CN102311795B - Hydrogenation method for producing high-octane gasoline components by diesel oil raw material - Google Patents
Hydrogenation method for producing high-octane gasoline components by diesel oil raw material Download PDFInfo
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Abstract
The invention provides a hydrogenation method for producing high-octane gasoline components by a diesel oil raw material. According to the hydrogenation method, two reaction areas which are respectively filled with a hydrogen refining catalyst and a hydrogen cracking catalyst are provided; a high-pressure separation system is arranged between two reaction areas and is used for controlling an aromatic hydrocarbon saturated depth of the first reaction area; by taking liquid-phase material flow of the first reaction area as the standard, the total aromatic hydrocarbon content is more than 55% by mass, the content of monocyclic ring aromatic hydrocarbon is increased to be more than 40% by mass, and the content of nitrogen of the liquid-phase material flow in the first reaction area is less than 100 micrograms/gram. Through utilizing the method provided by the invention, the diesel oil fractions with poor quality and high aromatic hydrocarbon content can be treated, low-sulfur and high-octane gasoline components can be produced, and clean diesel oil blended components with low sulfur also can be produced.
Description
Technical field
The present invention relates to a kind of in the situation that exist hydrogen for obtaining the hydrocarbon ils cleavage method of low boiler cut, more particularly, is a kind of method of hydrotreating by diesel raw material production high octane gasoline component.
Background technology
Along with the aggravation of crude oil heaviness, in poor quality process, the quality worse becoming of catalytic cracking diesel oil, output increase year by year, and this part catalytic cracking diesel oil accounts for 1/3rd of Chinese commodity diesel oil share.And refinery, for the more light-end products that abstract from crude oil, improves constantly working ability and the working depth of catalytic cracking unit, cause the further variation of quality of catalytic cracking diesel oil.Meanwhile, the environmental protection legislation is increasingly strict, and clean fuel is produced in market demands as far as possible, and, due to the petroleum resources worsening shortages, society also needs to effectively utilize as far as possible petroleum resources.Therefore, a kind of technology of catalytic cracking diesel oil with production high added value oil product of processing of market demand exploitation.On the other hand, at present in China's gasoline pool, the catalytic gasoline proportion, up to 78%, causes that the alkene of gasoline is high with sulphur content, aromaticity content is low, octane value is relative on the low side, and market also needs to develop a kind of production technology of producing low-sulfur, clean gasoline with high octane.
The technique of poor ignition quality fuel production high added value oil product mainly contains hydrofining and hydrocracking two classes.Adopt conventional hydrofining technology to process poor ignition quality fuel, although can effectively remove the impurity such as sulphur in diesel oil, nitrogen, diesel product cetane value increase rate is limited, and the diesel oil variable density is also little; Adopt traditional hydrocracking process processing poor ignition quality fuel, although can produce to greatest extent petroleum naphtha, and produce high-quality diesel product, the naphtha fraction octane value of its production is lower.
US 7,384, and 542B1 discloses a kind of method of producing low-sulfur diesel-oil and stop bracket gasoline.This patent enters hydrogenating desulfurization, hydrodenitrification reaction zone by straight-run diesel oil and/or light wax tailings (LCGO), catalytic cracking diesel oil (LCO) enters the hydrocracking reaction district, the product of two reaction zones enters cold high score, cold low dividing after mixing, then enter the fractionating system separation and obtain high-octane number component and low-sulfur diesel-oil.In this invention, the hydrocracking reaction district adopts hydrocracking catalyst amorphous or that contain low molecular sieve level.This invention can be processed straight-run diesel oil and/or LCGO, and the LCO of 149～343 ℃ of parts, and 87,>193 ℃ of sulphur content of diesel fraction of 88～193 ℃ of heavy naphtha fraction octane values that obtain are less than 10ppm, cetane index 46.
US 4,985, disclose a kind of technique of producing stop bracket gasoline in 134.The LCO that this invention raw material boiling spread is 150～327 ℃, i.e. light constituent in the catalytic cracking light cycle oil.The hydrocracking catalyst adopted contains Y zeolite, USY molecular sieve or dealuminzation Y zeolite.In addition, be greater than gasoline fraction in fractionation product oil and be less than 232 ℃ or be less than the middle runnings of 260 ℃ and be back to the hydrocracking reactor entrance or be back to catalytic cracking reaction zone.
