CN106582703B - A kind of catalyst for selective hydrodesulfurizationof of gasoline and the preparation method and application thereof - Google Patents
A kind of catalyst for selective hydrodesulfurizationof of gasoline and the preparation method and application thereof Download PDFInfo
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of catalyst for selective hydrodesulfurizationof of gasoline and the preparation method and application thereof.The catalyst includes carrier and the active component that is supported on carrier, and the carrier includes through organic alkali solution treated CeO2‑Al2O3Carrier, CeO2The 0.1~10% of vehicle weight is accounted for, the organic base is selected from one of ethanol amine, diethanol amine, triethanolamine, ethylene glycol amine, methylethanolamine, ethylenediamine or a variety of；The active component is MoO3And CoO；Based on the weight percent of catalyst, MoO3It accounts for 6~14%, CoO and accounts for 1~6%.Catalyst of the present invention can reduce the production quantity of secondary mercaptan during selective hydrodesulfurization, have good hydrodesulfurization activity and selectivity, be particularly suitable for the selective hydrodesulfurization of the higher catalytically cracked gasoline of sulfur content.
Description
Technical field
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and the preparation method and application thereof.
Background technique
With the pay attention to day by day of environmental pollution, motor petrol quality standard is continuously improved.V fuel oil standard requirements of state
Sulfur content in gasoline is less than 10 μ g/g.Currently, FCC gasoline accounts for about 70%-80%, and 80% or more sulphur in China's motor petrol
Carry out catalytic cracking (FCC) gasoline with alkene.Therefore, FCC gasoline deep desulfuration becomes the key of production clear gusoline.
Selective hydrodesulfurization technology avoids a large amount of saturations of alkene while to sulfide hydrogenation and removing, to drop
The low loss of octane number is domestic and international to use most wide one of technology.During FCC gasoline selective hydrodesulfurization, alkene
The H that hydrocarbon can be generated with hydrodesulfurization2S recombines generation mercaptan, and then increases mercaptan sulfur content in product, this becomes life
Produce the critical issue of clean gasoline.
Existing Hydrobon catalyst is usually with Al2O3、SiO2Equal oxides are carrier, the group vibs such as Co, Mo, Ni, W and
VIII group element is active component.K, Mg, P, B etc. improve the activity of catalyst as auxiliary agent.
US5525211 discloses a kind of catalyst for selectively hydrodesulfurizing, and carrier is mainly using with spinel structure
MgAl2O4、CaAl2O4、BaAl2O4Deng, metal active constituent is selected from the Ni or Co of the Mo or W of group VIB, group VIII, with
And group ia alkali metal, group iia alkaline-earth metal or lanthanide series.The catalyst has preferable hydrodesulfurization performance, but pungent
The loss of alkane value is higher.
CN103386327A discloses a kind of catalyst for selectively hydrodesulfurizing and its preparation and application, catalyst with Mo,
Co is active component, adds suitable organic matter and loads on the alumina support as complexing agent.The catalyst has preferable
Desulphurizing activated and lower alkene saturated activity, particularly suitable for sulphur and the higher raw material of olefin(e) centent.
CN104107695A discloses a kind of preparation method of Hydrobon catalyst and the application of the catalyst, carrier warp
Ammonia ammoniated treatment back loading active component Mo, Co.Catalyst has preferable hydrodesulfurization under lower pressure and temperature
Activity.
CN101905165A discloses the preparation and application of a kind of catalyst for selectively hydrodesulfurizing, and catalyst carrier uses
K modified ZrO2-Al2O3Complex carrier, active component use Mo, Co, and auxiliary agent uses Mg, P.The catalyst has preferable add
Hydrogen is desulphurizing activated, selectivity and stability, is suitable for sulphur and the higher catalytically cracked gasoline heavy constituent of olefin(e) centent, is able to produce
Sulfur content meets the gasoline of Europe IV standard.
CN1576351A discloses a kind of gasoline fraction Hydrobon catalyst and hydrodesulfurizationprocess process, catalyst with copper,
The aluminium oxide of at least one modification of zinc, yttrium, lanthanum, cerium, neodymium, samarium and ytterbium is carrier, with the Mo of group VIB or W, group VIII
Ni or Co is active component.When catalytic cracking distillate low-sulfur content using the catalyst treatment, have preferable desulfurization degree and
Lower alkene saturation factor.
