CN109718797A - A kind of preparation method of hydrotreating catalyst - Google Patents
A kind of preparation method of hydrotreating catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hydrotreating catalyst.This method comprises: smashing wood material at sawdust, with boehmite kneading, extrusion molding；Molding is subjected to Microwave Pretreatment again, charing process is then carried out under inert protective gas atmosphere；Material after charing carries out high-temperature activation again, and activation atmosphere is alkaline gas atmosphere, and the alumina supporter containing char combustion obtained after high-temperature activation is impregnated the solution containing active metal component, hydrotreating catalyst of the invention is made after dry, roasting.Interactively in the preparation method Effective Regulation of hydrotreating catalyst of the invention catalyst between active carbon and aluminium oxide, improve the acidity of catalyst support surface, catalyst obtained has good pore structure, surface nature, when for residual hydrocracking, hydrodemetallization, desulfurization, the efficiency of depitching matter are higher.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreating catalyst, relating in particular to one kind with aluminium containing char combustion is
The preparation method of the hydrotreating catalyst of carrier, the especially preparation for the hydrotreating catalyst of residuum hydrogenating and metal-eliminating
Method.
Background technique
Currently, with the aggravation of crude oil in poor quality, heaviness trend, the increase of light-end products demand and environmental regulation
It is increasingly strict, the research and development of Efforts To Develop residual hydrogenation technology are of great significance, and develop hydrodemetallization with high performance
Catalyst is then key point.The reactivity worth of Hydrodemetalation catalyst had both depended on the intrinsic catalysis characteristics of active component,
Support is depended on again.The carrier that residuum hydrogenating and metal-eliminating catalyst uses is substantially alumina support, aluminium oxide and work
Property component between have stronger interaction, influence the formation of active phase, reduce the activity of catalyst.
In recent years, active carbon is interested by researchers as the carrier of Hydrodemetalation catalyst.Active carbon has hole
The advantages that structure is adjustable, large specific surface area, small with active metal effect.US5358634, US5374350 disclose a kind of plus hydrogen
Catalyst for demetalation selects active carbon for carrier, dip loading active metal component.EP1537912A1 discloses a kind of work
Property charcoal be carrier method for preparing catalyst, load iron isoreactivity metal component.The above catalyst only using active carbon as carrier,
The mechanical strength of catalyst is lower, and stability when for hydrotreating reaction is poor.
CN200410000952.X and CN200810226918.2 disclose catalyst for hydrorefining distillate oil, wherein adopting
Be carrier with char combustion aluminium is covered, supported active metals component and obtain.The catalyst mainly considers to reduce containing high-area carbon and activity
Metal interaction, but the pore structure of the catalyst is not particularly suited for residuum hydrogenating and metal-eliminating catalyst.
CN201210323265.6 discloses a kind of active carbon/alumina composite type catalyst carrier and its preparation and answers
With.The catalyst carrier be first with acid-washed active carbon, then it is oxidation-treated after, with γ-Al2O3, auxiliary agent kneading and compacting and be made.
In this method, active carbon and γ-Al2O3It is the kneading and compacting again after pore structure formation, complex carrier is made.This method is not
Conducive to the pore structure and surface nature of interactively and catalyst carrier between regulation activity charcoal and aluminium oxide.
Summary of the invention
Aiming at the deficiencies in the prior art, the present invention provides a kind of preparation methods of hydrotreating catalyst.It should
Interactively in method Effective Regulation catalyst between active carbon and aluminium oxide, improves the acid of catalyst support surface
Property, the hydrotreating catalyst of preparation has porosity, and when being used for hydrotreating residual oil crude oil, hydrodemetallization, takes off desulfurization
The efficiency of asphalitine is higher, and this method also has the features such as simple process, processing cost is low.
