CN1769387A - Diesel fuel fraction hydrotreating method - Google Patents
Diesel fuel fraction hydrotreating method Download PDFInfo
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Abstract
The invention discloses the diesel oil distillate hydrotreating method. The method comprises the following steps: dividing the raw oil into light cut and heavy cut, entering the light cut into the first reaction area to touch the hydrofining catalyst, entering the heavy cut into the second reaction area to touch the hydrofining catalyst, mixing the liquid product of the two reaction areas to prepare the refined distillate oil. The first reaction area uses the hydrogenation catalyst which possesses high desulfurizing activity, and the second reaction area uses hydrogenation catalyst which possesses the high hydrogenation activity. Comparaed with the general diesel oil refined process, the said method can realize the deep hydrogenation and desulfuration. The method possesses the characteristics of simple process flow and easy operation. The said method can be used for various hydrotreating processes containing the diesel oil fraction raw oil.
Description
Technical field
The present invention relates to a kind of diesel oil hydrotreating method, special diesel fraction deep hydrogenation desulfuration processing method.
Background technology
Along with the strictness day by day of environmental regulation, the low-sulfur diesel-oil particularly production of ultra-low-sulphur diesel becomes the pressing problem that the oil refining worker faces.On the other hand, along with the atrophy in mink cell focus market, the degree of depth transforming degree of heavy residual oil improves constantly, and makes the downgrade of secondary processing product such as catalytic diesel oil (LCO) etc., is difficult to find competent low-sulfur diesel-oil component to be in harmonious proportion with it.Therefore people wait in expectation and can develop the new process that can reduce the diesel oil sulphur content.
The common method of processing diesel oil is hydrofining at present.For produce low-sulfur diesel-oil particularly ultra-low-sulphur diesel be the unifining process of purpose, need remove the sulphur compound (substituent dibenzothiophene is arranged) that difficulty removes.In order to remove the sulphur compound that difficulty removes, need to improve the device operating severity, for example, improve temperature of reaction, reduce air speed.Improve temperature of reaction, the saturated Equilibrium limit that is subjected to of aromatic hydrocarbons will be difficult to remove more, reduce air speed and mean the increase reactor volume.Selection of catalysts is faced adverse conditions equally, for direct desulfurization, and Mo-Co catalyst activity height, the sulphur compound that removes for difficulty, the route that needs desulfurization behind the first hydrogenation, Mo-Ni and W-Ni catalyzer are because of hydrogenation and the aromatic hydrocarbons saturability is good preponderates, so, in petroleum refining industry, usually adopt catalyst grade prescription formula, first section is adopted the Mo-Co catalyzer, and second section is adopted the Mo-Ni catalyzer, to reach the deep desulfuration purpose, grating can also can have multiple reactor in single reactor.But this arts demand rises the reactive hydrogen consumption the whole deep hydrogenations of diesel component significantly, and running cost also increases substantially thereupon.When Ultra-deep Desulfurization of Diesel Fuels, total air speed of this technology is low.
U.S. Pat 6551501 has been described the diesel fuel desulfurization technology that a kind of first fractionation by adsorption polarity contains the desulfurization of N compound repeated hydrogenation.This technology equally need be with the whole deep hydrogenations of diesel component.
Studies show that (as seen) by table 1 data, sulfocompound in the diesel oil is the most difficult, and what deviate from is the dibenzothiophene compounds that contains methyl, this be because methyl cause sterically hindered, sulphur atom in this class sulfocompound is difficult near the activity of such catalysts center, must abolishes through the hydrogenation route and sterically hinderedly just can carry out desulphurization reaction.Owing to contain the boiling point height of the dibenzothiophene compounds of methyl, it concentrates on the heavy part of boiling range in the diesel oil distillate.The method of final boiling point that therefore can be by reducing diesel oil distillate is removed the unmanageable dibenzothiophene compounds that contains methyl of part, to reduce the desulfurization difficulty of diesel oil distillate.This kind working method sees NPRA can document AM-03-119.This technology reduces diesel yield inevitably.
Chinese patent CN01133378.2 provides a kind of hydrocarbon raw material to carry out the method that deep desulfuration is produced clean fuel (particularly diesel oil).Include two reaction zones in this method: first reaction zone and second reaction zone.First reaction zone comprises at least one reactor: hydrofining/cracking case and at least one reaction bed; Second reaction zone comprises a catalysis stripping reactor, and this catalysis stripping reactor is by middle stripping stage, a upper reaction section and lower reaction section integrated reaction device constituting of totally three parts.Can process the diesel oil of the about 500ppm of sulphur content, processing high sulfur diesel needs first hydrofining, the stock oil sulphur content is dropped to below the 500ppm, and this technical process complexity, the total air speed of catalyzer is low.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of diesel oil hydrogenation treatment process, high-sulfur poor ignition quality fuel deep hydrodesulfurizationof technology particularly, compare with common diesel refining processing, this technology can realize deep hydrodesulfurizationof of diesel oil under the suitable condition of the total air speed of catalyzer, and the hydrogen consumption is low, operational condition relaxes.Compare with multistage hydrogenation treatment technique, have that technical process is simple, the characteristics of flexible operation.
Technical scheme of the present invention is: earlier with the stock oil fractionation, isolate lighting end and last running, first reaction zone is sent in lighting end, contacts with Hydrobon catalyst; Second reaction zone is sent in last running, contacts with Hydrobon catalyst; Two reaction zone liquid products are mixed into refining distillate.The final boiling point of lighting end (or initial boiling point of last running) generally may be controlled to 210~330 ℃, is preferably 220~320 ℃.
The reaction conditions of described two reaction zones is: reaction stagnation pressure 2MPa-15MPa, and preferred 3MPa-10MPa, temperature of reaction is 250 ℃-500 ℃, preferred 300 ℃-400 ℃, volume space velocity is generally 0.1h during liquid
-1-5.0h
-1, preferred 0.5h
-1-4.0h
-1, hydrogen to oil volume ratio is 100-3000, preferred 300-1000.Two catalyzer and/or processing condition differences that reaction zone uses.The reaction conditions of first reaction zone and second reaction zone is identical or different, preferred second reaction zone carries out under than the relative severe condition of first reaction zone: the second reaction zone reaction pressure is than the high 0~6MPa of first reaction zone, and the second reaction zone liquid hourly space velocity is than the low 0~3h of first reaction zone
-1, the second reaction zone hydrogen to oil volume ratio is higher by 0~700 than first reaction zone, and the temperature of two reaction zones can be identical or different.Two reaction zones can use identical hydrogenation catalyst, also can use different Hydrobon catalysts.First reaction zone preferably has the hydrogenation catalyst of high desulfurization activity, as Mo-Co, Mo-Co-Ni catalyzer etc.; Second reaction zone preferably has the hydrogenation catalyst of high hydrogenation activity, as Mo-Ni, W-Ni, W-Mo-Ni or W-Mo-Co-Ni catalyzer etc.Can be independent a kind of catalyzer in each reaction zone, also can several catalyst mix or grating use, preferred if grating is used along stock oil flow direction using in order by high desulfurization activity catalyzer and high hydrogenation activity catalyzer.Can select Mo-Co catalyzer and Mo-Co-Ni catalyst combination as first reaction zone; Second reaction zone can be selected Mo-Ni and W-Mo-Ni catalyst combination.
By table 1 as seen, the boiling point of the most difficult dibenzothiophene class sulfocompound that contains methyl that removes is higher in the diesel oil, weight cut separate machined, can be according to the difference of sulfocompound, adopt dissimilar catalyzer and processing condition, the characteristics of dissimilar catalyzer are not fully exerted, improve the catalyzer service efficiency, when reaching identical desulfurization depth, the total air speed height of catalyzer.The catalyzer of high desulfurization activity, low hydrogenation activity is used in lighting end, realizes shallow degree hydrogenation deep desulfuration; High hydrogenation activity catalyzer is used in last running, carries out deep desulfuration, aromatic hydrocarbons is saturated, needn't carry out full fraction deep hydrogenation desulfurization.When reaching identical desulfurization depth, use technological reaction hydrogen consumption of the present invention to be descended significantly, the overall operation condition relaxes, and is suitable for the large-scale industry device and uses.
