CN103897731A - Method for mixed production of light-weight aromatic hydrocarbon by use of catalytic cracking diesel and C10<+> distillate oil - Google Patents
Method for mixed production of light-weight aromatic hydrocarbon by use of catalytic cracking diesel and C10<+> distillate oil Download PDFInfo
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Abstract
The invention relates to a method for mixed production of light-weight aromatic hydrocarbon by use of catalytic cracking diesel and C10<+> distillate oil. The method comprises the following steps: firstly mixing the catalytic cracking diesel and the C10<+> distillate oil with hydrogen, performing a hydrofining reaction to remove sulfur and nitrogen, saturate olefin and appropriately saturate aromatic hydrocarbon; then, extracting a hydrofining product by using an extraction solvent to obtain extract oil containing rich aromatic hydrocarbon and raffinate oil containing rich alkane; using the raffinate oil as a clean diesel oil concoction component, and performing rectification separation on the extract oil to obtain aromatic hydrocarbon extract oil; performing a hydrocracking reaction on the aromatic hydrocarbon extract oil, performing cutting separation on a hydrocracking product, using a distillate oil product greater than 195 DEG C as the clean diesel oil concoction component, feeding the distillate oil product smaller than 195 DEG C as an aromatic hydrocarbon raw material into an aromatic hydrocarbon treatment device to obtain a light-weight aromatic hydrocarbon product and a clean gasoline concoction component. By adopting the method provided by the invention, the yield of the light-weight aromatic hydrocarbon is increased, and meanwhile high-quality clean fuel oil is obtained and the high additional value utilization of the C10<+> distillate oil is achieved.
Description
Technical field
The invention belongs to light aromatics preparation method in oil refining field, be specifically related to one and utilize catalytic cracking diesel oil and C
10 +distillate is produced the method for light aromatics and clean fuel oil product.
Background technology
Developing low-carbon economy, recycling economy, realizing under the situation of Sustainable development, China's oil quality upgrading paces are obviously accelerated, also more and more stricter to the requirement of aromaticity content in diesel oil.Produce clear gusoline and become one of emphasis of petroleum refining industry of current China development.During China's diesel oil forms, have 25～30%, catalytic cracking diesel oil.Catalytic cracking diesel oil has aromaticity content high (aromaticity content > 60%), feature that cetane value is low, its inferior quality, must just can be used as oil fuel blend component by hydrofining or hydro-upgrading, but hydro-upgrading process cost is high, condition is harsh, and cetane value improves limited, causes oil fuel cost unprecedented soaring.Therefore, catalytic cracking diesel oil becomes the bottleneck of restriction relevant unit production high standard clean diesel because aromaticity content is high, how to reduce aromaticity content in catalytic cracking diesel oil, becomes a difficult problem of puzzlement refinery thereby improve its cetane value.
Present stage, the industrial main method of improving catalytic cracking diesel oil quality is hydrofining and hydro-upgrading, and hydrorefined research is relatively many, on the basis of traditional Hydrofining Technology, is also significantly improved.Although hydrofining can realize deep desulfuration denitrogenation, cetane value generally only can improve 4～8, and especially, for the high poor quality catalytic cracking diesel of aromaticity content, hydrofining diesel oil cetane value is still less than 35, is difficult to do desirable diesel oil blending component.The another kind of method often adopting is hydro-upgrading, generally first pass through hydrofining desulfurization removing nitric, improve diesel cetane-number through hydro-upgrading again, the hydro-upgrading of this poor quality catalytic cracking diesel need to consume a large amount of hydrogen and adopt lower reaction velocity, corresponding process cost is high, therefore in catalytic cracking diesel oil when aromaticity content high (cetane value <25), taking hydrogenation modification method to produce diesel oil has not been an economically viable route in some cases, and a large amount of aromatic hydrocarbon resources that wherein contain fail to make full use of.
By-product C in oil refining processing and ethylene production
9 +distillate, C
9 +distillate is mainly derived from byproduct, the byproduct of refinery catalytic reforming unit etc. of light oil cracking production ethylene unit.In recent years, along with the continuous lifting of China's ethene ability and the operation in succession of large petrochemical plant continuous reformer, C
9 +distillate output increases substantially.C
9 +the comprehensive utilization of distillate is the problem that people are concerned about, at present more existing ripe methods.Wherein, catalytic reforming C
9the processing and utilization of A is widely used as the raw material of toluene disproportionation and transalkylation reaction, as manufacturing benzene and dimethylbenzene; Cracking C
9cut is as solvent oil or produce C
9petroleum resin.And heavy distillate C
10and C
10above component, composition is complicated, and heavy aromatics content is high, and boiling point is high, and purposes is less at present.Along with clear gusoline environmental requirement increasingly stringent, these components are all improper as the blend composition of diesel oil, and only some is as solvent oil, and a part is for separating durol wherein, and all the other major parts are burnt as fuel.
