CN104927912B - Hydrotreatment method of hydrocarbon oil raw material with high content of metals - Google Patents
Hydrotreatment method of hydrocarbon oil raw material with high content of metals Download PDFInfo
- Publication number
- CN104927912B CN104927912B CN201410108698.9A CN201410108698A CN104927912B CN 104927912 B CN104927912 B CN 104927912B CN 201410108698 A CN201410108698 A CN 201410108698A CN 104927912 B CN104927912 B CN 104927912B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- content
- weight
- pore volume
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A hydrotreatment method of hydrocarbon oil raw material with high content of metals is as follows: under the condition of hydrotreating reactions, raw oil sequentially contacts with a catalyst composition comprising a hydrotreatment protection catalyst I, a hydrotreatment catalyst II and a hydrotreatment catalyst III, wherein the hydrotreatment protection catalyst I contains a carrier and hydrogenation active metal components loaded on the carrier, the carrier contains alumina and at least one aid selected from boron, silicon and fluorine aids, and is characterized by mercury intrusion method, the pore volume of the alumina carrier is 0.5-1 ml/g, the specific surface area is 30-150m＜2＞/g, the most probable pore size is 80-300 nm, the carrier is in bimodal pore size distribution in the range of the diameter of 12-15nm and the diameter of 100-200nm, the pore volume of pores with the diameter of 12-15nm is 10-22% of the total pore volume, and the pore volume of pores with the diameter of 100-200nm is 40-70% of the total pore volume. The method disclosed in the invention has a better inferior raw oil hydrotreatment performance compared with the prior art.
Description
Technical field
The present invention is to be related to a kind of high hydrocarbon oil crude material hydrotreating method of tenor.
Background technology
Continuous aggravation and social development with crude oil heaviness trend are continuously increased to light-end products demand, will be bad
Matter heavy raw oil produces light-end products by hydroprocessing technique or the secondary processing of raw material of high-quality is widely adopted.In order to change
The product slates of kind secondary operations such as catalytic cracking process and operating process it is desirable to hydroprocessed product have relatively low metal,
The impurity content of sulfur, nitrogen and carbon residue, and the aggravation now with raw material in poor quality trend, in raw material, metal impurities content is continuous
Increase, so require hydroprocessing processes to need there is more preferable impurity removal ability and reaction stability.Improve impurity removal
Ability can be realized by improving the severity of hydrotreating reaction, but so also results in the contracting in catalyst runs life-span
Short.It is therefore the optimum selection producing high-quality secondary processing of raw material using new catalyst and processing and treating method.
Content of the invention
The technical problem to be solved in the present invention is for prior art requirement, provide a kind of new, to have higher impurity de-
Removing solid capacity and the hydrotreating method for high metal inferior heavy oil of reaction stability.
The present invention relates to herein below:
1st, the high hydrocarbon oil crude material hydrotreating method of a kind of tenor, including at hydrotreating reaction conditions, will weigh
Matter raw oil successively with include hydrotreating guard catalyst, the urging of hydrotreating catalyst and hydrotreating catalyst
Agent combination contact, by volume and on the basis of the total amount of described catalyst combination, described hydrotreating guard catalyst
Content is 5-60%, and the content of hydrotreating catalyst is 5-50%, and the content of hydrotreating catalyst is 10-60%；Its
In, described hydrotreating guard catalyst i contains carrier and load hydrogenation active metals component on this carrier, wherein, institute
State carrier and contain aluminium oxide and at least one selected from boron, silicon and fluorine auxiliary agent, characterized with mercury injection method, the pore volume of described carrier is 0.5-
1 ml/g, specific surface area is 30-150 rice2/ gram, most probable pore size is 80-300nm, and described carrier is in a diameter of 12-15nm
It is in bimodal pore distribution with a diameter of 100-200nm, the pore volume in described a diameter of 12-15nm hole accounts for the 10-22% of total pore volume, directly
Footpath is that the pore volume in 100-200nm hole accounts for the 40-70% of total pore volume.
2nd, the method according to 1 is it is characterised in that by volume and on the basis of the total amount of described catalyst combination,
The content of described hydrotreating guard catalyst is 10-50%, and the content of hydrotreating catalyst is 10-40%, hydrotreating
The content of catalyst is 20-50%；The pore volume of the described shaping carrier in described hydrotreating guard catalyst i is 0.5-0.8
Ml/g, specific surface area is 50-130 rice2/ gram, most probable pore size is 80-280nm, wherein, the hole in a diameter of 12-15nm hole
Volume accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 100-200nm hole accounts for the 45-70% of total pore volume.
3rd, the method according to 1 or 2 is it is characterised in that described hydrotreating guard catalyst i, in terms of oxide
Described auxiliary agent boron, the content of silicon are 0.1-8 weight %, and the Oil repellent counted with element is for 0.1-8 weight %.
4th, the method according to 3 it is characterised in that counted with oxide described auxiliary agent boron, the content of silicon is for 1-6 weight
Amount %, the Oil repellent counted with element is for 1-6 weight %.
5. the method according to 4 it is characterised in that counted with oxide described auxiliary agent boron, the content of silicon is for 1-4 weight
Amount %, the Oil repellent counted with element is for 1-4 weight %.
6th, the method according to 1 or 2 it is characterised in that the hydrogenation active metals group in described catalyst be selected to
A kind of few race and the metal component of at least one b race, are counted and on the basis of described catalyst by oxide, and described the
The content of race's metal component is to less than or equal to 8 weight % more than 0, and the content of b race metal component is to being less than more than 0
Equal to 10 weight %.
7th, the method according to 6 is it is characterised in that described race metal component is selected from nickel and/or cobalt, and described the
B race metal component is selected from molybdenum and/or tungsten, is counted and on the basis of described catalyst by oxide, described race metal component
Content is 0.2～4 weight %, and the content of b race metal component is 0.5～8 weight %.
