CN1493665A - Medium pressure hydrocracking and catalytic cracking combined process for producing low sulfur diesel oil - Google Patents
Medium pressure hydrocracking and catalytic cracking combined process for producing low sulfur diesel oil Download PDFInfo
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Abstract
A combined medium-pressure hydrocracking-catalytic cracking process for preparing low-S diesel oil from heavy hydrocarbon and providing the hydrogenating material to FCC equipment features that the raw material sequentially passes through cracking stage and refining stage and the FCC diesel oil component is returned back to hydrorefining reactor for refining it further.
Description
Technical field
The present invention relates to a kind of unite FCC apparatus once by middle pressure hydrocracking technology, this technology in production part hydrocracking light-end products, the poor ignition quality fuel that provides the charging of hydrogenation pre-refining to go forward side by side an one-step refining FCC apparatus output for FCC apparatus.
Background technology
Environmental regulation makes the oil fuel quality index harsh day by day.With clean diesel production specification standard is example: sulphur, nitrogen content, cetane value, density, indexs such as aromaticity content are strict day by day, require less than 50 μ g/g as the sulphur content of Sweden II level diesel oil, and aromatic hydrocarbons is less than 10%.The standard of sulphur content less than 30-50 μ g/g prepared to carry out in 2007 by the U.S..
Catalytic cracking (FCC) device is the important source of gasoline, and it also is the main source of sulphur in gasoline and the diesel oil simultaneously.Reduce sulphur content in the FCC oil fuel and mean or handle the FCC raw material, or handle the FCC product.Handling the FCC product need handle various products, must adopt multiple processing mode, for example the processing of the processing of the processing of petroleum naphtha, light cycle oil, stack gas etc.Handle the FCC raw material as it is carried out the hydrogenation pre-treatment, these multiple last handling processes are all carried out in a device, and handle the FCC raw material and can improve and adorn FCC and put transformation efficiency, increase purpose product yield, reduce the sulphur content in gasoline and the diesel oil, also can reduce the discharging of SOx, help the lifting of device benefit, refinery's profit to increase.
Though FCC apparatus is based on the oil that steams, some refinery wishes with requiring season and the market requirement changes the ratio of product.Here mainly be meant for example production of diesel oil of distillate product.But, obtain the middle distillate oil that more comprises diesel oil and guarantee that its quality can deal with more and more harsher environmental requirement, simply the FCC raw material is carried out the hydrogenation pre-treatment, perhaps the FCC product is carried out hydro-upgrading, on production control and cost, all be faced with serious challenge.
Hydrocracking is converted into one of main oil refining process of raw material production high grade light-end products as heavy distillate inferior, in the handiness of producing, to the characteristics in the handiness of raw material adaptive flexibility and production control, more and more paid close attention to and deep research.Simultaneously, hydrocracking process not only can satisfy harsh day by day environmental requirement, and the rocket engine fuel and the clean diesel product of energy maximum production market in urgent need, by selection to hydrocracking catalyst, it can handle worse, more difficult cracked heavier feeds, this also meets the refinery, and to be faced with the density that is processed raw material more and more heavier, quality reality worse and worse.In this case, the diesel oil that obtained of FCC technology can not satisfy existing specification of quality and product fully and is in harmonious proportion needs.Therefore, hydrocracking be attached to the pretreated notion of FCC hydrofining in, not only can utilize the hydrogenating function of hydrocracking process to solve the raw material hydro-upgrading of FCC apparatus, and can make full use of that the selective splitting of hydrocracking catalyst and open loop are active to come voluminous intermediate oil and catalytic diesel oil circulation repeated hydrogenation, selective splitting, the open loop of poor quality is converted into fine distillate product.
