CN1986748B - Diesel oil fraction overhydrogenating modification process - Google Patents
Diesel oil fraction overhydrogenating modification process Download PDFInfo
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Abstract
The diesel oil fraction overhydrogenating modification process includes the contact of the mixture of material oil and hydrogen with the hydrotreating catalyst in the first reaction region to produce hydrogenating modification reaction, separating the reaction product in a hot high pressure separator, feeding the separated gas phase matter to a cold high pressure separator, the reaction of the mixture of the separated liquid phase matter and hydrogen in the second reaction region under the action of hydrogenating modification catalyst, cooling and separating the effluent from the second reaction region, reusing the hydrogen-rich gas circularly, and fractionating the liquid product in the fractionating system to obtain diesel oil fraction and naphtha fraction. The process can improve the quality of diesel oil fraction greatly, including raising the cetane number, lowering the content of polycyclic aromatic hydrocarbon, and reducing the density.
Description
Technical field
The invention belongs to a kind ofly in the method that has under the situation of hydrogen refining hydrocarbon ils, more particularly, is a kind of method of diesel fraction deep hydrogenation upgrading.
Background technology
Along with the enforcement of environmental protection legislation in the world wide, people are also improving constantly the specification of quality of diesel oil, and the diesel oil specification constantly changes, and what wherein variation was bigger is sulphur content, aromaticity content and three indexs of cetane value.World fuel oil standard II class diesel oil standard requires: sulphur content is not more than 0.03 heavy %, and aromaticity content is not higher than 25 heavy %, and polycyclic aromatic hydrocarbon content is not higher than 5 heavy %, and cetane index is not less than 50; World fuel oil standard III class diesel oil standard requires: sulphur content is not more than 0.003 heavy %, and aromaticity content is not more than 15 heavy %, and polycyclic aromatic hydrocarbons is not more than 2 heavy %, and cetane index is not less than 52.As seen from the above, especially the requirement of polycyclic aromatic hydrocarbon content is harsh day by day for sulphur content, cetane value, aromaticity content in the diesel oil, reduces the diesel oil sulphur content, improves its cetane value and reduce the major objective that its polycyclic aromatic hydrocarbon content will be various countries.
On the other hand, the heaviness of crude oil and the development of catalytic cracking technology cause the further variation of character of catalytic cracking diesel oil, aspect such as be embodied in that catalytic cracking diesel oil density is big, foreign matter content height, aromaticity content height and cetane value such as sulphur and nitrogen are low.Employing is mixed refining straight-run diesel oil or is transformed existing hydro-refining unit (as reducing air speed or improving temperature of reaction) or change active higher Hydrobon catalyst and can make sulphur content reach requirement, but the reduction of the improvement of cetane value and aromaticity content is an a great problem.
CN1417301A discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, this method comprises two hydrogenators, in first reactor, load catalyst for hydro-upgrading, hydrocracking catalyst or Hydrobon catalyst, in second reactor, load Hydrobon catalyst, between two, be provided with a hydrogen stripped tower, to remove gaseous impurities such as hydrogen sulfide that first reactor generates and ammonia.This method adopts under middle pressure, adopts non-precious metal catalyst to remove sulphur, the aromaticity content of diesel raw material, but high pressure hydrogen gas stripping column, cost of investment and running cost height are set in this method.
CN1064988C discloses a kind of diesel oil fraction hydrogenation converting process, and to poor ignition quality fuel, particularly catalytic cracking diesel oil (LCO) carries out the method for hydrocracking.Present method comprises has selected the hydrogenation conversion catalyst that contains molecular sieve for use, adopts one-stage process, series connection one-stage process and two-phase method hydrogenation technique flow process to take off virtue, desulfurization and improvement diesel cetane-number.The characteristics of this hydroconversion process are to select special reaction conditions, make molecular sieve catalyst performance open loop and cracked performance not, reach the purpose that increases substantially diesel quality.But the diesel oil specification index that this method is produced is lower, and less than 0.05 heavy %, aromaticity content is less than 20 heavy %, and the content that does not have the product polycyclic aromatic hydrocarbons limits as sulphur content.
