CN105983416A - Preparation method and use of catalytic cracking raw material hydrodenitrogenation catalyst - Google Patents
Preparation method and use of catalytic cracking raw material hydrodenitrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method and use of a catalytic cracking raw material hydrodenitrogenation catalyst. In hydrodenitrogenation catalyst preparation, the preparation method of the denitrogenation agent comprises carrying out mixing kneading on gamma-Al2O3 as a carrier and pseudo-boehmite as a carrier precursor, extruding the mixture to obtain strips, carrying out drying and calcination, carrying out surface modification by silicon, molding the carrier, drying the carrier at a temperature of 60-150 DEG C for 1-10h, roasting the carrier at a temperature of 400-700 DEG C for 1-5h, adding an impregnation liquid composed of 0.05-4mol/L of a tungsten salt solution, 0.05-4mol/L of a molybdenum salt solution, 0.05-4mol/L of a cobalt salt and 0.05-4mol/L of a nickel salt solution into the carrier, carrying out dipping through a one-step dipping method for 1-10h, carrying out drying and carrying out calcination at a temperature of 300-800 DEG C for 1-6h. The catalyst has the advantages of low reaction temperature, low reaction pressure and high activity.
Description
Technical field
The present invention relates to a kind of catalytically cracked material hydrogenation pretreatment catalyst, can be simultaneously particularly to one
The hydrogenation pretreatment catalyst of nitrogen in removing faulty wax oil.
Background technology
In recent years, the heaviness trend of whole world crude oil is substantially being accelerated, and becomes heavy, variation at crude quality
, the demand of engine fuel and chemical industry light oil is but being increased year by year meanwhile, and to its prescription also
Increasingly harsh.In addition legislations of environmental protection is also being continually strengthened, and how to develop heavy, the crude oil with poor quality degree of depth adds
Work, increases production oils, improves petroleum product-quality, it has also become the problem of whole world petroleum refining industry,
The particularly petroleum refining industry of China, catalytic cracking (FCC) accounts for critically important status in China, and catalysis is split
The raw material of gasifying device is mainly vacuum gas oil (VGO) (VGO), and FCC apparatus mixes refining wax tailings (CGO) in recent years
It is continuously increased with the trend of the inferior raw materials such as deasphalted oil (DAO).
Delayed coking is the important process process of heavy oil lighting in secondary operations, and wax tailings (CGO) is made
For the fraction (accounting for 20%～30%) that coking plant is important, catalytic cracking raw material can be mixed, but coking
In wax oil, the impurity content such as sulfur, nitrogen is high, and cracking performance is poor, mixes refining and too much can have a strong impact on turning of catalytic cracking
Rate, petrol and diesel oil product quality, pollute the problems such as environment so that it is processing and utilization is by a definite limitation.China
What wax tailings directly did catalytically cracked material typically mixes refining ratio less than 25%, and a lot of delay coke of China
Gasifying device use partial circulating expand production capacity than even zero recycle ratio, cause wax tailings increasing number,
Quality is worse.
The main purpose of FCC feedstock weighted BMO spaces is in order to reduce the impurity such as sulfur, nitrogen in FCC feedstock
Content, and metal and the carbon residue content in FCC feedstock also contributes to FCC feedstock quality, and can shadow
Ring the effect to denitrogenation.It is therefore desirable to protective agent and metal remover before removing nitrogen, it is ensured that denitrogenation
Effect.
CN02133138.3 describes a kind of heavy hydrocarbon hydrotreating method, and residual oil raw material passes sequentially through protective agent bed
Layer, Hydrodemetalation catalyst bed, Hydrobon catalyst bed, hydrodenitrogeneration (cracking) catalyst bed
Layer, and after protective agent bed and before Hydrobon catalyst bed, introduce deasphalted oil and/or coking wax
Oil.
CN200610007532.3 describes a kind of method of hydrotreating producing catalytically cracked material.It is characterized in adding
Hydrogen protective agent and residuum hydrogenating and metal-eliminating agent are all carrier loaded molybdenum, tungsten, nickel, cobalt active metal with aluminium oxide.
The pore-size distribution of this carrier be 10～20nm pore volume account for the 70%～98% of total pore volume.Residuum hydrodesulfurization
Agent with aluminium oxide or silicon oxide as carrier, Supported Co, molybdenum 8%～20%, nickel, tungsten 0.3%～8%.
CN200610112926.5 describe a kind of remove from wax tailings coke powder, colloid, heterocyclic arene,
Basic nitrogen compound isopolarity impurity, improves the processing characteristics of wax tailings, is allowed to add suitable with straight-run gas oil
The preprocess method of hydrogen cracked stock.
