CN1162520C - Heavy oil and residual oil hydrogenating modification and combination process - Google Patents
Heavy oil and residual oil hydrogenating modification and combination process Download PDFInfo
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- CN1162520C CN1162520C CNB001107216A CN00110721A CN1162520C CN 1162520 C CN1162520 C CN 1162520C CN B001107216 A CNB001107216 A CN B001107216A CN 00110721 A CN00110721 A CN 00110721A CN 1162520 C CN1162520 C CN 1162520C
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Abstract
The present invention relates to the improvement of a hydrotreating technique of a heavy residual oil fixed bed. A residual oil hydrogenation process and a continuous separation process of a residual oil middle phase are organically combined. The present invention is characterized in that the present invention can be suitable for heavy residual oil hydrogenating raw materials and inferior residual oil hydrogenating raw materials, the running life of a residual oil hydrogenating device is also improved, and the operating severity of the residual oil hydrogenating device is reduced.
Description
The present invention relates to the improvement of weight, residual oil treatment technology.
Heavy and to the increase day by day of light-end products demand along with becoming day by day of crude oil, the heavy oil lighting has become oil refining worker's main task.The heavy-oil hydrogenation upgrading is one of main method of heavy oil lighting, and it not only can slough detrimental impurity such as metal in the residual oil, sulphur, nitrogen in a large number, the low boiling component that can also make heavily, slag oil crack becomes high value.Present more employing fixed-bed reactor of residual hydrogenation, the catalyzer of difference in functionality are sub-packed in different reactors or the different bed, and residual oil contacts with catalyzer during by bed and carries out hydrogenation reaction.But there is shortcoming in this Residue Hydrotreating Technology, the easy inactivation of catalyzer when that processes poor quality oil exactly, and bed easily stops up, and makes residue fixed-bed hydrotreater running life only about 1 year.Prove that according to test and industrial operation the reason of the easy inactivation of catalyzer is that metal deposition and sedimentation of coke cause in the residue fixed-bed hydrotreater.For hydrogenation unit, metal deposition is the major cause of hydrogenation catalyst inactivation, and the metal content that reduces in the resid feed is the residue fixed-bed hydrotreater of the prolongation effective measure of running life.
As everyone knows, heavy, residual oil is colloidal dispersion system.During heavy, residual oil liquid phase thermal transition, asphaltene molecules not only can take place straight-chain molecule chain reaction (as take off alkyl, from around other particles capture hydrogen atom) outside, and can also generate more high-molecular weight condensation bituminous matter by the auto-polymerization reaction.Heat cracking reaction and condensation reaction take place in colloid in the residual oil too, make colloid to oil content and asphaltenes conversion, finally can destroy part colloid by bituminous matter and surface or inner absorption, adsorption equilibrium between the bituminous matter micella that heavy arene constitutes and the micella that constitutes by saturated branch and fragrance branch between mutually, balance is moved towards phase direction between micella, cause bitum peptization state forfeiture and produce flocculation attitude coagulation thing, the intermediate phase of generation between bituminous matter and coke, it is a benzene insoluble, but can more high solubility parameter and capillary solvent are molten by other have.
The method that adopts the continuous separating treatment stock oil of residual oil intermediate phase is disclosed among the patent CN1152020A, its objective is to producing high-quality petroleum coke or heavy oil fluid catalytic cracking and supply raw materials, but outside this method removing heavy metals decreasing ratio is higher, the decreasing ratio of carbon residue, sulphur, nitrogen is very low, can not be directly used in the stock oil of catalytic cracking unit, if want product is directly used in the stock oil of catalytic cracking unit, the target product yield of this method will be very low so, and the thermal cracking reactor that generates the residual oil intermediate phase is easy to coking and blocking, causes operation unstable.
The objective of the invention is to improve the deficiency of above-mentioned intermediate phase continuous separation method and existing residue fixed-bed hydroprocessing technique, provide a kind of effective combination process, i.e. the combination process of residual oil intermediate phase continuous separation technology and residue fixed-bed hydroprocessing technique.This technology not only can be optimized the operation of residue fixed-bed hydroprocessing technique, enlarges the source of fixed bed residual hydrogenation raw material, and can also prolong the running life of residual hydrogenation equipment greatly.
