CN104403686A - Hydrocracking method for heavy oil - Google Patents
Hydrocracking method for heavy oil Download PDFInfo
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- CN104403686A CN104403686A CN201410707756.XA CN201410707756A CN104403686A CN 104403686 A CN104403686 A CN 104403686A CN 201410707756 A CN201410707756 A CN 201410707756A CN 104403686 A CN104403686 A CN 104403686A
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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
Abstract
The invention relates to a hydrocracking method for heavy oil. The method comprises the following steps that the heavy oil, hydrogen and a catalyst enter a first reaction zone, the mixture flow of the heavy oil, the hydrogen and the catalyst flows upwards in the first reaction zone and reacts under the condition of hydrocracking on a suspended bed; after the mixture flow flows out of the first reaction zone, the mixture flow is divided into gas phase flow and liquid phase flow by gas-liquid separation; the liquid phase flow enters a second reaction zone, flows downwards and is in counter-current contact and reacts with the nitrogen flowing upwards under the condition of hydrocracking on the suspended bed; after the liquid phase flow flows out of the second reaction zone, part or all of the liquid phase flow enters a separation system to carry out product separation. According to the hydrocracking method for the heavy oil, not only can the separation rate of the gas in the reactor be reduced, but also a hydrocracking effect of the heavy oil can be further improved.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking of heavy oil, particularly relate to a kind of hydrocracking heavy oil method with the different reaction zone of two operator schemes.
Background technology
In the hydrogenation process of heavy oil such as black petroleum products, coal tar, shale oil, the pollutents such as colloids a large amount of in system, bituminous matter, metal ion, solid particulate directly affect the work-ing life of hydrogenation conversion catalyst and the long-term operation of device, for this containing high pollution raw material, floating bed hydrogenation is a kind of more satisfactory technology.The reaction conditions of floating bed hydrogenation is generally: the temperature of reaction in reactor 320 ~ 480 DEG C, reaction pressure 8 ~ 25MPa, volume space velocity 0.3 ~ 3h
-1, hydrogen to oil volume ratio 500 ~ 2000.The catalyzer of floating bed hydrogenation can be divided into solid powder th-1 catalyst, oil-soluble catalyst and water-soluble catalyst three class, and wherein the total metal content of add-on general control active ingredient of catalyzer is 0.1:100 to 5:100 with the ratio of raw material weight.
" a kind of heterogeneous hydrogenation method for coal tar suspension bed " (CN103265971A) of China Coal Research Institute solves the problem deposited in rapid catalyst deactivation and reactor in coal tar hydrogenating process with suspended-bed reactor, achieve the stably manufactured of coal tar hydrocracking, obtain light oil products to greatest extent.But, the existing suspension bed hydrocracking method comprising the method all also exists an outstanding feature, be exactly that gas, liquid, solid three-phase flows from bottom to top in reactor, in this reactor, gas holdup is higher, under normal operating condition, gas holdup is all 30% ~ 40%, considerably reduces the efficiency of high-pressure reactor.In addition, existing suspension bed hydrocracking method, its hydrocracking effect still awaits further raising.
Summary of the invention
For the deficiency that prior art exists, the present invention proposes a kind of method for hydrogen cracking of heavy oil, the process employs the reaction zone that two operator schemes are different, not only can improve the volumetric loading of hydrogenator, and compared with existing suspension bed hydrocracking method, there is better hydrocracking effect.
Main contents of the present invention are as follows:
1. a method for hydrogen cracking for heavy oil, comprising: heavy oil, hydrogen and catalyzer enter the first reaction zone, the mixture flow of three in the first reaction zone on flowing, and to react under the condition of floating bed hydrocracking; After described mixture flow flows out the first reaction zone, be divided into gaseous stream and liquid phase stream through gas-liquid separation; Described liquid phase stream enters second reaction zone and flows downward, and enters second reaction zone and the hydrogen counter current contact that upwards flows, reacts under the condition of floating bed hydrocracking; Described liquid phase stream partly or entirely enters separation system and carries out product separation after flowing out second reaction zone.
