CN102604669A - Method for preparing chemical material by hydrocracking of heavy hydrocarbon oil - Google Patents
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Abstract
The invention relates to a method for preparing a chemical material by hydrocracking of heavy hydrocarbon oil, which comprises the step of catalytically hydrogenating a heavy hydrocarbon oil raw material with the nitrogen content of 0.1-2000mug/g by controlling the distillation range to 250-570 DEG C, wherein a catalyst comprises in percentage by weight: 10-65% of small crystalline ultra-stable Y-type molecular sieves, 10-60% of amorphous silicon aluminum, 10-60% of alumina, 12-30% of a metal oxide of the VIB group and 3-8% of a metal oxide of the VIII group; and the small crystalline ultra-stable Y-type molecular sieves are obtained by the steps of performing ammonium exchange on small crystalline NaY-type molecular sieves with high silicon-aluminum ratio and then performing hydrothermal treatment, wherein a silicon-aluminum ratio (a molar ratio of SiO2 to Al2O3) of a NaY framework is 6.0-7.0. The range of heavy raw oil suitable to be processed by the method is very wide, and the catalyst reflects high activity and high chemical material yield.
Description
Technical field
The present invention relates to the method that a kind of heavy hydrocarbon oil hydrogen cracking prepares industrial chemicals, this method is that the method with hydrogen cracking is converted into light naphthar, high arene underwater content heavy naphtha and low BMCI value tail oil with heavy hydrocarbon oil.
Background technology
Along with developing rapidly of petrochemical complex industry, China increases all kinds of industrial chemicals increasing demand.But the aggravation of crude oil heaviness and inferiorization trend, the ratio of suitable for producing industrial chemicals reduces day by day, thereby the industrial chemicals shortage becomes the bottleneck of serious restriction chemical industry development.According to statistics, China's ethylene yield was 626.64 ten thousand tons/year in 2004, and along with the newly-built and reorganization and expansion of cracking ethylene preparation device, ethylene yield increased to 1,050 ten thousand tons/year in 2007, increased about 19% every year; And the same period clean fuel average annual amplification about 9.0%, the speedup of preparing ethylene by steam cracking raw material consumption is a times of clean fuel rate of growth.The required industrial chemicals of the year two thousand twenty will reach 8,700 ten thousand tons, and petroleum refining industry only can provide 6,080 ten thousand tons, and breach will reach 26,000,000 tons.Therefore, the refinery of 21 century will make the transition to producing the incorporate oil refining enterprise of refinery that clean fuel and industrial chemicals are laid equal stress on from being main to produce oil product.
Hydrocracking technology is as one of important secondary processing means of heavy oil lighting; Because have that adaptability to raw material is strong, operation and products scheme flexibly and characteristics such as good product quality; Being proved to be the technology of modern oil refining enterprise oil, change combination, is production high-quality clean fuel and the important channel that solves the industrial chemicals source.Existing hydrocracking technology more is to produce fine automobile-used (or aircraft is used) transport fuel, to the correlation technique that is used for the more producing chemical industry raw material seldom.
US5447623 discloses a kind of hydrocracking catalyst.This catalyzer is made up of inorganic refractory oxide, Beta molecular sieve, the carrier loaded group vib of Y molecular sieve and group VIII metal component, and wherein the lattice constant of Y molecular sieve is preferably 2.425nm～2.435nm.When being used for the purpose of voluminous petroleum naphtha, the usage quantity of two kinds of molecular sieves is higher, general＞50%, so catalyzer shows higher activity and naphtha yield.Owing to used two kinds of molecular sieves, catalyst preparation process is comparatively complicated.
CN1174756 discloses a kind of light oil type hydrogen cracking catalyst, and catalyzer consists of high silica alumina ratio Y molecular sieve, little porous aluminum oxide, Tungsten oxide 99.999, nickel oxide.Used molecular sieve is the low-Na and high-Si Y-type molecular sieve that obtains after handling through the hexafluorosilicic acid aqueous ammonium in the carrier, and little porous aluminum oxide is the pseudo-boehmite crystalline phase.Because the moulding Y molecular sieve is carried out ammonium hexafluorosilicate solution-treated and steam treatment; Character such as the percent crystallinity of molecular sieve and specific surface, pore structure all can variation; And use the fluorine-containing aqueous solution in the treating processes, molecular sieve inevitably contains the low amount of fluorinated thing, influences the stability of catalyzer.