Embodiment
Preferred scheme of the present invention is: earlier with the stock oil fractionation, be separated into the weight cut, first reaction zone is sent in lighting end, uses catalyzer hydrofining under the mitigation condition of high desulfurization activity; Second reaction zone is sent in last running, and the catalyzer that uses high hydrogenation activity is relatively than hydrofining under the exacting terms.
Specific embodiments of the present invention can comprise the steps:
(1), isolates the weight cut with the hydrocarbons raw oil fractionation;
(2) lighting end that step 1 is fractionated out is directly delivered to first reaction zone and is adopted the catalyzer of high desulfurization activity to carry out hydrofining, obtains reaction effluent;
(3) last running that step 1 the is fractionated out catalyzer of directly delivering to the high hydrogenation activity of second reaction zone carries out hydrofining, obtains reaction effluent;
(4) reaction effluent that step 2 and step 3 are obtained is isolated hydrogen-rich gas and high pressure hydrocarbon liquid through high-pressure separator;
(5) will remove H from the hydrogen-rich gas of step 4 through washing or alkali cleaning
2S and NH
3After, send into circulating hydrogen compressor, recycle;
(6) will send into the light pressure separator separation from the high pressure hydrocarbon liquid of step 4 and obtain product.
The step that can select to use comprises:
(7) product that step 6 is obtained is sent into the steam gas stripping column and is further separated, and obtains gas, petroleum naphtha and final diesel product, also can not separate directly as diesel product.
The described stock oil of step 1 can be a kind of or mixture that contains the various hydro carbons of diesel oil distillate.As can being to be selected from oil, oil shale, gelatin liquefaction gained hydro carbons; Can be the straight run hydro carbons of refinery's atmospheric and vacuum distillation unit production, also can be in secondary processing device (as catalytic cracking, delayed coking, solvent deasphalting etc.) the gained hydro carbons one or more, comprise intermediate oil, wax oil cut etc.
The described fractionation of step 1 can be adopted conventional fractionating technology, pressure fractionating as usual.
The final boiling point of the described fractionation lighting end of step 1 (or initial boiling point of last running) generally may be controlled to 210~330 ℃, is preferably 220~320 ℃
The described reaction zone of step 2 adopts the known conventional Hydrobon catalyst of those skilled in the art of the present technique, and reactor is fixed-bed reactor; Employed catalyzer generally is that one or more are carrier with aluminum oxide, siliceous aluminum oxide, amorphous silicon aluminium, Y zeolite, beta molecular sieve and other refractory oxide, optionally adds among other various auxiliary agents such as Si, P, Ti, the Zr etc. one or more.
The described reaction zone of step 3 adopts the known conventional Hydrobon catalyst of those skilled in the art of the present technique, and reactor is fixed-bed reactor; Employed catalyzer generally is that one or more are carrier with aluminum oxide, siliceous aluminum oxide, amorphous silicon aluminium, Y zeolite, beta molecular sieve and other refractory oxide, optionally adds among other various auxiliary agents such as Si, P, Ti, the Zr etc. one or more.
The feature that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.Embodiment estimates with stock oil character and sees Table 2.
Embodiment 1
Present embodiment first reaction zone adopts the FDS-4 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation, this activity of such catalysts metal component is a cobalt-molybdenum, second reaction zone adopts the FH-98 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation, and this activity of such catalysts metal component is nickel-molybdenum-tungsten.Kuwait's mixing oil is divided into<300 ℃ of lighting ends and>300 ℃ of last running, first reaction zone is sent in<300 ℃ of lighting ends, and second reaction zone is sent in>300 ℃ of last running.Other processing condition see Table 3, and polishing oil production character sees Table 4.The main character of catalyzer sees Table 5.
Embodiment 2
Kuwait's mixing oil is divided into<320 ℃ of lighting ends and>320 ℃ of last running, first reaction zone is sent in<320 ℃ of lighting ends, and second reaction zone is sent in>320 ℃ of last running, and all the other conditions are with embodiment 1.Other processing condition see Table 3, and polishing oil production character sees Table 4.