Technical scheme of the present invention is as follows:
Adopt residual oil to relax the method that thermally splitting generates the residual oil intermediate phase earlier, take off more bituminous matter of metal content and/or part colloid, its metal content is reduced, directly carry out hydrotreatment again, realize the hydro-upgrading or the conversion of poor residuum.
Specifically, at first the residual oil raw material temperature is heated to heat cracking reaction and produces the required temperature of intermediate phase, enter thermal cracking reactor again and react, generate the intermediate phase between liquid phase and the solid phase.Resultant of reaction is through overcooling, reach temperature required after, enter separator and carry out separating of residual oil and intermediate phase.Resultant of reaction preferably adds thinner before entering separator, because, the colloidal oil system is adding the volume oil content when (saturated branch+fragrance divides (not comprising heavy arene)), the activity (or concentration) of colloid in oil content will reduce, and produce chemical potential difference between the colloid in adsorption layer colloid and the oil content thereby make.Under the promotion of chemical potential difference, a part of colloid molecule can break away from the peptization attitude and enter oil content, makes bituminous matter glue nuclear be in naked state and increase the coagulation tendency.Thinner used in the present invention is the gasoline products cut in this combination process.Separator is separated the residual oil intermediate phase from residual oil, and by the discharge of separator bottom, it can do the raw material of solid fuel or delayed coking unit, the dry gas that heat cracking reaction generates is discharged from the separator top, it can go the gas recovery system in downstream or make geseous fuel, purification back residual oil then enters separation column from the outflow of separator top and carries out fractionation, gas is discharged by the separation column top, gasoline fraction can go out device or thinner is made in circulation, diesel oil distillate goes out device as required or squeezes into residue fixed-bed hydrogenation unit in this technology, residue oil fraction is discharged at the bottom of the tower after boosting to mix with hydrogen and is entered process furnace jointly, be heated to and enter residual hydrogenation equipment after temperature required and carry out hydrotreatment, reacted hydrogenated oil enters Separate System of Water-jet to be separated, the gas-phase product that is rich in hydrogen recirculation after purifying of telling is returned residual hydrogenation equipment and is continued to use, liquid phase generates oil and then enters the product separation column, fractionates out gas, gasoline, diesel oil and hydrogenated residue.Gas and diesel oil go out device, and gasoline then can a part of be made the thinner of intermediate phase sepn process, and a part goes out device, also can all go out device.Hydrogenated residue goes out the catalytic cracking unit that can enter the downstream behind the device and further carries out lighting, or a part loops back residual hydrogenation equipment.Two separation columns among the present invention can be replaced by the hydrogenated oil separation column, residual oil is exactly hydrogenated residue and the mixture of removing the stock oil of residual oil intermediate phase at the bottom of the tower of that hydrogenated oil separation column, but this needs to decide according to the character index of catalytic cracking charging.But the present invention preferentially recommends to use two separation columns.
The reactor of described generation residual oil intermediate phase is a thermal cracking reactor, and its topmost operational condition is a temperature of reaction.Temperature of reaction to the influence that generates the residual oil intermediate phase clearly, it is high more, intermediate phase quantity is just many more, the metal impurities removal effect is just good more, but the parting liquid of residual oil is received and also can be reduced like this, and reactor coking possibility also can increase, and also can increase newly-generated bitum amount, therefore, the pretreated temperature of residual oil raw material thermally splitting among the present invention should be determined according to the response characteristic of stock oil medium pitch matter, gelationus content and molecule.Temperature of reaction is generally between 360～440 ℃, is preferably 380～440, is preferably 390～420 ℃; Reaction pressure is generally 0.1～0.5MPa, is preferably 0.2～0.5MPa, is preferably 0.2～0.4MPa; Volume space velocity is 0.2～2.5h during liquid
-1, be preferably 0.4～2.3h
-1, be preferably 0.5～2h
-1
Volume space velocity is meant during described liquid: the ratio of stock oil volume and reactor effecting reaction section volume.
Described residual oil intermediate phase separating unit is a tower type separator.The quality of separating effect is mainly relevant with their separate and subside temperature between residual oil and the intermediate phase.Because the fusing point of isolated bituminous matter intermediate phase is about 150 ℃ of (Lott R et al.proc int symp on Heavy Oil﹠amp from solvent matrix; ResidueUpgrading﹠amp; Utilizaiton.Fushun, China:1992.309), therefore too many if settlement separate temperature is higher than this temperature, intermediate phase will become liquid, and just can not intermediate phase occur and separate, otherwise, then the residual oil viscosity in the separator is too big, influences the settling velocity of intermediate phase again greatly.Separator temperature of the present invention is 150～240 ℃, is preferably at 150～230 ℃, and best is at 150～210 ℃.For making residual oil intermediate phase good separating effect and velocity of separation fast, the present invention also uses oil content to make thinner in the sepn process of residual oil intermediate phase.The adding thinner not only can increase the coagulation of residual oil intermediate phase, can also reduce the viscosity and the density of residual oil, increases the density difference of intermediate phase and residual oil, thereby improves the separation efficiency of residual oil and intermediate phase.The thinner that the present invention uses is the gasoline products cut of this combination process, and add-on is 15～50%, and concrete percentage is by the space size of separator and the conditional decisions such as settling velocity of intermediate phase.The settling velocity of intermediate phase can be calculated by the Stokes'theorem formula, thereby can calculate the residence time of residual oil in separator and required separator size.The residence time of residual oil among the present invention in separator is 30～150 minutes, is preferably 50～130 minutes, is preferably 60～120 minutes.
Described residual hydrocracking technology can be any technology of the present invention that is applicable to, as floating bed hydrogenation treatment technology, boiling bed hydrogenation technology, moving-bed hydrogen addition technology etc., with present industrial maturation residue fixed-bed hydrogen addition technology being arranged is example, its operational condition is generally: temperature of reaction 340-430 ℃, better be 360-420 ℃, preferably 360-410 ℃; Reaction pressure is 8.0-16.0MPa, is preferably 8.0-15.0MPa, is preferably 10.0-15.0MPa; Hydrogen to oil volume ratio is 500-2000, is preferably 700-2000, is preferably 700-1500; Volume space velocity is 0.1-2.0h during liquid
-1, be preferably 0.1-1.5h
-1, be preferably 0.2-1.5h
-1The heavy residual oil hydrocatalyst that is adopted be meant have weight, the single catalyst or the series catalyst of residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous refractory inorganic oxide such as aluminum oxide, the oxide compound of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. is an active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.In addition, also can suitably adjust the loading amount of catalyzer and the proportioning of different catalysts according to the situation that removes metal impurities in the character of heavy, residual oil raw material and the intermediate phase treatment technology of the present invention.For example, in the intermediate phase treating processes, under the metallic impurity decreasing ratio condition with higher, can suitably reduce the loading amount of Hydrodemetalation catalyst in the fixed bed hydrogenation processing reaction system.
In order to reduce the hydrocarbon ils condensation of thermal cracking process, increase the residual oil yield, COMBINED PROCESS of the present invention in thermal cracking process, can feed an amount of hydrogen-containing gas to thermal cracking reactor.
The present invention is applicable to normal slag and the hydro-upgrading that subtracts slag, is particularly useful for easily making the obstruction of fixed bed Residue Hydrotreating Technology device beds and the high metal of catalyst deactivation, the residual oil of high carbon residue content to carry out the fixed bed hydrogenation upgrading.
Compared with prior art, characteristics of the present invention are: 1, by adopting residual oil intermediate phase separating technology, reduce the heavy metal content in the residual oil raw material, reduce the operating severity of residue fixed-bed hydroprocessing technique, prolong the work-ing life of hydrogenation catalyst, increase the on-stream time 2 of residual hydrocracking device, by adopting the combination of residual oil hydrogen treatment process and residual oil intermediate phase separating technology, residual oil after residual oil intermediate phase separating technology is purified is applicable to the use of downstream residual oil lighting device more under the condition that does not reduce the residual oil yield, as catalytic cracking unit, coker etc.
Fig. 1 is the process flow diagram of scheme of the present invention.
For further specifying all main points of the present invention, be elaborated below in conjunction with drawings and Examples.