CN200610002376.1 describes a kind of method of hydrotreating producing fine quality catalytic cracking raw material, its feature
It is hydrogenation protecting agent and Hydrodemetalation catalyst is a kind of alumina support load molybdenum and/or tungsten, and nickel
And/or cobalt.Hydrotreating catalyst is metal load type catalyst, and carrier is silica-alumina, metal
Component is VI B race or VIII race's metal or combinations thereof.Consisting of: nickel oxide 1%～10%, fluorine
1%～10%, phosphorous oxide 0.5%～8%, surplus is silicon oxide and aluminium oxide.
USP4880524 proposes the method for petroleum hydrocarbon hydrotreating.This catalyst metals composition containing 1～
The Ni of 6%, 8～Mo or W of 40%, use gel method to prepare catalyst, specific surface area of catalyst is more than
300m2/ g, containing 70% aperture less than 7nm, this technology is applied to the hydrogenation of light ends oil and takes off
Sulfur.
US4780193 discloses a kind of method of hydrorefining catalyst cracked stock, and its raw material about 70% is
Aromatic hydrocarbons.The reaction temperature of hydro-refining unit is below 390 DEG C, and reaction pressure is at more than 12MPa.Having
Being beneficial to aromatic hydrocarbons saturated with under process conditions, hydrogenation improves the conversion ratio of catalytic cracking unit, produces sulfur content
Low gasoline blend component.
At present, the wax oil hydrogenation catalyst for refining usual imurity-removal sulfur of employing, nitrogen effect are poor, reaction temperature
Degree and reaction pressure are the highest, and active metal utilization rate is relatively low, and adaptability to raw material is bad, cause dress
Put energy consumption higher, it is achieved the problems such as long-term operation is difficult.
Summary of the invention
It is an object of the invention to provide a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method and application, make
It is low that it has reaction temperature, and reaction pressure is low, the advantage that activity is high.
For achieving the above object, the present invention provides a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method, adopts
Modified to catalyst support surface by organosilicon, inorganic silicon and titanium elements, use the method adding auxiliary agent to prepare
Hydrogenation catalyst, and use grading loading technology to carry out hydrogenation evaluation.
For achieving the above object, the present invention provides a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method, urges
Change cracked stock hydrodenitrogenation catalyst and include protective agent, metal remover, desulfurizing agent and denitrifier, wherein,
The preparation method of denitrifier mainly includes following several step:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes one
γ-Al2O3Carrier；A shaping carrier is made the most again after silicone surface-modifying；By described shaping carrier
Dry 1h～10h at 60 DEG C～150 DEG C, then roasting 1h～5h at 400 DEG C～700 DEG C, prepared Herba Trifolii Pratentis,
One or more shapes in Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball；
(2) by the tungsten salt solution of 0.05mol/L～4mol/L, 0.05mol/L～4mol/L molybdenum saline solution,
The impregnation liquid of the cobalt salt solution of 0.05mol/L～4mol/L and the nickel salt solution composition of 0.05mol/L～4mol/L adds
Enter in step (1) in carrier obtained by roasting, after using single-steeping method dipping 1h～10h, dry；Again
Roasting 1h～6h at temperature 300 DEG C～800 DEG C.
Wherein, in step (1), described γ-Al2O3The making step of carrier is particularly as follows: use and intend thin water aluminum
Stone (one in macropore boehmite, super big hole boehmite or its mixture), sesbania powder, silicon
Colloidal sol, nanometer grade silica, citric acid and Mg-bearing water solution are material, with water, binding agent, pore creating material
Carry out kneading, extrusion, dry, roasting, make described γ-Al2O3Carrier.
Wherein, in step (1), the making step (the most silicone surface-modifying step) of described shaping carrier
Particularly as follows: use in silicon, graphite, polyvinyl alcohol and the ethanol of organic surface active agent, propanol, butanol
One or more are to described γ-Al2O3Carrier processes, and makes described shaping carrier.
Wherein, in step (2), impregnation liquid is preferably the tungsten salt solution of 0.1mol/L～4mol/L,
0.1mol/L～4mol/L molybdenum saline solution, the cobalt salt solution of 0.1mol/L～4mol/L and 0.1mol/L～4mol/L
Nickel salt solution composition, dip time is preferably 1h～8h.
Wherein, in step (2), impregnation liquid is also added into the phosphate builder that phosphorus content is 0.001～0.2%.
Wherein, in step (2), in impregnation liquid the active metal tungsten in tungsten salt solution derive from ammonium metatungstate,
One or more in sodium tungstate or tungsten oxide, the molybdenum in molybdenum saline solution derives from sodium molybdate, ammonium molybdate or oxygen
Changing one or more in molybdenum, the cobalt in cobalt salt solution derives from basic cobaltous carbonate, cobalt oxide or cobalt nitrate
One or more, the nickel of nickel salt solution clock derives from the one in basic nickel carbonate, nickel oxide or nickel nitrate
Or it is several.
