CN1351118A - Medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction - Google Patents

Medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction Download PDF

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CN1351118A
CN1351118A CN 00129835 CN00129835A CN1351118A CN 1351118 A CN1351118 A CN 1351118A CN 00129835 CN00129835 CN 00129835 CN 00129835 A CN00129835 A CN 00129835A CN 1351118 A CN1351118 A CN 1351118A
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reactor
hydrogen
heavy
diesel oil
hydrobon catalyst
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CN1115390C (en
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高晓冬
陈若雷
石玉林
王哲
熊震霖
胡志海
聂红
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction includes contacting diesel oil and hydrogen with hydrorefining catalyst in the first reactor at 330-390 deg.C and 6-9 MPa, contacting its resultant without separation with hydrorefining catalyst in the second reactor at 250-290 deg.C and 6-9 MPa, gas-liquid separation, passing the liquid product into fraction system, and returning gas rich in hydrogen back to reactors. It has high effect.

Description

The aromatic hydrocarbons method is taken off in the medium-pressure hydrocracking of diesel oil distillate
The invention belongs to a kind of the existence under the situation of hydrogen for obtaining the method for the refining hydrocarbon ils of low boiler cut, more particularly, be a kind of in depress the hydrogenation aromatics-removing method of diesel oil distillate.
The environmental regulation of increasingly stringent constantly proposes strict more restriction to the aromaticity content and the sulphur content of diesel oil fuel in the world wide, the aromaticity content and the sulphur content that reduce derv fuel oil can reduce solid particulate matter and the sulfurous gas that discharges in the diesel combustion process, to reduce atmospheric pollution.Restriction to total aromatic hydrocarbons and the above aromatic hydrocarbons of dicyclo has all been proposed in the diesel oil specification that the U.S. and some countries of Europe have implemented.On June 4th, 1999, " the world fuel standard " of the issue of the world fuel council set up three other standards of different mass level to the diesel oil index, be about to diesel oil and be divided into three classes, wherein the total aromaticity content of second generic request is up to 25 heavy %, polycyclic aromatic hydrocarbon content is up to 5 heavy %, and sulphur content is 300ppm to the maximum; The total aromaticity content of the 3rd generic request is up to 15 heavy %, and polycyclic aromatic hydrocarbon content is up to 2 heavy %, and sulphur content is 30ppm to the maximum.Although the diesel oil standard that China carries out is not at present also done concrete requirement to aromaticity content, urgent day by day environmental protection situation has been put on agenda with the qualification of the aromaticity content in the diesel oil specification.Therefore each domestic oil refining enterprise all will face and reduce in the diesel oil aromaticity content to improve the particularly problem of catalytic cracking diesel oil quality of diesel oil.
Adopt conventional hydrofining technology or highly active Hydrobon catalyst to be difficult to reach the purpose that diesel fraction deep takes off aromatic hydrocarbons under the hydroprocessing condition of routine, this is because under the hydroprocessing condition of routine, and the aromatic hydrocarbons in the diesel oil distillate is difficult saturated.The diesel fraction deep of being reported at present takes off aromatic hydrocarbons technology and can be divided into two classes: a class is the refining aromatic hydrocarbons technology of taking off of high-pressure hydrogenation, another kind ofly is second section and adopts the two-stage hydrogenation of noble metal catalyst to take off aromatic hydrocarbons technology.
