1 2 = Hydrocarbon oil with effect of increasing hydrogen dissolved concentration 13 : Hydrogen 1 4 : Refined heavy hydrocarbon oil 1 5 : Refined light hydrocarbon oil -28-