CN105562063A - Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method - Google Patents
Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method Download PDFInfo
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Abstract
The invention discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the desulfurization catalyst, the desulfurization catalyst is prepared from the following components by weight: 1) 5-35% of aluminum oxide, 2) 5-35% of pillared clay, 3) 10-70% of a first metal oxide, 4) 2-20% of a second metal oxide, 5) 5-30% of a metal accelerator, 6) 0.5-10% of rare earth metal oxide based on rare earth oxide, and 7) 1-20% of a molecular sieve with an FAU structure. The desulfurization catalyst is better in desulfurization activity and activity stability.
Description
Technical field
The present invention relates to the method for a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil, particularly, relate to a kind of desulphurization catalyst, the method preparing desulphurization catalyst and the desulphurization catalyst obtained by the method, and use this desulphurization catalyst to carry out the method for desulfurization of hydrocarbon oil.
Background technology
The oxysulfide produced after combustion of sulfur in vehicle fuel, can suppress the activity of the noble metal catalyst in vehicle exhaust converter also can make it generation irreversibly poisoning.Thus make in vehicle exhaust containing unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide, these discharge gas are then easily formed photochemical fog by hydrophilic dye, cause acid rain, the oxysulfide itself simultaneously in air is also the one of the main reasons forming acid rain.Along with people are to the pay attention to day by day of environmental protection, environmental regulation is also day by day strict, and the sulfur content reducing gasoline and diesel oil is considered to one of most important measure improving air quality.
The existing gasoline products standard GB17930-2011 " motor petrol " of China required on December 31st, 2013, and sulfur content in gasoline must drop to 50 μ g/g; And gasoline quality standard can be stricter in the future.In this case, catalytically cracked gasoline has to pass through the requirement that deep desulfuration just can meet environmental protection.
At present, the process for deep desulphurization of oil product mainly contains hydrofinishing and adsorption desulfurize two kinds of methods, but in China because the problem of hydrogen source makes hydrorefined cost higher.SZorb adsorption desulfurize belongs to and faces hydrogen desulfur technology, realizes the adsorbing and removing of sulfide under certain temperature and pressure condition.Due to this technology, removing the sulfur-containing compound in gasoline, to have hydrogen consumption low, and not high to the purity requirement of hydrogen, and this technology is had broad application prospects removing in the sulfur-containing compound in fuel oil.
From liquid state, desulfurization often adopts the method for fixed bed traditionally, but the reaction uniformity of the method and regeneration all have obvious inferior position.Fluidized-bed process has the advantage of the better aspect such as heat transfer and pressure drop compared with fixed-bed process, therefore has broad application prospects.Fluidized-bed reactor generally adopts granular reactant, but for great majority reaction, reactant used does not generally have enough wearabilities.Therefore, find anti-wear performance well to have the adsorbent of better desulfurization performance significant simultaneously.
CN1355727A discloses a kind of adsorbent composition being applicable to remove sulphur from cracking gasoline and diesel fuel, be made up of zinc oxide, silica, oxidation al and ni, wherein nickel is substantially to reduce valence state existence, and its amount can remove sulphur from the cracking gasoline contacted with described nickeliferous adsorbent composition under desulfurization conditions or diesel fuel stream.Said composition forms particle by compound particles granulation zinc oxide, silica and aluminium oxide formed, and with nickel or nickel compound containing dipping after dry, roasting, then drying, roasting, reduction obtain.
CN1382071A discloses a kind of adsorbent composition being applicable to remove sulphur from cracking gasoline and diesel fuel, be made up of zinc oxide, silica, aluminium oxide and cobalt, wherein cobalt exists substantially to reduce valence state, and its amount can from removing sulphur under desulfurization conditions with the described cracking gasoline that contacts containing cobalt adsorbent composition or diesel fuel stream.All only mention desulphurizing activated in CN1355727A and CN1382071A, adsorbent physical and chemical performance (such as abrasion strength resistance) and stability are not all introduced.
Adsorbent disclosed in US6150300, CN1130253A and CN1258396A is: the granular adsorbent composition comprising the mixture of zinc oxide, silica, aluminium oxide, reduction valence state nickel or cobalt.Preparation method mainly adopts the methods such as shearing that silica, aluminium oxide and zinc oxide are mixed merga pass comminutor and prepares solid particle, floods nickel thus obtained adsorbent after drying and roasting.Although the adsorbent of these patent Introductions has good desulfurization performance, for its physical and chemical performance, mainly tear strength is not introduced in the patent.
CN1208124A discloses and adopts promoter metals to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide as cobalt and nickel dipping, then reduces this promoter at appropriate temperatures, for the preparation of the adsorbent removing cracking gasoline medium sulphide content.
CN1627988A discloses a kind of adsorbent composition being suitable for removing elementary sulfur and sulphur compound from cracking gasoline and diesel fuel, described adsorbent composition comprises: zinc oxide, expanded perlite, aluminate and promoter metals, wherein said promoter metals is will cause the amount of desulfurization from the stream of cracking gasoline or diesel fuel to exist when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it, and at least part of described promoter metals exists with 0 valence state.
CN1856359A discloses a kind of method of production combination thing, comprising: a) mixing material, zinc compound, containing earth silicon material, aluminium oxide and co-catalyst, to form its mixture; B) this mixture dry, to form the mixture of drying; C) mixture of this drying is calcined, to form the mixture through calcining; D) under suitable condition this mixture through calcining is reduced with suitable reducing agent, to produce in it composition of the co-catalyst content with reduction valence state, and e) reclaim reorganization compound.Co-catalyst contains various metals such as being selected from nickel.
