CN108786862B - Hydrogenation catalyst and continuous production method - Google Patents
Hydrogenation catalyst and continuous production method Download PDFInfo
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- CN108786862B CN108786862B CN201710299538.0A CN201710299538A CN108786862B CN 108786862 B CN108786862 B CN 108786862B CN 201710299538 A CN201710299538 A CN 201710299538A CN 108786862 B CN108786862 B CN 108786862B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses a kind of hydrogenation catalyst and continuous production methods.Hydrogenation catalyst of the invention includes alumina support, active metal and auxiliary agent, and wherein active metal is selected from one or more of VIII group and/or group vib metallic element；On the basis of catalyst weight, for active metal in terms of oxide, group VIII metal is 1wt%~9wt%, it is preferred that 1.0wt%~5.0wt%, group vib metal is 5wt%~25wt%, preferably 10wt%~20wt%, auxiliary agent is 2wt% ~ 5wt% based on the element, and alumina support is 61wt% ~ 92wt%.Table phase active metal and auxiliary agent density are bigger in hydrogenation catalyst, and the trend gradually increased is presented along partial size from inside to outside for active metal concentrations.The method of the present invention hydrogenation active metals utilization rate is higher, can be effectively improved catalyst surface acidity, slow down the deactivation rate of catalyst, realize the continuous production of hydrogenation catalyst, improve production efficiency, reduce production cost.
Description
Technical field
The present invention relates to distillate hydrogenation fields, more particularly to a kind of hydrogenation catalyst and continuous production method.
Background technique
Crude oil and from distillate obtained in crude oil contain sulphur, nitrogen, oxygen and metal impurities.The presence of these impurity
The stability of oil product is not only influenced, but also can also discharge SO in useX、NOXEqual pernicious gases pollute environment.In oil product
Secondary processing process in, the presence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning.Therefore, removing above-mentioned impurity is
Significant process in oil product processing.Distillate hydrogenation processing refers under certain temperature and pressure, feedstock oil and hydrogen and catalysis
Agent contact, the process of imurity-removal and aromatic hydrocarbons saturation.
Typical hydrotreating catalyst be periodic table VIII and group vib metal it is oxide carried in refractory oxides
On, the refractory oxides such as aluminium oxide, oxidation sial, silica, zeolite, titanium dioxide, zirconium oxide, boron oxide and it
Mixture.In general, by the aqueous solution of the one or many impregnating metal compounds of carrier, then these catalyst are
By one or more dryings and roasting process, this method is described in such as EP0469675, US4317746, US4738767
In patent document.
Coprecipitation prepares bulk phase catalyst technology, and using different coprecipitation modes, Gelation Conditions etc. can be in catalyst
Active metallic content and activated centre density, the distribution of different hydrogenation active metals and different hydrogenation activity gold on channel surfaces
Interaction relationship has a great impact between category.Using coprecipitation can make different hydrogenation active metals distribution do not allow it is easily-controllable
System, to influence the distribution of different hydrogenation active metals, reduces the interaction between active metal, while table phase in catalyst
Active metallic content is small and active metal density is lower, the final Hydrogenation for influencing catalyst.Therefore, how to regulate and control plus hydrogen is living
Property metal distribution, make that there is suitable mating reaction between hydrogenation active metal component, how to increase table in catalyst and mutually live
Property tenor and activated centre density, improve the utilization rate of hydrogenation active metal component, be to improve catalyst hydrogenation performance
It is crucial.
The production method of boehmite is mainly inorganic aluminate method and organic aluminium salt method at present, between production process mostly uses
Formula of having a rest tank reactor, there are unstable product quality, how the problems such as production efficiency is low realize that boehmite is continuous
Metaplasia production is current urgently problem to be solved.
CN101927197A is related to a kind of active metal and acidic assistant concentration reduces the hydrogenation catalyst of distribution in gradient
And preparation method.This method is by preparing denseer active metal solution and acid additive solution, during carrier impregnation, by
Step addition deionized water or the method for ammonium hydroxide dilute solution are saturated spray-stain carrier；This method is using repeatedly dipping, dry and roasting
Burning process, the dipping of multiple active metal and roasting easily cause the blocking of catalyst pore structure and the destruction in duct.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenation catalyst and continuous production method.The present invention adds
Table phase active metal and auxiliary agent density are bigger in hydrogen catalyst, and hydrogenation active metals utilization rate is higher, and active metal concentrations are along grain
The trend gradually increased is presented in diameter from inside to outside, can be effectively improved catalyst surface acidity, slows down the inactivation speed of catalyst
Degree.The method of the present invention realizes the continuous production of hydrogenation catalyst, improves production efficiency, reduces production cost.
Hydrogenation catalyst of the invention is body phase hydrogenation catalyst, including alumina support, active metal and auxiliary agent, wherein
Active metal is selected from one or more of VIII group and/or group vib metallic element；On the basis of catalyst weight, activity gold
Belong in terms of oxide, group VIII metal be 1wt%~9wt%, preferably 1.0wt%~5.0wt%, group vib metal be 5wt%~
25wt%, preferably 10wt%~20wt%, auxiliary agent are 2wt% ~ 5wt% based on the element, and alumina support is 61wt% ~ 92wt%；Wherein help
Agent is one of several combinations of following I, II and III: I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron.
In hydrogenation catalyst of the present invention, the concentration of active metal is in terms of oxide, from catalyst granules center to outer surface
Gradually increase, wherein at 1/3R active metal concentration be 6wt%~10wt%, 2/3R locate active metal concentration for 10wt%~
The concentration of active metal is 20wt%~30wt% at 20wt%, R；R is catalyst granules center to catalyst cross section outer most edge
The distance at any point；Wherein auxiliary agent is one of several combinations of following I, II and III: I- fluorine and phosphorus, II- fluorine and boron,
III- fluorine, phosphorus and boron, preferably III- fluorine, phosphorus and boron；When auxiliary agent is I, fluorine accounts for the 50%~55% of auxiliary agent quality, and phosphorus accounts for the total matter of auxiliary agent
The 45%~50% of amount；When auxiliary agent is II, fluorine accounts for the 50%~55% of auxiliary agent quality, and boron accounts for the 45%~50% of auxiliary agent gross mass；When helping
When agent is III, fluorine accounts for the 50%~55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, boron account for auxiliary agent total amount 15%~
20%.Active metal concentrations are measured using field emission scanning electron microscope on catalyst cross section.
Hydrogenation catalyst of the present invention, active metal is in terms of oxide, weight content and the body phase of table phase active metal component
The ratio of the weight content of active metal component is 3.0 ~ 15.0:1, preferably 3.0 ~ 14.0:1；Auxiliary agent based on the element, table phase auxiliary agent
The ratio of weight content and the weight content of body phase auxiliary agent is 3.0 ~ 10.0:1, preferably 3.0 ~ 5.0:1；Catalyst one kind of the present invention is excellent
Choosing composition are as follows: the weight content ratio of the active metal of table phase VIII group and body phase VIII group active metal is 2.0:1 ~ 6.0:1, excellent
It is selected as 2.0 ~ 5.0:1, the weight content ratio of table phase VIB active metal and body phase VIB active metal is 2.0:1 ~ 8.0:1, preferably
For 2.0:1 ~ 6.0:1.
