CN101724445B - Method for producing clean fuel by hydroprocessing - Google Patents
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- CN101724445B CN101724445B CN 200810228386 CN200810228386A CN101724445B CN 101724445 B CN101724445 B CN 101724445B CN 200810228386 CN200810228386 CN 200810228386 CN 200810228386 A CN200810228386 A CN 200810228386A CN 101724445 B CN101724445 B CN 101724445B
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Abstract
The invention discloses a method for hydroprocessing a static bed. The method is characterized in that raw material oil is mixed with hydrogen to pass through a hydroprocessing region with a catalyst bed layer under hydroprocessing technique condition, wherein the hydroprocessing region comprises a single-stage or multi-stage internal cross-flow reactor, and a part of hydrogenation products are mixed with the raw material oil for recycling. By using the method, the volume of hydrogen oil is smaller, thereby the apparatus investment and operating cost are greatly reduced; the used internal cross-flow reactor simultaneously has functions of catalyzing the hydrogenation reaction and extracting gases of reaction by-products such as H2S, NH3 and the like from a reaction system, thereby greatly improving the efficiency of the hydrogenation reaction. The invention not only can be used for distillate of gas, coal, diesel fuel and the like for hydrodesulphurization, hydrodenitrogenation and hydrodearomatization to refine, but also for distillate such as VGO raw material moderating the hydrocracking to produce clean fuel.
Description
Technical field
The present invention relates to a kind of fixed bed hydrogenation treatment method, the method does not need hydrogen recycle link and circulating hydrogen compressor.
Background technology
The fixed bed hydrogenation treating processes normally in order to remove from the sulphur in the raw material of crude oil, nitrogen, oxygen, metal impurities, or reduces the size of raw molecule and the catalytic reaction process that carries out.In this process, for the temperature of reaction of controlling beds with avoid the catalyst carbon deposit inactivation, usually adopt larger hydrogen-oil ratio.
Adopt larger hydrogen-oil ratio when hydrotreatment, after hydrogenation reaction is finished, must have a large amount of hydrogen more than needed.These hydrogen of having more than needed all pass through the hydrogen recycle link usually through continuing as the hydrogen feed of reacting after the circulating hydrogen compressor supercharging with after new hydrogen mixes.
The investment of hydrogen recycle link accounts for the significant proportion of whole process cost in the oil refining process.If the hydrogen flowing quantity in the hydrotreatment process can be reduced and save hydrogen gas circulating system and circulating hydrogen compressor, can greatly reduce investment outlay for enterprise, the road that also is about to carry out for China reduces cost with fuels cleaning.
The reaction kinetics rate equation of raw material in the trickle bed hydrogenator that generally contains simple sulfide can be expressed as:
Wherein: R
SBe the hydrodesulfurization reaction speed of this organic sulfide, K
O, K
S, K
H2SBe respectively the poisoning constant of reaction rate constant, organic nitrogen compound and the H in the gas phase
2S concentration (μ g/g), η
wThe wetting factor for catalyzer.As can be seen from the above equation, the speed of reaction of hydrogenating desulfurization has the relation except the concentration with organic sulfide, also is subjected to wetting situation, the organic nitrogen compound in the reactor assembly and the H of catalyzer
2The impact of the factors such as S concentration.The wetting factor η of catalyzer
wBy a kind of tolerance of liquid reactants institute infiltration degree to catalyst surface under hydrogenation conditions.The infiltration degree of catalyzer is higher, the wetting factor η of catalyzer
wJust higher, that is to say that the effective rate of utilization of catalyzer is higher.Under the condition that the factors such as catalyzer are determined, the principal element that affects the catalyst irrigation factor is the flow velocity of liquid in the reactor, and the ratio (hydrogen-oil ratio) of gas and flow rate of liquid.It is generally acknowledged that flow rate of liquid increases and strengthens the catalyst irrigation effect, and the wetting effect of the excessive reduction catalyzer of hydrogen-oil ratio, thereby to wetting factor η
wNegative impact is arranged.
