CN109718817A - The hydrofinishing process of Hydrobon catalyst and its preparation method and application and distillate - Google Patents
The hydrofinishing process of Hydrobon catalyst and its preparation method and application and distillate Download PDFInfo
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Abstract
The present invention relates to Hydrobon catalyst fields, disclose the hydrofinishing process of Hydrobon catalyst and its preparation method and application and distillate.Catalyst component containing inorganic refractory, active component and carboxylic acid, have the aperture 4-40nm and 100-300nm, and pore volume accounts for the 60-95% and 0.5-30% of total pore volume respectively；Inorganic refractory component is containing amorphous silicon aluminium and/or molecular sieve and aluminium oxide.Preparation method includes: that amorphous silicon aluminium and/or molecular sieve and alumina precursor are mixed and roasted, and obtains inorganic refractory component；By carboxylic acid and active component presoma is added to mix, obtain maceration extract, and mixed, forms with inorganic refractory component and dry.Catalyst has the aperture 100-300nm, better performances, and preparation flow shortens.
Description
Technical field
The present invention relates to Hydrobon catalyst fields, and in particular to a kind of Hydrobon catalyst, a kind of hydrofinishing
The preparation method of catalyst and the Hydrobon catalyst prepared by this method, the Hydrobon catalyst are in distillate hydrogenation
Application and a kind of hydrofinishing process of distillate in purification.
Background technique
Hydrotreating is the mainstay in modern petroleum refining industry, in production clean fuel, improves product quality, abundant
It is played an important role using petroleum resources and pretreatment of raw material etc..With the development of economic environmental protection and society, so that refining
Oily enterprise constantly puts forward higher requirements the activity and stability of hydrotreating catalyst, Hydrobon catalyst activity and choosing
Selecting property needs to be continuously improved.Wherein, hydrodesulfurization activity is an important indicator for measuring Hydrobon catalyst performance.
Usually, Hydrobon catalyst is using the sulfide of group vib metal (Mo and/or W) as main active component, and
Using the sulfide of group VIII metal (Co and/or Ni) as active component is helped, remaining group is divided into carrier in catalyst.Study table
Bright, the cellular structure of catalyst has large effect to its reactivity worth, and catalyst should have suitable cellular structure with suitable
Answer the diffusion of reactant.Therefore, many patents and research have been directed to the exploitation and research of carrier.It is bad with hydrogenating materials
The size of matter, reactant molecule incrementally increases, and needs just better meet reactant using the carrier of more macropore structure
The demand of diffusion.
The preparation method of general alumina support be using boehmite as raw material, be added extrusion aid and adhesive carry out at
Aluminium oxide is prepared by 100-200 DEG C of drying and 400-1000 DEG C of roasting after molding in type.Increase the common methods master in aperture
Will include using different boehmites mixing (such as CN1488441A), using expanding agent (such as CN1160602A, US4448896,
CN1055877C etc.) etc..For example, a water aluminium oxide is heat-treated by CN101450327A at a temperature of 150-300 DEG C, processing
It mediates uniformly, passes through after being mixed again with expanding agent one or more in graphite, stearic acid, odium stearate, aluminum stearate afterwards
Aluminium oxide is prepared using 700-1000 DEG C of roasting after 100-150 DEG C of drying.But the expanding method, expanding agent and intends thin water
Aluminium stone can not uniformly mix bad so as to cause reaming effect, and the addition of expanding agent also will increase cost.
In addition, CN1087289A discloses a kind of method for preparing macropore alumina supporter.This method will contain at room temperature
The moment containing boehmite of the extruded moulding of moisture is placed in high-temperature atmosphere, and high temperature range is 500-650 DEG C, and in this high temperature
Lower constant temperature 2-4h.This method carries out reaming to carrier using the moisture of rapid evaporation under high temperature, but aperture is still smaller, and uses
The activity of hydrogenation catalyst made from the carrier also needs to be further increased.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that the prior art is small there are Hydrobon catalyst aperture and active low,
A kind of Hydrobon catalyst is provided, pore volume of the aperture of the Hydrobon catalyst in 100-300nm accounts for total pore volume
Ratio is 0.5-30%, and catalytic activity is high.
To achieve the goals above, one aspect of the present invention provides a kind of Hydrobon catalyst, wherein the catalyst contains
Inorganic refractory component, Investigation On Hydrodesulfurizationof of Catalysts Derived component and carboxylic acid；
Wherein, the inorganic refractory component contains amorphous silicon aluminium and/or molecular sieve and aluminium oxide；
The aperture in aperture and 100-300nm of the catalyst with 4-40nm, wherein hole body of the aperture in 4-40nm
Product accounts for the 60-95% of total pore volume, and the pore volume of 100-300nm accounts for the 0.5-30% of total pore volume.
Second aspect of the present invention provides a kind of preparation method of Hydrobon catalyst, this method comprises:
(1) amorphous silicon aluminium and/or molecular sieve and alumina precursor are mixed and is roasted, obtain inorganic refractory group
Point；
(2) carboxylic acid and the presoma of Investigation On Hydrodesulfurizationof of Catalysts Derived component are mixed, obtains maceration extract；
(3) the inorganic refractory component and the maceration extract are mixed, obtained mixture is formed and dried, institute is obtained
State Hydrobon catalyst.
Third aspect present invention provides the Hydrobon catalyst of method preparation as described above.
Fourth aspect present invention provides application of the Hydrobon catalyst as described above in fraction oil hydrogenation refining.
Fifth aspect present invention provides a kind of hydrofinishing process of distillate, this method comprises: will add as described above
Hydrogen catalyst for refining is vulcanized, and is then passed to hydrogen sweetened distillate oil to be added, is made hydrogen sweetened distillate oil to be added in hydrodesulfurization item
It is contacted under part with the vulcanization back end hydrogenation catalyst for refining.
The cellular structure of catalyst provided by the invention is concentrated mainly between 4-40nm and 100-300nm.It is evaporated in poor quality
Divide in oil, the size of reactant molecule is larger, certainly will need biggish reaction compartment, the duct of 100-300nm can in catalyst
With enough places that the diffusion for reactant provides, the accessibility in reactant and activated centre is promoted, is urged to improve
The performance of agent.It is 9100ppm to sulfur content, nitrogen content 532ppm, arene content are 55 weights as documented by embodiment
The distillate for measuring % carries out hydrotreating, and sulfur content can reduce to 14ppm hereinafter, nitrogen content is reduced to 4.5ppm hereinafter, de-
Sulphur rate is up to 99.8% or more, and denitrification percent is up to 99.2% or more, and arene content is reduced to 37 weight % hereinafter, Porous deproteinized bone rate is reachable
32.7% or more.
The present inventor has found that usual alumina support is by the way that alumina precursor is (quasi- in the course of the research
Boehmite powder) with peptizing agent and extrusion aid by extruded moulding, then drying and roasting obtain.Due to hydrogenation reaction
Need catalyst that there is biggish cellular structure, and before roasting, general duct concentrates on 5-12nm, therefore, general by will be at
The load that carrier after type carries out calcination process to improve the pore size of carrier to improve the pore size of catalyst, after roasting
The duct of body is generally concentrated at 6-20nm, and the average pore size of carrier increases, and is generally acknowledged that maturing temperature is higher, pore size
It is bigger.However, the present inventor has found under study for action, with the increase of maturing temperature, the hole wall of carrier can collapse
Condensation.Although hole wall condensation can be such that the average pore size of carrier increases, the hole wall of condensation can reduce the utilization rate of aluminium oxide, from
And reduce the catalytic activity of catalyst.The preparation method of Hydrobon catalyst provided by the invention passes through before extrusion molding
Alumina precursor (boehmite powder) is roasted, alumina precursor can be reduced by, which being on the one hand heat-treated, (intends thin water
Aluminium mountain flour) hydroxyl quantity in particle, the probability of duct condensation is reduced, the aperture of catalyst is increased.Second aspect, it is after molding to urge
Agent does not need to be handled with higher temperature, and aluminium oxide hole wall does not need to carry out excessive condensation, improves aluminium oxide
Utilization rate.The third aspect is before the forming heat-treated alumina precursor (boehmite powder), part secondary
It can be condensed, this size that will lead to the aluminium oxide particles to be formed tends to be single, and duct will more in catalyst after molding
Uniformly, be conducive to the diffusion of reactant.It is more more effective than conventional catalyst especially for heavier and more inferior oil product.
Further, the process of the preparation method of Hydrobon catalyst provided by the invention is shorter, can biggish section
Save preparation cost and preparation time.On the other hand, the preparation of catalyst is added without peptizing agent nitric acid and auxiliary agent squeezes sesbania powder, reduces
The discharge of harmful substance (such as NOx) reduces material cost and environmentally friendly cost, realizes the green manufacturing of catalyst.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The first aspect of the present invention provides a kind of Hydrobon catalyst, which contains inorganic refractory component plus hydrogen
Desulfurization catalyst active component and carboxylic acid；
Wherein, the inorganic refractory component contains amorphous silicon aluminium and/or molecular sieve and aluminium oxide；
The aperture in aperture and 100-300nm of the catalyst with 4-40nm, wherein hole body of the aperture in 4-40nm
Product accounts for the 60-95% of total pore volume, and the pore volume of 100-300nm accounts for the 0.5-30% of total pore volume.
In addition, catalyst of the invention does not contain expanding agent, for example, carbon black, graphite, stearic acid, odium stearate, stearic acid
Aluminium, also without containing ingredients such as surfactants.
Preferably, aperture accounts for the 75-90% of total pore volume, hole body of the aperture in 100-300nm in the pore volume of 4-40nm
Product accounts for the 5-15% of total pore volume.
According to the present invention, the catalyst also has the aperture of 2-4nm, and the pore volume of 2-4nm is no more than total pore volume
3%, preferably 0.5-2%.
Preferably, the specific surface area of the Hydrobon catalyst is 80-250m2/ g, preferably 90-220 m2/ g, total hole
Volume is 0.2-0.8mL/g, preferably 0.3-0.7mL/g, average pore size 10-30nm, preferably 12-20nm.Wherein, compare table
The measurement of area, pore volume and average pore size refers to what catalyst was measured after 400 DEG C roast 3h.
According to the present invention, the pore size distribution of the specific surface area of catalyst and 2-4nm therein and 4-40nm, aperture, hole
Volume is measured using low temperature nitrogen absorption method (meeting GB/T5816-1995 standard), the pore size distribution of 100-300nm, aperture, hole
Volume is measured using mercury injection method.Pore volume of the aperture less than 100nm uses low temperature nitrogen determination of adsorption method, aperture in catalyst
Pore volume greater than 100nm is measured using mercury injection method, and the total pore volume of catalyst is sum of the two.Average pore size is according to cylinder
Pore model is calculated.
According to the present invention, in the case where no explanation on the contrary, the aperture of the 2-4nm refers to that aperture is more than or equal to 2nm,
Less than 4nm, the aperture of the 4-40nm refers to that aperture is greater than 4nm, is less than 40nm, the aperture of the 100-300nm refers to aperture
More than or equal to 100nm, it is less than 300nm.Average pore size is 10-30nm, and preferably 12-20nm refers to the porose hole of institute of catalyst
The average value of diameter is more than or equal to 10nm, preferably greater than or equal to 12nm, is less than or equal to 30nm, is preferably smaller than equal to 20nm.
According to the present invention, the Investigation On Hydrodesulfurizationof of Catalysts Derived component can be the existing Hydrobon catalyst that can be used for
The component of active component, for example, the active component can be group VIII metallic element and vib metals element.Wherein,
The content of the active component can also be changed in a wider scope, it is preferred that in the Hydrobon catalyst,
On the basis of the dry weight of catalyst and in terms of oxide, the content of group VIII metallic element is 2-20 weight %, preferably
For 4-15 weight %；The content of vib metals element is 20-75 weight %, preferably 30-50 weight %.
, according to the invention it is preferred to, on the basis of the dry weight of catalyst, the inorganic refractory constituent content is 5-75
Weight %, more preferably 25-60 weight %.
Herein it should be noted that inorganic refractory powder dry weight is by measuring sample in 600 DEG C of roasting 4h
Weight, the dry weight of catalyst is by measuring sample in 400 DEG C of roasting 3h.The dry weight hereinafter occurred is same
Sample is suitable for this definition.That is, inorganic refractory powder dry weight described herein is equal in the case where no explanation on the contrary
Refer to that the weight by measuring sample and roasting 4h at 600 DEG C, the dry weight of catalyst are by roasting sample at 400 DEG C
3h and measure.Those skilled in the art are able to know that, in the case where being calculated on the basis of dry weight, catalyst
In the organic acid that contains can decompose vapor away at high temperature, therefore, the content of organic acid is not calculated with dry weight.
A kind of preferred embodiment according to the present invention, the group VIII metallic element be selected from iron, cobalt, nickel, ruthenium, rhodium and
At least one of palladium, the vib metals element are selected from least one of chromium, molybdenum and tungsten.
The present inventor has found that introducing carboxylic acid compound, which can be improved, in Hydrobon catalyst urges under study for action
The activity of agent.Therefore, it plays guard catalyst active component as long as introducing carboxylic acid in the catalyst and mentions
The effect of high catalyst activity, and its additional amount is not particularly limited.A kind of preferred embodiment party according to the present invention
Formula, on the basis of the dry weight of the inorganic refractory component, the content of the carboxylic acid is 3-40 weight %, preferably 10-30
Weight %.
Under preferable case, the carboxylic acid be selected from C1-18 unitary saturated carboxylic acid (for example, C1, C2, C3, C4, C5, C6,
The unitary saturated carboxylic acid of C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18) (such as, but not limited to first
Acid, acetic acid, propionic acid, octanoic acid, valeric acid, caproic acid, capric acid, valeric acid, caproic acid, capric acid, stearic acid), the phenylic acid of C7-10 (for example,
The phenylic acid of C7, C8, C9, C10) (such as, but not limited to benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid (TPA)), lemon
At least one of acid, adipic acid, malonic acid, succinic acid, maleic acid and tartaric acid etc..
The present inventor also found in the course of the study, unformed by introducing in conventional catalyst carrier
Sial and/or molecular sieve can effectively improve the performance of Hydrobon catalyst.Therefore, as long as introducing nothing in the catalyst
Sizing sial and/or molecular sieve can improve catalyst activity, and its additional amount is not particularly limited.According to this
A kind of preferred embodiment is invented, on the basis of the dry weight of inorganic refractory component, amorphous silicon aluminium and/or molecular sieve
Content is 5-50 weight %, aluminium oxide surplus.It is furthermore preferred that on the basis of the dry weight of inorganic refractory component, unformed silicon
The content of aluminium and/or molecular sieve is 10-30 weight %, aluminium oxide surplus；Wherein, it is preferred that the amorphous silicon aluminium and/or
The weight content of molecular sieve is the 5-50%, more preferable 10-30% of alumina weight content.
, according to the invention it is preferred to, dioxide-containing silica is 5-30 weight % in the amorphous silicon aluminium, more preferably
10-20 weight %.
According to the present invention, the molecular sieve can be conventional various molecular sieves, but the present inventor is under study for action
It was found that the hydrogen type molecular sieve by using the sodium element content in terms of sodium oxide molybdena not higher than 0.5 weight % can further increase
The performance of catalyst.The hydrogen type molecular sieve without sodium can be but be not limited to 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, X
At least one of type molecular sieve, Y type molecular sieve, ZSM-5 molecular sieve and Beta molecular sieve.
A kind of preferred embodiment according to the present invention, in order to further increase the performance of catalyst, the hydrofinishing
Also contain P elements in catalyst, the P elements are preferably with P2O5Form exist.Preferably, with the dry weight of catalyst
On the basis of and with P2O5Meter, the content of the P elements are 0.8-10 weight %, more preferable 2-8 weight %.
, according to the invention it is preferred to, the catalyst is preformed catalyst, and the catalyst is preferably shaped to cylinder
Shape, cloverleaf pattern, bunge bedstraw herb shape or honeycombed.
According to the second aspect of the invention, a kind of preparation method of Hydrobon catalyst is provided, this method comprises:
(1) amorphous silicon aluminium and/or molecular sieve and alumina precursor are mixed and is roasted, obtain inorganic refractory group
Point；
(2) carboxylic acid and the presoma of Investigation On Hydrodesulfurizationof of Catalysts Derived component are mixed, obtains maceration extract；
(3) the inorganic refractory component and the maceration extract are mixed, obtained mixture is formed and dried, institute is obtained
State Hydrobon catalyst.
According to the present invention, the selection of the amorphous silicon aluminium, molecular sieve, carboxylic acid and Investigation On Hydrodesulfurizationof of Catalysts Derived component has been
Through hereinbefore having carried out detailed record, it is no longer repeated herein.
According to the present invention, the carboxylic-acid substance is introduced in the maceration extract can be effectively protected hydrodesulfurization catalytic work
Property component, while the molding of catalyst can also be promoted, to effectively improve the performance of catalyst.
According to the present invention, amorphous silicon aluminium or molecular sieve are introduced in the inorganic refractory component, can significantly be increased
Add the acidity of catalyst, to provide the performance of catalyst.
According to the present invention, the presoma of the aluminium oxide various can provide the object of alumina support to be existing
Matter, an example of the alumina precursor are boehmite.The present invention did not had the selection of the boehmite
More limitations, in order to further increase the performance of the catalyst finally prepared, the average pore size of the boehmite is 5-
20nm, preferably 8-15nm, the pore volume that aperture is 2-4nm account for the ratio of total pore volume no more than 15%, preferably 5-12%, aperture
The ratio of total pore volume is accounted for not less than 75% for the pore volume of 4-40nm, preferably 80-95%.
Wherein, the aperture of 2-4nm and 4-40nm, pore volume use low temperature nitrogen determination of adsorption method, meet GB/T5816-
1995 standards.Wherein, the aperture of the 2-4nm refers to that aperture is more than or equal to 2nm, is less than 4nm, the aperture of 4-40nm refers to aperture
More than or equal to 6nm, it is less than 40nm.Average pore size is 5-20nm, preferably 8-15nm refer to catalyst porose aperture it is flat
Mean value is more than or equal to 5nm, preferably greater than or equal to 8nm, is less than or equal to 20nm, is preferably smaller than equal to 15nm.
According to the present invention, in the presoma of the Investigation On Hydrodesulfurizationof of Catalysts Derived component, the presoma packet of the ferro element
Include but be not limited to one of ferric nitrate, iron oxide, basic carbonate iron, ferric acetate or a variety of, the presoma packet of the cobalt element
Include but be not limited to one of cobalt nitrate, basic cobaltous carbonate, cobalt acetate and cobalt oxide or a variety of, the presoma of nickel element include but
It is not limited to one of nickel nitrate, basic nickel carbonate, nickel acetate and nickel oxide or a variety of, the presoma of ruthenium element includes but unlimited
In one of nitric acid ruthenium, ruthenium acetate, ruthenium-oxide, hydroxide ruthenium or a variety of, the presoma of rhodium element includes but is not limited to nitric acid
One of rhodium, rhodium hydroxide, rhodium oxide are a variety of, and the presoma of palladium element includes but is not limited to palladium nitrate, palladium oxide, hydrogen-oxygen
Change one of palladium or a variety of, the presoma of chromium include but is not limited to chromic nitrate, chromium oxide, chromium hydroxide, in chromic acetate
It is one or more, the presoma of molybdenum element includes but is not limited to ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, one in molybdenum oxide
Kind is a variety of, and the presoma of wolfram element includes but is not limited to one of ammonium metatungstate, ethyl ammonium metatungstate, tungsten oxide or more
Kind.
According to the present invention, in preparation method as above, the dosage of amorphous silicon aluminium and/or molecular sieve, oxidation in step (1)
The dosage of aluminium presoma, the dosage of carboxylic acid and the dosage of Investigation On Hydrodesulfurizationof of Catalysts Derived component to be prepared in step (2)
Hydrobon catalyst in, amorphous silicon aluminium and/or molecular sieve, aluminium oxide, carboxylic acid and Investigation On Hydrodesulfurizationof of Catalysts Derived component
Contain respectively according to the content recorded in first aspect as above, it is no longer repeated herein.
According to the present invention, the presoma of Investigation On Hydrodesulfurizationof of Catalysts Derived component in the maceration extract in order to further increase preparation
Dissolubility improves the performance of the catalyst finally prepared, phosphorus containg substances is further preferably added in the process for preparation of the maceration extract,
The phosphorus containg substances are preferably phosphorous inorganic acid, further preferably in phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate
It is at least one.It is further preferred that the dosage of the phosphorus containg substances makes in the catalyst finally prepared, using dry weight as base
It is quasi- and with P2O5Meter, the content of the P elements are 0.8-10 weight %, preferably 1-8 weight %, more preferable 2-8 weight %.
A preferred embodiment of the invention, during preparing maceration extract first by carboxylic-acid substance with containing the
In the aqueous solution of group vib metallic element and the predecessor addition phosphorus containg substances containing group VIII metal, 1- is stirred at 40-100 DEG C
8h, until whole dissolutions.The addition sequence of phosphorus containg substances, carboxylic-acid substance and metal precursor can also be exchanged mutually.
According to the present invention, in step (1), the condition of the roasting can be selected in a wider scope, it is preferred that
The temperature of the roasting is 400-1000 DEG C, preferably 500-800 DEG C；The time of roasting is 1-15h, preferably 3-8h.
It was found by the inventors of the present invention that being passed through vapor during by roasting before shaping, can effectively mention
The aperture of carrier mass in the high inorganic refractory component, to can further improve the aperture of catalyst.Therefore, the present invention one
Kind preferred embodiment, the roasting carry out under the atmosphere of vapor.Wherein, the vapor is preferably to contain vapor
The form of air be passed through, the content of the water vapor in air containing vapor is preferably 5-20 weight %, more preferably
8-15 weight %.
According to the present invention, in step (3), the condition of the drying can be selected in a wider scope, it is preferred that
Dry temperature is 50-250 DEG C, preferably 100-200 DEG C；The dry time is 2-10h, preferably 3-8h.
According to the present invention, the molding mode can be existing various forming methods, such as can be extruded moulding,
It is also possible to roller forming.The mode of the extruded moulding is referred to prior art progress, will be to the inorganic resistance to of extruded moulding
The dipping solution of fiery component and metallic components is extruded into required shape after mixing, such as cylinder, cloverleaf pattern, bunge bedstraw herb
Shape, honeycombed etc..
In the prior art, the step of preparing Hydrobon catalyst generally comprises: (1) by alumina precursor (for example, quasi-
Boehmite) or squeeze after being mixed with the presoma containing other powders, element and mix with peptizing agent and auxiliary agent, (2) pass through extrusion
Mode prepares molding, and alumina support is prepared in alumina precursor after molding roasting by (3)；(4) group containing metal is prepared
The dipping solution divided；(5) alumina support after being burnt dipping solution homogeneous impregnation is prepared into catalyst precursor；(6) will
Catalyst precursor is dry or Hydrobon catalyst is prepared in roasting.It can thus be seen that the preparation flow is longer, manufacture
Higher cost.And it is as described above, process provided by the invention is shorter, can biggish saving preparation cost and preparation time.
On the other hand, the preparation of catalyst is added without peptizing agent nitric acid and auxiliary agent squeezes sesbania powder, reduces material cost and environmentally friendly cost,
Realize the green manufacturing of catalyst.
In addition, catalyst cellular structure provided by the invention is concentrated mainly between 4-40nm and 100-300nm.Bad
In matter distillate, the size of reactant molecule is larger, certainly will need biggish reaction compartment, and 100- in catalyst of the invention
The duct of 300nm can be the biggish place that provide of diffusion of reactant, promote the accessible of reactant and activated centre
Property, to improve the performance of catalyst.
In the prior art, as described above, usual alumina support be by by alumina precursor (for example, intending thin water
Aluminium stone) with peptizing agent and extrusion aid by extruded moulding, then drying and roasting obtain.Since hydrogenation reaction needs are urged
Agent has biggish cellular structure, and before roasting, general duct concentrates on 5-12nm, and therefore, general pass through will be after molding
Carrier carries out calcination process to improve the pore size of carrier to improve the pore size of catalyst, the hole of the carrier after roasting
Road is generally concentrated at 6-20nm, and the average pore size of carrier increases.And it is generally acknowledged that maturing temperature is higher, pore size is bigger.
However it was found by the inventors of the present invention that with maturing temperature increase, the hole wall of carrier can occur collapse condensation.Although hole wall contracts
Conjunction can be such that the average pore size of carrier increases, but the hole wall being condensed can reduce the utilization rate of aluminium oxide, to reduce catalyst
Catalytic activity.The present invention is by roasting boehmite powder before extrusion molding, and on the one hand heat treatment can be reduced
Hydroxyl quantity in alumina precursor particle reduces the probability of duct condensation, increases the aperture of catalyst.Second aspect, molding
Catalyst afterwards does not need to be handled with higher temperature, and aluminium oxide hole wall does not need to carry out excessive condensation, improves oxygen
Change the utilization rate of aluminium.The third aspect is before the forming heat-treated alumina precursor (boehmite powder), and part is secondary
Particle can be also condensed, this size that will lead to the aluminium oxide particles to be formed tends to be single, duct in catalyst after molding
Will be more uniform, be conducive to the diffusion of reactant.Especially for heavier and more inferior oil product, more than conventional catalyst
Effectively.
Third aspect present invention provides the Hydrobon catalyst of method preparation as described above.
Fourth aspect present invention provides application of the Hydrobon catalyst as described above in fraction oil hydrogenation refining.
According to the present invention, Hydrobon catalyst provided by the invention and the hydrofinishing catalysis prepared by method as above
Agent is 5000-30000ppm especially suitable for sulfur content, and nitrogen content 50-3000ppm, arene content is 20-80 weight %'s
Distillate.It is 9100ppm to sulfur content, nitrogen content 532ppm, arene content are 55 weight % as documented by embodiment
Distillate carry out hydrotreating, sulfur content can reduce to 14ppm hereinafter, nitrogen content is reduced to 4.5ppm hereinafter, desulfurization degree
Up to 99.8% or more, denitrification percent is up to 99.2% or more, and arene content is reduced to 37 weight % hereinafter, Porous deproteinized bone rate is reachable
32.7% or more
Fifth aspect present invention provides a kind of hydrofinishing process of distillate, this method comprises: will add as described above
Hydrogen catalyst for refining is vulcanized, and is then passed to hydrogen sweetened distillate oil to be added, is made hydrogen sweetened distillate oil to be added in hydrodesulfurization item
It is contacted under part with the vulcanization back end hydrogenation catalyst for refining.
According to the present invention, the conditions of vulcanization of the Hydrobon catalyst can urge to be existing for vulcanizing hydrofinishing
The condition of agent, for example, sulfide stress is 0.1-15MPa, volume space velocity 0.5-20h-1, hydrogen to oil volume ratio 100-2000:
1.Vulcanization is not particularly limited, and can vulcanize for dry pre-sulfiding or wet process.
According to the present invention, the condition of the hydrodesulfurization can carry out adding hydrogen de- using Hydrobon catalyst to be existing
The condition of sulphur, for example, pressure is 0.1-8MPa, temperature is 260-410 DEG C, volume space velocity 0.5-10h-1, hydrogen to oil volume ratio is
200-1000:1.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the hydrodesulfurization performance of catalyst is surveyed on 20mL high pressure reaction assembly
It is fixed, temperature programming vulcanization, which is directlyed adopt, by oxidized catalyst is converted into sulphided state catalyst.Conditions of vulcanization are as follows: sulfide stress
For 6.4MPa, sulfurized oil is containing CS2The kerosene of 2% weight, volume space velocity 2h-1, hydrogen-oil ratio 300v/v, first 230
DEG C/h constant temperature 6h, it is then warming up to 360 DEG C of vulcanization 8h again, the heating rate in each stage is 10 DEG C/h.Switch reaction after vulcanization
Raw material carry out hydrodesulfurization activity test, reaction raw materials be sulfur content be 9100ppm, nitrogen content 532ppm, arene content are
The high aromatic fraction oil of the high nitrogen of 55wt%.Test condition are as follows: pressure 6.4MPa, volume space velocity 1.5h-1, hydrogen-oil ratio is
300v/v, reaction temperature are 350 DEG C.7 days post analysis product sulfur levels of stable reaction.
The composition of catalyst is calculated according to inventory.The specific surface area of catalyst and 2-4nm therein and 4-
The pore size distribution of 40nm, aperture, pore volume use low temperature nitrogen determination of adsorption method (meeting GB/T5816-1995 standard), 100-
The pore size distribution of 300nm, aperture, pore volume are measured using mercury injection method.The specific surface area of boehmite and 2-4nm therein and
The pore size distribution of 4-40nm, aperture, pore volume use low temperature nitrogen determination of adsorption method (meeting GB/T5816-1995 standard).Catalysis
The average pore size of agent and boehmite is calculated according to cylindrical hole model.Using sulphur blood urea/nitrogen analyzer, (the silent winged generation that of match goes out
Product, model TN/TS3000) sulphur and nitrogen in analysis product mass fraction, the content of aromatic hydrocarbons is using near infrared spectroscopy point
Analysis.
Embodiment 1
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
(1) by boehmite (the boehmite powder of Chang Ling catalyst plant production, specific surface area 320m2/ g is put down
Equal aperture is 13nm, and the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is the pore volume of 4-40nm
Account for total pore volume ratio be 78%), amorphous silicon aluminium powder (SiO2Content be 10 weight %) be uniformly mixed, then 500
8h is roasted at DEG C, obtains inorganic refractory component.
Wherein, on the basis of the dry weight of inorganic refractory component, the content of amorphous silica-alumina is 15.4 weight %, oxygen
The content for changing aluminium is 84.6 weight %.
(2) by a certain amount of MoO3, basic cobaltous carbonate, citric acid be separately added into the aqueous solution of phosphoric acid, stirred in heating
It mixes down toward being completely dissolved, obtains the dipping solution containing active metal.
Wherein, citric acid quality is 10 weight % of inorganic refractory component.
(3) dipping solution is uniformly mixed with the inorganic refractory component, then by its extruded moulding.By at 200 DEG C
The oxidized catalyst that partial size is 1.6mm is prepared in lower dry 5h.
Wherein, dipping solution and the mixed proportion of the inorganic refractory component are made, is with the dry weight of catalyst
Benchmark and in terms of oxide, the content of molybdenum oxide is 50.0 weight % in catalyst, and the content of cobalt oxide is 15 weight %, P2O5
Content is 8 weight %, and the content of inorganic refractory component is 27 weight %.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 106m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 1.7%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 84.0%, 100-300nm and accounts for
The ratio of total pore volume is 10.5%, total pore volume 0.37mL/g, average pore size 14.0nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 10.4ppm, nitrogen content 1.6ppm,
Aromatic hydrocarbons is 33.0%.
Embodiment 2
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
(1) by boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 320m2/ g, it is average
Aperture is 13nm, and the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is that the pore volume of 4-40nm accounts for
The ratio of total pore volume be 78%), amorphous silicon aluminium powder (SiO2Content be 15 weight %) be uniformly mixed, then at 600 DEG C
Lower roasting 5h obtains inorganic refractory component.
Wherein, on the basis of the dry weight of inorganic refractory component, the content of amorphous silica-alumina is 20.6 weight %, oxygen
The content for changing aluminium is 79.4 weight %.
(2) by a certain amount of MoO3, basic nickel carbonate, acetic acid be separately added into the aqueous solution of phosphoric acid, in heating stirring
Down toward being completely dissolved, the dipping solution containing active metal is obtained.
Wherein, quality of acetic acid is 15 weight % of inorganic refractory component.
(3) dipping solution is uniformly mixed with the inorganic refractory component, then by its extruded moulding.By at 150 DEG C
The oxidized catalyst that partial size is 1.6mm is prepared in lower dry 8h.
Wherein, dipping solution and the mixed proportion of the inorganic refractory component are made, is with the dry weight of catalyst
Benchmark and in terms of oxide, the content of molybdenum oxide is 45.0 weight % in catalyst, and the content of nickel oxide is 10 weight %, P2O5
Content is 4 weight %, and the content of inorganic refractory component is 41 weight %.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 105m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 1.2%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 82.1%, 100-300nm and accounts for
The ratio of total pore volume is 14.7%, total pore volume 0.40mL/g, average pore size 15.2nm.
For catalyst after over cure and reaction test, obtaining sulfur content in product is 8.9ppm, nitrogen content 0.8ppm, virtue
Hydrocarbon is 28.7%.
Embodiment 3
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
(1) by boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 320m2/ g, it is average
Aperture is 13nm, and the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is that the pore volume of 4-40nm accounts for
The ratio of total pore volume be 78%), Y type molecular sieve (be free of sodium, hydrogen type molecular sieve) be uniformly mixed, then roasted at 800 DEG C
3h obtains inorganic refractory component.
Wherein, on the basis of the dry weight of inorganic refractory component, the content of Y type molecular sieve is 10.4 weight %, oxidation
The content of aluminium is 89.6 weight %.
(2) by a certain amount of MoO3, basic nickel carbonate, ammonium metatungstate, tartaric acid be separately added into the aqueous solution of phosphoric acid,
In heating stirring down toward being completely dissolved, the dipping solution containing active metal is obtained.
Wherein, tartaric acid quality is 30 weight % of inorganic refractory component.
(3) dipping solution is uniformly mixed with the inorganic refractory component, then by its extruded moulding.By at 100 DEG C
The oxidized catalyst that partial size is 1.6mm is prepared in lower dry 8h.
Wherein, dipping solution and the mixed proportion of the inorganic refractory component are made, is with the dry weight of catalyst
Benchmark and in terms of oxide, the content of molybdenum oxide is 20.0 weight % in catalyst, and the content of nickel oxide is 4.0 weight %, oxygen
The content for changing tungsten is 15.0 weight %, P2O5Content is 6 weight %, and the content of inorganic refractory component is 55 weight %.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 93m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole body of pore volume Zhan of 2-4nm
It is total that the pore volume that long-pending ratio is 1.4%, 4-40nm accounts for the pore volume Zhan that the ratio of total pore volume is 82.9%, 100-300nm
The ratio of pore volume is 13.7%, total pore volume 0.36mL/g, average pore size 15.5nm.
For catalyst after over cure and reaction test, obtaining sulfur content in product is 9.1ppm, nitrogen content 1.0ppm, virtue
Hydrocarbon is 31.4%.
Embodiment 4
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
(1) by boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 320m2/ g, it is average
Aperture is 13nm, and the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is that the pore volume of 4-40nm accounts for
The ratio of total pore volume be 78%), Y type molecular sieve (be free of sodium, hydrogen type molecular sieve) be uniformly mixed, then roasted at 600 DEG C
2h obtains inorganic refractory component.
Wherein, on the basis of the dry weight of inorganic refractory component, the content of Y type molecular sieve is 5.3 weight %, aluminium oxide
Content be 94.7 weight %.
(2) by a certain amount of MoO3, basic nickel carbonate, benzoic acid be separately added into the aqueous solution of phosphoric acid, stirred in heating
It mixes down toward being completely dissolved, obtains the dipping solution containing active metal.
Wherein, benzoic acid Mass is 5.0 weight % of inorganic refractory component.
(3) dipping solution is uniformly mixed with the inorganic refractory component, then by its extruded moulding.By at 250 DEG C
The oxidized catalyst that partial size is 1.6mm is prepared in lower dry 2h.
Wherein, dipping solution and the mixed proportion of the inorganic refractory component are made, is with the dry weight of catalyst
Benchmark and in terms of oxide, the content of molybdenum oxide is 35.0 weight % in catalyst, and the content of nickel oxide is 3.0 weight %, P2O5
Content is 4.0 weight %, and the content of inorganic refractory component is 58.0 weight %.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 108m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 2.0%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 88.9%, 100-300nm and accounts for
The ratio of total pore volume is 8.3%, total pore volume 0.32mL/g, average pore size 11.9nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 13.2ppm, nitrogen content 3.9ppm,
Aromatic hydrocarbons is 36.2%.
Embodiment 5
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
(1) by boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 330m2/ g, it is average
Aperture is 12nm, and the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 14%, and aperture is that the pore volume of 4-40nm accounts for
The ratio of total pore volume be 82%), amorphous silicon aluminium powder (SiO2Content be 15 weight %) be uniformly mixed, then at 900 DEG C
Lower roasting 2h obtains inorganic refractory component.
Wherein, on the basis of the dry weight of inorganic refractory component, the content of amorphous silica-alumina is 21.3 weight %, oxygen
The content for changing aluminium is 78.7 weight %.
(2) by a certain amount of MoO3, basic cobaltous carbonate, caproic acid be separately added into the aqueous solution of phosphoric acid, in heating stirring
Down toward being completely dissolved, the dipping solution containing active metal is obtained.
Wherein, caproic acid quality is 10.5 weight % of inorganic refractory component.
(3) dipping solution is uniformly mixed with the inorganic refractory component, then by its extruded moulding.By at 200 DEG C
The oxidized catalyst that partial size is 1.6mm is prepared in lower dry 5h.
Wherein, dipping solution and the mixed proportion of the inorganic refractory component are made, is with the dry weight of catalyst
Benchmark and in terms of oxide, the content of molybdenum oxide is 40.0 weight % in catalyst, and the content of cobalt oxide is 8.0 weight %, P2O5
Content is 5.0 weight %, and the content of inorganic refractory component is 47.0 weight %.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 120m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 1.9%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 87.6%, 100-300nm and accounts for
The ratio of total pore volume is 8.8%, total pore volume 0.33mL/g, average pore size 11.0nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 12.9ppm, nitrogen content 3.6ppm,
Aromatic hydrocarbons is 36.0%.
Embodiment 6
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
The preparation of Hydrobon catalyst and vulcanization and the reaction test of catalyst are carried out according to the method for embodiment 1,
Unlike, the air containing 10 weight % vapor is passed through during step (1) roasts.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 103m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 1.5%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 82.9%, 100-300nm and accounts for
The ratio of total pore volume is 12.1%, total pore volume 0.41mL/g, average pore size 15.9nm.
For catalyst after over cure and reaction test, obtaining sulfur content in product is 9.7ppm, nitrogen content 1.2ppm, virtue
Hydrocarbon is 32.3%.
Embodiment 7
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
The preparation of Hydrobon catalyst and vulcanization and the reaction test of catalyst are carried out according to the method for embodiment 1,
Unlike, the water with 6 same volume of embodiment is added during step (1) mixes each component, is then roasted.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 116m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 2.0%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 86.9%, 100-300nm and accounts for
The ratio of total pore volume is 10.1%, total pore volume 0.36mL/g, average pore size 12.4nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 11.9ppm, nitrogen content 1.8ppm,
Aromatic hydrocarbons is 34.5%.
Embodiment 8
The present embodiment is for illustrating Hydrobon catalyst provided by the invention and preparation method thereof
The preparation of Hydrobon catalyst and vulcanization and the reaction test of catalyst are carried out according to the method for embodiment 1,
Unlike, in step (2), phosphoric acid is not used, by MoO3Ammonium heptamolybdate and cobalt nitrate are replaced with basic cobaltous carbonate.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 118m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 2.3%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 88.5%, 100-300nm and accounts for
The ratio of total pore volume is 6.7%, total pore volume 0.33mL/g, average pore size 11.2nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 13.5ppm, nitrogen content 4.2ppm,
Aromatic hydrocarbons is 36.7%.
Comparative example 1
This comparative example is for illustrating existing Hydrobon catalyst and preparation method thereof
By boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 320m2/ g, average pore size
For 13nm, the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is the total hole body of pore volume Zhan of 4-40nm
Long-pending ratio be 78%), amorphous silicon aluminium powder, sesbania powder according to a certain percentage after mixing, 130mL concentration, which is added, is
The aqueous solution of nitric acid of 1.5wt%, and it is again stirring for uniform extruded moulding.6h is roasted at 500 DEG C, is obtained containing amorphous silica-alumina
Alumina support.By the dipping solution prepared in embodiment 1 according to hole be saturated impregnation carrier, using aluminium oxide,
Amorphous silicon aluminium powder is identical with the dosage of metal component, and catalyst is prepared, and catalyst is dried at identical conditions.To urging
Agent is characterized using BET and mercury injection method, finds the duct that 100-300nm is free of in catalyst.Catalyst is through over cure and reaction
After test, obtaining sulfur content in product is 47.6ppm, nitrogen content 8.8ppm, aromatic hydrocarbons 46.1%.
Comparative example 2
This comparative example is for illustrating existing Hydrobon catalyst and preparation method thereof
By boehmite, (Chang Ling catalyst plant produces boehmite powder, specific surface area 320m2/ g, average pore size
For 13nm, the ratio that the pore volume that aperture is 2-4nm accounts for total pore volume is 10%, and aperture is the total hole body of pore volume Zhan of 4-40nm
Long-pending ratio be 78%), amorphous silicon aluminium powder, sesbania powder according to a certain percentage after mixing, 110mL concentration, which is added, is
The aqueous solution of nitric acid of 1.5wt%, and it is again stirring for uniform extruded moulding.3h is roasted at 600 DEG C, obtains alumina containing amorphous silicon
Change alumina supporter.The dipping solution prepared in embodiment 3 is saturated impregnation carrier according to hole, uses aluminium oxide, nothing
Amorphous silicon-alumina powder is identical with the dosage of metal component, and catalyst is prepared, and catalyst is dried at identical conditions.To catalysis
Agent is characterized using BET and mercury injection method, finds the duct that 100-300nm is free of in catalyst.Catalyst is surveyed through over cure and reaction
After examination, obtaining sulfur content in product is 40.6ppm, nitrogen content 9.3ppm, aromatic hydrocarbons 44.2%.
Comparative example 3
This comparative example is for illustrating Hydrobon catalyst of reference and preparation method thereof
The preparation of Hydrobon catalyst and vulcanization and the reaction test of catalyst are carried out according to the method for embodiment 1,
Unlike, in step (2), do not use citric acid.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 105m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 1.7%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 87.1%, 100-300nm and accounts for
The ratio of total pore volume is 5.6%, total pore volume 0.39mL/g, average pore size 14.9nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 23.8ppm, nitrogen content 11.4ppm,
Aromatic hydrocarbons is 41.2%.
Comparative example 4
This comparative example is for illustrating Hydrobon catalyst of reference and preparation method thereof
The preparation of Hydrobon catalyst and vulcanization and the reaction test of catalyst are carried out according to the method for embodiment 1,
Unlike, in step (1), do not use amorphous silicon aluminium powder.
Catalyst analyzes its pore-size distribution after 400 DEG C of roasting 3h, using low temperature nitrogen absorption and mercury injection method.Catalyst
Specific surface area is 109m2/ g, the aperture with 2-4nm, 4-40nm and 100-300nm, wherein the total hole pore volume Zhan of 2-4nm
The pore volume that the ratio of volume is 2.0%, 4-40nm accounts for the pore volume that the ratio of total pore volume is 84.3%, 100-300nm and accounts for
The ratio of total pore volume is 10.0%, total pore volume 0.36mL/g, average pore size 13.2nm.
For catalyst after over cure and reaction test, obtaining in product sulfur content is 12.5ppm, nitrogen content 2.4ppm,
Aromatic hydrocarbons is 34.4%.
From embodiment and comparative example as can be seen that method provided by the invention can be prepared with the aperture 100-300 point
The Hydrobon catalyst of cloth, and the catalyst provided has preferable performance, not only makes to be catalyzed compared with customary preparation methods
The performance of agent gets a promotion, and shortens catalyst preparation process, reduces catalyst preparation cost, has good industrial application
Prospect.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (21)
1. a kind of Hydrobon catalyst, which is characterized in that the catalyst contains inorganic refractory component, Investigation On Hydrodesulfurizationof of Catalysts Derived
Component and carboxylic acid；
Wherein, the inorganic refractory component contains amorphous silicon aluminium and/or molecular sieve and aluminium oxide；
The aperture in aperture and 100-300nm of the catalyst with 4-40nm, wherein pore volume Zhan of the aperture in 4-40nm is total
The pore volume of the 60-95% of pore volume, 100-300nm account for the 0.5-30% of total pore volume.
2. Hydrobon catalyst according to claim 1, wherein the Investigation On Hydrodesulfurizationof of Catalysts Derived group is divided into Section VIII
Race's metallic element and vib metals element, the group VIII metallic element are preferably selected from iron, cobalt, nickel, ruthenium, rhodium and palladium
At least one, the vib metals element is preferably selected from least one of chromium, molybdenum and tungsten；And in the hydrofinishing
In catalyst, on the basis of the dry weight of catalyst and in terms of oxide, the content of group VIII metallic element is 2-20 weight
Measure %, preferably 4-15 weight %；The content of vib metals element is 20-75 weight %, preferably 30-50 weight %.
3. Hydrobon catalyst according to claim 1 or 2, wherein pore volume Zhan total hole body of the aperture in 4-40nm
Long-pending 75-90%, aperture account for the 5-15% of total pore volume in the pore volume of 100-300nm；
Preferably, the catalyst is preformed catalyst, and the catalyst is preferably shaped to cylinder, cloverleaf pattern, four leaves
Careless shape or honeycombed；
Preferably, the specific surface area of the Hydrobon catalyst is 80-250m2/ g, total pore volume 0.2-0.8mL/g, it is average
Aperture is 10-30nm；
Preferably, the catalyst also has the aperture of 2-4nm, and the pore volume of 2-4nm is no more than the 3% of total pore volume.
4. Hydrobon catalyst described in any one of -3 according to claim 1, wherein dioxy in the amorphous silica-alumina
SiClx content is 5-30 weight %；The molecular sieve is hydrogen type molecular sieve, and the content of the sodium element in terms of sodium oxide molybdena is not higher than
0.5 weight %.
5. Hydrobon catalyst described in any one of -4 according to claim 1, wherein be with the dry weight of catalyst
Benchmark, the inorganic refractory constituent content are 5-75 weight %, preferably 25-60 weight %；
Preferably, on the basis of the dry weight of inorganic refractory component, the content of amorphous silicon aluminium and/or molecular sieve is 5-50 weight
Measure %, aluminium oxide surplus；
It is furthermore preferred that the content of amorphous silicon aluminium and/or molecular sieve is 10- on the basis of the dry weight of inorganic refractory component
30 weight %, aluminium oxide surplus.
6. the Hydrobon catalyst according to any one of claim 2-5, wherein with the inorganic refractory component
On the basis of dry weight, the content of the carboxylic acid is 3-40 weight %, preferably 10-30 weight %；
Preferably, the carboxylic acid is selected from the unitary saturated carboxylic acid of C1-18, the phenylic acid of C7-10, citric acid, adipic acid, the third two
At least one of acid, succinic acid, maleic acid and tartaric acid etc..
7. Hydrobon catalyst according to claim 1, wherein the Hydrobon catalyst also contains P elements,
On the basis of the dry weight of catalyst and with P2O5Meter, the content of the P elements are 0.8-10 weight %, preferably 1-8 weight
Measure %.
8. a kind of preparation method of Hydrobon catalyst, which is characterized in that this method comprises:
(1) amorphous silicon aluminium and/or molecular sieve and alumina precursor are mixed and is roasted, obtain inorganic refractory component；
(2) carboxylic acid and the presoma of Investigation On Hydrodesulfurizationof of Catalysts Derived component are mixed, obtains maceration extract；
(3) the inorganic refractory component and the maceration extract are mixed, obtained mixture is formed and dried, obtain described add
Hydrogen catalyst for refining.
9. according to the method described in claim 8, wherein, in step (2), the Investigation On Hydrodesulfurizationof of Catalysts Derived component presoma is
The presoma of group VIII metallic element and the presoma of vib metals element, the group VIII metallic element preferably select
From at least one of iron, cobalt, nickel, ruthenium, rhodium and palladium, the vib metals element is preferably selected from chromium, molybdenum and tungsten at least
It is a kind of；And the dosage of the presoma of the presoma and vib metals element of group VIII metallic element makes in described plus hydrogen
In catalyst for refining, on the basis of the dry weight of catalyst and in terms of oxide, the content of group VIII metallic element is 2-
20 weight %, preferably 4-15 weight %；The content of vib metals element is 20-75 weight %, preferably 30-50 weight
Measure %.
10. method according to claim 8 or claim 9, wherein dioxide-containing silica is 5-30 weight in the amorphous silica-alumina
Measure %；The molecular sieve is hydrogen type molecular sieve, and the content of the sodium element in terms of sodium oxide molybdena is not higher than 0.5 weight %.
11. the method according to any one of claim 8-10, wherein the dosage of the inorganic refractory component makes
In the Hydrobon catalyst, on the basis of the dry weight of the Hydrobon catalyst, the inorganic refractory component
Content is 5-75 weight %, preferably 25-60 weight %；
Preferably, the dosage of the amorphous silicon aluminium and/or molecular sieve and alumina precursor makes in the inorganic refractory
In component, on the basis of the dry weight of inorganic refractory component, the content of amorphous silicon aluminium and/or molecular sieve is 5-50 weight
Measure %, aluminium oxide surplus；
It is furthermore preferred that the dosage of the amorphous silicon aluminium and/or molecular sieve and alumina precursor makes described inorganic resistance to
In fiery component, on the basis of the dry weight of inorganic refractory component, the content of amorphous silicon aluminium and/or molecular sieve is 10-30 weight
Measure %, aluminium oxide surplus.
12. the method according to any one of claim 9-11, wherein in step (2), with the inorganic refractory group
On the basis of the dry weight divided, the dosage of the carboxylic acid is 3-40 weight %, preferably 10-30 weight %；
Preferably, the carboxylic acid is selected from the unitary saturated carboxylic acid of C1-18, the phenylic acid of C7-10, citric acid, adipic acid, the third two
At least one of acid, succinic acid, maleic acid and tartaric acid etc..
13. described according to the method described in claim 8, wherein, also contain phosphorus containg substances in the maceration extract that step (2) obtains
The dosage of phosphorus containg substances makes on the basis of the dry weight of the Hydrobon catalyst and with P2O5Meter, the P elements
Content is 0.8-10 weight %, preferably 1-8 weight %；
Preferably, the phosphorus containg substances are selected from least one of phosphoric acid, hypophosphorous acid, ammonium phosphate and ammonium dihydrogen phosphate.
14. according to the method described in claim 8, wherein, in step (1), the condition of the roasting includes: that the temperature of roasting is
400-1000 DEG C, preferably 500-800 DEG C；The time of roasting is 1-15h, preferably 3-8h.
15. according to the method described in claim 8, wherein, in step (3), the condition of the drying includes: that dry temperature is
50-250 DEG C, preferably 100-200 DEG C；The dry time is 2-10h, preferably 3-8h.
16. according to the method described in claim 8, wherein, the alumina precursor is boehmite；
Preferably, the average pore size of the boehmite is 5-20nm, and aperture is that the pore volume of 2-4nm accounts for the ratio of total pore volume
Example is not more than 15%, and the pore volume that aperture is 4-40nm accounts for the ratio of total pore volume not less than 75%.
17. according to the method described in claim 8, wherein, in step (1), the roasting carries out under the atmosphere of vapor.
18. the Hydrobon catalyst of the preparation of method described in any one of claim 8-17.
19. application of the Hydrobon catalyst in fraction oil hydrogenation refining described in any one of claim 1-7 and 18.
20. application according to claim 19, wherein the sulfur content in the distillate is 5000-30000ppm, and nitrogen contains
Amount is 50-3000ppm, and arene content is 20-80 weight %.
21. a kind of hydrofinishing process of distillate, which is characterized in that this method comprises: by any in claim 1-7 and 18
Hydrobon catalyst described in one is vulcanized, and hydrogen sweetened distillate oil to be added is then passed to, and makes hydrogen sweetened distillate oil to be added
It is contacted under hydrodesulfurizationconditions conditions with the vulcanization back end hydrogenation catalyst for refining.
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| Title |
|---|
| 赵鹏泽等: "大孔介孔氧化铝的制备及加氢性能研究", 《应用化工》 * |
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|---|---|
| CN109718817B (en) | 2020-07-28 |
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