Embodiment 3
Present embodiment first reaction zone and second reaction zone all adopt the FDS-4 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation, and processing condition see Table 3, and polishing oil production character sees Table 4.All the other conditions are with example 1.
Comparative example 1
Adopt conventional hydrofining technology, the FDS-4 Hydrobon catalyst of filling Fushun Petrochemical Research Institute exploitation, other processing condition see Table 3, and polishing oil production character sees Table 4.All the other conditions are with example 1.
Comparative example 2
Adopt conventional hydrofining technology, the FH-98 Hydrobon catalyst of filling Fushun Petrochemical Research Institute exploitation, other processing condition see Table 3, and polishing oil production character sees Table 4.All the other conditions are with example 1.
Embodiment 4
Present embodiment first reaction zone adopts the FDS-4 and the combination of FF-14 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation, reactor top filling FDS-4 catalyzer, and this FF-14 catalyzer is loaded in the bottom, and two kinds of catalyst loading volume ratios are 50: 50.Second reaction zone adopts the FH-98 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation.The active metal component of FF-14 Hydrobon catalyst is nickel-cobalt-molybdenum.Straight run atmosphere 3rd side cut distillate is divided into<290 ℃ of lighting ends and>290 ℃ of last running, first reaction zone is sent in<290 ℃ of lighting ends, and second reaction zone is sent in>290 ℃ of last running.Other processing condition are seen continuous table 3, and polishing oil production character is seen continuous table 4.The main character of catalyzer sees Table 5.
Embodiment 5
Present embodiment first reaction zone adopts the FDS-4 of Fushun Petrochemical Research Institute's exploitation, and second reaction zone adopts the FH-98 Hydrobon catalyst of Fushun Petrochemical Research Institute's exploitation.Other processing condition are seen continuous table 3, and polishing oil production character is seen continuous table 4.All the other conditions are with example 4.
Than example 3
Adopt conventional hydrofining technology, the FDS-4 Hydrobon catalyst of filling Fushun Petrochemical Research Institute exploitation, other processing condition are seen continuous table 3, polishing oil production character is seen continuous table 4.All the other conditions are with example 4.
Than example 4
Adopt conventional hydrofining technology, the FDS-4 and the FF-14 Hydrobon catalyst of the exploitation of filling Fushun Petrochemical Research Institute, reactor top filling FDS-4 catalyzer, this FF-14 catalyzer is loaded in the bottom, and two kinds of catalyst loading volume ratios are 50: 50., other processing condition are seen continuous table 3, polishing oil production character is seen continuous table 4.All the other conditions are with example 4.
Than example 5
Adopt conventional hydrofining technology, the FH-98 Hydrobon catalyst of filling Fushun Petrochemical Research Institute exploitation, other processing condition are seen continuous table 3, polishing oil production character is seen continuous table 4.All the other conditions are with example 4.
Table 4 the result show, when desulfurization depth is close, adopt the total air speed of technological reaction of the present invention also obviously to reduce apparently higher than conventional hydrogenation technique and reactive hydrogen consumption.When reaction velocity is suitable, adopt the desulfurization depth of technology of the present invention to significantly improve, can carry out ultra-deep desulfurization.
This shows that technology of the present invention can make the characteristics of dissimilar catalyzer be not fully exerted, improve the catalyzer service efficiency, when reaching identical desulfurization depth, the total air speed height of catalyzer, low, the reaction conditions mitigation of hydrogen consumption.
