CN108970628A - A kind of preparation method of boiling bed hydrogenation treatment catalyst - Google Patents
A kind of preparation method of boiling bed hydrogenation treatment catalyst Download PDFInfo
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- CN108970628A CN108970628A CN201810893969.4A CN201810893969A CN108970628A CN 108970628 A CN108970628 A CN 108970628A CN 201810893969 A CN201810893969 A CN 201810893969A CN 108970628 A CN108970628 A CN 108970628A
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- 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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- 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
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a kind of preparation methods of boiling bed hydrogenation treatment catalyst, method includes the following steps: (1), by the aluminum carbonate basic ammonium kneading and compacting of boehmite and absorption carbon precursor solution, molding is through being dried；(2) material that step (1) obtains is sprayed with the solution of carbonaceous precursor, alumina support is made through drying, roasting in the material after spraying；(3) boiling bed hydrogenation treatment catalyst is made through drying, roasting after dipping in the alumina support obtained with the maceration extract impregnation steps (2) containing hydrogenation active component；The catalyst intensity with higher and wearability of method preparation of the invention, especially suitable for heavy oil boiling bed hydrogenation treatment process.
Description
Technical field
The present invention relates to a kind of preparation fields of hydrotreating catalyst, in particular to a kind of oil boiling bed suitable for heavy
The preparation method of hydrotreating catalyst.
Background technique
In recent years, crude oil increasingly becomes weight, and the demand of fraction product constantly increases between city's field alignment, to the need of astatki
It asks and gradually decreases, therefore it is the target that major refinery is pursued that the heavy oil of low value, which is transformed into the higher light-end products of added value,.
Catalytic hydrogenation process commonly used in heavy oil product is mainly fixed bed hydrogenation technique.The characteristics of fixed bed reactors be operation compared with
Steadily, easily controllable, but there are following several respects in fixed-bed process hydrotreating heavy oil product: since heavy oil oil product is heavier
And containing more mechanical admixture, catalytic reaction condition can be harsher；High-nitrogen stock meeting accelerator activator inactivation, catalyst use week
Phase is short, and product property not can guarantee；Catalyst bed pressure drop is high.
In order to meet product index, fixed bed reactor system is just needed using more complex design to make cost of investment
Increase.Boiling bed hydrogenation technique process is heavy oil deep processing because having the characteristics that strong to adaptability to raw material, processing scheme is flexible
One of effective means.In boiling bed hydrogenation treatment process, feedstock oil and hydrogen flow through catalyst bed, bed " boiling upwards
Rise ", catalyst granules is in irregular motion state in reactor, and collision and rubbing machine can be compared between catalyst granules
It is more, keep catalyst easy to wear or destroy, it requires catalyst not only hydrogenation activity with higher, should also have preferable resistance to
Grind performance.
USP5308472 discloses a kind of Y molecular sieve containing dealuminzation that uses of ebullated bed mild hydrocracking reaction that can be used for and urges
Agent.The catalyst can be used for the hydrodemetallization of heavy charge, hydrodesulfurization and be hydrocracked.The catalyst contains 1-
Group VIII metal oxide, the molybdenum oxide of 12-25wt% and the phosphoric-oxygenic compound of 1-5wt% of 6wt%.The catalyst have compared with
High lytic activity, but the intensity of catalyst and wearability need to be further increased.
CN200710010377.5 discloses boiling bed hydrogenation treatment catalyst and preparation method thereof.The invention boiling bed hydrogenation
The spherical shape that catalyst is diameter 0.1-1.8mm is handled, suitable adjuvants and hydrogenation active metal component, reasonable pore distribution are contained.This
Invention method for preparing catalyst uses ball type carrier infusion process, and ball type carrier preparation process is the catalyst carrier for being suitable for by humidity
The particle of suitable size is made in feed product, then by the particle spheroidising, spheric catalyst is made in round heating and is carried
Body.Boiling bed hydrogenation treatment catalyst in the prior art have the advantages that particle uniformly, function admirable, but catalyst is wear-resisting
Property needs to be further increased.
Summary of the invention
Shortcoming in view of the prior art, the present invention provides a kind of preparations of boiling bed hydrogenation treatment catalyst
Method.The catalyst intensity with higher and wearability of this method preparation, especially suitable for the processing of heavy oil boiling bed hydrogenation
Process.
