CN105498831A - Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same - Google Patents
Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same Download PDFInfo
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- CN105498831A CN105498831A CN201410559937.2A CN201410559937A CN105498831A CN 105498831 A CN105498831 A CN 105498831A CN 201410559937 A CN201410559937 A CN 201410559937A CN 105498831 A CN105498831 A CN 105498831A
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Abstract
The invention discloses a desulfurization catalyst, a preparation method thereof and application of the desulfurization catalyst to desulfurize sulfur-containing hydrocarbon oil. The desulfurization catalyst contains a non-aluminium oxide, a silicon oxide source, a first metal oxide, antimony oxide, a rare earth metal oxide, a phosphorus-aluminium molecular sieve and an active metal. The XRD spectrum of the desulfurization catalyst possesses the characteristic peak of a rare earth-antimony composite oxide. The desulfurization catalyst possesses relatively good desulfurization activity and desulfurization 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, non-aluminum oxide and nickel, 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 non-aluminum 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, non-aluminum 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, non-aluminum oxide, reduction valence state nickel or cobalt.Preparation method mainly adopts the methods such as shearing that silica, non-aluminum 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 non-aluminum 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, non-aluminum 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, non-aluminum 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, non-aluminum 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: 1) the non-aluminum oxide of 3-35 % by weight, and described non-aluminum oxide is at least one in titanium dioxide, zirconium dioxide and tin ash; 2) silica source of 5-30 % by weight; 3) first metal oxide of 10-80 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) antimony oxide of 2-20 % by weight; 5) active metal of 5-30 % by weight, described active metal is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-15 % by weight of rare earth oxide; 7) phosphate aluminium molecular sieve of 1-30 % by weight; The characteristic peak of rare earth-antimony composite oxides is there is in the XRD spectra of described desulphurization catalyst.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: the precursor of antimony oxide, rare earth compound, water and acidic liquid are mixed to get rare earth-antimony colloidal sol by (1); (2) non-al binder, silica source, the first metal oxide, phosphate aluminium molecular sieve, water and acidic liquid are mixed to form slurries, and contact obtain carrier mixture with described rare earth-antimony colloidal sol, described carrier mixture is carried out shaping, first dry and the first roasting, obtain carrier; (3) introduce the precursor of active metal on the carrier, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulphurization catalyst.
Present invention also offers the desulphurization catalyst obtained by preparation method provided by the invention.
Present invention also offers 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 antimony oxide containing the first metal oxide in desulphurization catalyst provided by the invention and absorb constituent element as sulphur, antimony 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, and with antimony oxide become rare earth-antimony composite oxides can further effectively oxidation reinforced antimony the first metal oxide and silicon, al composition are acted on mutually weaken effect.
By desulphurization catalyst provided by the invention, this desulphurization catalyst still can have better desulphurizing activated after carrying out repeatedly desulfurization regeneration course of reaction, desulfurization stability is better.And this desulphurization catalyst carry out desulfurization of hydrocarbon oil reaction can have less green coke amount, yield of gasoline is higher.In the product gasoline composition obtained, iso-component is more, and sulfur content is lower, and the octane number of product gasoline improves, product gasoline better quality.This desulphurization catalyst can obtain better mar proof in addition.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the XRD spectra of the desulphurization catalyst A1 containing lanthanum, and wherein 2 θ are 27.9 °, 32.3 °, 46.2 ° and 54.7 ° and the peak marking " ▼ " is the characteristic peak of the cubic system of lanthanum antimony composite oxides;
Fig. 2 is the XRD spectra of the desulphurization catalyst A2 containing neodymium, and wherein 2 θ are 28.0 °, 32.6 °, 46.7 ° and 55.4 ° and the peak marking " ▼ " is the characteristic peak of the cubic system of neodymium antimony composite oxides;
Fig. 3 is the XRD spectra of desulphurization catalyst B2, wherein, do not have the characteristic peak of 27.9 °, 32.3 °, 46.2 ° and 54.7 ° lanthanum antimony composite oxides, 2 θ are 22.1 °, 25.5 °, 31.5 °, 38.8 °, 45.0 °, 47.0 °, 48.9 °, 57.6 °, 59.5 °, 65.6 °, 65.8 ° and 68.7 ° and the peak marking " ■ " is the characteristic peak of zinc silicate.
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: 1) the non-aluminum oxide of 3-35 % by weight, and described non-aluminum oxide is at least one in titanium dioxide, zirconium dioxide and tin ash; 2) silica source of 5-30 % by weight; 3) first metal oxide of 10-80 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element; 4) antimony oxide of 2-20 % by weight; 5) active metal of 5-30 % by weight, described active metal is selected from least one in cobalt, nickel, iron and manganese; 6) in the rare-earth oxide of the 0.5-15 % by weight of rare earth oxide; 7) phosphate aluminium molecular sieve of 1-30 % by weight; The characteristic peak of rare earth-antimony composite oxides is there is in the XRD spectra of described desulphurization catalyst.
Preferably, with the gross weight of described desulphurization catalyst for benchmark, the content of described non-aluminum oxide is 5-25 % by weight, the content of described silica source is 10-20 % by weight, the content of described first metal oxide is 25-70 % by weight, and the content of antimony oxide is 2-20 % by weight, and the content of described active metal is 8-25 % by weight, described rare-earth oxide is in the content of rare earth oxide for 0.5-10 % by weight, and the content of described phosphate aluminium molecular sieve is 2-25 % by weight.
In the present invention, the content of described desulphurization catalyst middle rare earth metal oxide and antimony oxide can be conducive to forming rare earth-antimony composite oxides structure, thus be more conducive to that oxidation reinforced antimony acts on silicon, al composition mutually to the first metal oxide weaken effect, to improve the abrasion resistance properties of desulphurization catalyst, desulphurizing activated and product gasoline quality.
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, the rare-earth oxide contained in described desulphurization catalyst can combine with antimony oxide, makes desulphurization catalyst can have the crystal structure of rare earth-antimony composite oxides.Under preferable case, the rare earth element in described rare-earth oxide is selected from least one in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; Rare earth element in preferred described rare-earth oxide is at least one in La, Pr and Nd.
According to the present invention, under preferable case, as shown in Figure 1, when rare earth element is lanthanum, in the XRD spectra of described desulphurization catalyst, there is the characteristic peak (JCPDSNo.34-1130) that 2 θ are the cubic system of the lanthanum antimony composite oxides of 27.9 °, 32.3 °, 46.2 ° and 54.7 °; There is not the characteristic peak (JCPDSNo.5-0534) that 2 θ are the cubic system of the antimony oxide of 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 °, there is not the characteristic peak (JCPDSNo.4-0856) that 2 θ are the cubic system of the lanthana of 27.0 °, 31.4 °, 44.8 ° and 53.2 °.
According to the present invention, under preferable case, as shown in Figure 2, when rare earth element is neodymium, in the XRD spectra of described desulphurization catalyst, there is the characteristic peak (JCPDSNo.26-0111) that 2 θ are the cubic system of the neodymium antimony composite oxides of 28.0 °, 32.6 °, 46.7 ° and 55.4 °; There is not the characteristic peak of cubic system that 2 θ are the antimony oxides at 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 ° places, there is not the characteristic peak (JCPDSNo.6-0408) that 2 θ are the cubic system of the neodymia of 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 °.
In the present invention, rare earth-antimony composite oxides structure is formed in desulphurization catalyst, can accelerating oxidation antimony the first metal oxide is acted on mutually with silicon, al composition weaken effect, increase the active phase of zinc oxide, thus promote the desulphurizing activated of desulphurization catalyst further.Also can overcome desulphurization catalyst tear strength to decline, the problem that the life cycle caused shortens.In addition, the rare earth-antimony composite oxides of formation, can improve gasoline and diesel fuel desulfurization is active.Use the desulphurization catalyst containing rare earth-antimony composite oxides can also improve isomerization product content in the desulfurization product gasoline obtained, the octane number of product gasoline can be improved.
In the present invention, in described desulphurization catalyst, antimony oxide can reduce desulphurization catalyst in absorption and regeneration process, silicon in first metal oxide and carrier, the effect of al composition, reduce silicate and/or the aluminate of generation first metal, thus keep the activity of the first metal oxide, improve the desulphurizing activated of desulphurization catalyst.
According to the present invention, described active metal for promoting absorption and the cracking of the sulfur-containing compound in hydrocarbon oil containing surphur, for the sulphur of oxidation state being reduced to the metal of hydrogen sulfide.Described active metal can be selected from least one in cobalt, nickel, iron and manganese, is more preferably cobalt and/or nickel.
According to the present invention, described non-aluminum oxide can for providing cementation between component each in described desulphurization catalyst, and avoid described desulphurization catalyst when experiencing desulphurization reaction and regenerative process, al binder and the first metal oxide form spinel structure and make the defect that the performance of described desulphurization catalyst reduces.
According to the present invention, described silica source can for providing cementation between component each in described desulphurization catalyst.Under preferable case, the natural minerals that described silica source can be greater than 45 % by weight for pure silica or silica content.Preferably, described silica source can be selected from least one in laminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.Can also containing other component as Al in natural minerals
2o
3, K
2o, CaO, MgO, Fe
2o
3, TiO
2deng.In the present invention, the amount of other components contained in described silica source still can be regarded as the amount of silica source.
In the present invention, described phosphate aluminium molecular sieve is nearly body silicoaluminophosphate, is introduced by silicon in aluminum phosphate skeleton and obtains, and its skeleton is by PO
4 +, AlO
4 -and SiO
2tetrahedron forms.This molecular sieve analog comprises 13 kinds of three-dimensional microporous framework structures, and its hole size is
, pore volume is 0.18-0.48cm
3/ g.Under preferable case, described phosphate aluminium molecular sieve is at least one in SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve, and their hole size is respectively
(12 ring),
(10 ring),
(10 ring),
(8 ring) and
(6 ring); Pore volume is respectively 0.31,0.18,0.42,0.42 and 0.40cm
3/ g.Preferably, described phosphate aluminium molecular sieve is at least one in SAPO-11, SAPO-31 and SAPO-34.The SiO of described SAPO molecular sieve
2: Al
2o
3mol ratio be 0.05-0.1:1; Preferably, the SiO of described SAPO molecular sieve
2: Al
2o
3mol ratio be 0.1-0.5:1.
In the present invention, add effect or effect that phosphate aluminium molecular sieve can have the content raising gasoline products octane number promoting aromatization of hydrocarbons by increase aromatic hydrocarbons.
The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and the method comprises: the precursor of antimony oxide, rare earth compound, water and acidic liquid are mixed to get rare earth-antimony colloidal sol by (1); (2) non-al binder, silica source, the first metal oxide, phosphate aluminium molecular sieve, water and acidic liquid are mixed to form slurries, and contact obtain carrier mixture with described rare earth-antimony colloidal sol, described carrier mixture is carried out shaping, first dry and the first roasting, obtain carrier; (3) introduce the precursor of active metal on the carrier, and carry out second dry and the second roasting, obtain catalyst precarsor; (4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulphurization catalyst.
According to the present invention, the precursor of described antimony oxide is antimony oxide or the material that can change antimony oxide under the condition of described first roasting into.Under preferable case, the precursor of described antimony oxide is selected from least one in four antimony chlorides, antimony oxychloride, antimony acetate, aqua oxidation antimony and amorphous antimony.
According to the present invention, under preferable case, described rare earth compound can be selected from least one in the acetate of rare earth element, carbonate, nitrate, sulfate, oxalates, chloride and oxide; Preferably, described rare earth compound can be at least one in the carbonate of rare earth element, bicarbonate, formates and acetate.Wherein, described rare earth element is described above, repeats no longer one by one.
In the present invention, under preferable case, described non-al binder can be at least one in zirconium dioxide binding agent, titanium dioxide binding agent and tin ash binding agent.Described non-al binder can be zirconium dioxide, titanium dioxide or tin ash, or can change the material of zirconium dioxide, titanium dioxide or tin ash under the condition of described first roasting into.Particularly, described zirconium dioxide binding agent can be at least one in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide; Described tin ash binding agent can be at least one in butter of tin, four isopropyl alcohol tin, tin acetate, aqua oxidation tin and tin ash; The precursor of described titanium dioxide can for changing the material of anatase titanium dioxide under the condition of described first roasting, and described titanium dioxide binding agent can be at least one in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.Wherein anatase titanium dioxide still can generate anatase titanium dioxide after hydrolysis and the first roasting.
In the present invention, the precursor of described active metal can for changing the material of the oxide of active metal under the condition of described second roasting.Under preferable case, the precursor of described active metal can be selected from least one in the acetate of metal, carbonate, nitrate, sulfate, rhodanate and oxide.
In the present invention, as previously mentioned, this is no longer going to repeat them for described first metal oxide, silica source, phosphate aluminium molecular sieve and active metal.
According to the present invention, the step (1) of the preparation method of described desulphurization catalyst, by preparing rare earth-antimony colloidal sol, to form rare earth-antimony composite oxides structure by step (2).Desulphurization catalyst containing this structure is conducive to realizing object of the present invention.
In the present invention, obtaining described rare earth-antimony colloidal sol in step (1) can have multiple method, can be method one, comprise the following steps: the precursor of antimony oxide and acidic liquid are mixed to get antimony colloidal sol by (a); B described antimony colloidal sol and rare earth compound mix to contact with ammonia spirit again and obtain rare earth-antimony colloidal sol by ().Can also be method two, comprise the following steps: the precursor of antimony oxide and acidic liquid are mixed to get antimony colloidal sol by (a); B the aqueous solution of described antimony colloidal sol and rare earth compound is obtained rare earth-antimony colloidal sol by ().Also can be method three, comprise: the precursor of antimony oxide, rare earth compound and acidic liquid are mixed to get rare earth-antimony colloidal sol.
In said method, described acidic liquid is acid or aqueous acid, and described acid is selected from water-soluble inorganic acid and/or organic acid; Described acid can be at least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and the consumption of described acidic liquid makes the pH value of rare earth-antimony colloidal sol be 1-5, is preferably 1.5-4.The concentration of described acidic liquid can be 5-30 % by weight.The concentration of described ammonia spirit can be 10-30 % by weight.
In the present invention, forming slurries in step (2) can have multiple method, and a kind of preferred detailed description of the invention comprises: non-al binder, water contact with acidic liquid and obtains glue by (A); (B) this glue and silica source, the first metal oxide, phosphate aluminium molecular sieve are mixed to form slurries.Another kind of preferred detailed description of the invention comprises: non-al binder, silica source are contacted the silica source after obtaining non-aluminum adhesive gelatin and process with water with acidic liquid by (I) respectively, then are mixed into acidified slurries; (II) described acidified slurries and the first metal oxide, phosphate aluminium molecular sieve are mixed to form slurries.Wherein said acidic liquid is described above, and the consumption of described acidic liquid makes the pH value of described glue or described acidified slurries be less than 6, is preferably less than 4.
According to the present invention, shapingly described in step (2) described carrier mixture can be shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described carrier mixture be dough or paste mixture time, described carrier mixture shaping (preferred extrusion molding) can be made to form particle, and preferred diameter is at 1-8mm, length, at the cylindrical extrudates of 2-5mm, then makes the extrudate of gained carry out drying, roasting.If gained carrier mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably carrier mixture is slurry form, forms 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 mixture is 10-50 % by weight, is preferably 20-50 % by weight.Obtain can also comprising in the process of described carrier mixture adding water in step (2), there is no particular limitation for the addition of water, as long as the carrier mixture obtained meets above-mentioned solid content.
In the present invention, 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, 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 time of described first roasting is at least 0.5h.Preferably, the temperature of described first roasting is 400-500 DEG C, and the time of described 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 (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 active metal 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 active metal is easily oxidized, and the active metal 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 active metal substantially exist with reduction-state, obtains desulphurization catalyst of the present invention.
In the desulphurization catalyst obtained by method provided by the invention, the content of each component calculates according to inventory.
Preparation in accordance with the present invention, described non-al binder, the precursor of antimony oxide, rare earth compound, silica source, first metal oxide, the addition of the precursor of phosphate aluminium molecular sieve and active metal makes in the desulphurization catalyst obtained, with the gross weight of this desulphurization catalyst for benchmark, the content of described non-aluminum oxide is 3-25 % by weight, the content of described silica source is 5-30 % by weight, the content of described first metal oxide is 10-80 % by weight, the content of antimony oxide is 2-20 % by weight, the content of described active metal is 5-30 % by weight, described rare-earth oxide in the content of rare earth oxide for 0.5-15 % by weight, the content of described phosphate aluminium molecular sieve is 1-30 % by weight.
Preferably, with the gross weight of this desulphurization catalyst for benchmark, the content of described non-aluminum oxide is 5-25 % by weight, the content of described silica source is 10-20 % by weight, the content of described first metal oxide is 25-70 % by weight, and the content of antimony oxide is 2-20 % by weight, and the content of described active metal is 8-25 % by weight, described rare-earth oxide is in the content of rare earth oxide for 0.5-10 % by weight, and the content of described phosphate aluminium molecular sieve is 2-25 % by weight.
Present invention also offers the desulphurization catalyst obtained by preparation method provided by the invention.As previously mentioned, this is no longer going to repeat them for the composition of this desulphurization catalyst.
Present invention also offers 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 1-2MPa.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.
According to the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: regenerated by the desulphurization catalyst through reaction after reaction.The condition of regeneration comprises: regenerate under oxygen atmosphere (oxygen content can be 10-80 volume %); The temperature of regeneration is 450-600 DEG C, is preferably 480-520 DEG C; The pressure of regeneration is normal pressure.
In the present invention, the method of described desulfurization of hydrocarbon oil can also comprise: the desulphurization catalyst after regeneration needs to reduce under hydrogen atmosphere before reuse, and the condition of reduction comprises: reduce under hydrogen atmosphere (hydrogen content can be 30-60 volume %); The temperature of reduction can be 350-500 DEG C, preferred 400-450 DEG C; The pressure of reduction can be 0.2-2MPa, is preferably 0.2-1.5MPa.
In the present invention, described hydrocarbon ils comprises cracking gasoline and diesel fuel, and wherein " 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.Described " diesel fuel " means boiling range is the hydrocarbon mixture of 170 DEG C to 450 DEG C or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil, catalytic cracking diesel oil and hydroprocessed diesel etc. and combination thereof.
In the present invention, term used " 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.
The invention will be further described by the following examples.
In the following Examples and Comparative Examples, the composition of desulphurization catalyst calculates according to feeding intake.
Polycrystal X ray diffraction (XRD) adopts X-ray diffractometer (Siemens company D5005 type) to carry out the structure determination of desulphurization catalyst, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA.
Embodiment 1
The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.
(1) rare earth-antimony colloidal sol is prepared.The antimony oxide (Beijing Chemical Plant analyzes pure) of 0.5kg to be joined in nitric acid (Beijing Chemical Plant, the chemical pure) solution of 5 % by weight of 3.5kg and to stir 1h, obtaining water white antimony colloidal sol.After the lanthanum oxide powder (traditional Chinese medicines chemical reagents corporation analyzes pure) of 0.5kg being dissolved in the deionized water solution of 0.2kg and antimony colloidal sol be mixed to get lanthanum antimony colloidal sol.
(2) carrier is prepared.The zirconium chloride (Beijing Chemical Plant analyzes pure) of 2.28kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 3.1kg and makes pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
The deionized water of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.3kg) of 1.56kg and 4.0kg mixed, the red fuming nitric acid (RFNA) adding 200g stirs and makes pH=2.0, and is warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40 DEG C, (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO under agitation to add the SAPO-11 molecular sieve of the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg and 1.0kg
2: Al
2o
3mol ratio=1:1) after, then add above-mentioned zirconium colloidal sol and form slurries, then add above-mentioned lanthanum antimony colloidal sol, stir after mixing after 1 hour and obtain carrier mixture.
This carrier mixture is adopted NiroBowenNozzleTower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 8.5-9.5MPa, 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 650 DEG C, roasting 0.5h obtains carrier.
(3) active metal is introduced.By the carrier of 8.2kg 8.92kg Nickelous nitrate hexahydrate (Beijing chemical reagents corporation, purity is greater than 98.5 % by weight) and the aqueous impregnation of 1.6kg deionized water, the mixture obtained, after 250 DEG C of dry 5h, can obtain catalyst precarsor at air atmosphere 450 DEG C of roasting 1h.
(4) reduce.The 3h that reduced in the hydrogen atmosphere of 400 DEG C by catalyst precarsor can obtain desulphurization catalyst A1.
The chemical composition of A1 is: zinc oxide content is 40.0 % by weight, antimony oxide content is 5.0 % by weight, zirconium dioxide content is 12.0 % by weight, kaolin content is 13.0 % by weight, nickel content is 18.0 % by weight, lanthana content is 5.0 % by weight, SAPO-11 molecular sieve content is 7.0 % by weight.
A1 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 1.Be the characteristic peak that 27.9 °, 32.3 °, 46.2 ° and 54.7 ° of places exist the cubic system of lanthanum antimony composite oxides at 2 θ in spectrogram, be that 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 ° of places do not exist the characteristic peaks of the cubic system of antimony oxide at 2 θ, and be the characteristic peaks that 27.0 °, 31.4 °, 44.8 ° and 53.2 ° of places do not exist the cubic system of lanthana at 2 θ.Illustrate that in desulphurization catalyst A1, antimony oxide and lanthana define lanthanum antimony composite oxides structure.
Embodiment 2
The present embodiment is for illustration of the preparation method of desulphurization catalyst of the present invention.
(1) rare earth-antimony colloidal sol is prepared.The six nitric hydrate neodymiums (traditional Chinese medicines chemical reagents corporation, content is greater than 99.0 % by weight) of the antimony oxide of 0.6kg and 0.651kg to be joined in the dust technology of 15 % by weight of 2.7kg and to stir acidifying 1h, obtaining transparent neodymium antimony colloidal sol;
(2) carrier is prepared.By the stannic chloride pentahydrate (SnCl of 3.73kg
45H
2o, AlfaAesar company, 99 % by weight) slowly join in the hydrochloric acid solution of the concentration 3 % by weight of 5.0kg and make pH=1.5, and slowly stir and avoid tin oxide crystal to separate out, obtain water white tin oxide sol;
By diatomite (the catalyst Nanjing branch company of 1.24kg, containing butt 1.20kg) after the deionized water that adds 3.0kg mixes, the hydrochloric acid adding 30 % by weight of 75ml stirs and makes pH=2.0, is warming up to 80 DEG C of aging 2h after acidifying 1h, obtains the diatomite after processing;
Diatomite after above-mentioned tin oxide sol and process is mixed to form slurries, add zinc oxide (Beijing Chemical Plant's product of 4.56kg again, containing butt 4.5kg) powder, 0.6kg SAPO-34 molecular sieve (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.5kg, SiO
2: Al
2o
3mol ratio=0.25:1) and above-mentioned neodymium antimony colloidal sol, stir after mixing after 1 hour and obtain carrier mixture.
The spray drying forming of carrier mixture is carried out and roasting obtains carrier with reference to the method for embodiment 1.
(3) active metal is introduced.By Nickelous nitrate hexahydrate (the traditional Chinese medicines chemical reagents corporation of the carrier 5.94kg of 8.8kg, analyze pure)) and the aqueous impregnation of 0.8kg deionized water, then obtain catalyst precarsor with reference to method that is dry in embodiment 1 step (3) and roasting.
(4) reduce.Method reduction with reference to embodiment 1 step (4) obtains desulphurization catalyst A2.
The chemical composition of A2 is: zinc oxide content is 45.0 % by weight, and antimony oxide content is 6.0 % by weight, and tin oxide content is 16.0 % by weight, and diatomite content is 12.0 % by weight, and nickel content is 12.0 % by weight.Neodymia is 4.0 % by weight, SAPO-34 molecular sieve content is 5 % by weight.
A2 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 2.Be the characteristic peak that 28.0 °, 32.6 °, 46.7 ° and 55.4 ° of places exist the cubic system of neodymium antimony composite oxides at 2 θ in spectrogram, be that 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 ° of places do not exist the characteristic peaks of the cubic system of antimony oxide at 2 θ, and be the cubic system characteristic peaks that 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 ° of places do not exist neodymia at 2 θ.Illustrate that in desulphurization catalyst A2, antimony oxide and neodymia define the structure of neodymium antimony composite oxides.
Comparative example 1
The zirconium chloride of 3.20kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 3.7kg and make pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
The deionized water of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.3kg) of 1.56kg and 5.0kg mixed, the red fuming nitric acid (RFNA) adding 200g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40 DEG C, (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO under agitation to add the SAPO-11 molecular sieve of the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg and 1.0kg
2: Al
2o
3mol ratio=1:1) after, then add above-mentioned zirconium colloidal sol, then the deionized water of the lanthanum oxide powder and 0.2kg that add 0.5kg forms slurries, mix and blend obtained carrier mixture after 1 hour.
Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and dipping introduces active metal nickel, obtains desulphurization catalyst B1 after reduction.
The chemical composition of B1 is: zinc oxide content is 40.0 % by weight, and zirconium dioxide content is 17.0 % by weight, and kaolin content is 13.0 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 5.0 % by weight, SAPO-11 molecular sieve content is 7.0 % by weight.
Comparative example 2
The zirconium chloride of 2.27kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 2.6kg and make pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
The deionized water of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.3kg) of 1.56kg and 5.0kg mixed, the red fuming nitric acid (RFNA) adding 200g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40 DEG C, (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO under agitation to add the SAPO-11 molecular sieve of the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg and 1.0kg
2: Al
2o
3mol ratio=1:1) after, then the deionized water of the lanthanum oxide powder and 0.2kg that add 0.5kg forms the antimony oxide of slurries and 0.5kg, stirs after 1 hour and obtain carrier mixture after mixing.
Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and dipping introduces active group metallic nickel, obtains desulphurization catalyst B2 after reduction.
The chemical composition of B2 is: zinc oxide content is 40.0 % by weight, antimony oxide content is 5.0 % by weight, zirconium dioxide content is 12.0 % by weight, kaolin content is 13.0 % by weight, nickel content is 18.0 % by weight, lanthana content is 5.0 % by weight, SAPO-11 molecular sieve content is 7.0 % by weight.
Comparative example 3
The antimony oxide of 0.5kg to be joined in the salpeter solution of 5 % by weight of 3.5kg and to stir 1h, obtaining water white antimony colloidal sol;
The zirconium chloride (Beijing Chemical Plant analyzes pure) of 3.23kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 3.7kg and makes pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
The deionized water of the kaolin (catalyst asphalt in Shenli Refinery, containing butt 1.3kg) of 1.56kg and 5.0kg mixed, the red fuming nitric acid (RFNA) adding 200g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40 DEG C, (Shanghai Shen Tan environmental friendly material Co., Ltd, containing butt 0.70kg, SiO under agitation to add the SAPO-11 molecular sieve of the zinc oxide (traditional Chinese medicines chemical reagents corporation analyzes pure) of 4.05kg and 1.0kg
2: Al
2o
3mol ratio=1:1) after, then add above-mentioned zirconium colloidal sol, then add above-mentioned antimony colloidal sol, stir after mixing after 1 hour and obtain carrier mixture.
Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and dipping introduces active metal nickel, obtains desulphurization catalyst B3 after reduction.
The chemical composition of B3 is: zinc oxide content is 40.0 % by weight, and antimony oxide content is 5.0 % by weight, and zirconium dioxide content is 17.0 % by weight, and kaolin content is 13.0 % by weight, and nickel content is 18.0 % by weight, SAPO-11 molecular sieve content is 7.0 % by weight.
Comparative example 4
The antimony oxide of 0.5kg to be joined in the salpeter solution of 5 % by weight of 3.5kg and to stir 1h, obtaining water white antimony colloidal sol.After the lanthanum oxide powder of 0.5kg being dissolved in the deionized water solution of 0.2kg and antimony colloidal sol be mixed to get lanthanum antimony colloidal sol.
The zirconium chloride of 3.59kg is slowly joined in the salpeter solution of the concentration 5 % by weight of 4.12kg and make pH=2.0, and slowly stirring avoids crystal of zirconium oxide to separate out, and obtains water white zirconium colloidal sol;
The deionized water of the kaolin of 1.56kg and 4.5kg mixed, the red fuming nitric acid (RFNA) adding 200g stirs and makes pH=1.8, and is warming up to more than 60 DEG C acidifyings 1 hour.When temperature is reduced to below 40 DEG C, after under agitation adding the zinc oxide of 4.05kg, then add above-mentioned zirconium colloidal sol formation slurries, then add above-mentioned cerium antimony colloidal sol, stir after mixing after 1 hour and obtain carrier mixture.
Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and dipping introduces active metal nickel, obtains desulphurization catalyst B4 after reduction.
The chemical composition of B4 is: zinc oxide content is 40.0 % by weight, and antimony oxide content is 5.0 % by weight, and zirconium dioxide content is 19.0 % by weight, and kaolin content is 13.0 % by weight, and nickel content is 18.0 % by weight, and lanthana content is 5.0 % by weight.
Embodiment 4
Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A2 and B1-B4.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-A2 and B1-B4, 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 silicate assay.The crystalline phase composition of desulphurization catalyst A1-A2 and B1-B4 after the 6th circulation in embodiment 5 is analyzed, measures zinc silicate 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 silicate content of different desulphurization catalyst is as shown in table 1.
Wherein, B2 is carried out polycrystal X ray diffraction (XRD) and characterize, spectrogram is shown in Fig. 3.Be that the characteristic peak of zinc silicate has appearred in 22.1 °, 25.5 °, 31.5 °, 38.8 °, 45.0 °, 47.0 °, 48.9 °, 57.6 °, 59.5 °, 65.6 °, 65.8 ° and 68.7 ° of places at 2 θ, but there is not the characteristic peak of lanthanum antimony composite oxides, illustrate in desulphurization catalyst B2 and do not form lanthanum antimony composite oxides structure, and form zinc silicate component.
Table 1
| A1 | A2 | B1 | B2 | B3 | B4 | |
| Zn 2SiO 4, % by weight | 0 | 0 | 3.4 | 2.9 | 4.0 | 0 |
| Abrasion index (before sulfuration) | 4.3 | 4.5 | 5.3 | 4.9 | 5.4 | 4.3 |
| Abrasion index (after sulfuration) | 4.1 | 4.4 | 5.1 | 4.7 | 5.3 | 4.1 |
| Yield of gasoline, % | 99.8 | 99.7 | 99.0 | 99.1 | 98.4 | 99.8 |
| Product sulfur content, ppm | 4 | 6 | 20 | 18 | 23 | 4 |
| △RON | 0.72 | 0.66 | 0.45 | 0.50 | 0.36 | 0.27 |
| △MON | 0.65 | 0.63 | 0.40 | 0.46 | 0.32 | 0.24 |
| △(RON+MON)/2 | 0.68 | 0.64 | 0.42 | 0.48 | 0.34 | 0.26 |
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 (19)
1. a desulphurization catalyst, with the gross weight of this desulphurization catalyst for benchmark, this desulphurization catalyst contains:
1) the non-aluminum oxide of 3-35 % by weight, described non-aluminum oxide is at least one in titanium dioxide, zirconium dioxide and tin ash;
2) silica source of 5-30 % by weight;
3) first metal oxide of 10-80 % by weight, described first metal oxide is selected from least one in the metal oxide of IIB, VB and group vib element;
4) antimony oxide of 2-20 % by weight;
5) active metal of 5-30 % by weight, described active metal is selected from least one in cobalt, nickel, iron and manganese;
6) in the rare-earth oxide of the 0.5-15 % by weight of rare earth oxide;
7) phosphate aluminium molecular sieve of 1-30 % by weight;
The characteristic peak of rare earth-antimony composite oxides is there is in the XRD spectra of described desulphurization catalyst.
2. desulphurization catalyst according to claim 1, wherein, with the gross weight of described desulphurization catalyst for benchmark, the content of described non-aluminum oxide is 5-25 % by weight, the content of described silica source is 10-20 % by weight, the content of described first metal oxide is 25-70 % by weight, the content of antimony oxide is 2-20 % by weight, the content of described active metal is 8-25 % by weight, described rare-earth oxide is in the content of rare earth oxide for 0.5-10 % by weight, and the content of described phosphate aluminium molecular sieve is 2-25 % by weight.
3. desulphurization catalyst according to claim 1, wherein, the rare earth element in described rare-earth oxide is selected from least one in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
4. desulphurization catalyst according to claim 3, wherein, the rare earth element in described rare-earth oxide is at least one in La, Pr and Nd.
5. according to the desulphurization catalyst in claim 1-4 described in any one, wherein, rare earth element is lanthanum, there is the characteristic peak that 2 θ are the cubic system of the lanthanum antimony composite oxides of 27.9 °, 32.3 °, 46.2 ° and 54.7 ° in the XRD spectra of described desulphurization catalyst; There is not the characteristic peak that 2 θ are the cubic system of the antimony oxide of 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 °, there is not the characteristic peak that 2 θ are the cubic system of the lanthana of 27.0 °, 31.4 °, 44.8 ° and 53.2 °.
6. according to the desulphurization catalyst in claim 1-4 described in any one, wherein, rare earth element is neodymium, there is the characteristic peak that 2 θ are the cubic system of the neodymium antimony composite oxides of 28.0 °, 32.6 °, 46.7 ° and 55.4 ° in the XRD spectra of described desulphurization catalyst; There is not the characteristic peak that 2 θ are the cubic system of the antimony oxide of 13.7 °, 27.7 °, 32.1 °, 35.0 °, 46.0 °, 54.5 ° and 57.1 °, there is not the characteristic peak that 2 θ are the cubic system of the neodymia of 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 °.
7. desulphurization catalyst according to claim 1, 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.
8. desulphurization catalyst according to claim 1, wherein, described phosphate aluminium molecular sieve is at least one in SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieve.
9. the preparation method of the desulphurization catalyst in claim 1-8 described in any one, the method comprises:
(1) precursor of antimony oxide, rare earth compound, water and acidic liquid are mixed to get rare earth-antimony colloidal sol;
(2) non-al binder, silica source, the first metal oxide, phosphate aluminium molecular sieve, water and acidic liquid are mixed to form slurries, and contact obtain carrier mixture with described rare earth-antimony colloidal sol, described carrier mixture is carried out shaping, first dry and the first roasting, obtain carrier;
(3) introduce the precursor of active metal on the carrier, and carry out second dry and the second roasting, obtain catalyst precarsor;
(4) described catalyst precarsor is reduced in a hydrogen atmosphere, obtain desulphurization catalyst.
10. preparation method according to claim 9, wherein, the precursor of described antimony oxide is selected from least one in four antimony chlorides, antimony oxychloride, antimony acetate, aqua oxidation antimony and amorphous antimony.
11. preparation methods according to claim 9, wherein, described rare earth compound is selected from least one in the acetate of rare earth metal, carbonate, nitrate, sulfate, oxalates, chloride and oxide.
12. preparation methods according to claim 9, wherein, the precursor of described active metal can be selected from least one in the acetate of metal, carbonate, nitrate, sulfate, rhodanate and oxide.
13. preparation methods according to claim 9, wherein, described non-al binder is zirconium dioxide, titanium dioxide or tin ash, or can change the material of zirconium dioxide, titanium dioxide or tin ash under the condition of described first roasting.
14. preparation method according to claim 9, wherein, described acidic liquid is acid or aqueous acid, and described acid is selected from water-soluble inorganic acid and/or organic acid.
15. preparation methods according to claim 9, 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.
16. preparation methods according to claim 9, 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.
17. preparation methods according to claim 9, 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 %.
Desulphurization catalyst prepared by the method in 18. claim 9-17 described in any one.
The method of 19. 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 1-8 and 18 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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