CN1415706A discloses a kind of method of producing low-sulfur, low aromatic hydrocarbons clean diesel, this method comprises two reactors, first reactor is hydrofining/cracking case, second reactor is catalysis stripping reactor, is made of middle stripping stage, upper reaction section and lower reaction section three parts.This method can be produced the clean diesel that meets " world's fuel oil standard " II, III series products standard, but the stock oil that this method relates to is lighter, and the pressure-controlling complexity of the catalysis stripping reactor of mentioning in this method, and operation easier is big; The stripping of catalysis simultaneously structure of reactor complexity, the engineering design difficulty is bigger, performance difficulty.
US6623628B1 discloses a kind of method that adopts two-stage method to produce low-sulfur, low aromatic hydrocarbons and high hexadecane value diesel oil.Adopt two reactors in this method, one catalyzer in anti-adopt at least a from group vib and at least a be active ingredient from the element in the group VIII, it is active ingredient from the precious metal in the group VIII that two catalyzer in anti-adopt at least a.Between two reactors, be provided with stripper, gaseous impurities such as anti-hydrogen sulfide that produces and ammonia removed totally, to protect two anti-noble metal catalysts.It is 150 ℃～370 ℃ intermediate oil that this method can be processed boiling range, produces low-sulfur, low aromatic hydrocarbons and high hexadecane value diesel oil.But raw material used in this method is lighter, and aromaticity content is low; In addition, adopted noble metal catalyst to make cost up in this method, running has a big risk, flexibility of operation descends.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of diesel fraction deep hydrogenation upgrading.
Method provided by the invention is: stock oil and hydrogen are mixed into first reaction zone, contact with hydrogenation catalyst and to carry out the hydro-upgrading reaction, its resultant of reaction enters high pressure hot separator, isolated gaseous stream with remove cold high pressure separator after the resultant of reaction of second reaction zone mixes, the isolated liquid phase stream of high pressure hot separator with enter second reaction zone after hydrogen mixes, under the effect of catalyst for hydro-upgrading, react, the effluent of second reaction zone is through cooling, after the separation, isolated hydrogen-rich gas Returning reacting system recycles, product liquid enters fractionating system, obtains diesel oil distillate and naphtha fraction.
Method provided by the invention can be improved the diesel oil distillate quality to greatest extent, comprise ultra-deep desulfurization, improve cetane value and reduce polycyclic aromatic hydrocarbon content and density etc., and flexible operation, diesel yield height, investment and running cost is low.
Description of drawings
Accompanying drawing is the method flow diagram of diesel fraction deep hydrogenation upgrading provided by the invention.
Embodiment
Method provided by the invention comprises:
Stock oil and hydrogen are mixed into first reaction zone, contacts with hydrogenation catalyst, and at hydrogen dividing potential drop 3.0～12.0MPa, preferred 4.5～8.0MPa, 300～440 ℃ of temperature of reaction, preferred 350～400 ℃, hydrogen to oil volume ratio 400～1000Nm
3/ m
3, preferred 500～800Nm
3/ m
3, volume space velocity 0.1～6.0h
-1, preferred 0.2～3.0h
-1Reaction conditions under carry out hydrogenating desulfurization, hydrodenitrification, alkene is saturated and part naphthenic selective opening reaction.
The hydrogenation catalyst of first reaction zone can be that catalyst for hydro-upgrading loads separately, also can be hydrotreating catalyst and catalyst for hydro-upgrading combination loading.Load catalyst for hydro-upgrading separately no matter be, or when combination loading hydrotreating catalyst and catalyst for hydro-upgrading, can single bed or divide a plurality of beds to be packed in a reactor or a plurality of reactor, the reaction effluent between each reactor does not separate.A plurality of beds are arranged in the reactor, use the mode of annotating cold hydrogen between each bed to control bed temperature.When adopting hydrotreating catalyst and catalyst for hydro-upgrading combination loading mode, hydrotreating catalyst places the front portion of catalyst for hydro-upgrading.For example hydrotreating catalyst and catalyst for hydro-upgrading can fill in respectively in two reactors, load hydrotreating catalyst in the previous reactor; Also hydrotreating catalyst can be placed the top of catalyst for hydro-upgrading and be seated in a reactor.Hydrotreating catalyst is 5: 1～1: 10 with the admission space ratio of catalyst for hydro-upgrading, and preferred admission space ratio is 2: 1～1: 3.If carbon residue or metal content are higher in the raw material, can load a certain amount of protective material on the top of first reaction zone, rise and the protection Primary Catalysts with delayed response device bed pressure drop.
