CN107057756A - A kind of all-round bed hydroprocessing technique - Google Patents
A kind of all-round bed hydroprocessing technique Download PDFInfo
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- CN107057756A CN107057756A CN201710486409.2A CN201710486409A CN107057756A CN 107057756 A CN107057756 A CN 107057756A CN 201710486409 A CN201710486409 A CN 201710486409A CN 107057756 A CN107057756 A CN 107057756A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of all-round bed hydroprocessing technique, raw material includes reduced crude, decompression residuum, catalytic slurry, de-oiled asphalt, coal tar or distillate, coal dust can also be included, feedstock oil is first mixed with oil-soluble catalyst in feed/catalyst hybrid system, mixing temperature is 60 350 DEG C, and incorporation time is 20 200 minutes;Sulfidation is completed in the reactor;It is the cartridge reactor for the bed for not including fixation in wherein described all-round bed;The oil-soluble catalyst is:The oil-soluble catalyst active component is one or more combinations in Mo, Ni, Co, W, Fe.The present invention makes first dissolved each other with feedstock oil of oil-soluble catalyst mix (for the common hydrogenation technique of oily coal, thereafter add pulverized coal preparation coal, be swelled), add hydrogen, heating, boosting, reaction, separate and fractionation, this technique has that adaptability to raw material is strong, light oil yield is high, air and solid waste is few, temperature, pressure is relatively low advantage.
Description
Technical field
The present invention relates to a kind of all-round bed (All-Bed for oil (plus coal) processing) hydrogenation technique, category
In oil-refining chemical and coal chemical technology.
Background technology
Oil refining process is developed so far, and has formed with catalytic cracking, coking and be hydrogenated to the work flow of core.With routine
The continuous reduction of crude oil reserve, crude oil in poor quality trend is increasingly severe, and difficulty of processing is increasing;Conventional crude oil is processed to urge
Change based on cracking and coking, the atmosphere pollution of both techniques in process is more serious, and light oil yield is relatively low.
Under this actual environment, heavy oil and distillate hydrogenation technology are increasingly taken seriously.For heavy oil hydrogenation process, boiling
The inferior feedstock oil of high-sulfur, nitrogen, metal and asphalt content can be handled with it by rising bed and slurry bed system (suspension bed) hydrogen addition technology
The characteristics of be increasingly taken seriously.Both technologies also encounter restriction sex chromosome mosaicism in the application:To maintain light oil yield and production
Moral character matter is stable, and the catalyst of boiling bed hydrogenation technique has to last for updating, so fluidized bed device is required for setting catalyst
Handling system, the facility investment is larger;Complex operation, improves Raw material processing cost;Dead catalyst can carry out portion when drawing off
Divide light oil, cause to waste.Slurry bed system (suspension bed) hydrogenation technique maximum feature is that catalyst leaves reaction with reaction product
Device, catalyst consumption amount is larger, so various forms of slurry bed system hydrogenation techniques typically all use cheap solid catalysis
Agent.Solid catalyst is heterogeneous with feedstock oil, and mixing apparatus is complicated and mixture homogeneity is limited;Catalyst can be ground in operation
Damage key equipment, the shortening device cycles of operation such as pump valve, it is also possible to increase plant running risk, taken in catalyst separating device
Band part light oil, reduces light oil yield.Due to the limited activity of this catalyst, reaction temperature and reaction pressure are often higher,
This adds increased plant investment and operating cost.
The distillate that the devices such as catalytic cracking, ebullated bed and slurry bed system (suspension bed) hydrogenation are produced generally is added using fixed bed
The techniques such as hydrogen, reformation are further processed into the chemicals such as product oil and aromatic hydrocarbons, and fixed bed hydrogenation and reformed pre-hydrogenated technique are consolidated
Fixed bed reactor air speed is low, and needs maintenance every year, and this has all turned into the important restriction factor that oil refining enterprise has increased economic efficiency.