CN1871063A discloses a kind of method of production combination thing, and the method comprises: a) by liquid, zinc compound, containing earth silicon material, aluminium oxide mixing to form its mixture; B) by this mixing dry for described mixture to form the first drying mixture; C) described first drying mixture is calcined to form first through calcining mixt; D) promoter is attached to described first within calcining mixt or on formed through promote mixture; E) make described through promote mixture and be selected from citric acid, the acid of tartaric acid and combination thereof contacts to be formed through contact mixture; F) by described dry to form the second drying mixture through contact mixture; G) described second drying mixture is calcined to form second through calcining mixt; H) adopt applicable reducing agent reduction described second under suitable condition through calcining mixt to produce the composition wherein containing reduction valence state promoter content, and i) reclaim described composition.
CN101816918A discloses a kind of desulfuration adsorbent, and this adsorbent consists of rare earth metal, aluminium oxide, silica, promoter and is selected from the adsorbent of one or more metal oxides of IIB, VB and VIB.This adsorbent has good abrasion strength resistance and desulphurizing activated.
Although adsorbent prepared by these methods has good desulfurization performance, also there is obvious shortcoming.Above-mentioned adsorbent all adopts zinc oxide active component, and the temperature that zinc oxide absorbs sulphur and oxidation regeneration is all higher, and the silicon when desulphurization reaction and oxidation regeneration easily and in carrier, al composition generate zinc silicate and/or zinc aluminate, cause adsorbent activity to reduce.As can be seen here, need to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.
Summary of the invention
The object of the invention is the defect of desulphurizing activated low, the structural instability of adsorbent in order to overcome prior art and abrasion resistance properties difference, providing the method for a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve these goals, the invention provides a kind of desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains: the 1) aluminium oxide of 5-35 % by weight; 2) laminated clay column of 5-35 % by weight; 3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide; 5) metallic promoter agent of 5-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide; 7) molecular sieve with FAU structure of 1-20 % by weight.
Present invention also offers the preparation method of desulphurization catalyst of the present invention, the method comprises: the precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries by (1); (2) alumina binder, lamellar clay, water are mixed with acidic liquid, and form carrier pulp with described slurry liquid contacts, more described carrier pulp, the molecular sieve with FAU structure are carried out shaping, first dry and the first roasting, obtain carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
The present invention also provides the desulphurization catalyst prepared by method provided by the invention.
The invention provides a kind of method of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by hydrocarbon oil containing surphur and hydrodesulfurization catalyst provided by the invention, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa.
Mix with the second metal oxide containing the first metal oxide in desulphurization catalyst provided by the invention and absorb constituent element as sulphur, second metal oxide effectively can reduce the effect of silicon in the first metal oxide and carrier, al composition, reduce silicate and/or the aluminate of generation first metal, thus enable this desulphurization catalyst absorb sulphur at lower temperatures and through repeatedly carrying out reacting and regenerative process, still there is better desulphurizing activated and activity stability.
Containing rare earth oxide in desulphurization catalyst provided by the invention, that effectively can strengthen that the second metal oxide acts on silicon, al composition mutually to the first metal oxide further weakens effect.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the structural representation of rectorite of the present invention, and wherein A is nondistensible mica layer, and B is expansive smectite, and C is argillic horizon, and D is the exchangeable cations in smectite, and E is the fixing cation in mica layer; The basal spacing (d001) of rectorite is 1.9-2.9nm;
The chemical composition expression formula of this rectorite is:
{(Na
0.72K
0.02Ca
0.05)(Ca
0.24Na
0.07)}(Al
4.00Mg
0.02)[Si
6.58Al
1.62]O
22
Wherein (Na
0.72k
0.02ca
0.05) fix cation between part presentation layer; (Ca
0.24na
0.07) partly represent the exchangeable cationic type between layer; (Al
4.00mg
0.02) part expression hexa-coordinate ion; [Si
6.58al
1.62] part expression four-coordination ion;
Fig. 2 is the X-ray diffraction pattern of rectorite, and the feature of this rectorite is that 3.4 ° have a stronger peak (characteristic peak), join with layer post height correlation; The test of XRD is carried out on German Siemens company D5005 type X-ray diffractometer, Cu target, K
αradiation, solid probe, tube voltage 40kV, tube current 40mA.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains: the 1) aluminium oxide of 5-35 % by weight; 2) laminated clay column of 5-35 % by weight; 3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide; 5) metallic promoter agent of 5-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide; 7) molecular sieve with FAU structure of 1-20 % by weight.
Preferably, with the gross weight of this desulphurization catalyst for benchmark, the content of described aluminium oxide is 10-25 % by weight, the content of described laminated clay column is 10-25 % by weight, the content of described first metal oxide is 35-54 % by weight, the content of described second metal oxide is 5-15 % by weight, the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide in the content of rare earth oxide for 1-5 % by weight, described in there is the molecular sieve of FAU structure content be 2-10 % by weight.
According to the present invention, described first metal oxide is the metal oxide with storage sulphur performance, and preferably, described first metal oxide is at least one in zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide; More preferably, described first metal oxide is at least one in zinc oxide, molybdenum oxide and vanadium oxide; Most preferably described first metal oxide is zinc oxide.
According to the present invention, described second metal oxide can suppress described first metal oxide when the desulphurization reaction repeatedly experienced under high temperature and regenerative response, have an effect with the silicon contained in described desulphurization catalyst, al composition, reduce the loss of described first metal oxide.
According to the present invention, under preferable case, described laminated clay column is 0.4-2.0:1 with the ratio of the weight of described aluminium oxide, is preferably 0.6-1.5:1.The use consumption of described laminated clay column and non-aluminum oxide, in this number range, can improve the tear strength of catalyst, regulates physical and chemical performance, as bulk density, pore volume.
According to the present invention, described aluminium oxide can for providing cementation between component each in described desulphurization catalyst.Under preferable case, described aluminium oxide is at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide; Preferably, described aluminium oxide is gama-alumina.
According to the present invention, the characteristic indication of described laminated clay column is that interstratified minerals crystal is alternately arranged by two kinds of individual layer mineral clay component rules and forms, and its basal spacing is not less than 1.7nm, has a stronger peak in its XRD collection of illustrative plates at 3.4 °.Under preferable case, described laminated clay column is at least one in rectorite, Yun Mengshi, bentonite, imvite and smectite, but is not limited thereto; Preferably, described laminated clay column is rectorite.Rectorite belongs to the lamellar clay of regularly interstratified mineral structure, share adjacent 2:1 argillic horizon by nondistensible mica layer and expandable smectite, a kind of crystalline mineral clay of concrete alternately ordered arrangement, as shown in Figure 1, its XRD collection of illustrative plates has a stronger peak to structural representation as shown in Figure 2 at ° place, 2 θ=3.4.
In the present invention, can also containing the silica source except laminated clay column in described desulphurization catalyst, the natural crystal that such as silica source can be greater than 45 % by weight for silica or silica content.Preferably, described silica source can be at least one in diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.With the gross weight of this desulphurization catalyst for benchmark, the content of described silica source can be 0-30 % by weight, is preferably 0-20 % by weight.
According to the present invention, described metallic promoter agent can be any metal that oxidation state sulphur can be reduced to hydrogen sulfide, and preferably, described metallic promoter agent is nickel.
According to the present invention, described rare-earth oxide can and the second metal oxide between interaction, strengthen the second metal oxide to the effect improving catalyst abrasion intensity, the skeleton of heat-resistant inorganic oxide can be stablized simultaneously, weaken the interaction between the first metal oxide and silicon, al composition further, improve activity and the stability of desulfurization.Preferably, described rare-earth oxide is at least one in the oxide of lanthanum, cerium and neodymium.
According to the present invention, described FAU structure molecular screen is faujasite-type molecular sieve, and the type molecular sieve has three-dimensional twelve-ring duct, and aperture is
fAU structure molecular screen is mainly the molecular sieve of X-type and Y type, in general SiO
2/ Al
2o
3mol ratio be 2.2-3.0 for X-type molecular sieve, SiO
2/ Al
2o
3mol ratio be greater than 3.0 for Y zeolite.The skeleton structure of X-type and Y zeolite all belongs to hexagonal crystal system, and space group structure is the cell parameter of Fd3m, X-type molecular sieve
the cell parameter of Y zeolite
The molecular sieve with FAU structure also comprises this modified molecular sieve analog, and method of modifying can comprise hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC1
4vapor phase method) or hydro-thermal combine with chemical treatment, the modified molecular sieve that obtains includes but not limited to super-stable Y molecular sieves (USY), REUSY, REHY, REY containing rare earth element, and phosphorous PUSY, PREHY, PREY etc.Under preferable case, described in there is FAU structure molecular sieve be at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY and PREY.The described SiO with the molecular sieve of FAU structure
2: Al
2o
3mol ratio be 2.6-10:1; Preferably, there is described in the SiO of the molecular sieve of FAU structure
2: Al
2o
3mol ratio be 2.8-9:1.
In the present invention, add effect or effect that the molecular sieve with FAU structure can have the content raising gasoline products octane number promoting aromatization of hydrocarbons by increase aromatic hydrocarbons.
Present invention also offers the preparation method of desulphurization catalyst of the present invention, the method comprises: the precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries by (1); (2) alumina binder, laminated clay column, water are mixed with acidic liquid, and contact with described slurries, the molecular sieve with FAU structure and form carrier pulp, more described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier; (3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
In the present invention, under preferable case, described alumina binder is aluminium oxide or the material changing aluminium oxide under the condition of described first roasting into, such as hydrated alumina and/or Alumina gel; Wherein, described hydrated alumina is selected from least one in boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina.
In the present invention, the precursor of described second metal oxide is described second metal oxide or the material that can change described second metal oxide under the condition of described first roasting into.Under preferable case, the precursor of described second metal oxide is at least one in lead oxide, antimony oxide and bismuth oxide; Or at least one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide.
In the present invention, the precursor of described metallic promoter agent can for changing the material of the oxide of metallic promoter agent under the condition of described second roasting.Under preferable case, the precursor of described metallic promoter agent can be at least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
In the present invention, under preferable case, described rare earth compound can be at least one in the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate; Preferably, described rare earth compound can be at least one in the carbonate of rare earth metal, bicarbonate, formates and acetate.Wherein, described rare earth metal is preferably at least one in lanthanum, cerium and neodymium.
In the present invention, described first metal oxide, laminated clay column, metallic promoter agent and to have the molecular sieve of FAU structure described above, do not repeat them here.
The step (1) of the preparation method of desulphurization catalyst provided by the invention and (2) are for the preparation of carrier.
In step of the present invention (1), adding of described first metal oxide can be oxide powder form, also can be use as a slurry after the first metal oxide is prepared as slurries again.
