CN104403686B - A kind of method for hydrogen cracking of heavy oil - Google Patents
A kind of method for hydrogen cracking of heavy oil Download PDFInfo
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- CN104403686B CN104403686B CN201410707756.XA CN201410707756A CN104403686B CN 104403686 B CN104403686 B CN 104403686B CN 201410707756 A CN201410707756 A CN 201410707756A CN 104403686 B CN104403686 B CN 104403686B
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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
- 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
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Abstract
The present invention relates to the method for hydrogen cracking of a kind of heavy oil, including: heavy oil, hydrogen and catalyst enter the first reaction zone, and the mixing logistics of three flows up in the first reaction zone, and react under conditions of floating bed hydrocracking；After described mixing logistics flows out the first reaction zone, it is divided into gaseous stream and liquid phase stream through gas-liquid separation；Described liquid phase stream enters second reaction zone and also flows downward, and enters second reaction zone the hydrogen counter current contacting flowed up, and reacts under conditions of floating bed hydrocracking；After described liquid phase stream flows out second reaction zone, partly or entirely enter piece-rate system and carry out product separation.The present invention is possible not only to reduce the gas point rate in reactor, it is also possible to that improves heavy oil further is hydrocracked effect.
Description
Technical field
The present invention relates to the method for hydrogen cracking of a kind of heavy oil, particularly relate to a kind of there is different anti-of two operator schemes
Answer the hydrocracking heavy oil method in district.
Background technology
In the hydrogenation process of heavy oil such as black petroleum products, coal tar, shale oil, substantial amounts of colloid in system, asphalitine,
The pollutant such as metal ion, solid particle directly affects the service life of hydrogenation conversion catalyst and the long period fortune of device
Turn, for this containing high pollution raw material for, floating bed hydrogenation is a kind of more satisfactory technology.The reaction of floating bed hydrogenation
Condition is generally: the reaction temperature 320 in reactor～480 DEG C, reaction pressure 8～25MPa, volume space velocity 0.3～3h-1, hydrogen
Oil volume ratio 500～2000.The catalyst of floating bed hydrogenation can be divided into solid powder th-1 catalyst, oil-soluble catalyst and water solubility
Catalyst three class, wherein the total metal content of addition general control active component of catalyst is 0.1 with the ratio of raw material weight:
100 to 5:100.
" a kind of heterogeneous hydrogenation method for coal tar suspension bed " (CN103265971A) of China Coal Research Institute is with outstanding
Floating bed reactor solves rapid catalyst deactivation and the problem of the interior deposition of reactor during coal tar hydrogenating, it is achieved that coal tar
The steady production that oil is hydrocracked, obtains light oil products to greatest extent.But, the existing suspension bed including the method
Method for hydrogen cracking all also exists a prominent feature, it is simply that gas, liquid, solid three-phase flows in reactor from bottom to top, this
In planting reactor, gas holdup is higher, and under normal operating condition, gas holdup is all 30%～40%, considerably reduces reaction under high pressure
The efficiency of device.It addition, existing suspension bed hydrocracking method, it is hydrocracked effect and still awaits improving further.
Summary of the invention
The deficiency existed for prior art, the present invention proposes the method for hydrogen cracking of a kind of heavy oil, and the method uses
The reaction zone that two operator schemes are different, is possible not only to improve the volumetric loading of hydrogenation reactor, and with existing suspension
Bed hydroprocessing cracking method is compared, and has and is preferably hydrocracked effect.
The main contents of the present invention are as follows:
1. a method for hydrogen cracking for heavy oil, including: heavy oil, hydrogen and catalyst enter the first reaction zone, three's
Mixing logistics flows up in the first reaction zone, and reacts under conditions of floating bed hydrocracking；Described mixing logistics stream
After going out the first reaction zone, it is divided into gaseous stream and liquid phase stream through gas-liquid separation；Described liquid phase stream enters second reaction zone also
Flow downward, and enter second reaction zone the hydrogen counter current contacting that flows up, anti-under conditions of floating bed hydrocracking
Should；After described liquid phase stream flows out second reaction zone, partly or entirely enter piece-rate system and carry out product separation.