Meanwhile, also constantly accelerate the rate of growth of aromatic hydrocarbons demand world market.Along with the development of China's arene industrial, supply falls short of demand for the light aromaticss such as BTX, and added value of product is higher.Catalytic cracking diesel oil, cracking C
10 +distillate, reformation C
10 +in distillate, be all rich in a large amount of aromatic groups, approximately contain 50～90% aromatic hydrocarbons, this part aromatic component complexity, is difficult to extraction and application, is the potential resources of preparation BTX.
Along with the expansion of oil refining apparatus scale, catalytic cracking diesel oil output is high, and general plant catalytic cracking unit catalytic cracking diesel oil output is all more than 300,000 tons/year.And cracking C
10 +distillate, reformation C
10 +the relative dimensions of market of distillate is little, a set of 1,000,000 tons of ethylene units, cracking C
10 +distillate annual production is about more than 80,000 tons, a set of 800,000 tons of continuous reformer C
10 +distillate output is higher than 100,000 tons/year, due to these C
10 +distillate is not good outlet at present, and market supply is comparatively sufficient.For C
10 +distillate carries out separately hydrotreatment and exists plant investment large, the unfavorable factor that the payback period is long.Take catalytic cracking diesel oil and C 9 fraction of cracking oil and/or the processing of reformation C 9 fraction oil mixed hydrogenation, in the high low-carbon (LC) aromatic hydrocarbons while of production added value, hold concurrently and produce high-quality clean fuel oil product, embody unit scale effect, economic benefit is more remarkable; In addition, due to the low nitrogen of low-sulfur, high aromaticity content C
10 +adding of distillate, intractability while reducing the independent hydrofining of poor quality catalytic cracking diesel, improves light aromatics yield, therefore carries out catalytic cracking diesel oil and C
10 +distillate combination treatment volume increase low-carbon (LC) aromatic hydrocarbons technology has good market application foreground.
US6623628B1 discloses a kind of method that adopts two-stage method to produce low-sulfur, low aromatic hydrocarbons and high hexadecane value diesel oil.In the method, adopt two reactors, it is active ingredient from group vib and at least one from the element in group VIII that one catalyzer in anti-adopts at least one, and it is active ingredient from the precious metal in group VIII that two catalyzer in anti-adopt at least one.Between two reactors, be provided with stripper, an anti-gaseous impurities such as hydrogen sulfide and ammonia producing removed totally, to protect two anti-noble metal catalysts.It is the intermediate oil of 150 ℃～370 ℃ that the method can be processed boiling range, produces low-sulfur, low aromatic hydrocarbons and high hexadecane value diesel oil.But raw material used in the method is lighter, and aromaticity content is low; In addition, adopted noble metal catalyst to make cost up in the method, running has a big risk, flexibility of operation declines.
CN101760239A discloses a kind of method of utilizing of catalytic cracking diesel oil, catalytic cracking diesel oil is separated into boiling point is less than the component of 230 ℃ and boiling point is 230 ℃ of above components, boiling point is carried out to hydrogenation higher than the component of 230 ℃ polycyclic aromatic hydrocarbons is converted into mononuclear aromatics, finally from two kinds of components after treatment, isolate and be rich in the diesel oil of mononuclear aromatics and carry out catalytic cracking.The method can improve hydrogenation selectivity, make the FCC gasoline that aromaticity content and octane value are high, but because the diesel oil of taking catalyst cracking method to be rich in mononuclear aromatics to isolating is processed, must cause the generations such as a large amount of dry gas, liquefied gas and coke, in actual production, economy is not remarkable.
CN100404646C discloses a kind of method of modifying poor-quality diesel-oil by cut fraction, diesel oil distillate raw material and solvent inject respectively extraction tower, normal pressure, extraction tower tower top temperature be 70～75 ℃, extraction solvent with the weight ratio of raw material for) mix under the condition of 0.5～3:1, tower top is solvent-laden refined diesel oil, it at the bottom of tower, is the solvent-extracted oil that contains that is rich in sulphur and polycyclic aromatic hydrocarbons, isolate respectively refined diesel oil and extract oil out through separation column, after the isolated two bursts of solvent of separation column, recycling.The method make diesel oil distillate cetane value improve 10 it is more than unit that desulfurization degree reaches 50%, polycyclic aromatic hydrocarbons declines more than 60%.The method is relatively simple, but that cetane value improves is limited, and generates in oil sulphur content and fail deep removal, is difficult to reach clear gusoline specification of quality, and for extracting the oil method how effectively use has not had out.