Hydrogen pressure all has direct relation with the quality product that is obtained at hydrofining or hydrocracking process.And the weight of oil product and hydrogenation difficulty or ease also have direct relation.Depress hydrogenation reaction at high hydrogen branch and present first order reaction, reaction velocity constant can be weighed their hydrogenation reflection speed, studies have shown that the partial hydrogenation and the abscission ring speed of response maximum of polycyclic aromatic hydrocarbons, monocycle naphthenic abscission ring speed is less, and the hydrogenation speed of mononuclear aromatics and the speed of the complete hydrogenation of polycyclic aromatic hydrocarbons are all very little.Therefore intermediate oil is produced in the heavy-oil hydrogenation cracking, is preferably in higher hydrogen and depresses and carry out, and promotes the hydrogen balance that adds of condensed-nuclei aromatics in order to meaning.
US6387245 discloses a kind of hydrocracking process, and this process characteristic is that hydrocarbon material and the hot unconverted material of circulation cracked enter a high pressure hot separator after by the hydrocracking reaction section and carry in the reaction pressure therapeutic method to keep the adverse qi flowing downward with hydrogen-rich gas and obtain comprising hydrogen, hydrogen sulfide, ammonia and conversion product first vapor phase stream and defluent hot unconverted material liquid phase stream.The hydrogenation zone that this invention utilization is positioned at the high pressure hot separator bottom contacts the hydrogen of dirty material with Hydrobon catalyst and upper reaches, thereby it is made with extra care, and the hydrogen at upper reaches is carried the material gas that enters high pressure hot separator simultaneously.The per pass conversion of this technology is lower, generally at 15-45wt%.US5954944 discloses a kind of middle pressure hydrocracking technology of heavy hydrocarbon oil, this process using single hop tandem process, pressure comprises hydrocracking section and hydrofining section at 6.0-10MPa, and wherein hydrocracking catalyst and Hydrobon catalyst all contain the F modified component of 0.5-5wt%.And the middle pressure hydrocracking product can not reach the index request of clean fuel.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of diesel cycle purified and produce the middle pressure hydrocracking-catalytic cracking combined technology of clean fuel, being used for treatment of heavy hydrocarbon material obtains the high-quality intermediate oil and for FCC apparatus provides the material of hydrogenation, produces the low-sulfur diesel-oil of cleaning simultaneously.
The present invention relates to a kind of diesel cycle purified and produce the backward middle pressure hydrocracking-catalytic cracking combined technology of clean fuel, detailed process comprises:
(1) in the presence of hydrogen, petroleum hydrocarbon raw material contacted with hydrocracking catalyst at hydrocracking reactor and obtain material I;
(2) cracking material I enters hydrofining reactor and contacts with Hydrobon catalyst and obtain material II;
(3) material II enter behind gas-liquid separator that fractionating system obtains transforming light-end products comprise wide cut diesel fuel III and oil IV of the unconverted end;
(4) unconverted end oil IV enters FCC apparatus and carries out catalytic cracking and obtain light-end products and comprise catalytic diesel oil V;
(5) catalytic diesel oil V is back to that hydrofining reactor is refining to be re-refined.
The raw material of above-mentioned middle pressure hydrocracking technology is because through refining, and sulphur, nitrogen equal size are higher, therefore needs the hydrocracking catalyst of anti-sulphur, nitrogen.The present invention selects zeolite type hydrocracking catalyst and/or amorphous type hydrocracking catalyst:
The zeolite type hydrocracking catalyst, its composition comprises: (a) Y zeolite 1-30wt% is preferably 1～20wt%; (b) macropore refractory oxide 10-70wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.Wherein Y zeolite has following feature: SiO
2/ Al
2O
3Mol ratio is 5-20, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m
2/ g, infrared acidity 0.25-0.50mmol/g, Na
2O content＜0.2wt%.Above-mentioned macropore refractory oxide mainly comprises macroporous aluminium oxide (pore volume 0.8～1.5ml/g, specific surface 300～500m
2/ g), macropore sial (pore volume 0.8～1.5ml/g, specific surface 350～600m
2/ g, silica weight content 20%～60%) etc., the pore volume 0.4～0.8ml/g of little porous aluminum oxide, specific surface 150～300m
2/ g.