2. according to the method described in 1, it is characterised in that the reaction temperature of second reaction zone is than the reaction temperature of the first reaction zone
Spend high 20 DEG C～100 DEG C, the highest 20 DEG C～50 DEG C.
3. according to the method described in 1 or 2, it is characterised in that the reaction condition of the first reaction zone is, reaction temperature 380 DEG C
～450 DEG C, preferably 410 DEG C～440 DEG C；Reaction pressure is 5.0MPa～25.0MPa, preferably 10.0MPa～20.0MPa；
Volume space velocity is 0.1～1.0, preferably 0.2～0.6；Hydrogen to oil volume ratio is 200～1500, preferably 300～900；With
The reaction condition of second reaction zone is, reaction temperature 430 DEG C～480 DEG C, preferably 440 DEG C～470 DEG C；Reaction pressure
Power is 5.0MPa～25.0MPa, preferably 10.0MPa～20.0MPa；Volume space velocity is 0.1～1.0, preferably 0.2～0.6；
Hydrogen to oil volume ratio is 200～1500, preferably 300～900.
4., according to aforementioned arbitrary method, it is characterised in that in second reaction zone, the downward flow velocity of described liquid phase stream is little
In 60mm/s, preferably between 20mm/s～50mm/s.
5. according to aforementioned arbitrary method, it is characterised in that described first reaction zone is right by one or more reactors institute
The conversion zone composition answered, is preferably made up of the conversion zone corresponding to 1～4 reactor；Described reactor is preferably internal is
The reactor of empty bucket；The connecting relation of the plurality of reactor is preferably series connection；With
Described second reaction zone is made up of the conversion zone corresponding to one or more reactors, preferably by 1～4 reaction
Conversion zone composition corresponding to device；Described reactor preferably inside is the reactor of empty bucket；The connection of the plurality of reactor
Relation is preferably series connection.
6. according to the method described in 5, it is characterised in that be not provided with gas-liquid separator, institute between the first and second reaction zones
After stating mixing logistics flowing out the first reaction zone, enter the reactor top of second reaction zone, be separated on the top of this reactor
Gaseous stream and liquid phase stream.
7., according to aforementioned arbitrary method, it is characterised in that in described piece-rate system, the logistics entering this system is divided
From becoming light oil, vacuum distillate and decompression residuum；The end point of distillation of described light oil is preferably smaller than 380 DEG C, more preferably less than 370 DEG C；
The initial boiling point of described decompression residuum is preferably greater than 400 DEG C, more preferably greater than 450 DEG C.
8. according to aforementioned arbitrary method, it is characterised in that 5% recovered (distilled) temperature of described heavy oil is more than 200 DEG C.
9. according to aforementioned arbitrary method, it is characterised in that described heavy oil is black petroleum products, high temperature coal-tar, middle temperature coal
One of tar, coalite tar, shale oil or they combine arbitrarily；Or the group of the above-mentioned raw material chosen and recycle stock
Close, described recycle stock selected from the liquid phase stream of described outflow second reaction zone, described vacuum distillate, described decompression residuum it
One or their any combination, the liquid phase stream of the most described outflow second reaction zone, described vacuum distillate and described subtract
The combination of pressure residual oil.
10. according to aforementioned arbitrary method, it is characterised in that described catalyst is solid powder th-1 catalyst；Catalyst particles
Footpath be less than 0.1mm, one of catalyst activity metal chosen from Fe, cobalt, molybdenum, nickel, tungsten or they combine arbitrarily；With in heavy oil
Fresh feed quality be 100% meter, catalyst amount is 0.1%～5%.
Compared with existing floating bed hydrocracking technology, the method for hydrogen cracking of the present invention has a following advantage:
1. considerably reduce the gas point rate in reactor.In existing floating bed hydrogenation technology, the gas in reactor
Body divides rate typically in the range of 30～40%, and the gas point rate in the second reaction zone of the present invention can be controlled in less than 20%,
Thus significantly improve the volumetric loading (the heavy oil treating capacity in the unit volume unit interval) of second reaction zone.
2. improve purity and the hydrogen dividing potential drop, beneficially the carrying out of hydrogenation reaction of hydrogen in second reaction zone.
