CN105582974B - A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents

Abstract

The invention discloses a kind of desulphurization catalyst, the desulphurization catalyst for also disclosing a kind of preparation method of desulphurization catalyst and being obtained by this method, and application of the desulphurization catalyst in hydrocarbon oil containing surphur desulfurization.The desulphurization catalyst contains non-aluminum oxide, silica source, the first metal oxide, lead oxide, rare-earth oxide, molecular sieve and active metal；The characteristic peak of rare earth plumbum composite oxide in the XRD spectra of the desulphurization catalyst be present.The desulphurization catalyst has preferably desulphurizing activated and desulfurization stability.

Description

A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil

Technical field

The present invention relates to the method for a kind of desulphurization catalyst and preparation method thereof He desulfurization of hydrocarbon oil, in particular it relates to a kind of Desulphurization catalyst, the desulphurization catalyst for preparing the method for desulphurization catalyst and being obtained by this method, and use the desulfurization catalyst The method that agent carries out desulfurization of hydrocarbon oil.

Background technology

Caused oxysulfide after combustion of sulfur in vehicle fuel, can suppress the precious metal catalyst in vehicle exhaust converter The activity of agent simultaneously can be allowed to occur irreversibly to be poisoned.So that the oxygen containing unburned non-methane hydrocarbon and nitrogen in vehicle exhaust Compound and carbon monoxide, and these discharge gas are then easily formed photochemical fog by hydrophilic dye, trigger acid rain, while in air Oxysulfide be also one of the main reason for forming acid rain in itself.As people are to the pay attention to day by day of environmental protection, environmental law Rule are also increasingly strict, and the sulfur content for reducing gasoline and diesel oil is considered as one of most important measure for improving air quality.

The existing gasoline products standard GB 17930-2011 in China《Motor petrol》It is required that on December 31st, 2013, vapour Sulfur content must drop to 50 μ g/g in oil；And future, gasoline quality standard can be stricter.In this case, catalysis is split Change gasoline, which has to pass through deep desulfuration, can just meet the requirement of environmental protection.

At present, the process for deep desulphurization of oil product mainly have hydrofinishing and absorption two methods of desulfurization, but China due to The problem of hydrogen source, make it that the cost of hydrofinishing is higher.S-Zorb absorption desulfurization, which belongs to, faces hydrogen desulfurization technology, certain The adsorbing and removing of sulfide is realized under the conditions of temperature and pressure.Because sulfur-containing compound of the technology in gasoline is removed has hydrogen The characteristics of low is consumed, and the purity requirement to hydrogen is not high so that the technology has in terms of the sulfur-containing compound in removing fuel oil Have broad application prospects.

The method that traditionally desulfurization often uses fixed bed from liquid, but the reaction uniformity of this method and regeneration have Obvious inferior position.Fluidized-bed process has the advantages of preferably heat transfer and pressure drop etc. compared with fixed-bed process, therefore has Have broad application prospects.Fluidized-bed reactor typically uses granular reactant, but for most of reactions, reaction used The typically no enough wearabilities of thing.Therefore, the adsorbent for finding anti-wear performance well while having preferable desulfurization performance has important Meaning.

CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Thing, it is made up of zinc oxide, silica, non-aluminum oxide and nickel, wherein for nickel substantially to reduce valence state presence, its amount can be from Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under desulfurization conditions with the nickeliferous adsorbent composition.The combination Thing is granulated to form particle by the compound particles for forming zinc oxide, silica and non-aluminum oxide, dry, after roasting with nickel or Nickel compound containing impregnates, and re-dry, roasting, reduction obtain.

CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Thing, it is made up of zinc oxide, silica, non-aluminum oxide and cobalt, wherein for cobalt substantially to reduce valence state presence, its amount can be from Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under desulfurization conditions with the adsorbent composition containing cobalt. All be only referred in CN1355727A and CN1382071A it is desulphurizing activated, for adsorbent physical and chemical performance (such as abrasion strength resistance) with And stability is not all introduced.

Adsorbent is disclosed in US6150300, CN1130253A and CN1258396A：Include zinc oxide, silica, non-aluminum The granular adsorbent composition of the mixture of oxide, reduction valence state nickel or cobalt.Preparation method is mainly using the side such as shearing Silica, non-aluminum oxide and zinc oxide are mixed merga pass comminutor and prepare solid particle by method, impregnate nickel after drying and roasting So as to which adsorbent be made.It is main for its physical and chemical performance although the adsorbent of these patent introductions has preferable desulfurization performance If tear strength is not described in the patent.

CN1208124A discloses includes zinc oxide, expanded perlite and non-aluminum using promoter metals such as cobalt and nickel dipping The adsorbing agent carrier of oxide, the accelerator is then reduced at appropriate temperatures, prepare for removing sulfide in cracking gasoline Adsorbent.

CN1627988A discloses one kind and is suitable for removing elementary sulfur and vulcanization conjunction from cracking gasoline and diesel fuel The adsorbent composition of thing, the adsorbent composition include：Zinc oxide, expanded perlite, aluminate and promoter metals, its Described in promoter metals will cause from cracking when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it The amount of desulfurization in the stream of gasoline or diesel fuel is present, and at least partly described promoter metals exist with 0 valence state.

CN1856359A discloses a kind of method for producing composition, including：A) mixing liquid, zinc compound, containing two Silica material, non-aluminum oxide and co-catalyst, to form its mixture；B) mixture is dried, to be formed through dry Mixture；C) this is calcined through dry mixture, to form the mixture through calcining；D) with appropriate reducing agent in appropriate bar The mixture through calcining is reduced under part, to produce the composition of the co-catalyst content in it with reduction valence state, with And e) compound is reorganized in recovery.Co-catalyst contains selected from various metals such as nickel.