The amorphous type hydrocracking catalyst, its composition comprises: (a) acid amorphous aluminum silicide 10-75wt%; (b) aperture aluminum oxide 15-35wt%; (c) group vib metal oxide 10-40wt%; (d) VIII metal oxide 1-10wt%.Wherein acid invisible sial has following feature: SiO
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.Pore volume 0.4～the 0.8ml/g of above-mentioned little porous aluminum oxide, specific surface 150～300m
2/ g.
Technology of the present invention combines middle pressure hydrocracking and FCC technology, not only can utilize the hydrogenating function of hydrocracking process to solve the raw material hydro-upgrading of FCC apparatus, and can make full use of the selective splitting and the active next voluminous intermediate oil of open loop of hydrocracking catalyst.The present invention adopts first hydrocracking back end hydrogenation to make with extra care this backward (normal sequence is the cracking of first hydrofining back end hydrogenation) once by the hydrocracking flow process, make complex structure be difficult to remove the material of impurity such as sulphur, nitrogen, cracking is converted into the material that is easy to take off impurity, reaches the purpose that the degree of depth is taken off impurity under middle press strip spare.
Embodiment
Principal feature of the present invention is the combination and the reasonable assembly of scheme, and the operational condition of each technique unit is same as the prior art, and the formant process is as follows.
The present invention unites the backward of FCC apparatus, and (usually flow sequence is the cracking of first hydrofining back end hydrogenation, flow process of the present invention is that first hydrocracking back end hydrogenation is refining, therefore claims backward) be a kind of one-stage serial hydrocracking technical process that comprises the shared cover recycle hydrogen system of the series connection of hydrofining reactor and hydrocracking reactor once by middle pressure hydrocracking technology.The main petroleum hydrocarbon raw material of handling the heavy hydrocarbon material of 200-650 ℃ of boiling range is the vacuum gas oil that general frequent processing boiling range is 320-580 ℃.This middle pressure hydrocracking technology is the hydrocracking process that exists stock oil to contact with catalyzer at hydrogen, the reaction pressure 3～12Mpa of system, best 5～10Mpa; Hydrogen-oil ratio 100～5000,500～2000.The backward that the present invention the unites FCC apparatus once per pass conversion by the middle pressure hydrocracking technological process is preferably in 20-50wt% at 15-60wt%.The control of per pass conversion is based on the material balance of whole machinery, and Various Seasonal and and turn of the market product requirement is adjusted the output of gasoline and diesel oil.In addition, adapt to the different material cracking by control and reach the needed depth of conversion requirement of certain product quality indicator per pass conversion.Concrete reaction conditions can be determined by ordinary skill according to the requirement of feedstock property and products scheme.
The backward of the associating FCC apparatus that the present invention relates to can be conventional non-noble metal hydrogenation catalyst for refining by the employed Hydrobon catalyst of middle pressure hydrocracking technological process once, 3936 catalyzer of producing as the Fushun Petrochemical Company catalyst plant, 3996 catalyzer etc.
The backward of the associating FCC apparatus that the present invention relates to once can be used a kind of single amorphous type hydrocracking catalyst or a kind of single zeolite type hydrocracking catalyst by the middle pressure hydrocracking technological process; Also can be that two kinds of hydrocracking catalysts mix or grating is used, comprise the mechanically mixing filling.Because what relate to is a kind of backward hydrocracking flow process, therefore no matter use the sort of catalyzer or use which kind of catalyst combination loading mode, the hydrocracking catalyst of selection must have high anti-nitrogen/anti-nitrogen ability.Amorphous type hydrocracking catalyst itself just is to use under single hop list agent technology; The zeolite type hydrocracking catalyst then is that certain range of choice is arranged.Usually, the employed zeolite component content of the so high anti-nitrogen/zeolite type of anti-nitrogen hydrocracking catalyst is lower, and acidity is also lower, and Y zeolite is used more generally.Except selecting the lower tart Y zeolite that has of ad hoc approach processing for use, for Preparation of Catalyst, cooperate with other carrier component by the zeolite content of selecting to suit, make it on catalyzer, have moderate acid site density, the catalyzer coking inactivation that also can avoid the multidigit condensation reaction of intensive strong acid center to cause, with suitable hydrogenation active centre synergy, therefore has stronger anti-nitrogen performance simultaneously.In addition, this backward once by the hydrocracking flow process because the characteristics of the catalyzer that uses will help the improvement of middle distillates oil selectivity to a certain extent.