Main sulfocompound in table 1 diesel oil distillate
Reactant | Relative reaction rate | Boiling point, ℃ |
Thiophene | 100 | 85.5 |
Thionaphthene | 30 | 221 |
Dibenzothiophene | 30 | 310 |
Methyldibenzothiophene | 5 | 315.6-326.7 |
Dimethyl Dibenzothiophene | 1 | 332.2-343.3 |
The trimethylammonium dibenzothiophene | 1 | 348.9-360.0 |
Table 2 hydrofining stock oil character
Stock oil | Kuwait's mixing oil | Straight run atmosphere 3rd side cut distillate |
Ultimate analysis | ||
S,μg/g | 11280 | 15600 |
N,μg/g | 588 | 359 |
Density (20 ℃), g/cm 3 | 0.8995 | 0.8765 |
The boiling range scope, ℃ | 189~366 | 183~383 |
Table 3 hydrofining technology condition
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||||
Reaction zone | One | Two | One | Two | One | Two | / | / |
Catalyzer | FDS-4 | FH-98 | FDS-4 | FH-98 | FDS-4 | FDS-4 | FDS-4 | FH-98 |
Stock oil | Kuwait's mixing oil | |||||||
Processing condition | ||||||||
Reaction hydrogen pressure/MPa | 3.2 | 6.5 | 3.2 | 6.5 | 3.2 | 6.5 | 6.5 | 6.5 |
Hydrogen to oil volume ratio | 300∶1 | 450∶1 | 300∶1 | 450∶1 | 300∶1 | 450∶1 | 450∶1 | 450∶1 |
Volume space velocity/h -1 | 3.5 | 1.5 | 3.5 | 1.5 | 2.5 | 0.70 | 1.8 | 1.5 |
Cumulative volume air speed/h -1 | 2.9 | 3.1 | 1.8 | 1.8 | 1.5 | |||
Temperature of reaction/℃ | 350 | 350 | 350 | 350 | 350 | 350 | 350 | 350 |
Continuous table 3 hydrofining technology condition
Embodiment 4 | Embodiment 5 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |||
Reaction zone | One | Two | One | Two | / | / | |
Catalyzer | FDS-4/ FF-14 | FH-98 | FDS-4 | FH-98 | FDS-4 | FDS-4/ FF-14 | FH-98 |
Stock oil | Straight run atmosphere 3rd side cut distillate | ||||||
Processing condition | |||||||
Reaction hydrogen pressure/MPa | 3.2 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 | 6.5 |
Hydrogen to oil volume ratio | 300∶1 | 450∶1 | 450∶1 | 450∶1 | 450∶1 | 450∶1 | 450∶1 |
Volume space velocity/h -1 | 3.5 | 1.5 | 3.0 | 3.0 | 1.8 | 1.8 | 1.5 |
Cumulative volume air speed/h -1 | 2.5 | 3.0 | 1.8 | 1.8 | 1.8 | ||
Temperature of reaction/℃ | 340 | 350 | 350 | 350 | 350 | 350 | 350 |
The final hydrofined oil product property of table 4
Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
Density (20 ℃), g/cm 3 | 0.8713 | 0.8711 | 0.8665 | 0.8668 | 0.8652 |
Sulphur content, μ g/g | 147 | 156 | 45 | 247 | 152 |
The flow process scope, ℃ | 188~363 | 188~362 | 186~362 | 183~365 | 181~364 |
Hydrogen consumes relatively | 0.84 | 0.85 | 1.21 | 1 | 1.32 |
The final hydrofined oil product property of continuous table 4
Embodiment 4 | Embodiment 5 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
Density (20 ℃), g/cm 3 | 0.8573 | 0.8570 | 0.8565 | 0.8588 | 0.8552 |
Sulphur content, μ g/g | 381 | 377 | 422 | 509 | 386 |
The flow process scope, ℃ | 178~381 | 177~381 | 177~380 | 179~381 | 177~379 |
Hydrogen consumes relatively | 0.85 | 0.87 | 1.19 | 1 | 1.22 |
Table 5 uses the composition and the main character of catalyzer
Project | FDS-4 | FH-98 | FF-14 |
Chemical constitution, % | |||
MoO 3 | 19.8 | 9.3 | 24 |
WO 3 | 19.1 | ||
NiO | 4.3 | 2 | |
CoO | 3.72 | 1.9 | |
Carrier | Siliceous aluminum oxide | Aluminum oxide | Siliceous aluminum oxide |
Physico-chemical property | |||
Pore volume/mLg -1 | 0.41 | 0.32 | 0.38 |
Specific surface area/m 2·g -1 | 235 | 143 | 175 |
Claims (10)
1, a kind of diesel oil fraction hydrogenating treatment process, earlier with the stock oil fractionation, isolate lighting end and last running, first reaction zone is sent in lighting end, contact with Hydrobon catalyst, second reaction zone is sent in last running, contacts with Hydrobon catalyst, two reaction zone liquid products are mixed into refining distillate, and the final boiling point of lighting end or the initial boiling point of last running are controlled to be 210~330 ℃;
Two catalyzer and/or processing condition differences that reaction zone uses: second reaction zone carries out under than the relative severe condition of first reaction zone, and/or first reaction zone uses hydrogenation catalyst, second reaction zone with high desulfurization activity to use the hydrogenation catalyst with high hydrogenation activity.
