CN106622392A - Modified inorganic heat-resistant oxide and preparation method thereof, hydrodesulfurization catalyst, and method for reducing deactivation rate of hydrodesulfurization catalyst - Google Patents
Modified inorganic heat-resistant oxide and preparation method thereof, hydrodesulfurization catalyst, and method for reducing deactivation rate of hydrodesulfurization catalyst Download PDFInfo
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Abstract
The invention relates to a modified inorganic heat-resistant oxide and a preparation method thereof, a hydrodesulfurization catalyst, and a method for reducing the deactivation rate of the hydrodesulfurization catalyst. The modified inorganic heat-resistant oxide is characterized by comprising acidic hydroxyl and alkali hydroxyl; in the infrared spectrum, the peak of strong acidic hydroxyl is in a range of 3640 to 3700 cm-1, and the peak of strong alkali hydroxyl is in a range of 3740 to 3800 cm-1; and the peak height ratio of the strong acidic hydroxyl to the strong alkali hydroxyl is 1: (0.85-1.15). The modified inorganic heat-resistant oxide provided by the invention has higher catalytic activity when used as a carrier; meanwhile, the deactivation rate of the catalyst is reduced; and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention is with regard to a kind of modified inorganic refractory oxides and its preparation method and application and uses
Hydrobon catalyst and reduction Hydrobon catalyst of the modified inorganic refractory oxides as carrier
The method of deactivation rate.
Background technology
Hydrotreating is the mainstay in modern petroleum refining industry, in production clean fuel, improves product matter
Measure, make full use of the aspects such as petroleum resources and pretreatment of raw material to play an important role.With economy, ring
Protect and social development so that oil refining enterprise constantly proposes to the activity and stability of hydrotreating catalyst
Higher requirement.Common hydrotreating catalyst helps active component with group VIII metal Co, Ni, with
Group vib metal Mo, W decide active component, and carrier often selects aluminum oxide.
For example, CN201010236483.7 discloses a kind of hydrogenation with silica-alumina as carrier and takes off
Sulfur catalyst, containing 2～6wt% of cobalt oxide, 9～15wt% of molybdenum oxide, alkaline earth oxide 2～
8wt%, 2～6wt% of phosphorous oxide, 3～5wt% of alkali metal oxide, 2～6wt% of silica, oxidation
54～80wt% of aluminium.The hydrogenation activity of catalyst and selective high, good stability.
CN201010269179.2 describes a kind of Hydrobon catalyst and preparation method thereof, described to urge
Agent be with molybdenum, nickel, zinc, copper composite metal oxide at least two as active component, addition Si, Ti,
Ca, Ce, Mg, P oxide is at least one for auxiliary agent, balance of aluminum oxide.
CN200710177578.4 be related to a kind of combined aluminum oxide-based catalyst for selectively hydrodesulfurizing and
Then macroporous aluminium oxide and aperture alumina composite are loaded successively auxiliary agent magnesium by its preparation method, the method
With boron and active component cobalt and molybdenum, then drying and roasting, catalyst is made.
CN200710177577.X discloses a kind of catalyst with aluminum oxide and boron oxide as carrier, and Jing
The modification of multiple-addition agent magnesium, potassium and phosphorus is crossed, active component cobalt and molybdenum is supported.
CN200480005056.0 discloses a kind of containing non-noble metal group VIII metal, Yi Zhongfei
The vib metals of noble metal are selected from the element of aluminium, silicon, magnesium, titanium, zirconium, boron and zinc with one or more
Carbon monoxide-olefin polymeric.
CN201210268290.9 discloses carrier and is made up of and institute aluminum oxide, silica, magnesia
Active component is stated by WO3With NiO or MoO3With NiO compositions and containing with K2O and Ga2O3Group
Into auxiliary agent catalyst.
CN96120875.9 is disclosed containing active component Ni, W, Co, co-catalyst component be P or
The mixture of P and Mg, carrier is γ-Al2O3。
CN96106586.9 discloses a kind of catalyst, and it is by γ-Al2O3Ni, W, Co are active for load
Component, can also add the either element in Mg, Zn, Fe, Ca as co-catalyst component.
Although prior art has carried out substantial amounts of research, catalyst to composition of catalyst and preparation method thereof
Performance also achieve larger progress.However, increase fuel clean-up performance required with society with
And the trend of crude oil in poor quality aggravation, the performance need of hydrotreating catalyst further improves.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides it is a kind of can processability it is more superior
Modified inorganic refractory oxides of catalyst and its preparation method and application and Hydrobon catalyst.
, there are various acid hydroxy groups with varying strength and alkaline hydroxyl on the surface of aluminum oxide in document report
Base (497-532 of C.Morterra et al., Catalysis Today 27 (1996)).In oxidized catalyst,
Main active component (such as Mo or W) is dispersed in the form of the oxide the surface of carrier, Mo or W things
Plant and act on forming chemical bond with the various hydroxyls of alumina surface.The chemical bond of formation is sent out in sulfidation
Raw fracture simultaneously discharges metal, and metal and the sulphur of release react and generates sulphided state activity phase.Sulphided state
The disperse properties of active phase have material impact to the activity of catalyst.It was found by the inventors of the present invention that logical
The property of optimization carrier surface hydroxyl is crossed, active component can be made preferably to disperse, so as to obtain more work
Property center, thus catalyst activity is higher in actual application, and the deactivation rate of catalyst is obtained
To reduction, the service life of catalyst can be extended.
Based on this, according to the first aspect of the invention, the invention provides a kind of resistance to thermal oxide of modified inorganic
Thing, the modified inorganic refractory oxides have acid hydroxy group and basic hydroxide group, in infrared spectrum, highly acid
Hydroxyl peak is in 3640-3700cm-1Near, strong basicity hydroxyl peak is in 3740-3800cm-1Near, its feature
Be that the relative altitude of the strong basicity hydroxyl peak is 30-90%, the strong basicity hydroxyl peak with it is described
The ratio of peak of highly acid hydroxyl peak is 1:0.85-1.15.
According to the second aspect of the invention, the invention provides a kind of preparation of modified inorganic refractory oxides
Method, the method include by the precursor of inorganic refractory oxides and/or inorganic refractory oxides, extrusion aid,
Peptizing agent is molded after being well mixed, and is then successively dried gained article shaped and roasting, and it is special
Levy and be, the method is additionally included in before shaping and/or adds after shaping acid hydroxy group nertralizer and basic hydroxide group
Nertralizer, the acid hydroxy group nertralizer is alkaline earth oxide, alkaline earth nitrate and alkaline earth gold
Category hydroxide in one or more, the basic hydroxide group nertralizer be boracic, gallium, silicon, germanium, phosphorus,
One or more in oxide, the oxyacid of one or more in fluorine element, in the acid hydroxy group
In the infrared spectrum that the consumption of agent and basic hydroxide group nertralizer causes gained heat-resistant inorganic oxide, highly basic
Property hydroxyl peak relative altitude be 30-90%, the relative altitude of highly acid hydroxyl peak is 20-90%, described
Highly acid hydroxyl peak is in 3640-3700cm-1Near, strong basicity hydroxyl peak is in 3740-3800cm-1Near.
According to the third aspect of the invention we, the invention provides one kind is modified by obtained in above-mentioned preparation method
Inorganic refractory oxides.
According to the fourth aspect of the invention, the invention provides one kind is by above-mentioned modified inorganic refractory oxides
As the application of catalyst carrier.
According to the fifth aspect of the invention, the invention provides a kind of Hydrobon catalyst, the hydrogenation takes off
Sulfur catalyst contains carrier and the metal active composition being supported on carrier, it is characterised in that the carrier
For the modified inorganic refractory oxides of above-mentioned offer of the invention.
According to the sixth aspect of the invention, the invention provides a kind of reduce Hydrobon catalyst inactivation speed
The method of degree, the method includes preparing modified inorganic refractory oxides using said method, is then changed with this
The inorganic refractory oxides of property are the carrier loaded metal active composition with hydrodesulfurization activity.
The modified inorganic refractory oxides that the present invention is provided are due to strong basicity hydroxyl peak and highly acid hydroxyl peak
Peak height it is suitable so that it is higher as catalyst activity during carrier, and the deactivation rate of catalyst
It is reduced, the service life of catalyst can be extended.The Hydrobon catalyst that the present invention is provided passes through
Using above-mentioned modified inorganic refractory oxides are as carrier and further coordinate specific metal active constituent
Content, so as to the activity of catalyst is further significantly improved, the deactivation rate of catalyst further substantially drops
It is low.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
(a) is the infrared spectrum curve of aluminum oxide obtained in embodiment 1 in Fig. 1, (b) is that comparative example 1 is made
The infrared spectrogram of the aluminum oxide for obtaining.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
According to the first aspect of the invention, the invention provides a kind of modified inorganic refractory oxides, this changes
The inorganic refractory oxides of property have acid hydroxy group and basic hydroxide group, and in infrared spectrum, highly acid hydroxyl peak exists
3640-3700cm-1Near, strong basicity hydroxyl peak is in 3740-3800cm-1Near, it is characterised in that institute
It is 1 that strong basicity hydroxyl peak is stated with the ratio of peak of the highly acid hydroxyl peak:0.85-1.15, preferably
1:0.9-1.1。
In the present invention, the strong basicity hydroxyl peak is suitable with the peak height of the highly acid hydroxyl peak, thus institute
State strong basicity hydroxyl suitable with the highly acid hydroxyl quantity so that it is used as catalyst activity during carrier
It is higher, and the deactivation rate of catalyst is reduced, and can extend the service life of catalyst.And show
In having technology, the strong basicity hydroxyl peak of inorganic refractory oxides and the peak height of the highly acid hydroxyl peak
Than being usually 1：1.2-1.4.
Under preferable case, in the infrared spectrum of the inorganic refractory oxides that the present invention is provided, the strong basicity
The relative altitude of hydroxyl peak is 30-90%, more preferably preferably 40-85%, 55-75%；The strong acid
Property hydroxyl peak relative altitude be 20-90%, preferably 50-85%, more preferably 60-80%.
In the present invention, the implication of the relative altitude of hydroxyl peak is similar with the implication of existing relative crystallinity, tool
Body surface shows the height of the hydroxyl peak of the modified inorganic refractory oxides of the present invention and the inorganic resistance to thermal oxide of reference
The height ratio of the corresponding hydroxyl peak of thing, i.e. relative to the inorganic refractory oxides of reference, basic hydroxide group peak height
Degree reduction amplitude is controlled to 10-70%, preferably 15-60%；The reduction amplitude control of highly acid hydroxyl peak
For 10-80%, preferably 15-40%.The inorganic refractory oxides of so-called reference are referred in preparation process and not drawn
Enter the inorganic refractory oxides prepared when basic hydroxide group nertralizer and acid hydroxy group nertralizer, i.e., conventional nothing
Machine refractory oxides.
In the present invention, two kinds of acid hydroxy group amplitudes of variation can be with identical, it is also possible to different, as long as final
Highly ratio or relative altitude are controlled within the above range.Due to also there are other classes in alumina surface
Type hydroxyl, such as faintly acid and alkalescent hydroxyl, the quantity of these hydroxyls may become during modulation
Change, its variable quantity is not as Con trolling index.In addition new hydroxyl is likely to production, belongs to normal phenomenon,
It is not limited.
