CN106512984A - Preparation method of high-activity diesel hydrodesulfurization catalyst - Google Patents
Preparation method of high-activity diesel hydrodesulfurization catalyst Download PDFInfo
- Publication number
- CN106512984A CN106512984A CN201611149166.5A CN201611149166A CN106512984A CN 106512984 A CN106512984 A CN 106512984A CN 201611149166 A CN201611149166 A CN 201611149166A CN 106512984 A CN106512984 A CN 106512984A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrotalcite
- preparation
- magnesium
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a preparation method of a high-activity diesel hydrodesulfurization catalyst, and particularly relates to the preparation method of the high-activity diesel hydrodesulfurization catalyst adopting binary magnesium aluminum hydrotalcite as a carrier. The catalyst adopts binary magnesium aluminum hydrotalcite which is prepared through the coprecipitation method and is subjected to pretreatment as the carrier, and the carrier carries one or more transition metals in the VIB and/or VIII family. The catalyst prepared through the method has the characteristics of high mechanical strength, good anti hydration, and the like, the catalyst represents relatively high hydrodesulfurization activity after being applied to the diesel hydrodesulfurization reaction, and the conversion rate of the prepared catalyst for dibenzothiophene (DBT) is 95% or above; and besides, the method is simple in preparation technology, easy and convenient to operate and low in cost, and has good economic benefits and environmental benefits.
Description
Technical field
The invention belongs to field of catalyst preparation, specifically related to a kind of preparation side of high activity diesel hydrogenation for removal sulphur catalyst
Method.
Background technology
Diesel oil occupies very important status in current social economy as a kind of important energy.However, in diesel oil
The height of sulfur content has highly important impact to pollutant emission, such as to NOxProduce with particulate matter (PM) discharge obvious
Facilitation, and make the catalyst poisoning in Exhaust Gas Catalytic Converter for Automobiles.Therefore, in many physical and chemical parameters of diesel oil, sulfur
Content becomes a very important index.Particularly in recent years, the production of cleaning diesel oil has become the urgent of environmental conservation and has been essential
Will, requirement of the national governments to sulfur content in diesel oil is also more and more stricter so that low-sulfur even clean without sulfur the production of diesel oil into
For the major trend of the world today.
Up to the present, realize desulfurization to greatest extent, and then produce meet market low cost, the bavin of high-quality requirement
Oil has two paths available：The first utilizes existing industrial Hydrobon catalyst, improves operating severity, mainly
Improve the temperature and pressure of reaction；Which two is to maintain existing process units, changes higher active Hydrobon catalyst, from
Desulphurization problem is solved fundamentally.For the first paths, the raising of reaction temperature can not only greatly increase the consumption of the energy, also can
Catalyst is made to be easier because coking is inactivated；Meanwhile, improve pressure requirements production equipment and there is more preferable pressure performance.Undoubtedly,
These will all greatly improve oil manufacture cost.If with the existing industrial catalyst of higher active catalyst replaced,
Desulfurization to greatest extent can be not only realized, and is expected to reduce its production cost.Therefore develop highly active hydrodesulfurization to urge
Agent is significant.
At present the most widely used Hydrobon catalyst be with transition metal W or Mo as main active component, Ni or
Co is auxiliary agent, and aluminium oxide is the loaded catalyst of carrier.The carrier of hydrodesulfurization plays and supports active component, improves activearm
Point and auxiliary agent dispersion effect.Alumina support has excellent mechanical property and regenerability, special pore structure, relatively low
The advantages of price, but some shortcomings are there is also, between active component, such as there are stronger interaction, surface area relatively low and only L
Acid site, no B-acid center etc..The presence of these shortcomings limits its application in diesel deep desulfurization catalyst.