As shown in Figure 1, residual oil raw material 1 enters in the process furnace 2, and the bottom that is heated to after the required temperature of thermal cracking reactor 3 by reactor 3 enters, and then resultant of reaction enters heat exchange and/or cooling system 4 is lowered the temperature.Heat-obtaining logistics in heat exchange and/or the cooling system 4 can be stock oil 1 or other fluids that need heat, if resultant of reaction does not also drop to the required temperature of separator 6, can increase refrigerating work procedure.Resultant of reaction be cooled to temperature required after, mix with thinner 5, enter separator 6 jointly.Thinner 5 can be by introducing outside this Association Technology Devices when going into operation, and promptly thinner 16; Gasoline products by combination process after going into operation provides, it is thinner 14, the device back thinner that works well can be given birth to olefiant separation column 7 by heat cracking reaction substantially and be provided, but technology of the present invention can increase thinner and minimizing thinner by pipeline 14 and 17 according to the change of the operational condition of stock oil character, thermal cracking reactor and residual hydrogenation equipment etc.In separator 6, residual oil intermediate phase 15 is discharged by the separator bottom, can make fuel, also can make the raw material of downstream coker.The dry gas 26 that thermal response produces is discharged by the separator top, enter the gas recovery system in downstream or remove to do geseous fuel, purify residual oil 19 and then enter separation column 7 from the outflow of separator top, gas 28 is discharged by the separation column top, gasoline fraction then circulates and makes thinner, 27 of diesel oil distillates remove the diesel refining device as required or squeeze into residue fixed-bed hydrogenation unit in this technology, 20 in residual oil after the separation boosts and back the mixing with hydrogen 24 enters process furnace 25 jointly, be heated to and enter residue fixed-bed hydrogenation unit 8 after temperature required and carry out hydrotreatment, hydrogenated oil 21 afterwards enters separation system 9, the gas-phase product 23 that is rich in hydrogen loops back residual hydrogenation equipment through purification to be continued to use, liquid phase generates 22 of oil and enters product separation column 10, fractionates out gas 18, gasoline 13, diesel oil 12 and hydrogenated residue 11.Gas 18 and diesel oil 12 go out device, and gasoline 13 is divided into two-way, and one the tunnel goes out device, and thinner is made on another road.11 of hydrogenated residues enter the catalytic cracking unit in downstream and further carry out lighting.Two separation columns among the present invention can be replaced by hydrogenated oil separation column 10, residual oil is exactly hydrogenated residue 11 and the mixture of removing the stock oil 20 of residual oil intermediate phase at the bottom of the tower of that separation column 10, but this needs to decide according to the character index of catalytic cracking charging.Residual oil is divided into two-way at the bottom of the tower of hydrogenated oil separation column 10: the one tunnel advances catalytic cracking unit, another road slag input oil fixed bed hydrogenation device.But the present invention advocates to use two separation columns.
Present embodiment is mainly investigated operational condition in the residual oil intermediate phase continuous separation technology to purifying the influence of residual oil character.The main character of present embodiment test raw material oil sees Table-1, and operational condition in the residual oil intermediate phase continuous separation technology and purification residual oil main character see Table-2.