CN1871063A discloses a kind of method for producing composition, and this method includes：A) by liquid, zinc compound, Mixed containing earth silicon material, non-aluminum oxide to form its mixture；B) mixture is dried into the mixing to be formed First through drying composite；C) described first is calcined to form first through calcining mixt through drying composite；D) will promote Agent be attached to described first through within calcining mixt or on to form promoted mixture；E) the promoted mixture is made Contacted with the acid selected from citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) done described through contact mixture It is dry to be formed second through drying composite；G) described second is calcined to form second through calcining mixt through drying composite； H) suitable reducing agent reduction described second is used under suitable condition through calcining mixt to produce wherein containing also original cost The composition of state accelerator content, and i) reclaim the composition.

CN101816918A discloses a kind of desulfuration adsorbent, and adsorbent composition is rare earth metal, non-aluminum oxide, oxygen The adsorbent of SiClx, accelerator and one or more of metal oxides selected from IIB, VB and VIB.The adsorbent has preferable Abrasion strength resistance and desulphurizing activated.

Although these methods prepare adsorbent there is preferable desulfurization performance, there is also it is obvious the shortcomings that.Above-mentioned suction Attached dose uses zinc oxide active component, and it is higher to aoxidize the temperature of zinc-iron alloy solution sulphur and oxidation regeneration, in desulphurization reaction and Easily adsorbent activity is caused to reduce with the silicon in carrier, aluminium component generation zinc silicate and/or zinc aluminate during oxidation regeneration.By This is visible, it is desirable to provide a kind of new catalyst with more high desulfurization activity and abrasion resistance properties.

The content of the invention

The invention aims to overcome the desulphurizing activated low, structural instability of the adsorbent of prior art and wear resistance Can be poor the defects of, there is provided the method for a kind of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil.

To achieve these goals, the present invention provides a kind of desulphurization catalyst, using the gross weight of the desulphurization catalyst as base Standard, the desulphurization catalyst contain：1) 3-35 weight % non-aluminum oxide, the non-aluminum oxide are titanium dioxide, titanium dioxide At least one of zirconium and tin ash；2) 5-30 weight % silica source；3) 10-80 weight % the first metal oxidation Thing, first metal oxide are selected from least one of metal oxide of IIB, VB and group vib element；4) 2-20 weights Measure % lead oxide；5) 5-30 weight % active metal, the active metal are selected from least one of cobalt, nickel, iron and manganese； 6) rare-earth oxide of the 0.5-15 weight % in terms of rare earth oxide；7) 1-30 weight % molecular sieve, the molecule Sieve as at least one of X-type molecular sieve, Y type molecular sieve and beta-molecular sieve；Exist in the XRD spectra of the desulphurization catalyst dilute The characteristic peak of soil-plumbum composite oxide.

The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and this method includes：(1) by lead oxide Precursor, rare earth compound, water and acidic liquid are mixed to get rare earth-alucol；(2) by non-al binder, silica Source, the first metal oxide, molecular sieve, water and acidic liquid are mixed to form slurries, and contact to obtain with the rare earth-alucol Carrier mixture, the carrier mixture is molded, first dry and first roasting, obtain carrier；(3) in the carrier The upper precursor for introducing active metal, and the second drying and the second roasting are carried out, obtain catalyst precarsor；(4) by the catalyst Precursor reduces in a hydrogen atmosphere, obtains desulphurization catalyst.

Present invention also offers the desulphurization catalyst that preparation method provided by the present invention obtains.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur with Hydrodesulfurization catalyst provided by the invention, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5- 4MPa。

Mixed in desulphurization catalyst provided by the invention containing the first metal oxide with lead oxide and absorb constituent element as sulphur, Lead oxide can effectively reduce the effect of the first metal oxide and silicon, aluminium component in carrier, reduce the first metal of generation Silicate and/or aluminate, so that the desulphurization catalyst can absorb sulphur at lower temperatures and through reaction is repeated And regenerative process, still there is more preferable desulphurizing activated and activity stability.

Contain rare-earth oxide in desulphurization catalyst provided by the invention, and it is multiple with lead oxide to become rare earth-lead Close oxide effectively further oxidation reinforced lead can imitate to the first metal oxide and silicon, the decrease of aluminium component phase separation Fruit.

By desulphurization catalyst provided by the invention, the desulphurization catalyst still may be used after carrying out multiple desulfurization regeneration course of reaction Preferably desulphurizing activated to have, desulfurization stability is more preferable.And the desulphurization catalyst carries out desulfurization of hydrocarbon oil reaction and can had less Green coke amount, yield of gasoline is higher.Iso-component is more in obtained product gasoline composition, and sulfur content is lower, product gasoline Octane number improve, product gasoline better quality.The other desulphurization catalyst can obtain more preferable wear resistance.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description of the drawings

Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 be the desulphurization catalyst A1 containing lanthanum XRD spectra, wherein 2 θ be 28.3 °, 32.8 °, 47.1 ° and 55.8 ° simultaneously MarkPeak be lanthanum plumbum composite oxide cubic system characteristic peak；

Fig. 2 be the desulphurization catalyst A2 containing cerium XRD spectra, wherein 2 θ be 28.5 °, 33.1 °, 47.4 °, 56.3 ° and 59.0 ° and markPeak be cerium plumbum composite oxide cubic system characteristic peak；

Fig. 3 be the desulphurization catalyst A3 containing neodymium XRD spectra, wherein 2 θ be 28.3 °, 32.8 °, 47.0 °, 55.8 ° and 58.5 ° and markPeak be neodymium plumbum composite oxide cubic system characteristic peak；

Fig. 4 is desulphurization catalyst B2 XRD spectra, without the lanthanum lead that 2 θ are 28.3 °, 32.8 °, 47.1 ° and 55.8 ° The characteristic peak of composite oxides, wherein 2 θ be 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 mark " ■ " peak be zinc silicate characteristic peak.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The present invention provides a kind of desulphurization catalyst, and on the basis of the gross weight of the desulphurization catalyst, the desulphurization catalyst contains Have：1) 3-35 weight % non-aluminum oxide, the non-aluminum oxide be titanium dioxide, zirconium dioxide and tin ash in extremely Few one kind；2) 5-30 weight % silica source；3) 10-80 weight % the first metal oxide, the first metal oxidation Thing is selected from least one of metal oxide of IIB, VB and group vib element；4) 2-20 weight % lead oxide；5) 5-30 weights % active metal is measured, the active metal is selected from least one of cobalt, nickel, iron and manganese；6) in terms of rare earth oxide 0.5-15 weight % rare-earth oxide；7) 1-30 weight % molecular sieve, the molecular sieve are X-type molecular sieve, Y types point At least one of son sieve and beta-molecular sieve；The spy of rare earth-plumbum composite oxide in the XRD spectra of the desulphurization catalyst be present Levy peak.