CN1727447 discloses a kind of hydrocracking catalyst and preparation method thereof.This catalyzer is made up of the carrier loaded group vib and the group VIII metal component that contain matrix and zeolite, and wherein said zeolite is a P-contained zeolite, is benchmark in oxide compound and with said zeolite, and the content of phosphorus is 0.1wt%～15wt%.When this catalyzer is used for the hydrocarbon hydrocracking reaction, have higher intermediate oil selectivity, but the heavy naphtha selectivity ratios is lower.
Summary of the invention
The purpose of this invention is to provide the method that a kind of heavy hydrocarbon oil hydrogen cracking prepares industrial chemicals.Adopting one-stage serial technology, is high-quality industrial chemicals such as raw material production light naphthar, heavy naphtha and hydrocracking tail oil with heavy hydrocarbon oil.Wherein, the heavy naphtha of production has the characteristics of low-sulfur, low nitrogen and high arene underwater content (being called for short virtue dives), can be directly as catalytic reforming raw material; Light naphthar and tail oil have characteristics such as low-sulfur, low nitrogen and saturated hydrocarbon content height, can be directly as the preparing ethylene by steam cracking raw material.
A kind of heavy hydrocarbon oil hydrogen cracking of the present invention prepares the method for industrial chemicals; Be at 250 ℃～570 ℃ with the boiling range scope; Nitrogen content is in the heavy hydrocarbon oil catalytic material hydrogenation reaction of 0.1 μ g/g～2000 μ g/g; 330 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 8MPa～20MPa, volume space velocity 0.5hr during liquid
-1～3.0hr
-1, hydrogen to oil volume ratio is 500: 1～2000: 1;
Used hydrocracking catalyst; With amorphous aluminum silicide, aluminum oxide is carrier; With little crystal grain super-stable Y molecular sieves is acidic components; With group vib metal and VIII family metal is the hydrogenation activity component, and wherein the group vib metal oxide content is 10wt%～40wt%, is preferably 12wt%～30wt%.VIII family metal oxide content is 1wt%～15wt%, is preferably 3wt%～8wt%.
The weight of the employed little crystal grain super-stable Y molecular sieves of preparation industrial chemicals type hydrocracking catalyst is 10wt%～65wt%, is preferably 20wt%～50wt%, the skeleton SiO of little crystal grain super-stable Y molecular sieves
2/ Al
2O
3Mol ratio 6.0～20.0 is preferably 9.0～18.0, and crystal grain diameter 100nm～700nm is preferably 100nm～300nm, and lattice constant is 2.436nm～2.444nm, and sodium oxide content is lower than 2.0wt%.
Preparation of catalysts method of the present invention is following:
(1) amorphous aluminum silicide involved in the present invention, aluminum oxide, little crystal grain super-stable Y molecular sieves, tackiness agent and extrusion aid are mixed; Extruded moulding; Support shapes is generally cylindrically after the extrusion, also can be made into special-shaped bars such as trifolium, and above-mentioned forming composition drying is prepared into carrier.
(2) (1) is prepared carrier carries out roasting.
(3) with the compound preparation dipping solution that contains the active metal component element.
(4) carrier that step (2) is worth floods with the solution that step (3) is worth, and dry, roasting make catalyzer of the present invention.
Its medium and small crystal grain super-stable Y molecular sieves is to be SiO with framework si-al ratio
2/ Al
2O
3After the ammonium exchange, further again hydrothermal treatment consists obtains mol ratio at the small crystal grain NaY molecular sieve between 6.0～7.0, and concrete preparation method is:
The little crystal grain high silica alumina ratio NaY of raw material type molecular sieve is added NH
4Carry out the ammonium exchange first time in the Cl aqueous solution.The mass ratio of each material, NaY: NH
4Cl: H
2O is 1: (0.5～2.0): (5～20), 50 ℃～120 ℃ of liquid temps of exchange, stirrings swap time is 0.5hr～24hr, uses 0.1mol/L～5mol/L hydrochloric acid soln to regulate and exchanges liquid pH value between 2.0～6.0.After the exchange, suction filtration, washing, drying is collected after grinding to form fine powder, obtains NH4NaY.Place retort furnace to above-mentioned NH4NaY molecular sieve, temperature programming to 500 ℃～800 ℃, roasting 1hr～6hr obtains the HY sample.The HY sample is carried out the ammonium exchange second time, and method is with ammonium exchange for the first time.Sample after the ammonium exchange for the second time carries out hydrothermal treatment consists again, and condition is temperature programming to 500 ℃～800 ℃, handles 1hr～6hr under 20%～100% water vapor condition, obtains little crystal grain super-stable Y molecular sieves.