In the present invention, the infrared spectrogram is to obtain sample, Ran Hou initially with self-supporting pressed disc method
After pre-processing to sample in infrared pond again with infrared spectrometer scanning obtain sample hydroxyl spectrogram (with
It is referred to as self-supporting pressed disc method down).Self-supporting pressed disc method is well known in the art technology, repeats no more.
Before carrier hydroxyl measurement is carried out, sample is pre-processed, pretreatment carries out 3h at 400 DEG C
More than, room temperature is cooled the temperature to after process.The measuring method is technology commonly used in the art, and here is no longer
Describe in detail.
The modified inorganic refractory oxides provided according to the present invention can be that prior art is various be can act as
The modifier of the inorganic refractory oxides of catalyst carrier, can be aluminum oxide, silica, oxygen for example
Change the modifier of one or more in zirconium, aluminium oxide-titanium oxide and aluminium oxide-silicon oxide.It is so-called to change
Property thing is strong basicity hydroxyl and alkalescent hydroxyl quantity quite so as to strong basicity hydroxyl peak and the strong acid
Property hydroxyl peak ratio of peak be 1:0.85-1.15, preferably 1:0.9-1.1 and further preferred basic hydroxide group
The product weakened with acid hydroxy group.
The inorganic refractory oxides before modified after shape may each be known in the art and various make
With the shape as catalyst carrier, for example, can be graininess, strip or trilobes, it is and inorganic resistance to
The size of thermal oxide is 0.2-15 millimeters.
In the present invention, the size of (modified) inorganic refractory oxides refers to inorganic refractory oxides from a bit
To the maximum linear distance of another point, can be obtained by sieving.
According to the second aspect of the invention, the invention provides a kind of preparation side of inorganic refractory oxides
Method, the method include by the precursor of inorganic refractory oxides and/or inorganic refractory oxides, extrusion aid,
Peptizing agent is molded after being well mixed, and is then successively dried gained article shaped and roasting, and it is special
Levy and be, the method is additionally included in before shaping and/or adds after shaping acid hydroxy group nertralizer and basic hydroxide group
Nertralizer, the acid hydroxy group nertralizer is alkaline earth oxide, alkaline earth nitrate and alkaline earth gold
Category hydroxide in one or more, the basic hydroxide group nertralizer be boracic, gallium, silicon, germanium, phosphorus,
One or more in oxide, the oxyacid of one or more in fluorine element, in the acid hydroxy group
With the strong basicity hydroxyl peak that the consumption of agent and basic hydroxide group nertralizer causes gained heat-resistant inorganic oxide
Relative altitude is 30-90%, and the relative altitude of highly acid hydroxyl peak is 20-90%, the highly acid hydroxyl
Peak is in 3640-3700cm-1Near, strong basicity hydroxyl peak is in 3740-3800cm-1Near.
It should be noted that the acid-base neutralization neutralized on not ordinary meaning of the present invention, but change hydroxyl
The neutralization of mafic matter, particularly reduces the reaction of hydroxyl peak heights.For example, although nitric acid has acidity,
Alkaline matter can be neutralized, but the basic hydroxide group nertralizer of the present invention can not be used as.It is demonstrated experimentally that nothing
By be plus nitric acid during wonderful works peptizing agent consumption, or after follow-up mixing or in forming process it is extra
Nitric acid is added, can not play a part of to reduce hydroxyl peak heights.
, according to the invention it is preferred in the case of, the acid hydroxy group nertralizer be beryllium hydroxide, magnesium hydroxide,
Calcium hydroxide, barium hydroxide, beryllium oxide, magnesia, calcium oxide, strontium oxide strontia, barium monoxide, barium nitrate,
One or more in calcium nitrate, magnesium nitrate, beryllium nitrate, more preferably beryllium hydroxide, calcium nitrate
With one or more in magnesium nitrate.
, according to the invention it is preferred in the case of, the basic hydroxide group nertralizer is that HF, fluosilicic acid, silicon are molten
One or more in glue, boric acid, phosphoric acid, phosphorous acid, germanic acid, more preferably HF, fluorine silicon
One or more in acid, Ludox, boric acid.
The preparation method of the modified inorganic refractory oxides provided according to the present invention, relative to 1 mole of nothing
The precursor of machine refractory oxides, the consumption of the acid hydroxy group nertralizer is 0.02-0.08 mole, institute
The consumption for stating basic hydroxide group nertralizer is 0.02-0.1 mole.It was found by the inventors of the present invention that by by
Control within the above range, basic hydroxide group fall can be made substantially in aforementioned value scope with the consumption of agent
Interior (30-90%), makes acid hydroxy group fall (20-90%) in the range of aforementioned value.Due to difference
Inorganic refractory oxides in amount of hydroxyl groups it is different, the strong basicity hydroxyl can be made by further experiment determination
Base peak is 1 with the ratio of peak of the highly acid hydroxyl peak:0.85-1.15, preferably 1:In the range of 0.9-1.1
Specific consumption.Specifically it is referred to following methods to determine：
Pure alumina carrier is conventionally prepared, is then prepared using hole saturation infusion process or kneading method
The molar fraction of addition element is 5% carrier, using ft-ir measurement strong basicity or highly acid hydroxyl
The relative altitude of base.The consumption of element when determining relative altitude within the required range using two-point defined line method.
For example, the boron that molar fraction is 5% is introduced in aluminum oxide, correspondence strong basicity hydroxyl relative altitude is 53%.
Due to strong basicity hydroxyl relative altitude and the inversely proportional relation of constituent content, therefore strong basicity can be calculated
The molar fraction of corresponding boron element when hydroxyl relative altitude is 30-90%.In the same manner, other elements are corresponding
The molar fraction scope of hydroxyl relative altitude scope can also actually measure.
Need especially it is emphasised that, it is necessary to the consumption of strict control hydroxyl nertralizer is more than under above range
Limit value and less than the higher limit of above range, could obtain reduction hydroxyl peak heights and reduce amplitude above-mentioned
In the range of effect.In fact, prior art also adds B, P and Mg in the preparation process of carrier
As auxiliary component, but they be either only added thereto same property as only add acid acceptor or
Only add antalkali；The amount for either adding is larger or less, thus can not reach reduce simultaneously acid
The effect of property hydroxyl and basic hydroxide group peak heights, therefore the hydrodesulfurization performance of catalyst also cannot obtain
It is obviously improved.
The preparation method of the modified inorganic refractory oxides provided according to the present invention, the acid hydroxy group neutralization
Agent and basic hydroxide group nertralizer can be added simultaneously, it is also possible to each independent and asynchronously addition, Ke Yixian
Plus acidic hydroxyl nertralizer, afterwards plus basic hydroxide group nertralizer, it is also possible to first plus basic hydroxide group nertralizer, after
Plus acidic hydroxyl nertralizer.They can be added in the step of each in preparation process, for example, Ke Yiyu
The precursor of inorganic refractory oxides, extrusion aid and peptizing agent be mixed together it is uniform after be molded；Also may be used
Successively to add again after the precursor of inorganic refractory oxides, extrusion aid and peptizing agent are mixed together uniformly
Enter, be then molded；Can be with the precursor of inorganic refractory oxides, extrusion aid and peptizing agent one
Rise and add after being well mixed acid hydroxy group nertralizer or basic hydroxide group nertralizer, after shaping, dry and roasting
Add basic hydroxide group nertralizer or acid hydroxy group nertralizer.The mode added after shaping is preferably hole and satisfies
And infusion process.If adding basic hydroxide group nertralizer or acid hydroxy group nertralizer after roasting shaping,
Need to carry out roasting again to carrier.And the temperature of second roasting will be less than a front sintering temperature,
For example low 50-200 DEG C, remaining condition keeps identical.
In the preparation method of the present invention, the mode of shaping can be using existing various catalyst carrier shapings
Method, for example, can be extruded moulding method.
Can be with roasting direct after shaping, it is also possible to first dry roasting, preferably first dry roasting.It is dry
Dry temperature can be 60-150 DEG C, preferably 100-140 DEG C；The dry time can be 1-10 hours,
Preferably 3-6 hours.The temperature of roasting can be 300-800 DEG C, preferably 400-700 DEG C；Roasting
Time can be 2-10 hours, preferably 3-5 hours.
The preparation method of the modified inorganic refractory oxides provided according to the present invention, the inorganic resistance to thermal oxide
Thing and/or its precursor can carry out appropriate selection according to required modified inorganic refractory oxides, specifically
, the inorganic refractory oxides and/or its precursor can be for boehmite, boehmites, without fixed
Type aluminium hydroxide, gibbsite, silica, zirconium oxide, aluminium oxide-titanium oxide and aluminium oxide-silicon oxide
In one or more.
The extrusion aid and peptizing agent are referred to prior art and are selected, and for example, extrusion aid can be with
For one or more in the materials such as sesbania powder, methylcellulose and starch, peptizing agent can for nitric acid,
One or more in citric acid and acetic acid.
Third aspect present invention additionally provides the modified inorganic refractory oxides by obtained in above-mentioned preparation method.
Fourth aspect present invention additionally provides modified inorganic refractory oxides as the application of catalyst carrier.
Using the above-mentioned modified inorganic refractory oxides of present invention offer as catalyst carrier, can be effective
Improve the hydrodesulfurization activity of catalyst.
For this purpose, fifth aspect present invention additionally provides a kind of Hydrobon catalyst, the hydrodesulfurization catalytic
Agent contains carrier and the metal active composition being supported on carrier, it is characterised in that the carrier is this
The modified inorganic refractory oxides of bright above-mentioned offer.
Sixth aspect present invention additionally provides a kind of method of reduction Hydrobon catalyst deactivation rate, should
Method includes preparing modified inorganic refractory oxides using said method, then with the heat-resisting oxygen of the modified inorganic
Compound is the carrier loaded metal active composition with hydrodesulfurization activity.
The metal active composition of the Hydrobon catalyst can be various with hydrodesulfurization activity
Metal component, for example, can be VIII and group vib metallic element in the periodic table of elements, it is preferable that
The metal active composition is nickel and/or cobalt and tungsten and/or molybdenum.
In the Hydrobon catalyst, the atomic concentration of carrier surface group vib metallic element is 2-8
Atom/nm2, preferably 2.5-6 atom/nm2；VIII/ (VIII+VIB) atomic ratio scope is 0.2-0.4,
Preferably 0.3-0.4.When the metal active composition is nickel and/or cobalt and tungsten and/or molybdenum, carrier table
The total atom concentration of face Mo and/or W is 2-8 atom/nm2, preferably 2.5-6 atom/nm2；
Co (Ni)/(Co (Ni)+Mo+W) atomic ratio scope is 0.2-0.4, preferably 0.3-0.4.
In the present invention, carrier surface metal atom concentration by metal total atom number and carrier specific surface area it
Obtain than calculating, the specific surface area of carrier is measured by conventional nitrogen adsorption methods.
