CN105854929B - A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents
A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil Download PDFInfo
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Abstract
The invention discloses the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof He desulfurization of hydrocarbon oil.On the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst contains：1) 5 35 weight % heat-resistant inorganic oxide；2) 10 70 weight % metal oxide；3) 2 40 weight % silicon nitride；4) 3 30 weight % metallic promoter agent；5) rare-earth oxide of the 0.5 10 weight % in terms of rare earth oxide；And 6) the 1 20 weight % molecular sieve with BEA or FAU structures.The desulfurization of hydrocarbon oil catalyst has more preferable stability and Geng Gao's desulphurizing activated, and more preferable abrasion resistance properties, service life is longer.
Description
Technical field
The present invention relates to the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof He desulfurization of hydrocarbon oil, in particular it relates to
A kind of desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst for preparing the method for desulfurization of hydrocarbon oil catalyst and being obtained by this method, with
And the method that desulfurization of hydrocarbon oil is carried out using the desulfurization of hydrocarbon oil catalyst.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, can suppress the precious metal catalyst in vehicle exhaust converter
The activity of agent simultaneously can be allowed to occur irreversibly to be poisoned.So that the oxygen containing unburned non-methane hydrocarbon and nitrogen in vehicle exhaust
Compound and carbon monoxide, and these discharge gas are then easily formed photochemical fog by hydrophilic dye, trigger acid rain, while in air
Oxysulfide be also the one of the main reasons to form acid rain in itself.With pay attention to day by day of the people to environmental protection, environmental law
Rule are also increasingly strict, and the sulfur content for reducing gasoline and diesel oil is considered as to improve one of most important measure of air quality.
The existing gasoline products standard GB 17930-2011 of China《Motor petrol》It is required that on December 31st, 2013, vapour
Sulfur content must drop to 50 μ g/g in oil；And future, gasoline quality standard can be stricter.In this case, catalysis is split
Change gasoline, which has to pass through deep desulfuration, can just meet the requirement of environmental protection.
At present, the process for deep desulphurization of oil product mainly have hydrofinishing and absorption two methods of desulfurization, but China due to
The problem of hydrogen source, make it that the cost of hydrofinishing is higher.S Zorb absorption desulfurization, which belongs to, faces hydrogen desulfurization technology, certain
The adsorbing and removing of sulfide is realized under the conditions of temperature and pressure.Because sulfur-containing compound of the technology in removing gasoline has hydrogen
The characteristics of consuming low, and it is not high to the purity requirement of hydrogen so that have in terms of sulfur-containing compound of the technology in removing fuel oil
Have broad application prospects.
Traditionally from liquid desulfurization often use fixed bed method, but this method reaction uniformity and regeneration have
Obvious inferior position.Compared with fixed-bed process fluidized-bed process have the advantages that preferably heat transfer and pressure drop in terms of, therefore tool
Have broad application prospects.Fluidized-bed reactor typically uses granular reactant, but for most of reactions, reaction used
The typically no enough wearabilities of thing.Therefore, anti-wear performance is found well while the adsorbent for having preferable desulfurization performance has important
Meaning.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Thing, is made up of zinc oxide, silica, oxidation al and ni, and wherein nickel is substantially to reduce valence state presence, and its amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the nickeliferous adsorbent composition.Said composition is led to
Cross and be granulated to form particle by the compound particles of zinc oxide, silica and aluminum oxide formation, nickel or nickeliferous chemical combination are used after dry, roasting
Thing is impregnated, and re-dry, roasting, reduction are obtained.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Thing, is made up of zinc oxide, silica, aluminum oxide and cobalt, and wherein cobalt is substantially to reduce valence state presence, and its amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the adsorbent composition containing cobalt.CN1355727A
Be all only referred in CN1382071A it is desulphurizing activated, for adsorbent physical and chemical performance (such as abrasion strength resistance) and stability is all
Do not introduce.
Adsorbent is disclosed in US6150300, CN1130253C and CN1258396C：Include zinc oxide, silica, oxidation
The granular adsorbent composition of the mixture of aluminium, reduction valence state nickel or cobalt.Preparation method mainly will using methods such as shearings
Silica, aluminum oxide and zinc oxide, which mix merga pass comminutor and prepared, to be impregnated nickel to be made after solid particle, drying and roasting
Adsorbent.Although the adsorbent of these patent introductions has preferable desulfurization performance, for its physical and chemical performance, mainly wear and tear
Intensity is not described in the patent.
CN1208124C is disclosed includes zinc oxide, expanded perlite and oxidation using promoter metals such as cobalt and nickel dipping
The adsorbing agent carrier of aluminium, then reduces the accelerator at appropriate temperatures, prepares the suction for removing sulfide in cracking gasoline
Attached dose.
CN1627988A discloses one kind and is suitable for removing elementary sulfur and vulcanization conjunction from cracking gasoline and diesel fuel
The adsorbent composition of thing, the adsorbent composition is included：Zinc oxide, expanded perlite, aluminate and promoter metals, its
Described in promoter metals will cause from cracking when making cracking gasoline or diesel fuel stream is contacted under desulfurization conditions with it
The amount of desulfurization in the stream of gasoline or diesel fuel is present, and at least partly described promoter metals exist with 0 valence state.
CN1856359A discloses a kind of method for producing composition, including：A) mixing liquid, zinc compound, containing two
Silica material, aluminum oxide and co-catalyst, to form its mixture；B) mixture is dried, to be formed through dry mixing
Thing；C) this is calcined through dry mixture, to form the mixture through calcining；D) with appropriate reducing agent under suitable condition
By the mixture reduction through calcining, to produce the composition of the co-catalyst content in it with reduction valence state, and e)
Reclaim reorganization compound.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, and this method includes：A) by liquid, zinc compound,
Mix to form its mixture containing earth silicon material, aluminum oxide；B) mixture is dried the mixing to form first
Through drying composite；C) described first is calcined to form first through calcining mixt through drying composite；D) accelerator is tied
Close described first through within calcining mixt or on to form promoted mixture；E) the promoted mixture and choosing are made
Contacted from the acid of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) by it is described through contact mixture drying with
Second is formed through drying composite；G) described second is calcined to form second through calcining mixt through drying composite；H) exist
Suitable reducing agent reduction described second is used wherein to promote through calcining mixt to produce containing reduction valence state under conditions of appropriate
Enter the composition of agent content, and i) the recovery composition.
CN101816918A discloses a kind of desulfuration adsorbent, the adsorbent composition for alkali metal, aluminum oxide, silica,
Accelerator and the adsorbent of one or more of metal oxides selected from IIB, VB and VIB.The adsorbent has preferably resistance to
Tear strength and desulphurizing activated.
Although adsorbent prepared by these methods has preferable desulfurization performance, there is also obvious shortcoming.Above-mentioned suction
Attached dose uses zinc oxide active component, and the temperature of oxidation zinc-iron alloy solution sulphur and oxidation regeneration is higher, in desulphurization reaction and
Zinc silicate and zinc aluminate easily are generated with the sial component in carrier during oxidation regeneration, causes adsorbent activity to reduce.Thus may be used
See, it is desirable to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.
The content of the invention
The invention aims to overcome the desulphurizing activated low, structural instability of the adsorbent of prior art and wear resistance
There is provided the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof He desulfurization of hydrocarbon oil for defect that can be poor.
To achieve these goals, the present invention provides a kind of desulfurization of hydrocarbon oil catalyst, with the total of the desulfurization of hydrocarbon oil catalyst
On the basis of weight, the desulfurization of hydrocarbon oil catalyst contains：1) 5-35 weight % heat-resistant inorganic oxide, the heat resistant inorganic oxidation
Thing is selected from least one of aluminum oxide, titanium dioxide, zirconium dioxide and tin ash；2) 10-70 weight % metal oxidation
Thing, the metal oxide is selected from least one of metal oxide of IIB, VB and group vib element；3) 2-40 weight %
Silicon nitride；4) 3-30 weight % metallic promoter agent, the metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese；5)
The rare-earth oxide of 0.5-10 weight % in terms of rare earth oxide；6) 1-20 weight %'s there is BEA and/or FAU to tie
The molecular sieve of structure.
Present invention also offers a kind of method for preparing the desulfurization of hydrocarbon oil catalyst that the present invention is provided, this method includes：(1)
Heat-resistant inorganic oxide binding agent, silicon nitride, metal oxide, rare earth compound, water and acidic liquid are mixed to get
Mixed serum, then contact to form carrier pulp with the molecular sieve with BEA and/or FAU structures；The carrier pulp is carried out into
Type, first are dried and the first roasting, obtain carrier；(2) to the precursor of introducing metallic promoter agent on the carrier, and second is carried out
Dry and the second roasting, obtain catalyst precarsor；(3) catalyst precarsor is reduced under hydrogen atmosphere, obtains hydrocarbon ils
Desulphurization catalyst.
The present invention also provides the desulfurization of hydrocarbon oil catalyst that method provided by the present invention is prepared.
Present invention also offers a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur with
The desulfurization of hydrocarbon oil catalyst contact that the present invention is provided, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-
4MPa。
Containing stable silicon nitride in the composition for the desulfurization of hydrocarbon oil catalyst that the present invention is provided, reduce and the gold such as zinc oxide
Belong to the dependent interaction of oxide, it is to avoid the formation of silicic acid zinc material, the desulfurization of hydrocarbon oil for the acquisition of embodiment 1 that such as Fig. 1 show
The characteristic peak of zinc silicate is not present in XRD spectra after catalyst A1 hydrothermal aging.The desulfurization of hydrocarbon oil catalysis that the present invention is provided
Agent has more preferable stability and Geng Gao's desulphurizing activated, more effectively can inhale the sulphur in hydrocarbon ils during desulfurization of hydrocarbon oil
It is attached on desulfurization of hydrocarbon oil catalyst, obtains the lower hydrocarbon ils of sulfur content.And the desulfurization of hydrocarbon oil catalyst that the present invention is provided has
Catalyst attrition is lower in more preferable abrasion resistance properties, sweetening process, and service life is longer.
Contain rare earth oxide in the desulfurization of hydrocarbon oil catalyst that the present invention is provided, active metal oxidation can be efficiently reduced
The effect of sial component in thing and carrier, reduces generation silicate and aluminate, so that the desulfurization of hydrocarbon oil catalyst can be
Sulphur is absorbed under lower temperature and through reaction and regenerative process is repeated, still with preferably desulphurizing activated and activity stabilized
Property.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is XRD spectrums of the obtained desulfurization of hydrocarbon oil catalyst A1 of embodiment 1 before and after hydrothermal aging；
Fig. 2 is XRD spectrums of the obtained desulfurization of hydrocarbon oil catalyst B1 of comparative example 1 before and after hydrothermal aging.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the hydrocarbon ils
Desulphurization catalyst contains：1) 5-35 weight % heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from aluminum oxide, dioxy
Change at least one of titanium, zirconium dioxide and tin ash；2) 10-70 weight % metal oxide, the metal oxide
At least one of metal oxide selected from IIB, VB and group vib element；3) 2-40 weight % silicon nitride；4) 3-30 weights
% metallic promoter agent is measured, the metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese；5) in terms of rare earth oxide
0.5-10 weight % rare-earth oxide；6) the 1-20 weight % molecular sieve with BEA and/or FAU structures.
Preferably, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the content of the heat-resistant inorganic oxide is 10-
25 weight %, the content of the metal oxide is 25-60 weight %, and the content of the silicon nitride is 5-25 weight %, described
The content of metallic promoter agent is 10-20 weight %, and the content that the rare-earth oxide is counted using rare earth oxide is heavy as 1-5
% is measured, the content of the molecular sieve is 2-10 weight %.
According to the present invention, silicon nitride is white powder, and silicon nitride can be α phase silicon nitrides and/or beta phase silicon nitride, preferably
In the case of, silicon nitride is α phase silicon nitrides.The particle diameter of alpha-silicon nitride powders can be preferably (i.e. 6.5-25 μ between 2000-500 mesh
m)。
The desulfurization of hydrocarbon oil catalyst that the present invention is provided contains silicon nitride, can be effectively prevented from carrying out desulfurization of hydrocarbon oil process
In the catalyst composition in form zinc silicate, it is ensured that the catalyst have preferably it is desulphurizing activated.Preferably, the desulfurization of hydrocarbon oil
There is no the characteristic peak of zinc silicate at 2 θ is 22.0,25.54,48.9 and 59.4 in XRD spectra of the catalyst after hydrothermal aging.
The hydrothermal aging is that 500-700 DEG C of temperature, steam partial pressure are 10-30kPa, and processing time is 10-24h.
According to the present invention, the metal oxide is the metal oxide with storage sulphur performance, it is preferable that the metal oxygen
Compound is at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide；More
Preferably, the metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；Most preferably described metal oxide
For zinc oxide.
According to the present invention, the heat-resistant inorganic oxide can be offer between each component in the desulfurization of hydrocarbon oil catalyst
Cementation.The heat-resistant inorganic oxide in aluminum oxide, titanium dioxide, zirconium dioxide and tin ash at least one
Kind.Wherein, the aluminum oxide can be at least one of gama-alumina, η-aluminum oxide, θ-aluminum oxide and χ-aluminum oxide；It is excellent
Selection of land, the aluminum oxide is gama-alumina；The titanium dioxide can be anatase titanium dioxide.
According to the present invention, oxidation state sulphur can be reduced to the metal of hydrogen sulfide by the metallic promoter agent to be any,
Preferably, the metallic promoter agent can be nickel.
According to the present invention, the rare-earth oxide can stablize the skeleton of heat-resistant inorganic oxide, reduce metal oxygen
Compound and silicon, the effect of aluminium component in carrier, reduce generation silicate and aluminate, improve the activity and stability of desulfurization.It is excellent
Selection of land, the rare-earth oxide is at least one of oxide of lanthanum, cerium and neodymium.
In the present invention, the FAU structure molecular screens are faujasite-type molecular sieve.The type molecular sieve has three-dimensional 12
Membered ring channel, aperture isFAU structure molecular screens are mainly the molecular sieve of X-type and Y types, in general SiO2：
Al2O3Mol ratio is 2.2-3.0 for X-type molecular sieve, SiO2：Al2O3Mol ratio be more than 3.0 for Y type molecular sieve.X-type and Y types
The skeleton structure of molecular sieve belongs to hexagonal crystal system, and space group structure is Fd3m, the cell parameter of X-type molecular sieveThe cell parameter of Y type molecular sieve
In the present invention, the molecular sieve with FAU structures also includes this modified molecular sieve analog.Modified method can be wrapped
Include hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC14Vapor phase method) or hydro-thermal and change
Processing is combined, and the modified molecular sieve that obtains includes but is not limited to super-stable Y molecular sieves (USY), contains rare earth element
REUSY, REHY, REY, and phosphorous PUSY, PREHY, PREY etc..Rare earth can be carbonate, the bicarbonate of rare earth metal
At least one of salt, nitrate, chloride, formates and acetate；Preferably, the rare earth compound can be dilute
At least one of carbonate, bicarbonate, formates and acetate of earth metal.Wherein, the rare earth metal be preferably lanthanum,
At least one of cerium and neodymium.The SiO of the molecular sieve with FAU structures2：Al2O3Mol ratio be 2.6-10：1；It is preferred that
Ground, the SiO of the molecular sieve with FAU structures2：Al2O3Mol ratio be 2.8-9：1.
In the present invention, BEA structure molecular screens are mainly beta-molecular sieve, and its structural formula is (Nan[AlnSi64-nO128], n<7),
It is two structures differences but the polymorph A and B that are closely related mixed crystal, both with twelve-ring 3 D pore canal system：
Polymorph A a pair of enantiomers of formation, space group is P4122 and P4322, and cell parameter isMultiform
Body B belongs to achirality space group C2/c, cell parameterβ=114.5 °.BEA
Twelve-ring pore size is in structure molecular screen<100 directions>With<001 direction>.It is described
The SiO of molecular sieve with BEA structures2：Al2O3Mol ratio be 10-50：1；Preferably, the molecule with BEA structures
The SiO of sieve2：Al2O3Mol ratio be 15-30：1.
, according to the invention it is preferred in the case of, the molecular sieve with FAU and/or BEA structures is X-type molecular sieve, Y types
At least one of molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
In the present invention, the work of gasoline products octane number can be improved by adding the molecular sieve with FAU and/or BEA structures
With or effect.
Present invention also offers a kind of method for preparing the desulfurization of hydrocarbon oil catalyst that the present invention is provided, this method includes：(1)
Heat-resistant inorganic oxide binding agent, silicon nitride, metal oxide, rare earth compound, water and acidic liquid are mixed to get
Mixed serum, then contact to form carrier pulp with the molecular sieve with BEA and/or FAU structures；The carrier pulp is carried out into
Type, first are dried and the first roasting, obtain carrier；(2) to the precursor of introducing metallic promoter agent on the carrier, and second is carried out
Dry and the second roasting, obtain catalyst precarsor；(3) catalyst precarsor is reduced under hydrogen atmosphere, obtains hydrocarbon ils
Desulphurization catalyst.
In the present invention, under preferable case, the rare earth compound can be carbonate, the bicarbonate of rare earth metal
At least one of salt, nitrate, chloride, formates and acetate；Preferably, the rare earth compound can be dilute
At least one of carbonate, bicarbonate, formates and acetate of earth metal.Wherein, the rare earth metal be preferably lanthanum,
At least one of cerium and neodymium.
In the present invention, under preferable case, the heat-resistant inorganic oxide binding agent can for heat-resistant inorganic oxide or
It can be changed into the material of heat-resistant inorganic oxide under conditions of being calcined described first.Preferably, the heat resistant inorganic oxidation
Thing binding agent is alumina binder and non-al binder, and non-al binder can include zirconium dioxide binding agent, titanium dioxide
At least one of binding agent and tin ash binding agent.It is highly preferred that the alumina binder can be hydrated alumina
And/or Alumina gel, wherein, the hydrated alumina is selected from boehmite (boehmite), false boehmite and (intends thin water aluminium
Stone), at least one of hibbsite and amorphous hydroted alumina；The zirconium dioxide binding agent can be tetrachloro
At least one of zirconium, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide；The tin ash binding agent
Can be at least one of butter of tin, four isopropanol tin, tin acetate, aqua oxidation tin and tin ash；The titanium dioxide
Titanium binding agent can be titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and Detitanium-ore-type titanium dioxide
At least one of titanium.
In the present invention, the precursor of the metallic promoter agent can be that can be changed into gold under conditions of being calcined described second
Belong to the material of the oxide of accelerator.Under preferable case, the precursor of the metallic promoter agent can be the acetic acid of metallic promoter agent
At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.
In the present invention, the metal oxide, silicon nitride and molecular sieve with FAU and/or BEA structures as above institute
State, will not be repeated here.
The content of each component is calculated according to inventory in desulfurization of hydrocarbon oil catalyst made from method provided by the present invention
Go out.
The step of preparation method for the desulfurization of hydrocarbon oil catalyst that the present invention is provided (1), is used to prepare carrier.
The process mixed described in the preparation method step (1) for the desulfurization of hydrocarbon oil catalyst that the present invention is provided can be to nitridation
The addition opportunity of silicon, there is no particular limitation, and a kind of embodiment is：The process of step (1) described mixing includes：(i) will
Heat-resistant inorganic oxide binding agent, silicon nitride, water and acidic liquid contact to form mixture：(ii) by rare earth metal chemical combination
Thing, metal oxide and water mixing, and contacted with the mixture and obtain mixed serum.
Another embodiment is：The process of step (1) described mixing includes：(a) heat-resistant inorganic oxide is glued
Knot agent, water and acidic liquid contact to form mixture：(b) silicon nitride, metal oxide, rare earth compound and water are mixed
Close, and contacted with the mixture and obtain mixed serum.
In the present invention, the charged material weight ratio of the silicon nitride and the heat-resistant inorganic oxide binding agent is 0.4-2:1, it is excellent
Elect 0.6-1.5 as:1, it is possible thereby to provide the desulfurization of hydrocarbon oil catalyst with the caking property between more preferable each component.
In the present invention, the addition of the metal oxide can be oxide powder form or aoxidize metal
Thing is prepared as using as a slurry again after slurries.
In the present invention, the solid content of mixture described in step (1) can be 15-30 weight %.
In the present invention, the acidic liquid is acid or the aqueous solution of acid, and the acid can be selected from water-soluble inorganic acid
And/or organic acid, can be for example at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.In step (i) and (a), preferably
In the case of, the consumption of the acidic liquid makes the pH value of the mixture be 1-5, preferably 1.5-4.Wherein, when described heat-resisting
When inorganic oxide binder is non-al binder, the mixture of formation is colloidal sol；When the heat-resistant inorganic oxide binding agent
During for alumina binder, the mixture of formation is slurries.
In the present invention, step (i) and (a) middle amount for adding water can be not specially limited, as long as can obtain described mixed
Compound.For example add water amount and heat-resistant inorganic oxide binding agent or with heat-resistant inorganic oxide binding agent and nitrogen
The weight ratio of the weight summation of SiClx is 5-10:1.
In the present invention, described in step (1) shaping the carrier pulp can be shaped to extrudate, piece, pill, ball or
Micro-spherical particle.For example, when the carrier pulp is dough or paste mixture, the mixture shaping can be made (preferably to squeeze
Go out shaping) particle is formed, preferably diameter is in 1-8mm, and then length done extrudate in 2-5mm cylindrical extrudates
Dry, roasting.It if gained mixture is wet mixture form, can be thickened the mixture, by drying aftershaping.More preferably carry
Somaplasm liquid is slurry form, forms the microballoon that granularity is 20-200 microns by spray drying, reaches the purpose of shaping.In order to just
In spray drying, the solid content of the carrier pulp is 10-40 weight %, preferably 20-35 weight % before drying.In step
(1) obtain to include adding water during the carrier pulp in, there is no particular limitation for the addition of water, as long as
To carrier pulp meet above-mentioned solid content.
In the present invention, described first dries and the condition of the first roasting can be with known to those skilled in the art, preferably
In the case of, the described first temperature dried is 80-150 DEG C, and the described first time dried was 0.5-24h；First roasting
Temperature be 300-700 DEG C, it is described first roasting time be at least 0.5h.Preferably, the temperature of first roasting is
400-500 DEG C, the time of first roasting is 0.5-100h, and the time of more preferably described first roasting is 0.5-10h.
According to the present invention, step (2) is used to add metallic promoter agent.The precursor of the metallic promoter agent is can be second
It is changed into the material of the oxide of metallic promoter agent under roasting condition；Under preferable case, the precursor of the metallic promoter agent can be with
At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide selected from metallic promoter agent.
, according to the invention it is preferred in the case of, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitation.
The dipping can be the solution or suspension impregnation carrier of the precursor with metallic promoter agent；The precipitation can be to promote metal
The solution or suspension for entering the precursor of agent are mixed with carrier, then add ammoniacal liquor by the precursor precipitation of metallic promoter agent in carrier
On.
In the present invention, described second dries and the condition of the second roasting can be with known to those skilled in the art, preferably
In the case of, the described second temperature dried is 50-300 DEG C, and the described second time dried was 0.5-8h；Second roasting
Temperature is 300-700 DEG C, and the time of second roasting is 0.5-4h；Preferably, the described second temperature dried is 100-250
DEG C, the described second time dried was 1-5h；The temperature of second roasting is 400-500 DEG C, the time of second roasting
For 1-3h.Second roasting can be in the lower progress with the presence of oxygen or oxygen-containing gas, until volatile materials is removed simultaneously
And metallic promoter agent is converted into the form of metal oxide, obtains catalyst precarsor.
According to the present invention, in step (3), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal
Simple substance, the catalyst precarsor can be reduced, metallic promoter agent is substantially deposited with reduction-state under hydrogen atmosphere
Obtaining catalyst of the present invention.The condition of the reduction only turns the oxide of the metallic promoter agent in the catalyst precarsor
It is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is 300-
600 DEG C, time of the reduction is that hydrogen content is 10-60 volumes % in 0.5-6h, the hydrogen atmosphere；Preferably, institute
The temperature for stating reduction is 350-450 DEG C, and the time of the reduction is 1-3h.
In the present invention, step (3) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also
Carried out before use (before i.e. for desulfurization absorption).Because metallic promoter agent is easily aoxidized, and the metal in catalyst precarsor promotees
Enter agent in the form of an oxide to exist, therefore for ease of transport, catalyst precarsor is reduced and is carrying out desulfurization absorption by preferred steps (3)
It is preceding to carry out.The metal for being reduced to make in the oxide of metallic promoter agent substantially exists with reduction-state, obtains the present invention's
Desulfurization of hydrocarbon oil catalyst.
According to the preparation method that provides of the present invention, the heat-resistant inorganic oxide binding agent, the precursor of metal oxide,
Silicon nitride, rare earth compound, the addition of the precursor of the molecular sieve with FAU and/or BEA structures and metallic promoter agent
Amount so that in obtained desulfurization of hydrocarbon oil catalyst, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, contain 5-35 weight %
Heat-resistant inorganic oxide, 10-70 weight % metal oxide, 2-40 weight % silicon nitride, 3-30 weight % metal
Accelerator, the rare-earth oxide of 0.5-10 weight % in terms of rare earth oxide and 1-20 weight % have FAU and/
Or the molecular sieve of BEA structures.
Preferably, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the content of the heat-resistant inorganic oxide is 10-
25 weight %, the content of the metal oxide is 25-60 weight %, and the content of the silicon nitride is 5-25 weight %, described
The content of metallic promoter agent is 10-20 weight %, and the content that the rare-earth oxide is counted using rare earth oxide is heavy as 1-5
% is measured, the content of the molecular sieve with FAU and/or BEA structures is 2-10 weight %.
The present invention also provides the desulfurization of hydrocarbon oil catalyst that method provided by the present invention is prepared.
The invention provides a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and this
The desulfurization of hydrocarbon oil catalyst contact that invention is provided, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5-
4MPa；Preferably, the temperature of the contact is 400-450 DEG C, and the pressure of the contact is 1-2MPa.In the process in hydrocarbon ils
Sulphur be adsorbed on catalyst, so as to obtain the hydrocarbon ils of low sulfur content.
The method for the desulfurization of hydrocarbon oil that the present invention is provided preferably is carried out in a fluidized bed reactor, i.e., described contact is preferably in stream
Carried out in fluidized bed reactor.
In the present invention, reacted catalyst can be reused after regeneration.The regeneration is carried out under oxygen atmosphere,
The condition of regeneration includes：The pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C, preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before desulfurization of hydrocarbon oil is re-started, in addition it is also necessary to reduced under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes：Temperature is 350-500 DEG C, preferably 400-450 DEG C；Pressure is 0.2-2MPa,
Preferably 0.2-1.5MPa.
In the present invention, the hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " means that boiling range is 40
It is from making larger hydrocarbon molecule be cracked into heat or catalytic process compared with small molecule DEG C to 210 DEG C of hydrocarbon or its any cut
Product.The example of applicable catalytic cracking process includes but is not limited to fluid catalystic cracking and RFCC etc. and its group
Close.Therefore, applicable catalytically cracked gasoline includes but is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid bed
Catalytically cracked gasoline and heavy oil cracked gasoline and combinations thereof.In some cases, in the methods of the invention as hydrocarbon-containifluids fluids when
The cracking gasoline can be fractionated and/or hydrotreating before desulfurization.
Term used herein " diesel fuel " mean the hydrocarbon mixture that boiling range is 170 DEG C to 450 DEG C or its any evaporate
The liquid being grouped.Such hydrocarbon-containifluids fluids include but is not limited to light cycle oil, kerosene, straight-run diesel oil and hydroprocessed diesel etc. and
It is combined.
Term used herein " sulphur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine combustion
The organosulfur compound being commonly present in material.Sulphur present in hydrocarbon-containifluids fluids of the present invention includes but is not limited to carbonyl sulfide (COS), two
Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially including thiophene, benzothiophene, alkylthrophene,
The bigger thiophene-based chemical combination of the molecular weight that is commonly present in alkyl benzothiophenes and methyldibenzothiophene, and diesel fuel
Thing.
Containing nitridation silicon components in the composition for the desulfurization of hydrocarbon oil catalyst that the present invention is provided, the component is in the multiple of catalyst
Reaction and regenerative process in be difficult with the zinc oxide component effect of reacting, will not produce silicic acid zinc material urges the desulfurization of hydrocarbon oil
Agent reduces desulphurizing activated because losing zinc oxide.Catalyst of the present invention have it is very high desulphurizing activated, while also having obvious
Increase catalyst abrasion strength resistance property, be applicable to the reaction repeatedly and regeneration of catalytically cracked gasoline or diesel fuel
Sweetening process.
The present invention will be described in detail by way of examples below.
The desulfurization of hydrocarbon oil catalyst that embodiment and comparative example are obtained uses X-ray diffractometer (Siemens companies D5005 types)
XRD spectra is obtained, structure determination, Cu targets, K α radiation, solid probe, tube voltage 40kV, tube current 40mA is carried out.
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst is calculated according to feeding intake.
Embodiment 1
The present embodiment is used for the method for preparing desulfurization of hydrocarbon oil catalyst for illustrating the present invention.
(1) carrier is prepared.By 3.14kg zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure), 2.45kg silicon nitride
(purity>99.0%, the promise new high-tech material development corporation, Ltd. of Qinhuangdao one) and 430g lanthanum carbonate (traditional Chinese medicines chemical reagents corporation,
The weight % of lanthanum oxide content 45) it is mixed evenly in 8.5kg water, obtain containing zinc oxide, silicon nitride and lanthana
Mixed serum；
By 2.40kg boehmite (catalyst Nanjing branch company, containing butt 1.80kg) and 7.0kg deionized water
It is well mixed under agitation, stirring makes pH=1.8 to addition 200g concentrated nitric acid (Beijing Chemical Plant, chemistry is pure), and is warming up to 60
1h is acidified more than DEG C.When temperature is reduced to below 40 DEG C, above-mentioned mixed serum and 1.0kg beta-molecular sieve (catalyst are added
Nanjing branch company, 0.70kg containing butt, SiO2:Al2O3Mol ratio=20：1) carrier pulp is obtained after, stirring 1h after mixing；
The carrier pulp is used into Niro Bowen Nozzle TowerTMIt is dry that the spray dryer of model carries out spraying
Dry, spray drying pressure is that outlet temperature is about 150 DEG C below 8.5 to 9.5MPa, 500 DEG C of inlet temperature.By being spray-dried
The microballoon arrived first dries 1h at 150 DEG C, and 1h is then calcined at 480 DEG C obtains carrier；
(2) it is divided to two with the aqueous solution of the deionization formation of 7.0kg Nickelous nitrate hexahydrate and 1.10kg by 6.4kg carrier
Secondary dipping, obtained mixture is followed by calcined 1h by 150 DEG C of dry 4h at 480 DEG C, obtains catalyst precarsor；
(3) reduce.By catalyst precarsor in hydrogen atmosphere reductase 12 h at 425 DEG C, obtain desulfurization of hydrocarbon oil catalyst A1.
A1 chemical composition is：Zinc oxide content is 31.0 weight %, and silicon nitride content is 24.0 weight %, and aluminum oxide contains
Measure as 18.0 weight %, the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weights
Measure %.
Embodiment 2
The present embodiment is used for the method for preparing desulfurization of hydrocarbon oil catalyst for illustrating the present invention.
By 4.85kg Zinc oxide powder (Beijing Chemical Plant produces, containing butt 4.8kg), 0.60kg alpha-silicon nitride powders
(purity>99.0%, the promise new high-tech material development corporation, Ltd. of Qinhuangdao one) and 1.261kg cerous nitrate (traditional Chinese medicines chemical reagent is public
Department, purity is more than 99.0 weight %) mixed in 7.1kg deionized water, stirring is obtained after 30 minutes containing zinc oxide, nitridation
The slurries of silicon and cerous nitrate；
4.30kg zirconium chloride (Beijing Chemical Plant is analyzed pure) is slowly added into the 4.9kg weight % of concentration 5 nitre
Make pH=2.0 in acid solution, and be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；
By beta-molecular sieve (the catalyst Nanjing branch company, 0.3kg containing butt, SiO of above-mentioned slurries, zirconium colloidal sol and 0.43kg2:
Al2O3Mol ratio=40：1) it is mixed together stirring 1h and obtains carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A2.
A2 chemical composition is：Zinc oxide content is 48.0 weight %, and silicon nitride content is 6.0 weight %, zirconium dioxide
Content is 25.0 weight %, and beta-molecular sieve content is 3.0 weight %, and nickel content is 15.0 weight %, and cerium-oxide contents are 3.0 weights
Measure %.
Embodiment 3
The present embodiment is used for the method for preparing desulfurization of hydrocarbon oil catalyst for illustrating the present invention.
By the silicon nitride (purity of 4.86kg Zinc oxide powder, 0.6kg>99.0%, the exploitation of the promise new high-tech material of Qinhuangdao one
Co., Ltd) and 400g lanthana (traditional Chinese medicines chemical reagents corporation, analyze pure) mixed in 5kg deionized water, stirring 30
The slurries containing zinc oxide, silicon nitride and lanthana are obtained after minute；
3.3kg hydrated alumina (catalyst Nanjing branch company, containing butt 2.5kg) and 12.5kg deionized water are existed
After stirring is lower well mixed, adding 230g concentrated nitric acid stirring makes pH=1.8 and is warming up to more than 60 DEG C to be acidified 1h.Treat that temperature drops
It is low to less than 40 DEG C when, the diatomite and 0.6kg USY molecular sieve (catalyst Nanjing point public affairs added after above-mentioned slurries, processing
Department, 0.5kg containing butt, SiO2:Al2O3Mol ratio=8.5：1) mix, carrier pulp is obtained after stirring 1h.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A3.
A3 chemical composition is：Zinc oxide content is 48.0 weight %, and silicon nitride content is 6.0 weight %, and aluminum oxide contains
Measure as 25.0 weight %, the content of USY molecular sieve is 5.0 weight %, and nickel content is 12.0 weight %.Lanthanum oxide content is 4.0
Weight %.
Embodiment 4
The present embodiment is used for the method for preparing desulfurization of hydrocarbon oil catalyst for illustrating the present invention.
By the alpha-silicon nitride powders (purity of 4.04kg Zinc oxide powder (Beijing Chemical Plant, containing butt 4.0kg), 1.50kg>
99.0%, the promise new high-tech material development corporation, Ltd. of Qinhuangdao one) and 0.648kg lanthanum nitrate (traditional Chinese medicines chemical reagents corporation, purity
More than 99.0 weight %, the weight % of lanthanum oxide content 45) mixed in 12.5kg deionized water, stirring obtains oxygen after 30 minutes
Change the slurries of zinc, silicon nitride and lanthanum nitrate；
6.05kg titanium tetrachloride (Beijing Chemical Plant is analyzed pure) is slowly added into 8.00kg deionized water, and
It is slowly stirred and avoids oxidation titanium crystal from separating out, obtains the titanium colloidal sol of pale yellow transparent, pH=1.0；
By above-mentioned slurries, titanium colloidal sol and REHY molecular sieves (Qilu Petrochemical Company's catalyst plant, 0.7kg containing butt, SiO2:
Al2O3Mol ratio=7.2:1) 1h is stirred after being mixed together and obtains carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst A4.
A4 chemical composition is：Zinc oxide content is 40.0 weight %, and silicon nitride content is 15.0 weight %, titanium dioxide
Content is 25.0 weight %, and nickel content is 14.0 weight %, and lanthanum oxide content is that 3.0 weight %, REHY molecular sieve contents are 3.0
Weight %.
Comparative example 1
4.94kg zinc oxide and 430g lanthanum carbonate are mixed evenly in 12.5kg water, obtained containing oxidation
The slurries of zinc and lanthana；
2.88kg kaolin (catalyst asphalt in Shenli Refinery, containing butt 2.4kg), 2.40kg boehmite (are urged
Agent Nanjing branch company, containing butt 1.80kg) and 7.0kg deionized water be well mixed under agitation, add 200g dense nitre
Acid (chemistry pure, Beijing Chemical Plant produce) stirring makes pH=1.8, and is warming up to more than 60 DEG C and is acidified 1h.Treat that temperature is reduced to 40
When below DEG C, add above-mentioned mixed serum and 1.0kg beta-molecular sieve (catalyst Nanjing branch company, 0.70kg containing butt,
SiO2:Al2O3Mol ratio=20：1) carrier pulp is obtained after, stirring 1h after mixing；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B1.
B1 chemical composition is：Zinc oxide content is 31.0 weight %, and alumina content is 18.0 weight %, and kaolin contains
Measure as 24.0 weight %, the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0 weight %, and lanthanum oxide content is 2.0 weights
Measure %.
Comparative example 2
4.94kg zinc oxide and 1.45kg silicon nitride are mixed evenly in 12.5kg water, obtained containing aerobic
Change the slurries of zinc and silicon nitride；
By 1.60kg boehmite (catalyst Nanjing branch company, containing butt 1.20kg) and 7.0kg deionized water
It is well mixed under agitation, stirring makes pH=1.8 to addition 200g concentrated nitric acid (chemistry is pure, and Beijing Chemical Plant produces), and heats up
1h is acidified to more than 60 DEG C.When temperature is reduced to below 40 DEG C, the beta-molecular sieve for adding above-mentioned mixed serum and 1.0kg (is urged
Agent Nanjing branch company, 0.70kg containing butt, SiO2:Al2O3Mol ratio=20：1), stirred after mixing and carrier slurry is obtained after 1h
Liquid；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B2.
B2 chemical composition is：Zinc oxide content is 49.0 weight %, and silicon nitride content is 14.0 weight %, and aluminum oxide contains
Measure as 12.0 weight %, the content of beta-molecular sieve is 7 weight %, and nickel content is 18.0 weight %.
Comparative example 3
The lanthanum carbonate of 4.94kg zinc oxide, 1.45kg silicon nitride and 430g is mixed in 12.5kg water
It is even, obtain the mixed serum containing zinc oxide, silicon nitride and lanthana；
By 2.26kg boehmite (catalyst Nanjing branch company, containing butt 1.70kg) and 7.0kg deionized water
It is well mixed under agitation, stirring makes pH=1.8 to addition 200g concentrated nitric acid (chemistry is pure, and Beijing Chemical Plant produces), and heats up
1h is acidified to more than 60 DEG C.When temperature is reduced to below 40 DEG C, above-mentioned mixed serum is added, is carried after stirring 1h after mixing
Somaplasm liquid；
Method with reference to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction
To desulfurization of hydrocarbon oil catalyst B3.
B3 chemical composition is：Zinc oxide content is 49.0 weight %, and silicon nitride content is 14.0 weight %, and aluminum oxide contains
Measure as 17.0 weight %, nickel content is 18.0 weight %, lanthanum oxide content is 2.0 weight %.
Embodiment 5
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3.Using straight
Pipe abrasion method, method reference《Petrochemical Engineering Analysis method (RIPP) experimental method》Middle RIPP 29-90, the results are shown in Table 1.Test
Obtained numerical value is smaller, shows that abrasion strength resistance is higher.It is fine powder when wearing and tearing under certain condition that abrasion index is corresponding in table 1
The percentage of generation.
In order to more preferably represent activity of the desulfurization of hydrocarbon oil catalyst during commercial Application, to hydrocarbon ils after vulcanizing treatment
Desulphurization catalyst also carries out intensive analysis, and specific processing method is：The desulfurization of hydrocarbon oil catalyst for weighing appropriate mass is positioned over stream
Change in bed, be passed through the gaseous mixture of hydrogen sulfide (50 volume %) and nitrogen (50 volume %), and be heated to 400 DEG C of vulcanizing treatment 1h,
Desulfurization of hydrocarbon oil catalyst after vulcanizing treatment is obtained, and carries out abrasion strength resistance evaluation.It the results are shown in Table 1.
Embodiment 6
Desulfurization performance is evaluated.Desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3 are taken off using the micro- anti-experimental provision of fixed bed
Sulphur evaluation experimental, by 16 grams of desulfurization of hydrocarbon oil Catalyst packing in internal diameter is 30mm, a length of 1m fixed bed reactors.Raw material
Hydrocarbon ils is sulphur concentration 960ppm catalytically cracked gasoline, and reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, gasoline flow
For 80mL/h, reaction temperature is 380 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.To produce
Product sulfur content in gasoline is weighed desulphurizing activated.Sulfur content is public using An Jielun by offline chromatogram analysis method in product gasoline
The GC6890-SCD instruments of department are measured.In order to which accurate characterization goes out work of the desulfurization of hydrocarbon oil catalyst in industrial actual motion
Property, the catalyst after the completion of HDS evaluation experiment carries out regeneration treatment under 480 DEG C of air atmosphere.By desulfurization of hydrocarbon oil catalyst
HDS evaluation experiment is carried out, its activity after 6 circulations is regenerated and settles out substantially, and the catalyst after 6 circulations is taken out
The content of wherein zinc silicate is surveyed, the work of catalyst is represented with the sulfur content in the product gasoline after the 6th stable circulation of catalyst
Property, sulfur content is as shown in table 1 in product gasoline after stablizing.
Simultaneously product gasoline weigh and calculate its yield.
GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation
Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 1.
Table 1
| A1 | A2 | A3 | A4 | B1 | B2 | B3 | |
| Abrasion index | 2.4 | 3.1 | 3.5 | 3.1 | 6.8 | 2.6 | 2.5 |
| Yield of gasoline/% | 99.8 | 99.9 | 99.8 | 99.9 | 98.3 | 98.1 | 98.8 |
| Product sulfur content | 6 | 9 | 10 | 5 | 27 | 30 | 35 |
| △RON | 0.61 | 0.36 | 0.42 | 0.53 | -0.48 | -0.57 | -0.63 |
| △MON | 0.57 | 0.34 | 0.40 | 0.48 | -0.48 | -0.49 | -0.55 |
| △(RON+MON)/2 | 0.59 | 0.35 | 0.41 | 0.50 | -0.48 | -0.53 | -0.59 |
Note：
1st, the sulfur content of feed gasoline is 960ppm, and RON is that 93.7, MON is 83.6.
2nd, △ MON represent product MON value added；
3rd, △ RON represent product RON value added；
4th, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
From the result data of table 1 the desulfurization of hydrocarbon oil catalyst that provides of the present invention is provided in containing nitridation silicon components, hydrocarbon
Oily desulphurization catalyst has more preferable desulphurizing activated and activity stability.Also contain rare earth oxide, can further make the hydrocarbon
Oily desulphurization catalyst can absorb sulphur at lower temperatures and through reaction and regenerative process is repeated, still with preferably de-
Sulphur activity and activity stability.And the desulfurization of hydrocarbon oil catalyst has more preferable abrasion strength resistance, so that desulfurization of hydrocarbon oil is urged
Agent has longer service life.
Embodiment 7
Aging is carried out to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B3, condition is：Catalyst is positioned over 600 DEG C, water steaming
Qi leel is pressed and handles 16h under the atmosphere for 20kPa.
XRD spectra analysis is carried out to the A1-A4 before and after aging and B1-B3, Fig. 1 is the XRD spectra before and after A1 hydrothermal agings,
Fig. 2 is the XRD spectra before and after B1 hydrothermal agings.A2-A4 has similar XRD spectra to A1, does not show；B2-B3 has similar to B1
XRD spectra, do not show.In Fig. 1, do not occur in the XRD spectra after A1 hydrothermal agings zinc silicate 2 θ=22.0,
25.54th, 48.9 and 59.4 characteristic peak；In fig. 2, the above-mentioned spy of zinc silicate is occurred in that in the XRD spectra after B1 hydrothermal agings
Levy peak.Using the silicic acid Zn content in crystal content quantitative analysis B1-B3 XRD spectra, 2 are the results are shown in Table.
The desulfurization performance of A1-A4 and B1-B3 after aging are evaluated with evaluation method same as Example 6, be the results are shown in Table
2。
Table 2
| Catalyst | A1 | A2 | A3 | A4 | B1 | B2 | B3 |
| Silicic acid Zn content/weight % | 0 | 0 | 0 | 0 | 13.4 | 0 | 0 |
| Product gasoline sulfur content/ppm | 9 | 11 | 13 | 9 | 30 | 36 | 35 |
| △MON | 0.59 | 0.40 | 0.35 | 0.45 | -0.45 | -0.40 | -0.60 |
| △RON | 0.55 | 0.30 | 0.40 | 0.35 | -0.40 | -0.35 | -0.54 |
| △(RON+MON)/2 | 0.57 | 0.35 | 0.38 | 0.40 | -0.43 | -0.38 | -0.57 |
From the results shown in Table 2, after ageing process, without generation silicic acid in the desulfurization of hydrocarbon oil catalyst of embodiment
Zinc, and the catalyst in comparative example, zinc oxide can generate zinc silicate with the material of silicon oxide-containing, so that the desulfurization of catalyst is lived
Property reduction.
Claims (14)
1. a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst contains
Have：
1) 5-35 weight % heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from aluminum oxide, titanium dioxide, titanium dioxide
At least one of zirconium and tin ash；
2) 10-70 weight % zinc oxide；
3) 2-40 weight % silicon nitride；
4) 3-30 weight % metallic promoter agent, the metallic promoter agent is selected from least one of cobalt, nickel, iron and manganese；
5) rare-earth oxide of the 0.5-10 weight % in terms of rare earth oxide；
6) the 1-20 weight % molecular sieve with BEA and/or FAU structures.
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, using the gross weight of the desulfurization of hydrocarbon oil catalyst as base
Standard, the content of the heat-resistant inorganic oxide is 10-25 weight %, and the content of zinc oxide is 25-60 weight %, the silicon nitride
Content be 5-25 weight %, the content of the metallic promoter agent is 10-20 weight %, and the rare-earth oxide is with rare earth
The content of oxide meter is 1-5 weight %, and the content of the molecular sieve is 2-10 weight %.
3. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, the rare-earth oxide is lanthanum, cerium and neodymium
At least one of oxide.
4. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, silicon nitride is α phase silicon nitrides.
5. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, the molecular sieve be X-type molecular sieve, Y type molecular sieve,
At least one of USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
6. a kind of method for preparing the hydrocarbon ils desulfurization of hydrocarbon oil catalyst in claim 1-5 described in any one, this method includes：
(1) heat-resistant inorganic oxide binding agent, silicon nitride, zinc oxide, rare earth compound, water are mixed with acidic liquid
Contact to form carrier pulp to mixed serum, then with the molecular sieve with BEA and/or FAU structures；The carrier pulp is carried out
Shaping, first are dried and the first roasting, obtain carrier；
(2) to the precursor of introducing metallic promoter agent on the carrier, and the second drying and the second roasting are carried out, obtained before catalyst
Body；
(3) catalyst precarsor is reduced under hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
7. method according to claim 6, wherein, the heat-resistant inorganic oxide binding agent be heat-resistant inorganic oxide or
Person can be changed into the material of heat-resistant inorganic oxide under conditions of being calcined described first.
8. method according to claim 6, wherein, the rare earth compound is carbonate, the carbonic acid of rare earth metal
At least one of hydrogen salt, nitrate, chloride, formates and acetate.
9. method according to claim 6, wherein, the precursor of the metallic promoter agent for metallic promoter agent acetate,
At least one of carbonate, nitrate, sulfate, rhodanate and oxide.
10. method according to claim 6, wherein, the described first temperature dried is 80-120 DEG C, and described first dries
Time be 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least 0.5h.
11. method according to claim 6, wherein, the described second temperature dried is 50-300 DEG C, and described second dries
Time be 0.5-8h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4h.
12. method according to claim 6, wherein, the temperature of the reduction is 300-600 DEG C, the time of the reduction
For 0.5-6h, hydrogen content is 10-60 volumes % in the hydrogen atmosphere.
13. desulfurization of hydrocarbon oil catalyst made from the preparation method in claim 6-12 described in any one.
14. a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-5 and 13
Desulfurization of hydrocarbon oil catalyst contact described in middle any one, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is
0.5-4MPa。
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