The used amorphous silicon aluminium of catalyzer of the present invention can be by coprecipitation method or grafting copolymerization process preparation, press in the document ordinary method and prepares and get final product.SiO in the amorphous silicon aluminium that makes
2Content be 10wt%～60wt%, be preferably 30wt%～50wt%.The pore volume of amorphous silicon aluminium is 0.5ml/g～1.2ml/g, is preferably 0.8ml/g～1.2ml/g; Specific surface area is 200m
2/ g～550m
2/ g is preferably 350m
2/ g～550m
2/ g.
The used aluminum oxide of the present invention is macroporous aluminium oxide and/or little porous aluminum oxide, and wherein the macroporous aluminium oxide pore volume is 0.25ml/g～1.2ml/g, is preferably 0.8ml/g～1.1ml/g, and specific surface area is 100m
2/ g～600m
2/ g is preferably 300m
2/ g～450m
2/ g.Aperture aluminum oxide pore volume is that 0.1ml/g～0.6ml/g is preferably 0.4ml/g～0.6ml/g, specific surface area 100m
2/ g～450m
2/ g is preferably 180m
2/ g～340m
2/ g.
The used sticker of the present invention is to be processed by a kind of mineral acid.Used mineral acid can be one or both in hydrochloric acid, nitric acid, phosphoric acid and the sulfuric acid.
Extrusion aid of the present invention is the sesbania powder, and its content is 1.5wt%～5.0wt%.
Catalyzer specifically prepares process: amorphous aluminum silicide, aluminum oxide, little crystal grain super-stable Y molecular sieves are closed put into the mixed 30min～60min of stone roller of rolling machine; After mixing; The mixing solutions that adds sticker, vaal water; Carrier is processed in moulding on banded extruder, carrier temperature programming to 400 ℃～700 ℃ of roasting 2hr～8hr.
The impregnation method of carrier can be an incipient impregnation, also can be the supersaturation dipping, and time of immersion is 0.5hr～10hr, and soaked carrier is at 100～150 ℃ of dry 1hr～12hr, and 450 ℃～600 ℃ roasting 1hr～8hr make catalyzer of the present invention.
Catalyzer of the present invention is used for hydrocracking process; The heavy feed stock scope that is fit to processing is very wide; Can comprise coker gas oil, vacuum gas oil, atmospheric gas oil, the various heavy hydrocarbon chargings of dewaxing wet goods and compound thereof; The boiling range scope of raw material is at 250 ℃～570 ℃, nitrogen content 0.1 μ g/g～2000 μ g/g.
Catalyzer of the present invention is preferably under the one-stage serial hydrocracking condition and moves, and the hydrogenation pre-refining is used for removing the most of the nitrogen and the saturated polycyclic aromatic hydrocarbons of raw oil, to reduce the severity of hydrogen cracking section operation, gives full play to the activity of hydrocracking catalyst.Catalyzer of the present invention is when handling various heavier hydrocarbon feeds, and catalyzer needs prevulcanized to handle, and processing condition are conventional hydrocracking condition, like 330 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 8MPa～20MPa, volume space velocity 0.5hr during liquid
-1～3.0hr
-1, hydrogen to oil volume ratio is 500: 1～2000: 1.
Characteristics of the present invention are: adopted the carrier component of little crystal grain super-stable Y molecular sieves as catalyzer.Little crystal grain super-stable Y molecular sieves has high outer surface area, can better disperse hydrogenation metal, exposes more hydrogenation sites.Along with crystal grain diminishes, the molecular sieve pore passage path shortens, and has shortened the distance of hydrogenation metal and acidic site, and two kinds of active sites can be cooperated more closely, improves the selectivity and the yield of target product to greatest extent.Simultaneously, the crystal grain intracrystalline diffusional limitation that makes reactant that diminishes weakens, and reactant can react by the very fast acid sites that touches on the one hand, strengthens cracking activity; On the other hand, reaction product again can very fast spreading out, and reduces overcracking and hydrogen transfer reactions, thereby reduce green coke.But the surface energy of small crystal grain molecular sieve is bigger, usually can cause its stability under the critical operation condition to reduce.The little crystal grain ultra-steady Y molecular sieve that the present invention relates to, use be little crystal grain high silica alumina ratio NaY molecular sieve (skeleton SiO
2/ Al
2O
3Mol ratio 6.0～7.0) starting material for preparing are because more conventional NaY molecular sieve (the skeleton SiO of silica alumina ratio
2/ Al
2O
3About mol ratio 5.0) height, so its stability improves greatly, overcome the weakness of conventional small crystal grain molecular sieve this respect fully.