The main character of table-1 stock oil
| Project | Stock oil |
| Elementary composition | |
| S，w％ | 2.52 |
| N，w％ | 0.83 |
| Carbon residue, w% | 15.8 |
| Metal content | |
| Ni，μg/g | 51.0 |
| V，μg/g | 2.37 |
| Fe，μg/g | 14.8 |
| Ash content, μ g/g | 141 |
| Four components | |
| Saturated part, w% | 14.5 |
| Fragrance part, w% | 35.8 |
| Colloid, w% | 46.1 |
| Bituminous matter, w% | 3.6 |
Operational condition in table-2 residual oil intermediate phase continuous separation technologies and purification residual oil main character
| Embodiment |
| 1 | 2 | 3 | |
| Temperature of reaction, ℃ | 390 | 400 | 410 |
| Reaction velocity, h -1 | 1.0 | 1.5 | 2.0 |
| Reaction pressure, Mpa | 0.3 | 0.3 | 0.3 |
| Agent material ratio * | 0.3 | 0.4 | 0.5 |
| Separator temperature, ℃ | 190 | 170 | 175 |
| Separator pressure, MPa | 0.3 | 0.3 | 0.3 |
| The separate and subside time, minute | 100 | 100 | 100 |
| Purify residual oil character | |||
| Elementary composition | |||
| S，w％ | 1.76 | 1.70 | 1.60 |
| N，w％ | 0.75 | 0.73 | 0.65 |
| Carbon residue, w% | 14.6 | 13.7 | 14.1 |
| Metal content | |||
| Ni，μg/g | 15.9 | 12.3 | 9.8 |
| V，μg/g | 0.66 | 0.54 | 0.42 |
| Fe，μg/g | 2.01 | 1.9 | 1.2 |
| Ash content μ g/g | 28.0 | 23.0 | 12.0 |
| Four components | |||
| Saturated part, w% | 18.1 | 18.6 | 19.4 |
| Fragrance part, w% | 41.3 | 42.1 | 43.0 |
| Colloid, w% | 37.6 | 35.4 | 33.3 |
| Bituminous matter, w% | 3.0 | 3.9 | 4.3 |
*The material of agent described in table ratio is added thinner and the living olefiant weight ratio of thermal cracking reactor in the intermediate phase sepn process.
Comparative example 1～3 and embodiment 4～6
The main fixed bed hydrogenation performance of investigating residual oil of this experiment, the operational condition of residue fixed-bed hydrogenation sees Table-3 with the generation oil nature.The main character of test raw material oil sees Table-1.
The hydrogenation catalyst that uses in this test is heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.The Hydrodemetalation catalyst that uses in this test is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Filling ratio between each function catalyzer is: HDM/HDS/HDN=45/20/35 (V/V).Wherein also comprise protective material in the HDM catalyzer.
The operational condition and the product main character of table-3 residue fixed-bed hydrogenation
| Comparative example and embodiment | Comparative example 1 | Comparative example 2 | Comparative example 3 | | | |
| Residual oil intermediate phase separating unit | ||||||
| Temperature of reaction, ℃ | 390 | 400 | 410 | |||
| Reaction velocity, h -1 | 1.0 | 1.5 | 2.0 | |||
| Reaction pressure, MPa | 0.3 | 0.3 | 0.3 | |||
| Agent material ratio | 0.3 | 0.4 | 0.5 | |||
| Separator temperature, ℃ | 190 | 170 | 175 | |||
| Separator pressure, MPa | 0.3 | 0.3 | 0.3 | |||
| The separate and subside time, minute | 100 | 100 | 100 | |||
| The fixed bed hydrogenation unit | ||||||
| Temperature of reaction, ℃ | 385 | 390 | 395 | 385 | 390 | 395 |
| Reaction velocity, h -1 | 0.25 | 0.25 | 0.25 | 0.5 | 0.5 | 0.5 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 14.0 | 14.0 | 14.0 |
| Hydrogen-oil ratio | 800 | 800 | 800 | 800 | 800 | 800 |
| Generate oil nature | ||||||
| S，w％ | 0.45 | 0.26 | 0.15 | 0.32 | 0.20 | 0.08 |
| N，w％ | 0.41 | 0.34 | 0.20 | 0.39 | 0.31 | 0.16 |
| Carbon residue, w% | 9.6 | 7.5 | 5.3 | 8.5 | 6.9 | 4.2 |
| Ni，μg/g | 18.44 | 12.3 | 6.3 | 6.1 | 3.2 | 1.1 |
| V，μg/g | 1.5 | 1.1 | 0.9 | 0.31 | 0.20 | 0.1 |
| Four components (hydrogenated residue) | ||||||
| Saturated part, w% | 40.8 | 49.3 | 58.9 | 44.3 | 56.3 | 64.0 |
| Fragrance part, w% | 28.0 | 26.2 | 23.6 | 32.1 | 28.1 | 25.2 |
| Colloid, w% | 28.2 | 22.6 | 16.6 | 20.9 | 14.3 | 9.7 |
| Bituminous matter, w% | 3.0 | 1.9 | 0.9 | 2.7 | 1.3 | 1.1 |
Claims (6)
1, a kind of heavy, residual hydrogenation modification combined method, comprise: adopt method heavy, that residual oil relaxes thermally splitting generation residual oil intermediate phase earlier, then described intermediate phase is separated, take off more bituminous matter and/or the part colloid of metal content in the resid feed, its metal content is reduced, in the fixed bed hydrogenation treatment unit, carry out hydrotreatment again, realize the hydro-upgrading or the conversion of poor residuum; Described mitigation thermally splitting operational condition is: temperature of reaction is 360～＜410 ℃, and reaction pressure is 0.1～0.5MPa, and volume space velocity is 0.2～2.5h during liquid