3. the preferred embodiment of the present invention can save a high-temperature high-pressure separator equipment, thus reduce construction and throw
Money.
4. the load using two reaction zones is the most uniform, it is simple to stable operation controls.
5. use the inventive method, both can avoid the overcracking of light component, the component of relative inertness can be made again to obtain
To converting more fully.
Other features and advantages of the present invention will further describe in a specific embodiment.
Accompanying drawing explanation
Fig. 1 is the schematic flow diagram of the hydrocracking heavy oil method of the present invention.
Shown in Fig. 1, first stage reactor can be a reactor, it is also possible to be the reaction of two or more series connection
Device group；Second stage reactor can be a reactor, it is also possible to be the reactor group of two or more series connection；Separator 1
Can be a separator, it is also possible to be two or more separator groups；Separator 2 can be a separator, also
Can be two or more separator groups；Fractionating system includes normal pressure and decompression two parts, is respectively arranged with atmospheric tower
And vacuum tower.
Detailed description of the invention
Unless otherwise defined, the term in this specification all has the common implication in this area.When having conflict, with this explanation
The definition of book is as the criterion.
Unless expressly stated, in this specification NM content be the most directly suitable for as known in the art those and without
It is changed.
Can the most freely combine between embodiment in the present invention, the technical scheme being consequently formed all should be regarded
Original disclosed a part of for the present invention, and it is not considered as the new content the most not disclosing or expecting, unless ability
Field technique personnel think that this combination is the most unreasonable.All features disclosed in this invention can in any combination, and these combinations should
It is understood to content disclosed in this invention, unless those skilled in the art think that this combination is the most unreasonable.This specification institute
Disclosed numerical point, not only includes specifically disclosed numerical point, also includes the end points of each number range, and these numerical point institutes are arbitrarily
The scope of combination is regarded as the scope that the present invention is disclosed or records, no matter the most whether separately disclosing these numerical value
Right.
The method elaborating the present invention below in conjunction with Fig. 1.
The principle technological process of the present invention is as shown in Figure 1.After heavy oil mixes with catalyst, with hydrogen after raw material pump boosts
It is mixed into heating furnace, in heating furnace, raw material, catalyst, the mixture of hydrogen is heated to close to first paragraph reactor (its
In conversion zone be the first reaction zone) inlet temperature, subsequently into first paragraph reactor bottom, heavy oil, catalyst and hydrogen
The mixing logistics formed flows up in first paragraph reactor, and reacts under conditions of floating bed hydrocracking, reaction
Product flows out from the top of first paragraph reactor, and (conversion zone therein is the second reaction to fully enter second segment reactor
District) top, be divided into gaseous stream and liquid phase stream two parts on the top of second segment reactor, wherein gaseous stream is from second
The top of section reactor is flowed out, and is separated into hydrogen-rich gas, light oil and water after heat exchange condenses in cryogenic high pressure separator 1,
Wherein light oil enters fractionating system after decompression, and hydrogen-rich gas is through hydrogen purification Posterior circle to first paragraph, second segment reactive moieties；
At the liquid phase stream of second segment reactor top isolated from the top of second segment reactor under gravity to dirty
Dynamic, the hydrogen injected with second segment reactor lower part carries out counter current contacting, and reacts under conditions of floating bed hydrocracking, the
Excess hydrogen in second stage reactor and reaction generate gas, second segment reactor top be isolatable from first paragraph reactor
Flowing out from the top of second segment reactor after the gas mixing of product stream, the reacted liquid stream of second segment is anti-at second segment
The bottom answering device is discharged, and the part or all of of this liquid stream enters high temperature MP separator 2, the gas of separator 2 after decompression
Mutually part liquid phase part with separator 1 after heat exchange condensation, step-down is mixed into fractionating system, the liquid phase part of separator 2
Fractionating system is entered further after step-down；Liquid phase from separator 1 and separator 2 can respectively enter fractionating system, it is possible to
To enter fractionating system after mixing.After the system that is fractionated into separates, light oil, vacuum distillate and decompression residuum can be obtained.
