CN102311795A - 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 is the hydrocarbon ils cleavage method that obtains low boiler cut existing under the situation of hydrogen, 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, inferiorization process, the quality of catalytic cracking diesel oil variation, output day by day increases year by year, and this part catalytic cracking diesel oil accounts for 1/3rd of Chinese commodity diesel oil share.And the refinery improves constantly the working ability and the working depth of CCU for the more clean cargo that abstract from crude oil, and causes the further variation of quality of catalytic cracking diesel oil.Meanwhile, the environmental protection legislation is strict day by day, and clean fuel is produced in market demands as far as possible, and because the petroleum resources worsening shortages, society also need effectively utilize petroleum resources as far as possible.Therefore, a kind of technology of processing catalytic cracking diesel oil of market demand exploitation with production high added value oil product.On the other hand, at present the catalytic gasoline proportion is up to 78% in China's gasoline pool, and the alkene that causes gasoline is with the sulphur content height, aromaticity content is low, octane value is on the low side relatively, and a kind of production technology of producing low-sulfur, high-octane rating clean gasoline also need be developed in market.
The technology of poor ignition quality fuel production high added value oil product mainly contains two types of unifining and hydrogen cracking.Adopt conventional hydrogen refining process to handle poor ignition quality fuel, though can remove impurity such as sulphur in the diesel oil, nitrogen effectively, 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, though can produce petroleum naphtha to greatest extent, 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 gets into hydrogenating desulfurization, hydrodenitrification reaction zone with straight-run diesel oil and/or light wax tailings (LCGO); Catalytic cracking diesel oil (LCO) gets into the hydrocracking reaction district; The product of two reaction zones mixes the back and gets into cold high score, cold low branch, gets into the fractionating system separation then and obtains high-octane number component and low-sulfur diesel-oil.The hydrocracking reaction district adopts amorphous or contains the hydrocracking catalyst of low molecular sieve level in this invention.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 technology of producing stop bracket gasoline in 134.This invention raw material boiling spread is 150～327 ℃ LCO, i.e. light constituent in the catalytic cracking light cycle oil.The hydrocracking catalyst that is adopted contains Y zeolite, USY molecular sieve or dealuminzation Y zeolite.In addition, in the fractionation product oil greater than gasoline fraction less than 232 ℃ or be back to the hydrocracking reactor inlet or be back to catalytic cracking reaction zone less than 260 ℃ middle runnings.
In this year, along with crude oil heaviness process is quickened, the quality of China's catalytic cracking diesel oil worse and worse; Show that mainly foreign matter contents such as sulphur, nitrogen are high, aromaticity content is high; Because raw oil and catalytic cracking process is different, total aromaticity content difference of catalytic cracking diesel oil is bigger, and content does not wait from 50% to 90%; Wherein mononuclear aromatics content is more than 20%, and the above aromaticity content of dicyclo is more than 40%.Especially after CCU adopted and falls the alkene technology, aromatic hydrocarbon from catalytic cracking diesel oil content further increased.If adopt the method for conventional hydrogen cracking that this part poor ignition quality fuel is handled,, need comparatively harsh reaction conditions, and its naphtha fraction RON has only about 75 though can produce the low-sulfur diesel-oil blend component that obtains excellent property.
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 when 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 earlier in first reaction zone and Hydrobon catalyst contact reacts; The reaction effluent of first reaction zone separates, and the liquid phase stream of the reaction zone of winning mixes the back and gets into second reaction zone and hydrocracking catalyst contact reacts with hydrogen, and the reaction effluent of second reaction zone obtains hydrogen-rich gas and product liquid after cooling, separation; Control the aromatic hydrocarbons saturation depth of first reaction zone; Liquid phase stream with first reaction zone is a benchmark, and its total aromaticity content is more than 55 quality %, and mononuclear aromatics content is increased to more than the 40 quality %; And the nitrogen content of the liquid phase stream of first reaction zone is less than 100 μ g/g.