USP5,068, the diesel oil distillate aromatic saturation process of two kinds of non-precious metal catalysts of a kind of employing is disclosed in 025, diesel raw material and hydrogen are successively by two placed in-line hydrogenation catalyst beds, the active ingredient of first kind of hydrogenation catalyst is nickel, tungsten and phosphorus, carrier is an aluminum oxide, the operational condition of this bed is: temperature of reaction is 315~399 ℃ (600~750 °F), stagnation pressure is 4.14~17.24MPa (600~2500psig), the hydrogen dividing potential drop is that (500~2000psig), hydrogen-oil ratio is 178~890Nm to 3.44~15.17MPa 3/ m 3(1000~5000SCF/BBL), volume space velocity is 0.1~5h during liquid -1Hydrogen and raw material need not remove hydrogen sulfide and ammonia after through first beds, directly enter second beds, the active ingredient of second kind of hydrogenation catalyst is cobalt and/or nickel, molybdenum and phosphorus, carrier is an aluminum oxide, the operational condition of this bed is: temperature of reaction is 315~399 ℃ (600~750 °F), stagnation pressure is that (600~2500psig), the hydrogen dividing potential drop is that (500~2000psig), hydrogen-oil ratio is 178~890Nm to 3.44~15.17MPa to 4.14~17.24MPa 3/ m 3(1000~5000SCF/BBL), volume space velocity is 0.1~5h during liquid -1If adopt this method to require aromatics conversion rate greater than 50v%, stagnation pressure must be more than 10.0MPa, and high working pressure improves the investment of device and process cost greatly.
EP699,733 have proposed a kind of two-stage hydrogenation process of fraction oil of petroleum, first section employing is the Hydrobon catalyst of active component with cobalt-molybdenum or nickel-molybdenum, makes the outlet sulphur content not be higher than 0.05 heavy %, and second section is adopted noble metal catalyst to reduce aromaticity content.Between one, two section, have two high pressure hot separators at least, and the bottom of two separators is all introduced hydrogen or hydrogen-rich gas and is carried out gas and carry.The advantage of this method is that working pressure is lower, shortcoming is a noble metal catalyst cost height, and the generally anti-sulphur nitrogen of present noble metal catalyst ability, it is low that requirement enters second section reactant flow sulphur, nitrogen content, this just needs first section catalyzer to have higher desulfurization, denitrification activity, and first section effluent need isolate hydrogen sulfide and ammonia, so technical process is comparatively complicated.
The objective of the invention is to provide on the basis of existing technology a kind of in depress the method for diesel oil distillate being carried out hydrogenation aromatics-removing.
Method provided by the invention is: diesel raw material and hydrogen enter first reactor, volume space velocity 0.3~1.0h when 330 ℃~390 ℃ best 340 ℃~370 ℃ of temperature, stagnation pressure 7.0~9.5MPa, hydrogen dividing potential drop 6.0~9.0MPa, liquid -1, hydrogen-oil ratio 400~700v/v condition under contact with Hydrobon catalyst, the effluent of first reactor enters second reactor without separation, volume space velocity 1.5~5.0h when 250 ℃~290 ℃ of temperature, stagnation pressure 7.0~9.5MPa, hydrogen dividing potential drop 6.0~9.0MPa, liquid -1, hydrogen-oil ratio 400~700v/v condition under contact with Hydrobon catalyst, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
Described diesel raw material is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil or its mixture.The boiling range scope of diesel raw material is 140~390 ℃ and is preferably 180~370 ℃.
First reactor and second reactor are fixed-bed reactor, and each reactor has a bed at least.The severe reaction conditions of first reactor shows as the temperature height, air speed is low, and in this reactor, the aromatic hydrocarbons in the diesel raw material is mainly by saturated, and sulphur, nitrogen are by hydrogenation and removing significantly; And the reaction conditions of second reactor relaxes relatively, shows as that temperature is low, air speed is high, in this reactor, to improve the color of diesel oil distillate, a small amount of double ring arene is also arranged by saturated simultaneously.
The used Hydrobon catalyst of first reactor and second reactor is identical, this catalyzer can be VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, preferably consisting of of Hydrobon catalyst: 1~5 heavy % nickel oxide, 12~35 heavy % Tungsten oxide 99.999s, 1~9 heavy % fluorine and surplus aluminum oxide.When carbon residue, alkene and metal content are higher in the diesel raw material; for preventing that the beds coking from causing bed pressure drop too fast; can add a certain amount of hydrogenation protecting agent at the Hydrobon catalyst top of first reactor; with the running of assurance device long period ground, the add-on of hydrogenation protecting agent is generally 5~15 volume % of Hydrobon catalyst.This hydrogenation protecting agent is made up of the gamma-aluminium oxide carrier with diplopore distribution of 1.0~5.0 heavy % nickel oxide, 5.5~10.0 heavy % molybdenum oxides and surplus.
The invention has the advantages that:
1, working pressure is relatively low.Compared with prior art, when reaching identical aromatics conversion rate, method working pressure of the present invention is lower, or under identical pressure, method aromatics conversion rate of the present invention is higher.Because this method is operated under middle pressure, thereby has reduced plant investment, has reduced process cost;
2, the device flow process is simple.Only adopt a kind of non-noble metal hydrogenation catalyst for refining single hop operation, be seated in two fixed-bed reactor, in first reactor, diesel raw material is carried out the aromatic hydrocarbons saturated reaction under the condition of high temperature, low-speed, in second reactor, reactant flow is carried out the back refining reaction under the condition of low temperature, high-speed, to improve the color of reactant flow.This flow process is identical with general hydro-refining unit flow process, a just reactor and one group of interchanger of increasing more, and it is simple to have flow process, and the advantage of easy handling can be utilized existing apparatus transformation;
3, total aromatic hydrocarbons of product and the above aromatic hydrocarbons of dicyclo reduce significantly than raw material behind the hydrogenation, the reduction amplitude is bigger than general hydrofining technology arene engaging scraping amplitude, total aromatic hydrocarbons can be reduced to by 53.4 heavy % of raw material below the 30 heavy %, even can reduce to below the 25 heavy %, aromatics conversion rate can reach 50~70%.The cetane value of product increases substantially, and can improve 10~18 units, and this also is a distinguishing feature that is different from conventional hydrofining technology.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Diesel raw material character among the embodiment is as shown in table 1, and total aromaticity content of this raw material is 53.4 heavy %, and cetane value is 34.2.The trade names of employed Hydrobon catalyst, hydrogenation protecting agent are respectively RN-10, RG-1 among the embodiment, produce by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant, and its composition and physico-chemical property are as shown in table 2.
Embodiment 1
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 0.6h when 363 ℃ of temperature, stagnation pressure 6.4MPa, hydrogen dividing potential drop 6.15MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with hydrogenation protecting agent RG-1, Hydrobon catalyst RN-10 (RG-1 is the 10 volume % of RN-10) successively; the effluent of first reactor enters second reactor without separation, volume space velocity 2.7h when 290 ℃ of temperature, stagnation pressure 6.4MPa, hydrogen dividing potential drop 6.15MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, total aromaticity content of diesel oil distillate is 20.2 heavy % in the product, and the arene engaging scraping rate is 62.2%, and cetane value is 48.3, has improved 14.1 units.
Embodiment 2
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 0.6h when 363 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, the effluent of first reactor enters second reactor without separation, volume space velocity 2.7h when 290 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, total aromaticity content of diesel oil distillate is 20.1 heavy % in the product, and the arene engaging scraping rate is 62.4%, and cetane value is 49.0, has improved 14.8 units.
Embodiment 3
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 1.0h when 364 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, the effluent of first reactor enters second reactor without separation, volume space velocity 4.3h when 290 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 3, and as can be seen from Table 3, total aromaticity content of diesel oil distillate is 26.3 heavy % in the product, and the arene engaging scraping rate is 50.7%, and cetane value is 48.2, has improved 14.0 units.
Embodiment 4
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 1.0h when 363 ℃ of temperature, stagnation pressure 8.0MPa, hydrogen dividing potential drop 7.70MPa, liquid -1, hydrogen-oil ratio 700v/v condition under contact with Hydrobon catalyst RN-10, the effluent of first reactor enters second reactor without separation, volume space velocity 4.3h when 290 ℃ of temperature, stagnation pressure 8.0MPa, hydrogen dividing potential drop 7.70MPa, liquid -1, hydrogen-oil ratio 700v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, total aromaticity content of diesel oil distillate is 24.6 heavy % in the product, and the arene engaging scraping rate is 53.9%, and cetane value is 50.0, has improved 15.8 units.
Embodiment 5
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 0.37h when 363 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, the effluent of first reactor enters second reactor without separation, volume space velocity 1.6h when 290 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 500v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, total aromaticity content of diesel oil distillate is 12.8 heavy % in the product, and the arene engaging scraping rate is 76.0%, and cetane value is 51.5, has improved 17.3 units.