Two advantages of basic supports cause the concern of many scholars：(1) in the oxidation state presoma of catalyst, acid
The MoO of property3Acid-Base effect between basic supports can promote MoO3Stable and high dispersive；(2) alkalescence of carrier is conducive to holding back
The generation of catalyst processed carbon deposit during the course of the reaction.In recent years, many scholars attempt synthesis Al2O3- MgO complex carriers, it is desirable to
With reference to both advantages, overcome both respective shortcomings to improve the activity of hydrodesulfurization.But due to the relatively low mechanics of MgO itself
And structural behaviour, particularly when it is exposed in the air of moistening, MgO can generate Mg (OH)2And MgCO3, cause structure to be collapsed
Collapse, specific surface area is reduced.Either prepared by coprecipitation or mechanical mixture is all unable to reach the effect desired by people.
Hydrotalcite-based compound is the double-deck clay of an anionoid, has some special due to its special construction
Performance, the interchangeability of such as interlayer anion, surface are recalled function again in alkalescence and structure, make hydrotalcite lamellar compound
Wide application prospect is shown all in fields such as catalysis, sewage disposal, function luminescent material and quasiconductors.Especially in catalysis
Catalytic active species are inserted hydrotalcite layers by field, can prepare high dispersive metal composite oxide type catalyst by roasting,
The features such as typically there is these catalyst levels of transition metals height, active sites to be evenly distributed, can suppress sintering.With CO3 2-、NO3 -Deng
Hydrotalcite-based compound of the anion for interlayer anion, after 600 ~ 900 DEG C of high-temperature roastings, interlayer anion and moisture
Son can be decomposed or be volatilized, and cause hydrotalcite layered structure to collapse, and form unbodied bimetallic oxide (MgO and Al2O3)
Solid solution and spinelle.Therefore, if can be controlled by the improvement to hydrotalcite structure containing for bimetallic oxide and spinelle
Amount, then can solve the shortcoming of MgO anti-hydrations and heat stability difference to a certain extent.
The content of the invention
Present invention aims to Al in prior art2O3- MgO is existing for the Hydrobon catalyst of carrier
The shortcoming of anti-hydration and heat stability difference, there is provided one kind prepares high activity diesel oil hydrogenation by predecessor of binary magnesium aluminum-hydrotalcite
The preparation method of desulphurization catalyst.Obtained catalyst has good heat stability and anti-hydration energy, shows very strong
Hydrodesulfurization activity, obtained catalyst is to dibenzothiophenes (DBT) conversion ratio more than 95%.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, its catalyst is preprocessed with binary magnesium aluminum-hydrotalcite
Afterwards as carrier, then one or more transition metal in supported V IB and/or VIII, transiting metal oxidation in catalyst
Thing content is 0.5 ~ 20 wt%；Specifically include following steps：
(1) preparation of binary magnesium aluminum-hydrotalcite：The aqueous solution that magnesium salt and aluminium salt are constituted is slowly dropped to into sodium hydroxide and carbon
In the alkaline solution of sour sodium composition, it is sufficiently stirred for and the pH of control system is 9 ~ 12, reactant liquor is carried out always after completion of dropwise addition
Change, after aging end reacting liquid filtering, wash to neutral, drying, obtain binary magnesium aluminum-hydrotalcite；
(2) preparation of catalyst：To be catalyzed after the fired pretreatment of binary magnesium aluminum-hydrotalcite obtained in step (1), molding
The carrier of agent；Obtained catalyst carrier is soaked with the precursor solution containing the transition metal in VIB and/or VIII
After stain, drying and roasting, high activity diesel hydrogenation for removal sulphur catalyst is obtained final product.
In the step (1), magnesium salt is one or more in magnesium nitrate, magnesium chloride and magnesium sulfate；Aluminium salt be aluminum nitrate,
One or more in aluminum chloride and aluminum sulfate.
In the step (1), the mol ratio of aluminium salt and magnesium salt is 1:3~10:1.
In the step (1), the baking temperature of binary magnesium aluminum-hydrotalcite is 60 ~ 120 DEG C, and drying time is 4 ~ 24 hours.
In the step (2), the sintering temperature of pretreatment is 600 ~ 1000 DEG C, and roasting time is 4 ~ 10 hours.
Transition metal in the step (2) in the VIB and/or VIII of its load is the one kind in molybdenum, nickel, cobalt and tungsten
Or it is several, the presoma of described transition metal is the one kind or several in ammonium heptamolybdate, nickel nitrate, cobalt nitrate and ammonium metatungstate
Kind；Dipping method is incipient impregnation.
The present invention also protects application of the catalyst during diesel hydrogenation for removal sulphur obtained in above-mentioned preparation method.
The beneficial effects of the present invention is：The present invention prepares binary using the raw material cheap and easy to get such as magnesium nitrate, aluminum nitrate
Magnesium aluminum-hydrotalcite, makes simple, easy to operate, with low cost.Binary magnesium aluminum-hydrotalcite after roasting can be to a certain extent
Increase carrier mechanical strength, carrier radial direction anti-crushing power be 163 ~ 208 N/cm, make catalyst have good heat stability and
Anti-hydration energy, shows very strong hydrodesulfurization activity, and obtained catalyst exists to dibenzothiophenes (DBT) conversion ratio
More than 95%.
Description of the drawings
Fig. 1 be step 1 of the present invention) obtained in unfired binary magnesium aluminum-hydrotalcite X-ray diffraction (XRD) spectrogram；
Fig. 2 is the XRD spectra of obtained high activity diesel hydrogenation for removal sulphur catalyst after different temperatures roasting of the present invention.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, comprises the steps：
(1) in molar ratio 1:1 weighs 12.80 g Mg (NO respectively3)2∙6H2O and 18.75 g Al (NO3)3∙9H2O, and be dissolved in
In the deionized water of 350 mL, be then slowly dropped to sodium hydroxide and sodium carbonate composition alkaline solution in and be sufficiently stirred for,
During Deca, the pH of regulation system is 9, reactant liquor is stood after aging 12 hours at room temperature after completion of dropwise addition,
Reacting liquid filtering, it is washed with deionized to neutrality, drying at 80 DEG C obtains binary magnesium aluminum-hydrotalcite in 6 hours；
(2) by obtained binary magnesium aluminum-hydrotalcite in (1), roasting carried out the load that molding obtains catalyst after 6 hours at 600 DEG C
Body；The carrier after 15.00 g molding is weighed, is immersed in containing 1.29 g active metal Mo (with MoO3Meter) (NH4)6Mo7O24∙4H2In O aqueous solutions, the active metal Mo, the dipping temperature are impregnated on the carrier using equi-volume impregnating
Spend for room temperature, dip time is 12 hours, after 100 DEG C of Jing dryings 8 hours, 550 DEG C of roastings 4 hours, obtain final product described bavin
Oily Hydrobon catalyst A.
After testing, in terms of the gross mass of catalyst A, the MoO containing 7 wt% in the catalyst A3；The radial direction of catalyst A
Anti-crushing power is 163 N/cm.
Embodiment 2
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, comprises the steps：
(1) in molar ratio 8:1 weighs 10.83 g MgCl respectively2∙6H2O and 2.50 g Al (NO3)3∙9H2O, and it is dissolved in 350
In the deionized water of mL, be then slowly dropped to sodium hydroxide and sodium carbonate composition alkaline solution in and be sufficiently stirred for, drop
Plus during the pH of regulation system be 12, reactant liquor is stood after aging 12 hours at room temperature after completion of dropwise addition, instead
Liquid is answered to filter, be washed with deionized to neutrality, drying at 90 DEG C obtains binary magnesium aluminum-hydrotalcite in 6 hours；
(2) by obtained binary magnesium aluminum-hydrotalcite in (1), roasting carried out the load that molding obtains catalyst after 6 hours at 700 DEG C
Body；The carrier after 15.00 g molding is weighed, is immersed in containing 1.51 g active metal Ws (with WO3Meter) (NH4)6H2W12O40∙nH2In O aqueous solutions, the active metal W, the dipping temperature are impregnated on the carrier using equi-volume impregnating
Spend for room temperature, dip time is 12 hours, after 100 DEG C of Jing dryings 8 hours, 550 DEG C of roastings 4 hours, obtain final product described bavin
Oily Hydrobon catalyst B.
After testing, in terms of the gross mass of catalyst B, the WO containing 7 wt% in the catalyst B3；The radial direction of catalyst B
Anti-crushing power is 173 N/cm.
Embodiment 3
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, comprises the steps：
(1) in molar ratio 3:1 weighs 11.52 g Mg (NO respectively3)2∙6H2O and 5.13 g Al (SO4)3, and molten 350 mL
In deionized water, be then slowly dropped to sodium hydroxide and sodium carbonate composition alkaline solution in and be sufficiently stirred for, in Deca
During regulation system pH be 10, reactant liquor is stood at room temperature after aging 12 hours, reactant liquor after completion of dropwise addition
Filter, be washed with deionized to neutrality, drying at 80 DEG C obtains binary magnesium aluminum-hydrotalcite in 6 hours；
(2) by obtained binary magnesium aluminum-hydrotalcite in (1), roasting carried out the load that molding obtains catalyst after 6 hours at 800 DEG C
Body；The carrier after 15.00 g molding is weighed, and is impregnated in containing 1.17 g active metal Co (in terms of CoO) and 1.29 g
Active metal Mo is (with MoO3Meter) Co (NO3)2∙6H2O、(NH4)6Mo7O24∙4H2In O mixed aqueous solutions, using incipient impregnation
Method impregnates the active metal Co-Mo on the carrier, and the dipping temperature is room temperature, and dip time is 12 hours, afterwards
100 DEG C of Jing dryings 8 hours, 550 DEG C of roastings 4 hours, obtain final product described diesel hydrogenation for removal sulphur catalyst C.
After testing, in terms of the gross mass of catalyst C, the MoO of the CoO containing 2 wt% and 7 wt% in the catalyst C3；
The radial direction anti-crushing power of catalyst C is 181 N/cm.
Embodiment 4
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, comprises the steps：
(1) in molar ratio 5:1 weighs 14.22 g Mg (NO respectively3)2∙6H2O and 2.08 g Al (NO3)3∙9H2O, and molten 350
In the deionized water of mL, be then slowly dropped to sodium hydroxide and sodium carbonate composition alkaline solution in and be sufficiently stirred for, drop
Plus during the pH of regulation system be 11, reactant liquor is stood after aging 12 hours at room temperature after completion of dropwise addition, instead
Liquid is answered to filter, be washed with deionized to neutrality, drying at 100 DEG C obtains binary magnesium aluminum-hydrotalcite in 6 hours；
(2) by obtained binary magnesium aluminum-hydrotalcite in (1), roasting carried out the load that molding obtains catalyst after 4 hours at 900 DEG C
Body；The carrier after 15.00 g molding is weighed, and is impregnated in containing 0.58 g active metal Ni (in terms of NiO) and 1.65 g
Active metal Mo is (with MoO3Meter) Ni (NO3)2∙6H2O、(NH4)6Mo7O24∙4H2In O mixed aqueous solutions, using incipient impregnation
Method impregnates the active metal Ni-Mo on the carrier, and the dipping temperature is room temperature, and dip time is 12 hours, afterwards
100 DEG C of Jing dryings 8 hours, 550 DEG C of roastings 4 hours, obtain final product described diesel hydrogenation for removal sulphur catalyst D.
After testing, in terms of the gross mass of catalyst D, the MoO of the NiO containing 1 wt% and 9 wt% in the catalyst D3；
The radial direction anti-crushing power of catalyst D is 208 N/cm.
Fig. 1 is step 1 of the present invention) obtained in unfired binary magnesium aluminum-hydrotalcite XRD spectrum, can from figure
Go out the diffraction maximum for all occurring in that corresponding brucite thing phase (PDF#00-035-0965), 2 θ=11.3 °, 22.8 °, 34.7 °,
39.1 °, 46.3 °, 60.6 °, the XRD diffraction maximums that occur at 61.9 ° be respectively belonging to corresponding brucite crystalline phase (003),
(006), (012), (015), (018), (110), (113) crystal face, it is seen that in the case of unfired, which has had higher
Degree of crystallinity.
Fig. 2 is the XRD spectrum of obtained high activity diesel hydrogenation for removal sulphur catalyst after different temperatures roasting, can be with from figure
Find out the raising with sintering temperature, slowly occur in that spinelle, when sintering temperature reaches 900 DEG C, be fully converted to
Spinelle, this is because, with the raising of sintering temperature, the double-decker of brucite is destroyed, when its certain content of generation
Spinelle when, can not only improve its anti-hydration, also greatly enhance its mechanical strength.
Comparative example 1
Weighing the roasting at 600 DEG C of the aluminum hydroxide solid elastomer of 50 g carried out the carrier that molding obtains catalyst after 6 hours；Weigh
The carrier of 15.00 g, is immersed in containing 1.29 g active metal Mo (with MoO3Meter) (NH4)6Mo7O24∙4H2O aqueous solutions
In, the active metal Mo is impregnated on the carrier using equi-volume impregnating, the dipping temperature is room temperature, dip time
For 12 hours, after 100 DEG C of Jing dryings 8 hours, 550 DEG C of roastings 4 hours, obtain final product described diesel hydrogenation for removal sulphur catalyst E.
After testing, in terms of the gross mass of catalyst E, the MoO containing 7 wt% in the catalyst E3；The radial direction of catalyst E
Anti-crushing power is only 140 N/cm.
Application examples
Should use-case be that the hydrodesulfurization activity to 1 prepared catalyst of the embodiment of the present invention 1 ~ 4 and comparative example is evaluated.Tool
Body step is as follows：It is model compound raw material with dibenzothiophenes (DBT) content as the n-heptane solution of 1 ~ 5 wt%, to 10 mL
Load 1 gained catalyst of above-described embodiment 1 ~ 4 and comparative example in hydrogenation plant, under room temperature, first with hydrogen by gas piping
Air is sufficiently displaced from.Before the reaction, first with Carbon bisulfide (CS2) content carried out to catalyst for the cyclohexane solution of 2 ~ 10 wt%
Presulfurization, switching after the completion of sulfuration are reacted, and reaction condition is：2.0 ~ 8.0 MPa, 200 ~ 380 DEG C, hydrogen to oil volume ratio be 200 ~
1000, liquid hourly space velocity (LHSV) is 1.0 ~ 5.0 h-1, in 8 ~ 24 hours response time, concrete reaction condition is as shown in table 1.After reaction terminates,
Sample is analyzed using sulfur blood urea/nitrogen analyzer, activity is represented with the conversion ratio of DBT, experiment gained active testing the results are shown in Table 2.
Reaction conversion ratio is calculated as follows：
Represent the total sulfur content in raw material；Represent the total sulfur content in product
The active testing condition of 1 Hydrobon catalyst of table
The DBT hydrodesulfurization activity evaluation results of 2 catalyst of table
The DBT that high activity diesel hydrogenation for removal sulphur catalyst of the present invention (sample A-D) be can be seen that by the data of table 2 turns
Rate is more than 95%, and the DBT conversion ratios for preparing catalyst (sample E) with aluminum hydroxide solid elastomer are significant lower.
It can be seen from the results above that hydrodesulfurization of the catalyst of the present invention to diesel oil has higher activity.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, it is characterised in that：The catalyst is with dibasic magnesium
Aluminum hydrotalcite after pretreatment as carrier, then one or more transition metal in supported V IB and/or VIII, catalysis
In agent, transition metal oxide content is 0.5 ~ 20 wt%；Specifically include following steps：
(1) preparation of binary magnesium aluminum-hydrotalcite：The aqueous solution that magnesium salt and aluminium salt are constituted is slowly dropped to into sodium hydroxide and carbonic acid
In the alkaline solution of sodium composition, the pH of simultaneously control system is sufficiently stirred for, reactant liquor is carried out after completion of dropwise addition aging, aging knot
After beam reacting liquid filtering, wash to it is neutral, be dried, obtain binary magnesium aluminum-hydrotalcite；
(2) preparation of catalyst：To be catalyzed after the fired pretreatment of binary magnesium aluminum-hydrotalcite obtained in step (1), molding
The carrier of agent；Obtained catalyst carrier is soaked with the precursor solution containing the transition metal in VIB and/or VIII
After stain, drying and roasting, high activity diesel hydrogenation for removal sulphur catalyst is obtained final product.
