CN104250568A - Treatment process for coal tar-residual oil hydrocracking, catalytic cracking and aromatics extraction - Google Patents
Treatment process for coal tar-residual oil hydrocracking, catalytic cracking and aromatics extraction Download PDFInfo
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Abstract
The invention discloses a combined treatment method for coal tar-residual oil hydrocracking, catalytic cracking and diesel aromatics extraction. The method includes: subjecting coal tar to pressure reduced distillation to obtain light coal tar and heavy coal tar; mixing the light coal tar with residual oil, and then carrying out hydrocracking reaction to obtain gas, gasoline, diesel, pressure reduced gas oil and tail oil; mixing the tail oil with the heavy coal tar, and carrying out catalytic cracking reaction under supercritical conditions, thus obtaining cracked gas, catalytically cracked gasoline, catalytically cracked diesel, heavy distillate oil and cracked oil slurry; mixing the diesel obtained by hydrocracking with the catalytically cracked diesel, then performing aromatics extraction, partly or totally returning the extract oil and catalytically cracked heavy distillate oil to a catalytic cracking device to undergo cracking reaction, and discharging the raffinate oil out of the device so as to obtain high cetane number diesel. The method provided by the invention can improve the conversion rate of the raw materials, reduce coking, increase the yield of light oil and prolong the service life of the catalytic cracking catalyst, thus obtaining a high cetane number diesel component.
Description
Technical field
The present invention relates to a kind of coal tar and residual oil combined treatment process, specifically relate to a kind of method of coal tar and residual hydrocracking-catalytic cracking-Aromatics Extractive Project combined treatment process production lightweight oil.
Background technology
Global economy is fast-developing, and living standards of the people improve constantly and environmental consciousness constantly strengthens, increasing to the demand of clean fuel oil.But at present, constantly can decline for the light crude proportion of exploitation and output, crude quality is in poor quality increasingly, and residual oil quality worse and worse, how effectively utilizing and transform the object that these residual oil realize light oil with high yield product, is one of current Refiners important topic urgently to be resolved hurrily.
The energy structure of China may be summarized to be " oil starvation, " weak breath ", " rich coal ".Along with the conventional resource proportions such as light crude reduce, the unconventional resource proportion of coal tar wet goods starts to become large, coal tar is the by product produced in high-temperature coking process, coal tar is mainly divided into following component: the products such as light oil, carbolic oil, washing oil, pitch, coal tar obtains different head products, as carbolic oil, naphtalene oil etc. by techniques such as underpressure distillation, air distillation and atmospheric and vacuum distillations; Coal tar is except as except industrial chemicals, and coal tar is developed hydrogenation gradually and produced light-weight fuel oil.Coal tar hydrogenating is produced in light ends oil process exists certain difficult problem, especially coal-tar heavy oil, in raw material, the condensed-nuclei aromatics content such as aromatic hydrocarbons is very high, during this Raw material processing, condensed-nuclei aromatics is easy to polymerization green coke and causes catalyzer coking and deactivation on the one hand, affect catalyst life and device running period, in addition, aromatic hydrogenation is saturated by kinetics and the dual restriction of thermodynamics, hydrotreated lube base oil difficulty is large, even if adopt special Hydrobon catalyst to react under severe conditions, aromatic saturation limitation, a large amount of aromatic component is still there is in corresponding generation oil, the diesel cetane-number causing coal tar hydrogenating to generate lower being difficult to reaches specification requirement.Therefore comprehensive, the current coal-tar industryization of this Ye Shi China needs the problem solved.
Poor residuum processing aspect, complete processing mainly comprises decarburization and hydrogenation two class, decarburization mainly comprises RFCC, coking and solvent deasphalting etc., hydrogenation technique mainly comprises fixed bed hydrogenation, boiling bed hydrogenation, moving-bed hydrogenation etc., wherein with fixed bed and boiling bed hydrogenation the most ripe, easy and simple to handle, to the strong adaptability of raw material, but still have some limitations, especially when process asphaltene or the higher poor residuum of metal content, along with transformation efficiency improves, residual oil colloidal structure destroys, just coking phenomenon is there will be when transformation efficiency is lower, cause the coking of catalyst surface carbon distribution, both transformation efficiency and the yield of light oil of residual oil had been affected, affect again the device operational cycle, therefore the transformation efficiency and the prolong operating period that how to improve poor residuum are as much as possible the problems being badly in need of at present solving.
Patent CN102443414A discloses a kind of heavy raw material boiling bed hydrogenation treatment method, use boiling bed hydrogenation treatment reactor, heavy raw oil and hydrogen enter reactor from bottom and react, reacting rear material discharges reactor from top, use the mixed catalyst of at least two kinds of catalyzer in boiling bed hydrogenation treatment reactor, its mixed volume is than being 1:(0.1 ~ 10).This method is that heavy raw oil enters ebullated bed reactor separately, hydrotreatment reaction is carried out under hydrogen and catalyzer existence condition, but when heavy feed stock oil nature poor especially as asphalt content height time, in this case, heavy raw oil itself easily improves and bad stability with transformation efficiency, cause the phenomenon occurring reaction product phase-splitting coking in follow up device, then cause device to block, affect the long-term operation of device.
Patent CN1307086A discloses method for catalytic cracking residue in a kind of supercutical fluid, use catalyst cracker, gasoline fraction, diesel oil distillate, benzene, dimethylbenzene etc. is adopted to be supercritical medium, carry out catalytic cracking reaction at supercritical conditions, finally obtain reacted gas, light ends oil, heavy distillate and cracking residue wet goods.Patent of the present invention compares traditional method for catalytic cracking residue, increases to adaptability to raw material, but still restricted; When feedstock property is poor, catalyzer coking and deactivation speed can be very fast, has a strong impact on catalyzer work-ing life.Supercutical fluid is a kind of solvent of the very friendly chemical enginnering process exploitation of control environment, and have the advantages that density is large, viscosity is little, spread coefficient is large, this is by the raising movement velocity of fluid and the rate of mass transfer of sepn process, and rate of mass transfer is much higher than liquid phase cracking process.The above-mentioned characteristic that supercutical fluid has, makes the chemical reaction carried out in supercutical fluid have and improves the advantage such as rate of diffusion, increase reactants dissolved.Current residual oil or coal tar under supercritical solvent, carry out separately chemical reaction research or application appears in the newspapers, but two kinds of inferior raw materials are blended in certain proportion the research carrying out chemical reaction in supercritical solvent not yet to be reported.
CN102443436A discloses a kind of residual hydrocracking, catalytic cracking and arylhydrocarbon in diesel oil extracting combined method.In this method, residual oil carries out hydrotreatment under hydrogen and hydrogenation catalyst exist, effluent is separated and obtains gas phase and liquid product, liquid product directly enters catalytic cracking unit without fractionation and reacts, reaction effluent is separated and obtains dry gas, liquefied gas, catalytically cracked gasoline, urges bavin and heavy distillate, urge bavin through Aromatics Extractive Project, extract oil out and filter Posterior circle to hydrotreater with catalytic cracking heavy distillate, device of raffinating oil out obtains high hexadecane value diesel oil.In this method, hydrocracking reaction effluent directly enters catalytic cracking unit reaction without fractionation, increases the load of catalytic cracking unit undoubtedly, have impact on the processing power of device; Secondly contain a certain amount of light constituent in hydrocracking reaction effluent, after this part light constituent enters catalytic cracking unit, secondary reaction can occur, cause light ends oil to reduce, and gas yield increases, and causes certain financial loss.
Summary of the invention
For in existing technique, the low and ropy problem of poor residuum and the easy coking of the independent hydrocracking of coal tar, low conversion rate, yield of light oil, the invention provides a kind of by poor residuum and coal tar combination treatment method.The inventive method can prolong operating period, improves light oil yield and quality product.
The invention provides a kind of coal tar and residual hydrocracking-catalytic cracking-Aromatics Extractive Project combination treatment method, comprise following content:
(1) coal tar is after underpressure distillation, obtains light tar and heavy coal tar;
(2), after the light tar in step (1) and residual oil mix, enter ebullated bed reactor together with hydrogen, contact with hydrocracking catalyst, carry out hydrocracking reaction;
(3) step (2) gained hydrocracking effluent enters separator, and be separated and obtain gas and liquid product, described liquid product enters separation column fractionation and obtains gasoline, diesel oil, vacuum gas oil and tail oil;
(4) tail oil in step (3) and the heavy coal tar in step (1) enter surge tank and mix with supercritical solvent, be forced into emergent pressure or the supercritical pressure of described supercritical solvent, after the critical temperature being heated to described supercritical solvent or supercritical temperature, enter catalytic cracking unit to contact with catalytic cracking catalyst and carry out catalytic cracking reaction, obtain reacted gas, catalytic gasoline, catalytic diesel oil, heavy distillate, cracking residual oil;
(5) catalytic diesel oil obtained in the diesel oil that obtains of step (3) and step (4) is mixed into aromatic extraction unit, after contacting with aromatic hydrocarbon extraction solvent, extract the oily heavy distillate obtained with step (4) after recycling design out to mix, partly or entirely loop back catalytic cracking unit and continue reaction, raffinate oil obtains high hexadecane value diesel oil after recycling design.
In the inventive method, doing of light tar described in step (1) is 480 ~ 520 DEG C.
In the inventive method, in step (2), light tar and the mixed weight of residual oil are than being 1:10 ~ 1:1, preferred 1:8 ~ 1:1.
In the inventive method, in step (3), gained vacuum gas oil all can go out device, also some or all ofly can loop back ebullated bed reactor and carry out hydrocracking reaction, vacuum gas oil and residual oil circulation weight ratio 0 ~ 0.25.
In the inventive method, the light tar in step (1) can also enter ebullated bed reactor from the position of one or more different heights of ebullated bed reactor beds along reactor tangential direction.
The hydrocracking catalyst adopted in the inventive method is loaded catalyst, wherein the active metal of catalyzer can be nickel, cobalt, molybdenum or tungsten etc. one or more, with metal oxide, nickel or cobalt contents are 1wt% ~ 12wt%, and molybdenum or tungsten are 2wt% ~ 15wt%.Catalyst particle diameter is 0.3mm ~ 0.8mm, and bulk density is 0.6 ~ 0.9g/cm
3, specific surface area is 100 ~ 280m
2/ g.
In the inventive method, ebullated bed reactor hydrocracking reaction condition is: temperature of reaction 380 ~ 450 DEG C, reaction pressure 8 ~ 20MPa, air speed 0.2 ~ 3.0h
-1, hydrogen to oil volume ratio 600 ~ 2500.Preferred reaction conditions is: temperature of reaction 400 DEG C ~ 440 DEG C, reaction pressure 12 ~ 16MPa, air speed 0.5 ~ 1.5h
-1, hydrogen to oil volume ratio 800 ~ 1200.
In the inventive method, described supercritical solvent is one or more in benzene,toluene,xylene, hexanaphthene, pentamethylene, gasoline fraction, diesel oil distillate, preferred gasoline and/diesel oil distillate.
The weight ratio of supercritical solvent described in step (4) and surge tank fresh feed oil (mixture of tail oil and heavy coal tar) is called agent-oil ratio, and ratio is 0.05 ~ 8.0, preferably 1.5 ~ 6.0.
In the inventive method, described catalytic cracking reaction condition is: temperature of reaction is 360 ~ 505 DEG C, and reaction pressure is 3.0 ~ 18MPa, and weight space velocity is 25 ~ 80h
-1.Preferred reaction conditions is: temperature of reaction is 390 ~ 455 DEG C, and reaction pressure is 5.0 ~ 16.0MPa, and weight space velocity is 45 ~ 60h
-1.Described catalyst cracker can be conventional catalyst cracker, as riser reactor.
In the inventive method, catalytic cracking unit used catalyst is Conventional catalytic cracking catalyzer, and the zeolite molecular sieve wherein containing 5 ~ 25wt%, all the other 75 ~ 95wt% are pure aluminium silicate carrier.
In the inventive method, in step (4), catalytic cracking gained heavy distillate all can go out device, also partly device can be gone out, remainder is extracted oily mixing out as recycle stock and Aromatics Extractive Project and carry out catalytic cracking reaction together with fresh feed, also all can loop back catalytic cracking unit as recycle stock, recycle stock and fresh feed weight ratio are 0 ~ 0.6.
In the inventive method, arene extracting process can be anyly be applicable to prior art of the present invention in step (5), preferred solvent pairs extraction process, extracting solvent for use can be one or more that furfural, methyl-sulphoxide, N, dinethylformamide and aromaticity content are not more than in the lightweight oil of 4wt%.The furfural of the present invention preferably containing metal ion, as the first solvent, can strengthen the ability of extraction mononuclear aromatics and the above aromatic hydrocarbons of dicyclo containing metal ion; Lightweight oil as the second solvent, solvent ratio and raw material: furfural: lightweight oil weight ratio is 1:0.4 ~ 3.0:0.5 ~ 1.5, preferred 1:0.5 ~ 1.2:0.6 ~ 1.2.Described extraction tower tower top temperature 60 ~ 100 DEG C, temperature 50 ~ 70 DEG C in tower, column bottom temperature 30 ~ 40 DEG C.
In the inventive method, in step (3), gained gasoline and/or diesel oil distillate can use as supercritical solvent.
In the inventive method, described residual oil can be long residuum, vacuum residuum, high viscous crude, one or more in visbreaking residue, tar-bitumen, oil sands bitumen, ethylene cracker tar or refinery's sump oil.
In the inventive method, described coal tar can be coal at the viscous liquid product of high temperature carbonization and gasification byproduct in process, and productive rate accounts for the 3wt% ~ 5wt% of coking dry coal.
The separating device adopted in the inventive method comprises hot high score, low point of heat, cold high score and coldly lowly to grade, and fractionation apparatus can be atmospheric fractional tower or vacuum fractionation tower.
The inventive method tool has the following advantages:
1, when coal tar or the independent hydrogenation reaction of poor residuum, because raw material self component characteristic there will be the easy coking of system, the problems such as low conversion rate; Be light tar and heavy coal tar by coal tar fractional distillation, by light tar and residual oil combined treatment, under supercritical solvent existence condition, catalytic cracking unit process is entered by after heavy coal tar and tail oil mixing, effectively can improve the aromaticity of mixed system, aromaticity uprises and can improve mixed system colloidal stability and to bitum dissolving power, and then allows raw material to have higher transformation efficiency, reduces coking, improve yield of light oil, prolong operating period.
2, in residual oil colloidal structure, the graviational interaction that in absorption-solvated layer, some hydro carbons adds by glue core, even if it reaches boiling point and is also difficult to proceed to gas phase under without additional active additive effect, finally be trapped in condensed-nuclei aromatics and form coke, phenol in light tar cut is a kind of well active additive, it can make pitch micelle and glue core have an effect, weaken the gravitational field that it is additional, the hydro carbons being adsorbed and wrap up is released more, can yield of light oil be improved on the one hand, coke can be reduced on the other hand and produce.
3, after hydrocracking tail oil and heavy coal tar mix, under supercritical solvent exists, enter catalytic cracking unit react, reactants dissolved performance can be increased under supercritical solvent conditions, reduce temperature of reaction, major part either shallow condensation reaction products is kept in cracking residual oil in liquid form, only generate micro-coke on a catalyst, slow down green coke speed, the extending catalyst life-span, strengthen the ability of process inferior raw material, expand raw material range, prevent stock oil from carrying out deep condensation's reaction.
4, light tar takes the tangential direction from the position of several different heights of ebullated bed reactor beds along reactor to enter ebullated bed reactor, adopt sectional feeding mode at high operating temperatures, two kinds of raw materials can realize dissolving each other better under boiling state, strengthen aromaticity and the colloidal stability of whole system.
5, in the inventive method, in vacuum gas oil, be rich in aromatic hydrocarbon, loop back ebullated bed reactor, can improve further mixing raw material system stability and to bitum solubleness, retardation is played to the coking reaction of residual oil.
6, in the inventive method, there is a large amount of aromatic hydrocarbons in coal tar hydrocracking liquid product, the diesel oil distillate cetane value that fractionation obtains is on the low side, adopts aromatic extraction unit extraction aromatic component wherein, can obtain the diesel oil of high hexadecane value; Extract oil out and can be mixed into catalytic cracking unit with fresh feed after filtering with heavy catalytic cycle oil, because extracting out in oil containing a large amount of aromatic hydrocarbons, the stability of fresh feed can be improved, reduce the coking in catalytic cracking reaction process, extending catalyst work-ing life.
7, the present invention is that residual oil that added value is lower and coal tar provide a kind of working method improving its economy, under the present situation of crude supply growing tension and environmental requirement increasingly stringent, adopts this technique to reduce discharging synergy to refinery useful.
Accompanying drawing explanation
Fig. 1 is coal tar of the present invention and residual hydrocracking/change cracking/hydrocarbon extracting combination process schematic flow sheet.
Embodiment
As shown in Figure 1, coal tar 1 enters vacuum still 2, light tar 3 and heavy coal tar 4 is obtained after fractionation, reactor is entered from boiling reactor 7 bottom after residual oil 5 and hydrogen 6 mix, light tar 3 can enter ebullated bed reactor 7 from the different heights position of ebullated bed reactor 7 beds along the tangential direction of reactor, mixing raw material contacts with hydrocracking catalyst and carries out hydrocracking reaction, hydrocracking effluent 8 is after separator 9 is separated, gas 10 gas is outer row after the operations such as alkali cleaning, liquid product 11 enters separation column 12, gasoline 13 is obtained after fractionation, diesel oil 14, vacuum gas oil 15 and tail oil 18, wherein, vacuum gas oil 15 part loops back ebullated bed reactor 7 as turning oil 16, remainder vacuum gas oil 17 can go out device, and it is used.Tail oil 18 and heavy coal tar 4 enter surge tank 20, after mixing with supercritical solvent 19, be forced into emergent pressure or the supercritical pressure of described supercritical solvent, be heated to critical temperature or the supercritical temperature of described supercritical solvent, then enter catalytic cracking unit 21 to contact with catalytic cracking catalyst and carry out catalytic cracking reaction, reaction product enters flashing tower 22 after decompression, tower top obtains reacted gas 23, obtain product liquid 24 at the bottom of tower and enter separation column 25 after decompression, solvent 26 is obtained respectively after fractionation, catalytic gasoline 27, catalytic diesel oil 28, heavy distillate 29, cracking residual oil 30, wherein, supercritical solvent 26 can be arranged in addition through water cooler 31 cooling condensation rear portion, a part enters surge tank 20 and recycles, heavy distillate 29 all can go out device, also can arrange outside a part, a part loops back catalytic cracking unit as turning oil 32 and reacts, also all catalytic cracking unit can be looped back, diesel oil 14 and catalytic cracking diesel oil 28 that hydrocracking obtains are mixed into aromatic extraction unit 33, extraction oil after solvent recuperation enters strainer 36 with catalytic cracking heavy distillate, through removing catalyst fines, the logistics obtained after the solid impurity such as mechanical impurity and solid particulate and fresh feed are mixed into catalytic cracking unit 21 and carry out catalytic cracking reaction, to raffinate oil 34 diesel oil that can obtain high hexadecane value after recycling design.
Further illustrate technical solution of the present invention below by specific embodiment, but protection domain is not limited to described embodiment.
Test adopt feed residue and coal tar character to list in table 1, as shown in Figure 1, reaction conditions is in table 2 in technical process.Ebullated bed reactor hydrocracking catalyst take aluminum oxide as the tungsten-nickel catalyzator of carrier, and wherein in catalyzer, nickeliferous 6wt%(presses NiO calculating), tungstenic 12wt%(presses WO
3calculate).Catalyst particle diameter is 0.5mm, and bulk density is 0.79g/cm
3, specific surface area is 260m
2/ g.
Embodiment 1
Test adopt doing of light tar in raw material to be 485 DEG C, in ebullated bed reactor charging, the weight ratio of residual oil and light tar is 5:1, and test technology flow process is as shown in Figure 1.Ebullated bed reactor hydrocracking catalyst take aluminum oxide as the tungsten-nickel catalyzator of carrier, and wherein in catalyzer, nickeliferous 6wt%(presses NiO calculating), tungstenic 12wt%(presses WO
3calculate).Catalyst particle diameter is 0.5mm, and bulk density is 0.79g/cm
3, specific surface area is 260m
2/ g.Catalytic cracking catalyst is the zeolite molecular sieve containing 10w%, all the other are the catalytic cracking catalyst of pure aluminium silicate carrier, and supercritical solvent is gasoline fraction, and Aromatics Extractive Project treatment process adopts solvent pairs extraction process, furfural is as the first solvent, and sherwood oil is as the second solvent.Reaction conditions, product slates and product property are in table 2 ~ table 4.Vacuum gas oil component loops returns ebullated bed reactor, and the vacuum gas oil and the residua weight ratio that loop back ebullated bed reactor are 0.1.The heavy distillate that catalytic cracking obtains and Aromatics Extractive Project are extracted oil out and are all looped back catalytic cracking unit after filtering.
Embodiment 2
Test adopt doing of light tar in raw material to be 485 DEG C, in ebullated bed reactor charging, the weight ratio of residual oil and light tar is 1:1, and test technology flow process is as shown in Figure 1.Ebullated bed reactor hydrocracking catalyst take aluminum oxide as the tungsten-nickel catalyzator of carrier, and wherein in catalyzer, nickeliferous 6wt%(presses NiO calculating), tungstenic 12wt%(presses WO
3calculate).Catalyst particle diameter is 0.5mm, and bulk density is 0.79g/cm
3, specific surface area is 260m
2/ g.Catalytic cracking catalyst is the zeolite molecular sieve containing 10w%, all the other are the catalytic cracking catalyst of pure aluminium silicate carrier, and supercritical solvent is diesel oil distillate, and Aromatics Extractive Project treatment process adopts solvent pairs extraction process, furfural is as the first solvent, and sherwood oil is as the second solvent.Reaction conditions, product slates and product property are in table 2 ~ table 4.Vacuum gas oil component loops returns ebullated bed reactor, and the vacuum gas oil and the residua weight ratio that loop back ebullated bed reactor are 0.15.The heavy distillate that catalytic cracking obtains and Aromatics Extractive Project are extracted oily component loops out and are returned catalytic cracking unit, and circulation weight ratio is 0.2.
Comparative example 1
Identical with embodiment 1, be only residual oil unlike raw materials used, treatment process condition is identical with embodiment 1, and feedstock property, reaction conditions, product slates and product property are in table 1 ~ 4.
Comparative example 2
Raw material is identical with embodiment 2, this comparative example adopts conventional hydrogenation and catalystic cracking combined process for residual oil, hydrogenated residue enters catalytic cracking unit and carries out cracking reaction, heavy catalytic cycle oil is in the process of catalytic cracking unit internal recycle, the diesel oil that hydrocracking and catalytic cracking obtain is without Aromatics Extractive Project, directly go out device, feedstock property, reaction conditions, product slates and product property are in table 1 ~ 4.
Table 1 residual oil and coal tar raw material character.
| Project | Residual oil | Coal tar | Light tar | Heavy coal tar |
| Density (20 DEG C), g/cm 3 | 1.01 | 1.15 | 1.05 | 1.20 |
| Ultimate analysis, % | ? | ? | ? | ? |
| C | 86.07 | 89.3 | 88.43 | 91.61 |
| H | 8.6 | 6.46 | 8.15 | 4.04 |
| S | 3.31 | 0.67 | 0.53 | 0.76 |
| N | 0.5 | 0.67 | 0.55 | 0.73 |
| Carbon residue, % | 21.02 | 4.1 | 0.34 | 9.71 |
| PONA analysis, % | ? | ? | ? | ? |
| Stable hydrocarbon | 16.7 | 28.4 | 30.8 | 11.5 |
| Aromatic hydrocarbon | 45.82 | 31.3 | 18.8 | 45 |
| Colloid | 30.19 | 19.1 | 49.8 | 14.8 |
| Bituminous matter | 7.28 | 21.2 | 0.6 | 28.7 |
Table 2 hydrocracking-catalytic cracking-arene extracting process condition.
| Numbering | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Hydrocracking process condition | ? | ? | ? | ? |
| Temperature of reaction, DEG C | 415 | 430 | 415 | 430 |
| Reaction pressure, MPa | 13 | 15 | 13 | 15 |
| Hydrogen to oil volume ratio | 400 | 400 | 400 | 400 |
| Reaction velocity, h -1 | 0.5 | 0.5 | 0.5 | 0.5 |
| Catalytic cracking process condition | ? | ? | ? | ? |
| Temperature of reaction, DEG C | 430 | 420 | 430 | 420 |
| Reaction pressure, MPa | 12 | 15 | 12 | 15 |
| Agent-oil ratio | 5.5 | 5.0 | 5.5 | 5.0 |
| Weight space velocity, h -1 | 45 | 55 | 45 | 55 |
| Arene extracting process condition | ? | ? | ? | ? |
| Solvent ratio (raw material: furfural: lightweight oil) | 1:0.8:0.7 | 1:0.9:0.7 | 1:0.8:0.7 | / |
| Tower top temperature, DEG C | 80 | 85 | 80 | / |
| Tower middle portion temperature, DEG C | 60 | 65 | 60 | / |
Table 3 hydrocracking-catalytic cracking-Aromatics Extractive Project product slates.
| Numbering | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Hydrocracking (being as the criterion with fresh feed), wt% | ? | ? | ? | ? |
| Gas | 2.02 | 2.25 | 1.52 | 2.25 |
| Gasoline | 2.50 | 2.84 | 1.94 | 2.84 |
| Diesel oil | 25.6 | 56.4 | 15.6 | 56.4 |
| Vacuum gas oil | 21.4 | 15.9 | 24.3 | 15.9 |
| Tail oil | 48.5 | 24.61 | 56.64 | 24.61 |
| Catalytic cracking (being as the criterion with fresh feed), wt% | ? | ? | ? | ? |
| Reacted gas | 1.42 | 1.86 | 1.28 | 1.54 |
| <200℃ | 78.32 | 80.69 | 63.26 | 78.11 |
| 200℃～350℃ | / | / | / | 12.36 |
| Heavy distillate | / | 3.25 | / | 2.33 |
| Coke | 5.26 | 4.12 | 8.86 | 5.66 |
| Aromatics Extractive Project product slates, wt%(is in single covering device inlet amount 100%) | ? | ? | ? | ? |
| Low arene content diesel oil | 38.23 | 42.65 | 24.31 | -- |
Table 4 embodiment and comparative example product property.
| Numbering | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Hydrocracking gasoline | ? | ? | ? | ? |
| Sulphur content, % | 0.26 | 0.06 | 0.28 | 0.06 |
| Octane value (RON) | 90.8 | 91.4 | 90.2 | 91.4 |
| Hydrocracking diesel oil | ? | ? | ? | ? |
| Cetane value | 35 | 32 | 36 | 32 |
| S，% | 0.84 | 0.31 | 1.1 | 0.31 |
| N，% | 0.20 | 0.18 | 0.21 | 0.18 |
| Hydrocracked vacuum gas oils | ? | ? | ? | ? |
| Density (20 DEG C), g/cm 3 | 0.9184 | 0.9116 | 0.9282 | 0.9116 |
| Carbon residue, % | 0.03 | 0.04 | 0.05 | 0.04 |
| Condensation point/DEG C | 32 | 28 | 35 | 28 |
| Catalytic gasoline | ? | ? | ? | ? |
| S，ppm | 56.2 | 45.4 | 108 | 52 |
| Octane value | 90.5 | 89.3 | 91 | 89.4 |
| Catalytic diesel oil | ? | ? | ? | ? |
| S，ppm | / | / | / | 2206 |
| Cetane value | / | / | / | 22 |
| Catalytic residue | ? | ? | ? | ? |
| Density (20 DEG C), g/cm 3 | 1.0926 | 1.1023 | 1.0795 | 1.1041 |
| Carbon residue, % | 9.46 | 12.54 | 8.56 | 12.30 |
| Aromatics Extractive Project-Porous deproteinized bone diesel oil | ? | ? | ? | ? |
| Density (20 DEG C), g/cm 3 | 0.9152 | 0.9031 | 0.9231 | / |
| S，ppm | 3025 | 2103 | 3351 | / |
Real-world operation result is also more known in conjunction with comparative example, adopts coal tar and residual oil boiling bed hydrogenation cracking-catalytic cracking combination process to improve feed stock conversion, and the liquid improving hydrocracking process receives yield; In addition, in subsequent catalyst cracking treating processes, adopt supercritical solvent as reaction medium, the solubleness of reactant, rate of mass transfer can be improved, reduce temperature of reaction, slow down coking, reduce coke yield, improve product slates, implement device long-term operation; All in all, this combined technical method is that processing poor residuum and coal tar provide a path for transformation.
Claims (18)
1. coal tar and residual hydrocracking-catalytic cracking-Aromatics Extractive Project combination treatment method, comprises following content:
Coal tar, after underpressure distillation, obtains light tar and heavy coal tar;
After light tar in step (1) and residual oil mix, enter ebullated bed reactor together with hydrogen, contact with hydrocracking catalyst, carry out hydrocracking reaction;
Step (2) gained hydrocracking effluent enters separator, and be separated and obtain gas and liquid product, described liquid product enters separation column fractionation and obtains gasoline, diesel oil, vacuum gas oil and tail oil;
Heavy coal tar in tail oil in step (3) and step (1) enters surge tank and mixes with supercritical solvent, be forced into emergent pressure or the supercritical pressure of described supercritical solvent, after the critical temperature being heated to described supercritical solvent or supercritical temperature, enter catalytic cracking unit to contact with catalytic cracking catalyst and carry out catalytic cracking reaction, obtain reacted gas, catalytic gasoline, catalytic diesel oil, heavy distillate, cracking residual oil;
The catalytic diesel oil obtained in the diesel oil that step (3) obtains and step (4) is mixed into aromatic extraction unit, after contacting with aromatic hydrocarbon extraction solvent, extract the oily heavy distillate obtained with step (4) after recycling design out to mix, partly or entirely loop back catalytic cracking unit and continue reaction, raffinate oil obtains high hexadecane value diesel oil after recycling design.
2. in accordance with the method for claim 1, it is characterized in that: light tar described in step (1) is the cut before coal tar underpressure distillation intercepts 480 ~ 520 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: in step (2), light tar and the mixed weight of residual oil are than being 1:10 ~ 1:1.
4. in accordance with the method for claim 1, it is characterized in that: ebullated bed reactor hydrocracking reaction condition is: temperature of reaction 380 ~ 450 DEG C, reaction pressure 8 ~ 20MPa, air speed 0.2 ~ 3.0h
-1, hydrogen to oil volume ratio 600 ~ 2500.
5. in accordance with the method for claim 4, it is characterized in that: ebullated bed reactor hydrocracking reaction condition is: temperature of reaction 400 DEG C ~ 440 DEG C, reaction pressure 12 ~ 16MPa, air speed 0.5 ~ 1.5h
-1, hydrogen to oil volume ratio 800 ~ 1200.
6. in accordance with the method for claim 1, it is characterized in that: supercritical solvent is one or more in benzene,toluene,xylene, hexanaphthene, pentamethylene, gasoline fraction, diesel oil distillate.
7. in accordance with the method for claim 6, it is characterized in that: supercritical solvent is gasoline fraction and/or diesel oil distillate.
8. in accordance with the method for claim 1, it is characterized in that: the weight ratio of supercritical solvent described in step (4) and the charging of surge tank fresh feed oil is called agent-oil ratio, and agent-oil ratio is 0.05 ~ 8.0.
9. in accordance with the method for claim 1, it is characterized in that: catalytic cracking unit reaction conditions is: temperature of reaction is 360 ~ 505 DEG C, reaction pressure is 3.0 ~ 18MPa, and weight space velocity is 12 ~ 90h
-1.
10. in accordance with the method for claim 1, it is characterized in that: step (3) gained vacuum gas oil is outer discharger all, partly or entirely loops back ebullated bed reactor, vacuum gas oil and residual oil circulation weight ratio 0 ~ 0.25.
11. in accordance with the method for claim 1, it is characterized in that: in step (4), catalytic cracking gained heavy distillate all goes out device, or part goes out device, remainder to mix with fresh feed as recycle stock and carries out catalytic cracking reaction, or all loop back catalytic cracking unit as recycle stock, recycle stock and fresh feed weight ratio are 0 ~ 0.6.
12. in accordance with the method for claim 1, it is characterized in that: in step (2), hydrocracking catalyst is loaded catalyst, wherein, active metal is one or more in nickel, cobalt, molybdenum, tungsten, with metal oxide, nickel or cobalt contents are 1wt% ~ 12wt%, and molybdenum or W content are 2wt% ~ 15wt%.
13., according to the method described in claim 1 or 12, is characterized in that: in step (2), the character of hydrocracking catalyst is: catalyst particle diameter is 0.3 ~ 0.8mm, and bulk density is 0.6 ~ 0.9g/cm
3, specific surface area is 100m
2/ g ~ 280m
2/ g.
14. in accordance with the method for claim 1, it is characterized in that: the light tar in step (1) enters ebullated bed reactor from the position of one or more different heights of ebullated bed reactor beds along reactor tangential direction.
15. in accordance with the method for claim 1, it is characterized in that: residual oil is one or more in long residuum, vacuum residuum, high viscous crude, visbreaking residue, tar-bitumen, oil sands bitumen, ethylene cracker tar, refinery's sump oil.
16. in accordance with the method for claim 1, it is characterized in that: aromatic hydrocarbon extraction solvent is furfural, methyl-sulphoxide, N, N-dimethyl formyl case and aromaticity content are not more than in the lightweight oil of 4wt% one or more.
17., according to the method described in claim 1 or 16, is characterized in that: described Aromatics Extractive Project is solvent pairs extracting, are respectively the furfural containing metal ion and lightweight oil, and wherein, Medium diesel oil, furfural, lightweight oil weight ratio are: 1:0.4 ~ 3.0:0.5 ~ 1.5.
18. in accordance with the method for claim 1, it is characterized in that: in aromatic extraction unit, extraction tower tower top temperature 70 ~ 110 DEG C, tower middle portion temperature 55 ~ 80 DEG C, column bottom temperature 30 ~ 50 DEG C.
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