However, above-mentioned Hydrobon catalyst is de- in the selective hydrogenation for being applied to the higher catalytically cracked gasoline of sulfur content
When sulphur, effect be not it is very ideal, especially the production quantity of secondary mercaptan is still higher during selective hydrodesulfurization, needs
It is further improved.
Summary of the invention
It is an object of the present invention to provide a kind of improved selective hydrogenation desulfuration catalyst for catalytically cracking gasoline,
With good hydrodesulfurization activity and selectivity, and it can be reduced the generation of secondary mercaptan during selective hydrodesulfurization.
Another object of the present invention is to provide the preparation sides of the selective hydrogenation desulfuration catalyst for catalytically cracking gasoline
Method.
Another object of the present invention is to provide the applications of the selective hydrogenation desulfuration catalyst for catalytically cracking gasoline, special
It is not its selective hydrodesulfurization for being used for the higher FCC gasoline of sulfur content.
On the one hand, the present invention provides a kind of catalyst for selective hydrodesulfurizationof of gasoline, which includes carrier and load
The active component being loaded on carrier, in which:
The carrier includes through organic alkali solution treated CeO2-Al2O3Carrier；Wherein, CeO2Account for vehicle weight
0.1~10%；
The active component is MoO3And CoO；Based on the weight percent of catalyst, MoO3Account for 6~14%, CoO account for 1~
6%.
Catalyst for selective hydrodesulfurizationof of gasoline of the invention, with CeO2-Al2O3For carrier, CeO2Account for carrier gross mass
0.1~10%.Inventor has found under study for action, uses cerium modified CeO2-Al2O3Carrier can reduce itself and metal active group
/ interaction, and then promote metal active constituent vulcanization, make catalyst have preferable hydrodesulfurization activity and
Selectivity.Meanwhile the introducing of cerium improves the stability of catalyst, it is suppressed that the carbon distribution of catalyst surface.
Specific embodiment according to the present invention, the present invention is using organic base to CeO2-Al2O3Carrier is handled, can be with
Improve carrier surface Al2O3Crystalline structure reduces support surface acidity, to promote active metal component in point of carrier surface
Divergence reduces the interaction of active metal component and carrier, reduces the saturation of alkene, inhibits H2S and olefine reaction generate two
Secondary mercaptan.Specifically, organic base used in the present invention is selected from ethanol amine, diethanol amine, triethanolamine, ethylene glycol amine, methyl ethanol
One of amine, ethylenediamine are a variety of.More specifically, the present invention, when preparing organic alkali solution, the mass fraction of organic base is 1
~20%, preferably 3~15%.In this data area, using described through organic alkali solution treated CeO2-Al2O3Carrier obtains
The catalyst arrived has preferable catalytic performance.
Specific embodiment according to the present invention, in catalyst of the invention, described through organic alkali solution, treated
CeO2-Al2O3Carrier is prepared in accordance with the following methods: by boehmite dry powder and sesbania powder and containing the dilute of cerium salt
Nitric acid solution is uniformly mixed, and in 80~120 DEG C of dry 6~10h after extruded moulding, then in 500-600 DEG C of 3~5h of roasting, is obtained
To CeO2-Al2O3Carrier；By the CeO2-Al2O3Carrier, which is placed in the solution comprising organic base, to be impregnated, and neutrality is then washed to,
80~120 DEG C of dry 2~5h are obtained described through organic alkali solution treated CeO2-Al2O3Carrier.
Specific embodiment according to the present invention, in catalyst of the invention, using Mo, Co as active metal component, by urging
The weight percent meter of agent, MoO36~14%, the CoO for accounting for total catalyst weight accounts for the 1~6% of total catalyst weight.Herein
In range, the obtained catalyst of Mo, Co hydrodesulfurization activity, selectivity and stabilization with higher are loaded using modified support
Property.
On the other hand, the present invention also provides a kind of method for preparing the catalyst for selective hydrodesulfurizationof of gasoline,
This method comprises:
(1) CeO is prepared2-Al2O3Carrier: dilute nitric acid solution of the boehmite dry powder with sesbania powder and containing cerium salt is mixed
It closes uniformly, in 80~120 DEG C of dry 6~10h after extruded moulding, then in 500-600 DEG C of 3~5h of roasting, obtains CeO2-Al2O3
Carrier；
(2)CeO2-Al2O3Carrier surface processing: by prepared CeO2-Al2O3Carrier is placed in the solution comprising organic base
Middle immersion, is then washed to neutrality, 80~120 DEG C of dry 2~5h, obtains through organic alkali solution treated CeO2-Al2O3It carries
Body；
(3) preparation of catalyst: active component Mo and Co are carried on through at organic alkali solution using equi-volume impregnating
CeO after reason2-Al2O3On carrier, 20~60 DEG C of 2~5h of dipping, then 80~120 DEG C of dry 1~6h, later in 450~600
DEG C roasting 3-6h, obtain the catalyst for selectively hydrodesulfurizing.
Specific embodiment according to the present invention, in the preparation method of catalyst of the invention, in the step (1), field
Dosage, the concentration of dilute nitric acid solution and the dosage of cyanines powder can be carried out according to the routine operation of fields, and the present invention does not do this
Particular/special requirement.
Specific embodiment according to the present invention, in the preparation method of catalyst of the invention, to have in the step (2)
On the basis of the weight of machine aqueous slkali, the mass fraction of organic base is 1~20%, preferably 3~15% in solution.
Specific embodiment according to the present invention, it is organic in the step (2) in the preparation method of catalyst of the invention
Aqueous slkali is to CeO2-Al2O3The condition that carrier is handled are as follows: 30~80 DEG C of temperature, soaking time is 2~20h.Preferably, have
Machine aqueous slkali and CeO2-Al2O3The mass ratio of carrier is 1:1~10:1.
Specific embodiment according to the present invention is to match in the step (3) in the preparation method of catalyst of the invention
The solution for making the presoma (preferably ammonium molybdate and cobalt nitrate) containing Mo, Co, using equi-volume impregnating by active component Mo and
Co is carried on through organic alkali solution treated CeO2-Al2O3On carrier.
On the other hand, the present invention also provides the catalyst is catalyzed as catalytic gasoline selective hydrodesulfurizationmodification
The application of agent.That is, this method includes using this present invention also provides a kind of catalytic gasoline selective hydrodesulfurizationmodification method
The invention catalyst is used as catalyst for selectively hydrodesulfurizing.
Specific embodiment according to the present invention, in catalytic gasoline selective hydrodesulfurizationmodification method of the invention, institute
Catalyst is stated for first passing through vulcanizing treatment, the vulcanizing treatment condition in advance before catalytic gasoline selective hydrodesulfurizationmodification are as follows:
260~350 DEG C of temperature, 4~14h of time, 1~3MPa of pressure, hydrogen to oil volume ratio 100~300.
Specific embodiment according to the present invention, in catalytic gasoline selective hydrodesulfurizationmodification method of the invention, control
Make the reaction condition of the selective hydrodesulfurization process are as follows: 200~300 DEG C of temperature, 1~3MPa of pressure, volume space velocity 2~
6h, hydrogen to oil volume ratio 100~300.
In technical solution of the present invention, by using cerium to Al2O3Carrier is modified, and with organic base to CeO2-Al2O3
Carrier is handled, and gained catalyst shows good hydrodesulfurization activity, selectivity when handling catalyst cracking gasoline
And stability, it is able to suppress H in reaction process2S and alkene recombine generation mercaptan.Selective hydrodesulfurization catalysis of the present invention
Agent is applicable to full fraction FCC gasoline or cut FCC gasoline heavy distillat, is particularly suitable for the FCC gasoline of high sulfur content.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now in conjunction with specific implementation
Example carries out technical solution of the present invention described further below, it should be understood that these examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.In embodiment, each Starting reagents material is commercially available, and test method without specific conditions is
Conventional method and normal condition known to fields.
Embodiment 1
(1)CeO2-Al2O3The preparation of carrier
It weighs 2.7g cerous nitrate to be dissolved in the dilute nitric acid solution of 124.5g 3wt%, which is added to 150.0g and is intended
In boehmite and 3.2g sesbania powder, it is uniformly mixed, extruded moulding, subsequent 100 DEG C of drying 8h, 560 DEG C of roasting 4h.It is made
CeO2-Al2O3Carrier.
(2) preparation of catalyst carrier
4.8g ethanol amine is dissolved in 55.2g deionized water, by organic alkali solution and CeO2-Al2O3The mass ratio 8 of carrier:
1 ratio is added to CeO obtained by step (1)2-Al2O3In carrier, 16h is handled under conditions of 40 DEG C.Then, by carrier
It is washed with deionized to neutrality, 110 DEG C of dry 4h, obtains through organic alkali solution treated CeO2-Al2O3Carrier.
(3) preparation of catalyst
It prepares 50ml and contains 6.0g ammonium molybdate and 5.4g cobalt nitrate dipping liquor.At room temperature, 30g step is taken
(2) gained is through organic alkali solution treated CeO in2-Al2O3Carrier impregnates 4h with maceration extract, then 110 DEG C of dry 4h, 550
DEG C roasting 4h, be made catalyst sample Cat-1.
Embodiment 2
Step is with embodiment 1, the difference is that taking cerous nitrate 5.4g, is dissolved in the dilute nitric acid solution of 124.5g 3wt%
In, which is added in 150.0g boehmite and 3.2g sesbania powder, is uniformly mixed, extruded moulding, subsequent 110 DEG C of bakings
Dry 6h, 540 roasting 5h.Catalyst sample Cat-2 is finally made.
Embodiment 3
Step is with embodiment 1, the difference is that taking 9.6g ethanol amine to be dissolved in 55.2g deionized water, by organic alkali soluble
Liquid and CeO2-Al2O3The ratio of the mass ratio 6:1 of carrier is added to CeO obtained by step (1)2-Al2O3In carrier, at 60 DEG C
Under conditions of handle 12h.Then, carrier is washed with deionized to neutrality, 100 DEG C of dry 3h.Catalyst sample is finally made
Product Cat-3.
Embodiment 4
Step is with embodiment 1, the difference is that taking 8.4g methylethanolamine to be dissolved in 55.2g deionized water, by organic
Aqueous slkali and CeO2-Al2O3The ratio of the mass ratio 5:1 of carrier is added to CeO obtained by step (1)2-Al2O3In carrier,
14h is handled under conditions of 70 DEG C.Then, carrier is washed with deionized to neutrality, 120 DEG C of dry 4h are obtained through organic base
Solution treated CeO2-Al2O3Carrier.Catalyst sample Cat-4 is finally made.
Embodiment 5
Step is with embodiment 1, the difference is that taking 6.8g ethylene glycol amine to be dissolved in 55.2g deionized water, by organic base
Solution and CeO2-Al2O3The ratio of the mass ratio 4:1 of carrier is added to CeO obtained by step (1)2-Al2O3In carrier, 40
6h is handled under conditions of DEG C.Then, carrier is washed with deionized to neutrality, 100 DEG C of dry 5h are obtained through organic alkali solution
Treated CeO2-Al2O3Carrier.Catalyst sample Cat-5 is finally made.
Embodiment 6
Step is with embodiment 1, the difference is that taking 5.8g ethylenediamine to be dissolved in 55.2g deionized water, by organic alkali soluble
Liquid and CeO2-Al2O3The ratio of the mass ratio 2:1 of carrier is added to CeO obtained by step (1)2-Al2O3In carrier, at 50 DEG C
Under conditions of handle 4h.Then, carrier is washed with deionized to neutrality, 100 DEG C of dry 4h are obtained through at organic alkali solution
CeO after reason2-Al2O3Carrier.Catalyst sample Cat-6 is finally made.
Comparative example 1
Step is with embodiment 1, the difference is that being added without cerous nitrate when preparing carrier, carrier does not have to ethanolamine solutions
Processing.Catalyst sample Cat-7 is made.
Comparative example 2
Step is with embodiment 1, the difference is that CeO2-Al2O3Carrier difference ethanolamine solutions are handled, and are made and are urged
Agent sample Cat-8.
Comparative example 3
Step is with embodiment 1, the difference is that being added without cerous nitrate during preparing carrier, catalyst sample is made
Cat-9。
The each component content of the above-mentioned catalyst Cat-1~Cat-9 being prepared is shown in Table 1.
The content of 1 catalyst components of table
Catalyst choice hydrodesulfurization reaction performance evaluation
Catalyst reaction performance evaluation procedure: catalyst Cat-1~Cat-9 is urged respectively in fixed bed reactors
Change performance evaluation, loaded catalyst 8ml.Before reaction, vulcanizing treatment is carried out to catalyst, sulfurized oil is containing 2.0wt%CS2
Petroleum ether, conditions of vulcanization are as follows: pressure 1.6Mpa, air speed 2.0h-1, hydrogen to oil volume ratio 300, curing temperature 250 and 320 DEG C difference
Vulcanizing treatment 4h.
With (65~180 DEG C) of catalytically cracked gasoline heavy distillat for raw material, reaction condition are as follows: 250 DEG C of temperature, pressure
1.8Mpa, hydrogen to oil volume ratio 300, air speed 4h-1.The results are shown in Table 2 for each catalyst reaction.
2 catalyst reaction performance evaluation result of table
From table 2 it can be seen that under identical reaction conditions, catalyst provided by the present invention has preferably plus hydrogen is de-
Sulphur activity and selectivity.
It is divided into raw material with the recombination of above-mentioned catalytically cracked gasoline, makes in product sulfur content less than 10 μ by adjusting reaction condition
G/g investigates the selectivity of each catalyst.
3 catalyst choice hds evaluation result of table
From table 3 it can be seen that the catalyst provided according to the present invention meets state V for producing sulfur content (less than 10 μ g/g)
The gasoline of standard, reduce alkene adds hydrogen saturation, reduces the loss of octane number, has preferable selectivity.
The stability experiment result of catalyst Cat-1
Using above-mentioned FCC heavy constituent gasoline as raw material, the stability of catalyst Cat-1 hydrodesulfurization is investigated, the results are shown in Table 4.
4 catalyst stability evaluation result of table
| Reaction time/h | Sulfur content/μ g ﹒ g-1 | Mercaptans content/μ g ﹒ g-1 | Alkene/v% | RON |
| Raw material | 421.5 | 32.4 | 31.8 | 91.3 |
| 100 | 8.9 | 2.1 | 25.6 | 89.3 |
| 300 | 9.2 | 2.1 | 25.4 | 89.2 |
| 500 | 8.9 | 2.7 | 25.6 | 89.3 |
| 800 | 9.6 | 2.3 | 25.2 | 89.2 |
For the data from table 4 it is found that during 800h operation, catalyst provided by the invention is living with good hydrodesulfurization
Property, selectivity and stability, and sulfur content is respectively less than 10ppm in product.
Evaluation result of the catalyst Cat-1 to different sulfur content FCC heavy constituent gasoline stocks
Using different sulfur content FCC heavy constituent gasoline as raw material, the selective hydrodesulfurization performance of catalyst Cat-1 is investigated,
It the results are shown in Table 5.
5 catalyst choice hds evaluation result of table
As can be seen from Table 5, the catalyst provided according to the present invention meets state V for handling different material production sulfur content
Hydrodesulfurization performance is had good selectivity when the gasoline of (less than 10 μ g/g) standard.
Finally, it is stated that: above embodiments are merely to illustrate implementation process and feature of the invention, rather than limit this hair
Bright technical solution, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art answer
Work as understanding: it is still possible to modify or equivalently replace the present invention, without departing from the spirit and scope of the present invention any
Modification or part replacement, should all cover in protection scope of the present invention.
Claims (8)
1. a kind of catalyst for selective hydrodesulfurizationof of gasoline, which includes carrier and the active component that is supported on carrier,
Wherein:
The carrier includes through organic alkali solution treated CeO2-Al2O3Carrier；Wherein, CeO2Account for vehicle weight 0.1~
10%；Wherein, described through organic alkali solution treated CeO2-Al2O3Carrier is prepared in accordance with the following methods: will intend
Dilute nitric acid solution of the boehmite dry powder with sesbania powder and containing cerium salt is uniformly mixed, at 80~120 DEG C dry 6 after extruded moulding
~10h obtains CeO then in 500-600 DEG C of 3~5h of roasting2-Al2O3Carrier；By the CeO2-Al2O3Carrier, which is placed in, includes
It is impregnated in the solution of organic base, 30~80 DEG C of temperature, soaking time is 2~20h, is then washed to neutrality, 80~120 DEG C of dryings
2~5h is obtained described through organic alkali solution treated CeO2-Al2O3Carrier；Wherein, the organic base is selected from ethanol amine, two
One of ethanol amine, triethanolamine, ethylene glycol amine, methylethanolamine, ethylenediamine are a variety of；
The active component is MoO3And CoO；Based on the weight percent of catalyst, MoO3It accounts for 6~14%, CoO and accounts for 1~6%.
2. a kind of method for preparing catalyst for selective hydrodesulfurizationof of gasoline described in claim 1, this method comprises:
(1) CeO is prepared2-Al2O3Carrier: dilute nitric acid solution of the boehmite dry powder with sesbania powder and containing cerium salt is mixed
It is even, in 80~120 DEG C of dry 6~10h after extruded moulding, then in 500-600 DEG C of 3~5h of roasting, obtain CeO2-Al2O3It carries
Body；
(2)CeO2-Al2O3Carrier surface processing: by prepared CeO2-Al2O3Carrier, which is placed in the solution comprising organic base, to be soaked
Bubble, 30~80 DEG C of temperature, soaking time is 2~20h, is then washed to neutrality, 80~120 DEG C of dry 2~5h are obtained through organic
CeO after alkaline solution treatment2-Al2O3Carrier；
(3) preparation of catalyst: active component Mo and Co are carried on after organic alkali solution is handled using equi-volume impregnating
CeO2-Al2O3On carrier, 20~60 DEG C of 2~5h of dipping, then 80~120 DEG C of dry 1~6h, roast in 450~600 DEG C later
3-6h is burnt, the catalyst for selectively hydrodesulfurizing is obtained.
3. according to the method described in claim 2, wherein, in the step (2) on the basis of the weight of organic alkali solution, solution
The mass fraction of middle organic base is 1~20%.
4. according to the method described in claim 2, wherein, in the step (2) on the basis of the weight of organic alkali solution, solution
The mass fraction of middle organic base is 3~15%.
5. according to the method described in claim 2, wherein, organic alkali solution and CeO2-Al2O3The mass ratio of carrier be 1:1~
10:1。
6. the application that catalyst described in claim 1 is used as selective hydrogenation desulfuration catalyst for catalytically cracking gasoline.
7. a kind of catalytic gasoline selective hydrodesulfurizationmodification method, this method includes using catalyst described in claim 1
As catalyst for selectively hydrodesulfurizing, wherein the catalyst is used for before catalytic gasoline selective hydrodesulfurizationmodification in advance
By vulcanizing treatment, the vulcanizing treatment condition are as follows: 260~350 DEG C of temperature, 4~14h of time, 1~3MPa of pressure, hydrogen oil body
Product ratio 100~300.
8. according to the method described in claim 7, wherein, controlling the reaction condition of the selective hydrodesulfurization process are as follows: temperature
200~300 DEG C, 1~3MPa of pressure, 2~6h of volume space velocity of degree, hydrogen to oil volume ratio 100~300.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611214787.7A CN106582703B (en) | 2016-12-26 | 2016-12-26 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and the preparation method and application thereof |
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| CN108993525B (en) * | 2018-08-01 | 2021-06-11 | 黄淮学院 | Bifunctional mercaptan etherification catalyst and preparation method and application thereof |
| CN111389467B (en) * | 2020-03-19 | 2022-05-24 | 河北中垒新能源科技有限公司 | Limestone-gypsum wet desulphurization catalyst |
| CN113877597B (en) * | 2021-08-06 | 2023-10-20 | 南京工业大学 | Organic matter contaminated soil thermal desorption monoatomic catalyst and preparation method thereof |
| CN114029083B (en) * | 2021-12-03 | 2022-11-04 | 中国石油大学(北京) | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN114950424B (en) * | 2022-06-15 | 2023-07-14 | 万华化学（宁波）有限公司 | Circulating gas two-stage desulfurization catalyst, preparation method and application thereof |
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