The content of the invention
The present invention proposes a kind of all-round bed hydroprocessing technique on the basis of to oil refining process further investigation and technological accumulation,
The raw material fitness of the technique is wide, can handle reduced crude, decompression residuum, catalytic slurry, de-oiled asphalt, coal tar and coal
Powder, and the distillate such as wax oil, diesel oil and naphtha, the technique use oil-soluble catalyst, pass through distinctive hybrid technique energy
Enough realize its being uniformly distributed in the feed.The present invention makes first dissolved each other with raw material of oil-soluble catalyst mix (common for oily coal
Hydrogenation technique, adds thereafter pulverized coal preparation coal, is swelled), heating, boosting, reaction, separation and be fractionated, finally give mesh
Mark product.All-round bed hydroprocessing technique is using empty cartridge type, natural internal-circulation type or forces inner-loop reactor processing.
Technical solution of the present invention is as follows:
A kind of all-round bed hydroprocessing technique, it is characterised in that raw material includes reduced crude, decompression residuum, catalytic slurry, de-oiling
Pitch, coal tar or distillate, raw material are first mixed with oil-soluble catalyst in feed/catalyst hybrid system, mixing temperature
Spend for 60-350 DEG C, incorporation time is 20-200 minutes;Mix after the reaction mass completed and catalyst and hydrogen boosting heating
Into all-round bed reactor, mode of entrance is bottom in and top out;Sulfidation is completed in the reactor;It is in wherein described all-round bed
Do not include the cartridge reactor of fixed bed;The oil-soluble catalyst active component is one kind in Mo, Ni, Co, W, Fe
Or multiple combinations.
Another all-round bed hydroprocessing technique, it is characterised in that raw material includes reduced crude, decompression residuum, catalytic slurry, de-
Oil asphalt, coal tar or distillate, and coal dust, feedstock oil first enter with oil-soluble catalyst in feed/catalyst hybrid system
Row mixing, adds coal dust, through more than two grades be swelled, and swelling temperature is 60-300 DEG C, and the time is 30-180 minutes, makes catalysis
Concentration of the agent in reaction mass reaches uniform state;Mix the reaction mass completed and catalyst and hydrogen boosting heating are laggard
Enter all-round bed reactor, mode of entrance is bottom in and top out;It is anti-not include the cartridge type of fixed bed in wherein described all-round bed
Answer device;The oil-soluble catalyst is:The oil-soluble catalyst active component is the one or more in Mo, Ni, Co, W, Fe
Combination.It is preferred that catalyst and feedstock oil mixing temperature be 60-250 DEG C, incorporation time is 30-90 minutes.
It is preferred that the distillate for wax oil, diesel oil, boat coal and naphtha in one or more.
The reaction mass that preferably mixing is completed enters with entering all-round bed reactor after catalyst and hydrogen boosting heating
Mode is bottom in and top out;Reaction product enters piece-rate system, and the hydrogen after gas phase separation is recycled, and waste water is arranged after this separation
Go out system, oil phase enters the whole or wherein several that Distallation systm cuts out naphtha, kerosene, diesel oil, wax oil cut and tail oil
Combination, all or part of circulation hydrogenation of wax oil and tail oil.
It is preferred that oil-soluble catalyst include hydrogenating function catalyst and cracking function catalyst or hydrogenation and the double work(of cracking
Energy catalyst, hydrogenating function catalyst includes with selective desulfurization, selective denitrogenation, selective demetalization and is combined selection
Sexual function.It is preferred that oil-soluble catalyst include following component:VIII and one or more in group vib metallic compound,
Carboxylic acid type organic and one or more and vulcanizing agent in alcohol type organic, the wherein quality of metallic element are in the catalyst
Weight content be 0.5-15%, the vulcanizing agent is molten sulfur or can resolve into H2S unstable sulfide under conditions of vulcanization,
The quality of elementary sulfur is 0.8-4 times of metallic element quality in catalyst in vulcanizing agent.The further metal is molybdenum and iron;
The organic matter is:One or more in C2-C6 carboxylic acid, C2-C5 single methanol, glycol, triol;The vulcanizing agent is C2S
Or dimethyl disulfide.