In hydrogenation catalyst of the present invention, the weight content of table phase VIII group active metal is VIII group active metal in table phase
Weight content, the weight content of table phase auxiliary agent is the weight content of auxiliary agent in table phase, body phase VIII group active metal component
Weight content is the weight content of VIII group active metal in catalyst；The weight content of body phase auxiliary agent is auxiliary agent in catalyst
Weight content；The weight content of table phase VIB active metal component is the weight content of VIB active metal in table phase, and body phase VIB is living
Property metal weight content be catalyst in VIB active metal weight content.Catalyst table phase active metallic content uses X-
X-ray photoelectron spectroscopy X (XPS) measurement, caltalyst phase active metallic content use inductively coupled plasma body atomic emissions light
Compose (ICP-AES) measurement.
In the present invention, so-called " catalyst granules " center " refers to the central point of catalyst cross section, " the catalyst cross
Section " refers to the whole table of exposure after the geometric center cutting for passing through its shape along the minimum dimension direction of a catalyst granules
Face.For example, the cross section refers to passing through along the radius or short-axis direction of the ball when the catalyst granules is spherical
The whole surface of exposure after the cutting of its centre of sphere.Alternatively, the cross section refers to vertically when the catalyst granules is column
The whole surface of exposure after the length dimension direction of the column is by the central point cutting of the length dimension.The exposed surface
Periphery is known as the outer most edge of the cross section, and the geometric center (than the centre of sphere as the aforementioned or the central point of length dimension) is known as
Central point on the cross section, as catalyst granules center.
Hydrogenation catalyst of the present invention has the property that 0.4~0.6mlg of Kong Rongwei-1；Aperture is 90~150；Abrasion
≤ 0.05%, preferably≤0.03%；Bulk density is 0.80~0.95g/ml.
The centralized particle diameter of hydrogenation catalyst of the invention, particle diameter distribution are as follows: 200 μm of partial size proportions of < are
0.5%~1%, 200~300 μm of partial size proportions are that 5%~10%, >, 300 μm of partial size proportions are 85%~90%.
The continuous production method of hydrogenation catalyst of the invention, including following content:
(1) bottom water of certain volume is added in reactor tank and swing tank, is heated to certain temperature, then starting stirring
Device, opens acid solution feed inlet and lye feed inlet at the top of reactor tank, acid aluminium salt solution I and basic aluminium salt solution I respectively with
Certain flow velocity respectively from the top of reactor tank acid solution feed inlet and lye feed inlet be continuously added to, adjust pH value be 7.0 ~ 8.5
Between, after a period of stabilisation, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank I；
(2) after the overflow port trickle of reactor tank, the lye feed inlet for swinging the upper end tank I is opened, stream adds certain dense
The basic aluminium salt solution II of degree, basic activated metal salt solution I and the ionic liquid containing auxiliary agent, adjusting pH value to 10.0~
Between 11.5, after reacting a period of time, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；
(3) after the overflow port trickle for swinging tank I, the acid solution feed inlet for swinging the upper end tank II is opened, stream adds certain
The acid aluminium salt solution III of concentration, acidity active metal salt solution II and and the ionic liquid containing auxiliary agent, adjust pH value to
Between 3.0~5.0, after reacting a period of time, the overflow port for swinging the bottom tank II is opened, makes to generate liquid stream into ageing can；
(4) after the overflow port trickle for swinging tank II, the lye feed inlet of ageing can upper end is opened, stream adds certain dense
The basic aluminium salt solution IV of degree, basic activated metal salt solution III and and the ionic liquid containing auxiliary agent, adjust pH value to 7.0
Between~8.5, after aging for a period of time, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, warp
Filtering, dry and roasting, obtain hydrogenation catalyst.
In the method for the present invention, reactor tank, each volume for swinging bottom water in tank account for the tank volume in the step (1)
1/5~1/4, the temperature of reactor tank is less than each temperature for swinging tank, and the temperature of reactor tank is 50~80 DEG C, each swing tank
Temperature be the reaction temperature be 60~100 DEG C, reactor tank and the temperature difference swung between tank are 10~30 DEG C.Reactor tank
Stirring rate be higher than each stirring rate for swinging tank, the stirring rate of reactor tank is 300~700rad/min, each to stir
The stirring rate for mixing tank is 100~400rad/min, and reactor tank and the rotational speed difference swung between tank are 100~200rad/min.
In the method for the present invention, the acid aluminium salt solution can be AlCl3、Al2(SO4)3Or Al (NO)3Aqueous solution in
One or more, preferably Al2(SO4)3、AlCl3Aqueous solution, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/
100ml, flow velocity are 10~80ml/min；The basic aluminium salt solution is selected from NaAlO2Or KAlO2One of aqueous solution or two
Kind, preferably NaAlO2Aqueous solution, the concentration of basic aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/100ml, flow velocity is 10~
80ml/min；
Acid aluminium salt solution I wherein in step (1) is identical with the concentration of basic aluminium salt solution I, with Al2O3Meter.
In the method for the present invention, basic aluminium salt solution I, basic aluminium salt solution II, acid aluminium salt solution III and basic aluminium salt are molten
Al in liquid IV2O3Concentration is in the trend being gradually reduced, and reduction amplitude is 10~20g/100ml.
In the method for the present invention, the acid active metal salt solution be molybdenum nickel phosphorus, molybdenum cobalt phosphorus, molybdenum cobalt nickel phosphorus, tungsten nickel phosphorus,
One of tungsten nickel phosphorus, tungsten nickel cobalt phosphorus or tungsten cobalt phosphorus aqueous solution, the concentration of acid active metal salt solution is with oxide
It is calculated as 15~100g/100ml, pH value is 1.0~4.0, and acid active metal saline solution flow is 5~50ml/min；It is described
Basic activated metal salt solution be molybdenum nickel ammonia, molybdenum cobalt ammonia, molybdenum cobalt nickel ammonia, tungsten nickel ammonia, tungsten nickel ammonia, tungsten nickel cobalt ammonia or tungsten
The concentration of one of cobalt ammonia spirit, basic activated metal salt solution is calculated as 15~100g/100ml with oxide, and pH value is
10.0~12.0, alkalinous metal saline solution flow is 5~50ml/min；Basic activated metal salt solution I, acid active metal
Active metal concentrations are become in terms of reactive metal oxides in what is gradually increased in salting liquid II and basic activated metal salt solution III
Gesture, increasing degree are 15~25g/100ml.
The preparation method of acid active metal salt solution belongs to content well known to those skilled in the art, water-soluble with molybdenum nickel phosphorus
It is illustrated for liquid, the preparation method is as follows: molybdenum oxide and basic nickel carbonate is taken to be put into more mouthfuls of flasks, a certain amount of go is added
After ionized water, be stirred until vial matter is in pulpous state, be then slowly added phosphoric acid, wait startings reaction later again slowly plus
Heat, being kept for 90~110 DEG C of times of solution temperature is 1~3 hour, after stopping heating, filters to acquired solution, is then added while hot
Phosphoric acid adjusts the pH value of solution to 1.0~4.0 to arrive molybdenum nickel phosphorus aqueous solution.