No matter aforesaid method, be hydrofining or solvent treatment, is all only absorbed in the improvement of catalytic cracking diesel oil character, and aromatic hydrocarbons is not wherein fully utilized the maximization of generating profit.In prior art, the liquid liquid extracting in aromatics extraction process and extractive distillation technique are all very ripe, but mainly concentrate on the separating treatment aspect of C6～C8 aromatic hydrocarbons, less for the separation applied research of the heavy arene in diesel oil distillate.
CN103214332A discloses a kind of method of being produced light aromatics and high-quality oil product by catalytic cracking diesel oil, comprise the steps: that catalytic cracking diesel oil extraction solvent carries out extracting by (1), obtain being rich in the extraction oil of polycyclic aromatic hydrocarbons and be rich in raffinating oil of alkane, (2) by extractions oil under hydrogenation conditions, carry out hydrofining and hydrocracking production light aromatics,
Stop bracket gasoline cut.The method is in obtaining light aromatics, high diesel oil and the stop bracket gasoline of energy by-product cetane value, but first take extraction solvent to carry out extracting for catalytic cracking diesel oil raw material, because catalyzed cracking processing technique has determined to contain in catalytic cracking diesel oil the olefin(e) compound of more amount, in addition the existence of the compound such as sulphur nitrogen, must cause extraction solvent loss large, extraction rate was acquired is poor.If gained is raffinated oil without hydrofining, sulfur-nitrogen compound content is high, is difficult to meet clean fuel specification of quality.
CN101357876B discloses a kind of C
9 +the method of heavy aromatic hydrocarbon light, a kind of C
9 +the method of heavy aromatic hydrocarbon light, comprises and makes C
9 +heavy virtue gently hydrogen exist under, under 380～600 ℃, the condition of 0.1～5.0MPa, carry out lighting with catalyzer contact reacts, described catalyzer comprises high-temperature inorganic oxide carrier and take carrier as the content that calculates benchmark is as the halogen of 0.01～3.0 quality % and the iridium of 0.01～5.0 quality %.This method is for C
9 +the lighting of heavy arene, lighting transformation efficiency is high, and dimethylbenzene productive rate is high, and catalyst carbon deposit is few, and can effectively reduce full boiling point and the gum level of heavy arene.
CN1082539C discloses the separation method of a kind of heavy arenes lightening catalyst and lighting product.Described catalyzer is made up of the zeolite with MOR structure, the ZSM-5 zeolite of 20～50 heavy % and the aluminum oxide of 20～40 heavy % of the platinum of 0.05～0.3 heavy % or palladium, 20～59 heavy %.Heavy arene raw material is contacted with above-mentioned catalyzer under 350～450 ℃, 0.5～3.5MPa condition, and gained lighting product can obtain the organic raw material such as BTX and sym-trimethylbenzene, unsym-trimethyl benzene, durol through fractionation.
Above-mentioned distillate lighting utilization is produced light aromatics, uses precious metal System Catalyst, unit scale hour, and economic benefit is more not obvious.If utilize the advantage of Integrated Refinery And Petrochemical enterprise, by catalytic cracking diesel oil hydro-upgrading, Aromatic Hydrocarbon United Plant, ethylene cracker, optimize existing apparatus raw material and process structure, can make full use of all kinds of raw material resources, be expected to solve the problem that aromatic hydrocarbons industry and clean fuel face simultaneously.On the one hand, utilize the hydrogen addition technology can be to catalytic cracking diesel oil and C
10 +distillate is realized deep desulfuration denitrogenation, utilizes on the other hand solvent extraction technology (Aromatics Extractive Project) can significantly reduce the aromaticity content in oil fuel, realizes and increases aromatic production simultaneously in conjunction with hydrogen addition technology, alleviates the demand and supply contraction.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide one to utilize catalytic cracking diesel oil and C
10 +distillate is produced the method for light aromatics, and this method, can high clean diesel and the high clean gasoline of octane value of production cetane value in obtaining light aromatics.