It is preferred that hydrogen be divided into two-way heating, after mix all the way with raw material enter raw materials furnace and heating heating, all the way into hydrogen
Gas heats stove heat, and the logistics of the raw materials furnace and heating outlet is mixed with all or part of hydrogen of the hydrogen furnace outlet
Enter hydrogenation reactor afterwards.
It is preferred that circulation wax oil and tail oil be back to reactor secondary response again, or first mixed with raw material and catalyst,
Enter back into reactor reaction.
It is preferred that catalyst in terms of active metal addition be no more than reaction raw materials amount 2wt%.
It is preferred that reactor be empty barrel structure all-round bed reactor, or nature inner circulation structure all-round bed reactor,
Or the all-round bed reactor of inner circulation structure is forced, reactor serial number is 1-3 platforms.
It is preferred that reaction temperature be no more than 480 DEG C, reaction pressure be no more than 25MPa, further can 370-420 DEG C,
15-18MPa。
The technique effect of the present invention is as follows:
The present invention makes oil-soluble catalyst first dissolve each other and mix with feedstock oil (for the common hydrogenation technique of oily coal, again to add thereafter
Enter pulverized coal preparation coal, be swelled), add hydrogen, heating, boosting, into all-round bed reaction, separate and fractionation, and define
Specific operating condition, catalyst is evenly distributed in the feed, and then plays good catalytic effect.The oil-soluble is urged
Agent activated centre is the one or more in Mo, Ni, Fe, Co or W, and vehicle organics are C2-C5 liquid alcohols or carboxylic acid
Class.The present invention can be used for residual oil, crude refining and oily coal to refine altogether, not have restricted want during for crude refining to oil property
Ask.The core of the technique is all-round bed reactor and oil-soluble catalyst, all-round bed hydroprocessing technique using empty cartridge type, naturally interior follow
Ring type forces inner-loop reactor processing, and not including fixed bed, catalyst enters with charging and follows the dregs of fat to discharge.Dress
Putting all can bed hydroprocessing cracking (refined altogether for oily coal be oily coal all-round bed hydroprocessing), the all-round bed of distillate including crude distillation, residual oil
Hydrogenation, catalytic reforming, isomerization, hydrogen manufacturing, lighter hydrocarbons recovery, sulphur recovery.The all-round bed hydroprocessing technique processing crude oil of present invention use,
Or residual oil or residual oil and coal dust, with such as following outstanding advantages:
1st, after using the invention, full plant can be greatly decreased, only the all-round bed hydroprocessing of heavy oil (for common sweetening process,
Then that oily coal all can bed hydroprocessing), distillate all can bed hydroprocessing, catalytic reforming, isomerization (if not steaming oil, this can be cancelled
Device), lighter hydrocarbons recovery, hydrogen manufacturing, sulfur recovery facility, it is possible to achieve full plant process flow is short, and security risk is low, maintenance load
It is few.
2nd, the technique is to the requirement of feedstock oil unrestriction, and processing weight (bad) matter oil and the economic benefit of low-order coal are best.
3rd, using the technique, product oil+aromatics yield is up to 85%, can farthest play high utilization of resources effect
Rate.
4th, the component oil of the technique is few, and diesel oil and kerosene are only a kind of respectively, and gasoline only has Reformed Gasoline and isomerization vapour
Oil, it is not necessary to petroleum products blending system.
5th, the finished product oil quality of the technique is high, low-quality oil product and the petroleum coke such as no heavy diesel fuel, catalytic slurry, fuel oil, oil
The atmosphere pollution of product in use is few, and diesel and gasoline ratio is smaller than 1.
