CN106512984B - A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst - Google Patents
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst Download PDFInfo
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- CN106512984B CN106512984B CN201611149166.5A CN201611149166A CN106512984B CN 106512984 B CN106512984 B CN 106512984B CN 201611149166 A CN201611149166 A CN 201611149166A CN 106512984 B CN106512984 B CN 106512984B
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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
- B01J23/16—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
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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
- B01J23/16—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
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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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- 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
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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
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The present invention discloses a kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, in particular to a kind of using binary magnalium hydrotalcite as the preparation method of the high activity diesel hydrogenation for removal sulphur catalyst of carrier.Related catalyst is the binary magnalium hydrotalcite using coprecipitation preparation after pretreatment as carrier, one or more of supported V IB and/or VIII group transition metal.Have the characteristics that high mechanical strength, anti-hydration can be good using catalyst prepared by method provided by the invention, it is applied in diesel hydrogenation for removal sulphur reaction and shows higher hydrodesulfurization activity, obtained catalyst is to dibenzothiophenes (DBT) conversion ratio 95% or more.In addition, the method for the present invention preparation process is simple, easy to operate, low in cost, with good economic efficiency and environmental benefit.
Description
Technical field
The invention belongs to field of catalyst preparation, more particularly to a kind of preparation side of high activity diesel hydrogenation for removal sulphur catalyst
Method.
Background technique
Diesel oil occupies very important status as a kind of important energy in current social economy.However, in diesel oil
The height of sulfur content has highly important influence to pollutant emission, such as to NOxIt is generated with particulate matter (PM) discharge apparent
Facilitation, and make the catalyst poisoning in Exhaust Gas Catalytic Converter for Automobiles.Therefore, in many physical and chemical parameters of diesel oil, sulphur
Content becomes a very important index.Especially in recent years, the production for cleaning diesel oil has become the urgent of environmental protection and is essential
It wants, requirement of the national governments to sulfur content in diesel oil is also increasingly stringenter, so that low-sulfur even being produced into without sulphur cleaning diesel oil
For the main trend of the world today.
Up to the present, it realizes maximum desulfurization, and then produces and meet market low cost, the bavin that high quality requires
Oil has two paths available: one is improving operating severity, mainly using existing industrial Hydrobon catalyst
Improve the temperature and pressure of reaction；Secondly being to maintain existing process units, higher active Hydrobon catalyst is replaced, from
Fundamentally solve desulphurization problem.For the first paths, the raising of reaction temperature can not only greatly increase the consumption of the energy, also can
Catalyst is set to be easier to inactivate because of coking；Meanwhile pressure requirements production equipment is improved with preferably pressure-resistant performance.Undoubtedly,
These will all greatly improve the production cost of oil product.If replacing existing industrial catalyst with higher active catalyst,
Desulfurization to the maximum extent not only may be implemented, and be expected to reduce its production cost.Therefore the hydrodesulfurization of exploitation high activity is urged
Agent is significant.
Current the most widely used Hydrobon catalyst be using 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, which plays, to be supported active component, improves active group
Point and auxiliary agent dispersion degree effect.Alumina support has excellent mechanical property and regenerability, special pore structure, lower
The advantages that price, but there is also some disadvantages, such as have stronger interaction, surface area lower between active component and only L
Acid site, without the acid site B etc..The presence of these disadvantages 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 MoO3Stabilization and high dispersive；(2) alkalinity of carrier is conducive to hold back
The generation of catalyst processed carbon deposit during the reaction.In recent years, many scholars attempt synthesis Al2O3- MgO complex carrier, it is desirable to
In conjunction with the advantages of the two, respective disadvantage both is overcome to improve the activity of hydrodesulfurization.But due to the lower mechanics of MgO itself
And structural behaviour, especially when it is exposed in wet air, MgO can generate Mg (OH)2And MgCO3, structure is caused to be collapsed
It collapses, specific surface area reduces.Effect desired by people is all either unable to reach by coprecipitation preparation or mechanical mixture.