The present invention provides a kind of preparation methods of hydrotreating catalyst, comprising:
(1) wood material is dried, is ground into sawdust；
(2) sawdust obtained by step (1) and boehmite are subjected to kneading, extrusion molding；
(3) molding obtained by step (2) is subjected to Microwave Pretreatment at 200 ~ 500 DEG C, pretreatment time is 0.5 ~ 5.0h, micro-
Wave power is 1 ~ 6kW；Then charing process is carried out under inert protective gas atmosphere, carbonization temperature is 450 ~ 600 DEG C, charing
0.5 ~ 8.0h of time；
(4) material after step (3) charing is subjected at 700 ~ 1100 DEG C 3 ~ 8h high-temperature activation, is prepared into the load of aluminium containing char combustion
Body, wherein activation atmosphere is alkaline gas atmosphere；
(5) alumina supporter containing char combustion obtained by step (4) is impregnated into active metal component, through drying, roasting, obtained hydrotreating is urged
Agent.
Wood material can be one of timber, wood sawdust, shell, bark, bamboo wood or more in step (1) of the present invention
Kind, drying condition are as follows: dry 3 ~ 8h at 100 ~ 150 DEG C.The granularity of the sawdust is 100 ~ 300 mesh, preferably 200 ~ 250 mesh.
Sawdust and boehmite are in step (2) of the present invention with Al2O3The mass ratio of meter is 2 ~ 7:3 ~ 8, preferably 3 ~ 5:5 ~ 7.
The property of the boehmite is as follows: 0.8 ~ 1.2mL/g of Kong Rongwei, and specific surface area is 150 ~ 400m2/ g, pore-size distribution are as follows:
10% ~ 20% of Kong Rongwei total pore volume shared by hole of the bore dia less than 10nm, bore dia are the total hole Kong Rongwei shared by the hole of 10 ~ 20nm
20% ~ 36% held, bore dia are greater than 44% ~ 70% of Kong Rongwei total pore volume shared by the hole of 20nm.It, can be according to need in forming process
Conventional shaping assistant, such as peptizing agent, extrusion aid etc. is added, the peptizing agent is hydrochloric acid, nitric acid, acetic acid and citric acid
One of or a variety of mixing, the extrusion aid include one or both of sesbania powder, water etc. mixing.
Step (3) pretreatment temperature of the present invention be 200 ~ 500 DEG C, preferably 300 ~ 450 DEG C, pretreatment time be 0.5 ~
5.0h, preferably 1.0 ~ 3.0h；Carbonization temperature is 450 ~ 600 DEG C, and preferably 500 ~ 550 DEG C, wherein carbonization temperature is than pretreatment temperature
Degree is at least 50 DEG C high, and carbonization time is 0.5 ~ 8.0h, preferably 2.0 ~ 8.0h.The inert protective gas can be inert gas
And/or nitrogen, wherein inert gas is one of argon gas, helium or a variety of mixing.
700 ~ 1100 DEG C of high-temperature activation temperature of step (4) of the present invention, preferably 800 ~ 1000 DEG C；Activation time is 3 ~ 8h, excellent
Select 4 ~ 6h；Activation atmosphere be alkaline gas atmosphere, such as: the vapor containing ammonia, wherein in the vapor containing ammonia ammonia volume fraction
It is 5% ~ 20%；It can also be added in vapor containing ammonia one or more of in the protection gas such as inert gas, carbon dioxide and nitrogen.
The ratio between the volume of the protection gas and the volume of vapor containing ammonia are for 10 hereinafter, preferably 5 hereinafter, the inert gas is
One of argon gas, helium or a variety of mixing.
Step (5) active metal of the present invention be group VIII and vib metals, wherein group VIII metal be Co and/
Or Ni, vib metals are Mo and/or W.On the basis of the weight of hydrotreating catalyst, group VIII metal is with oxide
The content of meter is 1% ~ 5%, and content of the vib metals in terms of oxide is 5% ~ 15%.
Dipping described in step (5) of the present invention using conventional infusion process, can using the method that sprays, saturation infusion process,
Any one in supersaturated infusion process；The drying condition are as follows: dry 2 ~ 5 h, roasting condition at 100 ~ 200 DEG C are as follows:
2 ~ 5h is roasted at 300 ~ 600 DEG C.