Preferably, on the basis of the gross weight of the desulphurization catalyst, the content of the non-aluminum oxide is 5-25 weights Measure %, the content of the silica source is 10-20 weight %, and the content of first metal oxide is 25-70 weight %, oxygen The content for changing lead is 2-20 weight %, and the content of the active metal is 8-25 weight %, and the rare-earth oxide is with dilute The content of native oxide meter is 0.5-10 weight %, and the content of the molecular sieve is 2-25 weight %.

In the present invention, the content of the desulphurization catalyst middle rare earth metal oxide and lead oxide can advantageously form dilute Soil-plumbum composite oxide structure, so as to be more beneficial for oxidation reinforced lead to the first metal oxide and silicon, aluminium component phase separation Weaken effect, to improve the abrasion resistance properties of desulphurization catalyst, desulphurizing activated and product gasoline quality.

According to the present invention, first metal oxide is the metal oxide with storage sulphur performance, it is preferable that described the One metal oxide be zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide in extremely Few one kind；It is highly preferred that first metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；Most preferably First metal oxide is zinc oxide.

According to the present invention, the rare-earth oxide contained in the desulphurization catalyst can be combined with lead oxide, be made The crystal structure of rare earth-plumbum composite oxide can be had by obtaining desulphurization catalyst.Under preferable case, the rare-earth oxide In rare earth element be selected from least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu；It is excellent It is at least one of La, Ce, Pr and Nd to select the rare earth element in the rare-earth oxide.

In the case of, according to the invention it is preferred to, as shown in figure 1, when rare earth element is lanthanum, the XRD of the desulphurization catalyst is composed Characteristic peak (the JCPDS of the cubic system for the lanthanum plumbum composite oxide that 2 θ are 28.3 °, 32.8 °, 47.1 ° and 55.8 ° in figure be present No.52-0318)；In the absence of the tetragonal crystal system for the lead oxide that 2 θ are 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° Characteristic peak (JCPDSNo.5-0561), in the absence of 2 θ be 27.0 °, 31.4 °, 44.8 ° and 53.2 ° lanthana cubic system Characteristic peak (JCPDS No.4-0856).

In the case of, according to the invention it is preferred to, as shown in Fig. 2 when rare earth element is cerium, the XRD of the desulphurization catalyst The feature of the cubic system for the cerium plumbum composite oxide that 2 θ are 28.5 °, 33.1 °, 47.4 °, 56.3 ° and 59.0 ° in spectrogram be present Peak (JCPDS No.48-0059)；In the absence of the lead oxide that 2 θ are 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° The characteristic peak of tetragonal crystal system, in the absence of the characteristic peak of the cubic system for the cerium oxide that 2 θ are 28.5 °, 33.1 °, 47.5 ° and 56.3 ° (JCPDS No.03-065-2975)。

In the case of, according to the invention it is preferred to, as shown in figure 3, when rare earth element is neodymium, the XRD of the desulphurization catalyst The feature of the cubic system for the neodymium plumbum composite oxide that 2 θ are 28.3 °, 32.8 °, 47.0 °, 55.8 ° and 58.5 ° in spectrogram be present Peak (JCPDS No.47-0875)；In the absence of the lead oxide that 2 θ are 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° The characteristic peak of tetragonal crystal system, it is 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 ° in the absence of 2 θ The characteristic peak (JCPDS No.6-0408) of the cubic system of neodymia.

In the present invention, rare earth-plumbum composite oxide structure is formed in desulphurization catalyst, lead oxide can be promoted to first Metal oxide and silicon, the decrease effect of aluminium component phase separation, increase the active phase of zinc oxide, so as to further promote desulfurization to urge Agent it is desulphurizing activated.Desulphurization catalyst tear strength can also be overcome to decline, the problem of caused service life shortens.Separately Outside, rare earth-plumbum composite oxide of formation, gasoline and diesel fuel desulfurization activity can be improved.Using containing rare earth-lead combined oxidation The desulphurization catalyst of thing can also improve isomerization product content in obtained desulfurization product gasoline, can improve product gasoline Octane number.

In the present invention, in the desulphurization catalyst, lead oxide can reduce desulphurization catalyst in absorption and regenerative process In, the effect of the first metal oxide and silicon, aluminium component in carrier, reduce the silicate and/or aluminic acid for generating the first metal Salt, so as to keep the activity of the first metal oxide, improve the desulphurizing activated of desulphurization catalyst.

According to the present invention, the active metal is used for the absorption and cracking for promoting the sulfur-containing compound in hydrocarbon oil containing surphur, is The sulphur of oxidation state can be reduced to the metal of hydrogen sulfide.The active metal can be in cobalt, nickel, iron and manganese at least one Kind, more preferably cobalt and/or nickel.

According to the present invention, the non-aluminum oxide can be to provide to bond between each component in the desulphurization catalyst to make With, and the desulphurization catalyst is avoided when undergoing desulphurization reaction and regenerative process, al binder and the first metal oxide shape Into spinel structure and make the desulphurization catalyst performance reduce the defects of.