Wherein, in step (2), described drying be at 60 DEG C～150 DEG C dry, after having dried
Roasting 1h～6h at temperature 300 DEG C～700 DEG C.
The present invention also provides for a kind of catalytically cracked material hydrodenitrogenation catalyst, and described catalytically cracked material is hydrogenated with
Denitrification catalyst is to prepare via said method.
The present invention also provides for the application of a kind of above-mentioned catalytically cracked material hydrodenitrogenation catalyst: by hydrodenitrogeneration
Catalyst carries out level according to the order being from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and denitrifier
Equipped fill out that (protective agent, metal remover and desulfurizing agent are the adjuvant of hydrogenation catalyst, and denitrifier is that hydrogenation is urged
The host of agent).
Wherein, hydrodenitrogenation catalyst each component admission space ratio is: protective agent: metal remover: desulfurizing agent:
Denitrifier=0.1～4:0.5～8:0.5～8:5～40.
Wherein, catalyst grating includes grain size distribution and activity grating.
Wherein, in the grain size distribution of hydrodenitrogenation catalyst, protective agent, metal remover, desulfurizing agent and denitrogenation
The granularity of agent be respectively 3.0mm～4.0mm, 2.0mm～3.0mm, 1.5mm～2.0mm and 1.2mm～
1.8mm。
Wherein, in the active grating of hydrodenitrogenation catalyst, in the ratio of carried metal amount, protective agent: de-
Metal agent: desulfurizing agent: denitrifier=0～4%:1%～12%:1%～23%:1%～33% (active level
Joining, active metal load capacity improves step by step).
Wherein, with above-mentioned hydrodenitrogenation catalyst reaction temperature 350～390 DEG C, pressure 6.0～15.0MPa,
Hydrogen to oil volume ratio 500～2500:1, liquid hourly space velocity (LHSV) 0.1～5.0h-1Under the conditions of process faulty wax oil (VGO
And CGO) and deasphalted oil (DAO).With this understanding, have higher desulfurization degree, denitrification percent,
De-Residual carbon, demetallization per.
Details are as follows for the know-why of the present invention and beneficial effect:
The catalytically cracked material hydrodenitrogenation catalyst that the present invention provides, uses organosilicon, inorganic silicon and titanium unit
Element is modified to catalyst support surface, uses the metallic solution of the high-concentration stable of low phosphorus content preparation, passes through
The most saturated dipping makes the method for catalyst, prepares hydrodenitrogeneration agent, is greatly improved active metal at carrier
The dispersion on surface, thus improve the hydrogenation activity of catalyst.
The catalytically cracked material hydrodenitrogenation catalyst that the present invention provides, before catalyst carrier impregnates, first
One in rear employing silicon, graphite, polyvinyl alcohol and the ethanol of organic surface active agent, propanol, butanol or
Multiple carry out pretreatment, use the metallic solution of the high-concentration stable of low phosphorus content solution preparation, by once
Saturated dipping makes the method for catalyst, prepares hydrodenitrogeneration agent.It is substantially reduced through pretreated carrier
Surface tension, institute adding assistant can improve the stability of solution and increase the specific surface area of catalyst.Work as leaching
When stain liquid contacts with carrier surface, silicon molecule gradually decomposes, and produces a large amount of fresh highly active silicone hydroxyl, easily
In forming Me-O-Si-O-Al (Me represents metal) structure at alumina carrier surface, due to Si-O key key
Long more than Al-O key bond distance, it is mutual that the existence of Si-O key reduces between active metal and alumina support
Active force, additionally, the existence of surfactant has delayed the hydrolysis rate of silicon molecule, has delayed activity simultaneously
Metal ion is in the reunion speed of carrier surface.Carrier, after metallic solution impregnates, is urged in roasting process
Agent Surface Creation a large amount of nanoscale silicon, produce sterically hindered, it is suppressed that active metal is at high temperature
Agglomeration.
The present invention also prepares protective agent, HDM agent, hydrogen desulfurization agent, in conjunction with hydrodenitrogeneration agent, adopts
By grading loading method by above-mentioned four kinds of catalyst combination, process faulty wax oil (VGO and CGO) and take off
Coal tar (DAO), improves the desulfurization degree of catalyst, denitrification percent, de-Residual carbon, demetallization per.Former
Material can be directly as FCC feedstock or hydrocracking raw material after hydrotreating.
Therefore, the preparation method of the present invention improve metal active constituent dispersity and with the phase of carrier
Interaction, is greatly improved the active metal dispersion at carrier surface, improve the utilization ratio of active component from
And improve the activity of catalyst, in short, the catalyst of the present invention to have reaction temperature low, reaction pressure is low,
The advantage that activity is high.
Describe the present invention below in conjunction with specific embodiment, but not as a limitation of the invention.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described in detail, and cited enforcement
Mode is only used as illustration, is not intended as the restriction of the present invention.
Low for making catalyst have reaction temperature, reaction pressure is low, and the advantage that activity is high, the present invention provides one
Planting catalytically cracked material hydrodenitrogenation catalyst preparation method, catalytically cracked material hydrodenitrogenation catalyst includes protection
Agent, metal remover, desulfurizing agent and denitrifier, wherein, the preparation method of denitrifier mainly includes the most several
Step:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes one
γ-Al2O3Carrier；A shaping carrier is made the most again after silicone surface-modifying；By described shaping carrier
Dry 1h～10h at 60 DEG C～150 DEG C, then roasting 1h～5h at 400 DEG C～700 DEG C, prepared Herba Trifolii Pratentis,
One or more shapes in Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball；
(2) by the tungsten salt solution of 0.05mol/L～4mol/L, 0.05mol/L～4mol/L molybdenum saline solution,
The impregnation liquid of the cobalt salt solution of 0.05mol/L～4mol/L and the nickel salt solution composition of 0.05mol/L～4mol/L adds
Enter in step (1) in carrier obtained by roasting, after using single-steeping method dipping 1h～10h, dry；Again
Roasting 1h～6h at temperature 300 DEG C～800 DEG C.
Wherein, in step (1), described γ-Al2O3The making step of carrier is particularly as follows: use and intend thin water aluminum
Stone (one in macropore boehmite, super big hole boehmite or its mixture), sesbania powder, silicon
Colloidal sol, nanometer grade silica, citric acid and Mg-bearing water solution are material, with water, binding agent, pore creating material
Carry out kneading, extrusion, dry, roasting, make described γ-Al2O3Carrier.
Wherein, in step (1), the making step (the most silicone surface-modifying step) of described shaping carrier
Particularly as follows: use in silicon, graphite, polyvinyl alcohol and the ethanol of organic surface active agent, propanol, butanol
One or more are to described γ-Al2O3Carrier processes, and makes described shaping carrier.
Wherein, in step (2), impregnation liquid is preferably the tungsten salt solution of 0.1mol/L～4mol/L,
0.1mol/L～4mol/L molybdenum saline solution, the cobalt salt solution of 0.1mol/L～4mol/L and 0.1mol/L～4mol/L
Nickel salt solution composition, dip time is preferably 1h～8h.
Wherein, in step (2), impregnation liquid is also added into the phosphate builder that phosphorus content is 0.001～0.2%.
Wherein, in step (2), in impregnation liquid the active metal tungsten in tungsten salt solution derive from ammonium metatungstate,
One or more in sodium tungstate or tungsten oxide, the molybdenum in molybdenum saline solution derives from sodium molybdate, ammonium molybdate or oxygen
Changing one or more in molybdenum, the cobalt in cobalt salt solution derives from basic cobaltous carbonate, cobalt oxide or cobalt nitrate
One or more, the nickel of nickel salt solution clock derives from the one in basic nickel carbonate, nickel oxide or nickel nitrate
Or it is several.
Wherein, in step (2), described drying be at 60 DEG C～150 DEG C dry, after having dried
Roasting 1h～6h at temperature 300 DEG C～700 DEG C.
The present invention also provides for a kind of catalytically cracked material hydrodenitrogenation catalyst, and described catalytically cracked material is hydrogenated with
Denitrification catalyst is to prepare via said method.
The present invention also provides for the application of a kind of above-mentioned catalytically cracked material hydrodenitrogenation catalyst: by hydrodenitrogeneration
Catalyst carries out level according to the order being from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and denitrifier
Equipped fill out that (protective agent, metal remover and desulfurizing agent are the adjuvant of hydrogenation catalyst, and denitrifier is that hydrogenation is urged
The host of agent).
Wherein, hydrodenitrogenation catalyst each component admission space ratio is: protective agent: metal remover: desulfurizing agent:
Denitrifier=0.1～4:0.5～8:0.5～8:5～40.
Wherein, catalyst grating includes grain size distribution and activity grating.
Wherein, in the grain size distribution of hydrodenitrogenation catalyst, protective agent, metal remover, desulfurizing agent and denitrogenation
The granularity of agent be respectively 3.0mm～4.0mm, 2.0mm～3.0mm, 1.5mm～2.0mm and 1.2mm～
1.8mm。
Wherein, in the active grating of hydrodenitrogenation catalyst, in the ratio of carried metal amount, protective agent: de-
Metal agent: desulfurizing agent: denitrifier=0～4%:1%～12%:1%～23%:1%～33% (active level
Joining, active metal load capacity improves step by step).
Wherein, with above-mentioned hydrodenitrogenation catalyst reaction temperature 350～390 DEG C, pressure 6.0～15.0MPa,
Hydrogen to oil volume ratio 500～2500:1, liquid hourly space velocity (LHSV) 0.1～5.0h-1Under the conditions of process faulty wax oil (VGO
And CGO) and deasphalted oil (DAO).With this understanding, have higher desulfurization degree, denitrification percent,
De-Residual carbon, demetallization per.
Embodiment a
The present embodiment provides a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method, and catalytically cracked material is hydrogenated with
Denitrification catalyst includes protective agent, metal remover, desulfurizing agent and denitrifier, wherein, the preparation side of denitrifier
Method mainly includes following several step:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes one
γ-Al2O3Carrier (uses the boehmite (one in macropore boehmite, super big hole boehmite
Or its mixture), sesbania powder, Ludox, nanometer grade silica, citric acid and Mg-bearing water solution be material
Material, carries out kneading, extrusion, dry, roasting with water, binding agent, pore creating material, makes described γ-Al2O3
Carrier)；After silicone surface-modifying, make a shaping carrier the most again (use silicon, graphite, poly-second
One or more in enol and the ethanol of organic surface active agent, propanol, butanol are to described γ-Al2O3Carry
Body processes, and makes described shaping carrier)；By described shaping carrier dry 1h at 60 DEG C, then
Roasting 1h at 400 DEG C, prepares one or more in Herba Trifolii Pratentis, Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball
Shape；
(2) by the tungsten salt solution (ammonium metatungstate) of 0.05mol/L, 0.05mol/L molybdenum saline solution (sodium molybdate),
The cobalt salt solution (basic cobaltous carbonate) of 0.05mol/L and the nickel salt solution (basic nickel carbonate) of 0.05mol/L
The impregnation liquid (being also added into the phosphate builder that phosphorus content is 0.001% in impregnation liquid) of composition adds step (1)
In carrier obtained by middle roasting, after using single-steeping method dipping 1h, dry at 60 DEG C；Again in temperature
Roasting 1h at 300 DEG C.
The present embodiment also provides for a kind of catalytically cracked material hydrodenitrogenation catalyst, and described catalytically cracked material adds
Hydrogen denitrification catalyst is to prepare via said method.
The present embodiment also provides for the application of a kind of above-mentioned catalytically cracked material hydrodenitrogenation catalyst: taken off by hydrogenation
Nitrogen catalyst is carried out according to the order being from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and denitrifier
(protective agent, metal remover and desulfurizing agent are the adjuvant of hydrogenation catalyst to grading loading, and denitrifier is hydrogenation
The host of catalyst).Hydrodenitrogenation catalyst each component admission space ratio is: protective agent: metal remover:
Desulfurizing agent: denitrifier=0.1:0.5:0.5:5.Catalyst grating includes grain size distribution and activity grating.Add
In the grain size distribution of hydrogen denitrification catalyst, the granularity of protective agent, metal remover, desulfurizing agent and denitrifier is respectively
For 3.0mm, 2.0mm, 1.5mm and 1.2mm.In the active grating of hydrodenitrogenation catalyst, by load
The ratio of amount of metal, protective agent: metal remover: desulfurizing agent: denitrifier=0:1%:1%:1%.Above
State hydrodenitrogenation catalyst when reaction temperature 350 DEG C, pressure 6.0MPa, hydrogen to oil volume ratio 500:1, liquid
Air speed 0.1h-1Under the conditions of process faulty wax oil and deasphalted oil.
Embodiment b
The present embodiment provides a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method, and catalytically cracked material is hydrogenated with
Denitrification catalyst includes protective agent, metal remover, desulfurizing agent and denitrifier, wherein, the preparation side of denitrifier
Method mainly includes following several step:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes one
γ-Al2O3Carrier (uses the boehmite (one in macropore boehmite, super big hole boehmite
Or its mixture), sesbania powder, Ludox, nanometer grade silica, citric acid and Mg-bearing water solution be material
Material, carries out kneading, extrusion, dry, roasting with water, binding agent, pore creating material, makes described γ-Al2O3
Carrier)；After silicone surface-modifying, make a shaping carrier the most again (use silicon, graphite, poly-second
One or more in enol and the ethanol of organic surface active agent, propanol, butanol are to described γ-Al2O3Carry
Body processes, and makes described shaping carrier)；By described shaping carrier dry 10h at 150 DEG C, then
Roasting 5h at 700 DEG C, prepares one or more in Herba Trifolii Pratentis, Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball
Shape；
(2) by the tungsten salt solution (ammonium metatungstate) of 4mol/L, 4mol/L molybdenum saline solution (sodium molybdate), 4mol/L
Cobalt salt solution (basic cobaltous carbonate) and the impregnation liquid that forms of the nickel salt solution (basic nickel carbonate) of 4mol/L
(being also added into the phosphate builder that phosphorus content is 0.2% in impregnation liquid) adds the obtained load of roasting in step (1)
In body, after using single-steeping method dipping 10h, dry at 150 DEG C；Roasting at temperature 800 DEG C again
6h。
The present embodiment also provides for a kind of catalytically cracked material hydrodenitrogenation catalyst, and described catalytically cracked material adds
Hydrogen denitrification catalyst is to prepare via said method.
The present embodiment also provides for the application of a kind of above-mentioned catalytically cracked material hydrodenitrogenation catalyst: taken off by hydrogenation
Nitrogen catalyst is carried out according to the order being from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and denitrifier
(protective agent, metal remover and desulfurizing agent are the adjuvant of hydrogenation catalyst to grading loading, and denitrifier is hydrogenation
The host of catalyst).Hydrodenitrogenation catalyst each component admission space ratio is: protective agent: metal remover:
Desulfurizing agent: denitrifier=4:8:8:40.Catalyst grating includes grain size distribution and activity grating.Add
In the grain size distribution of hydrogen denitrification catalyst, the granularity of protective agent, metal remover, desulfurizing agent and denitrifier is respectively
For 4.0mm, 3.0mm, 2.0mm and 1.8mm.In the active grating of hydrodenitrogenation catalyst, by load
The ratio of amount of metal, protective agent: metal remover: desulfurizing agent: denitrifier=4%:12%:23%:33%
(activity grating, active metal load capacity improves step by step).With above-mentioned hydrodenitrogenation catalyst in reaction temperature
390 DEG C, pressure 15.0MPa, hydrogen to oil volume ratio 2500:1, liquid hourly space velocity (LHSV) 5.0h-1Under the conditions of process poor quality
Wax oil and deasphalted oil.
Embodiment c
The present embodiment provides a kind of catalytically cracked material hydrodenitrogenation catalyst preparation method, and catalytically cracked material is hydrogenated with
Denitrification catalyst includes protective agent, metal remover, desulfurizing agent and denitrifier, wherein, the preparation side of denitrifier
Method mainly includes following several step:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes one
γ-Al2O3Carrier (uses the boehmite (one in macropore boehmite, super big hole boehmite
Or its mixture), sesbania powder, Ludox, nanometer grade silica, citric acid and Mg-bearing water solution be material
Material, carries out kneading, extrusion, dry, roasting with water, binding agent, pore creating material, makes described γ-Al2O3
Carrier)；After silicone surface-modifying, make a shaping carrier the most again (use silicon, graphite, poly-second
One or more in enol and the ethanol of organic surface active agent, propanol, butanol are to described γ-Al2O3Carry
Body processes, and makes described shaping carrier)；By described shaping carrier dry 5h at 100 DEG C, then
Roasting 3h at 500 DEG C, prepares one or more in Herba Trifolii Pratentis, Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball
Shape；
(2) by the tungsten salt solution (ammonium metatungstate) of 0.1mol/L, 0.1mol/L molybdenum saline solution (sodium molybdate),
The cobalt salt solution (basic cobaltous carbonate) of 0.1mol/L and nickel salt solution (basic nickel carbonate) group of 0.1mol/L
The impregnation liquid (being also added into the phosphate builder that phosphorus content is 0.1% in impregnation liquid) become adds roasting in step (1)
Burn in obtained carrier, after using single-steeping method dipping 8h, dry at 100 DEG C；Again in temperature 700
Roasting 3h at DEG C.
The present embodiment also provides for a kind of catalytically cracked material hydrodenitrogenation catalyst, and described catalytically cracked material adds
Hydrogen denitrification catalyst is to prepare via said method.
The present embodiment also provides for the application of a kind of above-mentioned catalytically cracked material hydrodenitrogenation catalyst: taken off by hydrogenation
Nitrogen catalyst is carried out according to the order being from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and denitrifier
(protective agent, metal remover and desulfurizing agent are the adjuvant of hydrogenation catalyst to grading loading, and denitrifier is hydrogenation
The host of catalyst).Hydrodenitrogenation catalyst each component admission space ratio is: protective agent: metal remover:
Desulfurizing agent: denitrifier=2:4:5:20.Catalyst grating includes grain size distribution and activity grating.Hydrogenation is de-
In the grain size distribution of nitrogen catalyst, the granularity of protective agent, metal remover, desulfurizing agent and denitrifier is respectively
3.5mm, 2.5mm, 1.8mm and 1.5mm.In the active grating of hydrodenitrogenation catalyst, by gold-supported
The ratio of genus amount, protective agent: metal remover: desulfurizing agent: denitrifier=2%:6%:10%:20% (lives
Property grating, active metal load capacity improves step by step).With above-mentioned hydrodenitrogenation catalyst in reaction temperature 370
DEG C, pressure 10.0MPa, hydrogen to oil volume ratio 1000:1, liquid hourly space velocity (LHSV) 2.0h-1Under the conditions of process faulty wax oil
And deasphalted oil.
Details are as follows for the know-why of the present invention and beneficial effect:
The catalytically cracked material hydrodenitrogenation catalyst that the present invention provides, uses organosilicon, inorganic silicon and titanium unit
Element is modified to catalyst support surface, uses the metallic solution of the high-concentration stable of low phosphorus content preparation, passes through
The most saturated dipping makes the method for catalyst, prepares hydrodenitrogeneration agent, is greatly improved active metal at carrier
The dispersion on surface, thus improve the hydrogenation activity of catalyst.
The catalytically cracked material hydrodenitrogenation catalyst that the present invention provides, before catalyst carrier impregnates, first
One in rear employing silicon, graphite, polyvinyl alcohol and the ethanol of organic surface active agent, propanol, butanol or
Multiple carry out pretreatment, use the metallic solution of the high-concentration stable of low phosphorus content solution preparation, by once
Saturated dipping makes the method for catalyst, prepares hydrodenitrogeneration agent.It is substantially reduced through pretreated carrier
Surface tension, institute adding assistant can improve the stability of solution and increase the specific surface area of catalyst.Work as leaching
When stain liquid contacts with carrier surface, silicon molecule gradually decomposes, and produces a large amount of fresh highly active silicone hydroxyl, easily
In forming Me-O-Si-O-Al (Me represents metal) structure at alumina carrier surface, due to Si-O key key
Long more than Al-O key bond distance, it is mutual that the existence of Si-O key reduces between active metal and alumina support
Active force, additionally, the existence of surfactant has delayed the hydrolysis rate of silicon molecule, has delayed activity simultaneously
Metal ion is in the reunion speed of carrier surface.Carrier, after metallic solution impregnates, is urged in roasting process
Agent Surface Creation a large amount of nanoscale silicon, produce sterically hindered, it is suppressed that active metal is at high temperature
Agglomeration.
The present invention also prepares protective agent, HDM agent, hydrogen desulfurization agent, in conjunction with hydrodenitrogeneration agent, adopts
By grading loading method by above-mentioned four kinds of catalyst combination, process faulty wax oil (VGO and CGO) and take off
Coal tar (DAO), improves the desulfurization degree of catalyst, denitrification percent, de-Residual carbon, demetallization per.Former
Material can be directly as FCC feedstock or hydrocracking raw material after hydrotreating.
Therefore, the preparation method of the present invention improve metal active constituent dispersity and with the phase of carrier
Interaction, is greatly improved the active metal dispersion at carrier surface, improve the utilization ratio of active component from
And improve the activity of catalyst, in short, this catalyst to have reaction temperature low, reaction pressure is low, activity
High advantage.
Below by embodiment and experimental data thereof, preparation method and the catalyst prod thereof of the present invention are made into one
Step explanation, to clearly show that its technique effect.
Embodiment 1
The preparation of denitrifier
First, using macropore and/or super big hole raw material is carrier predecessor, through kneading, extrusion, be dried,
Roasting forms.By the magnesia alumina spinel-zirconia alumina supporter silicon prepared, graphite, polyvinyl alcohol and organic
The ethanol of surfactant, propanol, butanol carry out surface process, dried at 30 DEG C～50 DEG C, in room temperature
Or addition metallic solution is configured to solution, by the most saturated impregnation under heating condition
W-Mo-Co-Ni metallic solution, aging 1～10h, 100 DEG C～120 DEG C of dry 2h～8h, 400 DEG C～800
Calcination process 2h～6h under DEG C air, prepare denitrifier.
Protective agent, metal remover, desulfurizing agent, the composition of denitrifier and character made above is as shown in table 1,
Selecting faulty wax oil (VGO:CGO:DAO=5:5:3) is that raw material carries out catalyst hydrogenation evaluation,
Feedstock property is as shown in table 2.At reaction temperature 350 DEG C～390 DEG C, pressure 6 MPa～15.0MPa, hydrogen
Oil volume is than 500:2500, liquid hourly space velocity (LHSV) 0.5～5.0h-1Under the conditions of process faulty wax oil, its evaluation result
As shown in table 3, in embodiment 1, catalyst is at reaction temperature 380 DEG C, reaction pressure 10.0MPa, hydrogen
Oil volume is than 1000:1, volume space velocity 1.0h-1Process conditions under, desulfurization degree 97.9%, denitrification percent 85.2
%, de-Residual carbon 94.2%, metal removal rate 96.3%.Compared with comparative catalyst, as table 3 contrasts
Shown in example, its desulfurization degree, denitrification percent, de-Residual carbon, demetallization per all increase.
Table 1 faulty wax oil hydrotreating catalyst
Table 2 faulty wax oil feedstock property
Table 3 catalyst hydrogenation evaluation
Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and the feelings of essence thereof
Under condition, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but this
A little corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.