Compared with prior art, the present invention having the advantage that
The method of the present invention using sawdust as carbide, with macropore boehmite kneading and compacting after, first through Microwave Pretreatment, then
Through carbonizing, the complex carrier of aluminium containing char combustion is obtained after carrying out high-temperature activation under alkaline atmosphere, then load active component, obtains
Hydrotreating catalyst of the invention.Because containing a large amount of hemicelluloses and cellulose in sawdust, in the condition of Microwave Pretreatment
Under, on the one hand the high molecular decomposition of control hemicellulose and cellulose etc. and polymerization degree of carbonization advantageously form certain proportion
Suitable macropore active carbon, while improving carrier pore structure improve carrier mechanical strength, on the other hand also help
Its decomposition product and boehmite act on to be formed it is a certain amount of cover char combustion aluminium, and adjust the work between aluminium oxide and active carbon
With relationship.It is activated under the conditions of alkaline atmosphere later, advantageously reduces the loss of carrier surface hydroxyl, improve carrier surface
Acidity.The alumina supporter containing char combustion as made from the method for the present invention has micropore, mesoporous, macropore duct, makes its cellular structure
It is more advantageous to processing residual oil, promotes the reaction and diffusion of macromolecular, while increasing the ability for holding impurity again, and carrier and activity
The active force of metal is substantially reduced, and active metal is easier to vulcanize, and is conducive to active raising.
When the hydrotreating catalyst of preparation of the invention is used for residual hydrocracking, hydrodemetallization, adds hydrodesulfurization
The efficiency of hydrogen depitching matter is relatively high, and activity and stability are preferable.
Specific embodiment
Below with reference to embodiment to further illustrate the technical scheme of the present invention and technical effect, but it is not limited to following
Embodiment.In the present invention, wt% is mass fraction.
Wherein the property of boehmite used in all embodiments and comparative example is as follows: Kong Rongwei 0.95mL/g, than
Surface area is 298 m2/ g, pore size distribution are as follows: bore dia less than 10nm hole shared by Kong Rongwei total pore volume 10%, bore dia be 10 ~
The 34% of Kong Rongwei total pore volume shared by the hole of 20nm, bore dia are greater than 56% of Kong Rongwei total pore volume shared by the hole 20nm.
Embodiment 1
Wood sawdust is dried into 5h at 130 DEG C, is then comminuted into the sawdust of 200 mesh；By sawdust and boehmite with Al2O3Meter
It is mixed according to mass ratio 3:7, and 5wt% acetic acid and 3wt% sesbania powder is added to carry out kneading, extrusion molding；By molding 350
Microwave Pretreatment 1h, microwave power 1kW are carried out at DEG C, 4h charing process is then carried out under helium atmosphere, and carbonization temperature is
500℃；Material after charing is subjected to high-temperature activation at 900 DEG C, activation atmosphere is that the water of the ammonia containing volume fraction 10% steams
Gas, activation time 3h are prepared into the complex carrier of aluminium containing char combustion；Char combustion aluminium complex carrier dipping will be contained and contain active metal
The solution of molybdenum, nickel component, it is 4 hours dry at 150 DEG C later, it is then roasted 3 hours at 450 DEG C, preparation cost invention adds
Hydrogen handles catalyst A, and catalyst property is shown in Table 2.
Embodiment 2
Wood sawdust is dried into 4h at 150 DEG C, is then comminuted into the sawdust of 100 mesh；By sawdust and boehmite with Al2O3Meter
It is mixed according to mass ratio 3:7, and adds 5wt% acetic acid and 3wt% sesbania powder, carry out kneading, extrusion molding；Molding is existed
Microwave Pretreatment 2h, microwave power 3kW are carried out at 300 DEG C, and 5h charing process, carbonization temperature are then carried out under helium atmosphere
It is 510 DEG C；Material after charing is subjected to high-temperature activation at 850 DEG C, activation atmosphere is carbon dioxide and contains volume fraction 10%
Ammonia vapor, the volume ratio of carbon dioxide and the vapor containing ammonia is 5:5, and activation time 5h is prepared into aluminium containing char combustion
Complex carrier；The complex carrier of aluminium containing char combustion is impregnated into the solution containing molybdenum, nickel component, it is 4 hours dry at 140 DEG C later,
Then it is roasted 3 hours at 550 DEG C, preparation cost invention hydrotreating catalyst B, catalyst property is shown in Table 2.