-1Described intermediate phase separation operation condition is: separation temperature is 150～240 ℃, and the residence time of residual oil in separator is 30～150 minutes, and in sepn process, the gasoline fraction that adds separator charging 15～50wt% is a thinner; Described fixed bed hydrogenation is handled operational condition: temperature of reaction 340-430 ℃, reaction pressure is 8.0-16.0MPa, and hydrogen to oil volume ratio is 500-2000, and volume space velocity is 0.1-2.0h during liquid
-1
2, according to described heavy, the residual hydrogenation modification combined method of claim 1, the hydro-upgrading or the method for transformation that it is characterized in that described poor residuum are: at first the residual oil raw material temperature is heated to heat cracking reaction and produces the required temperature of intermediate phase, enter thermal cracking reactor again and react, generate the intermediate phase between liquid phase and the solid phase; Resultant of reaction is through overcooling, reach temperature required after, enter separator and carry out separating of residual oil and intermediate phase, separator is separated the residual oil intermediate phase from residual oil, and by the discharge of separator bottom, the dry gas that heat cracking reaction generates is discharged from the separator top, purification back residual oil then enters separation column from the outflow of separator top and carries out fractionation, purify residue oil fraction and discharge at the bottom of the tower after boosting to mix and enter process furnace jointly, be heated to and enter residual hydrogenation equipment after temperature required and carry out hydrotreatment with hydrogen; Entering Separate System of Water-jet through the reacted hydrogenated oil of residual hydrogenation equipment separates, the gas-phase product that is rich in hydrogen recirculation after purifying of telling is returned residual hydrogenation equipment and is continued to use, liquid phase generates oil and then enters the product separation column, fractionates out gas, gasoline, diesel oil and hydrogenated residue; Described mitigation thermally splitting operational condition is: temperature of reaction is 360～＜410 ℃, and reaction pressure is 0.1～0.5MPa, and volume space velocity is 0.2～2.5h during liquid
-1Described intermediate phase separation operation condition is: separation temperature is 150～240 ℃, and the residence time of residual oil in separator is 30～150 minutes; Described fixed bed hydrogenation is handled operational condition: temperature of reaction 340-430 ℃, reaction pressure is 8.0-16.0MPa, and hydrogen to oil volume ratio is 500-2000, and volume space velocity is 0.1-2.0h during liquid
-1
3,, it is characterized in that in thermal cracking reactor, carrying out in described process heavy, that residual oil relaxes thermally splitting generation residual oil intermediate phase according to claim 1 or 2 described heavy, residual hydrogenation modification combined methods.
4,, it is characterized in that in tower type separator, carrying out in described residual oil intermediate phase separation according to claim 1 or 2 described heavy, residual hydrogenation modification combined methods.
5,, it is characterized in that the heavy residual oil hydrocatalyst that is adopted is is carrier with the porous refractory inorganic oxide, to be selected from group vib and/or VIII family metal component is an active ingredient according to claim 1 or 2 described heavy, residual hydrogenation modification combined methods.
6,, it is characterized in that at described thinner be the gasoline fraction that the gasoline fraction told through separation column of the reactant after heavy, residual oil raw material removes intermediate phase and/or the reactant after the residual hydrocracking are told through separation column according to described heavy, the residual hydrogenation modification combined method of claim 1.
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| CN111004647A (en) * | 2019-12-03 | 2020-04-14 | 沈阳化工大学 | Heavy oil hydrogenation upgrading process for coupling cracking and reforming hydrogen production |
| CN113088330B (en) * | 2021-03-15 | 2023-01-13 | 西安近代化学研究所 | Thermal cracking coupling mild hydrogenation method for heavy oil |
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