Embodiment 6
Catalytic cracking diesel oil raw material and hydrogen enter first reactor, volume space velocity 0.7h when 340 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 700v/v condition under contact with Hydrobon catalyst RN-10, the effluent of first reactor enters second reactor without separation, volume space velocity 3.2h when 290 ℃ of temperature, stagnation pressure 7.0MPa, hydrogen dividing potential drop 6.73MPa, liquid -1, hydrogen-oil ratio 700v/v condition under contact with Hydrobon catalyst RN-10, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
The character of processing condition and main products is as shown in table 4, and as can be seen from Table 4, total aromaticity content of diesel oil distillate is 26.1 heavy % in the product, and the arene engaging scraping rate is 51.1%, and cetane value is 48.5, has improved 14.3 units.
Table 1
Material name Catalytic cracking diesel oil
Colourity (D1500) ????3.0
Sulphur content, ppm ????1518
Nitrogen content, ppm ????959
The bromine valency, gBr/100g ????25.3
Total aromatic hydrocarbons (mass spectrum), heavy % ????53.4
Monocycle, heavy % ????18.1
Dicyclo, heavy % ????28.2
Three rings, heavy % ????7.1
The above aromatic hydrocarbons of dicyclo, heavy % ????35.3
Cetane value (motor mensuration) ????34.2
Boiling range (ASTM D-86), ℃ ????191~365
Table 2
Catalyst type Hydrofining Protective material
The catalyzer trade mark ????RN-10 ????RG-1
Nickel oxide, heavy % ????4.0 ????1.2
Tungsten oxide 99.999, heavy % ????26.0 (5.5 molybdenum oxide)
Fluorine, heavy % ????2.0 ?????-
Specific surface, rice 2/ gram ????230 ????205
Pore volume, milliliter/gram ????0.27 ????0.68
Crushing strength, Newton/millimeter ????27.5 ????14.0
Table 3
Embodiment ????1 ????2 ????3
Processing condition
Stagnation pressure, MPa ????6.4 ????7.0 ????7.0
The hydrogen dividing potential drop, MPa ????6.15 ????6.73 ????6.73
Temperature of reaction, ℃
First reactor ????363 ????363 ????364
Second reactor ????290 ????290 ????290
Volume space velocity, h -1
First reactor ????0.6 ????0.6 ????1.0
Second reactor ????2.7 ????2.7 ????4.3
Hydrogen-oil ratio, v/v ????500 ????500 ????500
Liquid is received, heavy % ????101.7 ????101.9 ????101.6
Colourity (D1500) ????0.5 ????0.5 ????<1.0
Sulphur content, ppm ????<30 ????<30 ????<50
Nitrogen content, ppm ????0.7 ????0.6 ????1.2
The bromine valency, gBr/100g ????0.2 ????0.2 ????0.3
Cetane value (motor actual measurement) ????48.3 ????49.0 ????48.2
Cetane value improves unit ????14.1 ????14.8 ????14.0
Boiling range (ASTM D-86), ℃ ??180~363 ??179~364 ??176~362
Total aromatic hydrocarbons (mass spectrum), heavy % ????20.2 ????20.1 ????26.3
The above aromatic hydrocarbons of dicyclo ????2.6 ????2.7 ????3.6
Take off fragrant rate, % ????62.2 ????62.4 ????50.7
Table 4
Embodiment ????4 ????5 ????6
Processing condition
Stagnation pressure, MPa ????8.0 ????7.0 ????7.0
The hydrogen dividing potential drop, MPa ????7.7 ????6.73 ????6.73
Temperature of reaction, ℃
First reactor ????363 ????363 ????340
Second reactor ????290 ????290 ????290
Volume space velocity, h -1
First reactor ????1.0 ????0.37 ????0.7
Second reactor ????4.3 ????1.6 ????3.2
Hydrogen-oil ratio, v/v ????700 ????500 ????700
Liquid is received, heavy % ????101.9 ????101.7 ????101.9
Colourity (D1500) ????<0.5 ????<0.5 ????<0.5
Sulphur content, ppm ????<30 ????<5 ????<30
Nitrogen content, ppm ????0.7 ????0.4 ????0.7
The bromine valency, gBr/100g ????0.3 ????0.2 ????0.2
Cetane value (motor actual measurement) ????50.0 ????51.5 ????48.5
Cetane value improves unit ????15.8 ????17.3 ????14.3
Boiling range (ASTM D-86), ℃ ??177~364 ??174~363 ??179~364
Total aromatic hydrocarbons (mass spectrum), heavy % ????24.6 ????12.8 ????26.1