At first reaction zone, i.e. hydrofining reaction district, the poor ignition quality fuel raw material mainly carries out reactions such as hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons are saturated.Pass through the degree of depth of control hydrofining reaction process among the present invention; Impel the above aromatic hydrocarbons of dicyclo and dicyclo to be saturated to 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 aromatic hydrocarbons saturation depth of preferred control first reaction zone; Liquid phase stream with first reaction zone is a benchmark, and its total aromaticity content is more than 65 quality %, and mononuclear aromatics content is increased to more than the 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; Promptly in the hydrocracking reaction district; Liquid ingredient in the reaction effluent of first reaction zone (unifining product oil) carries out reactions such as selective opening, cracking on hydrogenation-cracking function catalyzer; Make the low mononuclear aromatics side chain selectivity of cetane value such as short-side chain korenyl, naphthane carry out reactions such as open loop, cracking effectively; Impel in the diesel oil distillate mononuclear aromatics than small molecules to be converted into high-octane number components such as benzene in the gasoline fraction, toluene, thereby reach the purpose of improving gasoline fraction product hydrocarbon composition, improving gasoline fraction product octane value.Keep simultaneously more macromolecular long chain alkane in the diesel oil distillate as far as possible or have the high hexadecane value components such as naphthenic hydrocarbon or aromatic hydrocarbons of long side chain, thereby reach the purpose that improves the diesel product cetane value, improves the product diesel quality.Be shown in the following figure, the present invention impels reaction to be undertaken by (1)-(3)-(5) route through the control unifining and the hydrocracking reaction degree of depth, 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 preferred 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 %, preferred 40～65 quality %.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 one or more.
The loadings of first reaction zone and the second reaction zone catalyzer is confirmed according to the nitrogen content and the above aromaticity content of dicyclo of the diesel raw material oil of being processed.The admission space ratio of Hydrobon catalyst and hydrocracking catalyst is 5: 1～1: 5, preferred 2: 1～1: 2.If carbon residue or metal content are higher in the diesel raw material oil; For falling, the pressure that prevents beds reaches limit value too fastly; Can load the hydrogenation protecting agent that accounts for unifining agent volume total amount 5～20% at Hydrobon catalyst bed top respectively, to protect Primary Catalysts, to avoid the quick coking of bed.Protective material is made up of the gamma-aluminium oxide carrier with diplopore distribution of 1.0～5.0 heavy % nickel oxide, 5.5～10.0 heavy % molybdenum oxides and surplus.
The present invention adopts a kind of two-part technical process.High pressure separating step in the middle of between first reaction zone and second reaction zone, being provided with removes the NH that the hydrofining reaction district generates with part
3And H
2S is for the hydrocracking reaction district provides the cracking stock of low nitrogen content oily.
One of them embodiment preferred is: the technical process of unifining-high pressure hot separator-hydrogen cracking; Diesel raw material oil is at first reaction zone; Remove impurity such as sulphur, nitrogen; And the above aromatic hydrocarbons of saturated bicyclic, the reaction effluent of said first reaction zone carries out gas-liquid separation in high pressure hot separator, obtain being rich in the gaseous stream of impurity such as hydrogen sulfide, ammonia and the liquid phase stream of first reaction zone.The gained liquid phase stream gets into 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 embodiment preferred is: the technical process of unifining-high pressure gas stripper-hydrogen cracking; The reaction effluent of said first reaction zone carries out gas and carries in the high pressure gas stripper; After gas is carried impurity such as removing hydrogen sulfide, ammonia, obtain the liquid phase stream of first reaction zone at the bottom of the gas stripping column.
The reaction conditions of described first reaction zone is: hydrogen dividing potential drop 3.0～10.0MPa, preferred 4.0～7.0MPa, 300～450 ℃ of temperature of reaction, preferred 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
-1The 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 ℃, preferred 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 that loads on composite alumina and/or the combined oxidation silicon carrier.Preferred Hydrobon catalyst consists of: in oxide compound and with the catalyzer total amount is benchmark, and the content of nickel and/or cobalt is 1～10 heavy %, and molybdenum and tungsten sum are greater than 10～50 heavy %, and fluorine 1～10 weighs %, and all the other are aluminum oxide and silicon oxide.This Hydrobon catalyst has good hydrogenating desulfurization, hydrodenitrification performance; And the saturated performance of aromatic hydrocarbons of part; Can be used for the hydrotreatment of poor-quality diesel-oil by cut fraction, impurity such as the sulphur in the ability effective elimination raw material, nitrogen, and appropriateness is carried out the aromatic hydrocarbons saturated reaction; Impel the above aromatic hydrocarbons of dicyclo and dicyclo to be saturated to mononuclear aromatics, avoiding supersaturation is naphthenic hydrocarbon.