For solving the problems of the technologies described above, the present invention is achieved by the following technical programs:
The invention provides a kind of catalytic cracking diesel oil and C
10 +distillate mixes the method for producing light aromatics, comprises the steps:
1) by catalytic cracking diesel oil, C
10 +after distillate mixes with hydrogen, carry out hydrofining reaction, to carry out, sulphur nitrogen removes, olefin saturated and polycyclic aromatic hydrocarbons hydrogenation saturated as mononuclear aromatics; Described catalytic cracking diesel oil and C
10 +the mass ratio of distillate is 3:2～4:1;
2) through step 1) hydrotreated product that obtains of hydrofining enters the organic solvent that adopts boiling point to be not more than 180 ℃ in extraction tower and carries out extracting as extraction solvent, obtain being rich in the extraction oil of aromatic hydrocarbons and being rich in raffinating oil of alkane; The wherein said equal <10 μ of the sulphur nitrogen content g/g that raffinates oil that is rich in alkane, cetane value is not less than 45, discharges as clean diesel blend component;
3) the extraction oil that is rich in aromatic hydrocarbons described in separates by rectifying mode, obtains the aromatic hydrocarbons extraction oil that aromaticity content is no less than 90wt% at the bottom of tower, and tower top obtains extraction solvent and returns to described extraction tower recycle;
4) step 3) the described aromatic hydrocarbons that obtains extracts oil out under hydrogenation conditions, to carry out, mononuclear aromatics disconnected side chain reaction saturated take polycyclic aromatic hydrocarbons is main hydrocracking reaction;
5) aromatic hydrocarbons is extracted oily isocrackate out through cutting and separating, and wherein the distillate product of >195 ℃ is as clean diesel blend component; The distillate of <195 ℃ enters aromatic hydrocarbons treatment unit as aroamtic hydrocarbon raw material, finally obtains light aromatics product and clean gasoline blend component.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes in the method for producing light aromatics, it is characterized in that, step 1) described in the Hydrobon catalyst that loads in hydrofining reaction be MoNi system Hydrobon catalyst, reaction conditions is 320～390 ℃ of temperature of reaction, hydrogen dividing potential drop 3.5～8.0MPa, stock oil mass space velocity 1.0～2.0h
-1, hydrogen/oil volume is than 300～800:1.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes in the method for producing light aromatics; it is characterized in that; step 1) in described hydrofining reaction; account for the hydrogenation protecting agent of hydrofining agent volume total amount 5～20% at Hydrobon catalyst bed top loading; to protect Primary Catalysts, to avoid the quick coking of bed; while preventing in catalytic cracking diesel oil stock oil that carbon residue or metal content are higher, the Pressure Drop of beds reaches limit value too quickly.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes to be produced in the method for light aromatics, step 2) described in extraction solvent be preferably furfural.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes to be produced in the method for light aromatics, step 2) described in the mass ratio of distillate after extraction solvent and hydrofining be 0.5～2.0:1.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes in the method for producing light aromatics, step 4) described in hydrocracking reaction in the hydroeracking unit that is filled with hydrocracking catalyst, carry out, consisting of of described hydrocracking catalyst: take catalyzer as benchmark, nickel oxide 6～12wt%, surplus is HY molecular sieve-HZSM-5 molecular sieve-alumina supporter; Take carrier as benchmark, HY molecular sieve content is 20～30wt%, and HZSM-5 molecular sieve content is 10～20wt%, and alumina content is 50～70wt%; The temperature of reaction of hydrocracking reaction is 380～430 ℃, and hydrogen dividing potential drop is 4.0～10.0MPa, and it is 0.5～1.5h-1 that aromatic hydrocarbons is extracted oil quality air speed out, and hydrogen/oil volume ratio is 300～800:1.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes in the method for producing light aromatics, step 4) a small amount of conventional Hydrobon catalyst of middle hydroeracking unit bottom filling, loadings accounts for 5～15% of hydrocracking catalyst device inner catalyst total filling amount, makes a small amount of alkene in hydrocracking after product carry out that deep hydrogenation is saturated to be removed.
At catalytic cracking diesel oil of the present invention and C
10 +distillate mixes in the method for producing light aromatics, and the cetane value of described catalytic cracking diesel oil is less than 35, wherein containing the paraffinic hydrocarbons of 15～50wt% and the aromatic hydrocarbons of 50～85wt%; Described C
10 +distillate is cracking C
10 +distillate and/or reformation C
10 +distillate.