The above aromatic hydrocarbons of dicyclo ????3.1 ????1.7 ????3.1
Take off fragrant rate, % ????53.9 ????76.0 ????51.1

Claims (7)

1, the aromatic hydrocarbons method is taken off in a kind of medium-pressure hydrocracking of diesel oil distillate, it is characterized in that diesel raw material and hydrogen enter first reactor, volume space velocity 0.3~1.0h when 330 ℃~390 ℃ of temperature, stagnation pressure 7.0~9.5MPa, hydrogen dividing potential drop 6.0~9.0MPa, liquid -1, hydrogen-oil ratio 400~700v/v condition under contact with Hydrobon catalyst, the effluent of first reactor enters second reactor without separation, volume space velocity 1.5~5.0h when 250 ℃~290 ℃ of temperature, stagnation pressure 7.0~9.5MPa, hydrogen dividing potential drop 6.0~9.0MPa, liquid -1, hydrogen-oil ratio 400~700v/v condition under contact with Hydrobon catalyst, reaction effluent is through gas-liquid separation, isolated product liquid enters fractionating system, rich hydrogenous gas circulation is returned two reactors.
2,, it is characterized in that described diesel raw material is straight-run diesel oil, catalytic cracking diesel oil, coker gas oil or its mixture according to the method for claim 1.
3, according to the method for claim 1, the temperature that it is characterized in that first reactor is 340 ℃~370 ℃.
4, according to the method for claim 1, it is characterized in that the used Hydrobon catalyst of first reactor and second reactor is identical, this catalyzer can be VIB and/or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports.
5, according to the method for claim 1 or 4, it is characterized in that consisting of of described Hydrobon catalyst: 1~5 heavy % nickel oxide, 12~35 heavy % Tungsten oxide 99.999s, 1~9 heavy % fluorine and surplus aluminum oxide.
6, according to the method for claim 1, it is characterized in that adding the hydrogenation protecting agent at the Hydrobon catalyst top of first reactor, the add-on of hydrogenation protecting agent is 5~15 volume % of Hydrobon catalyst.
7,, it is characterized in that described hydrogenation protecting agent is made up of the gamma-aluminium oxide carrier that diplopore distributes that has of 1.0~5.0 heavy % nickel oxide, 5.5~10.0 heavy % molybdenum oxides and surplus according to the method for claim 1.
CN 00129835 2000-10-30 2000-10-30 Medium-pressure hydrogenating process for removing arylhydrocarbon from diesel oil fraction Expired - Lifetime CN1115390C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323140C (en) * 2004-08-31 2007-06-27 中国石油化工股份有限公司 Two-step super-depth method for removing arenes from natural gas synthetic oil
CN101942330A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil
CN101092575B (en) * 2006-06-22 2011-08-10 中国石油化工股份有限公司 Method for producing diesel oil with low sulphur and low arene
CN1990830B (en) * 2005-12-30 2011-12-21 中国石油化工股份有限公司 hydrorefining method for coker gasoline

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323140C (en) * 2004-08-31 2007-06-27 中国石油化工股份有限公司 Two-step super-depth method for removing arenes from natural gas synthetic oil
CN1990830B (en) * 2005-12-30 2011-12-21 中国石油化工股份有限公司 hydrorefining method for coker gasoline
CN101092575B (en) * 2006-06-22 2011-08-10 中国石油化工股份有限公司 Method for producing diesel oil with low sulphur and low arene
CN101942330A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司抚顺石油化工研究院 Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil
CN101942330B (en) * 2009-07-09 2013-06-19 中国石油化工股份有限公司 Method for deep hydrogenation, sulfur removal and aromatics removal of diesel oil

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