CN1101457C - Treatment method for inferior heavy and residual oil - Google Patents
Treatment method for inferior heavy and residual oil Download PDFInfo
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- CN1101457C CN1101457C CN97121845A CN97121845A CN1101457C CN 1101457 C CN1101457 C CN 1101457C CN 97121845 A CN97121845 A CN 97121845A CN 97121845 A CN97121845 A CN 97121845A CN 1101457 C CN1101457 C CN 1101457C
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Abstract
The present invention discloses a combined technological method for processing poor-quality heavy oil and residual oil. Crude oil or residual oil obtained by distillation is continuously hydrocracked in a reaction apparatus of a suspension bed, and a water-soluble hydrogenation catalyst is used for the hydrogenation reaction of the suspension bed. The raw material of the residual oil and the catalyst uniformly distributed in the raw material of the residual oil enter a suspension bed reactor together to be cracked into a light component when high-pressure hydrogen (5 to 20MPa) exists. Cut fraction oil is hydrorefined after products are separated, and tail oil is used as coking feed or is used as an asphalt blending component.
Description
The present invention relates to a kind of floating bed hydrogenation and coking or combined technological process of mixing asphalt of processing inferior heavy, residual oil.
The weight that the present invention relates to, residual oil can be the residual oils that crude distillation obtains, heavy-gravity heavy crude oil, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.
Along with the increase to the light-end products demand of the minimizing of low-sulfur light crude and market, the former oil require of some inferior heavy is used.Main purpose heavy, that residual oil transforms is the light-end products that obtain having higher-value to greatest extent the heavier feedstocks oil of the residue that obtains from petroleum distillation or other low value.
The residual oil of sweet crude oil adopts coking process to be transformed in a large number.The main drawback of coking process is that coke and dry gas output are big, and the liquid oil yield is low, and when processing the poor residuum of the high metal content of high nitrogen, these shortcomings are particularly outstanding.For example the vacuum residuum of Liaohe River commingled crude is processed through coking, and its liquid product yield has only about 60w%, and coke output is up to 30w%.Contain the about 50w% of viscous crude in the commingled crude of the Liaohe River, if processing Liaohe River viscous crude, then the stock oil of several nearly half will become coke.A large amount of coke brings some difficulties for accumulating and sale, and liquid product yield decline has also reduced the economic benefit of refinery significantly.Produce coke and dry gas less, the Technology of voluminous liquid feul is the target that tackles the high metal heavy oil of high nitrogen inferior that the refining of petroleum worker seeks always.
Compare with coking process, residual hydrocracking has many-sided advantage.It does not produce a large amount of by-product cokes, and dry gas content is also lower in the gaseous product, but and all products be the defeated liquid of pump.In addition, hydrocracking quality product also is much better than coking and generates oil.Yet when the inferior heavy of the conventional high metal of the high nitrogen of residual hydrogenation technical finesse low-sulfur, residual oil, both do not reached the high cracking transformation efficiency of hope, can not effectively remove unwanted components such as nitrogen in the raw material, metal.This is because the C-S key in the residual oil macromole is easy to fracture, thereby causes the easy cracking of high-sulfur residual oil, and the element sulphur under splitting is with H
2It is again the prerequisite of keeping activity of hydrocatalyst that the S form is present in the recycle hydrogen.The C-S key is few in the residual oil of the high metal of the high nitrogen of low-sulfur, and the nitrogen element is present in the heterocycle macromole more, make cracking difficulty with conventional fixed bed residual hydrogenation technical finesse the time, high nitrogen and high metal content cause the quick poisoning and deactivation of catalyzer and bed to stop up again, production equipment can't long-term operation, the catalyzer consumption is big, shutting down is frequent, and production cost height, efficient are low, deficiency in economic performance is inevitable the result.
In order effectively to utilize poor residuum, many countries and major oil companies all adopt the floating bed hydrogenation technology of disperse type catalyzer in research.The suspension bed technology adopts disperse type catalyzer, does not have the bed blockage problem, obtains higher cracking transformation efficiency thereby therefore can react under comparatively high temps.But high conversion has caused the increase of impurity in the hydrogenation tail oil or solid materials, thereby has brought difficulty for processing and the utilization of tail oil.