2. according to the method described in 1, it is characterized in that, the temperature of reaction of second reaction zone is higher than the temperature of reaction of the first reaction zone 20 DEG C ~ 100 DEG C, preferably high 20 DEG C ~ 50 DEG C.
3. according to the method described in 1 or 2, it is characterized in that, the reaction conditions of the first reaction zone is, temperature of reaction 380 DEG C ~ 450 DEG C, is preferably 410 DEG C ~ 440 DEG C; Reaction pressure is 5.0MPa ~ 25.0MPa, is preferably 10.0MPa ~ 20.0MPa; Volume space velocity is 0.1 ~ 1.0, is preferably 0.2 ~ 0.6; Hydrogen to oil volume ratio is 200 ~ 1500, is preferably 300 ~ 900; With
The reaction conditions of second reaction zone is, temperature of reaction 430 DEG C ~ 480 DEG C, is preferably 440 DEG C ~ 470 DEG C; Reaction pressure is 5.0MPa ~ 25.0MPa, is preferably 10.0MPa ~ 20.0MPa; Volume space velocity is 0.1 ~ 1.0, is preferably 0.2 ~ 0.6; Hydrogen to oil volume ratio is 200 ~ 1500, is preferably 300 ~ 900.
4. according to aforementioned arbitrary method, it is characterized in that, in second reaction zone, the downward flow velocity of described liquid phase stream is less than 60mm/s, preferably between 20mm/s ~ 50mm/s.
5. according to aforementioned arbitrary method, it is characterized in that, the conversion zone of described first reaction zone corresponding to one or more reactor forms, and the conversion zone preferably corresponding to 1 ~ 4 reactor forms; Described reactor preferably inside is the reactor of empty bucket; The connecting relation of described multiple reactor is preferably series connection; With
The conversion zone of described second reaction zone corresponding to one or more reactor forms, and the conversion zone preferably corresponding to 1 ~ 4 reactor forms; Described reactor preferably inside is the reactor of empty bucket; The connecting relation of described multiple reactor is preferably series connection.
6. according to the method described in 5, it is characterized in that, between the first and second reaction zones, gas-liquid separator is not set, after described mixture flow flows out the first reaction zone, enter the reactor top of second reaction zone, be separated into gaseous stream and liquid phase stream on the top of this reactor.
7. according to aforementioned arbitrary method, it is characterized in that, in described separation system, the logistics entering this system is separated into light oil, vacuum distillate and vacuum residuum; The final boiling point of described light oil is preferably less than 380 DEG C, is more preferably less than 370 DEG C; The initial boiling point of described vacuum residuum is preferably greater than 400 DEG C, more preferably greater than 450 DEG C.
8. according to aforementioned arbitrary method, it is characterized in that, 5% recovered temperature of described heavy oil is greater than 200 DEG C.
9., according to aforementioned arbitrary method, it is characterized in that, described heavy oil be one of black petroleum products, coal-tar heavy oil, coal-tar middle oil, coalite tar, shale oil or they combine arbitrarily; Or the combination of the above-mentioned raw material chosen and recycle stock, described recycle stock is selected from one of the liquid phase stream of described outflow second reaction zone, described vacuum distillate, described vacuum residuum or their arbitrary combination, is preferably the combination of the liquid phase stream of described outflow second reaction zone, described vacuum distillate and described vacuum residuum.
10. according to aforementioned arbitrary method, it is characterized in that, described catalyzer is solid powder th-1 catalyst; Catalyst particles footpath is less than 0.1mm, one of catalyst activity metal chosen from Fe, cobalt, molybdenum, nickel, tungsten or they combine arbitrarily; In the fresh feed quality in heavy oil for 100%, catalyst levels is 0.1% ~ 5%.