2. method according to claim 1, it is characterised in that：In the step (1), magnesium salt is magnesium nitrate, magnesium chloride and sulfur
One or more in sour magnesium；The aluminium salt is one or more in aluminum nitrate, aluminum chloride and aluminum sulfate.
3. method according to claim 1, it is characterised in that：In the step (1), the mol ratio of aluminium salt and magnesium salt is 1:3
~10:1。
4. method according to claim 1, it is characterised in that：In the step (1), pH is 9 ~ 12.
5. method according to claim 1, it is characterised in that：In the step (1), binary magnesium aluminum-hydrotalcite is dried temperature
Spend for 60 ~ 120 DEG C, drying time is 4 ~ 24 hours.
6. method according to claim 1, it is characterised in that：In the step (2) sintering temperature of pretreatment be 600 ~
1000 DEG C, roasting time is 4 ~ 10 hours.
7. method according to claim 1, it is characterised in that：The VIB and/or VIII of its load in the step (2)
In transition metal be molybdenum, nickel, cobalt and tungsten in one or more；The presoma of the transition metal is ammonium heptamolybdate, nitric acid
One or more in nickel, cobalt nitrate and ammonium metatungstate；The dipping method is incipient impregnation.
8. catalyst obtained in a kind of preparation method as any one of claim 1 ~ 7 is during diesel hydrogenation for removal sulphur
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149166.5A CN106512984B (en) | 2016-12-14 | 2016-12-14 | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611149166.5A CN106512984B (en) | 2016-12-14 | 2016-12-14 | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106512984A true CN106512984A (en) | 2017-03-22 |
| CN106512984B CN106512984B (en) | 2019-09-13 |
Family
ID=58343189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611149166.5A Active CN106512984B (en) | 2016-12-14 | 2016-12-14 | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106512984B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107115853A (en) * | 2017-05-15 | 2017-09-01 | 中国海洋石油总公司 | Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof |
| CN109453781A (en) * | 2018-09-26 | 2019-03-12 | 上海智冠高分子材料有限公司 | A kind of hydrotalcite catalyst and its preparation method and application |
| CN113559884A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst for sulfurized heavy oil and its preparing process and application |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
| CN115106107A (en) * | 2022-07-29 | 2022-09-27 | 湖北中圣科技有限公司 | Desulfurization catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335361A (en) * | 2001-09-11 | 2002-02-13 | 中国石油天然气股份有限公司 | Method and catalyst for selective hydrogenation desulfurization of cracked gasoline |
| CN101053846A (en) * | 2006-04-12 | 2007-10-17 | 北京化工大学 | High dispersion diesel hydrogenation for removal sulphur catalyst preparing method |
| CN101530792A (en) * | 2009-04-09 | 2009-09-16 | 浙江工业大学 | Carrier zirconium oxide catalyst ZrO2-Mg/Al-LDO and preparation and application thereof |
| CN102921427A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Method for preparing gasoline hydrodesulfurization catalyst |
| CN104971731A (en) * | 2015-06-17 | 2015-10-14 | 福州大学 | Wide-temperature sulfur-tolerance shift catalyst and preparation method therefor |
-
2016
- 2016-12-14 CN CN201611149166.5A patent/CN106512984B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335361A (en) * | 2001-09-11 | 2002-02-13 | 中国石油天然气股份有限公司 | Method and catalyst for selective hydrogenation desulfurization of cracked gasoline |
| CN101053846A (en) * | 2006-04-12 | 2007-10-17 | 北京化工大学 | High dispersion diesel hydrogenation for removal sulphur catalyst preparing method |
| CN101530792A (en) * | 2009-04-09 | 2009-09-16 | 浙江工业大学 | Carrier zirconium oxide catalyst ZrO2-Mg/Al-LDO and preparation and application thereof |
| CN102921427A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Method for preparing gasoline hydrodesulfurization catalyst |
| CN104971731A (en) * | 2015-06-17 | 2015-10-14 | 福州大学 | Wide-temperature sulfur-tolerance shift catalyst and preparation method therefor |
Non-Patent Citations (4)
| Title |
|---|
| RUIYU ZHAO等: "Synthesis, characterization, and application of hydotalcites in hydrodesulfurization of FCC gasoline", 《FUEL PROCESSING TECHNOLOGY》 * |
| 上海市经济团体联合会等编著: "《节能减排新途径与新技术》", 31 May 2010, 华东理工大学出版社 * |
| 张振莉等: "镁铝复合氧化物载体的制备与性质研究", 《燃料化学学报》 * |
| 欧育湘等: "《稳定剂》", 30 June 2011, 国防工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107115853A (en) * | 2017-05-15 | 2017-09-01 | 中国海洋石油总公司 | Mg Al houghite catalyst for handling residual oil and extra heavy oil raw material and preparation method thereof |
| CN109453781A (en) * | 2018-09-26 | 2019-03-12 | 上海智冠高分子材料有限公司 | A kind of hydrotalcite catalyst and its preparation method and application |
| CN109453781B (en) * | 2018-09-26 | 2022-02-08 | 上海智冠高分子材料有限公司 | Hydrotalcite catalyst and preparation method and application thereof |
| CN113559884A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst for sulfurized heavy oil and its preparing process and application |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
| CN115106107A (en) * | 2022-07-29 | 2022-09-27 | 湖北中圣科技有限公司 | Desulfurization catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106512984B (en) | 2019-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106512984B (en) | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst | |
| CN101970105B (en) | Preparation of desulphurisation materials | |
| CN102029140B (en) | Desulfurizing agent with nuclear/shell structure and preparation method | |
| CN106268976B (en) | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application | |
| CN104117362B (en) | A kind of catalyst and preparation method of raising NiMo diesel oil hydrofining catalyst hydrogenation activities | |
| CN105521792B (en) | A kind of load type double-metal hydrogenation catalyst and its preparation method and application | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN109395770B (en) | Iron-based hydrogenation catalyst and preparation method thereof | |
| CN109701537A (en) | A kind of catalyst for pre-hydrogenation and its preparation method and application | |
| CN103657671B (en) | Dialkenes selective hydrogenation catalyst and preparation method and application of dialkenes selective hydrogenation catalyst | |
| CN109364956A (en) | A kind of preparation method and applications of high activity molybdenum sulfide-zirconia catalyst | |
| CN107398282A (en) | The preparation of nickel aluminium zirconium tungsten hydrotalcite catalyst and its application in hydrodesulfurization | |
| CN108465484A (en) | A kind of preparation method of FCC gasoline desulfurization-hydrogenation modifying catalyst | |
| CN108236965A (en) | A kind of Hydrobon catalyst of modification and preparation method thereof | |
| CN111250096A (en) | Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof | |
| CN103418401A (en) | Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof | |
| CN102423712B (en) | Preparation method of high-activity inferior diesel oil hydrorefining catalyst | |
| CN106964363A (en) | A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN103157518A (en) | Mesoporous magnesium oxide, hydrodesulfurization catalyst loading CoMo metal sulfide and application thereof | |
| CN1766047A (en) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method | |
| CN104549286A (en) | Hydrorefining catalyst as well as preparation method thereof and application thereof | |
| CN108404976A (en) | A kind of FCC gasoline desulfurization-hydrogenation method for modifying | |
| CN104923244B (en) | Diesel oil hydrofining catalyst and preparation method thereof | |
| CN110721738B (en) | Hydrofining catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220609 Address after: 354000 phase III of Jintang Industrial Park, Shaowu City, Nanping City, Fujian Province Patentee after: Shaowu Lumin Environmental Protection Technology Co.,Ltd. Address before: 350108 new campus of Fuzhou University, No. 2, Xue Yuan Road, University Town, Minhou street, Minhou, Fujian. Patentee before: FUZHOU University |