Compared with prior art, the advantage of the inventive method is:
1, adopt method provided by the invention, can obtain sulphur content, aromaticity content and polycyclic aromatic hydrocarbon content and all meet the IV class of " world's fuel oil standard ", the clean diesel of V class standard.Because the present invention utilizes difficult reacting thiourea compound and polycyclic aromatic hydrocarbons to be distributed in catalytic cracking diesel oil cut, take and the low nitrogen C of low-sulfur
10 +distillate mixed hydrogenation processing mode, sulphur nitrogen impurity content in stock oil is significantly reduced, reduce hydrofining difficulty, before extracting, first carry out hydrofining reaction, make sulphur in the distillate after hydrofining, Control of Nitrogen Content at <10 μ g/g, adopt again the method for solvent extraction to realize the enrichment of being rich in aromatic fraction, be rich in raffinating oil of alkane and there is the characteristic that sulphur nitrogen content is low, cetane value is high.
2, the inventive method adopts the method for solvent extraction to realize the enrichment of being rich in aromatic fraction, before extracting, carry out hydrofining, after extracting, obtain being rich in after aromatic hydrocarbons is extracted oil out and carry out again hydrocracking, carry out the saturated open loop of polycyclic aromatic hydrocarbons, the disconnected side chain of mononuclear aromatics, avoid the excessive hydrogenation of aromatic hydrocarbons, guarantee to maximize obtaining light aromatics product.
3, adopt the inventive method, adaptability to raw material is good, can process the catalytic cracking diesel oil cut that high-sulfur, high nitrogen, boiling range wide ranges and metal content are high, and for there is no at present compared with the C of good utilisation approach
10 +distillate, carries out hydrotreatment, volume increase aromatic hydrocarbons and clean fuel oil product, and it is high that the hydrocracking catalyst that the present invention simultaneously adopts has catalyst activity, and activity stability is good, and the device cycle of operation is long.
4, the preferred version of the inventive method, step 5) in the distillate of described <195 ℃ that obtains, BTX light aromatics content is no less than 60wt%, enters aromatic hydrocarbons treatment unit as aroamtic hydrocarbon raw material, light aromatics product yield is high.
Accompanying drawing explanation
The schematic flow sheet of a kind of preferred implementation that accompanying drawing 1 is the inventive method.
The 1st, stock oil, the 2nd, C
10 +distillate, the 3rd, hydrogen, the 4th, hydrofining reaction device, the 5th, hydrotreated product, the 6th, extraction tower, the 7th, be rich in raffinating oil of alkane, the 8th, be rich in the extraction oil of aromatic hydrocarbons, the 9th, solvent recovery tower, 10 extraction solvents, the 11st, aromatic hydrocarbons is extracted oil out, the 12nd, hydroeracking unit, the 13rd, isocrackate, the 14th, distillation tower, the 15th, >195 ℃ of distillate, the 16th, <195 ℃ of distillate
Embodiment
To be further detailed method provided by the invention below in conjunction with drawings and Examples, but not thereby limiting the invention.
Fig. 1 is catalytic cracking diesel oil of the present invention and C
10 +distillate mixes the schematic flow sheet of a kind of preferred implementation of the method for producing light aromatics, in figure, omit much equipment, as pump, interchanger, compressor, hydrogenation section high-pressure separator and light pressure separator, extracting section water wash column and dehydration tower etc., but this is known to those of ordinary skills.As shown in Figure 1, the flow process of method provided by the invention is described in detail as follows:
Catalytic cracking diesel oil stock oil 1, cracking C
10 +distillate 2 and/or reformation C
10 +distillate 2 enters hydrofining reaction device 4 with hydrogen 3 after pipeline mixes, and carries out desulfurization, denitrogenation, olefin saturated and the reaction of appropriate aromatic saturation, and wherein the saturated polycyclic aromatic hydrocarbons hydrogenation that is mainly of aromatic hydrocarbons appropriateness generates mononuclear aromatics reaction.Hydrofining after product 5 enters extraction tower 6 middle and lower parts, and extraction solvent 10 enters extraction tower 6 tops, countercurrent exchange extraction.Due to the extraction of a large amount of aromatic hydrocarbons, it is low that what extraction tower tower top distillated be rich in the middle aromaticity content of raffinating oil of alkane, cetane value is not less than 45, in addition diesel oil sulphur, the equal <10 μ of nitrogen content g/g, can be used as the diesel oil blending component of high hexadecane value after (not shown) through conventional washing, dehydration.The extraction oil 8 that is rich in aromatic hydrocarbons distillating at the bottom of extraction tower 6 towers enters solvent recovery tower 9, through adding thermal distillation, isolated extraction solvent 10 is discharged by tower top, turn back to recycle in extraction tower 6, the aromatic hydrocarbons of discharging at the bottom of solvent recovery tower 9 towers is extracted oil 11 out, its aromaticity content is no less than 90 quality %, enters hydroeracking unit 12 carry out take the saturated open loop of polycyclic aromatic hydrocarbons, the disconnected side chain reaction of mononuclear aromatics as main hydrocracking reaction with hydrogen 3 after mixing.Isocrackate 13 enters distillation tower 14 through cutting and separating, separation obtains >195 ℃ of distillate 15 and <195 ℃ of distillate 16, wherein >195 ℃ of distillate 15 can be used as clean diesel blend component, <195 ℃ of distillate 16 can be used as aroamtic hydrocarbon raw material and enters follow-up aromatic hydrocarbons treatment unit (not marking in figure), finally processes and separate to obtain light aromatics and gasoline component.
Due to the low nitrogen C of low-sulfur
10 +the interpolation of distillate, in stock oil, sulphur nitrogen impurity content significantly reduces, the more independent catalytic cracking diesel oil hydrofining of hydrofining severity reduces, and the selection of processing condition, is advisable at <10 μ g/g with sulphur, Control of Nitrogen Content in hydrofining after cut oil.
1. in embodiment, the trade names of Hydrobon catalyst used are CK-II.
In embodiment aromatic hydrocarbons used to extract the preparation process of oily hydrocracking catalyst out as follows:
Pseudo-boehmite (Shandong Aluminum Plant's production), HY type molecular sieve are mixed with extrusion aid, tackiness agent with HZSM-5 (molecular sieve factory of Nankai University), after adding water, through kneading, extrusion, make three leaf stripe shapes.Extrudate is dried at 130 ℃, then roasting 4 hours at 550 ℃, HY-HZSM-5-alumina composite carrier obtained.Complex carrier is immersed in the nickel nitrate aqueous solution preparing, flood 4 hours, be then dried 4 hours at 120 ℃, at 500 ℃, roasting obtains hydrocracking catalyst I for 8 hours.
The composition of obtained hydrocracking catalyst: in oxide compound and take total catalyst weight as benchmark, nickel oxide is
8.0wt%, the specific surface area of hydrocracking catalyst I is 225m
2/ g, pore volume is 0.35ml/g.Take complex carrier as benchmark,
HY molecular sieve content is 25wt%, and HZSM-5 molecular sieve content is 12wt%, and alumina content is 63wt%.
In embodiment, in raw materials used oil, the main character of catalytic cracking diesel oil is as shown in table 1.
Table 1
| Stock oil | Catalytic cracking diesel oil |
| Density (20 ℃), g/cm 3 | 0.9132 |
| Sulphur content, μ g/g | 2895 |
| Nitrogen content, μ g/g | 1369 |
| Bromine valency, gBr/100g | 3.5 |
| Aromatic hydrocarbons, wt% | 75.8 |
| Polycyclic aromatic hydrocarbons, wt% | 22.3 |
| Boiling range ASTM D-1160, ℃ | ? |
| IBP | 185 |
| 5％ | 211 |
| 10％ | 239 |
| 50％ | 288 |
| 90％ | 372 |
| FBP | 390 |
cracking C in embodiment Raw oil
10 +the main character of distillate is as shown in table 2.
Table 2
| Stock oil | Cracking C 10 +Distillate |
| Density (20 ℃), g/cm 3 | 0.8451 |
| Sulphur content, μ g/g | 385 |
| Nitrogen content, μ g/g | 54 |
| Bromine valency, gBr/100g | 10.2 |
| IBP，℃ | 187 |
| Aromatic hydrocarbons, wt% | 85.4 |
| Polycyclic aromatic hydrocarbons, wt% | 21.6 |
C reforms in embodiment Raw oil
10 +the main character of distillate is as shown in table 3.
Table 3
| Stock oil | Reformation C 10 +Distillate |
| Density (20 ℃), g/cm 3 | 0.8752 |
| Sulphur content, μ g/g | <1 |
| Nitrogen content, μ g/g | <1 |
| Bromine valency, gBr/100g | 0.8 |
| IBP，℃ | 189 |
| Aromatic hydrocarbons, wt% | >99 |
| Tetramethyl-benzene isomer, wt% | 42 |
| Indan derivative, wt% | 6.5 |
| Naphthalene derivatives, wt% | 16 |
| Biphenyl derivatives, wt% | 2 |
| Other alkylbenzene, wt% | 33.5 |
Embodiment 1
Be rich in catalytic cracking diesel oil, the C of aromatic hydrocarbons by the inventive method processing
10 +distillate, produces light aromatics and clean fuel oil product.
With catalytic cracking diesel oil, cracking C
10 +distillate mixing raw material (mass ratio is 65:35) is stock oil, enters fixed bed High-pressure Hydrogenation Unit with hydrogen after mixing, and Hydrobon catalyst loadings is 200mL.Temperature of reaction is 360 ℃, and hydrogen dividing potential drop is 5.5MPa, and hydrofining section stock oil mass space velocity is 1.2h
-1, hydrogen/oil volume is than being 500:1.
The mass ratio of taking furfural and hydrofining after cut oil is that 1:1 carries out solvent extraction, gets 500g hydrotreated product, 500g furfural joins in separating funnel, and fully vibration mixes it, stratification.Get upper strata and raffinate oil, its quality is 125g, adds wherein 125g water, and fully vibration mixes, and after stratification, separating oil water, obtains 124g and raffinate oil, and can be used as clean diesel blend component.
It is 875g that the extract phase quality that Yu Xianghou obtains is taken out in separation, is carried out underpressure distillation, steams extraction solvent 501g, obtains 374g and extracts oil out.
Repeat extraction steps and obtain aromatic hydrocarbons extraction oil samples 5000g, extract aromatic hydrocarbons out oil and pass into the fixed bed High-pressure Hydrogenation Unit of loading hydrocracking catalyst, hydrocracking catalyst loadings is 100mL.At 390 ℃ of temperature of reaction, hydrogen dividing potential drop 5.5MPa, raw material volume space velocity 0.8h
-1, hydrogen/oil volume is than carrying out hydrocracking reaction under the condition of 500:1.
Get 500g and extract oily isocrackate out through cutting and separating, wherein obtain >195 ℃ of distillate 95g, can be used as clean diesel blend component with above-mentioned raffinating oil after mixing, its character is in table 5.
<195 ℃ of distillate 405g can be used as aromatic hydrocarbons treatment unit raw material, produces light aromatics and stop bracket gasoline blend component, and its character is in table 6.
Embodiment 2～5
Press the method steps of embodiment 1 successively to catalytic cracking diesel oil, C
10 +distillate carries out processing treatment, and different is selection and the extraction solvent amount of proportioning raw materials, reaction conditions, and the test conditions of choosing is in table 4.
With catalytic cracking diesel oil and C
10 +distillate mixing raw material calculates, and different fractions oil production character is in table 5, table 6, and different fractions oil production yield is in table 7.
Table 4 test conditions
Table 5 clean diesel distillate character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Density (20 ℃), g/cm 3 | 0.835 | 0.836 | 0.838 | 0.836 | 0.832 |
| Sulphur content, μ g/g | 8 | 7 | 4 | 8 | 7 |
| Nitrogen content, μ g/g | 7 | 6 | 5 | 7 | 8 |
| Aromatic hydrocarbons, wt% | 19.8 | 22.5 | 18.3 | 18.5 | 20.4 |
| Polycyclic aromatic hydrocarbons, wt% | 1.5 | 2.2 | 1.4 | 1.2 | 2.3 |
| Cetane value | 46 | 45 | 47 | 47 | 46 |
show 6<195 ℃ of distillate character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Density (20 ℃), g/cm 3 | 0.735 | 0.726 | 0.728 | 0.726 | 0.732 |
| Sulphur content, μ g/g | <1 | <1 | <1 | <1 | <1 |
| Nitrogen content, μ g/g | <1 | <1 | <1 | <1 | <1 |
| Aromatic hydrocarbons, wt% | 67.8 | 68.9 | 69.5 | 70.7 | 66.2 |
| BTX，wt％ | 62.2 | 63.3 | 63.4 | 63.8 | 62.1 |
| Polycyclic aromatic hydrocarbons, wt% | 0.4 | 1.1 | 0.8 | 0.5 | 1.4 |
| Research octane number (RON) | 94.7 | 94.5 | 95.1 | 94.4 | 94.8 |
BTX: represent benzene, toluene and dimethylbenzene
Table 7 different fractions oil production yield
From table 5～table 7 result, catalytic cracking diesel oil and C
10 +distillate is by the inventive method processing, and in the clean diesel cut obtaining, sulphur, nitrogen content are all less than 10 μ g/g, and aromaticity content significantly declines, and cetane value all reaches more than 45.Take solvent extraction method, extract Determination of Alkane Content in oil out and significantly decline, aromaticity content >90wt%.Through follow-up hydrogenation cracking reaction, obtain appropriate light aromatics (BTX) again, gasoline fraction and diesel oil distillate, the research octane number (RON) of <195 ℃ of gasoline fraction reaches more than 94.With the catalytic cracking diesel oil and the C that process
10 +distillate mixing raw material calculates, and BTX light aromatics yield >35wt% can obtain clean gasoline and clean diesel product simultaneously.
Claims (8)
1. a catalytic cracking diesel oil and C
10 +distillate mixes the method for producing light aromatics, it is characterized in that, comprises the steps:
1) by catalytic cracking diesel oil, C
10 +after distillate mixes with hydrogen, carry out hydrofining reaction, to carry out, sulphur nitrogen removes, olefin saturated and polycyclic aromatic hydrocarbons hydrogenation saturated as mononuclear aromatics; Described catalytic cracking diesel oil and C
10 +the mass ratio of distillate is 3:2～4:1;
2) through step 1) hydrotreated product that obtains of hydrofining enters the organic solvent that adopts boiling point to be not more than 180 ℃ in extraction tower and carries out extracting as extraction solvent, obtain being rich in the extraction oil of aromatic hydrocarbons and being rich in raffinating oil of alkane; The wherein said equal <10 μ of the sulphur nitrogen content g/g that raffinates oil that is rich in alkane, cetane value is not less than 45, discharges as clean diesel blend component;
3) the extraction oil that is rich in aromatic hydrocarbons described in separates by rectifying mode, obtains the aromatic hydrocarbons extraction oil that aromaticity content is no less than 90wt% at the bottom of tower, and tower top obtains extraction solvent recycle;
4) step 3) the described aromatic hydrocarbons that obtains extracts oil out under hydrogenation conditions, to carry out, mononuclear aromatics disconnected side chain reaction saturated take polycyclic aromatic hydrocarbons is main hydrocracking reaction;
5) aromatic hydrocarbons is extracted oily isocrackate out through cutting and separating, and wherein the distillate product of >195 ℃ is as clean diesel blend component; The distillate of <195 ℃ enters aromatic hydrocarbons treatment unit as aroamtic hydrocarbon raw material, finally obtains light aromatics product and clean gasoline blend component.
2. method according to claim 1, it is characterized in that, step 1) described in the Hydrobon catalyst that loads in hydrofining reaction be MoNi system Hydrobon catalyst, reaction conditions is 320～390 ℃ of temperature of reaction, hydrogen dividing potential drop 3.5～8.0MPa, stock oil mass space velocity 1.0～2.0h
-1, hydrogen/oil volume is than 300～800:1.
3. method according to claim 2, is characterized in that step 1) in described hydrofining reaction, the hydrogenation protecting agent that accounts for Hydrobon catalyst volume total amount 5～20% at Hydrobon catalyst bed top loading.
4. method according to claim 1, is characterized in that step 2) described in extraction solvent be preferably furfural.
5. method according to claim 1, is characterized in that step 2) described in the mass ratio of extraction solvent and described hydrotreated product be 0.5～2.0:1.
6. method according to claim 1, it is characterized in that, step 4) described in hydrocracking reaction in the hydroeracking unit that is filled with hydrocracking catalyst, carry out, consisting of of described hydrocracking catalyst: take catalyzer as benchmark, nickel oxide 6～12wt%, surplus is HY molecular sieve-HZSM-5 molecular sieve-alumina supporter; Take carrier as benchmark, HY molecular sieve content is 20～30wt%, and HZSM-5 molecular sieve content is 10～20wt%, and alumina content is 50～70wt%; The temperature of reaction of hydrocracking reaction is 380～430 ℃, and hydrogen dividing potential drop is 4.0～10.0MPa, and it is 0.5～1.5h-1 that aromatic hydrocarbons is extracted oil quality air speed out, and hydrogen/oil volume ratio is 300～800:1.
7. method according to claim 6, is characterized in that step 4) a small amount of conventional Hydrobon catalyst of middle hydroeracking unit bottom filling, loadings accounts for 5～15% of hydrocracking catalyst device inner catalyst total filling amount.
8. method according to claim 1, is characterized in that, the cetane value of described catalytic cracking diesel oil is less than 35, wherein containing the paraffinic hydrocarbons of 15～50wt% and the aromatic hydrocarbons of 50～85wt%; Described C
10 +distillate is cracking C
10 +distillate and/or reformation C
10 +distillate.
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