PetroCanada proposes iron cpd (mainly being ferrous sulfate) and coal dust are ground in oil in the patent application CN1035836 that China proposes, and makes a kind of iron-coal paste shape catalyzer, mixes with heavy oil then and carries out floating bed hydrogenation.Resultant of reaction has the tail oil of 20w% approximately after isolating product liquid.Because the hydrogenation activity of iron catalyst is very low, must add a large amount of catalyzer in the reaction process, account for 2～4w% of inlet amount usually.These catalyzer all are enriched in the tail oil at last, and this tail oil that contains a large amount of solid catalyst particles is handled and utilized all very difficult.Particularly when this catalyzer is used for the inferior raw material of low-sulfur, high nitrogen, high metal content, must further improve catalyst levels, the tail oil intractability is further increased, tooling cost rises.
The EXXON oil company is at U.S. Pat P4, announced that a kind of coking and floating bed hydrogenation combination process handle the method for heavy oil in 569,752.The advanced coking of residual oil raw material, the liquid product that coking is obtained is isolated the wax tailings less than 524 ℃ of cuts then, adds the laggard floating bed hydrogenation reactor of phospho-molybdic acid aqueous catalyst solution and further transforms.Floating bed hydrogenation tail oil partly returns coking, and part throws away device.Though this technology has reduced the tail oil amount of floating bed hydrogenation process, can not fundamentally reduce the coke output of whole process, can not reduce the generation of dry gas, thereby total liquid product yield is still not high.Use the inferior raw material of this method processing as the viscous crude of the Liaohe River, coking can only obtain the product liquid less than 50w%, product liquid is handled through floating bed hydrogenation again, what will produce about 10w% again must return coking or outer whipping oil and portion gas product, finally can only obtain the liquid product less than 40w%.Therefore, there is not a using value industrial.
The objective of the invention is to find a kind of combination complete processing, this combination process can obtain liquid oil to greatest extent and produce coke and dry gas yied as far as possible less when the processing poor-quality heavy residuum.This combination process comprises that the hydrogenation of residual oil suspended bed that uses efficient disperse type catalyzer transforms and floating bed hydrogenation tail oil advances the further conversion of coking or concocts pitch with hydrogenation tail oil.When weighing residual oil, can obtain benzoline to greatest extent, and solve the problem of utilizing of floating bed hydrogenation tail oil with such method processing.Another object of the present invention is to utilize the efficient aqueous dispersion type catalyzer for preparing to carry out the floating bed hydrogenation of low-sulfur poor-quality heavy residuum, this catalyzer promptly has very high hydrogenation activity under the condition of add-on very low (50～800 μ g/g), the green coke of inhibited reaction process significantly, thereby the problem of too high solids content makes hydrogenation tail oil can be directly used in coking or mixing asphalt in the tail oil of having avoided producing owing to a large amount of solid additive of adding in raw material.The 3rd purpose of the present invention is to find a kind of suitable mixing asphalt scheme, makes the hydrogenation of residual oil suspended bed tail oil can be used for producing qualified asphaltic products. with other logistics blending of refinery.
The present invention includes the following aspects: adopt heavy dreg-oil suspension bed catalytic hydrogenation method and water-soluble disperse type catalyzer or other efficient disperse type catalyzer, be used for the hydro-upgrading of the poor-quality heavy residuum of low sulfur content, high nitrogen-containing, high metal content.At first water-soluble catalyst is scattered in the stock oil, the total add-on of catalyzer is 50～800 μ g/g, is preferably 150～600 μ g/g; Contain metal M o, Ni, Co etc. in the used water-soluble catalyst, each set of dispense is than being Ni/Mo=0.01～0.5: 1, Co/Mo=0～2: 1.Contain and enter the floating bed hydrogenation reactor after the stock oil of catalyzer and hydrogen mix.Hydrogenation and scission reaction take place in heavy residual oil in reactor, change into low boiler cut to greatest extent.The suspension bed hydrogenation process condition is: reaction pressure is 6～18MPa, better is 8～14MPa; Temperature of reaction is 420～460 ℃, better is 430～450 ℃; The reaction solution hourly space velocity is 0.2～1.5h
-1Be preferably 0.8～1.2h
-1Hydrogen to oil volume ratio (under the standard pressure) is 100～1500, better is 300～800.
Isolate distillate and tail oil from the material that suspended-bed reactor comes out through tripping device, distillate advances the further hydrogenation of fixed bed hydrogenation device, and part or all of tail oil is as coker feed or charging blending component, to obtain more light ends oil.Part or all of tail oil also can be used as the mixing asphalt component, produces pitch with residual oil or with catalytic cracking unit heavy cycle oil (also claiming slurry oil) or with the extraction wet goods blending of Process of Lube Solvent Refining.
Fig. 1 and Fig. 2 are seen in the flow process signal.Process explanation is as follows:
Residual oil raw material and aqueous catalyst solution enter mixing tank 3 from pipeline 1 and 2 respectively.Mixing tank 3 can be a stirred pot, also can be a colloidal mill or static mixer or other conventional mixing equipment, and residual oil and aqueous catalyst solution are mixed.If material viscosity is big especially, be difficult to use the ordinary method mixing below 100 ℃, also can earlier aqueous catalyst solution be mixed with a small amount of long residuum, and then mix with full-bodied charging.Charging after mixing enters well heater 8 through pipeline 4 and pump 5, pipeline 7, and hydrogen enters system via pipeline 6.Charging is heated to 350～440 ℃ in process furnace 8, enter reactor 10 through pipeline 9 then.Reactor operating condition is hydrogen pressure 6～18MPa, feeding liquid hourly space velocity 0.2～1.5h
-1, 420～460 ℃ of temperature of reaction, hydrogen-oil ratio 300～1500 (volume ratio).Reaction product enters high-pressure separator 12 via pipeline 11, tells gaseous products and removes fixed-bed reactor 14 further hydrogenation through pipeline 13, and hydrogenation products goes out device through pipeline 15.The tail oil that high-pressure separator 12 is told enters coker 17 (Fig. 1) through pipeline 16, and coking oil gas goes out device by pipeline 18.The tail oil that high-pressure separator 12 is told also can enter mixing asphalt device 18 (Fig. 2) through pipeline 16 and produce pitch with other logistics blending from pipeline 17, obtains asphaltic products. and goes out device via pipeline 19.
Advantage of the present invention is:
1, adopt dreg-oil suspension bed hydrogenation cracking and tail oil coking or accent bituminous combination process, this combination process can obtain liquid oil to greatest extent and produce coke and dry gas as far as possible less when the processing poor-quality heavy residuum.
2, in the floating bed hydrogenation process, adopted the efficient disperse type catalyzer of many metals, effectively avoided the green coke of process, thereby made and do not contain solid particulate substantially in the tail oil.
3, tail oil directly as the blending component of coking raw material or coking raw material, can further improve yield of light oil 5-8w%.
4, tail oil also can be produced qualified asphaltic products. with residual oil or with catalytic cracking unit heavy cycle oil (also claiming slurry oil) or with the extraction wet goods blending of Process of Lube Solvent Refining directly as bituminous blending raw material.
Fig. 1 is hydrogenation of residual oil suspended bed of the present invention and coking combination process schematic flow sheet;
Fig. 2 is hydrogenation of residual oil suspended bed of the present invention and mixing asphalt combination process schematic flow sheet.
For further specifying all main points of the present invention, enumerate following examples.
Test raw material character sees Table 1.This residual oil sulphur content is low as shown in Table 1, the metal content height, and only promptly near 120 μ g/g, gum level reaches 38.5w% for nickel, vanadium and iron, and carbon residue surpasses 13w%, and nitrogen content is a kind of more unmanageable low-sulfur poor residuum up to 0.62w%.
Table 1 test Liaohe River residual oil character
| Project | Numerical value | Project | Numerical value |
| Density (20 ℃), Kg/m 3 | 982.9 | Fe，μg/g | 22.0 |
| Carbon residue, w% | 13.37 | Ni，μg/g | 93.7 |
| C，w％ | 87.22 | V，μg/g | 2.37 |
| H，w％ | 11.69 | Na，μg/g | 5.65 |
| S，w％ | 0.40 | Ca，μg/g | 74.0 |
| N，w％ | 0.62 | ||
| Four proximate analysis w% | |||
| Stable hydrocarbon | 30.4 | ||
| Aromatic hydrocarbons | 26.0 | ||
| Colloid | 38.5 | ||
| Bituminous matter | 1.0 |
The conversion of residual oil and the coke forming property of reaction process when the catalyzer that uses different compositions is under certain condition investigated in this test.Coke forming property characterizes to measure the toluene insolubles that generates in the oil.At first prepare the aqueous catalyst solution that contains hydrogenation active metals, aqueous catalyst solution is joined carry out hydrogenation reaction in the residual oil then.Process of the test is as follows:
Take by weighing Liaohe River residual oil 200g and put into the autoclave that a 750mL band stirs, add the catalyzer of 250 μ g/g.Closed reactor, room temperature is filled hydrogen pressure to 7MPa behind the logical hydrogen exchange, begins then to stir to heat up, and reacts 1h down at 435 ℃.Make reactor keep constant 10MPa pressure with the method for mending hydrogen continuously between the reaction period.Reaction product surveys toluene insolubles respectively, less than 350 ℃ of fractions (AGO) and 350-538 ℃ of fraction (VGO) yield.Test-results sees Table 2.
The table 2 different catalysts aqueous solution is used for the residual hydrogenation test-results
| Embodiment |
| 1 | 2 | 3 | 4 | 5 | 6 | |
| Catalyst metal is formed: | ||||||
| Ni/Mo | 0.01 | 0.15 | 0.15 | 0.23 | 0.23 | 0.35 |
| W/Mo | 0.00 | 1.00 | 0.00 | 1.00 | 1.00 | 4.00 |
| Co/Mo | 0.00 | 2.00 | 0.25 | 0.25 | 0.50 | 1.00 |
| Reaction generates oil nature: | ||||||
| Toluene insolubles w% | 0.57 | 0.36 | 0.27 | 0.73 | 0.82 | 1.01 |
| AGO w％ | 26.4 | 29.0 | 27.1 | 32.1 | 34.7 | 35.2 |
| VGO w％ | 40.0 | 43.1 | 44.0 | 44.3 | 44.3 | 48.3 |
The test-results explanation uses multicomponent catalyst can significantly improve the cracking transformation efficiency of floating bed hydrogenation process.In general, transformation efficiency raises and then generates also increase thereupon of toluene insolubles content in the oil.Suitably the metal composition of adjustment catalyzer can make the reaction process coking yield be controlled at below the 1.0w% and higher transformation efficiency is arranged.
Embodiment 7～13
Embodiment still can obtain expected result when 7～13 explanation reaction conditionss fluctuate in relative broad range.Reaction raw materials oil and process of the test adopt used catalyzer in the example 4 with embodiment 1～6, and test-results sees Table 3.
Residual hydrogenation test-results under table 3 different technology conditions
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Reaction conditions: | |||||||
| Temperature of reaction ℃ | 420 | 435 | 435 | 435 | 440 | 445 | 455 |
| | 8 | 8 | 12 | 10 | 10 | 15 | 20 |
| Reaction times min | 60 | 75 | 90 | 60 | 45 | 60 | 40 |
| Catalyzer add-on μ g/g | 351 | 300 | 150 | 250 | 400 | 200 | 50 |
| Reaction generates oil nature: | |||||||
| Toluene insolubles w% | 0.15 | 0.75 | 0.62 | 0.73 | 0.72 | 0.56 | 0.82 |
| AGOw％ | 24.5 | 34.1 | 35.1 | 32.1 | 36.0 | 42.2 | 47.3 |
| VGOw％ | 37.5 | 42.2 | 43.5 | 44.3 | 43.8 | 44.3 | 44.1 |
Test-results explanation limits within the acceptable range as long as the processing parameter collocation suitably, still can obtain the toluene insolubles that higher distillate yield will generate in the oil simultaneously when processing condition change in the larger context.
The hydrogenation of residual oil suspended bed reaction that this test explanation is carried out on continuous apparatus.
Fig. 1 and Fig. 2 are seen in the signal of hydrogenation of residual oil suspended bed continuous apparatus flow process.Residual oil raw material and aqueous catalyst solution mix in mixing tank 3.Charging after mixing enters well heater 8 through pipeline 4 and pump 5, pipeline 7, and hydrogen enters system via pipeline 6.Charging is heated to 350～440 ℃ in process furnace, enter reactor 10 through pipeline 9 then.Reaction product enters high-pressure separator 12 via pipeline 11, tells gas-phase product and removes distillate fixed bed hydrogenation device 14 through pipeline 13, and the unconverted tail oil of telling enters coking or mixing asphalt device through pipeline 16.Floating bed hydrogenation operational condition and reaction result see Table 4.
Table 4
| | 14 | 15 | 16 | 17 | 18 | 19 |
| Catalyzer is formed: | ||||||
| Ni/Mo | 0.15 | 0.15 | 0.15 | 0.23 | 0.23 | 0.15 |
| W/Mo | 0.00 | 1.00 | 0.00 | 0 | 1.00 | 4.00 |
| Co/Mo | 0.00 | 0.00 | 0.25 | 0 | 0.50 | 1.00 |
| Reaction conditions: | ||||||
| | 10 | 10 | 10 | 10 | 14 | 14 |
| | 1 | 1.2 | 1 | 0.8 | 1 | 1 |
| Temperature, ℃ | 430 | 440 | 420 | 435 | 440 | 445 |
| Catalyzer add-on μ g/g | 200 | 300 | 200 | 250 | 250 | 400 |
| Reaction product character: | ||||||
| Toluene insolubles, w% | 0.45 | 0.6 | 0.05 | 0.55 | 0.42 | 0.69 |
| AGO，w％ | 30.5 | 37.1 | 25.1 | 31.1 | 39.0 | 43.2 |
| VGO，w％ | 40.5 | 40.2 | 38.5 | 42.3 | 40.8 | 42.3 |
Embodiment 20
The tail oil that this test explanation residual oil obtains behind floating bed hydrogenation can be separately as coker feed.
With embodiment 15 resulting hydrogenation tail oils is raw material, this raw material proportion 1.05g/cm
3, carbon residue 36.5w%.Carry out coking test on packaged unit, the coke chemicals yield is: gas 10.6w%, normal pressure fraction oil 22.8w%, decompression fraction oil 16.5w%, coke 51.0w%.The presentation of results floating bed hydrogenation tail oil advances coker further to be processed, and can obtain higher light oil total recovery.
Embodiment 21
Be mixed into raw material with embodiment 17 gained floating bed hydrogenation tail oils and Liaohe River vacuum residuum, blending ratio is 1: 1, carries out coking test on small-sized coker, the coking products distribution is as follows: gas 10.0w%, normal pressure fraction oil 29.4w%, decompression fraction oil 22.5w%, coke 38.0w%.The present embodiment explanation adopts the present technique floating bed hydrogenation tail oil also to can be used as the blending component of coker feed.
Embodiment 22～26
Embodiment 22～26 can be used as the mixing asphalt material in order to the explanation floating bed hydrogenation tail oil, fully is used.Respectively with floating bed hydrogenation tail oil and refinery's lubex, catalytic cracking unit circulation slurry oil, long residuum etc. as blending component, concoct out and meet the different asphaltic products.es that require, test-results sees Table 5.
The asphaltic nature that the different blending components of table 5 access
| Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | |
| Blending component | The two wires is extracted oil out | Three-way extraction oil | Catalytic slurry | Normal slag | Subtract slag |
| Add-on, w% | 30 | 30 | 35 | 40 | 50 |
| Asphaltic nature: | |||||
| Penetration degree, 1/10mm | 125 | 104 | 86 | 95 | 60 |
| Softening temperature, ℃ | 44 | 45 | 46 | 45 | 47 |
| Extensibility, 25 ℃, cm | 132 | 126 | 98 | 116 | 125 |
Comparative example 1
Test raw material is with embodiment 1.The advanced coker of residual oil raw material carries out pyrogenic reaction, and the distillate that obtains advances floating bed hydrogenation, and coker is returned in tail oil recirculation.Each process product yield sees Table 6.Table 6 coking and suspension bed process product yield
| Yield | Coking | The suspension bed process |
| Gas, w% | 10.8 | 4.0 |
| ＜350 ℃ of distillates, w% | 23.4 | 32.4 |
| 350-538 ℃ of distillate, w% | 25.5 | 43.2 |
| Product liquid adds up to, w% | 48.9 | 75.6 |
The 350-538 that coking obtains ℃ distillate further loss in the floating bed hydrogenation process (liquid of floating bed hydrogenation process is received and is 72.6w%), total liquid product yield of the combined process 43w% that only has an appointment.This example shows that liquid yield is too low when adopting after the first coking floating bed hydrogenation scheme processing Liaohe River viscous crude, does not have industrial application value.
Claims (9)
1. the treatment process of an inferior heavy, residual oil is characterized in that heavily, the advanced floating bed hydrogenation device reaction of residual oil raw material that cracking generates light ends oil and a small amount of end transforms tail oil, and hydrogenation tail oil advances coker and further transforms; Described hydrogenation of residual oil suspended bed adopts water-soluble catalyst, and aqueous catalyst solution directly disperses to join in the resid feed, and at 420～460 ℃, residual oil raw material carries out cracking and hydrogenation reaction under 6～18MPa hydrogen pressure; Contain metal M o, Ni, Co in the described water-soluble catalyst, each set of dispense is than being Ni/Mo=0.01～0.5: 1, Co/Mo=0～2: 1.
2. according to the method for claim 1, the catalyst levels that it is characterized in that the floating bed hydrogenation process is 50～800 μ g/g.
3. according to the method for claim 1, the catalyst levels that it is characterized in that the floating bed hydrogenation process is 150～600 μ g/g.
4. according to the method for claim 1, the liquid hourly space velocity that it is characterized in that the floating bed hydrogenation process is 0.2～1.5h
-1
5. according to the method for claim 1, the hydrogen to oil volume ratio that it is characterized in that the floating bed hydrogenation process is 100～1500.
6. according to the method for claim 1, the hydrogen to oil volume ratio that it is characterized in that the floating bed hydrogenation process is 300～800.
7. according to the method for claim 1, it is characterized in that resid feed directly with the aqueous catalyst solution mixing, mixed resid feed enters conversion zone and carries out hydrocracking.
8. according to the method for claim 1, the tail oil that it is characterized in that the floating bed hydrogenation process is as coker feed.
9. according to the method for claim 1, it is characterized in that floating bed hydrogenation process tail oil is directly as the mixing asphalt component.
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| CN101418222B (en) * | 2007-10-26 | 2012-09-12 | 中国石油化工股份有限公司 | Composite process for treatment of inferior residual oil |
| CN103059997B (en) * | 2011-10-21 | 2014-08-20 | 中国石油化工股份有限公司 | Combined technique of hydrotreating and delay coking of residual oil |
| US9644157B2 (en) * | 2012-07-30 | 2017-05-09 | Headwaters Heavy Oil, Llc | Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
| CN104650976B (en) * | 2013-11-22 | 2016-07-13 | 中国石油天然气股份有限公司 | A kind of inferior heavy oil treatment process |
| US11414608B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor used with opportunity feedstocks |
| US11414607B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with increased production rate of converted products |
| US11421164B2 (en) | 2016-06-08 | 2022-08-23 | Hydrocarbon Technology & Innovation, Llc | Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product |
| US11732203B2 (en) | 2017-03-02 | 2023-08-22 | Hydrocarbon Technology & Innovation, Llc | Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling |
| US11118119B2 (en) | 2017-03-02 | 2021-09-14 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with less fouling sediment |
| CN108179028B (en) * | 2017-12-25 | 2020-03-31 | 中石化炼化工程（集团）股份有限公司 | Heavy oil processing method and system |
| CA3057131A1 (en) | 2018-10-17 | 2020-04-17 | Hydrocarbon Technology And Innovation, Llc | Upgraded ebullated bed reactor with no recycle buildup of asphaltenes in vacuum bottoms |
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|---|---|---|---|---|
| US4204943A (en) * | 1978-03-24 | 1980-05-27 | Exxon Research & Engineering Co. | Combination hydroconversion, coking and gasification |
| US4569752A (en) * | 1983-12-14 | 1986-02-11 | Exxon Research And Engineering Co. | Combination coking and hydroconversion process |
| CN1158883A (en) * | 1995-11-22 | 1997-09-10 | 中国石油化工总公司 | Hydrocracking process of heavy oil and residual oil in suspension bed |
| CN1162620A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Process for hydrogenation of heavy and residual oil by midium pressure suspension bed |
| CN1162621A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Dispersive catalyst for hydrogenation of heavy and residual oil |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4204943A (en) * | 1978-03-24 | 1980-05-27 | Exxon Research & Engineering Co. | Combination hydroconversion, coking and gasification |
| US4569752A (en) * | 1983-12-14 | 1986-02-11 | Exxon Research And Engineering Co. | Combination coking and hydroconversion process |
| CN1158883A (en) * | 1995-11-22 | 1997-09-10 | 中国石油化工总公司 | Hydrocracking process of heavy oil and residual oil in suspension bed |
| CN1162620A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Process for hydrogenation of heavy and residual oil by midium pressure suspension bed |
| CN1162621A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Dispersive catalyst for hydrogenation of heavy and residual oil |
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