Compared with existing floating bed hydrocracking technology, method for hydrogen cracking of the present invention has following advantage:
1. considerably reduce the gas point rate in reactor.In existing floating bed hydrogenation technology, gas in reactor divides rate generally in 30 ~ 40% scopes, and the gas point rate in second reaction zone of the present invention can be controlled in less than 20%, thus significantly improve the volumetric loading (the heavy oil treatment capacity in the unit volume unit time) of second reaction zone.
2. improve purity and the hydrogen dividing potential drop of hydrogen in second reaction zone, be conducive to the carrying out of hydrogenation reaction.
3. the preferred embodiment of the present invention can save a high-temperature high-pressure separator equipment, thus reduces construction investment.
4. adopt the load of two reaction zones relatively even, be convenient to stable operation and control.
5. adopt the inventive method, both can avoid the overcracking of light constituent, the component of relative inertness can be made again to be transformed more fully.
Other features and advantages of the present invention will further describe in a specific embodiment.
Accompanying drawing explanation
Fig. 1 is the block diagram of hydrocracking heavy oil method of the present invention.
Shown in Fig. 1, first stage reactor can be a reactor, also can be the reactor group of two or more series connection; Second stage reactor can be a reactor, also can be the reactor group of two or more series connection; Separator 1 can be a separator, also can be two or more separator group; Separator 2 can be a separator, also can be two or more separator group; Fractionating system comprises normal pressure and decompression two portions, is respectively arranged with atmospheric tower and vacuum distillation tower.
Embodiment
Unless otherwise defined, the term in this specification sheets all has the common implication in this area.When having conflict, be as the criterion with the definition of this specification sheets.
Unless expressly stated, in this specification sheets NM content all be directly suitable for as known in the art those and without the need to changing.
Can freely combine by any way between embodiment in the present invention, the technical scheme formed thus all should be regarded as the original disclosed part of the present invention, and should not be considered to be the fresh content not disclosing or expected herein, unless those skilled in the art think that this combination is obviously unreasonable.All features disclosed in this invention can arbitrary combination, and these combinations should be understood to content disclosed in this invention, unless those skilled in the art think that this combination is obviously unreasonable.Numerical point disclosed in this specification sheets, not only comprise concrete disclosed numerical point, also comprise the end points of each numerical range, the scope of these numerical point institute arbitrary combination all should be regarded as the scope that the present invention is open or record, no matter whether separately disclose these numerical value pair herein.
Method of the present invention is elaborated below in conjunction with Fig. 1.
Principle technical process of the present invention as shown in Figure 1.After heavy oil and catalyst mix, process furnace is mixed into hydrogen after feedstock pump boosting, by raw material in process furnace, catalyzer, the mixture of hydrogen is heated to close to first paragraph reactor (conversion zone is wherein the first reaction zone) temperature in, then first paragraph reactor bottom is entered, heavy oil, the mixture flow that catalyzer and hydrogen form in first paragraph reactor on flow, and react under the condition of floating bed hydrocracking, resultant of reaction flows out from the top of first paragraph reactor, all enter the top of second segment reactor (conversion zone is wherein second reaction zone), gaseous stream and liquid phase stream two portions are divided on the top of second segment reactor, wherein gaseous stream flows out from the top of second segment reactor, in cryogenic high pressure separator 1, hydrogen-rich gas is separated into after heat exchange condensation, light oil and water, wherein light oil enters fractionating system after decompression, hydrogen-rich gas through hydrogen purification Posterior circle to first paragraph, second segment reactive moieties, flow downward under gravity from the top of the liquid phase stream obtained from second segment reactor in second segment reactor upper part, the hydrogen injected with second segment reactor lower part carries out counter current contact, and react under the condition of floating bed hydrocracking, the gas that excess hydrogen in second segment reactor and reaction generate, flow out from the top of second segment reactor after the gas and vapor permeation of first paragraph reactor product logistics with being separated on second segment reactor top, the reacted liquid stream of second segment is discharged in the bottom of second segment reactor, the part or all of of this liquid stream enters high temperature MP (medium pressure) separator 2 after decompression, the gas phase portion of separator 2 is through heat exchange condensation, fractionating system is mixed into the liquid phase part of separator 1 after step-down, fractionating system is entered after the further step-down of liquid phase part of separator 2, liquid phase from separator 1 and separator 2 can enter fractionating system respectively, enters fractionating system after also can mixing.After fractionating system is separated, light oil, vacuum distillate and vacuum residuum can be obtained.
According to the present invention, described catalyzer is the various catalyzer being applicable to floating bed hydrocracking, such as solid powder th-1 catalyst, oil-soluble catalyst, water-soluble catalyst etc.The present invention preferably adopts powder solid catalyzer.The particle diameter of described solid catalyst is less than 0.1mm, is preferably less than 0.01mm.One of the active metal chosen from Fe, cobalt, molybdenum, nickel, tungsten of described solid catalyst or they combine arbitrarily.In the fresh feed quality in heavy oil for 100%, catalyst levels is 0.1% ~ 5%, is preferably 0.5% ~ 3%.
According to the present invention, described heavy oil is the various raw materials being suitable for adopting floating bed hydrocracking; In preferred situation, 5% recovered temperature of described heavy oil is greater than 200 DEG C.Described heavy oil both can be selected from one of black petroleum products, coal-tar heavy oil, coal-tar middle oil, coalite tar, shale oil or they combine arbitrarily; Also can be the combination of the above-mentioned raw material chosen and recycle stock.Described recycle stock is one of the liquid phase stream of described outflow second reaction zone, described vacuum distillate, described vacuum residuum or their arbitrary combination, is preferably the liquid phase stream of described outflow second reaction zone, described vacuum distillate and described vacuum residuum.
According to the present invention, preferably using a part for the liquid phase stream of described outflow second reaction zone as recycle stock, the liquid phase stream of this part and the mass ratio of fresh feed are generally 1 ~ 5, preferably between 1.5 ~ 3.5.
According to the present invention, those skilled in the art are easy to determine suitable recycle ratio (mass ratio of the vacuum distillate of circulation and/or vacuum residuum and fresh feed).In the present invention, recycle ratio is generally 0.2 ~ 1.0, is preferably 0.3 ~ 0.8.
According to the present invention, should be understood that, for avoiding heavy constituent constantly to accumulate in reactor, at least need the described vacuum residuum discharger of part, this ratio shared by part reduced pressure residual oil is also that those skilled in the art are easy to determine.Generally speaking, the vacuum residuum of discharger accounts for 10% ~ 80% of vacuum residuum total amount, is preferably 20% ~ 60%.
According to the present invention, as the preferred recycle stock mode of one, the liquid phase stream part of described outflow second reaction zone enters subsequent separation system and is separated; In described separation system, the logistics entering this system is separated into light oil, vacuum distillate and vacuum residuum; A part for described vacuum distillate and described vacuum residuum is mixed with fresh feed, then after feedstock pump boosting, process furnace is mixed into hydrogen, this mixture flow is after process furnace heating, the liquid phase stream flowing out second reaction zone at furnace outlet and another part mixes, and then jointly enters the first reaction zone.
According to the present invention, if using described vacuum distillate as recycle stock, in described separation system, be preferably cut to the vacuum distillate that 5% recovered temperature is greater than 300 DEG C.
According to the present invention, when adopting solid powder th-1 catalyst, containing this solid powder th-1 catalyst in described vacuum residuum.
According to the present invention, all adopt the reaction conditions of floating bed hydrocracking in described first reaction zone and second reaction zone, the two namely can be identical, also can be different; The temperature of reaction of preferred second reaction zone is higher than the temperature of reaction of the first reaction zone 20 DEG C ~ 100 DEG C, more preferably high 20 DEG C ~ 50 DEG C.
In preferred situation, the reaction conditions of the first reaction zone is, temperature of reaction 380 DEG C ~ 450 DEG C, is preferably 410 DEG C ~ 440 DEG C; Reaction pressure is 5.0MPa ~ 25.0MPa, is preferably 10.0MPa ~ 20.0MPa; Volume space velocity is 0.1 ~ 1.0, is preferably 0.2 ~ 0.6; Hydrogen to oil volume ratio is 200 ~ 1500, is preferably 300 ~ 900; With
The reaction conditions of second reaction zone is, temperature of reaction 430 DEG C ~ 480 DEG C, is preferably 440 DEG C ~ 470 DEG C; Reaction pressure is 5.0MPa ~ 25.0MPa, is preferably 10.0MPa ~ 20.0MPa; Volume space velocity is 0.1 ~ 1.0, is preferably 0.2 ~ 0.6; Hydrogen to oil volume ratio is 200 ~ 1500, is preferably 300 ~ 900.
According to the present invention, in flow process as shown in Figure 1, between the first and second reactors, gas-liquid separator is not set, namely eliminates a high-temperature high-pressure separator.
In the present invention, any existing known mode can also be adopted, introduce reaction promoter, such as catalyst aid and/or coke inhibitor and/or hydrogen supply agent.Described catalyst aid is any existing known material for improving hydrocracking catalyst for suspension bed activity, and the active metal in catalyzer is changed into the material of metallic sulfide by such as elementary sulfur, sulfide etc.
The present invention does not limit the various order by merging of the material of mixing and the mode of needing, any existing known mode all can adopt, such as first by described heavy oil, catalyzer, reaction promoter mixing, then after feedstock pump boosting, then be mixed into process furnace with hydrogen.
In the present invention, volume space velocity calculates with heavy oil volumetric flow rate and reactor cumulative volume.
Embodiment 1
Adopt the flow process shown in Fig. 1, stock oil is the long residuum with Liaohe Oil Field district crude oil, and its character lists in table 1.Catalyzer adopts solid powder th-1 catalyst, and maximum particle diameter is 5 μm, and median size is 0.8 μm, catalyzer Containing Sulfur ferrous 90m%, Containing Sulfur molybdenum 10m%.Adopt the empty bucket reactor that two of series connection identical, the volume of reactor is 500ml, and first reactor is by previously described first reaction zone operation, and second reactor is by the operation of previously described second reaction zone, concrete operations condition lists in table 2, and the product slates obtained lists in table 3.
In process of the test, by measuring the pressure differential deltap P of reactor top and the bottom, the difference of altitude Δ H of reactor top and the bottom, the density (ρ of gas phase under reactor condition can be calculated by process modeling software according to the composition of liquid phase (comprising solid catalyst) and character
gas) and the density (ρ of liquid phase (comprising solid catalyst)
liquid), then can calculate the gas holdup in reactor, calculating formula is as follows:
Gas holdup=(ρ
liquid-Δ P/g/ Δ H)/(ρ
liquid-ρ
gas)
In formula, g is gravity acceleration constant.
The gas holdup of two reactors calculated lists in table 3.
The character of table 1 long residuum
| Density (20 DEG C), kg/m 3 | 983.1 |
| Viscosity (80 DEG C), mm 2/s | 575.1 |
| Condensation point, DEG C | 16 |
| Carbon residue, m% | 9.80 |
| Nickel content, ppm | 55 |
| Content of vanadium, ppm | 2 |
| Iron level, ppm | 70 |
| Stable hydrocarbon, m% | 32.15 |
| Aromatic hydrocarbons, m% | 33.08 |
| Colloid+bituminous matter, m% | 34.77 |
| Sulphur content, m% | 0.35 |
| Nitrogen content, m% | 0.58 |
| Carbon content, m% | 88.15 |
| Hydrogen richness, m% | 10.92 |
Table 2 long residuum two-stage hydrogenation processing condition
| Hydrogen dividing potential drop, MPa | 15.0 |
| Volume space velocity, h -1 | 0.5 |
| One section of temperature of reaction, 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 hydrocracking product slates of table 3 embodiment 1
| The side of entering | |
| Stock oil | 100.00 |
| Hydrogen | 2.10 |
| Catalyzer | 2.50 |
| The side of going out |
| H 2S | 0.21 |
| NH 3 | 0.29 |
| C1～C4 | 4.89 |
| C5～350℃ | 49.90 |
| 350℃～500℃ | 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
Be with the difference of embodiment 1: second reactor adopts the normal operating mode of floating bed hydrogenation, namely the outlet streams of the first reactor obtains liquid phase stream after gas-liquid separation, this liquid phase stream and hydrogen enter the bottom of the second reactor jointly, and in the second reactor and stream move upward.Other unlisted aspects are as the operation of stock oil, catalyzer, the first reactor and other operations of the second reactor, all identical with embodiment 1.Product slates lists in table 4.
The two-stage hydrocracking product slates of table 4 comparative example 1
| The side of entering | |
| Stock oil | 100.00 |
| Hydrogen | 2.20 |
| Catalyzer | 2.50 |
| The side of going out | |
| H 2S | 0.20 |
| NH 3 | 0.26 |
| C1～C4 | 5.58 |
| C5～350℃ | 45.89 |
| 350℃～500℃ | 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 difference of the present embodiment and embodiment 1 is: the temperature of first paragraph reactor is 435 DEG C, and the service temperature of the second reactor is 455 DEG C.Other unlisted aspects are all identical with embodiment 1.The product slates obtained lists in table 5.
Table 5 embodiment 2 two-stage hydrocracking product slates
| The side of entering | |
| Stock oil | 100.00 |
| Hydrogen | 2.40 |
| Catalyzer | 2.50 |
| The side of going out | |
| H 2S | 0.23 |
| NH 3 | 0.31 |
| C1～C4 | 5.10 |
| C5～350℃ | 54.26 |
| 350～500℃ | 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 difference of the present embodiment and embodiment 2 is: vacuum distillate separation system obtained and part reduced pressure residual oil (containing solid catalyst) are as recycle stock, and recycle ratio is 0.5; Catalyst levels reduces.Other unlisted aspects are all identical with embodiment 2.The product slates obtained lists in table 6.
Table 6 embodiment 3 two-stage hydrocracking product slates
| The side of entering | |
| Stock oil | 100.00 |
| Hydrogen | 2.85 |
| Catalyzer | 1.50 |
| The side of going out | |
| H 2S | 0.28 |
| NH 3 | 0.37 |
| C1～C4 | 7.59 |
| C5～350℃ | 89.61 |
| 350～500℃ | 0 |
| Residue | 6.50 |
| Average Air Content in first stage reactor | 21.8 |
| Average Air Content in second stage reactor | 21.1 |
Embodiment 4
Adopt the flow process shown in Fig. 1, stock oil is middle coalite tar, and its character lists in table 7.Catalyzer adopts solid powder th-1 catalyst, and maximum particle diameter is 5 μm, and median size is 0.8 μm, catalyzer Containing Sulfur ferrous 88m%, Containing Sulfur molybdenum 10m%, Containing Sulfur nickel 2m%.Adopt the empty bucket reactor that two of series connection identical, the volume of reactor is 500ml, and first reactor is by previously described first reaction zone operation, and second reactor is by the operation of previously described second reaction zone, concrete operations condition lists in table 8, and the product slates obtained lists in table 9.
Table 7 coal tar oil properties
| Density (20 DEG C), kg/m 3 | 1015 |
| Condensation point, DEG C | 21 |
| Carbon residue, % | 15.2 |
| Solid content, % | 1.31 |
| Oxygen level, % | 6.80 |
| Sulphur content, % | 0.31 |
| Nitrogen content, % | 0.90 |
| Carbon content, % | 84.08 |
| Hydrogen richness, % | 7.91 |
Table 8 coal tar two-stage hydrogenation processing condition
| Hydrogen dividing potential drop, MPa | 15.0 |
| Volume space velocity, h -1 | 0.5 |
| One section of temperature of reaction, 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 hydrocracking product slates
| The side of entering | |
| Stock oil | 100.00 |
| Hydrogen | 3.65 |
| Catalyzer | 2.50 |
| The side of going out | |
| H 2S | 0.26 |
| NH 3 | 0.53 |
| H 2O | 4.50 |
| CO X | 0.08 |
| C 1-C 4 | 8.23 |
| C 5-350℃ | 85.02 |
| Residue | 7.53 |
Claims (10)
1. a method for hydrogen cracking for heavy oil, comprising: heavy oil, hydrogen and catalyzer enter the first reaction zone, the mixture flow of three in the first reaction zone on flowing, and to react under the condition of floating bed hydrocracking; After described mixture flow flows out the first reaction zone, be divided into gaseous stream and liquid phase stream through gas-liquid separation; Described liquid phase stream enters second reaction zone and flows downward, and enters second reaction zone and the hydrogen counter current contact that upwards flows, reacts under the condition of floating bed hydrocracking; Described liquid phase stream partly or entirely enters separation system and carries out product separation after flowing out second reaction zone.
2. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of second reaction zone is higher than the temperature of reaction of the first reaction zone 20 DEG C ~ 100 DEG C.
3. according to the method described in claim 1 or 2, it is characterized in that, the reaction conditions of the first reaction zone is, temperature of reaction 380 DEG C ~ 450 DEG C, and reaction pressure is 5.0MPa ~ 25.0MPa, and volume space velocity is 0.1 ~ 1.0, and hydrogen to oil volume ratio is 200 ~ 1500; With
The reaction conditions of second reaction zone is, temperature of reaction 430 DEG C ~ 480 DEG C, and reaction pressure is 5.0MPa ~ 25MPa, and volume space velocity is 0.1 ~ 1.0, and hydrogen to oil volume ratio is 200 ~ 1500.
4. in accordance with the method for claim 1, it is characterized in that, in second reaction zone, the downward flow velocity of described liquid phase stream is less than 60mm/s.
5. in accordance with the method for claim 1, it is characterized in that, the conversion zone of described first reaction zone corresponding to one or more reactor forms; With
The conversion zone of described second reaction zone corresponding to one or more reactor forms.
6. in accordance with the method for claim 5, it is characterized in that, between the first and second reaction zones, gas-liquid separator is not set, after described mixture flow flows out the first reaction zone, enter the reactor top of second reaction zone, be separated into gaseous stream and liquid phase stream on the top of this reactor.
7. in accordance with the method for claim 1, it is characterized in that, in described separation system, the logistics entering this system is separated into light oil, vacuum distillate and vacuum residuum.
8. in accordance with the method for claim 1, it is characterized in that, 5% recovered temperature of described heavy oil is greater than 200 DEG C.
9., according to the method described in claim 1 or 7, it is characterized in that, described heavy oil be one of black petroleum products, coal-tar heavy oil, coal-tar middle oil, coalite tar, shale oil or they combine arbitrarily; Or the combination of the above-mentioned raw material chosen and recycle stock, described recycle stock is selected from one of the liquid phase stream of described outflow second reaction zone, described vacuum distillate, described vacuum residuum or their arbitrary combination.
10. in accordance with the method for claim 1, it is characterized in that, described catalyzer is solid powder th-1 catalyst, and catalyst particles footpath is less than 0.1mm, one of catalyst activity metal chosen from Fe, cobalt, molybdenum, nickel, tungsten or they combine arbitrarily; In the fresh feed quality in heavy oil for 100%, catalyst levels is 0.1% ~ 5%.
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| CN108273448A (en) * | 2018-03-07 | 2018-07-13 | 吴剑华 | A kind of Continuous Liquid Phase hydrogenation reduction device and its application method |
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