The preparation method of basic activated metal salt solution belongs to content well known to those skilled in the art.It is molten with molybdenum nickel ammonium hydroxide
It is illustrated for liquid, specific preparation process is as follows: ammonium molybdate and nickel nitrate being taken to be put into more mouthfuls of flasks, a certain amount of go is added
After ionized water, be stirred until vial matter is in pulpous state, be then slowly added ammonium hydroxide, wait startings reaction later again slowly plus
Heat, being kept for 70~80 DEG C of times of solution temperature is 1~2 hour, after stopping heating, filters to acquired solution, is then added while hot
Ammonium hydroxide adjusts the pH of solution to 10.0~12.0 to arrive molybdenum nickel ammonia solution.
In the method for the present invention, the preparation method of the ionic liquid containing auxiliary agent can be used conventional method and carry out M generally1With
M2It is added to the water, is heated to reaction temperature under agitation, isothermal reaction, after reaction, cooling, centrifugation obtains ionic liquid
Body；Wherein M1With M2Molar ratio be 1:1~1:2, reaction condition be generally reaction temperature be 60~150 DEG C, preferably 70~100
DEG C, the isothermal reaction time is 1~4h, preferably 1~2h.The M1For ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate hexafluoro
One or more of ammonium phosphate, sodium hexafluoro phosphate, Potassium Hexafluorophosphate etc., preferably ammonium hexafluorophosphate and/or ammonium tetrafluoroborate.
The M2One or more of the alkyl ammonium halide for being 1 ~ 12 for carbon atom number, alkyl are preferably methyl, in ethyl
One or more, the preferred chlorine of halogen, further preferably dimethy lammonium chloride and/or diethyl ammonium halide, halogenation triethyl ammonium,
Halogenation tetraethyl ammonium, ethyl ammonium halide, halogenated methyl tri-n-butylamine, halogenation dimethyl di-n-butylamine, halogenation propyl tri-n-butylamine,
One of halogenation dipropyl di-n-butylamine, halogenated methyl puratized agricultural spray, halogenation dimethyl puratized agricultural spray, halogenation trimethyl puratized agricultural spray etc. are several
Kind, preferably one or more of halogenated methyl puratized agricultural spray, halogenation dimethyl di-n-butylamine, the preferred chlorine of halogen.
In the method for the present invention, step (2), (3), (4) middle additional amount that the ionic liquid containing auxiliary agent is added are identical, step
Suddenly (2), (3), (4) intermediate ion liquid additional amount account for step (2), (3), inlet amount in (4) respectively in terms of auxiliary element
1wt%~4wt%, wherein inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides.
In the method for the present invention, ageing time described in step (4) is 0.5~2.0h, preferably 0.5~1.5h.The present invention
In method, drying temperature described in step (4) is 40~200 DEG C, preferably 60~150 DEG C；Drying time is 1~5 hour, preferably
2~4 hours.
It, can also be according to actual needs after swinging tank II in the method for the present invention, the swing tank for certain amount of connecting is excellent
Choosing 1 ~ 4 swing tank of series connection, repeats the process of step (2) and (3)；When even number of connecting swings tank, such as 2 or 4 pendulum of series connection
When dynamic tank, the last one material for swinging the overflow of tank enters ageing can and carries out step (4), swing it is acid in tank and ageing can or
The concentration of basic aluminium salt solution is successively decreased in terms of oxide by logistics direction, reduction amplitude be 10~20g/100ml, swing tank and
The active metal concentrations of ageing can neutral and alkali active metal salt solution are incremented by terms of reactive metal oxides by logistics direction, are increased
Adding amplitude is 15~25g/100ml；It is identical with the additional amount of the ionic liquid in ageing can containing auxiliary agent to swing tank；When series connection odd number
When a swing tank, when such as 1 or 3 swing tank of series connection, after the last one swings tank repetition step (2), carry out step (4 '): to
After the overflow port trickle for swinging tank, the lye feed inlet of ageing can upper end is opened, it is molten that certain density acid aluminium salt is added dropwise
Liquid, acid active metal salt solution and the ionic liquid containing auxiliary agent adjust pH value between 7.0~8.5, and aging is for a period of time
Afterwards, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting, is added
Hydrogen handles catalyst；Acid or basic aluminium salt solution concentration is in terms of oxide in swing tank and ageing can, according to logistics direction
Gradually successively decrease, reduction amplitude is 10~20g/100ml, swings the active metal of tank and ageing can neutral and alkali active metal salt solution
Concentration is incremented by terms of reactive metal oxides by logistics direction, and increasing degree is 15~25g/100ml；Swing tank and ageing can
In the ionic liquid containing auxiliary agent additional amount it is identical.
Present invention simultaneously provides a kind of hydrogenation catalyst continuous production devices, including reactor tank, swing tank I, swing tank
II and ageing can are composed in series；Setting acid solution feed inlet and lye feed inlet at the top of the reactor tank, centre are blender, bottom
Portion is equipped with overflow port, and overflow port is connected to through pipeline with tank top is swung；It swings and acid/base liquid feed inlet is set at the top of tank I, centre is
Blender, bottom are equipped with overflow port, and overflow port is connected to through pipeline with the top tank II is swung；It swings and acid/base liquid is set at the top of tank II
Feed inlet, centre are mixing plant, and bottom is equipped with overflow port, and overflow port at the top of pipeline and ageing can through being connected to；At the top of ageing can
Acid/base liquid feed inlet is set, and bottom is equipped with discharge port；The acid/base liquid feed inlet connects corresponding material pipeline.
In apparatus of the present invention can also as needed after swinging tank II increase certain amount swing tank, preferably 1 ~
4 swing tanks swing serial communication between tank, the last one swings tank and is connected to ageing can.Apparatus of the present invention can also basis
It is in parallel to need to be arranged multiple ageing cans.
Flow control valve is installed in the respective lines of the connection reactor tank, the overflow port for swinging tank and ageing can,
For controlling the flow of disengaging material.
In apparatus of the present invention, swinging setting acid/base feed inlet at the top of tank and ageing can is the same feed inlet, when addition acid
Then it is acid feed inlet when property solution, is then alkaline feed inlet when alkaline solution is added.
Compared with prior art, the invention has the following advantages that
1, the method for the present invention realizes pH value swing method continuous production spherical phase hydrogenation catalyst, improves catalyst
Production efficiency, while can the excellent hydrogenation catalyst of processability, it is more time saving and energy saving than intermittent, substantially increase plus
The output of hydrogen catalyst reduces production cost, and economic, environmental protection；
2, body phase hydrogenation catalyst, active metal concentrations prepared by the method for the present invention increase trend and ionic liquid in gradient
Body is introduced into catalyst in a manner of co-precipitation together, after the auxiliary element in ionic liquid and active metal coordination, by altogether
The precipitation method are deposited to particle surface, the novel active metal phase precursor of generation, and auxiliary element can carry out active phase periphery
Effectively modification improves active phase surface activity, weakens the mutual rental between active metal and aluminium oxide, it is easier to be sulfided into
II class activity phase with higher hydrogenation activity, reduces the formation for not having spinelle with hydrogenation efficiency；Furthermore ionic liquid with
The presence of active metal ligand, more active metals can be exposed in catalyst channel surfaces after roasting, to improve
The density of table phase active metal, gradient distribution of the bigger table phase active metal density with active metal concentrations in the catalyst
Combination to substantially increase hydrodemetallization, hydrodesulfurization and the hydrodenitrogenationactivity activity of catalyst, and the preparation side
Method is simple, production cost is low；
3, in the method for the present invention, the method swung using pH value, the hydrogenation catalyst centralized particle diameter of preparation, crystallinity
Height, aperture and hole appearance are larger, and pore-size distribution is concentrated, and the hydrogenation reaction for inferior raw materials such as wax oil, residual oil is well suited for.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of hydrogenation catalyst continuous production device of the invention.
Wherein, 1- reactor tank；2- swings tank I；3- swings tank II；4- ageing can；1-1- acid solution feed inlet；1-2- lye into
Material mouth；1-3- overflow port；2-1- lye feed inlet；3-1- acid solution feed inlet；4-1- lye feed inlet.
Specific embodiment
In the method for the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen determination of adsorption method, catalyst table phase active metal
Content is measured using x-ray photoelectron spectroscopy (XPS), and caltalyst phase active metallic content uses inductively coupled plasma body
Atomic emission spectrum (ICP-AES) measurement；Active metal concentrations are surveyed using field emission scanning electron microscope on catalyst cross section
It is fixed.
It is described in more detail below by preparation method of the specific embodiment to hydrogenation catalyst of the invention.Implement
Example is not only to the specific embodiment of the method for the present invention for example, constitute the limitation of the scope of the present invention.Wherein
" percentage of the additional amount of ionic liquid in terms of auxiliary agent " is the percentage that ionic liquid accounts for each tank inlet amount in terms of auxiliary element
Number, wherein inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides.In the method for the present invention, swing in tank and ageing can into
Stream amount is adjusted according to pH value.The additional amount of active metal salt solution in each tank is in terms of reactive metal oxides according to most
The active component content requirement of whole catalyst.
Embodiment 1
The present embodiment introduces the preparation method of Mo, Ni, ammonia original solution.The present embodiment only prepares a kind of concentration and ratio
Mo, Ni, ammonia original solution can prepare the solution of other ratios and concentration according to the method introduced.
296g ammonium molybdate is taken, 105g nickel nitrate is put into more mouthfuls of flasks, after a certain amount of deionized water is added, is stirred
Until vial matter is in pulpous state, it is then slowly added 150g ammonium hydroxide, waits startings reaction to be slowly heated again later, keeps solution temperature
70~80 DEG C of times are 1~2 hour, after stopping heating, are filtered while hot to acquired solution, and ammonium hydroxide is then added by the pH tune of solution
It saves to 10.0~12.0 to get required solution is arrived.Solution composition is MoO3: 58.2g/100ml；NiO:10.5g/100ml.
Embodiment 2
Alkyl dimethyl ammonium chloride 300g, ammonium tetrafluoroborate 190g, pure water 450g, mixing are heated to 80 DEG C, constant temperature under stiring
After 1h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid 300g, aqueous about 3.5wt%, yield
73wt%。
In reactor tank, each bottom water for swinging addition 2L in tank, the temperature of reactor tank is heated to 60 DEG C, by each swing
Tank is heated to 90 DEG C, reactor tank stirring rate is adjusted to 200rad/min, each reactor tank speed of agitator is adjusted to 400rad/
min；Reactor upper end feed inlet is opened, by concentration is 100g/100mlAl with the flow velocity of 60ml/min2O3Aluminum sulfate solution with
And with the flow velocity of 40ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution be added in reactor tank, adjust pH
It is worth between 8.5, after stablizing 10min, opens the overflow port of reaction pot bottom, makes to generate liquid stream into swing tank I；Open pendulum
The alkaline feed inlet of the dynamic upper end tank I, addition concentration are 80g/100mlAl2O3Sodium aluminate solution, 20g/100ml alkalinity it is living
Property metal salt solution and ionic liquid (additional amount is calculated as 2.0% with auxiliary agent) mixed solution, adjust pH value to 10.5, reaction
After 20min, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acidity for swinging the upper end tank II
Feed inlet, addition concentration are 70g/100mlAl2O3Aluminum sulfate solution, 45g/100ml acidity active metal salt solution and ion
The mixed solution of liquid (additional amount is calculated as 2.1% with auxiliary agent) adjusts pH value to 3.5, after reacting 20min, opens and swing the bottom tank II
The overflow port in portion makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, the alkali of ageing can upper end is opened
Property feed inlet, addition concentration be 60g/100ml Al2O3Sodium aluminate solution, the basic activated metal salt solution of 60g/100ml and
The mixed solution of ionic liquid (additional amount is calculated as 2.0% with auxiliary agent) adjusts pH value to 8.2, after aging 2h, by the ball of preparation
Shape catalyst precursor is discharged from the discharge port of aging pot bottom, and required spherical shape is obtained after filtering, drying and roasting and adds hydrogen
Handle catalyst A.
Embodiment 3
Triethyl ammonium chloride 400g, sodium hexafluoro phosphate 220g, pure water 450g, mixing are heated to 90 DEG C, constant temperature under stiring
After 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I450g, aqueous about 3.5wt%, yield
72wt%。
In reactor tank, each bottom water for swinging addition 3L in tank, the temperature of reactor tank is heated to 80 DEG C, by each swing
Tank is heated to 100 DEG C, reactor tank stirring rate is adjusted to 300rad/min, each reactor tank speed of agitator is adjusted to
500rad/min；Reactor upper end feed inlet is opened, by concentration is 80g/100mlAl with the flow velocity of 80ml/min2O3Aluminum sulfate
Solution and with the flow velocity of 30ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution be added in reactor tank,
PH value is adjusted between 7.5, after stablizing 20min, opens the overflow port of reaction pot bottom, makes to generate liquid stream to swinging in tank I；
The alkaline feed inlet for swinging the upper end tank I is opened, addition concentration is 80g/100mlAl2O3Sodium metaaluminate, 25g/100ml alkalinity it is living
Property metal salt solution and ionic liquid (additional amount is calculated as 2.2% with auxiliary agent) mixed solution, adjust pH value to 11.0, reaction
After 15min, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acidity for swinging the upper end tank II
Feed inlet, addition concentration are 70g/100mlAl2O3Aluminum sulfate solution, 50g/100ml acidity active metal salt solution and ion
The mixed solution of liquid (additional amount is calculated as 2.3% with auxiliary agent) adjusts pH value to 3.0, after reacting 20min, opens and swing the bottom tank II
The overflow port in portion makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, the alkali of ageing can upper end is opened
Property feed inlet, addition concentration be 50g/100ml Al2O3Sodium aluminate solution, the basic activated metal salt solution of 70g/100ml and
The mixed solution of ionic liquid (additional amount is calculated as 2.1% with auxiliary agent) adjusts pH value to 7.6, after aging 1.5h, by preparation
Spheric catalyst presoma is discharged from the discharge port of aging pot bottom, and required spherical shape is obtained after filtering, drying and roasting and is added
Hydrogen handles catalyst B.
Embodiment 4
Trimethylphenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing are heated to 90 DEG C under stiring,
After constant temperature 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I550g, aqueous about 3.5wt%,
Yield 74wt%.
In reactor tank, each bottom water for swinging addition 5L in tank, the temperature of reactor tank is heated to 70 DEG C, by each swing
Tank is heated to 80 DEG C, reactor tank stirring rate is adjusted to 350rad/min, each reactor tank speed of agitator is adjusted to 550rad/
min；Reactor upper end feed inlet is opened, by concentration is 70g/100mlAl with the flow velocity of 90ml/min2O3Aluminum sulfate solution with
And with the flow velocity of 50ml/min by concentration be 90g/100ml Al2O3Sodium aluminate solution be added in reactor tank, adjust pH value
To between 8.5, after stablizing 20min, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank I；It opens and swings
The alkaline feed inlet of the upper end tank I, addition concentration are 55g/100mlAl2O3Sodium aluminate solution, the basic activated gold of 30g/100ml
Belong to the mixed solution of salting liquid and ionic liquid (additional amount is calculated as 3.0% with auxiliary agent), adjusts pH value to 10.8, react 20min
Afterwards, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acid charging for swinging the upper end tank II
Mouthful, addition concentration is 40g/100mlAl2O3Aluminum sulfate solution, 50g/100ml acidity active metal salt solution and ionic liquid
The mixed solution of (additional amount is calculated as 3.2% with auxiliary agent) adjusts pH value to 4.0, after reacting 20min, opens and swing 2 bottom of tank
Overflow port makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, open ageing can upper end it is acid into
Material mouth, addition concentration are 20g/100ml Al2O3Aluminum sulfate solution, 75g/100ml acidity active metal salt solution and ionic liquid
The mixed solution of body (additional amount is calculated as 2.8% with auxiliary agent) adjusts pH value to 8.3, after aging 2h, by the spherical catalyst of preparation
Agent presoma is discharged from the discharge port of aging pot bottom, and required spherical hydrotreating is obtained after filtering, drying and roasting and is urged
Agent C.
Embodiment 5
Aminomethyl phenyl ammonium chloride 500g, sodium hexafluoro phosphate 260g, pure water 450g, mixing are heated to 90 DEG C, perseverance under stiring
After warm 3h, clarification naturally cools to 30 DEG C or so, centrifugally filters out solid and obtain ionic liquid I550g, aqueous about 3.5wt%, receives
Rate 74wt%.
In reactor tank, each bottom water for swinging addition 4L in tank, the temperature of reactor tank is heated to 80 DEG C, by each swing
Tank is heated to 90 DEG C, reactor tank stirring rate is adjusted to 250rad/min, each reactor tank speed of agitator is adjusted to 450rad/
min；Reactor upper end feed inlet is opened, by concentration is 85g/100mlAl with the flow velocity of 110ml/min2O3Aluminum sulfate solution with
And with the flow velocity of 80ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution be added in reactor tank, adjust pH
It is worth between 8.2, after stablizing 10min, opens the overflow port of reaction pot bottom, makes to generate liquid stream into swing tank I；Open pendulum
The alkaline feed inlet of the dynamic upper end tank I, addition concentration are 75g/100mlAl2O3Sodium aluminate solution, 20g/100ml it is basic activated
The mixed solution of metal salt solution and ionic liquid (additional amount is calculated as 3.3% with auxiliary agent) adjusts pH value to 11.5, reacts 20min
Afterwards, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acid charging for swinging the upper end tank II
Mouthful, addition concentration is 55g/100mlAl2O3Aluminum sulfate solution, 40g/100ml acidity active metal salt solution and ionic liquid
The mixed solution of (additional amount is calculated as 3.5% with auxiliary agent) adjusts pH value to 4.5, after reacting 20min, opens and swing the bottom tank II
Overflow port makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, open ageing can upper end alkalinity into
Material mouth, addition concentration are 35g/100ml Al2O3Aluminum sulfate solution, 65g/100ml acidity active metal salt solution and ionic liquid
The mixed solution of body (additional amount is calculated as 3.6% with auxiliary agent) adjusts pH value to 8.0, after aging 2.5h, the spherical shape of preparation is urged
Agent presoma is discharged from the discharge port of aging pot bottom, and required spherical hydrotreating is obtained after filtering, drying and roasting
Catalyst D.
Embodiment 6
In reactor tank, each bottom water for swinging addition 4L in tank, the temperature of reactor tank is heated to 80 DEG C, by each swing
Tank is heated to 90 DEG C, reactor tank stirring rate is adjusted to 250rad/min, each reactor tank speed of agitator is adjusted to 450rad/
min；Reactor upper end feed inlet is opened, by concentration is 85g/100mlAl with the flow velocity of 110ml/min2O3Aluminum sulfate solution with
And with the flow velocity of 80ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution be added in reactor tank, adjust pH
It is worth between 7.6, after stablizing 10min, opens the overflow port of reaction pot bottom, makes to generate liquid stream into swing tank I；Open pendulum
The alkaline feed inlet of the dynamic upper end tank I, addition concentration are 75g/100mlAl2O3Sodium aluminate solution, 20g/100ml it is basic activated
The mixed solution of metal salt solution and ionic liquid (additional amount is calculated as 4.0% with auxiliary agent) adjusts pH value to 10.9, reacts 20min
Afterwards, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acid charging for swinging the upper end tank II
Mouthful, addition concentration is 55g/100mlAl2O3Aluminum sulfate solution, 40g/100ml alkalinity active metal salt solution and ionic liquid
The mixed solution of body (additional amount is calculated as 4.1% with auxiliary agent) adjusts pH value to 4.2, after reacting 20min, opens and swing the bottom tank II
Overflow port, make generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, the alkalinity of ageing can upper end is opened
Feed inlet, addition concentration are 35g/100ml Al2O3Aluminum sulfate solution, 65g/100ml acidity active metal salt solution and ion
The mixed solution of liquid (additional amount is calculated as 4.2% with auxiliary agent) adjusts pH value to 8.2, after aging 2.5h, by the spherical shape of preparation
Catalyst precursor is discharged from the discharge port of aging pot bottom, and required spherical shape is obtained after filtering, drying and roasting and is added at hydrogen
Manage catalyst E.
Comparative example 1
In reactor tank, each bottom water for swinging addition 4L in tank, the temperature of reactor tank is heated to 80 DEG C, by each swing
Tank is heated to 90 DEG C, reactor tank stirring rate is adjusted to 250rad/min, each reactor tank speed of agitator is adjusted to 450rad/
min；Reactor upper end feed inlet is opened, by concentration is 85g/100mlAl with the flow velocity of 110ml/min2O3Liquor alumini chloridi and
With the flow velocity of 80ml/min by concentration for 100g/100ml Al2O3Sodium aluminate solution is added in reactor tank, adjust pH value to
Between 8.2, after stablizing 10min, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank I；It opens and swings tank
The alkaline feed inlet of the upper end I, addition concentration are 75g/100mlAl2O3Sodium aluminate solution adjusts pH value to 11.0, reacts
After 20min, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；Open the acidity for swinging the upper end tank II
Concentration is 55g/100mlAl by feed inlet2O3Aluminum sulfate solution, adjust pH value to 3.5, after reacting 20min, open and swing tank
The overflow port of the bottom II makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, ageing can upper end is opened
Alkaline feed inlet, addition concentration be 35g/100ml Al2O3Sodium aluminate solution, adjust pH value to 7.5, aging 2.5h it
Afterwards, the spheric catalyst presoma of preparation is discharged from the discharge port of aging pot bottom, institute is obtained after filtering, drying and roasting
The spherical hydrotreating catalyst F needed.
Comparative example 2
In reactor tank, each bottom water for swinging addition 2L in tank, the temperature of reactor tank is heated to 60 DEG C, by each swing
Tank is heated to 90 DEG C, reactor tank stirring rate is adjusted to 200rad/min, each reactor tank speed of agitator is adjusted to 400rad/
min；Reactor upper end feed inlet is opened, by concentration is 100g/100mlAl with the flow velocity of 60ml/min2O3Aluminum sulfate solution with
And with the flow velocity of 40ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution be added in reactor tank, adjust pH
It is worth between 8.5, after stablizing 10min, opens the overflow port of reaction pot bottom, makes to generate liquid stream into swing tank I；Open pendulum
The acid feed inlet of the dynamic upper end tank I, addition concentration are 80g/100mlAl2O3Aluminum sulfate solution and the acid activity of 20g/100ml
The mixed solution of metal salt solution adjusts pH value to 3.0, after reacting 20min, opens the overflow port for swinging the bottom tank I, make to generate
Liquid stream is into swing tank II；The alkaline feed inlet for swinging the upper end tank II is opened, addition concentration is 70g/100mlAl2O3Meta-aluminic acid
The mixed solution of sodium solution and the basic activated metal salt solution of 45g/100ml adjusts pH value to 11.0, after reacting 20min, opens
The overflow port for swinging the bottom tank II makes to generate liquid stream into ageing can；After the overflow port trickle of tank to be aging, aging is opened
The acid feed inlet of tank upper end, addition concentration are 60g/100ml Al2O3Aluminum sulfate solution and the acid activity gold of 60g/100ml
Belong to the mixed solution of salting liquid, adjust pH value to 8.0, after aging 2h, by the spheric catalyst presoma of preparation from ageing can
The discharge port of bottom is discharged, and required spherical hydrotreating catalyst G is obtained after filtering, drying and roasting.
Comparative example 3
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 80 DEG C, reactor tank stirring rate is adjusted to
250rad/min；Reactor upper end feed inlet is opened, by concentration is 85g/100mlAl with the flow velocity of 110ml/min2O3Sulfuric acid
The mixed solution of the acid active metal solution of aluminum solutions and 50g/100ml (additional amount of ionic liquid is calculated as 3.2% with auxiliary agent)
And with the flow velocity of 80ml/min by concentration be 100g/100ml Al2O3Sodium aluminate solution and 60g/100ml alkalinity it is living
Property metallic solution mixed solution (additional amount of ionic liquid is calculated as 3.3% with auxiliary agent) be added in reactor tank, adjust pH value to
Between 8.2, stop feeding after reaction 2h, carry out aging, after aging 2.5h, by the catalyst precursor of preparation from ageing can
The discharge port of bottom is discharged, and required spherical hydrotreating catalyst H is obtained after filtering, drying and roasting.
Comparative example 4
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 80 DEG C, reactor tank stirring rate is adjusted to
250rad/min；Reactor upper end feed inlet is opened, by concentration is 85g/100mlAl with the flow velocity of 110ml/min2O3Sulfuric acid
The mixed solution of the acid active metal solution of aluminum solutions and 50g/100ml and with the flow velocity of 80ml/min it is by concentration
100g/100ml Al2O3Sodium aluminate solution and the mixed solution of basic activated metallic solution of 60g/100ml be added to instead
It answers in tank, between adjusting pH value to 8.2, stops feeding after reaction 2h, progress aging, after aging 2.5h, by urging for preparation
Agent presoma is discharged from the discharge port of aging pot bottom, and required spherical hydrotreating is obtained after filtering, drying and roasting
Catalyst I.
Comparative example 5
The bottom water of 4L is added in reactor tank, the temperature of reactor tank is heated to 100 DEG C, reactor tank stirring rate is adjusted to
500rad/min；Reactor upper end feed inlet is opened, by concentration is 90g/100mlAl with the flow velocity of 120ml/min2O3Sulfuric acid
The mixed solution of the acid active metal solution of aluminum solutions and 60g/100ml and with the flow velocity of 100ml/min it is by concentration
90g/100ml Al2O3Sodium aluminate solution and the mixed solution of basic activated metallic solution of 80g/100ml be added to reaction
In tank, between adjusting pH value to 7.5, stop feeding after reaction 2h, progress aging, after aging 2.5h, by the catalysis of preparation
Agent presoma is discharged from the discharge port of aging pot bottom, and required spherical hydrotreating is obtained after filtering, drying and roasting and is urged
Agent J.
Above-described embodiment and the hydrogenation catalyst property of comparative example preparation are shown in Table 1, catalyst table phase reactive metal oxides
2 are shown in Table with the ratio between the weight content of body phase reactive metal oxides.
The hydrogenation catalyst property of 1 Examples and Comparative Examples of table preparation.
Table 1(is continuous) the hydrogenation catalyst property of Examples and Comparative Examples preparation.
Its bulk density of hydrogenating catalyst composition prepared by the method for the present invention it can be seen from the data of table 1 is lower,
Kong Rong, aperture are larger, and crystal grain distribution is concentrated, and the concentration of active metal and auxiliary agent increases distribution in gradient in the catalyst, very
The preparation of hydrotreating catalyst suitable for weight inferior raw material.
The ratio between the weight content of table 2 catalyst table phase reactive metal oxides and body phase reactive metal oxides.
Embodiment 7
Catalyst activity evaluation experimental carries out on 50mL small hydrogenation device, carries out pre- sulphur to catalyst before activity rating
Change.Catalyst is in reaction stagnation pressure 8.0MPa, volume space velocity 1.0h-1, hydrogen to oil volume ratio 700:1, reaction temperature is 380 DEG C, is carried out
Operating evaluation, raw material oil nature and evaluation result be shown in Table 3 ~ table 4 respectively.
3 raw material oil nature of table.
4 catalyst activity evaluation result of table
The catalyst prepared by the method for the present invention it can be seen from the data of table 4 is under the conditions of same process, due to activity
Metal concentration increases distribution in gradient in the catalyst, while the density of the active metal and auxiliary agent in table phase is greater than in body phase
The density of active metal and auxiliary agent effectively improves the hydrogenation activity of catalyst.
Claims (12)
1. a kind of hydrogenation catalyst, which is body phase hydrogenation catalyst, including alumina support, active metal and auxiliary agent,
It is characterized by: for active metal in terms of oxide, group VIII metal is 1wt%~9wt%, group vib on the basis of catalyst weight
Metal is 5wt%~25wt%, and auxiliary agent is 2wt% ~ 5wt% based on the element, and alumina support is 61wt% ~ 92wt%；Wherein auxiliary agent is
One of following several combinations of I, II and III: I- fluorine and phosphorus, II- fluorine and boron, III- fluorine, phosphorus and boron；The concentration of active metal
In terms of oxide, gradually increased from catalyst granules center to outer surface, wherein at 1/3R active metal concentration be 6wt%~
The concentration of active metal is 10wt%~20wt% at 10wt%, 2/3R, and the concentration of active metal is 20wt%~30wt% at R；R is
Distance of the catalyst granules center to catalyst cross section outer most edge any point；The weight content of table phase active metal component with
The ratio of the weight content of body phase active metal component is 3.0 ~ 15.0:1；Auxiliary agent based on the element, the weight content of table phase auxiliary agent with
The ratio of the weight content of body phase auxiliary agent is 3.0 ~ 10.0:1；The continuous production method of the hydrogenation catalyst includes in following
Hold: (1) bottom water of certain volume being added in reactor tank and swing tank, is heated to certain temperature, then starts blender, open
Acid solution feed inlet and lye feed inlet at the top of reactor tank, acid aluminium salt solution I and basic aluminium salt solution I are respectively with certain stream
Speed respectively from the top of reactor tank acid solution feed inlet and lye feed inlet be continuously added to, adjust pH value be 7.0 ~ 8.5 between, stablize
After a period of time, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank I；(2) to the overflow port stream of reactor tank
Out after liquid, the lye feed inlet for swinging the upper end tank I, stream plus certain density basic aluminium salt solution II, basic activated gold are opened
Belong to salting liquid I and the ionic liquid containing auxiliary agent, adjusts pH value between 10.0~11.5, after reacting a period of time, open pendulum
The overflow port of the dynamic bottom tank I makes to generate liquid stream into swing tank II；(3) it after the overflow port trickle for swinging tank I, opens
Swing the upper end tank II acid solution feed inlet, stream plus certain density acid aluminium salt solution III, acidity active metal salt solution II and
With the ionic liquid containing auxiliary agent, pH value is adjusted between 3.0~5.0, after reacting a period of time, opens and swings the bottom tank II
Overflow port makes to generate liquid stream into ageing can；(4) after the overflow port trickle for swinging tank II, ageing can upper end is opened
Lye feed inlet, stream plus certain density basic aluminium salt solution IV, basic activated metal salt solution III and and containing auxiliary agent from
Sub- liquid, adjusts pH value between 7.0~8.5, after aging for a period of time, by the spheric catalyst presoma of preparation from ageing can
The discharge port of bottom is discharged, and through filtering, drying and roasting, obtains hydrogenation catalyst；Basic aluminium salt solution I, basic aluminium salt solution
Al in II, acid aluminium salt solution III and basic aluminium salt solution IV2O3Concentration is in the trend that is gradually reduced, and the amplitude that reduces is 10~
20g/100mL；It is living in basic activated metal salt solution I, acidity active metal salt solution II and basic activated metal salt solution III
Property metal concentration in terms of reactive metal oxides in trend is gradually increased, increasing degree is 15~25g/100mL；Containing auxiliary agent from
The preparation method of sub- liquid: M1 and M2 are added to the water, and are heated to reaction temperature, isothermal reaction, reaction knot under agitation
Shu Hou, cooling, centrifugation obtains ionic liquid；Wherein the molar ratio of M1 and M2 is 1:1~1:2, and reaction temperature is 60~150 DEG C,
The isothermal reaction time is 1~4h；The M1 is ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, hexafluoro
One or more of sodium phosphate, Potassium Hexafluorophosphate；The M2 is one in the alkyl ammonium halide that carbon atom number is 1 ~ 12
Kind is several；Step (2), (3), be added the ionic liquid containing auxiliary agent in (4) additional amount it is identical, step (2), (3),
(4) additional amount of intermediate ion liquid accounted for respectively in terms of auxiliary element step (2), (3), in (4) inlet amount 1wt%~4wt%,
Middle inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides.
2. catalyst described in accordance with the claim 1, it is characterised in that: when auxiliary agent is I, fluorine accounts for the 50%~55% of auxiliary agent quality,
Phosphorus accounts for the 45%~50% of auxiliary agent gross mass；When auxiliary agent is II, fluorine accounts for the 50%~55% of auxiliary agent quality, and boron accounts for auxiliary agent gross mass
45%~50%；When auxiliary agent is III, fluorine accounts for the 50%~55% of auxiliary agent total amount, and phosphorus accounts for the 30% ~ 35% of auxiliary agent total amount, and boron accounts for auxiliary agent
The 15%~20% of total amount.
3. catalyst described in accordance with the claim 1, it is characterised in that: active metal is in terms of oxide, the work of table phase VIII group
Property metal and body phase VIII group active metal weight content ratio be 2.0:1 ~ 6.0:1, table phase VIB active metal and body phase VIB
The weight content ratio of active metal is 2.0:1 ~ 8.0:1.
4. catalyst described in accordance with the claim 1, it is characterised in that: hydrogenation catalyst have the property that Kong Rongwei 0.4~
0.6mL·g-1；Aperture is 90~150；Abrasion≤0.05%；Bulk density is 0.80~0.95g/mL.
5. catalyst described in accordance with the claim 1, it is characterised in that: the particle diameter distribution of hydrogenation catalyst is as follows: 200 μm of grains of <
Diameter proportion is 0.5%~1%, and 200~300 μm of partial size proportions are that 5%~10%, >, 300 μm of partial size proportions are 85%
~90%.
6. a kind of continuous production method of hydrogenation catalyst described in claim 1 ~ 5 any claim, it is characterised in that
Including following content: (1) bottom water of certain volume being added in reactor tank and swing tank, is heated to certain temperature, then starts
Blender opens acid solution feed inlet and lye feed inlet at the top of reactor tank, acid aluminium salt solution I and basic aluminium salt solution I point
Not with certain flow velocity respectively from the top of reactor tank acid solution feed inlet and lye feed inlet be continuously added to, adjust pH value be 7.0 ~
Between 8.5, after a period of stabilisation, the overflow port of reaction pot bottom is opened, makes to generate liquid stream into swing tank I；(2) wait react
After the overflow port trickle of tank, the lye feed inlet for swinging the upper end tank I, stream plus certain density basic aluminium salt solution are opened
II, basic activated metal salt solution I and the ionic liquid containing auxiliary agent adjust pH value between 10.0~11.5, react one section
After time, the overflow port for swinging the bottom tank I is opened, makes to generate liquid stream into swing tank II；(3) the overflow port stream of tank I to be swung
Out after liquid, the acid solution feed inlet for swinging the upper end tank II, stream plus certain density acid aluminium salt solution III, acid activity are opened
Metal salt solution II and and the ionic liquid containing auxiliary agent, adjust pH value between 3.0~5.0, after reacting a period of time, open
The overflow port for swinging the bottom tank II makes to generate liquid stream into ageing can；(4) it after the overflow port trickle for swinging tank II, opens
Open the lye feed inlet of ageing can upper end, stream plus certain density basic aluminium salt solution IV, basic activated metal salt solution III and
With the ionic liquid containing auxiliary agent, pH value is adjusted between 7.0~8.5, after aging for a period of time, by the spheric catalyst of preparation
Presoma is discharged from the discharge port of aging pot bottom, through filtering, drying and roasting, obtains hydrogenation catalyst；Basic aluminium salt solution
I, Al in basic aluminium salt solution II, acid aluminium salt solution III and basic aluminium salt solution IV2O3Concentration is in the trend being gradually reduced, and is subtracted
It is by a small margin 10~20g/100mL；Basic activated metal salt solution I, acidity active metal salt solution II and basic activated metal
For active metal concentrations in the trend that gradually increases in terms of reactive metal oxides, increasing degree is 15~25g/ in salting liquid III
100mL；The preparation method of ionic liquid containing auxiliary agent: M1 and M2 being added to the water, are heated to reaction temperature under agitation,
Isothermal reaction, after reaction, cooling, centrifugation obtains ionic liquid；Wherein the molar ratio of M1 and M2 is 1:1~1:2, reaction temperature
Degree is 60~150 DEG C, and the isothermal reaction time is 1~4h；The M1 is ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, six
One or more of fluorophosphoric acid ammonium, sodium hexafluoro phosphate, Potassium Hexafluorophosphate；The M2 is the alkyl that carbon atom number is 1 ~ 12
One or more of ammonium halide；Step (2), (3), (4) middle additional amount that the ionic liquid containing auxiliary agent is added are identical, step
Suddenly (2), (3), (4) intermediate ion liquid additional amount account for step (2), (3), inlet amount in (4) respectively in terms of auxiliary element
1wt%~4wt%, wherein inlet amount is in terms of the sum of aluminium oxide and reactive metal oxides.
7. according to the method for claim 6, it is characterised in that: reactor tank, each swing tank indsole in the step (1)
The volume of water accounts for the 1/5~1/4 of the tank volume, and the temperature of reactor tank is less than each temperature for swinging tank, the temperature of reactor tank
It is 50~80 DEG C, it is 60~100 DEG C that each temperature for swinging tank, which is the reaction temperature, the temperature between reactor tank and swing tank
Degree difference is 10~30 DEG C.
8. according to the method for claim 6, it is characterised in that: the stirring rate of reactor tank is higher than each stirring for swinging tank
Rate, the stirring rate of reactor tank are 300~700rad/min, and the stirring rate of each agitator tank is 100~400rad/min,
Reactor tank and the rotational speed difference swung between tank are 100~200rad/min.
9. according to the method for claim 6, it is characterised in that: the acid aluminium salt solution is AlCl3、Al2(SO4)3Or
Al(NO)3One or more of aqueous solution, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 10~100g/100mL, is flowed
Speed is 10~80mL/min；The basic aluminium salt solution is selected from NaAlO2Or KAlO2One or both of aqueous solution, alkalinity
The concentration of aluminum saline solution is with Al2O3It is calculated as 10~100g/100mL, flow velocity is 10~80mL/min.
10. according to the method for claim 6, it is characterised in that: acid aluminium salt solution I and basic aluminium salt in step (1)
The concentration of solution I is identical, with Al2O3Meter.
11. according to the method for claim 6, it is characterised in that: the acid active metal salt solution is molybdenum nickel phosphorus, molybdenum
One of cobalt phosphorus, molybdenum cobalt nickel phosphorus, tungsten nickel phosphorus, tungsten nickel phosphorus, tungsten nickel cobalt phosphorus or tungsten cobalt phosphorus aqueous solution, acid active metal
The concentration of salting liquid is calculated as 15~100g/100mL with oxide, and pH value is 1.0~4.0, acid active metal saline solution stream
Amount is 5~50mL/min；The basic activated metal salt solution is molybdenum nickel ammonia, molybdenum cobalt ammonia, molybdenum cobalt nickel ammonia, tungsten nickel ammonia, tungsten
One of nickel ammonia, tungsten nickel cobalt ammonia or tungsten cobalt ammonia spirit, the concentration of basic activated metal salt solution is calculated as with oxide
15~100g/100mL, pH value are 10.0~12.0, and alkalinous metal saline solution flow is 5~50mL/min.
12. according to the method for claim 6, it is characterised in that: after swinging tank II, 1 ~ 4 swing tank of connecting is repeated
The process of step (2) and (3)；When connecting 2 or 4 swing tanks, the last one material for swinging the overflow of tank enters ageing can
It carries out step (4), swings acid or basic aluminium salt solution concentration in tank and ageing can and passed in terms of oxide by logistics direction
Subtract, reduction amplitude is 10~20g/100mL；Swing the active metal concentrations of tank and ageing can neutral and alkali active metal salt solution with
Reactive metal oxides meter is incremented by by logistics direction, and increasing degree is 15~25g/100mL；It swings to contain in tank and ageing can and help
The additional amount of the ionic liquid of agent is identical；When connect odd wobbles tank when, such as connect 1 or 3 swings tank when, the last one put
It after dynamic tank repeats step (2), carries out step (4 '): after the overflow port trickle for swinging tank, opening ageing can upper end
Certain density acid aluminium salt solution, acid active metal salt solution and the ionic liquid containing auxiliary agent is added dropwise in lye feed inlet,
PH value is adjusted between 7.0~8.5, after aging for a period of time, by the spheric catalyst presoma of preparation from aging pot bottom
Discharge port excludes, and through filtering, drying and roasting, obtains hydrotreating catalyst；Swing acid or alkaline aluminium in tank and ageing can
The concentration of salting liquid is gradually successively decreased in terms of oxide according to logistics direction, reduction amplitude be 10~20g/100mL, swing tank and
The active metal concentrations of ageing can neutral and alkali active metal salt solution are incremented by terms of reactive metal oxides by logistics direction, are increased
Adding amplitude is 15~25g/100mL；It is identical with the additional amount of the ionic liquid in ageing can containing auxiliary agent to swing tank.
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| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal and acid additive concentration in gradient increasing distribution and preparation method thereof |
| CN105820296A (en) * | 2016-05-10 | 2016-08-03 | 嘉兴艾尔瑞环境科技有限公司 | Preparation method for crosslinking acrylamide grafted starch |
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| CN1421511A (en) * | 2001-11-30 | 2003-06-04 | 中国石油天然气集团公司 | Prepn process of paraffin hydrofining catalyst |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal and acid additive concentration in gradient increasing distribution and preparation method thereof |
| CN105820296A (en) * | 2016-05-10 | 2016-08-03 | 嘉兴艾尔瑞环境科技有限公司 | Preparation method for crosslinking acrylamide grafted starch |
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