Described hydrocracking catalyst is VIII family and/or the group vib non-precious metal catalyst that loads on the complex carrier.In oxide compound and with the catalyzer total amount is benchmark, contains nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～38 heavy % in this catalyzer, contains fluorine 0.5～5.0 heavy %, and all the other are carrier.This carrier is made up of the aluminum oxide of 20～90 heavy % and the zeolite of 10～80 heavy %; Its mesolite is the mesopore or the large pore zeolite of acidity value 1.0～2.0 mmole/grams; Aluminum oxide is the aluminum oxide of acidity value 0.5～0.8 mmole/gram, and the acidity value of said aluminum oxide or zeolite is used NH
3-TPD method is measured.Said zeolite is selected from one or more in faujusite, mordenite, ZSM-5 zeolite, Beta zeolite, the zeolite.The precursor of said aluminum oxide is by being selected from the diaspore content of deceiving sodium aluminate-carbon dioxide process, aluminum alkyls or aluminum alkoxide hydrolysis method, sodium metaaluminate-Tai-Ace S 150 method preparation one or more hydrated aluminum oxides greater than 60 heavy %.Described hydrocracking catalyst has good selective cracking function; Reactions such as the fracture of mononuclear aromatics side chain, naphthane selective opening and disconnected side chain there is good selectivity; Make the mononuclear aromatics generation selective cracking reaction in the diesel oil distillate generate high octane 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, is the raw oil that second reaction zone provides low-sulfur, low nitrogen.Improve the cetane value compared with techniques with conventional distillate hydrogenation upgrading, the present invention adopts than low hydrogen dividing potential drop and higher cracking invert point.
(2) adopt method provided by the invention; Can handle the poor-quality diesel-oil by cut fraction of high aromaticity content; And the production sulphur content can the production sulphur content improve 10 clean diesel blend components more than the unit less than 10 μ g/g, cetane value than raw oil simultaneously less than the gasoline fraction of 10 μ g/g, RON about 95.
Description of drawings
Fig. 1 is the preferred version one flow process synoptic diagram that the present 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 synoptic diagram that the present 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 explained.Accompanying drawing is a schematic flow sheet of being produced the stop bracket gasoline method by poor ignition quality fuel provided by the invention.Omitted many equipment among the figure, like 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 first reactor drum 3 from pipeline 27 hydrogen; Contact with Hydrobon catalyst, carry out desulfurization, denitrogenation and appropriate aromatic hydrocarbons saturated reaction.The reaction effluent of first reactor drum 3 gets into high pressure hot separators 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 after pipeline 14 and entering second reactor drum 6 after hydrogen from pipeline 26 mixes.Mixture contacts with hydrocracking catalyst in second reactor drum 6, carries out the cracking reaction of suitable selectivity side chain fracture.
The reaction effluent of second reactor drum 6, gets into cold high pressure separator 7 and carries out gas-liquid separation with after gaseous stream from the high pressure hot separator gained of pipeline 15 mixes through pipeline 16.Cold high pressure separator separates the sour water that obtains and is extracted out by pipeline 23.Cold high pressure separator 7 separates the hydrogen-rich gas that obtains and gets into desulphurization of recycle hydrogen jar 31 through pipeline 25; The hydrogen-rich gas that removes partial vulcanization hydrogen gets into circulating hydrogen compressor 11 through pipeline 32; After pressurization, extract out by pipeline 26; A part is removed the catalyst bed interlayer of first reactor drum 3 and second reactor drum 6 as quenching hydrogen, and another part mixes after pipeline 27 extractions with new hydrogen from pipeline 30 as recycle hydrogen.The product liquid that cold high pressure separator 7 obtains gets into cold low separator 8 through pipeline 18 and further carries out gas-liquid separation; Separating the sour water that obtains is extracted out by pipeline 24; Separating obtained gas is through pipeline 29 dischargers, and the product liquid of gained gets into separation column 9 through pipeline 19 and carries out the component cutting.The entering return tank of top of the tower 10 of overhead stream, separating obtained light naphthar is extracted out through pipeline 28.Separating obtained gasoline fraction is extracted out through pipeline 20.Isolating diesel oil distillate 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: the diesel raw material oil from pipeline 1 passes through raw oil pump 2; Through pipeline 12 be mixed into first reactor drum 3 from pipeline 27 hydrogen; Contact with Hydrobon catalyst, carry out desulfurization, denitrogenation and appropriate aromatic hydrocarbons saturated reaction.The reaction effluent of first reactor drum 3 gets into high pressure gas stripper 40 through pipeline 13.Through carrying from the hydrogen or the hydrogen-rich gas gas of pipeline 30, the gas of gas stripping column 40 gets into digester 44 through pipeline 43, removes H in high pressure gas stripper 40
2Hydrogen-rich gas behind the S mixes with hydrogen-rich gas from pipeline 25 after pipeline 32 gets into the recycle hydrogen systems through pipeline 45.Liquid efflunent at the bottom of gas stripping column 40 towers is after pipeline 42 and hot oil pump 5 pressurizations, through pipeline 14 and entering second reactor drum 6 after hydrogen from pipeline 26 mixes.Mixture contacts with hydrocracking catalyst in second reactor drum 6, carries out the cracking reaction of suitable selectivity side chain fracture.
The reaction effluent of second reactor drum 6 gets into cold high pressure separator 7 through pipeline 17 and carries out gas-liquid separation.Cold high pressure separator separates the sour water that obtains and is extracted out by pipeline 23.Cold high pressure separator 7 separates the hydrogen-rich gas that obtains and gets into circulating hydrogen compressor 11 through pipeline 25, pipeline 32; After pressurization, extract out by pipeline 26; A part is removed the catalyst bed interlayer of first reactor drum 3 and second reactor drum 6 as quenching hydrogen, and another part mixes after pipeline 27 extractions with new hydrogen from pipeline 30 as recycle hydrogen.The product liquid that cold high pressure separator 7 obtains gets into cold low separator 8 through pipeline 18 and further carries out gas-liquid separation; Separating the sour water that obtains is extracted out by pipeline 24; Separating obtained gas is through pipeline 29 dischargers, and the product liquid of gained gets into separation column 9 through pipeline 19 and carries out the component cutting.Overhead stream gets into 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.Isolating diesel oil distillate is extracted out through pipeline 21, and tower base stream is extracted out through pipeline 22.
Following embodiment will further explain the present invention, but therefore not limit this
The trade names of Hydrobon catalyst A are RN-10 among the embodiment; 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.
Raw oil D used among the embodiment is from the technological CCU of MIP, and its character is listed in table 1.Can find out that from table 1 total aromaticity content of raw oil D is up to more than the 76.5 quality %, the content of the dicyclo of raw oil D and the above aromatic hydrocarbons of dicyclo is up to 46.9 quality %, and cetane value is merely 20.6, is the poor-quality diesel-oil by cut fraction of high aromaticity content.
Raw oil D gets into first reaction zone with hydrogen, and with Hydrobon catalyst A contact reacts, the reaction effluent of first reaction zone gets into high pressure hot separator, obtains gaseous stream through removing section H
2S and NH
3After, as the hydrogen-rich gas recycle, the liquid phase stream of first reaction zone mixes the back and gets into second reaction zone with hydrogen-rich gas, with hydrocracking catalyst C contact reacts.Reacted elute 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 hydrocarbons saturation depth of first reaction zone; Liquid phase stream with first reaction zone is a benchmark; Its total aromaticity content is at 68.0 quality %, and mononuclear aromatics content is increased to 47.0 quality %, and the nitrogen content of the liquid phase stream of 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.
Can find out the sulphur content 6 μ g/g of gasoline fraction, gasoline fraction RON 91.4, motor-method octane number 81.6 from table 3; The actual measurement cetane value of diesel oil distillate product is 35.4, compares with raw material, and cetane value improves 14.8 units, and sulphur content is less than 10 μ g/g.
Embodiment 2
Adopt the technical process same with embodiment 1, different is to adopt Hydrobon catalyst B.Hydrobon catalyst is 2: 3 with the admission space ratio of hydrocracking catalyst; Control the aromatic hydrocarbons saturation depth of first reaction zone; Liquid phase stream with first reaction zone is a benchmark; Its total aromaticity content is at 68.4 quality %, and mononuclear aromatics content is increased to 45.1 quality %, and the nitrogen content of the liquid phase stream of 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.
Can find out the sulphur content 5.0 μ g/g of gasoline fraction product, gasoline fraction RON 94.8, motor-method octane number 83.1 from table 3; The actual measurement cetane value of diesel oil distillate product is 33.7, compares with raw material, and cetane value improves 13.1 units, and sulphur content is less than 10 μ g/g.
Embodiment 3
Raw oil D gets into first reaction zone with hydrogen, and with Hydrobon catalyst A contact reacts, the reaction effluent of first reaction zone gets into the high pressure gas stripper, after hydrogen or hydrogen-rich gas gas are carried, removes H
2S and NH
3, the gained liquid phase stream mixes back entering second reaction zone at the bottom of the high pressure gas stripper with hydrogen-rich gas, with hydrocracking catalyst C contact reacts.Reacted elute 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 hydrocarbons saturation depth of first reaction zone; Liquid phase stream with first reaction zone is a benchmark; Its total aromaticity content is at 72.0 quality %, and mononuclear aromatics content is increased to 48.2 quality %, and the nitrogen content of the liquid phase stream of 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.
Can find out that from table 3 sulphur content of gasoline fraction product is less than 10 μ g/g, gasoline fraction RON 95.7, motor-method octane number 85.1; The actual measurement cetane value of diesel oil distillate product is 34.7, compares with raw material, and cetane value improves 14.1 units, sulphur content 5 μ g/g.
Table 1
| Raw 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), ℃ | |
| Over point | 206 |
| 10％ | 231 |
| 30％ | 255 |
| 50％ | 280 |
| 70％ | 311 |
| 90％ | 343 |
| Final boiling point | 365 |
Table 2
| |
Embodiment 2 | Embodiment 2 | |
| Unifining/hydrocracking catalyst | A/C | B/C | A/C |
| Middle separating device | HP separator | HP separator | The high pressure gas stripper |
| 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 2 | Embodiment 3 | |
| 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 |
| 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 |
| Cetane value raising 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 (11)
1. method of hydrotreating by diesel raw material production high octane gasoline component; The diesel raw material oil-hydrogen mixture is earlier in first reaction zone and Hydrobon catalyst contact reacts, and the reaction effluent of first reaction zone separates, and the liquid phase stream of the reaction zone of winning mixes the back and gets into second reaction zone and hydrocracking catalyst contact reacts with hydrogen; The reaction effluent of second reaction zone obtains hydrogen-rich gas and product liquid after cooling, separation; It is characterized in that, control the aromatic hydrocarbons saturation depth of first reaction zone, is benchmark with the liquid phase stream of first reaction zone; Its total aromaticity content is more than 55 quality %; Mononuclear aromatics content is increased to more than the 40 quality %, and the nitrogen content of the liquid phase stream of first reaction zone is less than 100 μ g/g.
2. according to the described method of claim 1; It is characterized in that, control the aromatic hydrocarbons saturation depth of first reaction zone, is benchmark with the liquid phase stream of first reaction zone; Its total aromaticity content is more than 65 quality %; Mononuclear aromatics content is increased to more than the 50 quality %, and the nitrogen content of the first reaction zone liquid phase stream is 20 μ g/g～50 μ g/g.
3. according to the described method of claim 1, it is characterized in that the boiling spread of described diesel raw material oil is 165～400 ℃, total aromaticity content is higher than 60 quality %, and wherein the content of dicyclo and the above aromatic hydrocarbons of dicyclo is higher than 40 quality %.
4. according to the described method of 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.
5. according to the described method of claim 1, it is characterized in that the admission space ratio of described Hydrobon catalyst and hydrocracking catalyst is 5: 1～1: 5.
6. according to the described method of claim 1, it is characterized in that the reaction effluent of said first reaction zone carries out gas-liquid separation in high pressure hot separator, obtain the gaseous stream of first reaction zone and the liquid phase stream of first reaction zone.
7. according to the described method of claim 1, it is characterized in that the reaction effluent of said first reaction zone carries out gas to be carried, and obtains the liquid phase stream of first reaction zone at the bottom of the gas stripping column in the high pressure gas stripper.
8. according to the described method of claim 1, it is characterized in that the reaction conditions of described 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
-1The 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
9. according to the described method of claim 1, it is characterized in that described Hydrobon catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on composite alumina and/or the combined oxidation silicon carrier.
10. according to the described method of claim 1; It is characterized in that; Described hydrocracking catalyst is VIII family base metal and/or the group vib non-precious metal catalyst that loads on the complex carrier, is benchmark in oxide compound and with the catalyzer total amount, contains nickel oxide 2.5～6.0 heavy %, Tungsten oxide 99.999 10～38 heavy % in this catalyzer; Contain fluorine 0.5～5.0 heavy %, all the other are carrier.
11. according to the described method of claim 9; It is characterized in that; Said complex carrier is made up of the aluminum oxide of 20～90 heavy % and the zeolite of 10～80 heavy %; Its mesolite is the mesopore or the large pore zeolite of acidity value 1.0～2.0 mmole/grams, and aluminum oxide is the aluminum oxide of acidity value 0.5～0.8 mmole/gram, and the acidity value of said aluminum oxide or zeolite is used NH
3-TPD method is measured.
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