Embodiment 3
Wood sawdust is dried into 8h at 100 DEG C, is ground into the sawdust of 300 mesh；By sawdust and large aperture boehmite with Al2O3
Meter is mixed according to mass ratio 4:6, and adds 5wt% acetic acid and 3wt% sesbania powder, carries out kneading, extrusion molding；Molding is existed
Microwave Pretreatment 2h, microwave power 2kW are carried out at 400 DEG C, and 3h charing process, carbonization temperature are then carried out under helium atmosphere
It is 550 DEG C；Material after charing is subjected to high-temperature activation at 950 DEG C, activation atmosphere is helium and 10% ammonia containing volume fraction
The volume ratio of vapor, helium and the vapor containing ammonia is 6:4, activation time 4h, is prepared into the complex carrier of aluminium containing char combustion；It will
The complex carrier of aluminium containing char combustion impregnates the solution containing molybdenum, nickel component, 4 hours dry at 150 DEG C later, then at 460 DEG C
Lower roasting 3 hours, preparation cost invention hydrotreating catalyst C, catalyst property is shown in Table 2.
Embodiment 4
By wood sawdust in 130 DEG C of dry 7h, it is ground into the sawdust of 300 mesh；By sawdust and large aperture boehmite with Al2O3Meter
It is mixed according to mass ratio 3:7, and adds 5wt% acetic acid and 3wt% sesbania powder, carry out kneading, extrusion molding；Molding is existed
Microwave Pretreatment 2h, microwave power 4kW are carried out at 280 DEG C, and 5h charing process, charing are then carried out under atmosphere of inert gases
Temperature is 520 DEG C；Material after charing is subjected to high-temperature activation at 930 DEG C, activation atmosphere is nitrogen and contains volume fraction 10%
Ammonia vapor, both nitrogen and vapor containing ammonia volume ratio are 8:2, and activation time 7h is prepared into aluminium containing char combustion
Complex carrier；The complex carrier of aluminium containing char combustion is impregnated into the solution containing molybdenum, nickel component, it is 4 hours dry at 180 DEG C later,
Then it is roasted 3 hours at 440 DEG C, preparation cost invention hydrotreating catalyst D, catalyst property is shown in Table 2.
Comparative example 1
With embodiment 1, only wood sawdust changes carbonaceous pitch gel into, and other conditions are same as Example 1, and obtained comparative example adds hydrogen
Catalyst E is handled, catalyst property is shown in Table 2.
Comparative example 2
With embodiment 1, only without using the pre- charing process of microwave, molding is directly subjected to charing process, other conditions with
Embodiment 1 is identical, and comparative example hydrotreating catalyst F is made, and catalyst property is shown in Table 2.
Comparative example 3
Select ready-made granularity for 200 mesh, specific surface area 960m2The active carbon of/g uses concentration to carry out for the hydrochloric acid of 25wt%
Then pickling is cleaned with deionized water, 30wt% nitric acid oxidation is recycled to handle 10h.Then with boehmite in terms of aluminium oxide
It is that 3:7 is mixed according to weight ratio, adds 5wt% acetic acid and the sesbania powder of 3wt%, extruded moulding, 130 DEG C of dry 3h,
The lower 900 DEG C of roastings 3h of nitrogen atmosphere is prepared into carrier, impregnates the solution containing active metal component molybdenum, nickel, does at 150 DEG C
It dry 4 hours, is then roasted 3 hours at 450 DEG C, comparative example hydrotreating catalyst G is made, catalyst property is shown in Table 2.