According to the present invention, described catalyst is the various catalyst being applicable to floating bed hydrocracking, such as pressed powder
Catalyst, oil-soluble catalyst, water-soluble catalyst etc..Present invention preferably employs powder solid catalyst.Described solid catalysis
The particle diameter of agent is less than 0.1mm, preferably smaller than 0.01mm.The active metal chosen from Fe of described solid catalyst, cobalt, molybdenum, nickel, tungsten it
One or they combine arbitrarily.Be in terms of 100% by the fresh feed quality in heavy oil, catalyst amount be 0.1%～
5%, preferably 0.5%～3%.
According to the present invention, described heavy oil is the various raw materials being suitable for use with floating bed hydrocracking；In the case of You Xuan, institute
State 5% recovered (distilled) temperature of heavy oil more than 200 DEG C.Described heavy oil both can be selected from black petroleum products, high temperature coal-tar, middle temperature coal tar
One of oil, coalite tar, shale oil or they combine arbitrarily；It can also be the group of the above-mentioned raw material chosen and recycle stock
Close.Described recycle stock is one of the liquid phase stream of described outflow second reaction zone, described vacuum distillate, described decompression residuum
Or their any combination, the liquid phase stream of the most described outflow second reaction zone, described vacuum distillate and described decompression
Residual oil.
According to the invention it is preferred to using a part for the liquid phase stream of described outflow second reaction zone as recycle stock, should
The liquid phase stream of part is generally 1～5, preferably between 1.5～3.5 with the mass ratio of fresh feed.
According to the present invention, those skilled in the art are prone to determine the suitable recycle ratio (vacuum distillate of circulation and/or subtract
Pressure residual oil and the mass ratio of fresh feed).In the present invention, recycle ratio is generally 0.2～1.0, preferably 0.3～0.8.
According to the present invention, it should be understood that for avoiding heavy constituent constantly to accumulate in reactor, at least need part
Described decompression residuum discharger, this ratio shared by part reduced pressure residual oil is also that those skilled in the art are prone to determine.One
For as, the decompression residuum of discharger accounts for the 10%～80% of decompression residuum total amount, preferably 20%～60%.
According to the present invention, as one preferred recycle stock mode, the liquid phase stream portion of described outflow second reaction zone
Entrance subsequent separation system is divided to separate；In described piece-rate system, the logistics entering this system is separated into gently
Oil, vacuum distillate and decompression residuum；A part for described vacuum distillate and described decompression residuum is mixed with fresh feed,
Then after raw material pump boosts, it is mixed into heating furnace with hydrogen, after this mixture flows through heating furnace heating, at furnace outlet
The liquid phase stream flowing out second reaction zone with another part mixes, and the most jointly enters the first reaction zone.
According to the present invention, if using described vacuum distillate as recycle stock, preferably by it in described piece-rate system
Cut into 5% recovered (distilled) temperature vacuum distillate more than 300 DEG C.
According to the present invention, when using solid powder th-1 catalyst, containing this solid powder th-1 catalyst in described decompression residuum.
According to the present invention, in described first reaction zone and second reaction zone, all use the reaction bar of floating bed hydrocracking
Part, the two i.e. can be identical, it is also possible to different；The preferably reaction temperature of second reaction zone is higher than the reaction temperature of the first reaction zone
20 DEG C～100 DEG C, the highest 20 DEG C～50 DEG C.
In the case of You Xuan, the reaction condition of the first reaction zone is, reaction temperature 380 DEG C～450 DEG C, preferably 410 DEG C
～440 DEG C；Reaction pressure is 5.0MPa～25.0MPa, preferably 10.0MPa～20.0MPa；Volume space velocity is 0.1～1.0,
It is preferably 0.2～0.6；Hydrogen to oil volume ratio is 200～1500, preferably 300～900；With
The reaction condition of second reaction zone is, reaction temperature 430 DEG C～480 DEG C, preferably 440 DEG C～470 DEG C；Reaction pressure
Power is 5.0MPa～25.0MPa, preferably 10.0MPa～20.0MPa；Volume space velocity is 0.1～1.0, preferably 0.2～0.6；
Hydrogen to oil volume ratio is 200～1500, preferably 300～900.