6th, full factory is without heat processing techniques such as catalysis, coking, solvent deasphaltings, and atmosphere pollution and solid waste yield are few.
The present invention can be widely applied for reduced crude, decompression residuum, catalytic slurry, de-oiled asphalt, coal tar, wax oil,
The hydrogenation technique and the pre- hydrogenation technique of catalytic reforming of the distillate such as diesel oil and naphtha.Add compared to the heat such as catalytic cracking, coking
Work technique, this technique has that adaptability to raw material is strong, light oil yield is high, air and the few advantage of solid waste;Compared to fixed bed or
Ebullated bed mink cell focus processing technology, this technique does not have restrictive requirement to feedstock property, and reaction velocity can be higher than 0.5h-1, light oil
Yield is more than 85%.The disposal ability of reactor, the extension fixture cycle of operation can be improved, light oil yield is improved, reduced solid
Waste;Compared to fixed bed distillate processing technology, this technique can improve the disposal ability of reactor, extension fixture operation week
Phase.The operation temperature and pressure of this technique can be less than fixed bed and boiling bed hydrogenation technique, further can 370-420 DEG C,
15-18MPa, overcomes the inferior position that original process high-temperature high pressure easily causes coking and catalyst poisoning.Compared to fixed bed catalyst
Vulcanization to complete before reactions, vulcanization of the invention is completed in the reactor, and technique has also obtained further optimization.This
Technique can be not only used for new device, be also convenient for the transformation for fixed bed and boiling bed hydrogenation technique, improve light oil yield and matter
Amount, the extension fixture cycle of operation, improve Business Economic Benefit.
Brief description of the drawings
Fig. 1 is the general flow chart of the embodiment of the present invention 1,
Fig. 2 is the general flow chart of the embodiment of the present invention 2,
Fig. 3 is the general flow chart of the embodiment of the present invention 4.
Each label lists as follows in figure:
1- feed/catalyst mixing apparatus, 2- catalyst, 3- raw materials, 4- feedstock oil delivery pumps, 5- circulating hydrogen compressors,
6- fresh hydrogens, 7- residual oil heating furnaces, 8- hydrogen heating furnaces, 9- temperature control cold oil, the cold hydrogen of 10- temperature controls, 11- first-stage reactors, 12- bis-
Stage reactor, 13- reaction product piece-rate systems, 14- waste water, 15- dry gas, 16- liquefied gas, 17- naphtha cuts, 18- kerosene
Cut, 19- diesel oil distillates, 20- wax oil cuts, 21- distillation diced systems, 22- hydrogenation tail oils, the inverse circulation pumps of 23- mono-, 24- bis-
Inverse circulation pump, 25- gasoline splitters, 26- gasoline.
Embodiment
For the specific features of the present invention are expanded on further, it is explained below according to embodiment combination accompanying drawing.
Embodiment 1:
The present embodiment processes decompression residuum using the all-round bed hydroprocessing technique of empty barrel structure reactor, and Fig. 1 is shown in technological process,
2 are processed raw material for decompression residuum, Vacuum Residue Properties are shown in Table 1, and catalyst 3 is Mo-Ni systems oil-soluble catalyst, and addition accounts for slag
The 0.08wt% of oily inlet amount, first catalyst are mixed with feedstock oil in feed/catalyst mixing apparatus 1, mixing temperature
For 200 DEG C, incorporation time is 90 minutes, concentration of the catalyst in reaction mass is reached uniform state.Also include in system
Feedstock oil delivery pump 4, circulating hydrogen compressor 5, residual oil heating furnace 7, hydrogen heating furnace 8, the connection conveying mixing according to figure
The concentration of catalyst is 1000~1200ppm in raw material and fresh hydrogen 6 afterwards, first-stage reactor 11 and second reactor 12, instead
It is 410 DEG C to answer temperature, and reaction pressure is 18MPa, and air speed is 0.5h-1, hydrogen-oil ratio is 650, and vulcanizing agent is liquid-state sulfur, addition
For 0.5%, by the way of the vulcanization of side border ring, reactor is empty barrel structure, and reaction mass bottom in and top out once passes through, can
Temperature runaway is prevented by temperature control cold oil 9, the cold control system temperature of hydrogen 10 of temperature control, product first passes through reaction product piece-rate system 13, hydrogen
Gas is recycled, and discharges waste water 14, and other products enter back into distillation diced system 21 and obtain reaction product for dry gas 15, liquefied gas
16th, naphtha cut 17, kerosene distillate 18, diesel oil distillate 19 and wax oil cut 20, hydrogenation tail oil 22 and wax oil cut 20 are all
Circulation hydrogenation.Wherein dry gas yied is 2.06%, and liquefied gas yield is 2.18%, and oil-phase product property, which collects, is shown in Table 2.