Comparative example 4
By the sesbania powder of boehmite, 5wt% acetic acid and 3wt%, mixing, extruded moulding, 130 DEG C of dry 3h, 900 DEG C of roastings
3h is prepared into alumina support, which is contained to the solution of active metal molybdenum, nickel, 4 hours dry at 150 DEG C, so
It is roasted 3 hours at 450 DEG C afterwards, comparative example hydrotreating catalyst H is made, catalyst property is shown in Table 2.
The property of 1 feedstock oil of table
| Project | Raw material |
| Density (20 DEG C), g/cm3 | 1.0074 |
| S, wt% | 4.6 |
| Ni, μ g/g | 36 |
| V, μ g/g | 84 |
| CCR, wt% | 15 |
Table 1 is handled feedstock oil: feedstock oil is Sha Zhongchang slag, and reaction carries out in fixed bed hydrogenation reactor, reacts item
Part is as follows: reaction temperature is 385 DEG C, and volume space velocity is 0.2 h when liquid-1, hydrogen to oil volume ratio 800, hydrogen partial pressure 15.4MPa, even
Reforwarding turns 3000 hours, and obtained evaluation result is shown in Table 2.
The property and test evaluation result of catalyst obtained by 2 embodiment and comparative example of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Catalyst number | A | B | C | D | E | F | G | H |
| Specific surface area, m2/g | 162 | 159 | 168 | 165 | 180 | 170 | 165 | 135 |
| Kong Rong, mL/g | 1.18 | 1.12 | 1.25 | 1.15 | 1.05 | 1.10 | 0.89 | 0.75 |
| Intensity, N/mm | 12 | 13 | 11 | 12 | 13 | 12 | 9 | 15 |
| Pore size distribution, % | ||||||||
| <100nm | 68 | 73 | 59 | 72 | 90 | 81 | 90 | 100 |
| 100-1000nm | 24 | 21 | 30 | 24 | 10 | 15 | 8 | 0 |
| >1000nm | 8 | 6 | 11 | 4 | 0 | 4 | 2 | 0 |
| Catalyst composition | ||||||||
| MoO3, wt% | 11.3 | 11.2 | 11.3 | 11.1 | 11.2 | 11.3 | 11.2 | 11.1 |
| NiO, wt% | 2.5 | 2.5 | 2.6 | 2.6 | 2.5 | 2.5 | 2.6 | 2.5 |
| Evaluation test result | ||||||||
| Desulfurization degree, wt% | 90.3 | 90.1 | 90.5 | 91.9 | 86.3 | 87.1 | 86.5 | 74.5 |
| Demetallization per, wt% | 91.5 | 92.3 | 91.2 | 92 | 83.3 | 84.2 | 88.2 | 72.5 |
| Depitching matter rate, wt% | 84.22 | 85.3 | 84.5 | 86.2 | 81.2 | 82.3 | 82.5 | 79.2 |
From Table 2, it can be seen that when hydrotreating catalyst prepared by the present invention is used for residual hydrocracking, hydrodemetallization,
The efficiency of hydrodesulfurization plus hydrogen depitching matter is relatively high, and especially hydrodemetallization efficiency is obviously improved.
Claims (10)
1. a kind of preparation method of hydrotreating catalyst, which comprises the following steps:
(1) wood material is dried, is ground into sawdust；
(2) sawdust obtained by step (1) and boehmite are subjected to kneading, extrusion molding；
(3) molding obtained by step (2) is subjected to Microwave Pretreatment at 200 ~ 500 DEG C, pretreatment time is 0.5 ~ 5.0h, micro-
Wave power is 1 ~ 6kW；Then charing process is carried out under inert protective gas atmosphere, carbonization temperature is 450 ~ 600 DEG C, charing
Time is 0.5 ~ 8.0h；
(4) material after step (3) charing is subjected at 700 ~ 1100 DEG C 3 ~ 8h high-temperature activation, is prepared into the load of aluminium containing char combustion
Body, wherein activation atmosphere is alkaline gas atmosphere；
(5) alumina supporter containing char combustion obtained by step (4) is impregnated into active metal component, through drying, roasting, obtained hydrotreating is urged
Agent.