The modification treating processes of the Y zeolite of high anti-nitrogen/anti-nitrogen ability is as follows: with Na
2O content is raw material less than the Y zeolite of 3.0wt%, places the high-temperature roasting stove, at self water vapour or feed water vapour, and 450-600 ℃, under the 0.01-0.2MPa pressure water steam roasting 0.5-3.0 hour.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, and at self water vapour or feeding water vapour, 550-700 ℃, 0.01-1.0MPa pressure water steam was handled 0.5-10 hour down, promptly got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.The above-mentioned super-hydrophobic Y zeolite that obtains with chemical process dealuminzation optionally, can be got SiO
2/ Al
2O
3Mol ratio is the super-hydrophobic Y zeolite of 5-20.
The FCC process adopts common catalyzer and processing condition.
Embodiment 1
The present invention program is: (1) at hydrocracking reactor, with petroleum hydrocarbon raw material and hydrocracking catalyst at volume space velocity 0.92h
-1Contact obtains material I; (2) at hydrofining reactor, cracking material I makes with extra care Medium diesel oil at volume space velocity 0.92h with waiting
-1Contact with Hydrobon catalyst and to obtain material II; (3) material II enter behind gas-liquid separator that fractionating system obtains transforming light-end products comprise wide cut diesel fuel III and oil IV of the unconverted end; (4) unconverted end oil IV enters FCC apparatus and carries out the light-end products that catalytic cracking obtains comprising catalytic diesel oil V; (5) catalytic diesel oil V is back to that hydrofining reactor is refining to be re-refined.
The catalyst loading scheme: hydrofining reactor loads 3936 Hydrobon catalysts.Hydrocracking reactor loads a kind of Y zeolite type hydrocracking reactor, and catalyzer consists of: Y zeolite 20wt%, sial (specific surface 520m
2/ g, SiO
2Content 35wt%, pore volume 1.2ml/g) 25wt%, little porous aluminum oxide (specific surface 240m
2/ g, pore volume 0.4ml/g) 25wt%, nickel oxide 8wt%, Tungsten oxide 99.999 22wt%.
Y zeolite modifying process wherein is as follows: with Na
2O content is less than the SiO of 3.0wt%
2/ Al
2O
3Be that 5 Y zeolite is a raw material, place the high-temperature roasting stove, feed water vapour, 580 ℃, roasting is 2.0 hours under the 0.12MPa pressure water steam.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, is feeding water vapour, and 600 ℃, 0.4MPa pressure water steam was handled 7.0 hours down, got super-hydrophobic Y zeolite.With the above-mentioned super-hydrophobic Y zeolite concentration that obtains is the nitric acid treatment of 1.0mol/L, obtains SiO
2/ Al
2O
3Mol ratio is 18 super-hydrophobic Y zeolite.The secondary pore pore volume that obtains Y zeolite 2～10nm accounts for 45% of total pore volume, specific surface 705m
2/ g, infrared acidity 0.28mmol/g.
This process program is handled a kind of heavy vacuum distillate VGO, and this petroleum hydrocarbon material main character is: proportion 0.8985cm
3/ g, 340 ℃-545 ℃ of boiling ranges, carbon residue 0.20wt%, sulphur 1.78wt%, nitrogen 1420 μ g/g.The sulphur content of purified catalytic diesel oil of wherein circulating is 2000 μ g/g.
This process program operating parameters: reaction pressure 9.5MPa, hydrogen-oil ratio 1500.Hydrofining section air speed 0.92h
-1, hydrocracking section air speed 0.92h
-1
392 ℃ of hydrocracking average reaction temperature, per pass conversion 50wt%; 385 ℃ of hydrofining section average reaction temperature.The sulphur content of product diesel oil is 45 μ g/g.
Embodiment 2
Flow process is identical with embodiment 1, changes part to be:
Hydrocracking catalyst is selected a kind of amorphous silicon catalyzer for use, consists of: (a) acid amorphous aluminum silicide 50wt%; (b) aperture aluminum oxide 20wt%; (c) Tungsten oxide 99.999 21wt%; (d) nickel oxide 9wt%.Wherein acid invisible sial has following feature: SiO
2Content is 45%, specific surface 480m
2/ g, pore volume 1.0ml/g, infrared acidity 0.5mmol/g.The pore volume 0.4ml/g of above-mentioned little porous aluminum oxide, specific surface 240m
2/ g.
410 ℃ of cracking zone temperature of reaction, reaction pressure 9.5MPa, hydrogen-oil ratio 1500, hydrocracking section air speed 0.8h
-1, 385 ℃ of hydrofining section average reaction temperature, hydrofining section air speed is 0.8h
-1Per pass conversion 45%.The sulphur content 45 μ g/g of diesel product.
Embodiment 3
Flow process is identical with embodiment 1, changes part to be:
Catalyzer consists of: Y zeolite 10wt%, sial (specific surface 520m
2/ g, SiO
235wt%, pore volume 1.2ml/g) 35wt%, little porous aluminum oxide (specific surface 240m
2/ g, pore volume 0.4ml/g) 25wt%, nickel oxide 8wt%, Tungsten oxide 99.999 22wt%.
Wherein Y zeolite modification treating processes is as follows: with Na
2O content is the SiO of 3.0wt%
2/ Al
2O
3Be that 5 Y zeolite is a raw material, place the high-temperature roasting stove, feed water vapour, 500 ℃, roasting is 0.8 hour under the 0.5MPa pressure water steam.Carry out ion-exchange techniques then and make Na
2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation
2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, is feeding water vapour, and 650 ℃, 0.8MPa pressure water steam was handled 2 hours down, got super-hydrophobic Y zeolite.With the above-mentioned super-hydrophobic Y zeolite concentration that obtains is the nitric acid treatment of 0.5mol/L, obtains Y zeolite character and is: SiO
2/ Al
2O
3Mol ratio is that the secondary pore pore volume of 14,2～10nm accounts for 38% of total pore volume, specific surface 670m
2/ g, infrared acidity 0.3mmol/g.
This process program operating parameters: reaction pressure 9.5MPa, hydrogen-oil ratio 1500.Hydrofining section air speed 0.9h
-1, hydrocracking section air speed 1.0h
-1
390 ℃ of hydrocracking average reaction temperature, per pass conversion 40wt%; 385 ℃ of hydrofining section average reaction temperature.Product diesel oil sulphur content is 45 μ g/g.
Claims (10)
1, a kind of middle pressure hydrocracking and catalytic cracking combined technology of producing low-sulfur diesel-oil is characterized in that technological process comprises:
(1) in the presence of hydrogen, petroleum hydrocarbon raw material contacted with hydrocracking catalyst at hydrocracking reactor and obtain material I;
(2) cracking material I enters hydrofining reactor and contacts with Hydrobon catalyst and obtain material II;
(3) material II enter behind gas-liquid separator that fractionating system obtains transforming light-end products comprise wide cut diesel fuel III and oil IV of the unconverted end;
(4) unconverted end oil IV enters FCC apparatus and carries out catalytic cracking and obtain light-end products and comprise catalytic diesel oil V and light cycle VI;
(5) catalytic diesel oil V is back to that hydrofining reactor is refining to be re-refined.
2,, it is characterized in that described middle pressure hydrocracking technology use zeolite type hydrocracking catalyst and/or amorphous type hydrocracking catalyst according to the described technology of claim 1.
3, according to the described technology of claim 2, it is characterized in that described zeolite type hydrocracking catalyst, its composition comprises: (a) Y zeolite 1-30wt%; (b) macropore refractory oxide 10-70wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%; Wherein Y zeolite has following feature: SiO
2/ Al
2O
3Mol ratio is 5-20, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m
2/ g, infrared acidity 0.25-0.50mmol/g, Na
2O content＜0.2wt%.
4, according to the described technology of claim 2, it is characterized in that described amorphous type hydrocracking catalyst, its composition comprises: (a) acid amorphous aluminum silicide 10-75wt%; (b) macropore refractory oxide 10-75wt%; (c) aperture aluminum oxide 15-35wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%; Wherein acid invisible sial has following feature: SiO
2Content is 20～60%, specific surface 350-600m
2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.Pore volume 0.4～the 0.8ml/g of above-mentioned little porous aluminum oxide, specific surface 150～300m
2/ g.
5,, it is characterized in that described petroleum hydrocarbon raw material is boiling range 200-650 ℃ a heavy hydrocarbon material according to the described technology of claim 1.
6,, it is characterized in that described heavy hydrocarbon material is a vacuum gas oil according to the described technology of claim 5.
7,, it is characterized in that described middle pressure hydrocracking technology is the hydrocracking process that exists stock oil to contact with catalyzer at hydrogen, the reaction pressure 3～12MPa of system according to the described technology of claim 1.
8,, it is characterized in that described reaction pressure is 5～10MPa according to the described technology of claim 7.
9, according to the described technology of claim 1, the per pass conversion that it is characterized in that described middle pressure hydrocracking technological process is 15-60wt%.
10,, it is characterized in that described per pass conversion is 20-50wt% according to the described technology of claim 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144537 CN1202218C (en) | 2002-11-02 | 2002-11-02 | Medium pressure hydrocracking and catalytic cracking combined process for producing low sulfur diesel oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144537 CN1202218C (en) | 2002-11-02 | 2002-11-02 | Medium pressure hydrocracking and catalytic cracking combined process for producing low sulfur diesel oil |
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| Publication Number | Publication Date |
|---|---|
| CN1493665A true CN1493665A (en) | 2004-05-05 |
| CN1202218C CN1202218C (en) | 2005-05-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443572C (en) * | 2005-09-28 | 2008-12-17 | 中国石油化工股份有限公司 | Hydrogenation cracking method of high-output diesel oil from high-nitrogen content heavy raw material |
| CN101333459B (en) * | 2007-06-26 | 2012-03-07 | 中国石油化工股份有限公司 | Hydrogenation conversion process |
| CN102453537A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation |
| CN105713662A (en) * | 2016-01-27 | 2016-06-29 | 北京宝塔三聚能源科技有限公司 | Hydrotreating and catalytic cracking combined process |
| CN107345155A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
-
2002
- 2002-11-02 CN CN 02144537 patent/CN1202218C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443572C (en) * | 2005-09-28 | 2008-12-17 | 中国石油化工股份有限公司 | Hydrogenation cracking method of high-output diesel oil from high-nitrogen content heavy raw material |
| CN101333459B (en) * | 2007-06-26 | 2012-03-07 | 中国石油化工股份有限公司 | Hydrogenation conversion process |
| CN102453537A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation |
| CN102453537B (en) * | 2010-10-14 | 2014-07-23 | 中国石油化工股份有限公司 | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation |
| CN105713662A (en) * | 2016-01-27 | 2016-06-29 | 北京宝塔三聚能源科技有限公司 | Hydrotreating and catalytic cracking combined process |
| CN105713662B (en) * | 2016-01-27 | 2017-12-19 | 北京宝聚能源科技有限公司 | A kind of group technology of hydrotreating and catalytic cracking |
| CN107345155A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
| CN107345155B (en) * | 2016-05-05 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
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| Publication number | Publication date |
|---|---|
| CN1202218C (en) | 2005-05-18 |
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