Therefore, the hydrogen-oil ratio of hydroprocessing technique should adopt and satisfy reaction needed and get final product, and is unsuitable excessive.In addition, the investment of hydrogen recycle link accounts for the significant proportion of whole process cost in the oil refining process.If the hydrogen flowing quantity in the hydrotreatment process can be reduced and save hydrogen gas circulating system and circulating hydrogen compressor, can greatly reduce investment outlay for enterprise, the road that also is about to carry out for China reduces cost with fuels cleaning.
Organic nitrogen compound is the poisonous substance of hydrogenation catalyst, and hydrodenitrification, hydrogenating desulfurization and hydrogenation dearomatization reaction are had obvious supression effect.This supression effect mainly is because some nitride and the intermediate reaction product of most of nitride and the hydrogenation reaction active centre of catalyzer have very strong sorptive power, has restrained the carrying out of other hydrogenation reactions from the angle of competitive adsorption.And will greatly dilute foreign matter content in the raw material by hydrogenation products circulation, be conducive to bring into play the performance of catalyzer.
Hydrogenating desulfurization by product H
2S also has obvious supression effect to hydrodesulfurization reaction, hydrodenitrification and hydrogenation dearomatization reaction.Document Sie S T.[J] .Reaction order and role of hydrogen sulfide in deephydrodesulfurization of gas oil:consequences for industrial reactor configuration, Fuel Processing Technology, 1999,61 (1-2): 149-171. think H
2S one is that the activation energy of hydrodesulfurization reaction is risen on affecting of hydrodesulfurization reaction.Be hydrogenated to example with toluene, hydrogen sulfide sectional pressure is 0 o'clock, and reaction activity is 16 kcal/mol, and when hydrogen sulfide sectional pressure reached 42 kPa, activation energy rose to 20kcal/mol; Another impact is a small amount of H
2S exists will reduce hydrogenating desulfurization speed greatly, and H
2S is in the monolayer adsorption that is adsorbed as of catalyst surface, in case adsorption center is by H
2S occupies, and speed of reaction will be no longer with H
2The S dividing potential drop improves and descends.Therefore, adopt effective means to eliminate H
2The impact of S is the key issue that solves deep desulfuration.And the present invention adopts in the middle of reactor or the bottom has the cross-flow reactor of stripping effect with hydrogenating desulfurization by product H
2S takes reactive system out of will improve the reaction efficiency of catalyzer greatly.
Chinese patent CN86108622 discloses a kind of hydrofining technology of reformed oil, and hydrogen to oil volume ratio is 200-1000:1; Chinese patent CN93101935.4 discloses a kind of inferior feedstock oil a period of hydrocracking processing method, hydrogen to oil volume ratio 1300-1500:1; Chinese patent CN94102955.7 discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, volume of hydrogen oil ratio 150-500:1; Chinese patent CN96109792.2 discloses a kind of method of serial hydrogenation explained hereafter high-quality vaseline, hydrogen to oil volume ratio 300-1400:1; Chinese patent CN96120125.8 discloses a kind of method of producing white oil by cycloalkyl straight run direct hydrogenation, hydrogen to oil volume ratio 500-1500:1.
The characteristics of these patents are to have higher hydrogen-oil ratio, therefore hydrogen recycle link and circulating hydrogen compressor must be set.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of cheaply hydroprocessing process.
Hydroprocessing process process of the present invention is as follows: stock oil mixes with hydrogen, under the hydrogenation technique condition by containing the hydrotreatment district of beds, described hydrotreatment district comprises single-stage or multistage inner cross-flow reactor, and partial hydrogenation product and stock oil mixed cycle are used.
In the methods of the invention, the structure of the inner cross-flow reactor of described single-stage is as follows: the reactor internal upper part is the beds district, bottom or bottom are the cross-flow stripping zone, at the filling structured packing of cross-flow stripping zone or inertia porous porcelain ball, the plank frame spare of gas-liquid conversed contact are set perhaps; Can realize stripping effect to reaction product being respectively arranged with baffle in the bottom of beds district and cross-flow stripping zone in order to ensure stripping zone.
Wherein the stripping gas by stripping zone can be device hydrogen, high-temperature high-pressure steam or other rare gas elementes.Stock oil is as follows by the process of inner cross-flow reactor with hydrogen: stock oil is with after hydrogen mixes, enter the reaction of beds district, reacted product leaves the beds district, enters the cross-flow stripping zone behind the baffle of flowing through, and goes out wherein H through the stripping gas stripping
2S and NH
3After, leave reactor from the bottom of cross-flow stripping zone, and stripping gas and H
2S and NH
3Then leave from stripping zone top.Certainly, if the hydrotreatment district comprises multistage inner cross-flow reactor, then its array configuration can variation.Described multistage inner cross-flow reactor comprises at least two single-stage cross-flow reactors that are one another in series, and they or series connection are arranged in the reactor, or are separately positioned in a plurality of reactors.Such as these many variations, it all is protection scope of the present invention.
In the methods of the invention, the partial hydrogenation product circulation mixes with fresh feed oil, with the quiet run of assurance hydrogenation reaction and the work-ing life of catalyzer.The internal circulating load of hydrogenation products can be determined according to the particular case of reactive system, suitably add big cycle volume when for example exothermic heat of reaction is larger, reactive chemistry hydrogen consumes and suitably adds big cycle volume etc. when high, in general the ratio of internal circulating load and fresh feed oil mass is 0.1:1～20:1 by volume, be preferably 0.5:1～5:1, in general internal circulating load is favourable to reaction process greatly, but can cause the unfavorable result such as power consumption increase, and comprehensively various factors is finally determined.The hydrogenation products that recycles can use by direct circulation, also can use through recirculation after the fractionating system.
Fixed bed hydrogenation treating processes of the present invention can comprise the hydrotreatment process of gasoline, kerosene, diesel oil, vacuum gas oil (VGO), wax tailings (CGO), catalytic cracking light cycle oil (LCO), residual oil, deasphalted oil and lubricating oil.
In the inventive method, the technology contents such as selection of concrete hydrogenation technique condition and catalyzer can according to feedstock property and quality product requirement, be determined according to the conventional knowledge in this area.Hydrotreatment process of the present invention is the hydrotreatment process under little hydrogen-oil ratio, and hydrogen to oil volume ratio is generally 10:1～100:1, is preferably 30:1～100:1, most preferably is 50:1～100:1.Other hydrogenation conditions can determine that by this area general knowledge in general, temperature of reaction is 150～450 ℃ according to raw material properties, quality product requirement etc., and reaction pressure is 1～17MPa, and volume space velocity is 0.5～10h during liquid
-1The processing condition of described inner cross-flow reactor stripping zone are: pressure is 1～17MPa, and gas-liquid volume ratio is 50～2000, and temperature is 50～400 ℃.
In hydroprocessing process of the present invention, foreign matter content in the raw material had both been diluted in the circulation of liquid-phase hydrogenatin product, the a large amount of reaction heat that produce in the reaction process have been taken away again, thereby decrease reactor temperature rise, reactor is operated under the condition closer to isothermal, the activity stability that can keep catalyzer, extending catalyst work-ing life.Simultaneously, the hydrogen to oil volume ratio of reaction process is less, and 10:1～100:1 is only arranged.Less hydrogen to oil volume ratio both can reduce the load of circulating hydrogen compressor greatly, had also saved the process cost of hydrogen recycle link, even can cancel hydrogen recycle link and circulating hydrogen compressor.Another feature of the present invention is that described hydrotreatment reaction is to carry out in inner cross-flow reactor.The use of inner cross-flow reactor has realized carrying out hydrotreatment and reaction product has been carried out steam stripped function in same reactor.The H that reaction process generates
2S and NH
3Can in time from reaction product, separate, greatly reduce the impact on hydrogenating desulfurization speed, thereby significantly improve the reaction efficiency of catalyzer.
Description of drawings
Fig. 1 is schematic process flow diagram of the present invention;
Wherein: the 1st, fresh feed, the 2nd, feedstock pump, the 3rd, new hydrogen, the 4th, turning oil, the 5th, parallel feeding comprises fresh feed, turning oil and new hydrogen, the 6th, inner cross-flow hydrotreating reactor, the 7th, separator, the 8th, variable valve, the 9th, liquid product, the 10th, turning oil, the 11st, the product of fractionation not, the 12nd, separation column, 13 and 14 is the finished product.
Fig. 2 is the inner cross-flow reactor of single-stage synoptic diagram:
The inner cross-flow reactor of single-stage as shown in Figure 2, the reactor internal upper part is catalyst loading bed A district, bottom or bottom are cross-flow stripping floor B district, load structured packing or inertia porous porcelain ball, also can be the plank frame spares with gas-liquid conversed contact; Wherein stripping gas can be device hydrogen or high-temperature high-pressure steam or other rare gas elementes.21 is fresh hydrogenating materials or the hydrogenating materials that comprises hydrogen among Fig. 2, the 22nd, and reacted product leaves reactor, and the 23rd, from the stripping gas that the stripping zone bottom enters, 24 is from stripping zone top stripping gas out, comprises simultaneously H
2S, NH
3Etc. hydrogenation byproduct.
Fig. 3 is the inner cross-flow reactor of single-stage stripping zone baffle synoptic diagram.31 is fresh hydrogenating materials or the hydrogenating materials that comprises hydrogen among Fig. 3, the 32nd, and reacted product leaves reactor, and the 33rd, from the stripping gas that the stripping zone bottom enters, 34 is from stripping zone top stripping gas out, comprises simultaneously H
2S, NH
3Etc. hydrogenation byproduct.The baffle of beds bottom avoids stripping gas 34 to enter beds above the stripping zone, the baffle of stripping zone bottom forms fluid-tight at the cross-flow reactor bottom, the liquid of having avoided beds to get off is taken stripping gas 33 out of, thereby can not bring into play the stripping effect.
Fig. 4 is multistage inner cross-flow reactor synoptic diagram.Multistage inner cross-flow reactor can arrange 2 or a plurality of cross-flow stripping zone according to reaction needed as shown in Figure 4 in whole reactor.Be respectively from top to bottom catalyst loading bed district A, cross-flow stripping zone B is followed successively by catalyst loading bed district E, cross-flow stripping zone F, and wherein the filling structured packing of cross-flow stripping zone or inertia porous porcelain ball also can be the plank frame spares with gas-liquid conversed contact; Wherein stripping gas can be device hydrogen, high-temperature high-pressure steam or other rare gas elementes.41 is fresh hydrogenating materials or the hydrogenating materials that comprises hydrogen among Fig. 4, the 42nd, and reacted product leaves reactor, and 43 and 45 is the stripping gases that enter from the stripping zone bottom, and 44 and 46 is from stripping zone top stripping gas out, comprises simultaneously H
2S, NH
3Etc. hydrogenation byproduct.
Embodiment
For further specifying hydrotreatment process of the present invention, here process of the present invention is described.As shown in Figure 1, then fresh feed 1 enters the inside cross-flow reactor 6 that is filled with hydrotreating catalyst through forming logistics 5 after fresh feed pump 2 pressurizations with after new hydrogen 9 and turning oil 4 mix, and enters separator 7 after the reaction.In separator 7, a small amount of more than needed hydrogen and a large amount of impurity such as hydrogen sulfide, ammonia, low-carbon alkanes are emitted system through variable valve 8, and liquid product is divided into the two-way logistics through exporting 9, and one the tunnel is that logistics 11, a tunnel as the finished product is the logistics 10 as circulation.Logistics 10 loops back reactor upstream 4 and mixes with fresh feed.Logistics 11 enters separation column 12 as the finished product, be product 13, product 14 according to the fractionation of production purpose, and in fact, more possible meeting is to fractionate out between the 1-10 kind product.
Embodiment 1
Adopt single-stage cross-flow reactor, the secondary processing of gasoline take sulphur content as 600 μ g/g is as raw material, and catalyzer is FH-98,230 ℃ of lower hydrofinings to remove sulphur and alkene.Reaction pressure is 3.0MPa, and hydrogen to oil volume ratio is 50:1, circulation ratio (turning oil volume: the fresh feed volume) be 2:1; The processing condition of cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 2.9MPa, 120 ℃ of temperature, hydrogen to oil volume ratio is 150:1.Product sulphur content 9 μ g/g behind the hydrogenation, 1.0 units of loss of octane number.
Adopt single-stage cross-flow reactor, the boat coal take sulphur content as 1000 μ g/g is as raw material, and 260 ℃ of lower hydrofining desulfurization, catalyzer is FH-98.Reaction pressure is 2.6MPa, and hydrogen-oil ratio is 40:1, circulation ratio (turning oil volume: the fresh feed volume) be 2:1; The processing condition of cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 2.5MPa, 180 ℃ of temperature, hydrogen to oil volume ratio is 160:1.Product sulphur content 15 μ g/g behind the hydrogenation.
Adopt single-stage cross-flow reactor, the straight-run diesel oil take sulphur content as 4500 μ g/g as raw material 350 ℃ of lower hydrofinings with desulfurization and denitrogenation, catalyzer is FH-DS.Reaction pressure is 7MPa, and hydrogen-oil ratio is 50:1, circulation ratio (turning oil volume: the fresh feed volume) be 3:1; The processing condition of cross-flow stripping zone are: take nitrogen as stripping gas, and pressure 6.9MPa, 200 ℃ of temperature, gas-oil ratio is 150:1.Product sulphur content 15 μ g/g behind the hydrogenation.
Embodiment 4
Adopt single-stage cross-flow reactor, take sulphur content as 1.2wt%, nitrogen content as the vacuum gas oil (VGO) of 650 μ g/g 390 ℃ of lower hydrotreatments to remove sulphur nitrogen, catalyzer is FF-36.Reaction pressure is 12MPa, and hydrogen-oil ratio is 80:1, circulation ratio (turning oil volume: the fresh feed volume) be 4:1; The processing condition of cross-flow stripping zone are: take nitrogen as stripping gas, and pressure 11.9MPa, 300 ℃ of temperature, gas-oil ratio is 200:1.Product sulphur content 90 μ g/g behind the hydrogenation, nitrogen content is 50 μ g/g.
Adopt secondary cross-flow reactor, take sulphur content as 8500 μ g/g, nitrogen content be the catalytic cracking light cycle oil LCO of 550 μ g/g 360 ℃ of first step reactors, 340 ℃ of lower hydrotreatments of second stage reactor, catalyzer is FH-98.Reaction pressure is 7.8MPa, and hydrogen-oil ratio is 80:1, recycle ratio (turning oil volume: the fresh feed volume) be 6:1; The processing condition of first step cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 7.8MPa, 350 ℃ of temperature, hydrogen to oil volume ratio is 150:1, and the processing condition of second stage cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 7.8MPa, 200 ℃ of temperature, hydrogen to oil volume ratio are 350:1.Hydrogenated products sulphur content 50 μ g/g, nitrogen content are 25 μ g/g.
Adopt secondary cross-flow reactor, take sulphur content as 1.6wt%, nitrogen content be the residual oil of 1200 μ g/g 400 ℃ of first step reactors, 380 ℃ of lower hydrotreatments of second stage reactor, catalyzer is FF-36.Reaction pressure is 12MPa, and hydrogen-oil ratio is 75:1, recycle ratio (turning oil volume: the fresh feed volume) be 4:1; The processing condition of first step cross-flow stripping zone are: take hydrogen as stripping gas, and 380 ℃ of temperature, pressure 12.0MPa, hydrogen to oil volume ratio is 150:1, and the processing condition of second stage cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 12.0MPa, 300 ℃ of temperature, hydrogen to oil volume ratio are 350:1.Hydrogenated products sulphur content 450 μ g/g, nitrogen content are 125 μ g/g.
Adopt secondary cross-flow reactor, take sulphur content as 1.3wt%, nitrogen content is 400 ℃ of the deasphalted oil first step reactors of 1500 μ g/g, 380 ℃ of lower hydrotreatments of second stage reactor, and catalyzer is FF-36.Reaction pressure is 13MPa, and hydrogen-oil ratio is 80:1, recycle ratio (turning oil volume: the fresh feed volume) be 4:1; The processing condition of first step cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 13.0MPa, 380 ℃ of temperature, hydrogen to oil volume ratio is 140:1, and the processing condition of second stage cross-flow stripping zone are: take hydrogen as stripping gas, and pressure 13.0MPa, 300 ℃ of temperature, hydrogen to oil volume ratio are 360:1.Hydrogenated products sulphur content 350 μ g/g, nitrogen content are 130 μ g/g.