Embodiment
Embodiment 1
With little crystal grain high silica alumina ratio NaY type molecular sieve (skeleton SiO
2/ Al
2O
3Mol ratio 6.2, crystal grain diameter 200nm～300nm, lattice constant are 2.462nm) adding NH
4Carry out the ammonium exchange first time in the Cl aqueous solution.The mass ratio NaY of each material: NH
4Cl: H
2O is 1: 0.5: 5,50 ℃ of liquid temps of exchange, and stirrings swap time is 24hr, uses the 5mol/L hydrochloric acid soln to regulate and exchanges liquid pH value between 2.1～2.2.After the exchange, suction filtration, washing, drying is collected after grinding to form fine powder, obtains NH
4NaY.Above-mentioned NH
4The NaY molecular sieve places retort furnace, temperature programming to 500 ℃, and roasting 6hr obtains the HY sample.The HY sample is carried out the ammonium exchange second time, and method is with ammonium exchange for the first time.Sample after the ammonium exchange for the second time carries out hydrothermal treatment consists again, and condition is temperature programming to 500 ℃, handles 6hr under the 100% water vapor condition, obtains Y zeolite I character and sees table 1.
Embodiment 2
Little crystal grain high silica alumina ratio NaY type molecular sieve is added NH
4Carry out the ammonium exchange first time in the Cl aqueous solution.The mass ratio NaY of each material: NH
4Cl: H
2O is 1: 1.2: 12,90 ℃ of liquid temps of exchange, and stirrings swap time is 12hr, uses the 2mol/L hydrochloric acid soln to regulate and exchanges liquid pH value between 3.5～3.6.After the exchange, suction filtration, washing, drying is collected after grinding to form fine powder, obtains NH
4NaY.Above-mentioned NH
4The NaY molecular sieve places retort furnace, temperature programming to 600 ℃, and roasting 4hr obtains the HY sample.The HY sample is carried out the ammonium exchange second time, and method is with ammonium exchange for the first time.Sample after the ammonium exchange for the second time carries out hydrothermal treatment consists again, and condition is temperature programming to 650 ℃, handles 4hr under the 50% water vapor condition, obtains Y zeolite II character and sees table 1.
Embodiment 3
Little crystal grain high silica alumina ratio NaY type molecular sieve is added NH
4Carry out the ammonium exchange first time in the Cl aqueous solution.The mass ratio NaY of each material: NH
4Cl: H
2O is 1: 2.0: 20,120 ℃ of liquid temps of exchange, and stirrings swap time is 0.5hr, uses the 0.1mol/L hydrochloric acid soln to regulate and exchanges liquid pH value between 4.8～4.9.After the exchange, suction filtration, washing, drying is collected after grinding to form fine powder, obtains NH
4NaY.Above-mentioned NH
4The NaY molecular sieve places retort furnace, temperature programming to 800 ℃, and roasting 1hr obtains the HY sample.The HY sample is carried out the ammonium exchange second time, and method is with ammonium exchange for the first time.Sample after the ammonium exchange for the second time carries out hydrothermal treatment consists again, and condition is temperature programming to 750 ℃, handles 1hr under the 20% water vapor condition, obtains Y zeolite III character and sees table 1.