The resultant of reaction of first reaction zone enters high pressure hot separator, its service temperature is 150 ℃～400 ℃, flash off than light constituent and most hydrogen sulfide and ammonia, the gaseous stream of extracting out by the top of high pressure hot separator with remove cold high pressure separator after the resultant of reaction of second reaction zone mixes; Remaining liquid phase stream is extracted out from the bottom of high pressure hot separator, is mixed into second reaction zone with hydrogen.Owing to do not enter second reaction zone than light constituent and most hydrogen sulfide and ammonia, make the atmosphere of second reaction zone improve greatly.Studies show that because the cause of competitive adsorption, the existence of hydrogen sulfide has adverse influence for hydrodesulfurization reaction, the existence of ammonia then all has serious restraining effect to aromatic hydrogenation and hydrodesulfurization reaction.In addition, do not enter second reaction zone, can reduce the catalyst volume of second reaction zone than light constituent, and corresponding minimizing hydrogen consumption and energy consumption.
The liquid phase stream that extract out the high pressure hot separator bottom contacts with catalyst for hydro-upgrading at second reaction zone, at hydrogen dividing potential drop 3.0～12.0MPa, and preferred 4.5～8.0MPa, 300～440 ℃ of temperature of reaction, preferred 350～400 ℃, hydrogen to oil volume ratio 400～1000Nm
3/ m
3, preferred 500～800Nm
3/ m
3, volume space velocity 0.1～6.0h
-1, preferred 0.2～3.0h
-1Reaction conditions under further carry out hydrogenating desulfurization, hydrodenitrification, alkene is saturated and part naphthenic selective opening reaction.The resultant of reaction of second reaction zone enters cold high pressure separator successively after cooling and light pressure separator carries out gas-liquid separation, isolated hydrogen-rich gas Returning reacting system recycles, isolated product liquid enters fractionating system, obtains fine diesel oil distillate and a spot of naphtha fraction.The catalyst for hydro-upgrading of second reaction zone can single bed or is divided a plurality of beds to be packed in a reactor or a plurality of reactor, reaction effluent between each reactor does not separate, a plurality of beds are arranged in the reactor, use the mode of annotating cold hydrogen between each bed to control bed temperature.
Described stock oil is one or more the mixture in straight-run diesel oil, catalytic cracking light cycle oil, heavy catalytic cycle oil, coker gas oil, the visbreaking diesel oil.The present invention can handle sulphur, nitrogen content is higher and aromaticity content is higher poor quality catalytic cracking diesel, and the heavier raw material of suitable processing, and the boiling spread of stock oil can be 180～400 ℃.
Described hydrotreating catalyst is a metal load type catalyst, and carrier is a silica-alumina, and metal component is group vib metal or group VIII metal or their combination; With the catalyzer is benchmark, and it consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina.With described carrier is benchmark, and the silica content in the silica-alumina is 2～45 heavy %, and the content of aluminum oxide is 55～98 heavy %.Because this catalyzer is highly active hydrotreating catalyst, has the saturated performance of good hydrogenating desulfurization and hydrodenitrification and aromatic hydrocarbons, the hydrotreatment of poor-quality diesel-oil by cut fraction can be used for, impurity such as sulphur in the raw material, nitrogen can be removed effectively, and saturated part aromatic hydrocarbons.
Described catalyst for hydro-upgrading contains silica-alumina, y-type zeolite, aluminum oxide and at least a metal component and at least a metal component that is selected from group vib that is selected from group VIII.With the catalyzer is benchmark, and it consists of: silica-alumina 1～70 heavy %, y-type zeolite 1～60 heavy %, aluminum oxide 5～80 heavy %, and in oxide compound, metal component 10～40 heavy % of group VIII metal component 1～15 heavy %, group vib.This catalyst for hydro-upgrading has the shape of selecting open loop ability, can make the open loop cracking of the above cyclic aromatic compounds of dicyclo in the raw material, thereby reaches the purpose that improves cetane value.Studies show that, the chemical reaction of double ring arene is followed following approach: become naphthane after most of double ring arene hydrogenation is saturated, become two Yuans naphthenic hydrocarbon after the further hydrogenation of part naphthane is saturated, another part naphthane becomes mononuclear aromatics through the open loop cracking reaction, and the further more saturated single-ring naphthene that becomes of hydrogenation of the mononuclear aromatics of part.Above-mentioned reaction network, except the open loop cracking reaction of naphthane does not have the reversed reaction, all the other hydrogenation saturated reactions all have reversed reaction to take place, and therefore a corresponding chemical equilibrium is arranged.The catalyst for hydro-upgrading that the present invention uses has good open loop cracking ability, promoted that naphthane open loop cracking is the generation of mononuclear aromatics reaction, thereby broken the chemical equilibrium of entire reaction network, make entire reaction to carry out smoothly along the saturated course of repeated hydrogenation after the naphthane open loop cracking, thereby reach higher depth of conversion, reduced the aromaticity content in the distillate, improved cetane value.In addition, this catalyzer has good anti-nitrogen ability.
The invention has the advantages that:
1, method provided by the invention can be applied to build and at hydrofining of building or MHUG device, also be applicable to old plant modification.Working pressure of the present invention is middle pressure, and catalyzer is a non-precious metal catalyst, so facility investment and process cost are all lower.
2, method catalyst utilization height provided by the invention, corresponding energy consumption and hydrogen consumption are low.This is because the weight component in the first reaction zone effluent is effectively separated at high pressure hot separator, most of have gases such as inhibiting hydrogen sulfide, ammonia not enter second reaction zone to catalyst activity, thereby improved the reaction atmosphere of second reaction zone effectively, made the utilization ratio of catalyzer improve greatly; Simultaneously second reaction zone is only to the further hydro-upgrading of last running, thereby reduced the loaded catalyst of second reaction zone, and reduced corresponding energy consumption and hydrogen consumption.
3, by method provided by the invention, can production sulphur content＜30ppm, the fine-quality diesel oil of the heavy % in polycyclic aromatic hydrocarbon content＜5, to compare with stock oil, product cetane value increase rate is 15 more than the unit, and diesel yield is more than 95 heavy %.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the method flow synoptic diagram of diesel fraction deep hydrogenation upgrading provided by the present invention.Some utility appliance among the figure such as interchanger etc. do not mark, but this is known to those of ordinary skills.The method flow of diesel fraction deep hydrogenation upgrading provided by the present invention is as follows:
Mix with hydrogen after raw oil pump 2 boosts from the stock oil of pipeline 1, enter first reactor 3 (first reaction zone) and contact, carry out the hydro-upgrading reaction with hydrogenation catalysts a kind of or two kinds of combination loadings from pipeline 10.The reaction effluent of first reactor 3 enters high pressure hot separator 5 through pipeline 12, carries out flash separation, and isolated gaseous stream is extracted out from high pressure hot separator 5 tops through pipeline 13, and isolated liquid phase stream is extracted out from high pressure hot separator 5 bottoms through pipeline 14.Be mixed into second reactor 4 (second reaction zone) from the liquid phase stream of pipeline 14 and hydrogen, contact, carry out deep hydrodesulfurizationof, take off aromatic hydrocarbons and improve the reaction of cetane value with catalyst for hydro-upgrading from pipeline 10.The effluent of second reactor 4 mixes with logistics from pipeline 13 after pipeline 15 is extracted out, enter cold high pressure separator 6 and carry out gas-liquid separation, isolated hydrogen-rich gas is extracted out after circulating hydrogen compressor 9 boosts with new hydrogen from pipeline 11 through pipeline 16 and is mixed, formed hydrogen gas stream recycles through pipeline 10 Returning reacting systems, wherein a part of hydrogen enters the middle part of reactor through pipeline 10, uses as the cold hydrogen of conditioned reaction bed temperature.Cold high pressure separator 6 isolated liquid phase streams enter light pressure separator 7 through pipeline 17 extractions and carry out further gas-liquid separation, isolated gas is through pipeline 21 withdrawing devices, light pressure separator 7 isolated liquid phase streams enter separation column 8 through pipeline 18, are extracted out through pipeline 20 and 19 respectively by separation column 8 isolated diesel oil distillates and a small amount of naphtha fraction.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Trade names at first reaction zone filling hydrotreating catalyst D among the embodiment are RN-32, trade names at first reaction zone and second reaction zone filling catalyst for hydro-upgrading E are RIC-2, produce by China PetroChemical Corporation's Chang Ling catalyst plant.
Used stock oil A, B, C is respectively light cycle oil and the heavy cycle oil from different catalytic cracking unit among the embodiment, or its mixing oil, and its character is listed in table 1.
Embodiment 1
Stock oil A with enter first reaction zone after hydrogen mixes, contact (the admission space ratio of hydrotreating catalyst and catalyst for hydro-upgrading is 1: 1) successively with catalyst for hydro-upgrading E with hydrotreating catalyst D, carry out the hydro-upgrading reaction, its resultant of reaction enters high pressure hot separator after 300 ℃ of flash distillations are handled, be separated into light, heavy constituent, heavy constituent with enter second reaction zone after hydrogen mixes after catalyst for hydro-upgrading E further handles, the light constituent that obtains with high pressure hot separator enters cold high pressure separator and carries out gas-liquid separation, isolated hydrogen-rich gas recycles, isolated product liquid enters fractionating system, obtain diesel oil distillate and a small amount of naphtha fraction, concrete reaction conditions is as shown in table 2, and products obtained therefrom yield and character are as shown in table 3.
As can be seen from Table 3, the yield of diesel oil distillate product is 96.7 heavy %, and sulphur content is 3.2ppm, and polycyclic aromatic hydrocarbon content is 3.2 heavy %; Cetane value is 43.3, and density is 0.8586g/cm
3Compare with raw material, cetane value improves 16.6 units, product density decline 0.0454g/cm
3
Stock oil B with enter first reaction zone after hydrogen mixes, contact (the admission space ratio of hydrotreating catalyst and catalyst for hydro-upgrading is 1: 1) successively with catalyst for hydro-upgrading E with hydrotreating catalyst D, carry out the hydro-upgrading reaction, its resultant of reaction enters high pressure hot separator after 300 ℃ of flash distillations are handled, be separated into light, heavy constituent, heavy constituent with enter second reaction zone after hydrogen mixes after catalyst for hydro-upgrading E further handles, the light constituent that obtains with high pressure hot separator enters cold high pressure separator and carries out gas-liquid separation, isolating hydrogen-rich gas recycles, isolating product liquid enters fractionating system, obtain diesel oil distillate and a small amount of naphtha fraction, concrete reaction conditions is as shown in table 2, and products obtained therefrom yield and character are as shown in table 3.
As can be seen from Table 3, the yield of diesel oil distillate product is 95.2 heavy %, and sulphur content is 5.2ppm, and polycyclic aromatic hydrocarbon content is 3.8 heavy %; Cetane value is 41.6, and density is 0.8734g/cm
3Compare with raw material, cetane value improves 15.7 units, product density decline 0.0474g/cm
3
Stock oil C with enter first reaction zone after hydrogen mixes, contact E with catalyst for hydro-upgrading, carry out the hydro-upgrading reaction, its resultant of reaction enters high pressure hot separator after 300 ℃ of flash distillations are handled, be separated into light, heavy constituent, heavy constituent with enter second reaction zone after hydrogen mixes after catalyst for hydro-upgrading E further handles, the light constituent that obtains with high pressure hot separator enters cold high pressure separator and carries out gas-liquid separation, isolating hydrogen-rich gas recycles, isolating product liquid enters fractionating system, obtain diesel oil distillate and a small amount of naphtha fraction, concrete reaction conditions is as shown in table 2, and products obtained therefrom yield and character are as shown in table 3.
As can be seen from Table 3, the yield of diesel oil distillate product is 95.7 heavy %, and sulphur content is 7.4ppm, and polycyclic aromatic hydrocarbon content is 1.8w%; Cetane value is 46.5, and density is 0.8422g/c
3Compare with raw material, cetane value improves 15.5 units, product density decline 0.0497g/cm
3
Table 1
| Stock oil | A | B | C |
| Density (20 ℃), g/cm 3 | 0.9040 | 0.9208 | 0.8919 |
| Condensation point, ℃ | -6 | -10 | -9 |
| The bromine valency, gBr/100g | 9.11 | 14.2 | 6.8 |
| Acidity, mgKOH/100ml | 3.9 | 0.5 | 1.0 |
| Refractive power, n D 20 | 1.5190 | 1.5352 | 1.5126 |
| Stock oil | A | B | C |
| Sulphur, ppm | 4400 | 5600 | 7600 |
| Nitrogen, ppm | 884 | 1327 | 583 |
| Existent gum, mg/100ml | 161 | 414 | 289 |
| Cetane value | 26.7 | 25.9 | 31.0 |
| Boiling range (ASTM D-86), ℃ | |||
| Initial boiling point | 186 | 192 | 173 |
| 5％ | 211 | 232 | 200 |
| 10％ | 223 | 246 | 211 |
| 20％ | 239 | 263 | 226 |
| 30％ | 254 | 277 | 240 |
| 50％ | 281 | 299 | 268 |
| 70％ | 317 | 324 | 305 |
| 80％ | 332 | 335 | 323 |
| 90％ | 347 | 351 | 345 |
| Final boiling point | 365 | 376 | 375 |
Table 2
| Numbering | Embodiment 1 | |
|
| Stock oil | A | B | C |
| Catalyzer (the first/the second reaction zone) | D，E/E | D，E/E | E/E |
| Test conditions |
| Numbering | Embodiment 1 | |
|
| First reaction zone | |||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.5 |
| Temperature of reaction, ℃ | 360 | 363 | 358 |
| Volume space velocity, h -1 | 1.2 | 1.1 | 1.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 600 | 700 | 600 |
| Second reaction zone | |||
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 350 | 353 | 352 |
| Volume space velocity, h -1 | 2.0 | 1.8 | 2.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 | 500 | 500 |
Table 3
| Numbering | Embodiment 1 | |
|
| Stock oil | A | B | C |
| Naphtha yield, heavy % | 3.3 | 4.8 | 4.3 |
| Diesel yield, heavy % | 96.7 | 95.2 | 95.7 |
| Diesel oil character | |||
| Density (20 ℃), g/cm 3 | 0.8586 | 0.8734 | 0.8422 |
| Viscosity (20 ℃), mm 2/s | 4.732 | 4.458 | 4.287 |
| Condensation point, ℃ | -11 | -14 | -12 |
| The bromine valency, gBr/100g | 0.32 | 0.44 | 0.67 |
| Acidity, mgKOH/100ml | 1.9 | ＜0.2 | 0.3 |
| Refractive power, n D 20 | 1.4756 | 1.4804 | 1.4688 |
| Numbering | Embodiment 1 | |
|
| Sulphur, ppm | 3.2 | 5.2 | 7.4 |
| Nitrogen, ppm | 5.2 | 4.5 | 2.2 |
| Existent gum, mg/100ml | 26 | 105 | 37 |
| Polycyclic aromatic hydrocarbon content, w% | 2.5 | 3.8 | 1.8 |
| Cetane value | 43.3 | 41.6 | 46.5 |
| The cetane value increased value | 16.6 | 15.7 | 15.5 |
| Boiling range, ASTM D-86, ℃ | |||
| Initial boiling point | 187 | 192 | 176 |
| 10％ | 212 | 231 | 206 |
| 30％ | 237 | 256 | 228 |
| 50％ | 266 | 281 | 256 |
| 70％ | 298 | 303 | 285 |
| 90％ | 342 | 344 | 336 |
| Final boiling point | 368 | 376 | 374 |
Claims (8)
1. the method for a diesel fraction deep hydrogenation upgrading, it is characterized in that stock oil and hydrogen are mixed into first reaction zone, contact with hydrogenation catalyst and to carry out the hydro-upgrading reaction, its resultant of reaction enters high pressure hot separator, isolated gaseous stream with remove cold high pressure separator after the resultant of reaction of second reaction zone mixes, the isolated liquid phase stream of high pressure hot separator with enter second reaction zone after hydrogen mixes, under the effect of catalyst for hydro-upgrading, react, the effluent of second reaction