This year, along with crude oil heaviness process is accelerated, the quality of China's catalytic cracking diesel oil worse and worse, be mainly manifested in that the foreign matter contents such as sulphur, nitrogen are high, aromaticity content is high, due to the difference of stock oil and catalytic cracking process, total aromaticity content difference of catalytic cracking diesel oil is larger, and from 50% to 90%, content does not wait, wherein mononuclear aromatics content is more than 20%, and the above aromaticity content of dicyclo is more than 40%.Especially, after catalytic cracking unit adopts and falls the alkene technology, aromatic hydrocarbon from catalytic cracking diesel oil content further increases.If adopt the method for conventional hydrocracking to be processed this part poor ignition quality fuel, although can produce the low-sulfur diesel-oil blend component that obtains excellent property, need comparatively harsh reaction conditions, and its naphtha fraction research octane number (RON) only have 75 left and right.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method by diesel raw material production high octane gasoline component.Specifically, be will solve prior art to process while being rich in aromatics diesel raw material production gasoline, and the low problem of gained gasoline products octane value.
Method provided by the invention, comprise: the diesel raw material oil-hydrogen mixture is first in the first reaction zone and Hydrobon catalyst contact reacts, the reaction effluent of the first reaction zone is separated, the liquid phase stream of gained the first reaction zone with enter second reaction zone and hydrocracking catalyst contact reacts after hydrogen mixes, the reaction effluent of second reaction zone is through cooling, obtain hydrogen-rich gas and product liquid after separation, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is more than 55 quality %, more than mononuclear aromatics content is increased to 40 quality %, and, the nitrogen content of the liquid phase stream of the first reaction zone is less than 100 μ g/g.
At the first reaction zone, i.e. hydrofining reaction district, the poor ignition quality fuel raw material mainly carries out the reactions such as hydrogenating desulfurization, hydrodenitrification and aromatic saturation.Pass through to control the degree of depth of hydrofining reaction process in the present invention, impel the above aromatic saturation of dicyclo and dicyclo to become mononuclear aromatics, avoiding supersaturation is naphthenic hydrocarbon, in reducing diesel oil in the foreign matter contents such as sulphur, nitrogen, reduce dicyclo and the above aromaticity content of dicyclo, and increase mononuclear aromatics content.The preferred aromatic saturation degree of depth of controlling the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, and its total aromaticity content is more than 65 quality %, more than mononuclear aromatics content is increased to 50 quality %, and the nitrogen content of the first reaction zone liquid phase stream is 20 μ g/g～50 μ g/g.
At second reaction zone, in the hydrocracking reaction district, liquid ingredient in the reaction effluent of the first reaction zone (hydrofining product oil) carries out selective opening on hydrogenation-cracking function catalyzer, the reactions such as cracking, effectively make the short-side chain alkylbenzene, the mononuclear aromatics side chain selectivity that the cetane value such as naphthane are low is carried out open loop, the reactions such as cracking, impel more micromolecular mononuclear aromatics in diesel oil distillate to be converted into the benzene in gasoline fraction, the high-octane rating components such as toluene, improve gasoline fraction product hydrocarbon composition thereby reach, improve the purpose of gasoline fraction product octane value.Retain as far as possible more macromolecular long chain alkane in diesel oil distillate or with high hexadecane value components such as the naphthenic hydrocarbon of long side chain or aromatic hydrocarbons simultaneously, thereby reach raising diesel product cetane value, improve the purpose of product diesel quality.As shown below, the present invention, by controlling hydrofining and the hydrocracking reaction degree of depth, impels reaction to be undertaken by (1)-(3)-(5) route, thereby produces the stop bracket gasoline blend component.
The boiling spread of diesel raw material oil of the present invention is 165～400 ℃, and total aromaticity content is higher than 60 quality %, and preferably total aromaticity content is 60～90 quality %, and wherein the content of dicyclo and the above aromatic hydrocarbons of dicyclo is higher than 40 quality %, preferably 40～65 quality %.One or more in the diesel oil distillate of the straight-run diesel oil of described diesel raw material grease separation catalytic cracking light cycle oil, heavy catalytic cycle oil, naphthenic base crude, the coker gas oil of naphthenic base crude, coal direct liquefaction oil, the diesel oil distillate of coal tar.