2, in accordance with the method for claim 1, it is characterized in that the final boiling point of described lighting end or the initial boiling point of last running are controlled to be 220~320 ℃.
3, in accordance with the method for claim 1, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: reaction stagnation pressure 2MPa-15MPa, temperature of reaction is 250 ℃-500 ℃, volume space velocity is 0.1h during liquid
-1-5.0h
-1, hydrogen to oil volume ratio is 100-3000.
4, in accordance with the method for claim 1, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: reaction stagnation pressure 3MPa-10MPa, temperature of reaction is 300 ℃-400 ℃, volume space velocity is 0.5h during liquid
-1-4.0h
-1, hydrogen to oil volume ratio is 300-1000.
5, according to claim 3 or 4 described methods, it is characterized in that the second reaction zone reaction pressure than the high 0~6MPa of first reaction zone, the second reaction zone liquid hourly space velocity is than the low 0~3h of first reaction zone
-1, the second reaction zone hydrogen to oil volume ratio is higher by 0~700 than first reaction zone.
6, in accordance with the method for claim 1, it is characterized in that the catalyzer with high desulfurization activity that described first reaction zone uses is Mo-Co or Mo-Co-Ni catalyzer; The catalyzer with high hydrogenation activity that second reaction zone uses is Mo-Ni, W-Ni, W-Mo-Ni or W-Mo-Co-Ni catalyzer.
7, in accordance with the method for claim 1, it is characterized in that described two reaction zone liquid products mix the refined diesel oil cut that obtains and can further separate and obtain petroleum naphtha and diesel oil.
8, in accordance with the method for claim 6, it is characterized in that one or more are carrier to described catalyzer with aluminum oxide, siliceous aluminum oxide, amorphous silicon aluminium, Y zeolite, beta molecular sieve and other refractory oxide, can optionally contain in Si, P, Ti and the Zr auxiliary agent one or more.
9, in accordance with the method for claim 1, it is characterized in that described first reaction zone and second reaction zone adopt solid-bed reactor.
10, in accordance with the method for claim 1, it is characterized in that described stock oil is a kind of or mixture that contains the various hydro carbons of diesel oil distillate.
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CN108102709A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | The processing and treating method of catalytic diesel oil |
CN108102703A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of processing and treating method of catalytic diesel oil |
CN108102702A (en) * | 2016-11-24 | 2018-06-01 | 中国石油化工股份有限公司 | The processing method of catalytic diesel oil |
CN108102709B (en) * | 2016-11-24 | 2020-05-19 | 中国石油化工股份有限公司 | Processing method of catalytic diesel oil |
CN108102703B (en) * | 2016-11-24 | 2020-06-09 | 中国石油化工股份有限公司 | Processing method of catalytic diesel oil |
CN108102713B (en) * | 2016-11-24 | 2020-09-11 | 中国石油化工股份有限公司 | Processing method of catalytic diesel oil |
CN108102702B (en) * | 2016-11-24 | 2020-09-11 | 中国石油化工股份有限公司 | Method for processing catalytic diesel oil |
CN108795495A (en) * | 2017-05-03 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of processing method of diesel raw material |
CN111286360A (en) * | 2020-03-31 | 2020-06-16 | 宁波同润和海科技有限公司 | Diesel oil hydrofining device and method |
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