Claims (12)
1. a catalytically cracked material hydrodenitrogenation catalyst preparation method, catalytically cracked material hydrodenitrogeneration is catalyzed
Agent includes protective agent, metal remover, desulfurizing agent and denitrifier, it is characterised in that the preparation method of denitrifier
Comprise the steps:
(1) using boehmite is carrier predecessor, through kneading, extrusion, dry, roasting, makes
One γ-Al2O3Carrier；A shaping carrier is made the most again after silicone surface-modifying；By described molding
Carrier is dried 1h～10h, then roasting 1h～5h at 400 DEG C～700 DEG C at 60 DEG C～150 DEG C, prepares three
One or more shapes in leaf grass, Herba Galii Bungei, dish, Raschig ring and seven apertures in the human head ball；
(2) by the tungsten salt solution of 0.05mol/L～4mol/L, 0.05mol/L～4mol/L molybdenum saline solution,
The cobalt salt solution of 0.05mol/L～4mol/L and the impregnation liquid of the nickel salt solution composition of 0.05mol/L～4mol/L
Add in step (1) in carrier obtained by roasting, after using single-steeping method dipping 1h～10h, dry；
Roasting 1h～6h at temperature 300 DEG C～800 DEG C again.
Catalytically cracked material hydrodenitrogenation catalyst preparation method the most according to claim 1, it is characterised in that
In step (1), use boehmite, sesbania powder, Ludox, nanometer grade silica, citric acid
It is material with Mg-bearing water solution, carries out kneading, extrusion, dry, roasting with water, binding agent, pore creating material,
Make described γ-Al2O3Carrier.
Catalytically cracked material hydrodenitrogenation catalyst preparation method the most according to claim 1, it is characterised in that
In step (2), impregnation liquid is the tungsten salt solution of 0.1mol/L～4mol/L, 0.1mol/L～4mol/L molybdenum salt
Solution, the cobalt salt solution of 0.1mol/L～4mol/L and the nickel salt solution composition of 0.1mol/L～4mol/L, dipping
Time is 1h～8h.
Catalytically cracked material hydrodenitrogenation catalyst preparation method the most according to claim 1, it is characterised in that
In step (2), impregnation liquid is also added into the phosphate builder that phosphorus content is 0.001～0.2%.
Catalytically cracked material hydrodenitrogenation catalyst preparation method the most according to claim 1, it is characterised in that
In step (2), in impregnation liquid the active metal tungsten in tungsten salt solution derive from ammonium metatungstate, sodium tungstate or
One or more in tungsten oxide, the molybdenum in molybdenum saline solution derives from sodium molybdate, ammonium molybdate or molybdenum oxide
One or more, the cobalt in cobalt salt solution derive from the one in basic cobaltous carbonate, cobalt oxide or cobalt nitrate or
Several, the nickel of nickel salt solution clock derives from one or more in basic nickel carbonate, nickel oxide or nickel nitrate.
Catalytically cracked material hydrodenitrogenation catalyst preparation method the most according to claim 1, it is characterised in that
In step (2), described drying is to dry, temperature 300 DEG C after having dried at 60 DEG C～150 DEG C
～roasting 1h～6h at 700 DEG C.
7. an application for hydrodenitrogenation catalyst obtained by any one in claim 1-6, it is special
Levy and be, by hydrodenitrogenation catalyst according to be from top to bottom followed successively by protective agent, metal remover, desulfurizing agent and
The order of denitrifier carries out grading loading.
The application of hydrodenitrogenation catalyst the most according to claim 7, it is characterised in that hydrogenation is de-
Nitrogen catalyst components admission space ratio is, protective agent: metal remover: desulfurizing agent: denitrifier=0.1～4:
0.5～8:0.5～8:5～40.
The application of hydrodenitrogenation catalyst the most according to claim 7, it is characterised in that catalyst
Grating includes grain size distribution and activity grating.
The application of hydrodenitrogenation catalyst the most according to claim 9, it is characterised in that hydrogenation is de-
In the grain size distribution of nitrogen catalyst, the granularity of protective agent, metal remover, desulfurizing agent and denitrifier is respectively
3.0mm～4.0mm, 2.0mm～3.0mm, 1.5mm～2.0mm and 1.2mm～1.8mm.
11. the application of hydrodenitrogenation catalyst according to claim 9, it is characterised in that hydrogenation is de-
In the active grating of nitrogen catalyst, in the ratio of carried metal amount, protective agent: metal remover: desulfurizing agent:
Denitrifier=0～4%:1%～12%:1%～23%:1%～33%.
The application of 12. hydrodenitrogenation catalysts according to claim 7, it is characterised in that will hydrogenation
Denitrification catalyst reaction temperature 350～390 DEG C, pressure 6.0～15.0MPa, hydrogen to oil volume ratio 500～
2500:1, liquid hourly space velocity (LHSV) 0.1～5.0h-1Under the conditions of process faulty wax oil and deasphalted oil.
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