8th, the method according to 1 is it is characterised in that described catalyst contains carrier, metal component molybdenum, cobalt and nickel,
Counted and on the basis of catalyst by oxide, the content of described molybdenum is 5～20 weight %, the content sum of cobalt and nickel is 1～6
Weight %, wherein, the atomic ratio of cobalt and nickel is 2～4.
9th, the method according to 8 is it is characterised in that counted and on the basis of catalyst by oxide, described catalyst
The content of middle molybdenum is 8～15 weight %, and the content sum of cobalt and nickel is 1.5～4 weight %, wherein, the atomic ratio of cobalt and nickel
For 2.2～3.2.
10th, the method according to 1 it is characterised in that described catalyst contain selected from aluminium oxide and/or silicon oxide-
The carrier of aluminium oxide, selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, with or without selected from fluorine, boron and phosphorus
In one or more adjuvant components, counted and on the basis of catalyst by oxide, the content of described nickel and/or cobalt is 1-5 weight
Amount %, the content of molybdenum and/or tungsten is 10-35 weight %, one or more adjuvant components in fluorine, boron and phosphorus in terms of element
Content be 0-9 weight %.
11st, the method according to 10 is it is characterised in that support selected from alumina in described catalyst.
12nd, the method according to 11 it is characterised in that described aluminium oxide pore volume be not less than 0.35 ml/g, Kong Zhi
Footpath is that the pore volume in 40～100 angstroms of holes accounts for more than the 80% of total pore volume.
13rd, the method according to 1 is it is characterised in that the reaction condition of described hydrotreating reaction is: hydrogen dividing potential drop 6-
20mpa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h-1, hydrogen to oil volume ratio is 600-1500.
14th, the method according to 13 is it is characterised in that the reaction condition of described hydrotreating reaction is: hydrogen dividing potential drop 10-
18mpa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h-1, hydrogen to oil volume ratio is 800-1100.
The carrier of heretofore described catalyst i, is characterized with mercury injection method, and its pore volume is 0.5-1 ml/g, specific surface area
For 30-150 rice2/ gram, wherein, the pore volume in a diameter of 12-15nm hole accounts for the 10-22% of total pore volume, a diameter of 100-200nm hole
Pore volume account for the 40-70% of total pore volume；The pore volume of preferably described shaping carrier is 0.5-0.8 ml/g, and specific surface area is
50-130 rice2/ gram, wherein, the pore volume in a diameter of 12-15nm hole accounts for the 10-20% of total pore volume, a diameter of 100-200nm hole
Pore volume accounts for the 45-70% of total pore volume.
On the basis of carrier, in described carrier, the content of auxiliary agent is 0.1-8 weight %, and preferably 1-6 weight % is excellent further
Elect 1-4 weight % as.Wherein, in terms of oxide, fluorine is in terms of element for boron and silicon.
The hydrogenation that hydrogenation active metals component in described catalyst i and its content are usually commonly used for hydrogenation protecting catalyst
Active metal component and content, for example, selected from least one viii race non-noble metal components and at least one vib race metal
Component.The metal component of preferred viii race is nickel and/or cobalt, and the metal component of preferred vib race is molybdenum and/or tungsten,
Counted and on the basis of described catalyst by oxide, the content of described viii race metal is to less than or equal to 8 weight % more than 0,
It is preferably 0.2～4 weight %, the content of described vib race metal component is to less than or equal to 10 weight % preferably 0.5 more than 0
～8 weight %.
The preparation method of carrier described in hydrogenation protecting catalyst i of the present invention, including by a kind of hydrated alumina with
A kind of mixing of Alpha-alumina simultaneously introduces containing at least one compound selected from boron, silicon and fluorine auxiliary agent, molding in the mixture, does
Dry and roasting, sintering temperature is 750-1000 DEG C, preferably 800-950 DEG C, and roasting time is 1-10 hour, and preferably 2-8 is little
When, wherein, for 20-75:25-80(wherein, 20-75 refers to often for the hydrated alumina counted with butt and the mixing ratio of Alpha-alumina
In hundred parts of hydrated alumina (in terms of butt) and the mixture of Alpha-alumina, the value of hydrated alumina number 20-75 it
Between change, 25-80 refers in hydrated alumina (in terms of butt) parts per hundred parts and the mixture of Alpha-alumina, Alpha-alumina number
Value change between 25-80), preferably 30-70:30-70.The pore volume of described hydrated alumina be 0.9-1.4 milliliter/
Gram, preferably 0.95-1.3 ml/g, specific surface is 100-350 rice2/ gram be preferably 120-300 rice2/ gram, most probable hole is straight
Footpath is 8-30nm, preferably 10-25nm.
It is selected from boron, silicon and fluorine auxiliary agent chemical combination to described hydrated alumina with introducing in Alpha-alumina mixture containing at least one
The method of thing is conventional method, for example, it may be directly by the desired amount of compound containing described adjuvant component in aforesaid water
It is mixed in conjunction aluminium oxide and Alpha-alumina mixed process.
In an embodiment specifically preparing carrier, draw in described hydrated alumina and Alpha-alumina mixture
Entering containing at least one method selected from boron, silicon and fluorine auxiliary compound is will to be selected from boron, silicon and fluorine auxiliary agent chemical combination containing at least one
Thing is configured to aqueous solution, and this aqueous solution is mixed into or described while described hydrated alumina is mixed with Alpha-alumina
This aqueous solution is mixed into after being mixed with Alpha-alumina by hydrated alumina again, aftershaping, drying roasting.Change containing described auxiliary agent
Compound is one or more of their water soluble compounds.For example, one of water-soluble inorganic salt containing described auxiliary agent or
Several.
Described Alpha-alumina can be commercially available commodity (commodity alpha-alumina) or by hydrated alumina (water
Close alumina powder) obtain through high-temperature roasting.Under conditions of being enough to for hydrated alumina roasting phase transformation to be converted into Alpha-alumina, this
One process can be realized using arbitrary existing method, and this present invention is not limited.
Described hydrated alumina is selected from arbitrary pore volume and is 0.9-1.4 ml/g, preferably 0.95-1.3 ml/g, than
Surface is 100-350 rice2/ gram, preferably 120-300 rice2/ gram, can and bore dia 8-30nm, the preferably hydration of 10-25nm
Aluminium oxide；It is preferably the hydrated alumina containing boehmite.Here, the pore volume of described hydrated alumina, specific surface area and
Can and aperture, be by described hydrated alumina after 600 DEG C of roastings 4 hours, by bet nitrogen absorption under low temperature characterize obtain.
Described hydrated alumina adopts conventional method with the mixing of Alpha-alumina, and meets the hydrated alumina in terms of butt
Mixing ratio with Alpha-alumina is 20-75:25-80, preferably 30-70:30-70.
Described carrier can be made into various easily operated article shaped depending on different requirements, for example spherical, cellular, nest like,
Tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).Molding can be carried out according to a conventional method.In molding, such as extruded moulding,
For ensure described molding be smoothed out, can add in described mixture water, extrusion aid and/or adhesive, with or without
Expanding agent, then extrusion molding, it is dried afterwards and roasting.Described extrusion aid, the species of peptizer and consumption are this area
Well known to technical staff, for example common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH
One or more of, described peptizer can be mineral acid and/or organic acid, and described expanding agent can be starch, synthesis
One or more of cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably hydroxymethyl cellulose, first
One or more of base cellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably poly- second two
One or more of alcohol, poly- propanol, polyvinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and
Its derivant, molecular weight are one or more of propylene alcohol copolymer and maleic acid copolymer of 200-10000.
The method of described molding, drying and roasting is conventional method.Wherein, the condition of roasting preferably includes sintering temperature and is
750-1000 DEG C, roasting time is 1-10 hour, and the condition of further preferred roasting includes sintering temperature and is 800-950 DEG C, roasting
The burning time is 2-8 hour.
The preparation method of described hydrogenation protecting catalyst i, including the introducing hydrogenation active metals component on described carrier
Step, hydrogenation active metals group therein is selected from least one viii race base metal and selected from least one vib race
The combination of metal.The metal component of preferred vib race is molybdenum and/or tungsten, is counted and on the basis of described catalyst by oxide,
It is to being less than or equal to more than 0 that the introduction volume of described vib race metal component makes the content of vib race metal component in final catalyst
10 weight %, preferably 0.5～8 weight %, the introduction volume of described viii race metal component makes viii race in final catalyst
The content of metal component is to less than or equal to 8 weight %, preferably 0.2～4 weight % more than 0.
Introduce hydrogenation active metals component on described carrier can be any means that those skilled in the art inform,
For example, it is possible to by the carrier described in solution impregnation with the compound containing described hydrogenation active metals component, be done afterwards
Dry, roasting or the step of not roasting.
Wherein, the described compound containing vib race metal be selected from they one or more of soluble compound.
For example, the compound containing molybdenum can be one or more of molybdenum oxide, molybdate, paramolybdate, molybdenum oxide preferably wherein,
Ammonium molybdate, ammonium paramolybdate；Tungstenic compound is selected from one or more of tungstates, metatungstate, ethyl metatungstate, preferably
Ammonium metatungstate therein, ethyl ammonium metatungstate.
The described compound containing viii race metal be selected from they one or more of soluble compound.Example
If the compound containing cobalt can be one or more of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride, preferably nitric acid
Cobalt, basic cobaltous carbonate；Nickel compound containing can be one or more of nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride.,
It is preferably nickel nitrate, basic nickel carbonate.
According to the present invention, the compound containing described active component can be prepared using various solvents commonly used in the art
Solution, as long as described compound can be dissolved in described solvent, formed stable homogeneous solution.For example: described molten
Agent can be water or alcohol (such as: ethanol) that carbon number is 1～5, preferably water and/or ethanol, more preferably water.
The method of described dipping can be various dipping methods commonly used in the art, for example, can be hole saturation infusion process.
The present invention was not particularly limited for the time of described dipping and the number of times of dipping, as long as being able to ensure that the catalyst finally giving
On the amount of the active component with catalytic action meet specific use requirement.Usually, the time of described dipping can
Think 0.5～12 hour.
The present invention, the method that is dried of carrier for the compound by being loaded with described hydrogenation active metals component and
Condition is not particularly limited.Usually, the temperature of described drying can be 80～350 DEG C, preferably 100～300 DEG C；Described dry
The dry time can be 0.5～24 hour, preferably 1～12 hour.
When catalyst after drying needs to carry out roasting, the present invention is not special to described method of roasting and condition
Limit, can be conventional method and the condition of this area.Usually, the temperature of described roasting can be 350～650 DEG C, preferably
For 400～500 DEG C；The time of described roasting can be 0.2～12 hour, preferably 1～10 hour.Described roasting can contain
Carry out in oxygen atmosphere it is also possible to carry out in an inert atmosphere.
In the present invention, the effect of described catalyst is to remove further organic metal impurity in raw material, asphalitine
With the macromole species such as colloid and partial vulcanization thing.
According to the present invention provide method, wherein, meet the present invention to described hydrotreating catalyst requirement before
Put, described hydrotreating catalyst can be commercially available commodity, it would however also be possible to employ arbitrary prior art preparation.For example,
20110276687.3 and catalyst and preparation method thereof disclosed in 201110039566.1 entirely appropriate for the present invention.With regard to
The more detailed preparation method of above-mentioned catalyst, all on the books in above-mentioned patent documentation, here in the lump using them as the present invention
A part for content is quoted.
In the present invention, the effect of described catalyst be the macromolecular compounds such as saturation polycyclic aromatic hydrocarbon so as in be more difficult to
The impurity such as the sulfur of removing, nitrogen remove further, and the carbon residue in removing raw oil, improves product property simultaneously.On enough to realize
On the premise of stating function, the present invention described catalyst is not had other restriction, that is, catalyst can be selected from arbitrarily existing
The catalyst such as the hydrofinishing of technology offer, hydrotreating.They can be commercially available commodity or adopt any existing method system
Standby.
Usually, such catalyst usually contains heat-resistant inorganic oxide carrier, hydrogenation active metals component.For example, institute
State catalyst and contain carrier selected from aluminium oxide and/or silica-alumina, selected from nickel and/or cobalt, molybdenum and/or tungsten plus
Hydrogen activity metal component, with or without one or more adjuvant components in fluorine, boron and phosphorus, in terms of oxide and with catalyst
On the basis of, the content of described nickel and/or cobalt is 1-5 weight %, and the content of molybdenum and/or tungsten is 10-35 weight %, in terms of element
In fluorine, boron and phosphorus one or more adjuvant components content be 0-9 weight %.
For example, a kind of Hydrobon catalyst disclosed in zl97112397, consisting of nickel oxide 1～5 weight %, tungsten oxide
12～35 weight %, fluorine 1～9 weight %, remaining is aluminium oxide, and this aluminium oxide is by little one or more porous aluminum oxide and one kind or many
Plant what macroporous aluminium oxide was composited according to 75: 25～50: 50 weight ratio, wherein little porous aluminum oxide is less than 80 angstroms for bore dia
The pore volume in hole accounts for the aluminium oxide of total pore volume more than 95%, and macroporous aluminium oxide is that the pore volume in 60～600 angstroms of holes of bore dia accounts for
The aluminium oxide of total pore volume more than 70%.
Zl00802168 discloses a kind of Hydrobon catalyst, and this catalyst contains a kind of alumina support and is supported on
At least one b race's metal on this alumina support and/or at least one race metal.Described alumina support
Pore volume is not less than 0.35 ml/g, and bore dia is that the pore volume in 40～100 angstroms of holes accounts for more than the 80% of total pore volume, and it is special that it adopts
Method preparation.
Zl200310117323 discloses a kind of Hydrobon catalyst, and this catalyst contains a kind of alumina support and bears
Carry molybdenum on this carrier, nickel and tungsten metal component, counted and on the basis of catalyst by oxide, described catalyst contains
The molybdenum of 0.5-10 weight %, the nickel of 1-10 weight %, the tungsten of 12-35 weight % and the carrier of aequum, described catalyst
Preparation method includes using successively the solution of molybdate compound and nickeliferous, tungsten compound solution impregnation of alumina carrier, wherein institute
The alumina support stated is dried after the solution impregnation with molybdate compound, with nickeliferous, tungsten compound solution impregnation
After be dried and roasting, baking temperature be 100-300 DEG C, drying time be 1-12 hour, sintering temperature be 320-500
DEG C, roasting time is 1-10 hour.
These catalyst all can be used for the present invention as described catalyst.More detailed preparation with regard to above-mentioned catalyst
Method, all on the books in above-mentioned patent documentation, in the lump they are quoted as a part for present invention here.
The method providing according to the present invention, at described inclusion hydrotreating catalyst i, hydrotreating catalyst and hydrogenation
Reason catalyst can be layered successively and fill in the reactor filling in several series connection in same reactor or successively
Middle use, is not particularly limited to this present invention.
The method providing according to the present invention, wherein, is including hydrotreating catalyst i, hydrotreating catalyst and is adding
Before the catalyst combination that hydrogen processes catalyst, afterwards or they between any two, can include any contribute to improving described
Other catalyst of catalyst combination performance or filler.For example, before described Hydrodemetalation catalyst i add as porcelain ball,
The fillers such as active supporter, to improve raw oil distribution in the reactor etc..Use with regard to this filler etc. is this area
Well known to technical staff, do not repeat here.
According to the conventional method in this area, described hydrotreating catalyst before the use, generally can exist in hydrogen
Under, with sulfur, hydrogen sulfide or carry out presulfurization containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be carried out outside device
Also can be In-situ sulphiding in device, the active metal component that it is loaded is converted into metal sulfide.
The method providing according to the present invention, the reaction condition of described hydrotreating reaction is the conventional strip of heavy oil hydrotreating
Part, for example, described reaction condition includes: hydrogen dividing potential drop 6-20mpa, and temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-
1.0h-1, hydrogen to oil volume ratio is 600-1500, wherein preferred hydrogen dividing potential drop 10-18mpa, and temperature is 350-420 DEG C, and during liquid, volume is empty
Speed is 0.2-0.6h-1, hydrogen to oil volume ratio is 800-1100.
The method providing according to the present invention, is particularly suitable for former for processing the higher hydrocarbon ils inferior of the tenors such as ferrum, calcium
Material, they can be selected from crude oil, decompression residuum, deep drawing wax oil, frivolous coal tar, wax tailings, coal tar inferior etc.
Plant or several.
Be can reach according to the weight of oil after the hydrotreating that methods described obtains: asphalt content is less than 1.2%, metal
Fe+ca content is below 15 μ g/g, and metal ni+v content is below 20 μ g/g, and below 0.5%, carbon residue content is sulfur content
Less than 6.0%.
Specific embodiment
The present invention is described further for the following examples.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Pressure hydrargyrum method (ripp149-90) measures (poplars such as specific surface area, pore volume and the pore size distribution of aluminium oxide shaping carrier
Emerald green fixed etc., Petrochemical Engineering Analysis method, publishing house of academy of science, 1990, the 421-423 page).
Bet nitrogen absorption under low temperature method (ripp151-90) measures specific surface area, pore volume and the pore size distribution of hydrated alumina
Deng (Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of academy of science, and 1990, the 424-426 page).
Butt assay method is to take appropriate amount of sample, in 600 DEG C of roasting temperature 3h, afterwards, calculates sample and roasting after roasting
The mass percent of sample before burning, is the butt of this sample.
(Yang Cui is fixed etc., Petrochemical Engineering Analysis side to measure constituent content in solid sample using xrf method (ripp132-90)
Method, publishing house of academy of science, 1990, the 371-375 page).
Hydrotreating guard catalyst i in the present invention and preparation method thereof:
Carrier of catalyst i of the present invention and preparation method thereof is prepared in the explanation of embodiment 1-5.
Embodiment 1
Weigh 200g hydrated alumina and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume is 1.05 millis
Rise/gram, specific surface area is 230 meters2/ gram, most probable bore dia is 20nm), 70 grams of alpha-aluminas (are used by the present embodiment
Hydrated alumina at 1400 DEG C roasting form within 6 hours), 9 grams of sesbania powders and the mixing of 15 grams of Boraxs, at room temperature this is mixed
330 milliliters of the ammonia spirit that thing is 4% with concentration mixes, after mix homogeneously, kneading use φ 2.0mm in double screw banded extruder
Cylindrical orifice plate extrusion, afterwards, wet bar obtains carrier of the present invention through 120 DEG C of dryings 4 hours after 850 DEG C of roastings 2 hours
zi1.Measurement carrier zi1 specific surface, can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 2
Weigh 180g dry glue powder and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume be 1.05 milliliters/
Gram, specific surface area is 285 meters2/ gram, most probable bore dia is 20nm), 120 grams of alpha-aluminas (are available commercially from Beijing Shun Chuan environmental protection
Science and Technology Ltd.), 9 grams of sesbania powders and the mixing of 8 grams of boron oxides, add 330 milliliters of the aqueous solution containing 10 grams of sodium borate afterwards,
After mix homogeneously in double screw banded extruder kneading the cylindrical orifice plate extrusion with φ 2.0mm, afterwards, wet bar is dry through 120 DEG C
After 850 DEG C of roastings 2 hours, obtain carrier zi2 of the present invention within dry 4 hours.Measurement carrier zi2 specific surface, can several apertures, hole
Appearance, pore size distribution, the results are shown in Table 1.
Embodiment 3
Weigh 150g dry glue powder and (be available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 68 weight %.Pore volume is 1.08 millis
Rise/gram, specific surface area is 188 meters2/ gram, most probable bore dia is 22nm), 150 grams of alpha-aluminas (are available commercially from Beijing Shun Chuan
Environmental Protection Technology Co., Ltd), 9 grams of sesbania powders, 9 grams of methylcellulose and 20 grams of Borax mixing, add afterwards and contain 35 grams of carbonic acid
330 milliliters of the aqueous solution of hydrogen ammonium, according to roller forming method molding after mix homogeneously, obtaining particle diameter is spherical of 5.5-6.5mm
Grain.Wet bar obtains carrier zi3 of the present invention through 120 DEG C of dryings 4 hours after 800 DEG C of roastings 2 hours.The ratio table of measurement carrier zi3
Face, can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 4
Weigh 260g dry glue powder and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume be 1.05 milliliters/
Gram, specific surface area is 220 meters2/ gram, most probable bore dia is 20nm), 140 grams of alpha-aluminas (with embodiment 1), 9 grams of sesbanias
Powder, 9 grams of methylcellulose and 10 grams of "Antifungin". mix homogeneously, add ammonia spirit 300 milli of 5% containing 10 grams of boric acid afterwards
Rise, mixing, afterwards add 300 milliliters of water, after mix homogeneously in double screw banded extruder kneading the cylindrical hole with φ 2.0mm
Plate is extruded, and wet bar obtains carrier zi4 of the present invention through 120 DEG C of dryings 4 hours after 800 DEG C of roastings 2 hours.Measurement carrier zi4's
Specific surface, can several apertures, pore volume, the results are shown in Table 1.
Embodiment 5
Weigh 260g dry glue powder and (be available commercially from Yantai Heng Hui Chemical Co., Ltd., butt is 68 weight %.Pore volume is 1.08 millis
Rise/gram, specific surface area is 200 meters2/ gram, most probable bore dia is 22nm), 140 grams of alpha-aluminas (with embodiment 1), 9 grams
Sesbania powder, 9 grams of methylcellulose mixing, 300 milliliters of the water containing 10 grams of nitric acid for the addition afterwards, extruded moulding after mix homogeneously is wet
Bar obtains carrier zi5 of the present invention through 120 DEG C of dryings 4 hours after 800 DEG C of roastings 2 hours.Measurement carrier zi5 specific surface, can
Several apertures, pore volume, the results are shown in Table 1.
Comparative example 1-4 explanation preparation reference catalyst carrier and preparation method thereof.
Comparative example 1
Weigh 300 grams of dry glue powders and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume be 0.8 milliliter/
Gram, specific surface area is 320 meters2/ gram, most probable bore dia is 10nm), 9 grams of sesbania powders, add after mix homogeneously and contain 12 grams of nitric acid
360 milliliters of mixed-formings of solution, wet bar obtains carrier dzi1 through 120 DEG C of dryings 4 hours after in 850 DEG C of roastings 2 hours.
Measurement carrier dzi1 specific surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 2
Weigh 300 grams of dry glue powders and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume be 0.8 milliliter/
Gram, specific surface area is 303 meters2/ gram, most probable bore dia is 11nm), 9 grams of sesbania powders, add after mix homogeneously and contain 12 grams of nitric acid
360 milliliters of mixed-formings of solution, wet bar obtains carrier dzi2 through 120 DEG C of dryings 4 hours after in 950 DEG C of roastings 2 hours.
Measurement carrier dzi2 specific surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 3
Weigh dry glue powder and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume is 0.8 ml/g, compares table
Area is 290 meters2/ gram, most probable bore dia is 11nm) 300 grams, add 24 grams of carbon black powder, 12 grams of mixing of sesbania powder, afterwards plus
Enter 360 milliliters of the aqueous solution of 2.4 grams of phosphoric acid being 85 weight % containing concentration, kneading 15 minutes, double screw banded extruder squeezes
Become the butterfly bar of φ 1.5mm, wet bar obtains carrier dzi3 through 120 DEG C of dryings 4 hours after 850 DEG C of roastings 2 hours.Measurement carries
The specific surface of body dzi3, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 4
Weigh 300 grams of dry glue powders and (be available commercially from Chang Ling catalyst branch company, butt is 65 weight %.Pore volume be 0.65 milliliter/
Gram, specific surface area is 288 meters2/ gram, most probable bore dia is 9nm), 9 grams of sesbania powders and 15 grams of Boraxs, add after mix homogeneously
Containing 12 grams 360 milliliters of mixed-formings of solution of potassium nitrate, wet bar, obtains after in 950 DEG C of roastings 2 hours through 120 DEG C of dryings 4 hours
To carrier dzi4.Measurement carrier dzi4 specific surface, can several apertures, pore volume, the results are shown in Table 1.
Table 1
Embodiment 6～10 is used for catalyst i of the present invention and preparation method thereof is described.Comparative example 5-6 explanation reference is urged
Agent and preparation method thereof.
Embodiment 6
Take drying and roasting after 100 grams of zi1 dippings of carrier, with saturation leaching mode molybdenum oxide containing 1.2g (containing moo399.9%)
Impregnate with 97 milliliters of the solution of 0.7g nickel nitrate (containing nio25%), in 120 DEG C of dryings 4 hours after dipping, little in 420 DEG C of roastings 3
When obtain guard catalyst ci1 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 7
Take 100 grams of zi2 of carrier, with saturation leaching mode ammonium molybdate containing 6.42g (containing moo382%) (contain with 4.35g nickel nitrate
Nio51% 96 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent ci2.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 8
Take 20 grams of zi3 of carrier, with saturation leaching mode ammonium molybdate containing 1.2g (containing moo382%) (contain with 2.0g nickel nitrate
Nio25% 25 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent ci3.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 9
Take 20 grams of zi4 of carrier, with saturation leaching mode ammonium molybdate containing 0.86g (containing moo382%) (contain with 1.25g nickel nitrate
Nio25% 13 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent ci4.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 10
Take 20 grams of zi5 of carrier, with saturation leaching mode ammonium molybdate containing 1.45g (containing moo382%) (contain with 1.30g nickel nitrate
Nio25% 13 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent ci5.Wherein, the content of hydrogenation active metals component is listed in table 2.
Comparative example 5-6 explanation reference catalyst and preparation method thereof.
Comparative example 5
Take 20 grams of dzi4 of carrier, with saturation leaching mode ammonium molybdate containing 1.2g (containing moo382%) (contain with 2.0g nickel nitrate
Nio25% 25 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent dci1.Wherein, the content of hydrogenation active metals component is listed in table 2.
Comparative example 6
Take 20 grams of dzi1 of carrier, with saturation leaching mode ammonium molybdate containing 0.86g (containing moo382%) (contain with 1.25g nickel nitrate
Nio25% 13 milliliters of dippings of solution), in 120 DEG C of dryings 4 hours after dipping, obtain present invention protection for 3 hours in 420 DEG C of roastings and urge
Agent dci2.Wherein, the content of hydrogenation active metals component is listed in table 2.
Table 2
The explanation of embodiment 11-12 is suitable for preparing carrier of hydrotreating catalyst and preparation method thereof.
Embodiment 11
The boehmite dry glue powder rpb110 that produce 300 grams of Chang Ling catalyst branch companies and 10 grams of sesbania powder mixing
Uniformly, the aqueous solution of nitric acid being 1% by the concentration of this mixture and 360 milliliters at room temperature, mix homogeneously, in twin screw extrusion
On machine continue kneading be plastic after, be extruded into the trilobal bar of 1.5 millimeters of ф, wet bar after 120 DEG C of dryings 3 hours, in 700 DEG C
Roasting obtains carrier z 1 in 3 hours.Measure specific surface, pore volume and the pore-size distribution of z 1, the results are shown in Table 3.
Carrier specific surface, pore volume and pore-size distribution adopt bet low-temperature nitrogen adsorption method to measure.
Embodiment 12
The boehmite dry glue powder of the boehmite dry glue powder rpb90 that 300 grams of Chang Ling catalyst branch companies are produced)
With 10 grams of sesbania powder mix homogeneously, 330 milliliters of concentration of addition are 1% aqueous solution of nitric acid, and mix homogeneously, in double screw banded extruder
Upper continuation kneading be plastic after, be extruded into the butterfly bar of 1.1 millimeters of ф, wet bar after 110 DEG C of dryings 2 hours, in 600 DEG C of roastings
Obtain carrier z 2 within 4 hours.Measure specific surface, pore volume and the pore-size distribution of z 2, result is as shown in table 3.
Table 3
Embodiment 13-16 illustrates catalyst by the present invention and preparation method thereof.
Embodiment 13
1200 grams of the carrier z of Example 11 preparation, contains moo3120 g/l with 500 milliliters, nio8 g/l, coo20
G/l ammonium molybdate, nickel nitrate, cobalt nitrate mixed solution impregnate 1 hour, filter after 120 DEG C dry 2 hours, 450 DEG C of roastings
4 hours, obtain catalyst c 1.On the basis of the gross weight of catalyst, catalyst c 1 is measured using x-ray fluorescence spectrophotometer
In molybdenum oxide, cobalt oxide, the content of nickel oxide, measurement result is as shown in table 4.(all appts are Rigaku electric machine industry
Co., Ltd. 3271 type x-ray fluorescence spectrophotometer, concrete grammar is shown in Petrochemical Engineering Analysis method ripp133-90)
Embodiment 14
2200 grams of the carrier z of Example 12 preparation, contains moo3172 g/l with 220 milliliters, nio9 g/l, coo32
G/l molybdenum oxide, basic nickel carbonate, basic cobaltous carbonate mixed solution impregnate 2 hours, in 120 DEG C dry 2 hours, 500 DEG C
Roasting 2 hours, obtains catalyst c 2.Molybdenum oxide in mensure catalyst c 2, oxidation according to the same manner as in Example 3
Cobalt, the content of nickel oxide, result is as shown in table 4.
Embodiment 15
2200 grams of the carrier z of Example 12 preparation, contains moo3122 g/l with 200 milliliters, nio9 g/l, coo18
G/l molybdenum oxide, basic nickel carbonate, basic cobaltous carbonate mixed solution impregnate 1 hour, in 120 DEG C dry 2 hours, 480 DEG C
Roasting 4 hours, obtains catalyst c 3.Molybdenum oxide in mensure catalyst c 3, oxidation according to the same manner as in Example 3
Nickel and the content of cobalt oxide, result is as shown in table 4.
Embodiment 16
1200 grams of the carrier z of Example 11 preparation, is soaked with 500 milliliters of cobalt nitrate mixed solutions containing coo12 g/l
Stain 1 hour, filters and dries 3 hours after 110 DEG C, and 350 DEG C of roastings 2 hours contain moo392 g/l with 200 milliliters, nio7 gram/
The molybdenum oxide rising, basic nickel carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 480 DEG C of roastings 4 hours are urged
Agent c 4.Measure containing of the molybdenum oxide in catalyst c 4, nickel oxide and cobalt oxide according to the same manner as in Example 3
Amount, result is as shown in table 4.
Table 4
Embodiment 17-21 illustrates the effect of the method provided by the present invention hydrotreating residual oil and coal tar mixed material.Contrast
Example 7-8 illustrates the effect of reference method hydrotreating residual oil raw material.
With fe+ca content as 79ppm, the coal tar that ni+v content is 85ppm, sulfur content is 3.7%, carbon residue is 11.5%
And residual oil mixing low grade oilses are raw material, catalyst is evaluated on 500 milliliters of fixed bed reactors.
In oil sample, the content of ferrum, calcium, nickel and vanadium adopts inductive coupling plasma emission spectrograph (icp-aes) to measure
(instrument is U.S.'s pe company pe-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method
Ripp124-90).
In oil sample, sulfur content measures (concrete grammar is shown in Petrochemical Engineering Analysis method ripp62-90) using coulometry.
In oil sample, carbon residue content is using microdetermination (concrete grammar is shown in Petrochemical Engineering Analysis method ripp149-90).
Hydrotreating catalyst:
Hydrotreating catalyst -1, prepares according to the embodiment 6 in patent zl97112397.7, consisting of nickel oxide
2.3 weight %, tungsten oxide 22.0 weight %, fluorine 4 weight %, remaining is aluminium oxide.
Hydrotreating catalyst -2, prepare according to the embodiment 37 in patent zl00802168.6, consisting of oxidation
Nickel 2.6 weight %, molybdenum oxide 23.6 weight %, fluorine 2.3 weight %, remaining is aluminium oxide.
Hydrotreating catalyst -3, prepare according to the embodiment 3 in patent zl200310117323.0, consisting of oxygen
Change nickel 2.1 weight %, molybdenum oxide 2.5 weight %, tungsten oxide 25.4 weight %, remaining is aluminium oxide.
Catalyst use ratio and process conditions are listed in Table 5 below, and after operating 1000 hours, product property is listed in Table 6 below.
Comparative example 7
Catalyst adopts the combination of dci1, cii1, c 1, and when process conditions are listed in table 5 to the volume of each catalyst amount
In, sample analysis after operating 1000 hours, result is listed in table 6.
Comparative example 8
Catalyst adopts the combination of dci2, cii2, c 2, and when process conditions are listed in table 5 to the volume of each catalyst amount
In, sample analysis after operating 1000 hours, result is listed in table 6.
Table 5
Table 6
As can be seen that the metal of 1000 hours back end hydrogenation process products of method operating being provided using the present invention, sulfur, carbon residue
Deng impurity content hence it is evident that being less than reference method.
Claims (14)
1. a kind of high hydrocarbon oil crude material hydrotreating method of tenor, including at hydrotreating reaction conditions, former by heavy
The material oil catalyst with inclusion hydrotreating guard catalyst, hydrotreating catalyst and hydrotreating catalyst successively
Combination contact, by volume and on the basis of the total amount of described catalyst combination, the content of described hydrotreating guard catalyst
For 5-60%, the content of hydrotreating catalyst is 5-50%, and the content of hydrotreating catalyst is 10-60%；Wherein,
Described hydrotreating guard catalyst i contains carrier and load hydrogenation active metals component on this carrier, wherein, described load
Body contains aluminium oxide and at least one selected from boron, silicon and fluorine auxiliary agent, is characterized with mercury injection method, and the pore volume of described carrier is 0.5-1 milli
Rise/gram, specific surface area is 30-150 rice2/ gram, most probable pore size is 80-300nm, and described carrier is in a diameter of 12-15nm and straight
Footpath is in bimodal pore distribution for 100-200nm, and the pore volume in described a diameter of 12-15nm hole accounts for the 10-22% of total pore volume, a diameter of
The pore volume in 100-200nm hole accounts for the 40-70% of total pore volume.
2. method according to claim 1 is it is characterised in that by volume and with the total amount of described catalyst combination as base
Standard, the content of described hydrotreating guard catalyst is 10-50%, and the content of hydrotreating catalyst is 10-40%, plus
The content that hydrogen processes catalyst is 20-50%；The pore volume of the described carrier in described hydrotreating guard catalyst i is 0.5-
0.8 ml/g, specific surface area is 50-130 rice2/ gram, most probable pore size is 80-280nm, wherein, a diameter of 12-15nm hole
Pore volume accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 100-200nm hole accounts for the 45-70% of total pore volume.
3. method according to claim 1 and 2 is it is characterised in that described hydrotreating guard catalyst i, with oxide
The described auxiliary agent boron of meter, the content of silicon are 0.1-8 weight %, and the Oil repellent counted with element is for 0.1-8 weight %.
4. method according to claim 3 it is characterised in that counted with oxide described auxiliary agent boron, the content of silicon is as 1-6
Weight %, the Oil repellent counted with element is for 1-6 weight %.
5. method according to claim 4 it is characterised in that counted with oxide described auxiliary agent boron, the content of silicon is as 1-4
Weight %, the Oil repellent counted with element is for 1-4 weight %.
6. method according to claim 1 and 2 is it is characterised in that the hydrogenation active metals group in described catalyst sorts
From the metal component of at least one race and at least one b race, counted and on the basis of described catalyst by oxide,
The content of described race metal component is that the content of b race metal component is more than 0 more than 0 to less than or equal to 8 weight %
To less than or equal to 10 weight %.
7. method according to claim 6 is it is characterised in that described race metal component is selected from nickel and/or cobalt, described
B race metal component is selected from molybdenum and/or tungsten, is counted and on the basis of described catalyst by oxide, described race metal group
The content divided is 0.2～4 weight %, and the content of b race metal component is 0.5～8 weight %.
8. method according to claim 1 it is characterised in that described catalyst contain carrier, metal component molybdenum, cobalt and
Nickel, is counted and on the basis of catalyst by oxide, and the content of described molybdenum is 5～20 weight %, and the content sum of cobalt and nickel is 1
～6 weight %, wherein, the atomic ratio of cobalt and nickel is 2～4.
9. method according to claim 8 is it is characterised in that counted and on the basis of catalyst by oxide, described urges
In agent, the content of molybdenum is 8～15 weight %, and the content sum of cobalt and nickel is 1.5～4 weight %, wherein, cobalt and nickel former
Son ratio is 2.2～3.2.
10. method according to claim 1 is it is characterised in that described catalyst contains selected from aluminium oxide and/or oxidation
The carrier of silicon-aluminium oxide, selected from the hydrogenation active metals component of nickel and/or cobalt, molybdenum and/or tungsten, with or without selected from fluorine, boron and
One or more adjuvant components in phosphorus, are counted and on the basis of catalyst by oxide, and the content of described nickel and/or cobalt is 1-5
The content of weight %, molybdenum and/or tungsten is 10-35 weight %, one or more the auxiliary agent groups in fluorine, boron and phosphorus in terms of element
The content divided is 0-9 weight %.
11. methods according to claim 10 are it is characterised in that support selected from alumina in described catalyst.
12. methods according to claim 11 it is characterised in that the pore volume of alumina catalyst support in described catalyst not
Less than 0.35 ml/g, bore dia is that the pore volume in 40～100 angstroms of holes accounts for more than the 80% of total pore volume.
13. methods according to claim 1 are it is characterised in that the reaction condition of described hydrotreating reaction is: hydrogen dividing potential drop
6-20mpa, temperature is 300-450 DEG C, and during liquid, volume space velocity is 0.1-1h-1, hydrogen to oil volume ratio is 600-1500.
14. methods according to claim 13 are it is characterised in that the reaction condition of described hydrotreating reaction is: hydrogen divides
Pressure 10-18mpa, temperature is 350-420 DEG C, and during liquid, volume space velocity is 0.2-0.6h-1, hydrogen to oil volume ratio is 800-1100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410108698.9A CN104927912B (en) | 2014-03-21 | 2014-03-21 | Hydrotreatment method of hydrocarbon oil raw material with high content of metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410108698.9A CN104927912B (en) | 2014-03-21 | 2014-03-21 | Hydrotreatment method of hydrocarbon oil raw material with high content of metals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104927912A CN104927912A (en) | 2015-09-23 |
| CN104927912B true CN104927912B (en) | 2017-01-18 |
Family
ID=54115343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410108698.9A Active CN104927912B (en) | 2014-03-21 | 2014-03-21 | Hydrotreatment method of hydrocarbon oil raw material with high content of metals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104927912B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433245B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate |
| CN116020497A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Composite carrier, hydrogenation catalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| CN103059929A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method for heavy residual oil |
-
2014
- 2014-03-21 CN CN201410108698.9A patent/CN104927912B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519603A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for hydrotreating high-sulfur and high-metal residual oil |
| CN103059929A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method for heavy residual oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104927912A (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102649068B (en) | Hydrogenation active protective agent with boron-containing aluminum oxide as carrier and preparation as well as application thereof | |
| CN104437517B (en) | A kind of heavy oil hydrogenating treatment catalyst and preparation and application thereof | |
| CN104437518A (en) | Selective hydrodesulfurization catalyst, and preparation and application thereof | |
| CN104324710B (en) | A kind of hydrogenation protecting catalyst and preparation method and application | |
| CN102649070B (en) | The Hydrogenation active protective agent being carrier with alkaline including earth metal aluminium oxide, preparation and application thereof | |
| CN104927912B (en) | Hydrotreatment method of hydrocarbon oil raw material with high content of metals | |
| CN104927911B (en) | Hydrotreatment method of hydrocarbon oil raw material with high content of iron and calcium | |
| CN104368393B (en) | A kind of aluminium oxide article shaped and preparation method thereof and the catalyst prepared as carrier by this article shaped | |
| CN104226323B (en) | A kind of heavy oil hydrogenating treatment catalyst and preparation thereof and application | |
| CN104927913B (en) | Inferior hydrocarbon oil material hydrotreating method | |
| CN104368349B (en) | A kind of hydrogenation activity guard catalyst and preparation and application thereof | |
| CN104927900B (en) | Inferior hydrocarbon oil material hydrotreating method | |
| CN104368352B (en) | A kind of hydrogenation activity guard catalyst and preparation and application thereof | |
| CN103923692B (en) | A kind of hydroprocessing process of heavy raw oil | |
| CN104449832B (en) | A kind of catalytically cracked stock weighted BMO spaces method | |
| CN104449815B (en) | A kind of method for hydrotreating hydrocarbon oil | |
| CN104226298B (en) | Heavy oil hydrotreatment catalyst, and preparation and application thereof | |
| CN104293390B (en) | A kind of process for hydrogenating residual oil | |
| CN104293389B (en) | A kind of process for hydrogenating residual oil | |
| CN104437579B (en) | Distillate-oil hydrofining catalyst, and preparation and application thereof | |
| CN104293381B (en) | A kind of method improving heavy-oil hydrogenation product property | |
| CN103923697B (en) | A kind of mink cell focus hydroprocessing process of high metal content | |
| CN103933997A (en) | Hydrogenation protection catalyst and preparation method thereof | |
| CN104368350B (en) | A kind of hydrogenation protecting catalyst and preparation method and application | |
| CN105754641B (en) | A kind of heavy oil hydrogenation treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |