JP3411998B2 - Method for producing low sulfur gas oil - Google Patents
Method for producing low sulfur gas oilInfo
- Publication number
- JP3411998B2 JP3411998B2 JP15846494A JP15846494A JP3411998B2 JP 3411998 B2 JP3411998 B2 JP 3411998B2 JP 15846494 A JP15846494 A JP 15846494A JP 15846494 A JP15846494 A JP 15846494A JP 3411998 B2 JP3411998 B2 JP 3411998B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- hydrogen
- gas oil
- oil
- light
- 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 - Fee Related
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims description 15
- 239000011593 sulfur Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 12
- 239000007789 gas Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000003464 sulfur compounds Chemical class 0.000 claims description 15
- 238000006477 desulfuration reaction Methods 0.000 claims description 11
- 230000023556 desulfurization Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 41
- 239000007788 liquid Substances 0.000 description 27
- 238000009835 boiling Methods 0.000 description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 alkylnaphthalenes Chemical compound 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 102200118166 rs16951438 Human genes 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 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、石油留分から低硫黄デ
ィーゼルエンジン用の軽油を製造する方法に関する。FIELD OF THE INVENTION This invention relates to a process for producing gas oil for low sulfur diesel engines from petroleum fractions.
【０００２】[0002]
【従来の技術】常圧蒸留装置で蒸留分離された軽油留分
（直留軽油と称する沸点範囲が１５０〜４００℃のも
の）全体を水素化脱硫し、この脱硫軽油に未脱硫の直留
軽油留分、直留灯油留分、重質留分の分解装置から得ら
れる分解軽油留分とを混合して硫黄分０.２％以下の軽
油を製造している。しかし、今後大型車両の排ガス規制
が強化されることから、この硫黄分規制値は０.０５％
に引き下げられることになっている。2. Description of the Related Art The whole gas oil fraction (boiling point range called straight-run gas oil having a boiling point range of 150 to 400 ° C.) distilled by an atmospheric distillation apparatus is hydrodesulfurized, and this desulfurized gas oil is not desulfurized straight-run gas oil. A distillate, a straight-run kerosene fraction, and a cracked gas oil fraction obtained from a cracker for heavy fractions are mixed to produce gas oil having a sulfur content of 0.2% or less. However, as the exhaust gas regulations for large vehicles will be tightened in the future, this sulfur content regulation value will be 0.05%.
It is supposed to be lowered to.
【０００３】[0003]
【発明が解決しようとする課題】従来技術では脱硫反応
の温度を高くするか、脱硫反応の時間を長くしないと最
終的に硫黄分０.０５％以下の軽油が得られない。しか
し、反応温度を高くすると製品軽油の色相が悪化するの
で、反応温度を高くすることはできない。従って、他の
手段である脱硫反応時間を長くする方法を取らならざる
を得ない。言い替えれば液空塔速度（ＬＨＳＶ）が小さ
くなり、処理能力が同じとしたら反応塔の容積が大きく
なり、水素化脱硫触媒の使用量も増大し脱硫コストが高
くなるという問題点がある。In the prior art, unless the temperature of the desulfurization reaction is raised or the time of the desulfurization reaction is lengthened, a gas oil having a sulfur content of 0.05% or less cannot be finally obtained. However, the reaction temperature cannot be increased because the hue of the light oil of the product is deteriorated when the reaction temperature is increased. Therefore, there is no other choice but to take a method of lengthening the desulfurization reaction time, which is another means. In other words, there is a problem that the liquid superficial velocity (LHSV) becomes small, the volume of the reaction column becomes large, the amount of the hydrodesulfurization catalyst used becomes large, and the desulfurization cost becomes high if the processing capacity is the same.
【０００４】本発明の目的は、色相を悪化させずに低硫
黄分の軽油を製造することにある。本発明の目的は、脱
硫触媒の使用量と水素消費量を低減することにある。An object of the present invention is to produce a light oil having a low sulfur content without deteriorating the hue. An object of the present invention is to reduce the amount of desulfurization catalyst used and the amount of hydrogen consumed.
【０００５】[0005]
【課題を解決するための手段】上記目的は、軽油中の主
として軽質分中の硫黄化合物と水素を触媒の存在下で反
応させて脱硫する第一工程と、この第一工程で処理され
た軽油を軽質分と重質分とに分留する第二工程と、この
第二工程で分留された前記重質分中の硫黄化合物と水素
とを触媒の存在下で反応させて脱硫する第三工程とを有
することにより達成される。SUMMARY OF THE INVENTION The above objects are primarily in gas oil
As a result, sulfur compounds and hydrogen in the light content are reacted in the presence of a catalyst.
And the first step of desulfurization and treatment in this first step
The second step of fractionating the gas oil that has been
Sulfur compounds and hydrogen in the heavy fraction fractionated in the second step
And a third step of reacting and in the presence of a catalyst to desulfurize .
【０００６】上記目的は、軽油中の主として軽質分中の
硫黄化合物と水素を触媒の存在下で、温度が２８０〜３
８０℃、圧力が１０〜８０Ｋｇ／ｃｍ ２ で反応させて脱
硫する第一工程と、この第一工程で処理された軽油を軽
質分と重質分とに分留する第二工程と、この第二工程で
分留された前記重質分中の硫黄化合物と水素とを触媒の
存在下で温度が１５０〜３６０℃、圧力が１０〜８０Ｋ
ｇ／ｃｍ ２ で反応させて脱硫する第三工程とを有するこ
とにより達成される。[0006] The above-mentioned object is mainly in light components in light oil.
In the presence of a sulfur compound and hydrogen in the presence of a catalyst, the temperature is 280 to 3
The reaction is carried out at 80 ° C. and a pressure of 10 to 80 kg / cm 2 , and the reaction is removed.
The first step of sulfurization and the light oil treated in this first step
In the second step of fractionating into mass and heavy fraction, and in this second step
The sulfur compound and hydrogen in the heavy fraction fractionated are used as a catalyst.
In the presence, the temperature is 150-360 ° C and the pressure is 10-80K.
The third step of reacting and desulfurizing at g / cm 2 is achieved.
【０００７】上記目的は、触媒の存在下で軽油中の硫黄
化合物と水素を温度が２８０〜３８０℃、圧力が１０〜
８０Ｋｇ／ｃｍ２で反応させる第一工程と、該第一工程
からの流体より、沸点３３０℃以上の留分を含む軽油重
質分を高温気液分離する第二工程と、該第二工程から前
記軽油重質分を取り込んで、前記第一工程の液空塔速度
より小さい触媒量の存在下で該軽油重質分中の硫黄化合
物と水素を温度が１５０〜３６０℃、圧力が１０〜８０
Ｋｇ／ｃｍ２で反応させる第三工程と、を有することに
より達成される。The above-mentioned object is to control the sulfur compound and hydrogen in light oil in the presence of a catalyst at a temperature of 280 to 380 ° C. and a pressure of 10 to 10.
A first step of reacting at 80 Kg / cm 2 and a gas oil heavy oil containing a fraction having a boiling point of 330 ° C. or higher from the fluid from the first step.
A second step of separating the mass into a high-temperature gas-liquid, and the second step before
Captures serial diesel heavies, the temperature of the sulfur compounds and hydrogen of the gas oil heavy component in the presence of a liquid superficial velocity smaller than a catalytic amount of the first step is 150 to 360 ° C., a pressure from 10 to 80
A third step of reacting in kg / cm 2, is achieved by having a.
【０００８】[0008]
【作用】軽油に含まれる硫黄化合物の中で脱硫反応が困
難なジベンゾチオフェン及びアルキルジベンゾチオフェ
ン類の沸点は３３０℃以上である。また脱硫反応が進行
し易いベンゾチオフェン及びアルキルベンゾチオフェン
類の沸点は主に３３０℃以下である。従って沸点３３０
℃以下の留分は短い滞留時間で水素化脱硫できるが、３
３０℃以上の留分は長い滞留時間を必要とする。従って
原料軽油を第一工程において短い滞留時間で脱硫して色
相の悪下を防止し、第二工程で沸点３３０℃以上の留分
を高温気液分離し、第三工程で脱硫反応が困難な硫黄化
合物を含む沸点３３０℃以上の留分のみを長い滞留時間
かけて脱硫し低硫黄分の軽油を製造することができる。
第三工程では第一工程より反応温度を低くし、沸点３３
０℃以上の留分の全製品軽油に占める割合が小さいこと
により色相の悪下は少ない。The boiling point of dibenzothiophene and alkyldibenzothiophenes, which are difficult to desulfurize among sulfur compounds contained in light oil, is 330 ° C. or higher. Further, the boiling points of benzothiophene and alkylbenzothiophenes in which the desulfurization reaction easily proceeds are mainly 330 ° C. or lower. Therefore, boiling point 330
Fractions below ℃ can be hydrodesulfurized with a short residence time.
Fractions above 30 ° C require long residence times. Therefore, the raw gas oil is desulfurized in the first step with a short residence time to prevent the deterioration of the hue, the distillate having a boiling point of 330 ° C. or higher is subjected to high temperature gas-liquid separation in the second step, and the desulfurization reaction is difficult in the third step. Only a distillate having a boiling point of 330 ° C. or higher containing a sulfur compound can be desulfurized over a long residence time to produce a light oil having a low sulfur content.
In the third step, the reaction temperature is lower than that in the first step, and the boiling point is 33
Since the proportion of the fraction of 0 ° C or higher in all the light oils of the product is small, the hue is less deteriorated.
【０００９】また、従来の２段水素化脱硫法は難脱硫性
硫黄化合物に合わせた長い滞留時間で全原料軽油を処理
するため、触媒使用量が多くかつ易脱硫性化合物や沸点
の低い芳香族化合物（インデン、アルキルインデン類、
ナフタレン、アルキルナフタレン類、フルオレン等）が
過度に水素化され水素消費量が大きくなるが、上記構成
では処理量の多い第一工程を短い滞留時間で行い、長い
滞留時間の第三工程は処理量が少ないことにより、全体
として必要な触媒使用量は従来より減少し水素消費量も
低減できる。Further, in the conventional two-stage hydrodesulfurization method, since all feed gas oils are treated for a long residence time according to the hardly desulfurizable sulfur compound, the amount of the catalyst used is large and the easily desulfurizable compound and the aromatic compound having a low boiling point are used. Compounds (indene, alkylindenes,
(Naphthalene, alkylnaphthalenes, fluorene, etc.) are excessively hydrogenated and hydrogen consumption increases, but with the above configuration, the first step with a large amount of treatment is performed with a short residence time, and the third step with a long residence time is treated with a treatment amount. Since the amount of hydrogen is small, the amount of catalyst used as a whole can be reduced and the amount of hydrogen consumption can be reduced.
【００１０】[0010]
【実施例】以下、本発明の実施例を図により説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１１】初にプロセスを構成する機器を説明する。First, the devices that make up the process will be described.
【００１２】図１は本発明の実施例の構成を説明するプ
ロセスフローシートである。FIG. 1 is a process flow sheet for explaining the configuration of the embodiment of the present invention.
【００１３】本図に示すように１は第１反応器、２は第
１熱交換器、３は第１気液分離器、４は第２反応器、５
は第２熱交換器、６は第２気液分離器、７は第３熱交換
器、８は第３気液分離器である。As shown in the figure, 1 is a first reactor, 2 is a first heat exchanger, 3 is a first gas-liquid separator, 4 is a second reactor, 5
Is a second heat exchanger, 6 is a second gas-liquid separator, 7 is a third heat exchanger, and 8 is a third gas-liquid separator.
【００１４】次にプロセスフローを説明する。Next, the process flow will be described.
【００１５】原料には常圧蒸留装置で蒸留された直留軽
油（沸点範囲が１５０〜４００℃程度のもの）と重質油
分解装置から得られる分解軽油とを混合した硫黄分０.
９ｗｔ％の混合軽油を用いる。この原料軽油を図示せざ
る原料軽油タンクからフィードポンプにより反応圧力ま
で昇圧し第１反応器１へ水素ガスと共に図示せざる加熱
手段により昇温して供給する。第１反応器１における反
応条件は温度２８０℃〜３８０℃、圧力１０〜８０ｋｇ
／ｃｍ2で触媒は多孔性担体のアルミナ、シリカ、チタ
ニア、ジルコニアまたはこれらの混合酸化物にＶ，Ｍ
ｏ，Ｗ，Ｎｉ，Ｃｏ，Ｐｄ，Ｐｔ，Ｒｅ，Ｒｕ，Ｒｈ等
の活性金属を担持させたものを用いる。第１反応器１か
らの気液混合の流体は第１熱交換器２で高温分離に必要
な温度に制御され、第１気液分離器３で水素、硫化水
素、沸点３３０℃以下の留分の蒸気からなる気相と、沸
点３３０℃以上の留分の液相とに分離する。第１気液分
離器３での気液分離は温度、圧力及び水素、硫化水素、
沸点３３０℃以下の留分、沸点３３０℃以上の留分の各
成分の気液平衡係数、気液のモル比で定まる気液平衡に
より行われ、１０〜８０ｋｇ／ｃｍ2の圧力下でも沸点
３３０℃以下の留分の分圧（圧力×沸点３３０℃以下の
留分のモル数／全気相のモル数）は低いから第１熱交換
器で温度を適宜定めることにより、沸点３３０℃以下の
留分は蒸気となり気液分離ができる。第１気液分離器３
で分離された液相の沸点３３０℃以上の留分は第２反応
器４へ新たな水素ガスと共に供給される。第２反応器４
における反応条件は温度１５０〜３６０℃、圧力１０〜
８０ｋｇ／ｃｍ2で触媒は第１反応器１と同等のものを
用いる。第２反応器４からの気液混合の流体は第２熱交
換器５により以後のプロセスに適した温度に制御され、
第２気液分離器６で沸点３３０℃以上の留分を主成分と
する重質軽油と、未反応の水素、硫化水素からなるオフ
ガスとに分離される。一方、第１気液分離器３で分離さ
れた水素、硫化水素、沸点３３０℃以下の留分の蒸気か
らなる気相は第３熱交換器７により沸点３３０℃以下の
留分のみが液化する温度に冷却され、第３気液分離器８
で沸点３３０℃以下の留分を主成分とする軽質軽油と、
未反応の水素、硫化水素からなるオフガスとに分離され
る。第３気液分離器８で分離された沸点３３０℃以下の
留分を主成分とする軽質軽油は、第２気液分離器６で分
離された沸点３３０℃以上の留分を主成分とする重質軽
油とブレンドされ図示せざるストリッパで水素化分解に
より生成した軽質分と硫化水素ストリッピングした後は
製品タンクに低硫黄軽油として出荷まで貯蔵される。第
２気液分離器６と第３気液分離器８で分離されたオフガ
スは図示せざるガススクラバにより硫化水素を除去し新
らたに水素を補給して第１反応器１へ供給する。As the raw material, a straight-distilled gas oil (boiling point range of about 150 to 400 ° C.) distilled by an atmospheric distillation apparatus and a cracked gas oil obtained from a heavy oil cracking apparatus were mixed with a sulfur content of 0.
9 wt% mixed gas oil is used. The feed gas oil is fed from a feed gas oil tank (not shown) to a reaction pressure by a feed pump, and is heated and supplied to the first reactor 1 together with hydrogen gas by a heating means (not shown). The reaction conditions in the first reactor 1 are a temperature of 280 ° C. to 380 ° C. and a pressure of 10 to 80 kg.
/ Cm 2 the catalyst is a porous carrier such as alumina, silica, titania, zirconia or a mixed oxide of V, M
A material carrying an active metal such as o, W, Ni, Co, Pd, Pt, Re, Ru or Rh is used. The gas-liquid mixed fluid from the first reactor 1 is controlled by the first heat exchanger 2 to a temperature necessary for high-temperature separation, and the first gas-liquid separator 3 is hydrogen, hydrogen sulfide, and a fraction having a boiling point of 330 ° C. or lower. And a liquid phase of a fraction having a boiling point of 330 ° C. or higher. Gas-liquid separation in the first gas-liquid separator 3 includes temperature, pressure and hydrogen, hydrogen sulfide,
It is carried out by vapor-liquid equilibrium determined by the vapor-liquid equilibrium coefficient of each component of the fraction having a boiling point of 330 ° C or lower, the fraction of the boiling point of 330 ° C or higher, and the vapor-liquid molar ratio, and the boiling point of 330 even under a pressure of 10 to 80 kg / cm 2. Since the partial pressure of the fraction having a temperature of ℃ or less (pressure × the number of moles of the fraction having a boiling point of 330 ° C or less / the number of moles of the entire gas phase) is low, the temperature is appropriately determined in the first heat exchanger so that The distillate becomes vapor and can be separated into gas and liquid. First gas-liquid separator 3
The fraction having a boiling point of 330 ° C. or higher in the liquid phase separated in step 2 is supplied to the second reactor 4 together with new hydrogen gas. Second reactor 4
The reaction conditions are as follows: temperature 150-360 ° C., pressure 10-
At 80 kg / cm 2 , the same catalyst as used in the first reactor 1 is used. The gas-liquid mixed fluid from the second reactor 4 is controlled by the second heat exchanger 5 to a temperature suitable for the subsequent process,
The second gas-liquid separator 6 separates the heavy gas oil having a boiling point of 330 ° C. or higher as a main component and unreacted hydrogen and off-gas composed of hydrogen sulfide. On the other hand, in the gas phase composed of hydrogen, hydrogen sulfide, and vapors of the fraction having a boiling point of 330 ° C. or lower separated by the first gas-liquid separator 3, only the fraction having a boiling point of 330 ° C. or lower is liquefied by the third heat exchanger 7. Cooled to temperature, third gas-liquid separator 8
And light gas oil whose main component is a fraction having a boiling point of 330 ° C or less
It is separated into unreacted hydrogen and off-gas composed of hydrogen sulfide. The light gas oil whose main component is the fraction having a boiling point of 330 ° C. or lower, which is separated by the third gas-liquid separator 8, has the main component of the fraction having a boiling point of 330 ° C. or more, which is separated by the second gas-liquid separator 6. Light sulfur produced by hydrocracking in a stripper (not shown) after being blended with heavy gas oil and stripped with hydrogen sulfide are stored in a product tank as low sulfur gas oil until shipment. The off gas separated by the second gas-liquid separator 6 and the third gas-liquid separator 8 is supplied to the first reactor 1 by removing hydrogen sulfide by a gas scrubber (not shown) and replenishing hydrogen newly.
【００１６】次に反応条件を具体的に説明する。Next, the reaction conditions will be specifically described.
【００１７】実施例１
原料として直留軽油と分解軽油とを混合した硫黄分０.
９ｗｔ％の混合軽油を用い表１に示す反応条件で水素化
脱硫した。触媒はシリンダ型またはトリローブ型のペレ
ットで１０〜３０ｃｃを２倍量のカーボランダムで希釈
した。Example 1 Sulfur content of a mixture of straight run gas oil and cracked gas oil as a raw material was 0.1
Hydrodesulfurization was performed under the reaction conditions shown in Table 1 using 9 wt% of mixed gas oil. The catalyst was a cylinder type or trilobe type pellet, and 10 to 30 cc was diluted with a double amount of carborundum.
【００１８】[0018]
【表１】 [Table 1]
【００１９】それぞれの反応器で水素化脱硫した軽油を
混合した製品軽油の性状及びプロセスの特性を表２に示
す。Table 2 shows the properties and process characteristics of the product gas oil mixed with the hydrodesulfurized gas oil in each reactor.
【００２０】[0020]
【表２】 [Table 2]
【００２１】以上述べたように本実施例によれば、硫黄
分０.０５ｗｔ％以下の軽油を色相の低下をきたすこと
なく製造できる。また、従来技術では脱硫が困難な難脱
硫性硫黄化合物の多い分解軽油を原料に混合し処理でき
る。As described above, according to this embodiment, a light oil having a sulfur content of 0.05 wt% or less can be produced without causing a decrease in hue. Further, cracked gas oil containing a large amount of hardly desulfurizable sulfur compounds, which is difficult to desulfurize by the conventional technique, can be mixed with the raw material and treated.
【００２２】そして、反応器容積即ち触媒量を減少さ
せ、水素消費量を減少させることができる。Then, the reactor volume, that is, the amount of catalyst can be reduced, and the hydrogen consumption can be reduced.
【００２３】[0023]
【発明の効果】本発明によれば、原料軽油を水素化脱硫
し、脱硫反応が進行し難い硫黄化合物を含む沸点３３０
℃以上の留分を高温分離して水素化脱硫することによ
り、色相の悪下を防止し低硫黄分の軽油を製造すること
ができる。EFFECTS OF THE INVENTION According to the present invention, a boiling point of 330 containing a sulfur compound in which a raw gas oil is hydrodesulfurized and the desulfurization reaction is difficult to proceed.
By distilling the distillate having a temperature of ℃ or higher at a high temperature to hydrodesulfurize, it is possible to prevent the deterioration of the hue and produce a light oil having a low sulfur content.
【００２４】また、最初の水素化脱硫を短い滞留時間で
行い、沸点３３０℃以上の留分のみを長い滞留時間で水
素化脱硫することにより、触媒使用量及び水素消費量を
低減できる。Further, by carrying out the first hydrodesulfurization with a short residence time and hydrodesulfurizing only the fraction having a boiling point of 330 ° C. or higher with a long residence time, the amount of catalyst used and the amount of hydrogen consumption can be reduced.
【図１】本発明の実施例の構成を説明するプロセスフロ
ーシートである。FIG. 1 is a process flow sheet illustrating a configuration of an example of the present invention.
１ 第１反応器 ２ 第１熱交換器 ３ 第１気液分離器 ４ 第２反応器 ５ 第２熱交換器 ６ 第２気液分離器 ７ 第３熱交換器 ８ 第３気液分離器 1st reactor 2 First heat exchanger 3 First gas-liquid separator 4 Second reactor 5 Second heat exchanger 6 Second gas-liquid separator 7 Third heat exchanger 8 Third gas-liquid separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 稲葉 利晴 千葉県市原市八幡海岸通１番地 三井造 船株式会社 千葉事業所内 (56)参考文献 特開 平６−25677（ＪＰ，Ａ) 特開 平４−46993（ＪＰ，Ａ) 特開 平５−311179（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C10G 65/04 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiharu Inaba 1 Yawata Kaigan Dori, Ichihara City, Chiba Mitsui Engineering & Shipbuilding Co., Ltd. Chiba Works (56) Reference JP-A-6-25677 (JP, A) JP-A 4-46993 (JP, A) JP-A-5-311179 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C10G 65/04
Claims (2)
と水素を触媒の存在下で反応させて脱硫する第一工程
と、該第一工程で処理された軽油を軽質分と重質分とに
分留する第二工程と、該第二工程で分留された前記重質
分中の硫黄化合物と水素とを触媒の存在下で反応させて
脱硫する第三工程とを有することを特徴とする低硫黄軽
油の製造方法。1. A sulfur compound mainly in light components of light oil.
First step of desulfurization by reacting hydrogen with hydrogen in the presence of a catalyst
And the light oil treated in the first step into light and heavy components
Second step of fractionating, and the heavy material fractionated in the second step
By reacting sulfur compounds in the minute with hydrogen in the presence of a catalyst
And a third step of desulfurizing, which is a method for producing low-sulfur gas oil.
と水素を触媒の存在下で、温度が２８０〜３８０℃、圧
力が１０〜８０Ｋｇ／ｃｍ ２ で反応させて脱硫する第一
工程と、該第一工程で処理された軽油を軽質分と重質分
とに分留する第二工程と、該第二工程で分留された前記
重質分中の硫黄化合物と水素とを触媒の存在下で温度が
１５０〜３６０℃、圧力が１０〜８０Ｋｇ／ｃｍ ２ で反
応させて脱硫する第三工程とを有することを特徴とする
低硫黄軽油の製造方法。2. A sulfur compound mainly in light components of light oil.
And hydrogen in the presence of a catalyst at a temperature of 280 to 380 ° C and a pressure of
Desulfurization by reacting with a force of 10 to 80 Kg / cm 2
Process, and the light oil treated in the first process as light and heavy components
The second step of fractionating into
In the presence of a catalyst, the temperature of sulfur compounds and hydrogen in heavy
150 to 360 ° C., a pressure reaction at 10~80Kg / cm 2
And a third step of desulfurizing the same, thereby producing a low-sulfur gas oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15846494A JP3411998B2 (en) | 1994-07-11 | 1994-07-11 | Method for producing low sulfur gas oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15846494A JP3411998B2 (en) | 1994-07-11 | 1994-07-11 | Method for producing low sulfur gas oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0820782A JPH0820782A (en) | 1996-01-23 |
| JP3411998B2 true JP3411998B2 (en) | 2003-06-03 |
Family
ID=15672318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15846494A Expired - Fee Related JP3411998B2 (en) | 1994-07-11 | 1994-07-11 | Method for producing low sulfur gas oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3411998B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001279274A (en) * | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | Fuel oil for fuel cell, desulfurization method and method for producing hydrogen |
| JP2001294874A (en) * | 2000-04-13 | 2001-10-23 | Idemitsu Kosan Co Ltd | Fuel oil for kerosene-based fuel cell |
| JP4546160B2 (en) * | 2003-06-10 | 2010-09-15 | ハルドール・トプサー・アクチエゼルスカベット | Hydrotreating method |
-
1994
- 1994-07-11 JP JP15846494A patent/JP3411998B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0820782A (en) | 1996-01-23 |
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