zone is through cooling, after the separation, isolated hydrogen-rich gas Returning reacting system recycles, product liquid enters fractionating system, obtain diesel oil distillate and naphtha fraction, described catalyst for hydro-upgrading, with the catalyzer is benchmark, it consists of: the silica-alumina of 1～70 heavy %, the y-type zeolite of 1～60 heavy %, the aluminum oxide of 5～80 heavy %, in oxide compound, the group VIII metal component of 1～15 heavy %, the metal component of the group vib of 10～40 heavy %.
2. according to the method for claim 1, it is characterized in that described stock oil is a kind of in straight-run diesel oil, catalytic cracking light cycle oil, heavy catalytic cycle oil, coker gas oil, the visbreaking diesel oil or greater than a kind of mixture.
3. according to the method for claim 1, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: hydrogen dividing potential drop 3.0～12.0MPa, 300～440 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1000Nm
3/ m
3, volume space velocity 0.1～6.0h
-1
4. according to the method for claim 1 or 3, it is characterized in that the reaction conditions of described first reaction zone and second reaction zone is: hydrogen dividing potential drop 4.5～8.0MPa, 350～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 500～800Nm
3/ m
3, volume space velocity 0.2～3.0h
-1
5. according to the method for claim 1, the hydrogenation catalyst that it is characterized in that described first reaction zone is the combination of independent catalyst for hydro-upgrading or hydrotreating catalyst and catalyst for hydro-upgrading.
6. according to the method for claim 5, the hydrotreating catalyst that it is characterized in that described first reaction zone is 5: 1～1: 10 with the admission space ratio of catalyst for hydro-upgrading.
7. according to the method for claim 5 or 6, the hydrotreating catalyst that it is characterized in that described first reaction zone is 2: 1～1: 3 with the admission space ratio of catalyst for hydro-upgrading.
8. according to the method for claim 5, it is characterized in that described hydrotreating catalyst is a metal load type catalyst, carrier is a silica-alumina, with the catalyzer is benchmark, it consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina.
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| CN1267709A (en) * | 1999-03-19 | 2000-09-27 | 中国石油化工集团公司 | Two-stage fraction oil hydrogenating and arene eliminating process |
| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| CN1580200A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing monox-alumina |
-
2005
- 2005-12-23 CN CN2005101321941A patent/CN1986748B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068025A (en) * | 1990-06-27 | 1991-11-26 | Shell Oil Company | Aromatics saturation process for diesel boiling-range hydrocarbons |
| US5114562A (en) * | 1990-08-03 | 1992-05-19 | Uop | Two-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
| CN1267709A (en) * | 1999-03-19 | 2000-09-27 | 中国石油化工集团公司 | Two-stage fraction oil hydrogenating and arene eliminating process |
| CN1417301A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Method of desulfurizing and dearomatizing diesel oil deeply |
| CN1580200A (en) * | 2003-07-31 | 2005-02-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing monox-alumina |
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| CN1986748A (en) | 2007-06-27 |
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