The Vacuum Residue Properties table of table 1
The oil property summary sheet of table 2
Project | Data |
Element is constituted | |
C, wt% | 91.47 |
H, wt% | 7.51 |
S, wt% | 0.27 |
N, wt% | 0.59 |
Carbon residue, wt% | 9.73 |
Asphalitine, wt% | 2.27 |
Toluene insolubles, wt% | 1.03 |
Distillation, DEG C | |
10% | 167.7 |
30% | 234.5 |
50% | 283.7 |
70% | 332.5 |
90% | 375.3 |
380 DEG C of < is distillated | 90.5 |
Impurity removal percentage, % | |
Desulfurization degree | 54.24 |
Denitrification percent | 34.45 |
Demetallization per | 99.1% |
De- carbon yield | 48.08 |
Embodiment 2:
The present embodiment is increased using the all-round bed hydroprocessing technique processing decompression residuum of inner circulation structure reactor in reactor
One inverse circulation pump 23 and two inverse circulation pumps 24, process chart is shown in Fig. 2, the property that processes raw material be the same as Example 1.Catalyst is
Mo-Ni systems oil-soluble catalyst, addition is 0.08wt%, and catalyst is mixed with feedstock oil, and mixing temperature is 200 DEG C,
Incorporation time is 90 minutes, concentration of the catalyst in reaction mass is reached uniform state, keeps catalyst reactor
Concentration is 1000~1200ppm, and reaction temperature is 370 DEG C, and reaction pressure is 16MPa, and air speed is 0.5h-1, hydrogen-oil ratio is 650,
Vulcanizing agent is liquid-state sulfur, and addition is 0.5%, by the way of the vulcanization of side border ring, the circulatory system built in reactor, reaction
Material bottom in and top out, heavy constituent circulates hydrogenation in the reactor, and internal circulating load is 3, whole hydrogenation tail oils and wax oil with inlet amount ratio
Circulation hydrogenation.Reaction product is dry gas, liquefied gas, naphtha, kerosene, diesel oil and wax oil cut, and wherein dry gas yied is 2.15,
Liquefied gas yield is 2.34%, and oil-phase product property, which collects, is shown in Table 3.
The oil property summary sheet of table 3
Project | Data |
C, wt% | 91.90 |
H, wt% | 7.38 |
S, wt% | 0.29 |
N, wt% | 0.61 |
Carbon residue, wt% | 10.29 |
Asphalitine, wt% | 2.71 |
Toluene insolubles, wt% | 1.16 |
Simulation distillation, DEG C | |
10% | 173.6 |
30% | 231.4 |
50% | 278.3 |
70% | 329.1 |
90% | 372.5 |
380 DEG C of < is distillated | 93.3 |
Impurity removal percentage, % | |
Desulfurization degree | 48.21 |
Denitrification percent | 37.12 |
Demetallization per | 99.3% |
De- carbon yield | 52.76 |
Embodiment 3:Residual oil boiling bed hydrogenation technique example (comparative example).
Using the raw material of boiling bed hydrogenation technique process embodiment 2, the operation temperature of ebullated bed, pressure, air speed, reactor
Ten days, ring was than same as Example 2, and catalyst is solid high-efficiency catalyst, and catalyst in reactor volume accounts for reaction compartment
50%.Reaction product is dry gas, liquefied gas, naphtha, kerosene, diesel oil and wax oil cut, and wherein dry gas yied is 2.35, liquefaction
Gas yield is 2.62%, and oil-phase product property, which collects, is shown in Table 4.
The oil property summary sheet of table 4
Project | Data |
C, wt% | 92.91 |
H, wt% | 5.71 |
S, wt% | 0.42 |
N, wt% | 0.86 |
Carbon residue, wt% | 15.84 |
Asphalitine, wt% | 4.93 |
Toluene insolubles, wt% | 1.79 |
Simulation distillation, DEG C | |
10% | 265.1 |
30% | 297.3 |
50% | 354.6 |
70% | 422.4 |
90% | 543.2 |
380 DEG C of distillates of < | 76.6% |
Impurity removal percentage, % | |
Desulfurization degree | 25.00 |
Denitrification percent | 11.34 |
De- carbon yield | 27.27 |
Demetallization per | 87.2% |
Embodiment 4:Using all-round bed process treated gasoline.
The present embodiment processes catalytic gasoline using the all-round bed hydroprocessing technique of empty barrel structure reactor, and its property is shown in Table 5, work
Skill flow chart is shown in Fig. 3, and catalyst is Mo-W systems oil-soluble catalyst, and addition is 0.02wt%, and catalyst is carried out with feedstock oil
Mixing, mixing temperature is 150 DEG C, and incorporation time is 60 minutes, concentration of the catalyst in reaction mass is reached uniform state,
The concentration for keeping catalyst reactor is 500~800ppm, and reaction temperature is 310 DEG C, and reaction pressure is 3.5MPa, and air speed is
3.5h-1, hydrogen-oil ratio is 550, and vulcanizing agent is liquid-state sulfur, and addition is 0.2%, by the way of the vulcanization of side border ring, reaction
Device is empty barrel structure, reaction mass bottom in and top out.Reaction product is separated into gasoline splitter 15 as dry gas 15, liquefied gas 16
With gasoline 26, wherein dry gas yied is 2.15, and liquefied gas yield is 2.34%, and yield of gasoline is 95.03%, oil-phase product property
Collect and be shown in Table 5.
The all-round gasoline refining raw material of table 5 and product property table
Project | Raw material | Product |
Density (20 DEG C, g/cm3) | 0.7253 | 0.7184 |
Boiling range DEG C | 46 | 54 |
Initial boiling point | 184 | 175 |
The end point of distillation | 210 | 205 |
Bromine valency (gBr/100g) | 68.5 | 0.14 |
Color number (GB/T3555) | ||
Sulphur (μ g/g) | 3998 | 2 |
Nitrogen (μ g/g) | 325 | Do not detect |
Conclusion:
1st, it can be found that using the reactor with inner circulation structure than empty barrel structure reactor in the contrast of Examples 1 and 2
Light oil (380 DEG C of distillates of <) high income 2.8%, reason is that the reactor with inner circulation structure can extend the anti-of heavy constituent
Between seasonable, deepen hydrogenation reaction depth.
2nd, find out with being apparent from from embodiment 2 and 3, relative to boiling bed process, all can bed do not improve reaction temperature
With the operating condition such as pressure, light oil (380 DEG C of distillates of <) high income 16.7%, thus all can bed have than boiling bed hydrogenation technique
Significant advantage.For generally, catalytic efficiency is obtained for good guarantee.
3rd, from embodiment 4 as can be seen that the air speed of all-round bed gasoline refining technique is 3.5h-1, higher than fixed bed hydrogenation, i.e.,
The disposal ability of reactor is higher.
Conclusion:
By embodiment as can be seen that all can bed hydroprocessing technique can process raw material in high yield oil and coal, the technique can
For new device, it can also be used to which catalytic cracking, coking, fixed bed hydrogenation, boiling bed hydrogenation, reformed pre-hydrogenated technique are carried out
Transformation, can increase substantially the economic benefit of enterprise, reduce atmosphere pollution and solid waste pollution.
The present invention preferably embodiment is the foregoing is only, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of all-round bed hydroprocessing technique, it is characterised in that raw material includes reduced crude, decompression residuum, catalytic slurry, de-oiling drip
Blue or green, coal tar or distillate, raw material are first mixed with oil-soluble catalyst in feed/catalyst hybrid system, mixing temperature
For 60-350 DEG C, incorporation time is 20-200 minutes;Mix the reaction mass completed and catalyst and hydrogen boosting heating are laggard
Enter all-round bed reactor, mode of entrance is bottom in and top out;Sulfidation is completed in the reactor;For not in wherein described all-round bed
Include the cartridge reactor of fixed bed;The oil-soluble catalyst active component be Mo, Ni, Co, W, Fe in one kind or
Multiple combinations.
2. a kind of all-round bed hydroprocessing technique, it is characterised in that raw material includes reduced crude, decompression residuum, catalytic slurry, de-oiling drip
Blue or green, coal tar or distillate, and coal dust, feedstock oil are first mixed with oil-soluble catalyst in feed/catalyst hybrid system
Close, add coal dust, through more than two grades be swelled, swelling temperature is 60-300 DEG C, and the time is 30-180 minutes, catalyst is existed
Concentration in reaction mass reaches uniform state;The reaction mass completed is mixed with entering complete after catalyst and hydrogen boosting heating
Energy bed reactor, mode of entrance is bottom in and top out;It is the cartridge reactor for the bed for not including fixation in wherein described all-round bed;
The oil-soluble catalyst is:The oil-soluble catalyst active component is one or more combinations in Mo, Ni, Co, W, Fe.
3. technique according to claim 1 or 2, it is characterised in that catalyst is 60-250 DEG C with feedstock oil mixing temperature,
Incorporation time is 30-90 minutes.
4. technique according to claim 1 or 2, it is characterised in that the distillate is wax oil, diesel oil, boat coal and naphtha
In one or more.
5. technique according to claim 1 or 2, it is characterised in that reaction product enters piece-rate system, after gas phase separation
Hydrogen is recycled, and waste water discharge system after this separation, oil phase cuts out naphtha, kerosene, diesel oil, wax into Distallation systm
The whole or wherein several combinations of oil distillate and tail oil, all or part of circulation hydrogenation of wax oil and tail oil.
6. technique according to claim 1 or 2, it is characterised in that hydrogen is divided into two-way heating, after being mixed all the way with raw material
Into raw materials furnace and heating heating, hydrogen is entered all the way and heats stove heat, the logistics and the hydrogen of the raw materials furnace and heating outlet
Enter hydrogenation reactor after all or part of hydrogen mixing of furnace outlet.
7. technique according to claim 1 or 2, it is characterised in that it is anti-again that the wax oil and tail oil of circulation are back to reactor
Should, or first mixed with raw material and catalyst, enter back into reactor reaction.
8. technique according to claim 1 or 2, it is characterised in that catalyst addition in terms of active metal is no more than reaction
The 2wt% of material quantity.
9. technique according to claim 1 or 2, it is characterised in that reactor is the all-round bed reactor of empty barrel structure, or
The all-round bed reactor of natural inner circulation structure, or the all-round bed reactor of inner circulation structure is forced, reactor serial number is
1-3 platforms.
10. technique according to claim 1 or 2, it is characterised in that reaction temperature is no more than 480 DEG C, and reaction pressure does not surpass
Cross 25MPa.
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