Embodiment 8
Adopt single-stage cross-flow reactor, the lubricating oil take sulphur content as 9600 μ g/g is 320 ℃ of lower hydrotreatments, and catalyzer is FF-36.Reaction pressure is 12MPa, and hydrogen-oil ratio is 20:1, recycle ratio (turning oil volume: the fresh feed volume) be 4:1; The processing condition of cross-flow stripping zone are: take nitrogen as stripping gas, and pressure 11.6MPa, 300 ℃ of temperature, gas-oil ratio is 300:1.Hydrogenated products sulphur content 75 μ g/g.
Claims (11)
1. inner cross-flow hydroprocessing process, stock oil mixes with hydrogen, be under 10: 1～100: 1 the hydrogenation technique condition by containing the hydrotreatment district of beds at hydrogen to oil volume ratio, it is characterized in that: described hydrotreatment district comprises single-stage or multistage inner cross-flow reactor, and at least part of hydrogenation products and fresh feed oil mixed cycle are used; The structure of the inner cross-flow reactor of described single-stage is as follows: the reactor internal upper part is the beds district, and bottom or bottom are the cross-flow stripping zone, at the filling structured packing of cross-flow stripping zone or inertia porous porcelain ball, the plank frame spare of gas-liquid conversed contact is set perhaps; Bottom at beds district and cross-flow stripping zone is respectively arranged with baffle.
2. hydroprocessing process according to claim 1 is characterized in that, the stripping gas by stripping zone is device hydrogen, high-temperature high-pressure steam or other rare gas elementes.
3. hydroprocessing process according to claim 1, it is characterized in that, described stock oil is as follows by the process of inner cross-flow reactor with hydrogen: stock oil is with after hydrogen mixes, enter the reaction of beds district, reacted product leaves the beds district, flowing through enters the cross-flow stripping zone behind the baffle, goes out wherein H through the stripping gas stripping
2S and NH
3After, leave reactor from the bottom of cross-flow stripping zone, and stripping gas and H
2S and NH
3Then leave from stripping zone top.
4. hydroprocessing process according to claim 1, it is characterized in that, described hydrotreatment district comprises multistage inner cross-flow reactor, described multistage inner cross-flow reactor comprises at least two single-stage cross-flow reactors that are one another in series, they or series connection are arranged in the reactor, or are separately positioned in a plurality of reactors.
5. hydroprocessing process according to claim 1 is characterized in that, the hydrogenation products that recycles is 0.1: 1～20: 1 with the ratio of fresh feed oil by volume.
6. hydroprocessing process according to claim 5 is characterized in that, the hydrogenation products that recycles is 0.5: 1～5: 1 with the ratio of fresh feed oil by volume.
7. hydroprocessing process according to claim 1 is characterized in that, described hydrogenation technique condition is: temperature of reaction is 150～450 ℃, and reaction pressure is 1～17MPa, and volume space velocity is 0.5～10h during liquid
-1
8. hydroprocessing process according to claim 1 is characterized in that, described hydrogen to oil volume ratio is 30: 1～100: 1.
9. hydroprocessing process according to claim 8 is characterized in that, described hydrogen to oil volume ratio is 50: 1～100: 1.
10. hydroprocessing process according to claim 1, it is characterized in that the processing condition of described cross-flow stripping zone are: pressure is 1～17MPa, and gas-liquid volume ratio is 50～2000, and temperature is 50～400 ℃.
11. hydroprocessing process according to claim 1, it is characterized in that described hydrotreatment process comprises the hydrotreatment process of gasoline, kerosene, diesel oil, vacuum gas oil, wax tailings, catalytic cracking light cycle oil, residual oil, deasphalted oil and lubricating oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020074262A1 (en) * | 2000-10-10 | 2002-06-20 | Ramesh Gupta | Two stage diesel fuel hydrotreating and stripping in a single reaction vessel |
| US6428686B1 (en) * | 1997-06-24 | 2002-08-06 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN1466619A (en) * | 2000-04-17 | 2004-01-07 | ����ɭ�о����̹�˾ | Cycle oil conversion process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428686B1 (en) * | 1997-06-24 | 2002-08-06 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN1466619A (en) * | 2000-04-17 | 2004-01-07 | ����ɭ�о����̹�˾ | Cycle oil conversion process |
| US20020074262A1 (en) * | 2000-10-10 | 2002-06-20 | Ramesh Gupta | Two stage diesel fuel hydrotreating and stripping in a single reaction vessel |
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