According to the present invention, the silica source can be to provide cementation between each component in the desulphurization catalyst. Under preferable case, the silica source can be the natural minerals that pure silica or silica content are more than 45 weight %.It is preferred that Ground, the silica source can be selected from laminated clay column, diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, big At least one of hole silica and silica gel.Other components such as Al can also be contained in natural minerals₂O₃、K₂O、CaO、MgO、 Fe₂O₃、TiO₂Deng.In the present invention, the amount of the other components contained in the silica source still can be regarded as the amount of silica source.

In the case of, according to the invention it is preferred to, the sial atomic molar ratio of the X-type molecular sieve is 1-3：1；The Y types point The sial atomic molar ratio of son sieve can be 3-25：1.The Y type molecular sieve can also include but is not limited to super-stable Y molecular sieves (USY), HY and phosphorous USY (PUSY)；The sial atomic molar ratio of the beta-molecular sieve can be 10-40：1.

In the present invention, promotion hydro carbons virtue can be had by adding at least one of X-type molecular sieve, Y type molecular sieve and beta-molecular sieve Structure improves effect or the effect of gasoline products octane number by increasing the content of aromatic hydrocarbons.

The present invention also provides the preparation method of desulphurization catalyst provided by the invention, and this method includes：(1) by lead oxide Precursor, rare earth compound, water and acidic liquid are mixed to get rare earth-alucol；(2) by non-al binder, silica Source, the first metal oxide, molecular sieve, water and acidic liquid are mixed to form slurries, and contact to obtain with the rare earth-alucol Carrier mixture, the carrier mixture is molded, first dry and first roasting, obtain carrier；(3) in the carrier The upper precursor for introducing active metal, and the second drying and the second roasting are carried out, obtain catalyst precarsor；(4) by the catalyst Precursor reduces in a hydrogen atmosphere, obtains desulphurization catalyst.

According to the present invention, the precursor of the lead oxide can turn for lead oxide or under conditions of the described first roasting It is changed into the material of lead oxide.Under preferable case, the precursor of the lead oxide is selected from lead tetrachloride, oxychlorination lead, lead acetate, water Close at least one of lead oxide and amorphous lead.

In the case of, according to the invention it is preferred to, the rare earth compound can be selected from acetate, the carbonic acid of rare earth element At least one of salt, nitrate, sulfate, oxalates, chloride and oxide；Preferably, the rare earth compound Can be at least one of carbonate, bicarbonate, formates and acetate of rare earth element.Wherein, the rare earth element As described above, no longer repeat one by one.

In the present invention, under preferable case, the non-al binder can be zirconium dioxide binding agent, titanium dioxide binding agent At least one of with tin ash binding agent.The non-al binder can be zirconium dioxide, titanium dioxide or tin ash, Or the material of zirconium dioxide, titanium dioxide or tin ash can be changed under conditions of the described first roasting.Specifically, The zirconium dioxide binding agent can be in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide At least one；The tin ash binding agent can be butter of tin, four isopropanol tin, tin acetate, aqua oxidation tin and two At least one of tin oxide；The precursor of the titanium dioxide can be that can be changed under conditions of the described first roasting The material of anatase titanium dioxide, the titanium dioxide binding agent can be titanium tetrachloride, tetraethyl titanate, isopropyl titanate, At least one of acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.Wherein anatase titanium dioxide through hydrolysis and Remain able to generate anatase titanium dioxide after first roasting.

In the present invention, the precursor of the active metal can be that can be changed into activity under conditions of the described second roasting The material of the oxide of metal.Under preferable case, the precursor of the active metal can be selected from the acetate of metal, carbonate, At least one of nitrate, sulfate, rhodanate and oxide.

In the present invention, the first metal oxide, silica source, molecular sieve and the active metal are as it was previously stated, herein not Repeat one by one again.

According to the present invention, the step of the preparation method of the desulphurization catalyst (1), by preparing rare earth-alucol, so as to Rare earth-plumbum composite oxide structure is formed by step (2).Desulphurization catalyst containing the structure is advantageously implemented the present invention's Purpose.

In the present invention, the rare earth-alucol is obtained in step (1) can a variety of methods, can be method one, including Following steps：(a) precursor of lead oxide and acidic liquid are mixed to get alucol；(b) by the alucol and rare earth gold Category compound mixing contacts to obtain rare earth-alucol again with ammonia spirit.It can also be method two, comprise the following steps：(a) will The precursor of lead oxide is mixed to get alucol with acidic liquid；(b) by the water-soluble of the alucol and rare earth compound Liquid is mixed to get rare earth-alucol.Can also be method three, including：By the precursor of lead oxide, rare earth compound and acid Property liquid is mixed to get rare earth-alucol.

In the above method, the acidic liquid for acid or acid the aqueous solution, it is described acid selected from water-soluble inorganic acid and/ Or organic acid；The acid can be at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, the dosage of the acidic liquid The pH value for making rare earth-alucol is 1-5, preferably 1.5-4.The concentration of the acidic liquid can be 5-30 weight %.It is described The concentration of ammonia spirit can be 10-30 weight %.

A variety of methods can be had by forming slurries in the present invention, in step (2), and a kind of preferred embodiment includes： (A) non-al binder, water are contacted with acidic liquid to obtain glue；(B) glue and the first metal oxide, molecular sieve are mixed Conjunction forms slurries.Another preferred embodiment includes：(I) non-al binder, silica source are used into water and acid respectively Property liquid contact to obtain silica source after non-aluminum adhesive gelatin and processing, remix as acidified slurries；(II) by the acid Slurrying liquid and the first metal oxide, molecular sieve are mixed to form slurries.Wherein described acidic liquid is as described above, the Acidic Liquid The dosage of body makes the pH value of the glue or the acidified slurries be less than 6, preferably smaller than 4.