Embodiment 4
Present embodiment prepares hydrocracking catalyst I, and concrete steps are following:
With 89.5g Y zeolite I (physico-chemical property is seen table 1), the amorphous aluminum silicide (SiO of 82.4g
2Content 38wt%, pore volume 0.98ml/g, specific surface area 420m
2/ g), 8.9 macroporous aluminium oxides (pore volume 1.01ml/g, specific surface area 380m
2/ g), 25.4 little porous aluminum oxide (pore volume 0.53ml/g, specific surface area 220m
2/ g) put into rolling machine with 6.0g sesbania powder, mix and grind 30min, add the mixing solutions of 9.5g concentrated nitric acid (96wt%) and 170g water behind the mixing, be extruded into the cylindrical bar of 1.5mm, 110 ℃ of dry 8hr, roasting 8hr gets support of the catalyst in 500 ℃ of air atmospheres.Be dissolved in the solution room temperature dipping 2hr of 100ml water again with 66.9g nickelous nitrate, 83.3g ammonium metawolframate, 110 ℃ of dry 8hr, roasting 8hr in 450 ℃ of air atmospheres makes hydrocracking catalyst I of the present invention, and character is seen table 2.
Embodiment 5
Present embodiment prepares hydrocracking catalyst II, and concrete steps are following:
With 52.1g Y zeolite II (physico-chemical property is seen table 1); 61.5g amorphous aluminum silicide, 32.1 macroporous aluminium oxides, 27.6 little porous aluminum oxides and 5.2g sesbania powder put into rolling machine; Mix and grind 30min, add the mixing solutions of 8.4g concentrated nitric acid (96wt%) and 198g water behind the mixing, be extruded into the cylindrical bar of 1.5mm; 120 ℃ of dry 6hr, roasting 6hr gets support of the catalyst in 550 ℃ of air atmospheres.Be dissolved in the solution room temperature dipping 2hr of 100ml water again with 44.2g nickelous nitrate, 79.6g ammonium metawolframate, 120 ℃ of dry 6hr, roasting 6hr in 500 ℃ of air atmospheres makes hydrocracking catalyst II of the present invention, and character is seen table 2.
Embodiment 6
Present embodiment prepares hydrocracking catalyst III, and concrete steps are following:
With 147.8g Y zeolite III (physico-chemical property is seen table 1), the amorphous aluminum silicide (SiO of 95.1g
2Content 38wt%, pore volume 0.98ml/g, specific surface area 420m
2/ g), 19.5 macroporous aluminium oxides (pore volume 1.01ml/g, specific surface area 380m
2/ g), 33.2 macroporous aluminium oxides (pore volume 0.53ml/g, specific surface area 220m
2/ g) put into rolling machine with 7.8g sesbania powder, mix and grind 30min, add the mixing solutions of 12.4g concentrated nitric acid (96wt%) and 221g water behind the mixing, be extruded into the cylindrical bar of 1.5mm, 130 ℃ of dry 2hr, roasting 4hr gets support of the catalyst in 600 ℃ of air atmospheres.Be dissolved in the solution room temperature dipping 2hr of 100ml water again with 89.4g nickelous nitrate, 98.1g ammonium metawolframate, 130 ℃ of dry 2hr, roasting 4hr in 550 ℃ of air atmospheres makes hydrocracking catalyst III of the present invention, and character is seen table 2.
Comparative example
A kind of industrial chemicals type hydrocracking catalyst IV (metal component is the catalyzer of W-Ni) of industrial application.
Embodiment 7
Get catalyst I, catalyst I I, catalyst I II and catalyst I V among the embodiment; With the high nitrogen heavy of high-sulfur VGO is raw material (character is seen table 3); On 200ml small stationary bed hydroprocessing evaluating apparatus, estimate appreciation condition: reaction stagnation pressure 15.0MPa, 380 ℃ of temperature of reaction; Hydrogen to oil volume ratio 1500: 1, air speed 1.5hr
-1Concrete steps are following:
(1) with vacuum distillate (VGO) raw material under the hydrogenation pretreatment condition, through hydrogen cracking pretreatment catalyst bed, remove impurity such as sulphur, nitrogen, carry out the aromatic hydrocarbons fractional saturation simultaneously;
(2) reaction stream that step (1) is obtained carries out hydrogen cracking under the condition of gas-liquid separation through the hydrocracking catalyst bed;
(3) reaction product that step (2) is obtained is separated, and obtains comprising various light-end productss and hydrogenation tail oils such as light naphthar, heavy naphtha, kerosene, diesel oil.
Each evaluating catalyst result sees table 4.
The character of table 1Y type molecular sieve
| Sample number into spectrum | I | II | III |
| Skeleton SiO 2/Al 2O 3 | 14.7 | 13.9 | 13.4 |
| Lattice constant, nm | 2.440 | 2.438 | 2.442 |
| Sodium oxide, wt% | 0.51 | 0.21 | 0.45 |
The composition and the character of each embodiment gained hydrocracking catalyst of table 2
Table 3 raw oil character
| Raw oil | VGO |
| Boiling range, ℃ | |
| Over point | 207 |
| 30％ | 407 |
| 50％ | 439 |
| 70％ | 467 |
| Final boiling point | 537 |
| Density, g/cm 3(20℃) | 0.9065 |
| The BMCI value | 45.0 |
| Condensation point, ℃ | 27.2 |
| Total sulfur, μ g/g | 12000 |
| Total nitrogen, μ g/g | 1179 |
| Form wt% | |
| Paraffinic hydrocarbons | 18.3 |
| Naphthenic hydrocarbon | 40.8 |
| Aromatic hydrocarbons | 40.9 |
Table 4 evaluating catalyst result
Annotate: industrial chemicals total recovery=light naphthar yield+heavy naphtha yield+tail oil yield
Claims (3)
1. a heavy hydrocarbon oil hydrogen cracking prepares the method for industrial chemicals; It is characterized in that: with the boiling range scope at 250 ℃～570 ℃; Nitrogen content is in the heavy hydrocarbon oil catalytic material hydrogenation reaction of 0.1 μ g/g～2000 μ g/g; 330 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 8MPa～20MPa, volume space velocity 0.5hr during liquid
-1～3.0hr
-1, hydrogen to oil volume ratio is 500: 1～2000: 1;
Catalyzer 100% is counted by weight: little crystal grain super-stable Y molecular sieves 10～65%, amorphous aluminum silicide 10～60%, aluminum oxide 10～60%, group vib MOX 12～30%, VIII family metal oxide 3～8%;
Little crystal grain super-stable Y molecular sieves be by little crystal grain high silica alumina ratio NaY type molecular sieve after ammonium exchange, obtain through hydrothermal treatment consists again, wherein the framework si-al ratio of NaY is SiO
2/ Al
2O
3Mol ratio is between 6.0～7.0;
Little crystal grain high silica alumina ratio NaY type molecular sieve ammonium switching method is following:
The little crystal grain high silica alumina ratio NaY of raw material type molecular sieve is added NH
4Carry out the ammonium exchange first time in the Cl aqueous solution, the mass ratio of each material, NaY: NH
4Cl: H
2O is 1: (0.5～2.0): (5～20), 50 ℃～120 ℃ of liquid temps of exchange, stirrings swap time is 0.5hr～24hr, uses 0.1mol/L～5mol/L hydrochloric acid soln to regulate and exchanges liquid pH value between 2.0～6.0; After the exchange, suction filtration, washing, drying is collected after grinding to form fine powder, obtains NH
4NaY; Above-mentioned NH
4The NaY molecular sieve places retort furnace, temperature programming to 500 ℃～800 ℃, and roasting 1hr～6hr obtains the HY sample; The HY sample is carried out the ammonium exchange second time, and method is with ammonium exchange for the first time; Sample after the ammonium exchange for the second time carries out hydrothermal treatment consists again, and condition is temperature programming to 500 ℃～800 ℃, handles 1hr～6hr under 20～100% water vapor conditions, obtains little crystal grain super-stable Y molecular sieves;
Crystal grain diameter 100～the 700nm of little crystal grain super-stable Y molecular sieves.
2. prepare the method for industrial chemicals according to the described heavy hydrocarbon oil hydrogen cracking of claim 1, it is characterized in that: the group vib metal is tungsten or molybdenum in the catalyzer, and VIII family metal is nickel or cobalt.
3. prepare the method for industrial chemicals according to the said heavy hydrocarbon oil hydrogen cracking of claim 1, it is characterized in that: described heavy hydrocarbon oil is coker gas oil, vacuum gas oil, atmospheric gas oil, pressed oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383922A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Heavy oil hydrogenation iron-based catalyst and application thereof |
| CN108246344A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic cracking diesel oil hydrocracking catalyst and preparation method thereof |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
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| CN104383922A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Heavy oil hydrogenation iron-based catalyst and application thereof |
| CN104383922B (en) * | 2013-07-18 | 2016-05-11 | 中国石油大学(北京) | A kind of heavy-oil hydrogenation ferrum-based catalyst and application thereof |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
| CN108246344A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of catalytic cracking diesel oil hydrocracking catalyst and preparation method thereof |
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