Hydrotalcite-based compound is the clay of an anionoid double-layer structure, and it is some special to have due to its special construction
Performance, such as the interchangeability of interlayer anion, surface recall function in alkalinity and structure again, makes hydrotalcite lamellar compound
Wide application prospect is all shown in fields such as catalysis, sewage treatment, function luminescent material and semiconductors.Especially it is being catalyzed
Catalytic active species are inserted into hydrotalcite layers by field, can prepare high dispersive metal composite oxide type catalyst by roasting,
These catalyst generally have the characteristics that levels of transition metals height, active sites are evenly distributed, can inhibit sintering.With CO3 2-、NO3 -Deng
Anion is the hydrotalcite-based compound of interlayer anion, after 600 ~ 900 DEG C of high-temperature roastings, interlayer anion and moisture
Son can decompose or volatilize, and hydrotalcite layered structure is caused to collapse, and form unbodied bimetallic oxide (MgO and Al2O3)
Solid solution and spinelle.It therefore, if can be by controlling the improvement of hydrotalcite structure containing for bimetallic oxide and spinelle
Amount, then can solve the disadvantage of MgO anti-hydration and thermal stability difference to a certain extent.
Summary of the invention
It is an object of the invention to for Al in the prior art2O3- MgO is present in the Hydrobon catalyst of carrier
The disadvantage of anti-hydration and thermal stability difference provides a kind of using binary magnalium hydrotalcite as predecessor preparation high activity diesel oil hydrogenation
The preparation method of desulphurization catalyst.Obtained catalyst has good thermal stability and anti-hydration energy, shows very strong
Hydrodesulfurization activity, obtained catalyst is to dibenzothiophenes (DBT) conversion ratio 95% or more.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst, catalyst are with binary magnalium hydrotalcite through pre-
Carrier is used as after processing, then one or more of supported V IB and/or VIII group transition metal, transition metal in catalyst
Oxide content is 0.5 ~ 20 wt%；Specifically includes the following steps:
(1) aqueous solution that magnesium salts and aluminium salt form the preparation of binary magnalium hydrotalcite: is slowly dropped to sodium hydroxide
With sodium carbonate composition alkaline solution in, be sufficiently stirred and control system pH be 9 ~ 12, after completion of dropwise addition by reaction solution into
Row aging is filtered, washed reaction solution to neutral, drying after aging, obtains binary magnalium hydrotalcite；
(2) it the preparation of catalyst: is obtained after binary magnalium hydrotalcite made from step (1) is fired pretreatment, molding
The carrier of catalyst；By catalyst carrier obtained with the precursor solution containing the transition metal in VIB and/or VIII group into
To get high activity diesel hydrogenation for removal sulphur catalyst after row dipping, dry and roasting.
Magnesium salts is one or more of magnesium nitrate, magnesium chloride and magnesium sulfate in the step (1)；Aluminium salt be aluminum nitrate,
One or more of aluminium chloride and aluminum sulfate.
Aluminium salt and the molar ratio of magnesium salts are 1:3 ~ 10:1 in the step (1).
The drying temperature of binary magnalium hydrotalcite is 60 ~ 120 DEG C in the step (1), and drying time is 4 ~ 24 hours.
Pretreated maturing temperature is 600 ~ 1000 DEG C in the step (2), and calcining time is 4 ~ 10 hours.
The transition metal in VIB and/or VIII group that its in the step (2) loads is one of molybdenum, nickel, cobalt and tungsten
Or it is several, the presoma of the transition metal is one of ammonium heptamolybdate, nickel nitrate, cobalt nitrate and ammonium metatungstate or several
Kind；Dipping method is incipient impregnation.
The present invention also protects application of the catalyst made from above-mentioned preparation method during diesel hydrogenation for removal sulphur.
The beneficial effects of the present invention are: the present invention prepares binary using the raw material cheap and easy to get such as magnesium nitrate, aluminum nitrate
Magnalium hydrotalcite, production is simple, easy to operate, low in cost.Binary magnalium 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 thermal stability and
Anti-hydration energy, shows very strong hydrodesulfurization activity, and obtained catalyst exists to dibenzothiophenes (DBT) conversion ratio
95% or more.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram of unfired binary magnalium hydrotalcite made from step 1) of the present invention；
Fig. 2 is the XRD spectra of high activity diesel hydrogenation for removal sulphur catalyst obtained after different temperatures of the present invention roasts.
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, includes the following steps:
(1) 1:1 weighs 12.80 g Mg (NO respectively in molar ratio3)2∙6H2O and 18.75 g Al (NO3)3∙9H2O, and it is molten
In the deionized water of 350 mL, then it is slowly dropped in the alkaline solution of sodium hydroxide and sodium carbonate composition and sufficiently stirs
It mixes, the pH of regulation system is 9 during dropwise addition, reaction solution is stood at room temperature aging 12 hours after completion of dropwise addition
Afterwards, reaction solution filtered, be washed with deionized to neutrality, obtain binary magnalium hydrotalcite within dry 6 hours at 80 DEG C；
(2) it is formed to obtain catalyst after roasting binary magnalium hydrotalcite obtained in (1) 6 hours at 600 DEG C
Carrier；15.00 g carrier after molding is weighed, is immersed in containing 1.29 g active metal Mo (with MoO3Meter)
(NH4)6Mo7O24∙4H2In O aqueous solution, the active metal Mo, the leaching are impregnated on the carrier using equi-volume impregnating
Stain temperature is room temperature, and dip time is 12 hours, after through 100 DEG C dry 8 hours, 550 DEG C roasting 4 hours to get described
Diesel hydrogenation for removal sulphur catalyst A.
Through detecting, 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, includes the following steps:
(1) 8:1 weighs 10.83 g MgCl respectively in molar ratio2∙6H2O and 2.50 g Al (NO3)3∙9H2O, and be dissolved in
In the deionized water of 350 mL, then it is slowly dropped in the alkaline solution of sodium hydroxide and sodium carbonate composition and is sufficiently stirred,
The pH of regulation system is 12, after reaction solution is stood aging 12 hours at room temperature after completion of dropwise addition during dropwise addition,
Reaction solution is filtered, is washed with deionized to neutrality, obtains binary magnalium hydrotalcite within dry 6 hours at 90 DEG C；
(2) it is formed to obtain catalyst after roasting binary magnalium hydrotalcite obtained in (1) 6 hours at 700 DEG C
Carrier；15.00 g carrier after molding is weighed, is immersed in containing 1.51 g active metal Ws (with WO3Meter) (NH4)6H2W12O40∙nH2In O aqueous solution, the active metal W, the dipping temperature are impregnated on the carrier using equi-volume impregnating
Degree is room temperature, and dip time is 12 hours, after through 100 DEG C dry 8 hours, 550 DEG C roasting 4 hours to get the bavin
Oily Hydrobon catalyst B.
Through detecting, 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, includes the following steps:
(1) 3:1 weighs 11.52 g Mg (NO respectively in molar ratio3)2∙6H2O and 5.13 g Al (SO4)3, and molten 350 mL
Deionized water in, be then slowly dropped to sodium hydroxide and sodium carbonate composition alkaline solution in and be sufficiently stirred, be added dropwise
During regulation system pH be 10, after reaction solution is stood aging 12 hours at room temperature after completion of dropwise addition, react
Liquid filtering is washed with deionized to neutrality, obtains binary magnalium hydrotalcite within dry 6 hours at 80 DEG C；
(2) it is formed to obtain catalyst after roasting binary magnalium hydrotalcite obtained in (1) 6 hours at 800 DEG C
Carrier；Weigh 15.00 g carrier after molding, and be impregnated in containing 1.17 g active metal Co (in terms of CoO) and
1.29 g active metal Mo are (with MoO3Meter) Co (NO3)2∙6H2O、(NH4)6Mo7O24∙4H2In O mixed aqueous solution, using etc. bodies
Product infusion process impregnates the active metal Co-Mo on the carrier, and the dipping temperature is room temperature, and dip time is 12 small
When, after through 100 DEG C dry 8 hours, 550 DEG C roasting 4 hours to get the diesel hydrogenation for removal sulphur catalyst C.
Through detecting, 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 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, includes the following steps:
(1) 5:1 weighs 14.22 g Mg (NO respectively in molar ratio3)2∙6H2O and 2.08 g Al (NO3)3∙9H2O, and it is molten
In the deionized water of 350 mL, then it is slowly dropped in the alkaline solution of sodium hydroxide and sodium carbonate composition and is sufficiently stirred,
The pH of regulation system is 11, after reaction solution is stood aging 12 hours at room temperature after completion of dropwise addition during dropwise addition,
Reaction solution is filtered, is washed with deionized to neutrality, obtains binary magnalium hydrotalcite within dry 6 hours at 100 DEG C；
(2) it is formed to obtain catalyst after roasting binary magnalium hydrotalcite obtained in (1) 4 hours at 900 DEG C
Carrier；Weigh 15.00 g carrier after molding, and be impregnated in containing 0.58 g active metal Ni (in terms of NiO) and
1.65 g active metal Mo are (with MoO3Meter) Ni (NO3)2∙6H2O、(NH4)6Mo7O24∙4H2In O mixed aqueous solution, using etc. bodies
Product infusion process impregnates the active metal Ni-Mo on the carrier, and the dipping temperature is room temperature, and dip time is 12 small
When, after through 100 DEG C dry 8 hours, 550 DEG C roasting 4 hours to get the diesel hydrogenation for removal sulphur catalyst D.
Through detecting, 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 anti-crushing power of catalyst D is 208 N/cm.
Fig. 1 is the XRD spectrum of unfired binary magnalium hydrotalcite made from step 1) of the present invention, can from figure
All occur the diffraction maximum of corresponding hydrotalcite object phase (PDF#00-035-0965) out, 2 θ=11.3 °, 22.8 °, 34.7 °,
At 39.1 °, 46.3 °, 60.6 °, 61.9 ° occur XRD diffraction maximum be respectively belonging to corresponding hydrotalcite crystal phase (003),
(006), (012), (015), (018), (110), (113) crystal face, it is seen that in unfired situation, had higher
Crystallinity.
Fig. 2 is the XRD spectrum of high activity diesel hydrogenation for removal sulphur catalyst obtained after different temperatures roasting, can be with from figure
Find out the raising with maturing temperature, spinelle slowly occur, when maturing temperature reaches 900 DEG C, has been fully converted to
Spinelle, this is because with the raising of maturing temperature the double-layer structure of hydrotalcite is destroyed, when it generates certain content
Spinelle when, its anti-hydration not only can be improved, also greatly enhance its mechanical strength.
Comparative example 1
Weigh 50 g aluminum hydroxide solid elastomer roasted 6 hours at 600 DEG C after formed to obtain the carrier of catalyst；
The carrier for weighing 15.00 g is immersed in containing 1.29 g active metal Mo (with MoO3Meter) (NH4)6Mo7O24∙4H2O water
In solution, the active metal Mo is impregnated on the carrier using equi-volume impregnating, the dipping temperature is room temperature, dipping
Time is 12 hours, after be catalyzed through 100 DEG C to get the diesel hydrogenation for removal sulphur within roasting 4 hours within dry 8 hours, 550 DEG C
Agent E.
Through detecting, 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
The application example is commented the hydrodesulfurization activity of 1 prepared catalyst of the embodiment of the present invention 1 ~ 4 and comparative example
Valence.Specific step is as follows: using the n-heptane solution that dibenzothiophenes (DBT) content is 1 ~ 5 wt% as model compound raw material, to
Above-described embodiment 1 ~ 4 and 1 gained catalyst of comparative example are packed into 10 mL hydrogenation plants, at room temperature, first with hydrogen by gas piping
In air be sufficiently displaced from.Before the reaction, carbon disulfide (CS is first used2) content be 2 ~ 10 wt% cyclohexane solution to catalyst
Presulfurization is carried out, switching reaction, reaction condition after the completion of vulcanization are as follows: 2.0 ~ 8.0 MPa, 200 ~ 380 DEG C, hydrogen to oil volume ratio is
200 ~ 1000, liquid hourly space velocity (LHSV) is 1.0 ~ 5.0 h-1, the reaction time 8 ~ 24 hours, specific reaction condition was as shown in table 1.Reaction terminates
Afterwards, sample is analyzed using sulphur blood urea/nitrogen analyzer, activity is indicated with the conversion ratio of DBT, and experiment gained active testing result is 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 result of 2 catalyst of table
It can be seen that high activity diesel hydrogenation for removal sulphur catalyst (sample A-D) of the present invention by the data of table 2
DBT conversion ratio is and significant lower with the DBT conversion ratio that aluminum hydroxide solid elastomer prepares catalyst (sample E) 95% or more.
It can be seen from the results above that catalyst of the present invention is to the hydrodesulfurization of diesel oil activity with higher.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
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 is used as carrier after pretreatment, then one or more of supported V IB and/or VIII group transition metal, catalysis
Transition metal oxide content is 0.5 ~ 20 wt% in agent；Specifically includes the following steps:
(1) aqueous solution that magnesium salts and aluminium salt form the preparation of binary magnalium hydrotalcite: is slowly dropped to sodium hydroxide and carbonic acid
In the alkaline solution of sodium composition, it is sufficiently stirred and the pH of control system is 10 ~ 12, the molar ratio of aluminium salt and magnesium salts is 1:3 ~ 10:
1；After completion of dropwise addition reaction solution is subjected to aging at room temperature, reaction solution is filtered, washed to neutral, dry after aging
It is dry, obtain binary magnalium hydrotalcite；
(2) preparation of catalyst: being that 900 ~ 1000 DEG C of roastings are pre- through temperature by binary magnalium hydrotalcite made from step (1) locates
The carrier of catalyst is obtained after reason 4 ~ 10 hours, molding, and carrier radial direction anti-crushing power is 163 ~ 208 N/cm；Obtained catalysis
Agent carrier impregnated, dried and roasted with the precursor solution containing the transition metal in VIB and/or VIII group after to get
High activity diesel hydrogenation for removal sulphur catalyst；Aluminium is fully converted to magnesia-alumina spinel structure in the catalyst.
2. according to the method described in claim 1, it is characterized by: magnesium salts is magnesium nitrate, magnesium chloride and sulphur in the step (1)
One or more of sour magnesium；The aluminium salt is one or more of aluminum nitrate, aluminium chloride and aluminum sulfate.
3. according to the method described in claim 1, it is characterized by: in the step (1) binary magnalium hydrotalcite dry temperature
Degree is 60 ~ 120 DEG C, and drying time is 4 ~ 24 hours.
4. according to the method described in claim 1, it is characterized by: VIB and/or VIII group that its in the step (2) loads
In transition metal be one or more of molybdenum, nickel, cobalt and tungsten；The presoma of the transition metal is ammonium heptamolybdate, nitric acid
One or more of nickel, cobalt nitrate and ammonium metatungstate；The dipping method is incipient impregnation.
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| 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 |
| CN113713800B (en) * | 2021-09-15 | 2024-06-04 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizing agent and preparation method thereof |
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