According to the present invention, described in step (2) shaping the carrier mixture can be shaped to extrudate, piece, pill, Ball or micro-spherical particle.For example, when the carrier mixture is dough or paste mixture, can make the carrier mixture into Type (preferably extrusion molding) forms particle, and for preferably diameter in 1-8mm, then length makes gained in 2-5mm cylindrical extrudates Extrudate be dried, be calcined.It if resulting vehicle mixture is wet mixture form, can be thickened the mixture, pass through Dry aftershaping.More preferably carrier mixture is slurry form, and the microballoon that granularity is 20-200 microns is formed by spray drying, Reach the purpose of shaping.For the ease of spray drying, the solid content of the carrier mixture is 10-50 weight % before drying, excellent Elect 20-50 weight % as.It can also include adding water during obtaining the carrier mixture in step (2), water adds Entering amount, there is no particular limitation, as long as obtained carrier mixture meets above-mentioned solid content.

In the present invention, the addition of first metal oxide can be oxide powder form or by first Metal oxide is prepared as using as a slurry again after slurries.

In the present invention, the condition of first drying and the first roasting can be with known to those skilled in the art, preferably In the case of, the described first temperature dried is 80-150 DEG C, and the described first time dried was 0.5-24h；First roasting Temperature be 300-700 DEG C, it is described first roasting time be at least 0.5h.Preferably, the temperature of first roasting is 400-500 DEG C, the time of first roasting is 0.5-100h, and the time of more preferably described first roasting is 0.5-10h.

According to the present invention, step (3) is used to add metallic promoter agent.The precursor of the metallic promoter agent is can be second The material of the oxide of metallic promoter agent can be changed under roasting condition；Under preferable case, the precursor of the metallic promoter agent At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide of metallic promoter agent can be selected from.

In the case of, according to the invention it is preferred to, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitation. The dipping can be the solution or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitation can be to promote metal The solution or suspension for entering the precursor of agent mix with carrier, then add ammoniacal liquor by the precursor precipitation of metallic promoter agent in carrier On.

In the present invention, the condition of second drying and the second roasting can be with known to those skilled in the art, preferably In the case of, the described second temperature dried is 50-300 DEG C, and the described second time dried was 0.5-8h；Second roasting Temperature is 300-700 DEG C, and the time of second roasting is 0.5-4h；Preferably, the described second temperature dried is 100-250 DEG C, the described second time dried was 1-5h；The temperature of second roasting is 400-500 DEG C, the time of second roasting For 1-3h.Second roasting can have lower progress existing for oxygen or oxygen-containing gas, until volatile materials is removed simultaneously And active metal is converted into the form of metal oxide, obtains catalyst precarsor.

According to the present invention, in step (4), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal Simple substance, the catalyst precarsor can be reduced under hydrogen atmosphere, metallic promoter agent is substantially deposited with reduction-state Obtaining catalyst of the present invention.The condition of the reduction only turns the oxide of the metallic promoter agent in the catalyst precarsor It is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is 300- 600 DEG C, time of the reduction is 0.5-6h, and hydrogen content is 10-60 volumes % in the hydrogen atmosphere；Preferably, institute The temperature for stating reduction is 350-450 DEG C, and the time of the reduction is 1-3h.

In the present invention, step (4) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also Carried out before use (before being adsorbed for desulfurization).Because active metal easily aoxidizes, and the active metal in catalyst precarsor Exist in the form of an oxide, therefore catalyst precarsor is reduced and is carrying out desulfurization absorption advance for ease of transport, preferred steps (4) OK.Described to be reduced to make the metal in the oxide of active metal substantially to exist with reduction-state, the desulfurization for obtaining the present invention is urged Agent.

The content of each component is calculated according to inventory in desulphurization catalyst made from method provided by the present invention.

Preparation in accordance with the present invention, the non-al binder, the precursor of lead oxide, rare earth compound, oxygen SiClx source, the first metal oxide, the addition of precursor of molecular sieve and active metal make in obtained desulphurization catalyst, with On the basis of the gross weight of the desulphurization catalyst, the content of the non-aluminum oxide is 3-25 weight %, and the silica source contains Measure as 5-30 weight %, the content of first metal oxide is 10-80 weight %, and the content of lead oxide is 2-20 weights % is measured, the content of the active metal is 5-30 weight %, and content of the rare-earth oxide in terms of rare earth oxide is 0.5-15 weight %, the content of the molecular sieve is 1-30 weight %.

Preferably, on the basis of the gross weight of the desulphurization catalyst, the content of the non-aluminum oxide is 5-25 weight %, The content of the silica source is 10-20 weight %, and the content of first metal oxide is 25-70 weight %, lead oxide Content be 2-20 weight %, the content of the active metal is 8-25 weight %, and the rare-earth oxide is with rare earth oxygen The content of compound meter is 0.5-10 weight %, and the content of the molecular sieve is 2-25 weight %.

Present invention also offers the desulphurization catalyst that preparation method provided by the present invention obtains.The group of the desulphurization catalyst Into as it was previously stated, this is no longer going to repeat them.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur with Hydrodesulfurization catalyst provided by the invention, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5- 4MPa；Preferably, the temperature of the contact is 400-450 DEG C, and the pressure of the contact is 1-2MPa.In the process in hydrocarbon ils Sulphur be adsorbed on catalyst, so as to obtain the hydrocarbon ils of low sulfur content.

The method of desulfurization of hydrocarbon oil provided by the invention is preferably carried out in a fluidized bed reactor, i.e., described contact is preferably being flowed Carried out in fluidized bed reactor.

According to the present invention, the method for the desulfurization of hydrocarbon oil can also include：By the desulphurization catalyst by reaction after reaction Regenerated.The condition of regeneration includes：Regenerated under oxygen atmosphere (oxygen content can be 10-80 volume %)；Regeneration Temperature be 450-600 DEG C, preferably 480-520 DEG C；The pressure of regeneration is normal pressure.

In the present invention, the method for the desulfurization of hydrocarbon oil can also include：Desulphurization catalyst after regeneration is before reuse Need to reduce under hydrogen atmosphere, the condition of reduction includes：Under hydrogen atmosphere (hydrogen content can be 30-60 volume %) Reduced；The temperature of reduction can be 350-500 DEG C, preferably 400-450 DEG C；The pressure of reduction can be 0.2-2MPa, excellent Elect 0.2-1.5MPa as.