The loadings of the first reaction zone and second reaction zone catalyzer is determined according to nitrogen content and the above aromaticity content of dicyclo of processed diesel raw material oil.The admission space ratio of Hydrobon catalyst and hydrocracking catalyst is 5: 1～1: 5, preferably 2: 1～1: 2.If in diesel raw material oil, carbon residue or metal content are higher; for the Pressure Drop that prevents beds reaches limit value too quickly; can load respectively at Hydrobon catalyst bed top the hydrogenation protecting agent that accounts for hydrofining agent volume total amount 5～20%, to protect Primary Catalysts, to avoid the quick coking of bed.Protective material is comprised 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 present invention adopts a kind of two stage process flow process.High pressure separating step in the middle of arranging between the first reaction zone and second reaction zone, remove with part the NH that the hydrofining reaction district generates
3and H
2s, for the hydrocracking reaction district provides the cracking stock oil that hangs down nitrogen content.
One of them preferred embodiment is: the technical process of hydrofining-high pressure hot separator-hydrocracking, diesel raw material oil is at the first reaction zone, remove the impurity such as sulphur, nitrogen, and the above aromatic hydrocarbons of saturated bicyclic, the reaction effluent of described the first reaction zone carries out gas-liquid separation in high pressure hot separator, obtains being rich in the gaseous stream of the impurity such as hydrogen sulfide, ammonia and the liquid phase stream of the first reaction zone.The gained liquid phase stream enters second reaction zone and proceeds cracking reaction, generates the stop bracket gasoline blend component that is rich in aromatic hydrocarbons, and production part low-sulfur diesel-oil blend component.
Wherein another preferred embodiment is: the technical process of hydrofining-high pressure gas stripper-hydrocracking, the reaction effluent of described the first reaction zone carries out air lift in the high pressure gas stripper, remove the impurity such as hydrogen sulfide, ammonia through air lift after, obtain the liquid phase stream of the first reaction zone at the bottom of gas stripping column.
The reaction conditions of described the first reaction zone is: hydrogen dividing potential drop 3.0～10.0MPa, preferred 4.0～7.0MPa, 300～450 ℃ of temperature of reaction, preferably 330～390 ℃, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, preferred 500～900Nm
3/ m
3, volume space velocity 0.2～6.0h during liquid
-1, preferred 0.5～3.0h
-1; The reaction conditions of second reaction zone is: hydrogen dividing potential drop 2.0～9.0MPa, and preferred 4.0～6.5MPa, temperature of reaction is 300～450 ℃, preferably 350～420 ℃, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, preferred 400～800Nm
3/ m
3, volume space velocity 0.2～6.0h during liquid
-1, preferred 0.5～2.5h
-1.
Described Hydrobon catalyst is VIII family base metal and/or the group vib non-precious metal catalyst loaded on composite alumina and/or combined oxidation silicon carrier.Preferred Hydrobon catalyst consists of: in oxide compound and take the catalyzer total amount as benchmark, the content of nickel and/or cobalt is 1～10 heavy %, and molybdenum and tungsten sum are greater than 10～50 heavy %, the heavy % of fluorine 1～10, and all the other are aluminum oxide and silicon oxide.This Hydrobon catalyst has good hydrogenating desulfurization, hydrodenitrification performance, and the aromatic saturation performance of part, can be for the hydrotreatment of poor-quality diesel-oil by cut fraction, the impurity such as the sulphur in energy effective elimination raw material, nitrogen, and appropriateness is carried out the aromatic saturation reaction, impel the above aromatic saturation of dicyclo and dicyclo to become mononuclear aromatics, avoiding supersaturation is naphthenic hydrocarbon.
Described hydrocracking catalyst is VIII family and/or the group vib non-precious metal catalyst loaded on complex carrier.In oxide compound and take the catalyzer total amount as benchmark, contain the heavy % of nickel oxide 2.5～6.0, the heavy % of Tungsten oxide 99.999 10～38 in this catalyzer, contain the heavy % of fluorine 0.5～5.0, all the other are carrier.This carrier is comprised of the aluminum oxide of 20～90 heavy % and the zeolite of 10～80 heavy %, the mesopore that its mesolite is acidity value 1.0～2.0 mmoles/gram or large pore zeolite, the aluminum oxide that aluminum oxide is acidity value 0.5～0.8 mmole/gram, the acidity value NH of described aluminum oxide or zeolite
3-TPD method is measured.Described zeolite is selected from one or more in faujusite, mordenite, ZSM-5 zeolite, Beta zeolite, zeolite.The precursor of described aluminum oxide is to deceive by being selected from one or more hydrated aluminum oxides that sodium aluminate-carbon dioxide process, aluminum alkyls or aluminum alkoxide hydrolysis method, the standby diaspore content of sodium metaaluminate-Tai-Ace S 150 legal system are greater than 60 heavy %.Described hydrocracking catalyst has good selective cracking function, the reactions such as the fracture of mononuclear aromatics side chain, naphthane selective opening and disconnected side chain are had to good selectivity, make the mononuclear aromatics generation selective cracking reaction in diesel oil distillate generate the high-octane rating gasoline components such as benzene, toluene, thereby improve the gasoline fraction hydrocarbon composition, increase the octane value of gasoline fraction.
Advantage of the present invention:
(1) the present invention has adopted the two-stage method technical process, in the middle of two reaction zones, separating step is set, and removes partial vulcanization hydrogen and ammonia in the first reaction zone liquid phase stream, for second reaction zone provides the stock oil of low-sulfur, low nitrogen.Improve the cetane value technology with conventional distillate hydrogenation upgrading and compare, the present invention adopts than low hydrogen dividing potential drop and higher cracking invert point.
(2) adopt method provided by the invention, can process the poor-quality diesel-oil by cut fraction of high aromaticity content, and the production sulphur content is less than the gasoline fraction of 10 μ g/g, research octane number (RON) 95 left and right, simultaneously can the production sulphur content be less than 10 μ g/g, cetane value improves 10 clean diesel blend components more than unit than stock oil.
The accompanying drawing explanation
Fig. 1 is the preferred version one flow process schematic diagram that the invention provides method, and high pressure hot separator is set in the middle of two reaction zones.
Fig. 2 is the preferred version two flow process schematic diagram that the invention provides method, and the high pressure gas stripper is set in the middle of two reaction zones.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.Accompanying drawing is the schematic flow sheet of being produced the stop bracket gasoline method by poor ignition quality fuel provided by the invention.Omitted much equipment in figure, as pump, interchanger, compressor etc., but this is known to those of ordinary skills.
As shown in Figure 1, preferred version one flow process of method provided by the invention is described in detail as follows: from the diesel raw material oil process raw oil pump 2 of pipeline 1, through pipeline 12 be mixed into the first reactor 3 from pipeline 27 hydrogen, contact with Hydrobon catalyst, carry out desulfurization, denitrogenation and the reaction of appropriate aromatic saturation.The reaction effluent of the first reactor 3 enters high pressure hot separator 4 through pipeline 13 and carries out gas-liquid separation, high pressure hot separator 4 separate the liquid phase stream that obtains through hot oil pump 5 pressurizations by pipeline 14 with enter the second reactor 6 after hydrogen from pipeline 26 mixes.Mixture contacts with hydrocracking catalyst in the second reactor 6, carries out the cracking reaction of suitable selectivity side chain fracture.
The reaction effluent of the second reactor 6, enters cold high pressure separator 7 and carries out gas-liquid separation with after the gaseous stream of high pressure hot separator gained from pipeline 15 mixes through pipeline 16.Cold high pressure separator separates the sour water obtained and is extracted out by pipeline 23.Cold high pressure separator 7 separates the hydrogen-rich gas obtained and enters desulphurization of recycle hydrogen tank 31 through pipeline 25, the hydrogen-rich gas that removes partial vulcanization hydrogen enters circulating hydrogen compressor 11 through pipeline 32, after pressurization, by pipeline 26, extracted out, a part is removed the catalyst bed interlayer of the first reactor 3 and the second reactor 6 as quenching hydrogen, another part mixes by pipeline 27 extractions with the new hydrogen from pipeline 30 as recycle hydrogen.The product liquid that cold high pressure separator 7 obtains enters cold low separator 8 through pipeline 18 and further carries out gas-liquid separation, separating the sour water obtained is extracted out by pipeline 24, separating obtained gas is through pipeline 29 dischargers, and the product liquid of gained enters separation column 9 through pipeline 19 and carries out the component cutting.Overhead stream enter return tank of top of the tower 10, separating obtained light naphthar is extracted out through pipeline 28.Separating obtained gasoline fraction is extracted out through pipeline 20.The diesel oil distillate separated is extracted out through pipeline 21, and tower base stream is extracted out through pipeline 22.
As shown in Figure 2, the preferred version of method provided by the invention and two flow processs are described in detail as follows: from the diesel raw material oil of pipeline 1 through raw oil pump 2, through pipeline 12 be mixed into the first reactor 3 from pipeline 27 hydrogen, contact with Hydrobon catalyst, carry out desulfurization, denitrogenation and the reaction of appropriate aromatic saturation.The reaction effluent of the first reactor 3 enters high pressure gas stripper 40 through pipeline 13.In high pressure gas stripper 40, through hydrogen or hydrogen-rich gas air lift from pipeline 30, the gas of gas stripping column 40 enters digester 44 through pipeline 43, removes H
2hydrogen-rich gas after S mixes by pipeline 32 and enters the recycle hydrogen system through pipeline 45 and hydrogen-rich gas from pipeline 25.Liquid efflunent at the bottom of gas stripping column 40 towers after 5 pressurizations of pipeline 42 and hot oil pump, through pipeline 14 with enter the second reactor 6 after hydrogen from pipeline 26 mixes.Mixture contacts with hydrocracking catalyst in the second reactor 6, carries out the cracking reaction of suitable selectivity side chain fracture.
The reaction effluent of the second reactor 6 enters cold high pressure separator 7 through pipeline 17 and carries out gas-liquid separation.Cold high pressure separator separates the sour water obtained and is extracted out by pipeline 23.Cold high pressure separator 7 separates the hydrogen-rich gas obtained and enters circulating hydrogen compressor 11 through pipeline 25, pipeline 32, after pressurization, by pipeline 26, extracted out, a part is removed the catalyst bed interlayer of the first reactor 3 and the second reactor 6 as quenching hydrogen, another part mixes by pipeline 27 extractions with the new hydrogen from pipeline 30 as recycle hydrogen.The product liquid that cold high pressure separator 7 obtains enters cold low separator 8 through pipeline 18 and further carries out gas-liquid separation, separating the sour water obtained is extracted out by pipeline 24, separating obtained gas is through pipeline 29 dischargers, and the product liquid of gained enters separation column 9 through pipeline 19 and carries out the component cutting.Overhead stream enters return tank of top of the tower 10, and separating obtained light naphthar is extracted out through pipeline 28, and the gained gasoline fraction is extracted out through pipeline 20.The diesel oil distillate separated is extracted out through pipeline 21, and tower base stream is extracted out through pipeline 22.
The following examples will be further described the present invention, but therefore not limit this
In embodiment, the trade names of Hydrobon catalyst A are RN-10, the trade names of Hydrobon catalyst B are RS-1000, the trade names of hydrocracking catalyst C are RT-5, and all catalyzer are produced by China PetroChemical Corporation's Chang Ling catalyst plant.
In embodiment, stock oil D used is from the catalytic cracking unit of MIP technology, and its character is listed in table 1.As can be seen from Table 1, total aromaticity content of stock oil D is up to more than 76.5 quality %, and the content of the dicyclo of stock oil D and the above aromatic hydrocarbons of dicyclo is up to 46.9 quality %, and cetane value is only 20.6, is the poor-quality diesel-oil by cut fraction of high aromaticity content.
Embodiment 1
Stock oil D enters the first reaction zone together with hydrogen, and with Hydrobon catalyst A contact reacts, the reaction effluent of the first reaction zone enters high pressure hot separator, obtains gaseous stream through removing part H
2s and NH
3after, as the hydrogen-rich gas recycle, the liquid phase stream of the first reaction zone with enter second reaction zone after hydrogen-rich gas mixes, with hydrocracking catalyst C contact reacts.Reacted effluent obtains gasoline fraction and diesel oil distillate after cooling, separation and fractionation.Hydrobon catalyst is 1: 1 with the admission space ratio of hydrocracking catalyst, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is at 68.0 quality %, mononuclear aromatics content is increased to 47.0 quality %, and the nitrogen content of the liquid phase stream of the first reaction zone is 25.0 μ g/g.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the sulphur content 6 μ g/g of gasoline fraction, gasoline fraction research octane number (RON) 91.4, motor-method octane number 81.6; The actual measurement cetane value of diesel oil distillate product is 35.4, with raw material, compares, and cetane value improves 14.8 units, and sulphur content is less than 10 μ g/g.
Adopt technical process similarly to Example 1, different is to adopt Hydrobon catalyst B.Hydrobon catalyst is 2: 3 with the admission space ratio of hydrocracking catalyst, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is at 68.4 quality %, mononuclear aromatics content is increased to 45.1 quality %, and the nitrogen content of the liquid phase stream of the first reaction zone is 30.0 μ g/g.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the sulphur content 5.0 μ g/g of gasoline fraction product, gasoline fraction research octane number (RON) 94.8, motor-method octane number 83.1; The actual measurement cetane value of diesel oil distillate product is 33.7, with raw material, compares, and cetane value improves 13.1 units, and sulphur content is less than 10 μ g/g.
Stock oil D enters the first reaction zone together with hydrogen, and with Hydrobon catalyst A contact reacts, the reaction effluent of the first reaction zone enters the high pressure gas stripper, after hydrogen or hydrogen-rich gas air lift, removes H
2s and NH
3, at the bottom of the high pressure gas stripper gained liquid phase stream with enter second reaction zone after hydrogen-rich gas mixes, with hydrocracking catalyst C contact reacts.Reacted effluent obtains gasoline fraction and diesel oil distillate after cooling, separation and fractionation.Hydrobon catalyst is 2: 3 with the admission space ratio of hydrocracking catalyst, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is at 72.0 quality %, mononuclear aromatics content is increased to 48.2 quality %, and the nitrogen content of the liquid phase stream of the first reaction zone is 30.0 μ g/g.Reaction conditions is as shown in table 2, and product yield and character are as shown in table 3.
As can be seen from Table 3, the sulphur content of gasoline fraction product is less than 10 μ g/g, gasoline fraction research octane number (RON) 95.7, motor-method octane number 85.1; The actual measurement cetane value of diesel oil distillate product is 34.7, with raw material, compares, and cetane value improves 14.1 units, sulphur content 5 μ g/g.
Table 1
| Stock oil | D |
| Density (20 ℃), g/cm 3 | 0.9340 |
| The bromine valency, gBr/100g | 10.8 |
| Sulphur, μ g/g | 7600 |
| Nitrogen, μ g/g | 1075 |
| Cetane value | 20.6 |
| Total aromaticity content, quality % | 76.5 |
| The above aromaticity content of dicyclo, quality % | 46.9 |
| Boiling range (ASTM D-86), ℃ | |
| Initial boiling point | 206 |
| 10％ | 231 |
| 30％ | 255 |
| 50％ | 280 |
| 70％ | 311 |
| 90％ | 343 |
| Final boiling point | 365 |
Table 2
| Embodiment 1 | |
|
|
| Hydrofining/hydrocracking catalyst | A/C | B/C | A/C |
| Middle separating device | High-pressure separator | High-pressure separator | The high pressure gas stripper |
| The first reaction zone: | |||
| The hydrogen dividing potential drop, MPa | 5.8 | 4.8 | 5.5 |
| Temperature of reaction, ℃ | 360 | 380 | 350 |
| Volume space velocity, h -1 | 2.0 | 2.0 | 2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 700 | 800 | 400 |
| Second reaction zone: | |||
| The hydrogen dividing potential drop, MPa | 5.5 | 4.5 | 4.5 |
| Temperature of reaction, ℃ | 390 | 400 | 405 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 2.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 800 | 700 | 600 |
Table 3
| Embodiment 1 | |
|
|
| Light naphthar: | |||
| Density (20 ℃), g/cm 3 | 0.6363 | 0.6434 | 0.6380 |
| Boiling range ASTM D-86, ℃ | |||
| IBP-FBP | 45-65 | 48-67 | 45-65 |
| Gasoline fraction character: | |||
| Density (20 ℃), g/cm 3 | 0.8145 | 0.8302 | 0.8293 |
| Sulphur content, μ g/g | 6.0 | 5.0 | ＜10 |
| Research octane number (RON) | 91.4 | 94.8 | 95.7 |
| Motor-method octane number | 81.6 | 83.1 | 85.1 |
| Boiling range ASTM D-86, ℃ | |||
| IBP | 86 | 92 | 91 |
| 10％ | 111 | 114 | 111 |
| 30％ | 128 | 126 | 130 |
| 50％ | 143 | 142 | 140 |
| 70％ | 161 | 164 | 165 |
| 90％ | 179 | 184 | 181 |
| FBP | 200 | 201 | 201 |
| Diesel oil distillate character: | |||
| Density (20 ℃), g/cm 3 | 0.8672 | 0.8745 | 0.8719 |
| Sulphur content, μ g/g | 9.5 | ＜10.0 | 5.0 |
| Cetane value | 35.4 | 33.7 | 34.7 |
| The cetane value improvement value | 14.8 | 13.1 | 14.1 |
| Boiling range ASTM D-86, ℃ | |||
| IBP | 204 | 204 | 163 |
| 10％ | 218 | 220 | 219 |
| 30％ | 232 | 235 | 233 |
| 50％ | 244 | 249 | 246 |
| 70％ | 284 | 286 | 284 |
| 90％ | 339 | 336 | 336 |
| FBP | 371 | 369 | 371 |
Claims (10)
1. the method for hydrotreating by diesel raw material production high octane gasoline component, the diesel raw material oil-hydrogen mixture is first in the first reaction zone and Hydrobon catalyst contact reacts, the reaction effluent of the first reaction zone is separated, the liquid phase stream of gained the first reaction zone with enter second reaction zone and hydrocracking catalyst contact reacts after hydrogen mixes, the reaction effluent of second reaction zone is through cooling, obtain hydrogen-rich gas and product liquid after separation, it is characterized in that, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is more than 55 quality %, more than mononuclear aromatics content is increased to 40 quality %, and, the nitrogen content of the liquid phase stream of the first reaction zone is less than 100 μ g/g, the boiling spread of described diesel raw material oil is 165～400 ℃, total aromaticity content is higher than 60 quality %, wherein the content of dicyclo and the above aromatic hydrocarbons of dicyclo is higher than 40 quality %.
2. in accordance with the method for claim 1, it is characterized in that, control the aromatic saturation degree of depth of the first reaction zone, the liquid phase stream of the first reaction zone of take is benchmark, its total aromaticity content is more than 65 quality %, more than mononuclear aromatics content is increased to 50 quality %, and the nitrogen content of the first reaction zone liquid phase stream is 20 μ g/g～50 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that one or more in the diesel oil distillate of the straight-run diesel oil of described diesel raw material grease separation catalytic cracking light cycle oil, heavy catalytic cycle oil, naphthenic base crude, the coker gas oil of naphthenic base crude, coal direct liquefaction oil, the diesel oil distillate of coal tar.
4. in accordance with the method for claim 1, it is characterized in that, the admission space ratio of described Hydrobon catalyst and hydrocracking catalyst is 5:1～1:5.
5. in accordance with the method for claim 1, it is characterized in that, the reaction effluent of described the first reaction zone carries out gas-liquid separation in high pressure hot separator, obtains the gaseous stream of the first reaction zone and the liquid phase stream of the first reaction zone.
6. in accordance with the method for claim 1, it is characterized in that, the reaction effluent of described the first reaction zone carries out air lift in the high pressure gas stripper, obtains the liquid phase stream of the first reaction zone at the bottom of gas stripping column.
7. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of described the first reaction zone is: hydrogen dividing potential drop 3.0～10.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, volume space velocity 0.2～6.0h during liquid
-1; The reaction conditions of second reaction zone is: hydrogen dividing potential drop 2.0～9.0MPa, temperature of reaction is 300～450 ℃, hydrogen to oil volume ratio 400～1600Nm
3/ m
3, volume space velocity 0.2～6.0h during liquid
-1.
8. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst is VIII family base metal and/or the group vib non-precious metal catalyst loaded on composite alumina and/or combined oxidation silicon carrier.
9. in accordance with the method for claim 1, it is characterized in that, described hydrocracking catalyst is VIII family base metal and/or the group vib non-precious metal catalyst loaded on complex carrier, in oxide compound and take the catalyzer total amount as benchmark, contain the heavy % of nickel oxide 2.5～6.0, the heavy % of Tungsten oxide 99.999 10～38 in this catalyzer, contain the heavy % of fluorine 0.5～5.0, all the other are carrier.
10. in accordance with the method for claim 9, it is characterized in that, described complex carrier is comprised of the aluminum oxide of 20～90 heavy % and the zeolite of 10～80 heavy %, the mesopore that its mesolite is acidity value 1.0～2.0 mmoles/gram or large pore zeolite, the aluminum oxide that aluminum oxide is acidity value 0.5～0.8 mmole/gram, the acidity value NH of described aluminum oxide or zeolite
3-TPD method is measured.
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