Above-mentioned Hydrobon catalyst can be by being supported on above-mentioned modified nothing by hydrogenation active metals component
It is obtained on machine refractory oxides.Hole saturation infusion process can for example be passed through.Following two can specifically be passed through
Kind of mode is loading.Mode 1：With cobalt nitrate, nickel nitrate, ammonium heptamolybdate and ammonium metatungstate as raw material,
Addition or without cosolvent in the case of be configured to dipping solution.Cosolvent mainly includes ammoniacal liquor,
Organic compounds containing nitrogen, such as ethylenediamine, EDTA, aminotriacetic acid, 1,2-diaminocyclohexane tetraacetic acid and amino
Acids.These materials are 0.5-2 with the mol ratio of Co (Ni).Mode 2：With basic cobaltous carbonate, alkali formula carbon
Sour nickel, molybdenum oxide, ammonium metatungstate and phosphoric acid be raw material, or add it is a kind of and/or it is various containing hydroxyl and/
Or the organic compound of carboxyl is that cosolvent prepares maceration extract.It is preferred that selecting tartaric acid, citric acid, second two
Alcohol, glycerine etc..Phosphorus is 0.5-2 with the atomic ratio of Co (Ni), and organic matter is with the atomic ratio of Co (Ni)
0.5-2.After maceration extract impregnated carrier 0.5-4h that method described above is prepared, it is dried at 50-180 DEG C
1-5h, then roasting 2-5h is prepared into catalyst at 300-500 DEG C.
The Hydrobon catalyst that the present invention is provided is dropped due to strong basicity therein and highly acid hydroxyl quantity
Low, on the one hand causing active component Mo or W to improve it with the active force reduction of hydroxyl can sulfidation energy
Power, the reduction of another aspect hydroxyl quantity causes coking material absorption property on a catalyst to reduce further
The deactivation rate of catalyst is reduced, service cycle can be extended.Simultaneously as strong basicity and highly acid
The reduction of hydroxyl quantity so that the hydroxyl Acidity of Aikalinity of carrier surface tends to more uniform, and then makes activearm
Divide the dispersion being more uniformly distributed.Thus method prepares the hydrodesulfurization activity and activity stability of catalyst more
For superior.
The present invention is described further for the following examples, but these embodiments can not be limited
The present invention.Aluminium hydrate powder used in following examples is the thin water aluminium of plan of Chang Ling catalyst plant production
Stone.Infrared spectrogram is obtained using self-supporting pressed disc method.Carrier specific surface area is surveyed using nitrogen adsorption methods
, metal atom concentration is then according to carrier specific surface area determining.
Comparative example 1
By boehmite, (the PB90 powder of Chang Ling catalyst plant production, specific surface area is 345m2/g)、
Sesbania powder is according to 100g：After 3g ratios are well mixed, 105mL nitric acid (1.5%) solution is added, and
It is again stirring for uniformly, then by its extruded moulding.Through be dried at 120 DEG C 3h and at 600 DEG C roast
4h steps are burnt, the pure alumina carrier D1 that particle diameter is 1.6mm is prepared.The specific surface of carrier D1
Product is 283m2/g。
Embodiment 1
By boehmite (with comparative example 1), sesbania powder according to 100g：3g ratios mix, and add
The beryllium hydroxide of 1.02g, is well mixed, add 105mL containing nitric acid (concentration be 1.5 weight %) and
The aqueous solution of the HF of 0.47g, and be again stirring for uniformly, then by its extruded moulding.Through at 120 DEG C
Under be dried 3h and the roasting 4h steps at 600 DEG C, prepare particle diameter be 1.6mm alumina support
Sup1.The specific surface area of carrier S up1 is 275m2/g。
The hydroxyl vibration for investigating the carrier that above-mentioned comparative example 1 and embodiment 1 are obtained using infra-red sepectrometry is special
Levy, spectrogram is as shown in Figure 1.It will be seen from figure 1 that Al2O3The strong basicity hydroxyl of carrier and highly acid
Hydroxyl vibration wave number is respectively in 3780-3750cm-1And 3700-3650cm-1.Compared to pure alumina carrier
The relative altitude of strong basicity hydroxyl and highly acid hydroxyl is respectively 40% and 35% in D1, Sup1 carrier,
The ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.14；And in pure alumina carrier D1, highly basic
Property hydroxyl and highly acid hydroxyl ratio of peak be 1：1.3.
Comparative example 2
By boehmite, (the PB100 powder of Chang Ling catalyst plant production, specific surface area is 330m2/g)、
Sesbania powder is according to 100g：After 3.5g ratios are well mixed, (concentration is 1.5 containing nitric acid to add 120mL
Weight %) solution, and be again stirring for uniform extruded moulding.Through be dried at 120 DEG C 3h and
Roasting 4h steps at 550 DEG C, prepare the pure alumina carrier D2 that particle diameter is 1.6mm.Carrier D2
Specific surface area be 292m2/g。
Embodiment 2
By boehmite (with comparative example 2), sesbania powder according to 100g：After 3.5g ratios are well mixed,
The aqueous solution of the addition 120mL containing nitric acid (concentration is 1.5 weight %) and boric acid (1.21g), and again
Stir extruded moulding.Carrier through 3h is dried at 120 DEG C and in roasting 4h at 600 DEG C after
To alumina support, the carrier after roasting is with the calcium nitrate of hole saturation infusion process introducing 9.01g, Ran Houjing
Cross 120 DEG C and be dried 3h and 550 DEG C of roasting 4h, obtain Sup2 carriers.The specific surface area of carrier S up2
For 284m2/g。
The hydroxyl vibration feature for investigating above-mentioned carrier using infra-red sepectrometry finds, carries compared to pure alumina
Body D2, the strong basicity hydroxyl of carrier and the relative altitude of highly acid hydroxyl are respectively 80% He in Sup2
55%, the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：0.96；And in pure alumina carrier D2,
The ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.4.
Comparative example 3
By boehmite, (the PB110 powder of Chang Ling catalyst plant production, specific surface area is 325m2/g)、
Sesbania powder is according to 100g：After 2.5g ratios are well mixed, (concentration is 2 weights containing nitric acid to add 120mL
Amount %) solution, and be again stirring for uniform extruded moulding.Through 5h being dried at 100 DEG C and at 650 DEG C
Lower roasting 3h steps, prepare the pure alumina carrier D3 that particle diameter is 1.6mm.The ratio of carrier D3
Surface area is 264m2/g。
Embodiment 3
By boehmite (with comparative example 3), sesbania powder according to 100g：After 2.5g ratios are well mixed,
It is firstly added the Ludox (SiO containing 7.07g2) stir, then add the dust technology of 120mL (dense
Spend for 2 weight %), and it is again stirring for uniform and extruded moulding.Carrier at 100 DEG C through being dried 5h
Alumina support is obtained with after roasting 3h at 650 DEG C, the carrier after roasting is introduced with hole saturation infusion process
The magnesium nitrate of 6.98g, is then dried 3h and 550 DEG C of roasting 4h through 120 DEG C, obtains Sup3 carriers.
The specific surface area of carrier S up3 is 253m2/g。
The hydroxyl vibration for investigating the carrier that above-mentioned comparative example 3 and embodiment 3 are obtained using infra-red sepectrometry is special
Levy existing, the strong basicity hydroxyl of carrier and the relative altitude of highly acid hydroxyl are respectively 70% He in Sup3
60%, and the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.07；And pure alumina carrier D3
In, the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.25.
Embodiment 4
It is similar to Example 3, by boehmite (with embodiment 3), sesbania powder according to 100g：2.5g
After ratio is well mixed, the Ludox (SiO containing 18.9g is firstly added2) stir, then add
The dust technology (concentration is 2 weight %) of 110mL, and it is again stirring for uniform and extruded moulding.Carrier Jing
Cross and 5h is dried at 100 DEG C and alumina support is obtained after roasting 3h at 650 DEG C, the load after roasting
Body introduces the magnesium nitrate of 11.64g with hole saturation infusion process, and 3h and 550 DEG C of roasting is then dried through 120 DEG C
4h is burnt, Sup4 carriers are obtained.The specific surface area of carrier S up4 is 248m2/g。
Investigated using infra-red sepectrometry and measure the strong basicity hydroxyl of carrier in Sup4 and the phase of highly acid hydroxyl
30% and 21% is respectively to height, and the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：0.88.
Comparative example 4
Method according to embodiment 3 prepares alumina support, and except for the difference that, the consumption of magnesium nitrate is reduced to
1.75g is measured, and obtains comparison vehicle D4.The specific surface area of carrier D4 is 260m2/g。
The hydroxyl vibration for investigating the carrier that above-mentioned comparative example 3 and comparative example 4 are obtained using infra-red sepectrometry is special
Levy existing, the strong basicity hydroxyl of carrier and highly acid hydroxyl relative altitude are respectively 85% and 95% in D4,
And the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.39.
Comparative example 5
Method according to embodiment 1 prepares alumina support, and except for the difference that, HF acid is by identical weight
Nitric acid replaces, and obtains comparison vehicle D5.The specific surface area of carrier D5 is 261m2/g。
The hydroxyl vibration for investigating the carrier that above-mentioned comparative example 1 and comparative example 5 are obtained using infra-red sepectrometry is special
Levy existing, the strong basicity hydroxyl of carrier and highly acid hydroxyl relative altitude are respectively 96% and 52% in D5,
And the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：0.68.
Comparative example 6
By hydroxide zirconium powder, (specific surface area is 260m2/ g), sesbania powder is according to 100g：2.5g ratios are mixed
Close it is uniform after, add the dust technology (concentration is 2 weight %) of 70mL, and be again stirring for uniform extrusion into
Type.Through 5h being dried at 100 DEG C and the roasting 3h steps at 500 DEG C, particle diameter is prepared for 1.6mm
Zirconia carrier D6.The specific surface area of carrier D6 is 108m2/g。
Embodiment 5
By hydroxide zirconium powder (with comparative example 6), sesbania powder according to 100g：After 2.5g ratios are well mixed,
It is firstly added the SiO containing 4.88g2Ludox stir, then add 70mL dust technology it is (dense
Spend for 2 weight %), and it is again stirring for uniform and extruded moulding.Carrier at 100 DEG C through being dried 5h
Zirconia carrier is obtained with after roasting 3h at 550 DEG C, the carrier after roasting is introduced with hole saturation infusion process
The magnesium nitrate of 4.81g, is then dried 3h and 500 DEG C of roasting 4h through 120 DEG C, obtains Sup5 carriers.
The specific surface area of carrier S up5 is 102m2/g。
The hydroxyl vibration for investigating the carrier that above-mentioned comparative example 6 and embodiment 5 are obtained using infra-red sepectrometry is special
Levy existing, the strong basicity hydroxyl of carrier and the relative altitude of highly acid hydroxyl are respectively 80% He in Sup5
75%, and the ratio of peak of strong basicity hydroxyl and highly acid hydroxyl is 1：1.01；And in carrier D6, highly basic
Property hydroxyl and highly acid hydroxyl ratio of peak be 1：1.35.
Embodiment 1-1
The catalyst Cat-Sup1 containing Ni and W is prepared by carrier of Sup1, wherein surface W atoms are dense
Spend for 3.5 atom/nm2, Ni/ (Ni+W) atomic ratio is 0.3.The activity rating of catalyst is respectively solid
Carry out on fixed bed hds evaluation device.Raw material oil nature is as follows：Density is 0.8457g/cm3, sulphur
Content is 1.1wt%, and nitrogen content is 223ppm.Reaction condition is：Temperature is 325 DEG C, and pressure is
3.2MPa, weight (hourly) space velocity (WHSV) is 2h-1, hydrogen-oil ratio is 300v/v.Reaction in 120h and 240h sulphur turn
The desulfurization conversion rate loss of rate and catalyst is as shown in table 1, and wherein desulfurization conversion rate loss is two
Period catalyst desulfurizing rate difference.
Comparative example 1-1
Using with Ni, W metal active constituent of embodiment 1-1 identical weight and using and embodiment 1-1
Identical method prepares the catalyst Cat-D1 containing Ni and W, and except for the difference that, carrier S up1 is by contrasting
Pure alumina carrier D1 obtained in example 1 replaces.Then adopt is carried out with embodiment 1-1 identical method
Hydrodesulfurization activity is evaluated, as a result as shown in table 1.
Embodiment 2-1
With basic cobaltous carbonate, molybdenum oxide, phosphoric acid and ethylene glycol as raw material, with Sup2 as carrier, pass through
Saturation infusion process prepares Cat-Sup2 catalyst.Carrier surface Mo atomic concentrations are 3.2 atoms
/nm2, Co/ (Co+Mo) atomic ratio is 0.32.Then adopt carries out adding with embodiment 1-1 identical method
The desulphurizing activated evaluation of hydrogen, as a result as shown in table 1.
Comparative example 2-1
Using with Co, Mo metal active constituent of embodiment 2-1 identical weight and using and embodiment 2-1
Identical method prepares the catalyst Cat-D2 containing Co and Mo, and except for the difference that, carrier S up2 is by right
Pure alumina carrier D2 obtained in ratio 2 replaces.Then adopt to enter with embodiment 1-1 identical method
Row hydrodesulfurization activity is evaluated, as a result as shown in table 1.
Embodiment 3-1
With basic nickel carbonate, molybdenum oxide, ammonium metatungstate, phosphoric acid and citric acid as raw material, it is with Sup3
Carrier, by saturation infusion process Cat-Sup3 catalyst is prepared.Carrier surface W atomic concentrations are
2.8 atom/nm2, Mo atomic concentrations are 0.4 atom/nm2, Ni/ (Ni+Mo+W) atomic ratio is
0.29.Then using hydrodesulfurization activity evaluation is carried out with embodiment 1-1 identical method, as a result such as table
Shown in 1.
Comparative example 3-1
Using with Ni, W and Mo metal active constituent of embodiment 3-1 identical weight and using and enforcement
Example 3-1 identicals method prepares the catalyst Cat-D3 containing Ni and W and Mo, except for the difference that, carrier
Sup3 pure alumina carrier D3 by obtained in comparative example 3 replace.Then using identical with embodiment 1-1
Method carry out hydrodesulfurization activity evaluation, as a result as shown in table 1.
Embodiment 4-1
Using with Ni, W and Mo metal active constituent of embodiment 3-1 identical weight and using and enforcement
Example 3-1 identicals method prepares the catalyst Cat-Sup4 containing Ni and W and Mo, except for the difference that, carries
Body Sup3 carriers by obtained in embodiment 4 replace Sup4.Then adopt and embodiment 1-1 identical side
Method carries out hydrodesulfurization activity evaluation, as a result as shown in table 1.
Comparative example 4-1
Using with Ni, W and Mo metal active constituent of embodiment 3-1 identical weight and using and enforcement
Example 3-1 identicals method prepares the catalyst Cat-D4 containing Ni and W and Mo, except for the difference that, carrier
Sup3 carrier D4 by obtained in comparative example 4 are substituted.Then adopt to enter with embodiment 1-1 identical method
Row hydrodesulfurization activity is evaluated, as a result as shown in table 1.
Comparative example 5-1
Using with Ni, W metal active constituent of embodiment 1-1 identical weight and using and embodiment 1-1
Identical method prepares the catalyst Cat-D5 containing Ni and W, and except for the difference that, carrier S up1 is by contrasting
Cat-D5 carriers obtained in example 5 replace.Then it is de- using hydrogenation is carried out with embodiment 1-1 identical method
Sulphur activity rating, as a result as shown in table 1.
Comparative example 6-1
Using with Ni, W metal active constituent of embodiment 1-1 identical weight and using and embodiment 1-1
Identical method prepares the catalyst Cat-D6 containing Ni and W, and except for the difference that, carrier S up3 is by contrasting
Carrier D6 obtained in example 6 replaces.Then adopt carries out hydrodesulfurization with embodiment 1-1 identical method
Activity rating, as a result as shown in table 1.
Embodiment 5-1
Using with Ni, W metal active constituent of embodiment 1-1 identical weight and using and embodiment 1-1
Identical method prepares the catalyst Cat-Sup5 containing Ni and W, and except for the difference that, carrier S up3 is by reality
Apply carrier S up5 obtained in example 5 to replace.Then adopt and be hydrogenated with embodiment 1-1 identical method
Desulphurizing activated evaluation, as a result as shown in table 1.
Embodiment 6-1
The catalyst Cat-Sup6 containing Ni and W is prepared using with embodiment 1-1 identical method, it is different
, adjust the consumption of raw material so that carrier surface W atomic concentrations are 3 atom/nm2, Ni/ (Ni+W)
Atomic ratio is 0.1.Then adopt carries out hydrodesulfurization activity evaluation with embodiment 1-1 identical method,
As a result it is as shown in table 1.
Table 1
From the results shown in Table 1, the carrier for being provided using the present invention and the metal work for being equipped with specified quantitative
Property the desulphurizing activated of catalyst obtained in composition is improved, and deactivation rate is suppressed.Thus may be used
To find out, after treatment, the desulphurizing activated of catalyst is improved the hydroxyl of carrier, deactivation rate
Reduced.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (18)
1. a kind of modified inorganic refractory oxides, the modified inorganic refractory oxides have acid hydroxy group and
Basic hydroxide group, in infrared spectrum, highly acid hydroxyl peak is in 3640-3700cm-1Near, strong basicity hydroxyl
Peak is in 3740-3800cm-1Near, it is characterised in that the strong basicity hydroxyl peak and the highly acid hydroxyl
The ratio of peak of base peak is 1:0.85-1.15.
2. modified inorganic refractory oxides according to claim 1, wherein, the strong basicity hydroxyl
Base peak is 1 with the ratio of peak of the highly acid hydroxyl peak:0.9-1.1.
3. modified inorganic refractory oxides according to claim 1 and 2, wherein, the highly basic
Property hydroxyl peak relative altitude be 30-90%, preferably 40-85%, more preferably 55-75%；It is described strong
The relative altitude at acid hydroxy group peak is 20-90%, more preferably preferably 50-85%, 60-80%.
4. modified inorganic refractory oxides according to any one in claim 1-3, wherein,
The modified inorganic refractory oxides are graininess, strip or trilobes, and inorganic refractory oxides is big
It is little for 0.2-15 millimeters；Preferably, the modified inorganic refractory oxides are modified aluminas and/or change
Property zirconium oxide.
5. a kind of preparation method of modified inorganic refractory oxides, the method is included inorganic resistance to thermal oxide
The precursor of thing and/or inorganic refractory oxides, extrusion aid, peptizing agent are molded after being well mixed, so
Gained article shaped is dried successively and roasting afterwards, it is characterised in that the method is additionally included in before shaping
And/or add acid hydroxy group nertralizer and the basic hydroxide group nertralizer, the acid hydroxy group nertralizer to be after shaping
One or more in alkaline earth oxide, alkaline earth nitrate and alkaline earth metal hydroxide, institute
State the oxidation that basic hydroxide group nertralizer is one or more in boracic, gallium, silicon, germanium, phosphorus, fluorine element
The consumption of one or more in thing, oxyacid, the acid hydroxy group nertralizer and basic hydroxide group nertralizer
So that in the infrared spectrum of gained heat-resistant inorganic oxide, the relative altitude of strong basicity hydroxyl peak is
30-90%, the relative altitude of highly acid hydroxyl peak is 20-90%, and the highly acid hydroxyl peak exists
3640-3700cm-1Near, strong basicity hydroxyl peak is in 3740-3800cm-1Near.
6. preparation method according to claim 5, wherein, the acid hydroxy group nertralizer and alkali
Property hydroxyl nertralizer consumption cause gained heat-resistant inorganic oxide infrared spectrum in, the strong basicity hydroxyl
Base peak is 1 with the ratio of peak of the highly acid hydroxyl peak:0.85-1.15, preferably 1:0.9-1.1.
7. the preparation method according to claim 5 or 6, wherein, the acid hydroxy group nertralizer
For beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, beryllium oxide, magnesia, calcium oxide,
One or more in strontium oxide strontia, barium monoxide, barium nitrate, calcium nitrate, magnesium nitrate, beryllium nitrate.
8. the preparation method according to any one in claim 5-7, wherein, the alkaline hydroxyl
Base nertralizer is HF, fluosilicic acid, Ludox, boric acid, phosphoric acid, hypophosphorous acid, silica and oxidation
One or more in boron.
9. the preparation method according to any one in claim 5-8, wherein, the acid hydroxyl
Base nertralizer and basic hydroxide group nertralizer are added simultaneously or successively.
10. the preparation method according to any one in claim 5-9, wherein, it is described inorganic resistance to
The precursor of thermal oxide and/or inorganic refractory oxides be boehmite, silica, zirconium hydroxide,
One or more in zirconium oxide, aluminium oxide-titanium oxide and aluminium oxide-silicon oxide, extrusion aid be sesbania powder,
One or more in methylcellulose and starch, peptizing agent is the one kind in nitric acid, citric acid and acetic acid
Or it is various.
Modified inorganic obtained in 11. preparation methods by described in any one in claim 5-10 is heat-resisting
Oxide.
Modified inorganic refractory oxides in 12. claims 1-4 and 11 described in any one are used as urging
The application of agent carrier.
A kind of 13. Hydrobon catalysts, the Hydrobon catalyst contains carrier and is supported on carrier
Metal active composition, it is characterised in that the carrier is any one institute in claim 1-4 and 11
The modified inorganic refractory oxides stated.
14. Hydrobon catalysts according to claim 13, wherein, the metal active into
Be divided into group vib metallic element and group VIII metal element in the periodic table of elements, preferred nickel and/or cobalt with
And tungsten and/or molybdenum.
15. Hydrobon catalysts according to claim 13 or 14, wherein, carrier surface
The atomic concentration of group vib metallic element is 2-8 atom/nm2, preferably 2.5-6 atom/nm2；
VIII/ (VIII+VIB) atomic ratio scope is 0.2-0.4, preferably 0.3-0.4.
A kind of 16. methods for reducing Hydrobon catalyst deactivation rate, the method includes will using right
The method in 5-11 described in any one is asked to prepare modified inorganic refractory oxides, then with the modified inorganic
Refractory oxides are the carrier loaded metal active composition with hydrodesulfurization activity.
17. methods according to claim 16, wherein, the metal active composition is element week
Group vib metallic element and group VIII metal element in phase table, preferred nickel and/or cobalt and tungsten and/or molybdenum.
18. methods according to claim 16 or 17, wherein, the amount of load causes carrier surface
The atomic concentration of group vib metallic element is 2-8 atom/nm2, preferably 2.5-6 atom/nm2；
VIII/ (VIII+VIB) atomic ratio scope is 0.2-0.4, preferably 0.3-0.4.
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| CN107961772A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and preparation method thereof |
| CN114433040A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
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| CN107961772A (en) * | 2016-10-20 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and preparation method thereof |
| CN107961772B (en) * | 2016-10-20 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and preparation method thereof |
| CN114433040A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
| CN114433040B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
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