In the present invention, add the precursor of described second metal oxide, directly can add the powder of at least one in lead oxide, antimony oxide and bismuth oxide, or the material of described second metal oxide can be changed under being added in the condition of described first roasting into, as the one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide; Also use as a slurry again after at least one in lead oxide, antimony oxide and bismuth oxide can being prepared as slurries.
In the present invention, the solid content of slurries described in step (1) can be 15-30 % by weight.
In the present invention, the addition of described laminated clay column and described alumina binder, makes in the desulphurization catalyst obtained, and described laminated clay column is 0.4-2.0:1 with the ratio of the weight of described aluminium oxide, is preferably 0.6-1.5:1.Caking property between the better each component of described desulphurization catalyst can be provided thus.
In step of the present invention (2), described mixing can be: alumina binder and laminated clay column are carried out acidification with water and acidic liquid respectively, then the mixture obtained separately is mixed into described slurries.Preferably, the pH value of described acidified slurries is 1-5, is preferably 1.5-4; The solid content of described acidified slurries is 15-30 % by weight.
In the present invention, described acidic liquid is acid or aqueous acid, and described acid can be selected from water-soluble inorganic acid and/or organic acid, such as, can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, shapingly described in step (2) described slurries can be shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described slurries be dough or paste mixture time, described mixture shaping (preferred extrusion molding) can be made to form particle, and preferred diameter is at 1.0-8.0mm, length, at the cylindrical extrudates of 2.0-5.0mm, then makes the extrudate of gained carry out drying, roasting.If gained mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably slurries are slurry form, form the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry.For the ease of spraying dry, before dry, the solid content of described carrier pulp is 10-40 % by weight, is preferably 20-35 % by weight.Obtain can also comprising in the process of described carrier pulp adding water in step (2), there is no particular limitation for the addition of water, as long as the carrier pulp obtained meets above-mentioned solid content.
In the present invention, the described first condition that is dry and the first roasting can be conventionally known to one of skill in the art, and under preferable case, the temperature of described first drying is 80-150 DEG C, and the time of described first drying is 0.5-24h; The temperature of described first roasting is 300-700 DEG C, and the time of described first roasting is at least 0.5 hour.Preferably, the temperature of described first roasting is 400-500 DEG C, and the time of described first roasting is 0.5-100 hour, and the time of more preferably described first roasting is 0.5-10 hour.
According to the present invention, step (3) is for adding metallic promoter agent.The precursor of described metallic promoter agent is the material that can change the oxide of metallic promoter agent under the second roasting condition into; Under preferable case, the precursor of described metallic promoter agent can be selected from least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
According to the present invention, under preferable case, carrier is introduced the method for the precursor of metallic promoter agent for dipping or precipitation.Described dipping can be the solution of the precursor by metallic promoter agent or suspension impregnation carrier; Described precipitation can be the solution of the precursor of metallic promoter agent or suspension are mixed with carrier, then adds ammoniacal liquor by the precursor precipitation of metallic promoter agent on carrier.
In the present invention, the described second condition that is dry and the second roasting can be conventionally known to one of skill in the art, and under preferable case, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; The temperature of described second roasting is 300-700 DEG C, and the time of described second roasting is 0.5-4h; Preferably, the temperature of described second drying is 100-250 DEG C, and the time of described second drying is 1-5h; The temperature of described second roasting is 400-500 DEG C, and the time of described second roasting is 1-3h.Described second roasting can be carried out under having oxygen or oxygen-containing gas to exist, until volatile materials is removed and metallic promoter agent is converted into the form of metal oxide, obtains catalyst precarsor.
According to the present invention, in step (4), change the oxide of the metallic promoter agent in described catalyst precarsor into metal simple-substance, described catalyst precarsor can be reduced under hydrogen atmosphere, metallic promoter agent is existed with reduction-state substantially, obtains catalyst of the present invention.The condition of described reduction only changes the oxide of the metallic promoter agent in described catalyst precarsor into metal simple-substance, and the metal oxide in described carrier can not change.Under preferable case, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %; Preferably, the temperature of described reduction is 350-450 DEG C, and the time of described reduction is 1-3h.
In the present invention, catalyst precarsor reduction can be carried out immediately by step (4) after obtained catalyst precarsor, also can before use (namely for desulfurization absorption before) carry out.Because metallic promoter agent is easily oxidized, and the metallic promoter agent in catalyst precarsor exists in the form of an oxide, and therefore for ease of transport, catalyst precarsor reduction is carried out by preferred steps (4) before carrying out desulfurization absorption.Described being reduced to makes the metal in the oxide of metallic promoter agent substantially exist with reduction-state, obtains desulphurization catalyst of the present invention.
According to preparation method provided by the invention, described alumina binder, laminated clay column, first metal oxide, second metal oxide precursor, rare earth compound, there is the addition of the molecular sieve of FAU structure and the precursor of metallic promoter agent, make in the desulphurization catalyst obtained, with the gross weight of this desulphurization catalyst for benchmark, aluminium oxide containing 5-35 % by weight, the laminated clay column of 5-35 % by weight, first metal oxide of 10-70 % by weight, second metal oxide of 2-20 % by weight, the metallic promoter agent of 3-30 % by weight, in the molecular sieve with FAU structure of the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide and 1-20 % by weight.
Preferably, the content of described aluminium oxide is 10-25 % by weight, the content of described laminated clay column is 10-25 % by weight, the content of described first metal oxide is 35-54 % by weight, the content of described second metal oxide is 5-15 % by weight, the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide in the content of rare earth oxide for 1-5 % by weight, described in there is the molecular sieve of FAU structure content be 2-10 % by weight.
In the present invention, step can also add silica source in (2), and described silica source is described above, and this is no longer going to repeat them.The addition of described silica source makes in the desulphurization catalyst obtained, with the gross weight of this desulphurization catalyst for benchmark, and the silica source containing 0-30 % by weight, preferably, the silica source of 0-20 % by weight.
The present invention also provides the desulphurization catalyst prepared by method provided by the invention.The composition of this desulphurization catalyst as previously mentioned, does not repeat them here.
The invention provides a kind of method of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by hydrocarbon oil containing surphur and hydrodesulfurization catalyst provided by the invention, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa; Preferably, the temperature of described contact is 400-450 DEG C, and the pressure of described contact is 1.0-2.0MPa.Sulphur in the process in hydrocarbon ils is adsorbed on catalyst, thus obtains the hydrocarbon ils of low sulfur content.
The method of desulfurization of hydrocarbon oil provided by the invention is preferably carried out in a fluidized bed reactor, and namely described contact is preferably carried out in a fluidized bed reactor.
In the present invention, reacted catalyst can be reused after regeneration.Described regeneration is carried out under oxygen atmosphere, and the condition of regeneration comprises: the pressure of regeneration is normal pressure, and the temperature of regeneration is 400-700 DEG C, is preferably 500-600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, and also need to reduce under hydrogen atmosphere, the reducing condition of the catalyst after regeneration comprises: temperature is 350-500 DEG C, is preferably 400-450 DEG C; Pressure is 0.2-2MPa, is preferably 0.2-1.5MPa.
Term used herein " cracking gasoline " means hydrocarbon or its any cut that boiling range is 40 to 210 DEG C, is the product from making larger crack hydrocarbon molecules become more micromolecular heat or catalytic process.The thermal cracking process be suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process be suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline be suitable for includes but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combination thereof.In some cases, be in the methods of the invention used as hydrocarbon-containifluids fluids time can by described cracking gasoline fractionation and/or hydrotreatment before desulfurization.
It is the hydrocarbon mixture of 170 to 450 DEG C or the liquid of its any fractional composition that term used herein " diesel fuel " means boiling range.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydroprocessed diesel etc. and combination thereof.
Term used herein " sulphur " represents any type of element sulphur if hydrocarbon-containifluids fluids is as the organosulfur compound existed normal in cracking gasoline or diesel fuel.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS
2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene, and the thiophenes that in diesel fuel, the normal molecular weight existed is larger.
Desulphurization catalyst provided by the invention has good abrasion strength resistance and desulphurizing activated, greatly can increase the service life, be applicable to adsorption desulfurize process.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst calculates according to feeding intake.
Embodiment 1
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
(1) carrier is prepared.By the Zinc oxide powder of 4.05kg, (Beijing Chemical Plant produces, containing butt 4.0kg), lead oxide powder (the traditional Chinese medicines chemical reagents corporation of 0.50kg, analyze pure) and anhydrous lanthanum chloride (the traditional Chinese medicines chemical reagents corporation of 301g, analyze pure) mixing and stirring in the water of 8.5kg, obtain the slurries containing zinc oxide, lead oxide and lanthanum chloride;
By rectorite (the Qilu Petrochemical catalyst plant of 1.97kg, containing butt 1.60kg) add after deionized water 1.6kg mixes, add the hydrochloric acid (Beijing Chemical Plant of 30 % by weight of 100ml, chemical pure) stir make pH=2.0, be warming up to 80 DEG C of aging 2h after acidifying 1h, obtain the mixture containing rectorite;
By aluminium oxide (Shandong Aluminum Plant of 1.60kg, containing butt 1.20kg) and after the deionized water of 3.6kg mixes, the hydrochloric acid (Beijing Chemical Plant, chemical pure) adding 30 % by weight of 300ml stirs and makes pH=2.0, is warming up to 80 DEG C of aging 2h after acidifying 1h.(Qilu Petrochemical Company's catalyst plant, containing butt 0.7kg, SiO to add the REHY molecular sieve of above-mentioned slurries, mixture and 1.0kg again
2: Al
2o
3mol ratio=7.2:1) mixing, stir and obtain carrier pulp after 30 minutes.
Described carrier pulp adopts NiroBowenNozzleTower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 8.5 to 9.5MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon obtained by spraying dry is dry 1h at 150 DEG C first, and then at 480 DEG C, roasting 1h obtains carrier.
(2) metallic promoter agent is introduced.Flooded at twice by the aqueous solution that the deionized water of the Nickelous nitrate hexahydrate of the carrier 8.91kg of 8.2kg and 1.10kg is formed, the mixture obtained then at 480 DEG C of roasting 1h, obtains catalyst precarsor after 150 DEG C of dry 4h;
(3) reduce.By catalyst precarsor reductase 12 h at 425 DEG C in hydrogen atmosphere, obtain desulphurization catalyst A1.
A1 consists of: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight, and alumina content is 12.0 % by weight, rectorite content is 16.0 % by weight, nickel content is 18.0 % by weight, REHY molecular sieve content is 7.0 % by weight, and lanthana content is 2.0 % by weight.
Embodiment 2
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant of 3.84kg, containing butt 3.8kg), bismuth oxide powder (the traditional Chinese medicines chemical reagents corporation of 0.90kg, analyze pure) and six water cerous nitrate (the traditional Chinese medicines chemical reagents corporations of 794g, analyze pure) mixing and stirring in the water of 8.5kg, obtain the slurries containing zinc oxide, bismuth oxide and cerous nitrate;
By rectorite (the catalyst Nanjing branch company of 1.85kg, containing butt 1.50kg) add after deionized water 1.6kg mixes, the hydrochloric acid adding 30 % by weight of 100ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite;
After the aluminium oxide (Shandong Aluminum Plant, containing butt 1.8kg) of 2.40kg and the deionized water of 4.8kg being mixed, the hydrochloric acid adding 30 % by weight of 275ml stirs and makes pH=3.0, is warming up to 80 DEG C of aging 2h after acidifying 1h.(catalyst Nanjing branch company, containing butt 0.30kg, SiO to add the PREY molecular sieve of above-mentioned slurries, mixture and 0.43kg again
2: Al
2o
3mol ratio=6.0:1) mixing, stir and obtain carrier pulp after 30 minutes.
Carrier pulp spraying dry is also flooded introducing active component nickel by the method with reference to embodiment 1, obtains desulphurization catalyst A2.
A2 consists of: zinc oxide content is 38.0 % by weight, and bismuth oxide content is 9.0 % by weight, and alumina content is 18.0 % by weight, rectorite content is 15.0 % by weight, nickel content is 14.0 % by weight, PREY molecular sieve content is 3.0 % by weight, and cerium-oxide contents is 3.0 % by weight.
Embodiment 3
The present embodiment is for illustration of the method preparing desulphurization catalyst of the present invention.
By the Zinc oxide powder (Beijing Chemical Plant of 4.76kg, containing butt 4.7kg), nitric acid antimony (the traditional Chinese medicines chemical reagents corporation of 0.9kg, analyze pure) and lanthana (the traditional Chinese medicines chemical reagents corporation of 400g, analyze pure) mixing and stirring in the deionized water of 8.5kg, obtain the slurries containing zinc oxide, antimony oxide and lanthana;
By rectorite (the catalyst Nanjing branch company of 1.23kg, containing butt 1.00kg) add after deionized water 1.6kg mixes, the hydrochloric acid adding 30 % by weight of 100ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite;
After the aluminium oxide (Shandong Aluminum Plant, containing butt 1.6kg) of 2.13kg and the deionized water of 4.8kg being mixed, the hydrochloric acid adding 30 % by weight of 275ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h.(catalyst Nanjing branch company, containing butt 0.5kg, SiO to add the USY molecular sieve of above-mentioned slurries, mixture and 0.6kg again
2: Al
2o
3mol ratio=8.5:1) mixing, stir and obtain carrier pulp after 30 minutes.
Carrier pulp spraying dry is also flooded introducing active component nickel by the method with reference to embodiment 1, obtains desulphurization catalyst A3.
Consisting of of adsorbent A 3: zinc oxide content is 47.0 % by weight, antimony oxide content is 6.0 % by weight, and alumina content is 16.0 % by weight, rectorite content is 10.0 % by weight, nickel content is 12.0 % by weight, and USY molecular sieve content is 5.0 % by weight, and lanthana content is 4.0 % by weight.
Comparative example 1
The deionized water of the Zinc oxide powder (Beijing Chemical Plant, containing butt 4.0kg) of 4.05kg, the anhydrous lanthanum chloride of 301g and 6.9kg is mixed, stirs the slurries obtaining zinc oxide and lanthanum nitrate after 30 minutes;
By rectorite (the Qilu Petrochemical catalyst plant of 1.97kg, containing butt 1.60kg) add after deionized water 1.6kg mixes, the hydrochloric acid adding 30 % by weight of 100ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite;
After the aluminium oxide (Shandong Aluminum Plant, containing butt 1.70kg) of 2.26kg and the deionized water of 4.5kg being mixed, the hydrochloric acid adding 30 % by weight of 420ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h.(Qilu Petrochemical Company's catalyst plant, containing butt 0.7kg, SiO to add the REHY molecular sieve of above-mentioned slurries, mixture and 1.0kg again
2: Al
2o
3mol ratio=7.2:1) mixing, stir and obtain carrier pulp after 30 minutes.
Carrier pulp spraying dry is also flooded introducing active component nickel by the method with reference to embodiment 1, obtains desulphurization catalyst B1.
B1 consists of: zinc oxide content is 40.0 % by weight, and alumina content is 17.0 % by weight, and rectorite content is 16.0 % by weight, and nickel content is 18.0 % by weight, REHY molecular sieve content is 7.0 % by weight, and lanthana content is 2.0 % by weight.
Comparative example 2
By the Zinc oxide powder (Beijing Chemical Plant produces, containing butt 4.0kg) of 4.05kg and lead oxide powder mixing and stirring in the water of 8.5kg of 0.50kg, obtain the slurries containing zinc oxide and lead oxide;
By rectorite (the Qilu Petrochemical catalyst plant of 1.97kg, containing butt 1.60kg) add after deionized water 1.6kg mixes, the hydrochloric acid adding 30 % by weight of 100ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite;
After the aluminium oxide (Shandong Aluminum Plant, containing butt 1.20kg) of 1.86kg and the deionized water of 4.0kg being mixed, the hydrochloric acid adding 30 % by weight of 350ml stirs and makes pH=1.8, is warming up to 80 DEG C of aging 2h after acidifying 1h.(Qilu Petrochemical Company's catalyst plant, containing butt 0.7kg, SiO to add the REHY molecular sieve of above-mentioned slurries, mixture and 1.0kg again
2: Al
2o
3mol ratio=7.2:1) mixing, stir and obtain carrier pulp after 30 minutes.
Carrier pulp spraying dry is also flooded introducing active component nickel by the method with reference to embodiment 1, obtains desulphurization catalyst B2.
B2 consists of: zinc oxide content is 40.0 % by weight, and lead oxide content is 5.0 % by weight, and alumina content is 14.0 % by weight, and rectorite content is 16.0 % by weight, and nickel content is 18.0 % by weight, REHY molecular sieve content is 7.0 % by weight.
Comparative example 3
By the Zinc oxide powder of 4.05kg, (Beijing Chemical Plant produces, containing butt 4.0kg), lead oxide powder (the traditional Chinese medicines chemical reagents corporation of 0.50kg, analyze pure) and anhydrous lanthanum chloride (the traditional Chinese medicines chemical reagents corporation of 301g, analyze pure) mixing and stirring in the water of 8.5kg, obtain the slurries containing zinc oxide, lead oxide and lanthanum chloride;
By rectorite (the Qilu Petrochemical catalyst plant of 1.97kg, containing butt 1.60kg) add after deionized water 1.6kg mixes, the hydrochloric acid adding 30 % by weight of 100ml stirs and makes pH=2.0, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the mixture containing rectorite;
After the aluminium oxide (Shandong Aluminum Plant, containing butt 1.90kg) of 2.53kg and the deionized water of 5.7kg being mixed, the hydrochloric acid adding 30 % by weight of 480ml stirs and makes pH=2.0, is warming up to 80 DEG C of aging 2h after acidifying 1h.Add above-mentioned slurries and mixture mixing again, stir and obtain carrier pulp after 30 minutes.
Carrier pulp spraying dry is also flooded introducing active component nickel by the method with reference to embodiment 1, obtains desulphurization catalyst B3.
Consisting of of adsorbent B 3: zinc oxide content is 40.0 % by weight, lead oxide content is 5.0 % by weight, and alumina content is 19.0 % by weight, and rectorite content is 16.0 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 2.0 % by weight.
Embodiment 4
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A3 and B1-B3.Adopt straight tube wearing and tearing method, method, with reference to RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", the results are shown in Table 1.Test the numerical value obtained less, show that abrasion strength resistance is higher.What in table 1, abrasion index was corresponding is fine powder generates when wearing and tearing under certain condition percentage.
In order to the activity of adsorbent in commercial Application process better can be represented, also intensive analysis is carried out to adsorbent after vulcanizing treatment, concrete processing method is: the adsorbent taking appropriate mass is positioned in fluid bed, pass into the gaseous mixture of hydrogen sulfide (50 volume %) and nitrogen (50 volume %), and be heated to 400 DEG C of vulcanizing treatment 1h.The results are shown in Table 1.
Embodiment 5
Desulfurization performance is evaluated.Adopt the micro-anti-experimental provision of fixed bed to carry out HDS evaluation experiment to desulphurization catalyst A1-A3 and B1-B3, the desulphurization catalyst of 16 grams being seated in internal diameter is in 30mm, the long fixed bed reactors for 1m.Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 960ppm, and reaction pressure is 1.38MPa, and hydrogen flowing quantity is 6.3L/h, and gasoline flow is 80mL/h, and 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.Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content is by off-line chromatogram analysis method, adopts the GC6890-SCD instrument of An Jielun company to measure.In order to accurate characterization goes out the activity of desulphurization catalyst in industrial actual motion, HDS evaluation tested after catalyst carry out under the air atmosphere of 480 DEG C regeneration process.Desulphurization catalyst is carried out HDS evaluation experiment, and after regenerating 6 circulations, its activity settles out substantially, represents the activity of catalyst with the sulfur content in the product gasoline after catalyst the 6th stable circulation, and after stable, in product gasoline, sulfur content is as shown in table 1.
Product gasoline is weighed simultaneously and calculate its yield.
The motor octane number (MON) of gasoline and research octane number (RON) (RON) before adopting GB/T503-1995 and GB/T5487-1995 to measure reaction respectively and after the 6th stable circulation, the results are shown in Table 1.
Embodiment 6
Zinc aluminate content measures.The crystalline phase composition of desulphurization catalyst A1-A3 and B1-B3 after the 6th circulation in embodiment 5 is analyzed, measures zinc aluminate content wherein.
Crystal phase analysis adopts X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans, Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), through revise Rietveld model (RIQASrietveldAnalysis, operation manual, MaterialData, Inc., Berkley, CA (1999)), analyze different sample, and adopt the method for matching to calculate the crystalline phase composition of sample.Use PhilipsXRG3100 generator (40kV, 30mA drive), Philips3020 digital goniometer, Philips3710MPD computer for controlling and the KevexPSIPeltier being equipped with long fine focusing copper X-ray source to cool silicon detector to carry out all X-ray diffractions and measure.Adopt Kevex4601 ion pump controller, Kevex4608Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer operation Kevex detector.PhilipsAPD4.1c version software is used to obtain diffraction pattern.Use MaterialData, Inc.Riqas3.1c version software (OutokumpuHSCChemistryforWindows: user's manual, OutokumpoResarchOy, Pori, Finland (1999)) to carry out all Rietveld to calculate.The zinc aluminate content of different desulphurization catalyst is as shown in table 1.
Table 1
| A1 | A2 | A3 | B1 | B2 | B3 | |
| ZnAl 2O 4, % by weight | 0 | 0 | 0 | 4.6 | 2.8 | 2.1 |
| Abrasion index | 3.8 | 4.0 | 4.5 | 7.6 | 6.8 | 5.6 |
| Yield of gasoline, % | 99.4 | 99.5 | 99.3 | 98.4 | 98.3 | 98.8 |
| Product sulfur content, ppm | 5 | 7 | 8 | 27 | 31 | 30 |
| △RON | 0.63 | 0.38 | 0.38 | -0.45 | -0.55 | -0.60 |
| △MON | 0.59 | 0.35 | 0.36 | -0.45 | -0.45 | -0.50 |
| △(RON+MON)/2 | 0.61 | 0.37 | 0.37 | -0.45 | -0.50 | -0.55 |
Note:
1, the sulfur content of feed gasoline is 960ppm, RON be 93.7, MON is 83.6.
2, △ MON represents the value added of product MON;
3, △ RON represents the value added of product RON;
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
As can be seen from the result data of table 1, desulphurization catalyst provided by the invention has better desulphurizing activated and activity stability.Desulphurization catalyst has better abrasion strength resistance, thus makes desulphurization catalyst have longer service life.
Claims (18)
1. a desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains:
1) aluminium oxide of 5-35 % by weight;
2) laminated clay column of 5-35 % by weight;
3) first metal oxide of 10-70 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element;
4) second metal oxide of 2-20 % by weight, described second metal oxide is selected from least one in lead oxide, antimony oxide and bismuth oxide;
5) metallic promoter agent of 5-30 % by weight, described metallic promoter agent is selected from least one in cobalt, nickel, iron and manganese;
6) in the rare-earth oxide of the 0.5-10 % by weight of rare earth oxide; And
7) molecular sieve with FAU structure of 1-20 % by weight.
2. desulphurization catalyst according to claim 1, wherein, with the gross weight of this desulphurization catalyst for benchmark, the content of described aluminium oxide is 5-25 % by weight, the content of described laminated clay column is 5-25 % by weight, the content of described first metal oxide is 35-54 % by weight, the content of described second metal oxide is 5-15 % by weight, the content of described metallic promoter agent is 10-20 % by weight, described rare-earth oxide in the content of rare earth oxide for 1-5 % by weight, described in there is the molecular sieve of FAU structure content be 2-10 % by weight.
3. desulphurization catalyst according to claim 1, wherein, described laminated clay column is 0.4-2.0:1 with the ratio of the weight of described aluminium oxide.
4. the desulphurization catalyst according to claim 1 or 3, wherein, described laminated clay column is at least one in rectorite, Yun Mengshi, bentonite, imvite and smectite.
5. desulphurization catalyst according to claim 1 and 2, wherein, described rare-earth oxide is at least one in the oxide of lanthanum, cerium and neodymium.
6. desulphurization catalyst according to claim 1 and 2, wherein, described first metal oxide is at least one in zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide.
7. desulphurization catalyst according to claim 1 and 2, wherein, described in there is FAU structure molecular sieve be at least one in X-type molecular sieve, Y zeolite, USY, REUSY, REHY, REY, PUSY, PREHY and PREY.
8. the preparation method of the desulphurization catalyst in claim 1-7 described in any one, the method comprises:
(1) precursor of rare earth compound, the first metal oxide, the second metal oxide and water are mixed to get slurries;
(2) alumina binder, laminated clay column, water are mixed with acidic liquid, and contact with described slurries, the molecular sieve with FAU structure and form carrier pulp, more described carrier pulp is carried out shaping, first dry and the first roasting, obtain carrier;
(3) on described carrier, introduce the precursor of metallic promoter agent, and carry out second dry and the second roasting, obtain catalyst precarsor;
(4) described catalyst precarsor is reduced under hydrogen atmosphere, obtain desulphurization catalyst.
9. preparation method according to claim 8, wherein, described alumina binder is aluminium oxide or the material that can change aluminium oxide under the condition of described first roasting into.
10. preparation method according to claim 8, wherein, the precursor of described second metal oxide is at least one in lead oxide, antimony oxide and bismuth oxide; Or at least one in the carbonate of metallic lead, antimony and bismuth, nitrate, chloride and hydroxide.
11. preparation methods according to claim 8, wherein, described rare earth compound is at least one in the carbonate of rare earth metal, bicarbonate, nitrate, chloride, formates and acetate.
12. preparation methods according to claim 8, wherein, the precursor of described metallic promoter agent is at least one in the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide.
13. preparation method according to claim 8, wherein, carrier is introduced the method for the precursor of described metallic promoter agent for dipping or precipitation.
14. preparation methods according to claim 8, wherein, the temperature of described first drying is 80-120 DEG C, and the time of described first drying is 0.5-24h; The temperature of described first roasting is 300-700 DEG C, and time of described first roasting is at least 0.5h.
15. preparation methods according to claim 8, wherein, the temperature of described second drying is 50-300 DEG C, and the time of described second drying is 0.5-8h; The temperature of described second roasting is 300-700 DEG C, and the time of described second roasting is 0.5-4h.
16. preparation methods according to claim 8, wherein, the temperature of described reduction is 300-600 DEG C, and the time of described reduction is 0.5-6h, and in described hydrogen atmosphere, hydrogen content is 10-60 volume %.
The desulphurization catalyst that preparation method in 17. claim 8-16 described in any one obtains.
The method of 18. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: in a hydrogen atmosphere, and by the hydrodesulfurization catalyst in hydrocarbon oil containing surphur and claim 1-7 and 17 described in any one, the temperature of described contact is 350-500 DEG C, and the pressure of described contact is 0.5-4MPa.
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| CN1355727A (en) * | 1999-08-25 | 2002-06-26 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
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