A kind of preparation method of boiling bed hydrogenation treatment catalyst of the invention, comprising:
Step (1), by the aluminum carbonate basic ammonium kneading and compacting of boehmite and absorption carbon precursor solution, molding is through dry
Dry processing；
Step (2) sprays the material that step (1) obtains with the solution of carbonaceous precursor, and the material after spraying is through drying, roasting
Alumina support is made；
Step (3), the alumina support obtained with the maceration extract impregnation steps (2) containing hydrogenation active component pass through after dipping
The boiling bed hydrogenation treatment catalyst is made in dry, roasting.
In the method for the present invention, aluminum carbonate basic ammonium described in step (1) can be commercially available or prior art preparation, preferably
Aluminum carbonate basic ammonium with club shaped structure, a length of 1-5 μm of rod-like basic type aluminium carbonate ammonium, diameter 100-300nm, basic carbonate
The additional amount of aluminium ammonium is the 15wt%-35wt% of step (1) described boehmite weight.
In the method for the present invention, carbon precursor described in step (1) be polyalcohol and/or glucide, polyalcohol be xylitol,
One or more of sorbierite, mannitol and arabite；Glucide is glucose, ribose, fructose, triose, tetrose, penta
One or more of sugared, sugared and non-sugar etc..Carbon precursor is to be adsorbed onto aluminum carbonate basic ammonium as a solution, carbon precursor
The mass concentration of solution is 20wt%-40wt%, and the dosage of solution is to be totally submerged aluminum carbonate basic ammonium, dip time 1-
3 hours.
In the method for the present invention, kneading and compacting described in step (1) is carried out using conventional method in that art, described to intend thin water aluminium
Stone is prepared by either method, and in forming process, conventional shaping assistant, such as peptizing agent, extrusion aid can be added as needed.Institute
The peptizing agent stated is one or more of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc.；The additional amount of peptizing agent is alumina support
The 0.5wt%-3wt% of weight.The extrusion aid is sesbania powder, and the additional amount of extrusion aid is carrying alumina body weight
0.1wt%-0.5wt%.The drying temperature is 100-160 DEG C, and drying time is 6-10 hours.
In the method for the present invention, carbon precursor solution described in step (2) is the aqueous solution of polyalcohol and/or glucide, more
First alcohol is one or more of xylitol, sorbierite, mannitol and arabite；Glucide is glucose, ribose, fruit
One or more of sugar, triose, tetrose, pentose, sugared and non-sugar etc..The mass concentration of carbon precursor solution is 10wt%-
20wt%, the dosage of solution are the 10wt%-20wt% of molding materials saturated absorption amount.
In the method for the present invention, drying temperature described in step (2) is 100-160 DEG C, and drying time is 6-10 hours.
In the method for the present invention, two-stage roasting, roasting first under an inert atmosphere, roasting are roasted to described in step (2)
Temperature is 600-750 DEG C, and calcining time is 4-8 hours, and the inert atmosphere is the gases, preferably nitrogen such as nitrogen, argon gas.
Then it is roasted under oxygen atmosphere, maturing temperature is 600-750 DEG C, and calcining time is 4-8 hours.
In the method for the present invention, hydrogenation active component maceration extract described in step (3) is to form to calculate according to final catalyst
It prepares.In hydrogenation active component maceration extract, vib metals content is calculated as 7-15g/100ml, group VIII metal with oxide
Content is calculated as 0.8-3g/100ml with oxide, can use volume impregnation, incipient impregnation or spray impregnating mode, leaching
The stain time is 1-5 hours.
In the method for the present invention, drying described in step (3), roasting condition are carried out by conventional method in that art, and described is dry
Dry condition is 6-10 hours dry at 80-120 DEG C；The roasting condition is to roast 3-6 hours at 400-600 DEG C.
The present invention achieves significant progress.
The technology of the present invention uses carbonaceous precursor solution to impregnate rod-like basic type aluminium carbonate ammonium, the aluminum carbonate basic after dipping first
Ammonium and boehmite kneading and compacting, drying, material unsaturation sprays carbonaceous precursor solution and roasts through drying, nitrogen atmosphere after drying
It burns, roast obtained alumina support under oxygen atmosphere, catalyst is made in final impregnating active component.
Due to the addition of rod-like basic type aluminium carbonate ammonium, the interlaced accumulation of club shaped structure, shape in forming process in the present invention
At the biggish duct conducive to heavy resid macromolecular transportation and diffusion.Since this duct is handed over by the rodlike aluminum carbonate basic ammonium of micron
Mistake accumulation is formed, and carrier mechanical strength with higher is made while guaranteeing macropore.Molding materials roast under an inert atmosphere
When carbon precursor formed and carbon material and be distributed at carrier surface and rod-like aluminum oxide, be passed through carbon material after oxygen and burn rapidly and put
Heat increases the temperature of alumina support part (carrier surface and containing rod-like aluminum oxide at), since the raising of temperature makes to aoxidize
Aluminium grain becomes larger or occurs crystal transition, and the mechanical strength and wearability of carrier are improved while improving macropore content.In addition
Due to the raising of local maturing temperature, the modulation chemical property of carrier surface improves the activity of catalyst.
Detailed description of the invention book
Fig. 1 is the stereoscan photograph of aluminum carbonate basic ammonium prepared by the present invention.
Specific embodiment
Below with reference to embodiment to further illustrate the technical scheme of the present invention, but it is not limited to following embodiment.This
In invention, wt% is mass fraction.
Using N2Physics suction-desorption characterization embodiment and comparative example catalyst pore structure, concrete operations are as follows: using
ASAP-2420 type N2Physics is inhaled-is desorbed instrument and characterizes to sample pore structure.Take a small amount of sample be vacuum-treated 3 at 300 DEG C~
4 hours, finally product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test.Wherein surface area according to
BET equation obtains, and pore-size distribution and pore volume are obtained according to BJH model.
Preparation Example 1: the preparation of aluminum carbonate basic ammonium.The aluminum carbonate basic ammonium that the technology of the present invention uses is according to document: with ammonia
Water and ammonium carbonate prepare comparative study [J] Chinese Journal of Inorganic Chemistry of aluminium oxide, 2004,20 (6) for precipitating reagent, and 688-692 is disclosed
Method preparation, the stereoscan photograph of the aluminum carbonate basic ammonium of preparation is as shown in Figure 1.
Embodiment 1
Aluminum carbonate basic ammonium 50g is weighed, is impregnated above-mentioned material 2 hours with the xylitol solution that mass concentration is 20wt%,
(Wenzhou essence crystal alumina Co., Ltd produces material after dipping, aluminium oxide with boehmite dry glue powder 200g after filtering
Contents on dry basis 70wt%), sesbania powder 0.2g is uniformly mixed, and is added in right amount dissolved with the aqueous solution of 3 grams of acetic acid, is squeezed into mixed material
Item molding, molding are 8 hours dry in 120 DEG C.
Weigh it is dry after 100 grams of strip-shaped materials be placed in and spray in rolling pot, the sorbierite for being 15% with 10mL mass concentration
Aqueous solution spray impregnates above-mentioned carrier, and the carrier after dipping is 7 hours dry in 120 DEG C, and the carrier after drying is first in nitrogen atmosphere
Under in 650 DEG C roast 6 hours, then in 650 DEG C of roastings, 6 hours obtained alumina supports under oxygen atmosphere.
It weighs 100 grams of above-mentioned alumina support to be placed in a beaker, contains MoO with 150 milliliters310 grams, NiO1.2 grams of molybdenum-
Nickel-phosphor active metal maceration extract oxide impregnation alumina supporter 5 hours, filters redundant solution, and the material after dipping dries 6 in 120 DEG C
Hour, then roasted 5 hours at 500 DEG C, catalyst C1 is made, the property of the catalyst is shown in Table 1.
Embodiment 2
With embodiment 1, only the additional amount of aluminum carbonate basic ammonium is 30 grams, and when impregnating aluminum carbonate basic ammonium is quality
Concentration is the tetrose solution of 40wt%, and when spraying impregnated shaped support is the mannitol solution that mass concentration is 20wt%,
The dosage of solution is 20ml, and it is 6 hours that maturing temperature of the carrier under nitrogen and oxygen atmosphere, which is 700 DEG C of calcining times, is made
The property of catalyst C2, the catalyst are shown in Table 1.
Embodiment 3
With embodiment 1, only the additional amount of aluminum carbonate basic ammonium is 40 grams, and when impregnating aluminum carbonate basic ammonium is quality
Concentration is the glucose solution of 30wt%, and when spraying impregnated shaped support is the pentose solution that mass concentration is 10wt%,
The dosage of solution is 15ml, and it is 6 hours that maturing temperature of the carrier under nitrogen and oxygen atmosphere, which is 750 DEG C of calcining times, is made
The property of catalyst C3, the catalyst are shown in Table 1.
Embodiment 4
With embodiment 1, only the additional amount of aluminum carbonate basic ammonium is 70 grams, and when impregnating aluminum carbonate basic ammonium is quality
Concentration be 25wt% fructose soln, spray impregnated shaped support when be that the mannitol that mass concentration is 12.5wt% is molten
Liquid, the dosage of solution are 17.5ml, catalyst C4 are made, the property of the catalyst is shown in Table 1.
Embodiment 5
With embodiment 1, only the additional amount of aluminum carbonate basic ammonium is 60 grams, and when impregnating aluminum carbonate basic ammonium is quality
Concentration is the arabinose alcoholic solution of 35wt%, and when spraying impregnated shaped support is the sweet dew that mass concentration is 17.5wt%
Alcoholic solution, the dosage of solution are 17.5ml, catalyst C5 are made, the property of the catalyst is shown in Table 1.
Comparative example 1
With embodiment 1, only unused carbon precursor solution impregnates aluminum carbonate basic ammonium and shaping carrier, but will be same amount of
Carbon precursor is added in carrier in the form of kneading when carrier is formed and comparative catalyst C6 is made, and the property of the catalyst is shown in Table
1。
Comparative example 2
With embodiment 1, only carrier is without two-stage roasting processing, but carrier is placed in air atmosphere and is carried out at roasting
It manages and comparative catalyst C7 is made, the property of the catalyst is shown in Table 1.
1 catalyst property of table
Note: * pore size distribution refers to that the Kong Rong of certain diameter range inner hole in carrier accounts for the percentage of total pore volume.
Table 1 the result shows that, while there is suitable pore structure using the catalyst of the method for the present invention preparation with compared with
High mechanical strength, the catalyst are suitable for heavy resid boiling bed hydrogenation process field.
Embodiment 6
The following examples illustrate the catalyst of the method for the present invention preparation and the catalytic performance of comparative example catalyst.
By above-described embodiment and comparative example catalyst, (CSTR) carries out activity rating, catalyst on continuously stirring autoclave
Filling be 100ml, fluidized bed reactor and continuously stir on autoclave (Continuous Stirred Tank Reactor,
CSTR) similar, all there is good full back-mixing performance, reacting dynamics characteristic is opposite.It is therefore possible to use CSTR replaces boiling
Bed reactor carries out catalyst performance.Raw material oil nature is shown in Table 2, and evaluation condition is shown in Table 3, and the activity with comparative catalyst C6 is
100, the Activity evaluation of other catalyst such as table 4.
2 raw material oil nature of table
| Project | |
| Density (20 DEG C), g/cm3 | 1.01 |
| Sulphur, wt% | 3.51 |
| Carbon residue, wt% | 20.86 |
| Nickel+vanadium, μ g/g | 249 |
3 process conditions of table
| Condition | |
| Reaction temperature, DEG C | 430 |
| Reaction pressure, MPa | 15 |
| Air speed, h-1 | 0.5 |
4 catalyst hydrogenation performance comparison of table
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | |
| Opposite demetallization per | 123 | 126 | 118 | 109 | 113 | 100 | 101 |
| Opposite desulfurization degree | 131 | 125 | 123 | 119 | 121 | 100 | 103 |
| Relatively de- carbon yield | 124 | 118 | 121 | 108 | 110 | 100 | 99 |
Using the catalyst demetalization with higher of the method for the present invention preparation, desulfurization and de- it can be seen from 4 data of table
Carbon residue activity, the catalyst are suitable for boiling bed hydrogenation demetalization field.
To fresh catalyst with react 24 hours rear catalyst intensity and abrasion test, test results are shown in figure 1.
5 catalyst strength of table and abrasion
As can be seen from Table 5 using the catalyst intensity with higher and wearability of the method for the present invention preparation.
Claims (9)
1. a kind of preparation method of boiling bed hydrogenation treatment catalyst, which comprises the following steps:
Step (1), by the aluminum carbonate basic ammonium kneading and compacting of boehmite and absorption carbon precursor solution, molding is through at dry
Reason；
Step (2) sprays the material that step (1) obtains with the solution of carbonaceous precursor, and the material after spraying is made through drying, roasting
Alumina support；
Step (3), the alumina support obtained with the maceration extract impregnation steps (2) containing hydrogenation active component, after dipping through drying,
The boiling bed hydrogenation treatment catalyst is made in roasting.
2. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(1) the aluminum carbonate basic ammonium described in is the aluminum carbonate basic ammonium with club shaped structure, a length of 1-5 μ of rod-like basic type aluminium carbonate ammonium
M, diameter 100-300nm, the additional amount of aluminum carbonate basic ammonium are the 15wt%- of boehmite weight described in step (1)
35wt%.
3. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(1) carbon precursor described in is polyalcohol and/or glucide；
The polyalcohol is one or more of xylitol, sorbierite, mannitol and arabite；
The glucide is one or more of glucose, ribose, fructose, triose, tetrose, pentose, hexose and non-sugar；
Carbon precursor is to be adsorbed onto aluminum carbonate basic ammonium as a solution, and the mass concentration of carbon precursor solution is 20wt%-40wt%,
The dosage of solution is to be totally submerged aluminum carbonate basic ammonium, and dip time is 1-3 hours.
4. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(1) in, during the kneading and compacting, peptizing agent and/or extrusion aid are added as needed；
The peptizing agent is one or more of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc.；The additional amount of peptizing agent is oxidation
The 0.5wt%-3wt% of alumina supporter weight；
The extrusion aid is sesbania powder, and the additional amount of extrusion aid is the 0.1wt%-0.5wt% of carrying alumina body weight；
Drying temperature described in step (1) is 100-160 DEG C, and drying time is 6-10 hours.
5. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(2) the carbonaceous precursor solution described in is the aqueous solution of polyalcohol and/or glucide；
The polyalcohol is one or more of xylitol, sorbierite, mannitol and arabite；
The glucide is one or more of glucose, ribose, fructose, triose, tetrose, pentose, hexose and non-sugar；
The mass concentration of carbonaceous precursor solution is 10wt%-20wt%, and the dosage of solution is the 10wt%- of molding materials saturated absorption amount
20wt%.
6. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, it is characterised in that step (2)
Described in drying temperature be 100-160 DEG C, drying time be 6-10 hours.
7. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(2) it is roasted to two-stage roasting described in, roasting first under an inert atmosphere, maturing temperature is 600-750 DEG C, calcining time
It is 4-8 hours, the inert atmosphere is the gases such as nitrogen, argon gas；Then it is roasted under oxygen atmosphere, maturing temperature 600-
750 DEG C, calcining time is 4-8 hours.
8. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(3) in, in the hydrogenation active component maceration extract, vib metals content is calculated as 7-15g/100ml with oxide, the
Group VIII metal content is calculated as 0.8-3g/100ml with oxide, uses volume impregnation, incipient impregnation or spray dipping side
Formula, dip time are 1-5 hours.
9. a kind of preparation method of boiling bed hydrogenation treatment catalyst according to claim 1, which is characterized in that step
(3) drying condition described in is 6-10 hours dry at 80-120 DEG C；The roasting condition is to roast 3- at 400-600 DEG C
6 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109967086A (en) * | 2019-03-06 | 2019-07-05 | 北京众智创新科技开发有限公司 | A kind of preparation method of boiling bed hydrogenation catalyst |
| CN111822012A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
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| CN115957770A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Preparation method of boiling bed residual oil hydrogenation catalyst |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109967086A (en) * | 2019-03-06 | 2019-07-05 | 北京众智创新科技开发有限公司 | A kind of preparation method of boiling bed hydrogenation catalyst |
| CN109967086B (en) * | 2019-03-06 | 2024-02-02 | 北京众智创新科技开发有限公司 | Preparation method of ebullated bed hydrogenation catalyst |
| CN111822012A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
| CN111822012B (en) * | 2019-04-17 | 2022-06-07 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
| CN112742425A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN112742425B (en) * | 2019-10-29 | 2022-07-08 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN115957770A (en) * | 2021-10-08 | 2023-04-14 | 中国石油化工股份有限公司 | Preparation method of boiling bed residual oil hydrogenation catalyst |
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