In the present invention, the hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " means that boiling range is 40 It is from making larger hydrocarbon molecule be cracked into compared with the heat of small molecule or the production of catalytic process to 210 DEG C of hydrocarbon or its any cut Product.Applicable thermal cracking process includes but is not limited to coking, thermal cracking and visbreaking etc. and combinations thereof.Applicable catalysis is split The example of change process includes but is not limited to fluid catalystic cracking and RFCC etc. and combinations thereof.Therefore, it is applicable to urge Change cracking gasoline and include but is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and again Oily cracking gasoline and combinations thereof.In some cases, in the methods of the invention as hydrocarbon-containifluids fluids when can be before desulfurization by institute State cracking gasoline fractionation and/or hydrotreating." diesel fuel " means the hydrocarbon mixture that boiling range is 170 DEG C to 450 DEG C Or the liquid of its any fractional composition.Such hydrocarbon-containifluids fluids include but is not limited to light cycle oil, kerosene, straight-run diesel oil, catalysis are split Change diesel oil and hydroprocessed diesel etc. and combinations thereof.

In the present invention, term " sulphur " used represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine The organosulfur compound being commonly present in fuel.Sulphur present in hydrocarbon-containifluids fluids of the present invention include but is not limited to carbonyl sulfide (COS), Carbon disulfide (CS₂), mercaptan or other thiophenes etc. and combinations thereof, especially including thiophene, benzothiophene, alkyl thiophene The bigger thiophene-based of the molecular weight that is commonly present in fen, alkyl benzothiophenes and methyldibenzothiophene, and diesel fuel Compound.

The invention will be further described by the following examples.

In the following Examples and Comparative Examples, the composition of desulphurization catalyst is calculated according to feeding intake.

Polycrystal X ray diffraction (XRD) carries out desulphurization catalyst using X-ray diffractometer (Siemens companies D5005 types) Structure determination, Cu targets, K α radiation, solid probe, tube voltage 40kV, tube current 40mA.

Embodiment 1

The present embodiment is used for the preparation method for illustrating the desulphurization catalyst of the present invention.

(1) rare earth-alucol is prepared.0.783kg lead tetrachloride (Beijing Chemical Plant, analysis are pure) is added to 1.0kg 5 weight % nitric acid (Beijing Chemical Plant, chemistry pure) solution in and stir 1h, obtain the alucol of water white transparency.By 0.5kg Lanthana (traditional Chinese medicines chemical reagents corporation, analysis pure) be dissolved in 0.2kg deionized water solution after be mixed to get with alucol Lanthanum alucol.

(2) carrier is prepared.2.28kg zirconium chloride (Beijing Chemical Plant, analysis are pure) is slowly added into the dense of 3.1kg Spending in 5 weight % salpeter solution makes pH=2.0, and is slowly stirred and avoids crystal of zirconium oxide from separating out, and obtains the zirconium of water white transparency Colloidal sol；

1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) is added to 0.5kg 2 weights Measure heating stirring in % salpeter solution and when temperature is reduced to below 40 DEG C, add 4.05kg Zinc oxide powder (Headhorse companies, the weight % of purity 99.7), 0.8kg USY molecular sieve (catalyst asphalt in Shenli Refinery, 0.7kg containing butt, Sial atomic molar ratio is 9.5：1) deionized water with 3.5kg mixes, and adds above-mentioned zirconium colloidal sol, it is molten to add above-mentioned lanthanum lead Glue, carrier mixture is obtained after being stirred 1 hour after mixing.

The carrier mixture is used into Niro Bowen Nozzle Tower^TMIt is dry that the spray dryer of model carries out spraying Dry, spray drying pressure is 8.5-9.5MPa, and below 500 DEG C of inlet temperature, outlet temperature is about 150 DEG C.By being spray-dried The microballoon arrived first dries 1h at 150 DEG C, and 0.5h is then calcined at 650 DEG C obtains carrier.

(3) active metal is introduced.By 8.2kg carrier with 8.92kg Nickelous nitrate hexahydrates (Beijing chemical reagents corporation, it is pure Degree be more than 98.5 weight %) and 1.6kg deionized waters the aqueous solution impregnate, obtained mixture after 250 DEG C of dry 5h, 450 DEG C of roasting 1h of air atmosphere can be prepared by catalyst precarsor.

(4) reduce.Catalyst precarsor is reduced into 3h in 400 DEG C of hydrogen atmosphere and can obtain desulphurization catalyst A1.

A1 chemical composition is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, zirconium dioxide Content is 12 weight %, and the weight % of expanded perlite 13.0, nickel content is 18.0 weight %, and lanthanum oxide content is 5.0 weight %, The weight % of USY molecular sieve 7.0.

A1 carries out polycrystal X ray diffraction (XRD) and characterized, and spectrogram is shown in Fig. 1.In spectrogram 2 θ be 28.3 °, 32.8 °, 47.1 ° With 55.8 ° at exist lanthanum plumbum composite oxide cubic system characteristic peak, 2 θ be 28.6 °, 31.8 °, 35.7 °, 48.6 °, At 54.8 ° and 59.9 ° in the absence of lead oxide tetragonal crystal system characteristic peak, and 2 θ be 27.0 °, 31.4 °, 44.8 ° and The characteristic peak of the cubic system of lanthana is not present at 53.2 °.Illustrate that lead oxide and lanthana form in desulphurization catalyst A1 Lanthanum plumbum composite oxide structure.

Embodiment 2

The present embodiment is used for the preparation method for illustrating the desulphurization catalyst of the present invention.

(1) rare earth-alucol is prepared.By 1.17kg oxychlorination lead (Aldrich, analyzing pure, 98.5 weight %) It is added in 2.0kg 15 weight % hydrochloric acid solution and stirs acidifying 1h, forms the alucol of water white transparency.By 0.3kg's Cerium oxide (traditional Chinese medicines chemical reagents corporation, analysis are pure) is added in alucol, and it is molten that 25 weight % ammoniacal liquor are added dropwise after being uniformly mixed Liquid is until into cerium alucol.

(2) carrier is prepared.3.09kg titanium tetrachloride (Beijing Chemical Plant, analysis are pure) is slowly added into the dense of 2.2kg Spending in 5 weight % salpeter solution makes pH=2.0, and is slowly stirred and avoids aoxidizing titanium crystal precipitation, obtains the titanium of water white transparency Colloidal sol；

After 1.2kg diatomite (silicon oxide-containing 1.00kg) and 8.0kg deionized water are well mixed under agitation, add Entering 200g concentrated nitric acid stirring makes pH=2.0, and is warming up to more than 60 DEG C and is acidified 1 hour.When temperature is reduced to below 40 DEG C, Add 5.06kg zinc oxide (traditional Chinese medicines chemical reagents corporation, analysis pure), 0.24kg beta-molecular sieve (Nanjing catalyst branch company, 0.20kg containing butt, sial atomic molar ratio are 20：1) and after 5.0kg deionized water mixing, above-mentioned titanium colloidal sol shape is added Into slurries, above-mentioned cerium alucol is added, carrier mixture is obtained after being stirred 1 hour after mixing.

Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and roasting obtains carrier.

(3) active metal is introduced.By 8.6kg carrier with 6.93kg Nickelous nitrate hexahydrate (Beijing chemical reagents corporation, Purity is more than 98.5 weight %) and 0.8kg deionized waters the aqueous solution dipping, referring next in the step of embodiment 1 (3) dry and Catalyst precarsor is made in the method for roasting.

(4) reduce.Reduce to obtain desulphurization catalyst A2 with reference to the method for the step of embodiment 1 (4).

A2 chemical composition is：Zinc oxide content is 50.0 weight %, and oxidation lead content is 8.0 weight %, titanium dioxide Content is 13.0 weight %, and diatomite content is 10.0 weight %, and nickel content is 14.0 weight %, and cerium-oxide contents are 3.0 weights Measure %, the weight % of beta-molecular sieve 2.0.

A2 carries out polycrystal X ray diffraction (XRD) and characterized, and spectrogram is shown in Fig. 2.In spectrogram 2 θ be 28.5 °, 33.1 °, 47.4 °, The characteristic peak of the cubic system of cerium plumbum composite oxide at 56.3 ° and 59.0 ° be present, 2 θ be 28.6 °, 31.8 °, 35.7 °, At 48.6 °, 54.8 ° and 59.9 ° in the absence of lead oxide tetragonal crystal system characteristic peak, and 2 θ be 28.5 °, 33.1 °, The characteristic peak of the cubic system of cerium oxide is not present at 47.5 ° and 56.3 °.Illustrate lead oxide and cerium oxide in desulphurization catalyst A2 Form the structure of cerium plumbum composite oxide.

Embodiment 3

The present embodiment is used for the preparation method for illustrating the desulphurization catalyst of the present invention.

(1) rare earth-alucol is prepared.By (the traditional Chinese medicines chemistry examination of 0.6kg lead oxide and 0.651kg six nitric hydrate neodymiums Agent company, content are more than 99.0 weight %) in the 15 weight % that are added to 2.7kg dust technology and acidifying 1h is stirred, obtain Bright neodymium alucol；

(2) carrier is prepared.By 3.73kg stannic chloride pentahydrate (SnCl₄·5H₂O, Alfa Aesar companies, 99 weights Amount %) be slowly added into 5.0kg the weight % of concentration 3 hydrochloric acid solution in make pH=1.5, and be slowly stirred and avoid tin oxide brilliant Body separates out, and obtains the tin oxide sol of water white transparency；

1.59kg expanded perlite (catalyst Nanjing branch company, containing butt 1.20kg) is added to 0.6kg 2 weight % Nitric acid stirring make pH=2.0, be warming up to 80 DEG C of aging 2h, the expanded perlite after being handled after being acidified 1h；

Expanded perlite after above-mentioned lead neodymium colloidal sol, tin oxide sol and processing is mixed to form slurries, adds 4.56kg oxygen Change zinc powder (Headhorse companies, the weight % of purity 99.7), 0.6kg X molecular sieve (Nanjing catalyst branch company, containing butt 0.5kg, sial atomic molar ratio are 3：1) deionized water with 4.65kg mixes, and adds above-mentioned neodymium alucol, is stirred after mixing Carrier mixture is obtained after mixing 1 hour.

Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and roasting obtains carrier.

(3) active metal is introduced.By 8.8kg carrier with 5.94kg Nickelous nitrate hexahydrate (traditional Chinese medicines chemical reagents corporation, Analyze pure)) and 0.8kg deionized waters the aqueous solution dipping, referring next in the step of embodiment 1 (3) dry and be calcined method Catalyst precarsor is made.

(4) reduce.Reduce to obtain desulphurization catalyst A3 with reference to the method for the step of embodiment 1 (4).

A3 chemical composition is：Zinc oxide content is 45.0 weight %, and oxidation lead content is 6.0 weight %, tin ash Content is 16.0 weight %, and expanded perlite content is 12.0 weight %, and nickel content is 12.0 weight %, and neodymia is 4.0 weights Measure %, the weight % of X molecular sieve 5.0.

A3 carries out polycrystal X ray diffraction (XRD) and characterized, and spectrogram is shown in Fig. 3.In spectrogram 2 θ be 28.3 °, 32.8 °, 47.0 °, The characteristic peak of the cubic system of neodymium plumbum composite oxide at 55.8 ° and 58.5 ° be present, 2 θ be 28.6 °, 31.8 °, 35.7 °, At 48.6 °, 54.8 ° and 59.9 ° in the absence of lead oxide tetragonal crystal system characteristic peak, and 2 θ be 26.8 °, 29.8 °, The characteristic peak of the cubic system of neodymia is not present at 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 °.Illustrate desulfurization Lead oxide and neodymia form the structure of neodymium plumbum composite oxide in catalyst A3.