According to the present invention, in flow process as shown in Figure 1, between the first and second reactors, it is not provided with gas-liquid separator,
I.e. eliminate a high-temperature high-pressure separator.
In the present invention, it is also possible to use any existing known mode, introduce reaction promoter, such as catalyst aid and/or
Coke inhibitor and/or hydrogen supply agent.Described catalyst aid is any existing known alive for improving hydrocracking catalyst for suspension bed
The material of property, the active metal in catalyst is changed into the material of metal sulfide by such as elementary sulfur, sulfide etc..
Order by merging and the mode of the various materials needing mixing are not limited by the present invention, any existing known mode
All can use, the most first by described heavy oil, catalyst, reaction promoter mixing, then after raw material pump boosts, then mix with hydrogen
Enter heating furnace.
In the present invention, volume space velocity calculates with heavy oil volume flow and reactor cumulative volume.
Embodiment 1
Using the flow process shown in Fig. 1, feedstock oil is the reduced crude with Liaohe Oil Field district crude oil, and its character is listed in table 1.
Catalyst uses solid powder th-1 catalyst, and maximum particle diameter is 5 μm, and average grain diameter is 0.8 μm, catalyst Containing Sulfur ferrous iron 90m%,
Containing Sulfur molybdenum 10m%.Using two identical empty bucket reactors of series connection, the volume of reactor is 500ml, first reactor
The first reaction zone operation as previously described, the second reaction zone operation as previously described of second reactor, concrete operations bar
Part is listed in table 2, and the product slates obtained is listed in table 3.
In process of the test, by measuring pressure differential deltap P of reactor top and the bottom, the difference in height Δ H of reactor top and the bottom, root
Composition and character according to liquid phase (including solid catalyst) can calculate gas under reactor condition by process modeling software
Density (the ρ of phaseGas) and the density (ρ of liquid phase (including solid catalyst)Liquid), then can calculate the gas holdup in reactor,
Calculating formula is as follows:
Gas holdup=(ρLiquid-ΔP/g/ΔH)/(ρLiquid-ρGas)
In formula, g is gravity acceleration constant.
The gas holdup of calculated two reactors is listed in table 3.
The character of table 1 reduced crude
| Density (20 DEG C), kg/m3 | 983.1 |
| Viscosity (80 DEG C), mm2/s | 575.1 |
| Condensation point, DEG C | 16 |
| Carbon residue, m% | 9.80 |
| Nickel content, ppm | 55 |
| Content of vanadium, ppm | 2 |
| Iron content, ppm | 70 |
| Saturated hydrocarbons, m% | 32.15 |
| Aromatic hydrocarbons, m% | 33.08 |
| Colloid+asphalitine, m% | 34.77 |
| Sulfur content, m% | 0.35 |
| Nitrogen content, m% | 0.58 |
| Carbon content, m% | 88.15 |
| Hydrogen content, m% | 10.92 |
Table 2 reduced crude two-stage hydrogenation process conditions
| Hydrogen dividing potential drop, MPa | 15.0 |
| Volume space velocity, h-1 | 0.5 |
| One section of reaction temperature, DEG C | 445 |
| One section of hydrogen-oil ratio, v/v | 500 |
| Second-stage reaction temperature, DEG C | 445 |
| Two sections of hydrogen-oil ratios, v/v | 500 |
| Catalyst charge, % | 2.50 |
| Recycle ratio | 0 |
The two-stage reforming product slates of table 3 embodiment 1
| The side of entering | |
| Feedstock oil | 100.00 |
| Hydrogen | 2.10 |
| Catalyst | 2.50 |
| The side of going out |
| H2S | 0.21 |
| NH3 | 0.29 |
| C1～C4 | 4.89 |
| C5～350 DEG C | 49.90 |
| 350 DEG C～500 DEG C | 38.71 |
| Residue | 10.60 |
| Average Air Content in first stage reactor | 25.2 |
| Average Air Content in second stage reactor | 19.5 |
Comparative example 1
It is with the difference of embodiment 1: second reactor uses the normal operating mode of floating bed hydrogenation, i.e. the
The outlet streams of one reactor obtains liquid phase stream after gas-liquid separation, and this liquid phase stream and hydrogen enter the second reactor jointly
Bottom, and in the second reactor and stream move upward.Other unlisted aspects, such as feedstock oil, catalyst, the first reaction
The operation of device and other operations of the second reactor, the most same as in Example 1.Product slates is listed in table 4.
The two-stage reforming product slates of table 4 comparative example 1
| The side of entering | |
| Feedstock oil | 100.00 |
| Hydrogen | 2.20 |
| Catalyst | 2.50 |
| The side of going out | |
| H2S | 0.20 |
| NH3 | 0.26 |
| C1～C4 | 5.58 |
| C5～350 DEG C | 45.89 |
| 350 DEG C～500 DEG C | 40.52 |
| Residue | 12.35 |
| Average Air Content in first stage reactor | 36.3 |
| Average Air Content in second stage reactor | 39.5 |
Embodiment 2
The present embodiment is with the difference of embodiment 1: the temperature of first paragraph reactor is 435 DEG C, the behaviour of the second reactor
It it is 455 DEG C as temperature.Other unlisted aspects are the most same as in Example 1.The product slates obtained is listed in table 5.
Table 5 embodiment 2 two-stage reforming product slates
| The side of entering | |
| Feedstock oil | 100.00 |
| Hydrogen | 2.40 |
| Catalyst | 2.50 |
| The side of going out | |
| H2S | 0.23 |
| NH3 | 0.31 |
| C1～C4 | 5.10 |
| C5～350 DEG C | 54.26 |
| 350～500 DEG C | 35.51 |
| Residue | 9.49 |
| Average Air Content in first stage reactor | 22.8 |
| Average Air Content in second stage reactor | 21.5 |
Embodiment 3
The present embodiment is with the difference of embodiment 2: vacuum distillate piece-rate system obtained and part reduced pressure residual oil
(containing solid catalyst), as recycle stock, recycle ratio is 0.5；Catalyst amount reduces.Other unlisted aspects all with
Embodiment 2 is identical.The product slates obtained is listed in table 6.
Table 6 embodiment 3 two-stage reforming product slates
| The side of entering | |
| Feedstock oil | 100.00 |
| Hydrogen | 2.85 |
| Catalyst | 1.50 |
| The side of going out | |
| H2S | 0.28 |
| NH3 | 0.37 |
| C1～C4 | 7.59 |
| C5～350 DEG C | 89.61 |
| 350～500 DEG C | 0 |
| Residue | 6.50 |
| Average Air Content in first stage reactor | 21.8 |
| Average Air Content in second stage reactor | 21.1 |
Embodiment 4
Using the flow process shown in Fig. 1, feedstock oil is middle coalite tar, and its character is listed in table 7.Catalyst uses solid powder
End catalyst, maximum particle diameter is 5 μm, and average grain diameter is 0.8 μm, catalyst Containing Sulfur ferrous iron 88m%, Containing Sulfur molybdenum 10m%, contains
Nickel sulfide 2m%.Using two identical empty bucket reactors of series connection, the volume of reactor is 500ml, and first reactor is pressed
Previously described first reaction zone operation, the second reaction zone operation as previously described of second reactor, concrete operations condition
Being listed in table 8, the product slates obtained is listed in table 9.
Table 7 coal tar oil properties
| Density (20 DEG C), kg/m3 | 1015 |
| Condensation point, DEG C | 21 |
| Carbon residue, % | 15.2 |
| Solid content, % | 1.31 |
| Oxygen content, % | 6.80 |
| Sulfur content, % | 0.31 |
| Nitrogen content, % | 0.90 |
| Carbon content, % | 84.08 |
| Hydrogen content, % | 7.91 |
Table 8 coal tar two-stage hydrogenation process conditions
| Hydrogen dividing potential drop, MPa | 15.0 |
| Volume space velocity, h-1 | 0.5 |
| One section of reaction temperature, DEG C | 435 |
| One section of hydrogen-oil ratio, v/v | 500 |
| Second-stage reaction temperature, DEG C | 455 |
| Two sections of hydrogen-oil ratios, v/v | 500 |
| Catalyst charge, % | 2.50 |
| Recycle ratio | 0.6 |
Table 9 coal tar two-stage reforming product slates
| The side of entering | |
| Feedstock oil | 100.00 |
| Hydrogen | 3.65 |
| Catalyst | 2.50 |
| The side of going out | |
| H2S | 0.26 |
| NH3 | 0.53 |
| H2O | 4.50 |
| COX | 0.08 |
| C1-C4 | 8.23 |
| C5-350℃ | 85.02 |
| Residue | 7.53 |
Claims (9)
1. a method for hydrogen cracking for heavy oil, including: heavy oil, hydrogen and catalyst enter the first reaction zone, the mixing of three
Logistics flows up in the first reaction zone, and reacts under conditions of floating bed hydrocracking；Described mixing logistics flows out the
Enter top, second reaction zone after one reaction zone, be separated into gaseous stream and liquid phase stream on top, second reaction zone；Described gas
Phase logistics mix with the gaseous stream of second reaction zone after in outflow second reaction zone, top, second reaction zone, and through hydrogen purify after
It is recycled to the entrance of the first reaction zone and the bottom of second reaction zone；Described liquid phase stream flows downward in second reaction zone, with
The hydrogen counter current contacting that bottom, second reaction zone is injected, reacts under conditions of floating bed hydrocracking；In second reaction zone
After liquid phase stream flows out second reaction zone, partly or entirely enter piece-rate system and carry out product separation.
The most in accordance with the method for claim 1, it is characterised in that anti-than the first reaction zone of the reaction temperature of second reaction zone
Answer temperature high 20 DEG C～100 DEG C.
3. according to the method described in claim 1 or 2, it is characterised in that the reaction condition of the first reaction zone is, reaction temperature
380 DEG C～450 DEG C, reaction pressure is 5.0MPa～25.0MPa, and volume space velocity is 0.1～1.0h-1, hydrogen to oil volume ratio be 200～
1500；With
The reaction condition of second reaction zone is, reaction temperature 430 DEG C～480 DEG C, reaction pressure is 5.0MPa～25MPa, volume
Air speed is 0.1～1.0h-1, hydrogen to oil volume ratio is 200～1500.
The most in accordance with the method for claim 1, it is characterised in that in second reaction zone, the flow velocity that described liquid phase stream is downward
Less than 60mm/s.
The most in accordance with the method for claim 1, it is characterised in that described first reaction zone is right by one or more reactors institute
The conversion zone composition answered；With
Described second reaction zone is made up of the conversion zone corresponding to one or more reactors.
The most in accordance with the method for claim 1, it is characterised in that in described piece-rate system, the logistics of this system will be entered
It is separated into light oil, vacuum distillate and decompression residuum.
The most in accordance with the method for claim 1, it is characterised in that 5% recovered (distilled) temperature of described heavy oil is more than 200 DEG C.
8. according to the method described in claim 1 or 6, it is characterised in that described heavy oil be black petroleum products, high temperature coal-tar, in
Temperature one of coal tar, coalite tar, shale oil or they combine arbitrarily；Or the above-mentioned heavy oil chosen and recycle stock
Combination, described recycle stock is selected from flowing out one of the liquid phase stream of second reaction zone, described vacuum distillate, described decompression residuum
Or their any combination.
The most in accordance with the method for claim 1, it is characterised in that described catalyst is solid powder th-1 catalyst, catalyst particles
Footpath be less than 0.1mm, one of catalyst activity metal chosen from Fe, cobalt, molybdenum, nickel, tungsten or they combine arbitrarily；With in heavy oil
Fresh feed quality be 100% meter, catalyst amount is 0.1%～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410707756.XA CN104403686B (en) | 2014-11-27 | 2014-11-27 | A kind of method for hydrogen cracking of heavy oil |
Applications Claiming Priority (1)
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| CN1107706C (en) * | 2000-07-24 | 2003-05-07 | 中国石油化工股份有限公司 | Heavy oil and residual oil hydrogenating conversion process |
| CN1123631C (en) * | 2000-11-08 | 2003-10-08 | 中国石油化工股份有限公司 | Technological process of treating infertor heavy and residual oil |
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