2. preparation method described in accordance with the claim 1, which is characterized in that step (1) wood material is timber, sawmilling
One of bits, shell, bark, bamboo wood are a variety of, drying condition are as follows: dry 3 ~ 8h at 100 ~ 150 DEG C；The grain of the sawdust
Degree is 100 ~ 300 mesh, preferably 200 ~ 250 mesh.
3. preparation method described in accordance with the claim 1, which is characterized in that sawdust and boehmite are in step (2) with Al2O3
The mass ratio of meter is 2 ~ 7:3 ~ 8, preferably 3 ~ 5:5 ~ 7.
4. according to preparation method described in claim 1 or 3, which is characterized in that the property of step (2) described boehmite is such as
Under: 0.8 ~ 1.2mL/g of Kong Rongwei, specific surface area are 150 ~ 400m2/ g, pore-size distribution are as follows: shared by hole of the bore dia less than 10nm
The 10% ~ 20% of Kong Rongwei total pore volume, bore dia are 20% ~ 36% of Kong Rongwei total pore volume shared by the hole of 10 ~ 20nm, and bore dia is greater than
The 44% ~ 70% of Kong Rongwei total pore volume shared by the hole of 20nm.
5. preparation method described in accordance with the claim 1, which is characterized in that in step (2) forming process, shaping assistant is added,
The shaping assistant is one or both of peptizing agent, extrusion aid, and further, the peptizing agent is hydrochloric acid, nitric acid, vinegar
One of acid and citric acid or a variety of mixing, further, the extrusion aid are mixed for one or both of sesbania powder, water
It closes.
6. preparation method described in accordance with the claim 1, which is characterized in that pretreatment temperature is 300 ~ 450 DEG C in step (3),
Pretreatment time is 1.0 ~ 3.0h；Carbonization temperature is 500 ~ 550 DEG C, and wherein carbonization temperature is higher than pretreatment temperature by least 50
DEG C, carbonization time is 2.0 ~ 8.0h；The inert protective gas is inert gas and/or nitrogen, and wherein inert gas is argon
One of gas, helium or a variety of mixing.
7. preparation method described in accordance with the claim 1, which is characterized in that step (4) high temperature activation temperature is 800 ~ 1000
DEG C, activation time is 4 ~ 6h.
8. preparation method described in accordance with the claim 1, which is characterized in that alkaline gas atmosphere described in step (4) is containing ammonia
Vapor, wherein in the vapor containing ammonia ammonia volume fraction be 5% ~ 20%；In vapor containing ammonia or be added protective gas,
The protective gas is one or more of in inert gas, carbon dioxide and nitrogen；The volume of the protection gas and the water containing ammonia
The ratio between volume of steam is 10 hereinafter, preferably 5 hereinafter, the inert gas is one of argon gas, helium or a variety of mixed
It closes.
9. preparation method described in accordance with the claim 1, which is characterized in that active metal is group VIII and the in step (5)
Group vib metal, wherein group VIII metal is Co and/or Ni, and vib metals are Mo and/or W；With hydrotreating catalyst
Weight on the basis of, content of the group VIII metal in terms of oxide be 1% ~ 5%, content of the vib metals in terms of oxide
It is 5% ~ 15%.
10. preparation method described in accordance with the claim 1, which is characterized in that dipping described in step (5) using spray method,
It is saturated infusion process, any one in supersaturated infusion process；The drying condition are as follows: dry 2 ~ 5 h, roasting at 100 ~ 200 DEG C
Burning condition are as follows: 2 ~ 5h is roasted at 300 ~ 600 DEG C.
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| CN113694913B (en) * | 2020-05-22 | 2024-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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| CN112337452B (en) * | 2020-10-28 | 2023-11-17 | 中海油天津化工研究设计院有限公司 | Preparation method of residual oil hydrodemetallization catalyst carrier |
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| CN114149816A (en) * | 2021-11-29 | 2022-03-08 | 常州大学 | Method for preparing hydrogen-rich gas by catalyzing cracking of biomass tar by using aluminum smelting waste residues |
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Effective date of registration: 20230922 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |