JPH0547594B2 - - Google Patents
Info
- Publication number
- JPH0547594B2 JPH0547594B2 JP21621291A JP21621291A JPH0547594B2 JP H0547594 B2 JPH0547594 B2 JP H0547594B2 JP 21621291 A JP21621291 A JP 21621291A JP 21621291 A JP21621291 A JP 21621291A JP H0547594 B2 JPH0547594 B2 JP H0547594B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- crude oil
- catalyst
- fraction
- petroleum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003921 oil Substances 0.000 claims description 100
- 238000000034 method Methods 0.000 claims description 70
- 239000010779 crude oil Substances 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000003208 petroleum Substances 0.000 claims description 19
- 238000007670 refining Methods 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000003209 petroleum derivative Substances 0.000 description 13
- 239000003079 shale oil Substances 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910017464 nitrogen compound Inorganic materials 0.000 description 9
- 150000002830 nitrogen compounds Chemical class 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 241000270666 Testudines Species 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 5
- 238000005504 petroleum refining Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010052804 Drug tolerance Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000026781 habituation Effects 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- -1 heavy naphtha Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【0001】[0001]
【産業上の利用分野】 本発明は、粗オイルシエ
ール油を触媒および水素の存在下で水素化改質精
製して得られる水素化改質製油を蒸留して得られ
る各留分と石油系原油を蒸留して得られる各留分
とを同一留分ごとに混合したのち、触媒および水
素の存在下で留分別に水素化処理をする方法によ
る粗オイルシエール油の精製法に関するものであ
る。[Industrial Application Field] The present invention relates to the distillation of each fraction obtained by distilling the hydrogenated reformed oil obtained by hydrorefining crude oil sierre oil in the presence of a catalyst and hydrogen, and petroleum crude oil. The present invention relates to a method for refining crude oil sierre oil by mixing the same fractions and then subjecting each fraction to hydrogenation treatment in the presence of a catalyst and hydrogen.
【0002】【0002】
【発明の背景】 一般に、地上乾留法あるりは地
下乾留法によつて得られる粗オイルシエール油の
性状は石油系原油の性状とは異なり、粘度および
流動点が高く、重金属および無機質などの夾雑物
を多量に含んでいる。さらに、粗オイルシエール
油には不飽和化合物および窒素化合物が多量に含
まれており、ガム質あるいは沈澱物が生成し易い
ことが特徴的である。とくに、粗オイルシエール
油には、窒素含有率が0.5〜3wt％にも及ぶ多量の
窒素化合物が含まれていることから、現行の石油
精製工程において適用される水素化処理、水素化
分解および接触分解などの触媒の活性を劣化さ
せ、また、窒素化合物の除去を十分に行うことが
困難であるため、水素化改質精製油が貯蔵中に着
色したり、ガム質あるいは沈澱物が生成すること
が粗オイルシエール油を現行石油生成工程に導入
できない障害の一つとなつている。[Background of the Invention] In general, the properties of crude oil shale oil obtained by above-ground carbonization method or underground carbonization method are different from those of petroleum-based crude oil, and it has a high viscosity and pour point, and contains contaminants such as heavy metals and inorganic substances. Contains a large amount of things. Furthermore, crude oil shale oil contains a large amount of unsaturated compounds and nitrogen compounds, and is characterized by the tendency to form gums or precipitates. In particular, crude oil siere oil contains a large amount of nitrogen compounds, with a nitrogen content of 0.5 to 3 wt%. Because it degrades the activity of catalysts such as decomposition, and it is difficult to remove nitrogen compounds sufficiently, hydrogenated reformed refined oil may become discolored during storage, and gums or precipitates may form. is one of the obstacles preventing the introduction of crude oil shale oil into the current oil production process.
【0003】 以上のことから、既存の触媒および水
素化精製装置に改良を加え、現行の水素化精製条
件よりも過酷な条件下で粗オイルシエール油を処
理して現行の石油製品並みに精製する方法が考え
られるが、一段の水素化精製により十分な脱硫
率、脱窒素率および分解率を達成するためには高
い過酷度が要求され、その結果、コーク生成速度
の上昇により触媒性能の劣化が促進されるととも
に固定床式の反応装置においては触媒層の閉塞が
起こり易いなどの欠点を有している。現在の触媒
および水素化精製装置などの技術レベルにおいて
は、粗オイルシエート油から現行の石油製品に匹
敵する品質を有する製品を製造する一段の水素化
精製には未だ多くの技術的問題点が残されてお
り、経済的で、かつ、安定した長期運転の達成が
難しいのが現状である。[0003] From the above, we will improve the existing catalyst and hydrorefining equipment and process crude oil siel oil under harsher conditions than the current hydrorefining conditions to refine it to the same level as current petroleum products. However, in order to achieve sufficient desulfurization, denitrification, and decomposition rates through one-stage hydrorefining, high severity is required, and as a result, catalyst performance may deteriorate due to an increase in coke formation rate. In addition to being accelerated, fixed bed reactors have drawbacks such as clogging of the catalyst bed. At the current level of technology such as catalysts and hydrorefining equipment, there are still many technical problems remaining in the one-step hydrorefining process that produces products with quality comparable to current petroleum products from crude oil siate oil. Currently, it is difficult to achieve economical and stable long-term operation.
【0004】 上記の如く、粗オイルシエール油の精
製は難しく、また、石油系原油の生産コストに匹
敵する乾留技術が未完成であることから、オイル
シエール資源はほとんど未利用のままであつた
が、近年、石油代替燃料の開発の見地から、現行
石油製品の性状に匹敵する製品の製造を目的とし
て、粗オイルシエール油の生産と精製を図る試み
が種々行われている。[0004] As mentioned above, it is difficult to refine crude oil sierre oil, and the carbonization technology comparable to the production cost of petroleum-based crude oil has not been developed, so oil sierre resources have remained almost unused. In recent years, from the standpoint of developing petroleum alternative fuels, various attempts have been made to produce and refine crude oil sier oil, with the aim of producing products comparable in properties to current petroleum products.
【0005】 これまでに述べたように、窒素含有率
が0.5〜3wt％にも及ぶ粗オイルシエール油の一段
水素化精製により、現行の石油製品に匹敵する性
状を有する製品を製造することは技術的に難し
く、また、経済的でないことから、一段目の水素
化精製工程に引き続いて後段に水素化処理あるい
は水素化分解工程を配置して二段あるいは三段の
工程で処理する方法が検討されている。この方法
においては、粗オイルシエール油を一段目の水素
化精製工程で処理することによつて、その窒素含
有率を一般の石油系原油並みに低下させることは
困難であり、二段目の水素化処理によつて製品規
格に合格するレベルまで脱窒素しなければならな
い。そのためには、窒素含有率の低い石油系原油
から得られる各留分の水素化処理を目的として設
計されている水素化処理設備を使用して精製する
ことは難しく、水素化処理設備の改造あるいは運
転方法の変更を余儀なくされる。一段目の水素化
精製によつて得られる水素化精製油を二段目の水
素化処理によつて十分に脱窒素するためには、反
応圧力および反応温度の上昇あるいは通油量の低
下を図ることが必要であるが、一段目の水素化精
製によつて得られる水素化精製油には脱窒素され
難しい構造の窒素化合物が窒素含有率として200
〜20000wtppm残存しているとともに、窒素化合
物とその水素化物との間の熱力学的平衡を考慮す
ると、反応温度の上昇により脱窒素反応速度の増
大を図ることは好ましくなく、また、触媒の性能
保持の見地からも有効な方法であるとは云えな
い。さらに、二段目の水素化処理工程でとくに重
要な点は、触媒系の硫黄バランスを保持すること
である。一段目の水素化精製により得られる水素
化精製油の硫黄含有率は50〜3000wtppmの範囲
で一般の石油系原油に比較して著しく低く、とく
に重質留分の硫黄含有率は石油系原油から得られ
る同じ沸点範囲の留分の硫黄含有率に比較して著
しく低い値を示す。このことは、一段目の水素化
精製工程において高い脱窒素率を達成しようとす
ればするほど顕著になり、水素化精製油の硫黄含
有率が著しく低い場合には、二段目の水素化処理
工程における触媒の硫化状態の保持が難しく、ま
た、一般に窒素化合物の炭素と窒素の結合の切断
は反応系中の適量の硫黄化合物の存在によつて促
進されることが知られており、触媒性能を十分に
発揮させることが難しい。[0005] As mentioned above, it is technologically difficult to produce products with properties comparable to current petroleum products through one-stage hydrorefining of crude oil shale oil with a nitrogen content of 0.5 to 3 wt%. Since this is technically difficult and uneconomical, a two- or three-stage process has been considered in which the first hydrorefining process is followed by a subsequent hydrotreating or hydrocracking process. ing. In this method, it is difficult to reduce the nitrogen content to the same level as that of general petroleum crude oil by treating the crude oil siere oil in the first stage hydrorefining process, and Nitrogen must be denitrified through chemical treatment to a level that meets product standards. To achieve this, it is difficult to refine using hydroprocessing equipment designed for the purpose of hydroprocessing each fraction obtained from petroleum crude oil with a low nitrogen content, and it is necessary to modify the hydroprocessing equipment or Forced to change driving methods. In order to sufficiently denitrify the hydrorefined oil obtained by the first-stage hydrotreating in the second-stage hydrotreating, it is necessary to increase the reaction pressure and reaction temperature or reduce the amount of oil passed. However, the hydrotreated oil obtained in the first stage of hydrorefining contains nitrogen compounds with a structure that is difficult to denitrify, with a nitrogen content of 200%.
~20,000 wtppm remains, and considering the thermodynamic equilibrium between nitrogen compounds and their hydrides, it is not desirable to increase the denitrification reaction rate by increasing the reaction temperature, and it is also important to maintain the performance of the catalyst. It cannot be said that it is an effective method from this point of view. Furthermore, a particularly important point in the second hydrotreating step is to maintain the sulfur balance of the catalyst system. The sulfur content of the hydrorefined oil obtained through the first stage of hydrorefining is in the range of 50 to 3000wtppm, which is significantly lower than that of general petroleum crude oil.In particular, the sulfur content of the heavy fraction is lower than that of petroleum crude oil. The sulfur content is significantly lower than that of the resulting fractions with the same boiling point range. This becomes more obvious the more you try to achieve a high denitrification rate in the first-stage hydrorefining process, and if the sulfur content of the hydrorefined oil is extremely low, the second-stage hydrorefining process It is difficult to maintain the sulfurized state of the catalyst during the process, and it is generally known that the cleavage of the bond between carbon and nitrogen in nitrogen compounds is promoted by the presence of an appropriate amount of sulfur compound in the reaction system, resulting in poor catalyst performance. It is difficult to make full use of
【0006】 以上述べた如く、粗オイルシエール油
を単独で一段目の水素化精製工程で処理して得ら
れる水素化精製油を二段目の水素化処理工程で現
行石油製品並みの品質に生成する方法は、二段目
の水素化処理工程の設備および反応条件を現行の
水素化処理工程の設備および反応条件から変更す
ることが必要であり、既存製油所に設置されてい
る設備の有効利用が難しいとともに、設備、触媒
ならびに反応条件の変更に伴い粗オイルシエール
油の精製のためのコストが増大するという欠点を
有していた。[0006] As mentioned above, the hydrotreated oil obtained by treating the crude oil siel oil alone in the first stage hydrotreating process is produced in the second stage hydrotreating process to a quality comparable to that of current petroleum products. This method requires changing the equipment and reaction conditions for the second-stage hydrotreating process from the current hydrotreating process equipment and reaction conditions, making effective use of the equipment installed in the existing refinery. This method has the disadvantage that it is difficult to process, and the cost for refining crude oil shale oil increases due to changes in equipment, catalysts, and reaction conditions.
【0007】[0007]
【発明が解決しようとする課題】 これまでに述
べた粗オイルシエール油の二段処理法の欠点を改
善した方法、すなわち、一段目の水素化精製工程
の後段に酸処理工程を設置して窒素化合物を除去
することによる精製法が知られている。この方法
は二段目の水素化処理工程の代りに塩酸、硫酸な
どの鉱酸あるいは酢酸、ギ酸などの有機溶剤を使
用して、一段目の水素化精製工程で処理されたの
ちの水素化精製油に残存する窒素化合物を除去す
る方法に関するものであるが、この方法に類似し
た方法として、二段目の工程にカチオン性イオン
交換樹脂による窒素化合物の吸着除去工程を設置
する方法についても知られている。これらの方法
によつて、現行石油製品の品質に匹敵する製品の
製造は可能であるが、窒素化合物除去用の抽出溶
剤あるいはカチオン性イオン交換樹脂の再生が必
要であり、工業的見地からは製品収率の低下、再
生廃液の処理などの問題点がある。Problems to be Solved by the Invention A method that improves the drawbacks of the two-stage treatment method for crude oil shale oil described so far, that is, an acid treatment step is installed after the first-stage hydrorefining step to reduce nitrogen Purification methods by removing compounds are known. This method uses a mineral acid such as hydrochloric acid or sulfuric acid or an organic solvent such as acetic acid or formic acid instead of the second-stage hydrotreating step, and the hydrorefining process is carried out after the first-stage hydrorefining step. This relates to a method for removing nitrogen compounds remaining in oil, but there is also a known method similar to this method in which a step for adsorption and removal of nitrogen compounds using a cationic ion exchange resin is installed in the second step. ing. Although it is possible to manufacture products comparable in quality to current petroleum products using these methods, it is necessary to regenerate the extraction solvent for removing nitrogen compounds or the cationic ion exchange resin, and from an industrial perspective, the products are difficult to manufacture. There are problems such as a decrease in yield and treatment of recycled waste liquid.
【0008】 そのほか、粗オイルシエール油の精製
法として、デイレード・コーキング法などにより
粗オイルシエール油をコーキング処理したのち、
水素化処理を行う方法も知られているが、コーキ
ング処理工程でのガス状精製物およびコークの発
生にともない、液状生成物の得率が低いことが欠
点であつた。また、粗オイルシエール油を水素化
精製することにより、接触分解触媒の性能を阻害
しない程度に水素化精製油の窒素含有率を低下さ
せたのち、接触分解する方法も知られているが、
接触分解法は主にガソリン製造を目的とした方法
であり、灯油あるいは軽油の製造を目的とする場
合には必ずしも適した方法ではない。[0008] In addition, as a refining method for crude oil sier oil, after coking the crude oil sier oil by a delayed coking method,
Hydrotreating methods are also known, but the disadvantage is that the yield of liquid products is low due to the generation of gaseous refined products and coke in the coking process. There is also a known method of hydrorefining crude oil siel oil to reduce the nitrogen content of the hydrorefined oil to an extent that does not impede the performance of the catalytic cracking catalyst, and then catalytically cracking the oil.
The catalytic cracking method is a method mainly aimed at producing gasoline, and is not necessarily a method suitable for producing kerosene or light oil.
【0009】 既存の石油精製工程において、粗オイ
ルシエール油を石油系原油と混合して処理するこ
とにより、現行石油製品規格に合格する製品の製
造を目的とした試みが種々行われている。オイ
ル・アンド・ガス・ジヤーナル誌79巻（29号）43
（1981）に既存の製油所において実施した試験運
転の結果が掲載されている。[0009] In existing petroleum refining processes, various attempts have been made to produce products that meet current petroleum product standards by processing crude oil shale oil by mixing it with petroleum crude oil. Oil and Gas Journal Volume 79 (Issue 29) 43
(1981) presents the results of a test run conducted at an existing refinery.
【0010】 その第一の例として、石油系残油留分
を処理するデイレード・コーカーの分留塔に粗オ
イルシエール油を供給することによつて得られる
ナフサ、ジエツト燃料、軽質軽油および重質軽油
留分をそれぞれ水素化処理し、塔底油をデイレー
ド・コーカーに循環するとともに、重質燃料油と
する製造方法が実施されているが、得られる各燃
料油はガム質あるいは沈澱物が生成し易く、貯蔵
安定性および熱安定性が悪いことが示されてい
る。各燃料油の規格に合格するためには、水素化
処理の圧力をさらに高めるか、あるいはクレイ処
理が必要であることが述べられている。[0010] As a first example, naphtha, jet fuel, light gas oil, and heavy oil obtained by feeding crude oil shale oil to a fractionating column of a delayed coker that processes petroleum residue fractions are A method of producing heavy fuel oil has been implemented in which each gas oil fraction is hydrotreated and the bottom oil is recycled to a delayed coker, but the resulting fuel oil has a gummy or precipitated appearance. It has been shown to be easy to clean, and to have poor storage and thermal stability. It is stated that in order to pass the standards for each fuel oil, it is necessary to further increase the pressure of hydrotreating or to perform clay treatment.
【0011】 第二の例として、現行石油精製工程に
おいて石油系原油に対して0.1〜1.0容量％の粗オ
イルシエール油を混合して処理を行う方法が実施
されている。蒸留して得られた留出油の比重、流
動点などの性状には粗オイルシエール油を混合し
た影響が観察されなかつたが、軽油留分は着色
し、沈澱物が精製したと報告されている。[0011] As a second example, in the current petroleum refining process, a method is implemented in which 0.1 to 1.0% by volume of crude oil shale oil is mixed with petroleum-based crude oil. Although no effect of mixing crude oil sier oil was observed on properties such as specific gravity and pour point of the distillate obtained by distillation, it was reported that the light oil fraction was colored and the precipitate was refined. There is.
【0012】【0012】
【課題を解決するための手段】 上述した現状に
鑑み、粗オイルシエール油を現行石油製品に匹敵
する性状に精製する方法について、従来技術の欠
点を解決すべく鋭意研究した結果、粗オイルシエ
ール油を触媒および水素の存在下、反応圧力50〜
200Kg／cm2、反応温度300〜500℃の条件で水素化
改質精製して得られる水素化改質精製油ならびに
石油系原油を個々に蒸留して得られる、軽質ナフ
サ、重質ナフサ、灯油、軽油および減圧軽油留分
を留分別に混合して窒素含有率をそれぞれ
100wtppm以下、150wtppm以下、300wtppm以
下、700wtppm以下および3000wtppm以下に調製
したのち、触媒および水素の存在下で水素化処理
をすることによつて、粗オイルシエール油を精製
する方法を見出すに至つた。[Means for Solving the Problems] In view of the above-mentioned current situation, as a result of intensive research to solve the drawbacks of the conventional technology for refining crude oil siere oil to properties comparable to current petroleum products, we have developed crude oil siere oil. In the presence of a catalyst and hydrogen, the reaction pressure is 50~
Light naphtha, heavy naphtha, and kerosene obtained by individually distilling hydroreformed refined oil and petroleum crude oil obtained by hydroreforming and refining at 200Kg/cm 2 and reaction temperature of 300 to 500℃. , the gas oil and vacuum gas oil fractions were mixed separately to determine the nitrogen content.
We have discovered a method for refining crude oil sier oil by adjusting it to 100 wtppm or less, 150 wtppm or less, 300 wtppm or less, 700 wtppm or less, and 3000 wtppm or less, and then subjecting it to hydrogenation treatment in the presence of a catalyst and hydrogen.
【0013】 すなわち、本発明によれば、一段目の
水素化改質精製工程で粗オイルシエール油を処理
して得られる水素化改質精製油および石油系原油
を分留して得られる各留分を各々単独に現行の水
素化処理工程で処理したのち、両者の水素化処理
油を混合して製品を製造する方法に比べて、二段
目の水素化処理を行うにあたり、硫黄含有率の低
い粗オイルシエール油の水素化改質精製油を蒸留
して得られる各留分と石油系原油を蒸留して得ら
れる各留分を留分別に混合したのちに留分別に二
段目の水素化処理を行うことによつて、脱硫、脱
窒素、水素化分解などの精製レベルを高く維持す
ると同時に、粗オイルシエール油の水素化改質精
製の条件を緩和することが可能となり、全体とし
て安定した粗オイルシエール油の精製法を提供す
るものである。また、設備、触媒、水素化処理条
件の変更をせずに既存設備の有効利用が可能であ
り、従来法には見られない新しい発明であること
は明らかである。[0013] That is, according to the present invention, each distillate obtained by fractionating the hydro-reformed refined oil and the petroleum crude oil obtained by processing the crude oil sier oil in the first-stage hydro-reforming refining step. Compared to the method of manufacturing a product by treating each oil separately in the current hydrotreating process and then mixing the two hydrotreated oils, it is possible to reduce the sulfur content in the second stage of hydrotreating. Each fraction obtained by distilling the hydrogenated reformed refined oil of low crude oil sierre oil and each fraction obtained by distilling petroleum crude oil are mixed separately, and then the second stage hydrogen is added to each fraction. By performing chemical treatment, it is possible to maintain high refining levels such as desulfurization, denitrification, and hydrocracking, while at the same time relaxing the conditions for hydroreforming and refining of crude oil siel oil, resulting in overall stability. The present invention provides a method for refining crude oil sierre oil. Furthermore, existing equipment can be used effectively without changing equipment, catalysts, or hydrotreating conditions, and it is clear that this is a new invention not found in conventional methods.
【0014】[0014]
【発明の具体的説明】 次に本発明の構成を詳細
に説明する。
本発明が実施される一段目の水素化改質精製工
程に使用される反応器は少なくとも１個の固定床
式反応器、または少なくとも１個の流動床式反応
器あるいは１個の移動床式反応器が設置される
が、粗オイルシエール油の金属含有率、触媒の性
能、水素化改質精製条件によつては、ガード・リ
アクターあるいは運転中に活性が劣化した触媒を
抜き出し、新触媒を供給できる設備を設置しても
良い。反応器に充填される触媒はアルミナ、シリ
カ・アルミナ、ゼオライトなどの耐火性無機酸化
物あるいはこれらの耐火性無機酸化物を混合して
得られる担体にNi、Co、Feなどの周期律表第
族金属の中から選ばれた１つ以上の金属および
Cr、Mo、Ｗなどの周期律表ａ族金属の中から
選ばれた１つ以上の金属を担持して得られる触媒
である。これらの担体、金属の種類、金属の組合
せ方法、担持量あるいは形状などは粗オイルシエ
ール油の性状および運転方法により決定される
が、流動床式反応器あるいは移動床式反応器に充
填される触媒は耐摩耗性などの強度にすぐれてい
ることが要求される。DETAILED DESCRIPTION OF THE INVENTION Next, the configuration of the present invention will be described in detail. The reactor used in the first hydroreforming refining step in which the present invention is implemented is at least one fixed bed reactor, at least one fluidized bed reactor, or one moving bed reactor. However, depending on the metal content of the crude oil siel oil, the performance of the catalyst, and the hydroreforming refining conditions, a guard reactor or a catalyst whose activity has deteriorated during operation may be extracted and a new catalyst may be supplied. You may install the necessary equipment. The catalyst packed in the reactor is a refractory inorganic oxide such as alumina, silica/alumina, and zeolite, or a carrier obtained by mixing these refractory inorganic oxides, and a support that contains elements from groups of the periodic table such as Ni, Co, and Fe. one or more metals selected from metals and
It is a catalyst obtained by supporting one or more metals selected from group a metals of the periodic table, such as Cr, Mo, and W. These carriers, types of metals, method of combining metals, supported amount, and shape are determined by the properties of the crude oil siere oil and the operating method, but the catalysts packed in the fluidized bed reactor or moving bed reactor are is required to have excellent strength such as wear resistance.
【0015】 一段目の水素化改質精製工程における
粗オイルシエール油の水素化改質精製において
は、反応圧力は一般に50〜200Kg／cm2であり、と
くに100〜150Kg／cm2の範囲が好ましく、反応温度
は300〜500℃であり、とくに350〜450℃の範囲が
好ましい。また、粗オイルシエール油の供給速度
は0.1〜2.0供給容量／触媒容量／時の範囲が好ま
しく、水素は2000〜10000scf／bblの範囲で供給
するのが好ましい。[0015] In the hydroreforming and refining of crude oil sier oil in the first stage hydroreforming and refining process, the reaction pressure is generally 50 to 200 Kg/cm 2 , and preferably in the range of 100 to 150 Kg/cm 2 . The reaction temperature is 300 to 500°C, particularly preferably 350 to 450°C. Further, the feed rate of the crude oil shale oil is preferably in the range of 0.1 to 2.0 feed volume/catalyst capacity/hour, and the hydrogen is preferably fed in the range of 2,000 to 10,000 scf/bbl.
【0016】 かくの如くして得た水素化改質精製油
および石油系原油を各々単独に蒸留したのち、留
分別に混合して水素化処理を行う方法を採用する
場合には、軽質ナフサ、重質ナフサ、灯油、軽油
および減圧軽油留分の窒素含有率が各々100、
150、300、700および3000wtppm以下になるよう
に、水素化改質精製油各留分と石油系原油各留分
の混合比率を決定する。[0016] When adopting a method of separately distilling the hydro-reformed refined oil and petroleum crude oil obtained in this manner and then mixing the fractions separately for hydrotreating, light naphtha, The nitrogen content of heavy naphtha, kerosene, gas oil and vacuum gas oil fraction is each 100,
The mixing ratio of each fraction of hydro-reformed refined oil and each fraction of petroleum crude oil is determined so that it is 150, 300, 700 and 3000wtppm or less.
【0017】 以上述べたように、粗オイルシエール
油の水素化改質精製油および石油系原油を各々単
独に蒸留したのち、留分別に所定の混合比率で混
合して調製した水素化処理用の原料油は後段の留
分別水素化処理工程に供給され、現行の石油製品
に匹敵する品質に精製される。[0017] As described above, after separately distilling the hydro-reformed refined oil of crude oil siere oil and petroleum crude oil, the hydroprocessing oil prepared by mixing each fraction at a predetermined mixing ratio. The feedstock oil is supplied to the subsequent fractional hydrotreating process, where it is refined to a quality comparable to that of current petroleum products.
【0018】 留分別の水素化処理は現行の石油精製
工程で実施され、各工程に設置される反応器およ
びその他の設備の性能は既存の製油所に記載され
ている設備の性能に匹敵するものであり、触媒の
性能も既存の触媒性能以上であることが要求され
る。留分別の水素化処理の条件は処理する各留分
に対して最適な条件が存在するが、水素化改質精
製油から得られる各留分の硫黄含有率が低い欠点
が石油系原油から得られる各留分と留分別に混合
することによつて補うことにより、触媒の硫化状
態を保持し、脱窒素反応が促進されることから、
現行の水素化処理条件下において、現行石油製品
規格に合格する水素化処理油を製造することがで
きる。[0018] Fraction-specific hydrotreatment is carried out in the current petroleum refining process, and the performance of the reactor and other equipment installed in each process is comparable to the performance of equipment listed in existing refineries. Therefore, the performance of the catalyst is required to be higher than that of existing catalysts. Hydrotreating conditions for each fraction have optimal conditions for each fraction to be treated, but the disadvantage of low sulfur content in each fraction obtained from hydro-reformed refined oil is that By supplementing by mixing each fraction separately, the sulfided state of the catalyst is maintained and the denitrification reaction is promoted.
Under current hydroprocessing conditions, hydroprocessed oils that pass current petroleum product standards can be produced.
【0019】 かくの如く、新しい知見を包含する本
発明を工業的見地からみれば、窒素含有率が石油
系原油に比較して著しく高く、ガム質あるいは沈
澱物が精製し易い粗オイルシエール油を一段目の
水素化改質精製工程で処理したのち、現行の石油
精製工程に導入することによつて、現行石油製品
に匹敵する品質に精製することができ、工業的に
貢献することは多大である。また、本発明によれ
ば、現行石油精製工程を改造することなく、有効
に活用することができ、しかも、一段目の水素化
改質精製工程で粗オイルシエール油を処理して得
られる水素化改質精製油および石油系原油からの
各留分を各々単独に現行の水素化処理工程で処理
した後、両者の水素化処理油を混合する方法に比
較して、脱窒素が極めて容易であり、また、現行
石油精製工程に新たに設備を追加する必要がな
く、製造コストの低減を図ることができる。上述
のとおり本発明の方法は、燃料油製造の分野にお
いて多大な工業的貢献をするものである。[0019] From an industrial standpoint, the present invention, which includes new knowledge, can be used to produce crude oil sier oil, which has a significantly higher nitrogen content than petroleum-based crude oil and which is easy to refine with gum or precipitate. By introducing it into the current petroleum refining process after processing it in the first stage hydroreforming refining process, it is possible to refine it to a quality comparable to that of current petroleum products, and the industrial contribution will be significant. be. Further, according to the present invention, it is possible to effectively utilize the existing petroleum refining process without modifying it, and in addition, the hydrogenation process obtained by processing crude oil sierre oil in the first stage hydroreforming refining process Compared to the method of treating each fraction from reformed refined oil and petroleum crude oil separately in the current hydrotreating process and then mixing the two hydrotreated oils, denitrification is extremely easy. Moreover, there is no need to add new equipment to the current oil refining process, and manufacturing costs can be reduced. As mentioned above, the method of the present invention makes a significant industrial contribution in the field of fuel oil production.
【0020】【0020】
【実施例】 本発明の方法をさらに次の実施例に
より具体的に説明するが、本発明の方法はこれら
実施例に限定されるものではない。
尚、以下において「部」とは、特に断わりのな
い限り、「重量部」を表す。[Examples] The method of the present invention will be explained in more detail with reference to the following examples, but the method of the present invention is not limited to these examples. In the following, "parts" means "parts by weight" unless otherwise specified.
【0021】 第１表に示すNi−Mo系触媒を沸騰床
式反応器に充填し、所定の予備硫化および慣化運
転を行つたのち、第２表に示す性状を有する粗オ
イルシエール油の水素化改質精製を反応圧力140
Kg／cm2、反応温度400℃、粗オイルシエール油供
給速度1.0通油容積／触媒容積／時、水素比
8000scf／bblの条件下で実施し、窒素含有率
1070wtppmの水素化改質精製油を得た。この水
素化改質精製油および1070wtppmの水素化改質
精製油を得た。この水素化改質精製油およびアラ
ビアン・ライト原油を蒸留することによつて、第
３表に示す重質ナフサ、灯油、軽油および残油留
分を得た。[0021] After filling the ebullated bed reactor with the Ni-Mo catalyst shown in Table 1 and carrying out the prescribed presulfurization and habituation operation, the hydrogen of the crude oil sier oil having the properties shown in Table 2 is Reaction pressure of 140
Kg/cm 2 , reaction temperature 400℃, crude oil sier oil feed rate 1.0 oil volume/catalyst volume/hour, hydrogen ratio
Conducted under conditions of 8000scf/bbl, nitrogen content
Hydrogenated reformed refined oil of 1070wtppm was obtained. This hydrogenated reformed refined oil and 1070 wtppm of hydrogenated reformed refined oil were obtained. By distilling this hydro-reformed refined oil and Arabian Light crude oil, heavy naphtha, kerosene, gas oil and residual oil fractions shown in Table 3 were obtained.
【0022】[0022]
【表１】 ■■■ 亀の甲 ［0071］ ■■■[Table 1] ■■■ Turtle shell [0071] ■■■
【0023】【0023】
【表２】 ■■■ 亀の甲 ［0072］ ■■■[Table 2] ■■■ Turtle shell [0072] ■■■
【0024】【0024】
【表３】 ■■■ 亀の甲 ［0073］ ■■■[Table 3] ■■■ Turtle shell [0073] ■■■
【0025】 水素化改質精製油およびアラビアン・
ライト原油から得た各留分を留分別に混合し後段
の水素化処理用の原料油を調製した。水素化処理
は固定式床反応器に第４表に示すNi−Mo系触媒
を充填し、所定の予備硫化および慣化運転を行つ
たのち留分別に実施した。比較例として、水素化
改質精製油およびアラビアン・ライト原油から得
られる各留分を混合せずに各々単独で水素化処理
したのち混合した結果を示す。[0025] Hydrogenated reformed refined oil and Arabian
Each fraction obtained from light crude oil was mixed separately to prepare feedstock oil for subsequent hydrotreatment. The hydrogenation treatment was carried out for each fraction after filling a fixed bed reactor with the Ni-Mo catalyst shown in Table 4 and carrying out prescribed pre-sulfurization and acclimatization operations. As a comparative example, the results are shown in which each fraction obtained from a hydro-reformed refined oil and an Arabian light crude oil was hydrotreated individually without being mixed, and then mixed.
【0026】【0026】
【表４】 ■■■ 亀の甲 ［0074］ ■■■[Table 4] ■■■ Turtle shell [0074] ■■■
【0027】 重質ナフサ留分については、反応圧力
30Kg／cm2、反応温度300℃、液空間速度4.0通油容
積／触媒容積／時、水素比200scf／bblなる条件
下で水素化処理を行つた。第５表に示す結果から
明らかなように、水素化改質精製油およびアラビ
アン・ライト原油から得られる重質ナフサを混合
して水素化処理することによつて、接触改質用原
料油の窒素含有率許容値0.5wtppm以下に脱窒素
することができた。比較例として、水素化改質精
製油およびアラビアン・ライト原油から得た重質
ナフサ留分を各々単独で水素化処理をしたのち混
合する方法の結果を示したが、混合水素化処理油
の窒素含有率は接触改質原料油の許容値を大幅に
上回つており、本発明による方法がすぐれている
ことを示している。[0027] For the heavy naphtha fraction, the reaction pressure
The hydrogenation treatment was carried out under the following conditions: 30 Kg/cm 2 , reaction temperature 300° C., liquid hourly space velocity 4.0 oil volume/catalyst volume/hour, and hydrogen ratio 200 scf/bbl. As is clear from the results shown in Table 5, by mixing and hydrotreating the hydro-reformed refined oil and heavy naphtha obtained from Arabian light crude oil, nitrogen in the feedstock for catalytic reforming can be reduced. It was possible to denitrify the content to below the allowable value of 0.5wtppm. As a comparative example, we have shown the results of a method in which hydro-reformed refined oil and heavy naphtha fraction obtained from Arabian Light crude oil are individually hydrotreated and then mixed. The content significantly exceeds the permissible value for catalytically reformed feedstocks, demonstrating the superiority of the process according to the invention.
【0028】【0028】
【表５】 ■■■ 亀の甲 ［0075］ ■■■[Table 5] ■■■ Turtle shell [0075] ■■■
【0029】 炉油留分については、反応圧力40Kg／
cm2、反応温度300℃、液空間速度4.0通油容積／触
媒容積／時、水素比500scf／bbnlなる条件下で水
素化処理を行つた。第６表に示す実施例２から明
らかなように、水素化改質精製油およびアラビア
ン・ライト原油から得られる灯油留分を混合して
水素化処理することによつて、窒素含有率は製品
灯油並みに低下するが、比較例２の場合には窒素
含有率が高いために黄褐色に変色し、沈澱物の生
成が観察された。よつて、本発明による方法がす
ぐれていることは明らかである。[0029] For the furnace oil fraction, the reaction pressure is 40Kg/
cm 2 , reaction temperature of 300° C., liquid hourly space velocity of 4.0 oil volume/catalyst volume/hour, and hydrogen ratio of 500 scf/bbnl. As is clear from Example 2 shown in Table 6, by mixing and hydrotreating the hydro-reformed refined oil and the kerosene fraction obtained from Arabian Light crude oil, the nitrogen content can be reduced to that of the product kerosene. However, in the case of Comparative Example 2, due to the high nitrogen content, the color changed to yellowish brown and the formation of precipitates was observed. Therefore, it is clear that the method according to the present invention is superior.
【0030】 軽油留分については、反応圧力50Kg／
cm2、反応温度350℃、液空間速度3.0通油容積／触
媒容積／時、水素比800scf／bbnlなる条件下で水
素化処理を行つた。第７表に示す実施例３から明
らかなように、水素化改質生成油およびアラビア
ン・ライト原油から得られる軽油留分を混合して
水素化処理することによつて、窒素含有率は製品
軽油並みに低下するが、比較例３の場合には窒素
含有率が高いために褐色に変色し、沈澱物の生成
が観察された。よつて、本発明による方法がすぐ
れていることは明らかである。[0030] For light oil fraction, the reaction pressure is 50Kg/
cm 2 , reaction temperature 350° C., liquid hourly space velocity 3.0 oil volume/catalyst volume/hour, and hydrogen ratio 800 scf/bbnl. As is clear from Example 3 shown in Table 7, by mixing and hydrotreating the hydrogenated reformed product oil and the gas oil fraction obtained from Arabian Light crude oil, the nitrogen content can be reduced to that of the product gas oil. However, in the case of Comparative Example 3, due to the high nitrogen content, the color changed to brown and the formation of precipitates was observed. Therefore, it is clear that the method according to the present invention is superior.
【0031】【0031】
【表６】 ■■■ 亀の甲 ［0076］ ■■■[Table 6] ■■■ Turtle shell [0076] ■■■
【0032】[0032]
【表７】 ■■■ 亀の甲 ［0077］ ■■■[Table 7] ■■■ Turtle shell [0077] ■■■
【0033】 本実施例を整理すると以下のようにな
る。
重質ナフサ留分の水素化処理油の硫黄含有率
および窒素含有率はともに接触改質用原料油の許
容値以下である、[0033] This embodiment can be summarized as follows. Both the sulfur content and nitrogen content of the hydrotreated heavy naphtha fraction oil are below the permissible values for feedstock oil for catalytic reforming.
【0034】 灯油留分の水素化処理油の煙点は
23.7であり、窒素含有率は1wtppm以下で着色、
ガム質あるいは沈澱物が生成しないため、製品規
格に合格する。[0034] The smoke point of hydrotreated oil of kerosene fraction is
23.7, and the nitrogen content is less than 1wtppm and colored.
It passes product standards because it does not produce gum or sediment.
【0035】 軽油留分の水素化処理油の動粘度
は4.491cst（30℃）、流動点は−５℃であり、ま
た、窒素含有率も低く特１号軽油の製品規格に合
格する。[0035] The kinematic viscosity of the hydrogenated gas oil fraction is 4.491cst (30°C), the pour point is -5°C, and the nitrogen content is low, so it passes the product standard of special No. 1 gas oil.
【0036】 減圧軽油留分の水素化処理油の硫
黄含有率および窒素含有率はともに接触分解およ
び水素化分解用原料油の許容値以下である。[0036] Both the sulfur content and nitrogen content of the hydrotreated oil of the vacuum gas oil fraction are below the permissible values for feedstock oil for catalytic cracking and hydrocracking.
【0037】 上述の結果から、本発明の方法は、粗
オイルシエール油を現行石油製品並みの品質に高
品質化する有効な方法であることを示している。[0037] The above results show that the method of the present invention is an effective method for improving the quality of crude oil shale oil to a level comparable to that of current petroleum products.
Claims (1)
水素の存在下、反応圧力50〜200Kg／cm2、反応温
度300〜500℃の条件で水素化改質精製して得られ
る水素化改質精製油ならびに石油系原油を個々に
蒸留して得られる、軟質ナフサ、重質ナフサ、灯
油、軽油および減圧軽油留分を留分別に混合して
窒素含有率をそれぞれ100wtppm以下、
150wtppm以下、300wtppm以下、700wtppm以
下および3000wtppm以下に調製したのち、触媒
および水素の存在下で水素化処理をすることを特
徴とする粗オイルシエール油の精製法。Claim 1: A hydroreformed refined oil obtained by refining crude oil sierre oil in the presence of a catalyst and hydrogen at a reaction pressure of 50 to 200 Kg/cm 2 and a reaction temperature of 300 to 500°C. Also, soft naphtha, heavy naphtha, kerosene, light oil and vacuum light oil fractions obtained by distilling petroleum crude oil individually are mixed to reduce the nitrogen content to 100wtppm or less, respectively.
1. A method for refining crude oil sierre oil, which comprises preparing the oil to 150 wtppm or less, 300 wtppm or less, 700 wtppm or less, and 3000 wtppm or less, and then subjecting it to hydrogenation treatment in the presence of a catalyst and hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21621291A JPH04356590A (en) | 1991-08-02 | 1991-08-02 | Refining of crude oil shale oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21621291A JPH04356590A (en) | 1991-08-02 | 1991-08-02 | Refining of crude oil shale oil |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4863683A Division JPS59174687A (en) | 1983-03-25 | 1983-03-25 | Purification of crude oil of shale oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04356590A JPH04356590A (en) | 1992-12-10 |
| JPH0547594B2 true JPH0547594B2 (en) | 1993-07-19 |
Family
ID=16685036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21621291A Granted JPH04356590A (en) | 1991-08-02 | 1991-08-02 | Refining of crude oil shale oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04356590A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097484C (en) * | 1999-05-27 | 2003-01-01 | 中国石油化工集团公司北京化工研究院 | Liquid phase hydrogenating catalyst, its preparation process and application |
| JP4578182B2 (en) * | 2004-08-27 | 2010-11-10 | Ｊｘ日鉱日石エネルギー株式会社 | Method for hydrotreating heavy hydrocarbon oil |
-
1991
- 1991-08-02 JP JP21621291A patent/JPH04356590A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04356590A (en) | 1992-12-10 |
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