Comparative example 1

3.23kg zirconium chloride is slowly added into the 4.4kg weight % of concentration 5 salpeter solution makes pH=2.0, And be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；

1.76kg expanded perlite (catalyst Nanjing branch company, containing butt 1.30kg) is added to 0.5kg 2 weights Measure heating stirring in % salpeter solution and when temperature is reduced to below 40 DEG C, add 4.05kg Zinc oxide powder (Headhorse companies, the weight % of purity 99.7), 0.80kg USY molecular sieve (Shandong catalyst branch company, containing butt 0.7kg, sial atomic molar ratio are 9.5：1) deionized water with 3.5kg mixes, and adds above-mentioned zirconium colloidal sol, adds The slurries that 0.5kg lanthana (traditional Chinese medicines chemical reagents corporation, analysis are pure) powder and 0.2kg deionized water are formed, mixing are stirred Carrier mixture is obtained after mixing 1 hour.

Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and impregnates introducing active metal nickel, also Desulphurization catalyst B1 is obtained after original.

B1 chemical composition is：Zinc oxide content is 40.0 weight %, and zirconium dioxide content is 17.0 weight %, and expansion is precious The weight % of pearl rock 13.0, nickel content are 18.0 weight %, and lanthanum oxide content is 5.0 weight %, the weight % of USY molecular sieve 7.0.

Comparative example 2

2.27kg zirconium chloride is slowly added into the 2.6kg weight % of concentration 5 salpeter solution makes pH=2.0, And be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；

1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) is added to 0.5kg 2 weights Measure heating stirring in % salpeter solution and when temperature is reduced to below 40 DEG C, add 4.05kg Zinc oxide powder (Headhorse companies, the weight % of purity 99.7), 0.8kg USY molecular sieve (catalyst asphalt in Shenli Refinery, 0.7kg containing butt, Sial atomic molar ratio is 9.5：1) deionized water with 3.5kg mixes, and adds above-mentioned zirconium colloidal sol, adds 0.5kg oxygen The deionized water for changing lanthanum powder and 0.2kg forms slurries and 0.783kg lead tetrachloride, and carrier is obtained after mixing 1 hour Mixture.

Carry out the spray drying forming of carrier mixture and impregnate to introduce activearm metallic nickel with reference to the method for embodiment 1, Desulphurization catalyst B2 is obtained after reduction.

B2 chemical composition is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, zirconium dioxide Content is 12.0 weight %, and the weight % of expanded perlite 13.0, nickel content is 18.0 weight %, and lanthanum oxide content is 5.0 weights Measure %, the weight % of USY molecular sieve 7.0.

Comparative example 3

0.783kg lead tetrachloride is added in 1.0kg 5 weight % salpeter solution and stirs 1h, obtained colourless Transparent alucol；

3.23kg zirconium chloride is slowly added into the 3.7kg weight % of concentration 5 salpeter solution makes pH=2.0, And be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；

1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) is added to 0.5kg 2 weights Measure heating stirring in % salpeter solution and when temperature is reduced to below 40 DEG C, add 4.05kg Zinc oxide powder (Headhorse companies, the weight % of purity 99.7), 0.8kg USY molecular sieve (catalyst asphalt in Shenli Refinery, 0.7kg containing butt, Sial atomic molar ratio is 9.5：1) deionized water with 3.5kg mixes, above-mentioned zirconium colloidal sol is added, it is molten to add above-mentioned lead Glue, carrier mixture is obtained after mixing 1 hour.

Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and impregnates introducing active metal nickel, also Desulphurization catalyst B3 is obtained after original.

B3 chemical composition is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, zirconium dioxide Content is 17.0 weight %, and the weight % of expanded perlite 13.0, nickel content is 18.0 weight %, the weight % of USY molecular sieve 7.0.

Comparative example 4

2.85kg lead tetrachloride is added in 3.5kg 5 weight % salpeter solution and stirs 1h, obtained colourless Bright alucol.It is molten that with alucol lanthanum lead is mixed to get after 1.261kg lanthanum nitrate is dissolved in 0.2kg deionized water solution Glue；

3.59kg zirconium chloride is slowly added into the 4.12kg weight % of concentration 5 salpeter solution makes pH=2.0, And be slowly stirred and avoid crystal of zirconium oxide from separating out, obtain the zirconium colloidal sol of water white transparency；

1.73kg expanded perlite (catalyst Nanjing branch company, containing butt 1.3kg) is added to 0.5kg 2 weights Measure heating stirring in % salpeter solution and when temperature is reduced to below 40 DEG C, add 4.05kg Zinc oxide powder (Headhorse companies, the weight % of purity 99.7) and 3.5kg deionized water mix, and add above-mentioned zirconium colloidal sol, add Lanthanum alucol is stated, carrier mixture is obtained after mixing 1 hour.

Method with reference to embodiment 1 carries out the spray drying forming of carrier mixture and impregnates introducing active metal nickel, also Desulphurization catalyst B4 is obtained after original.

B4 chemical composition is：Zinc oxide content is 40.0 weight %, and oxidation lead content is 5.0 weight %, zirconium dioxide Content is 19.0 weight %, and kaolin content is 13.0 weight %, and nickel content is 18.0 weight %, and lanthanum oxide content is 5.0 weights Measure %.

Embodiment 4

Abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulphurization catalyst A1-A3 and B1-B4.Ground using straight tube Damage method, method reference《Petrochemical Engineering Analysis method (RIPP) experimental method》Middle RIPP29-90, the results are shown in Table 1.What test obtained Numerical value is smaller, shows that abrasion strength resistance is higher.It is that fine powder generates when wearing under certain condition corresponding to abrasion index in table 1 Percentage.

In order to more preferably represent activity of the adsorbent during commercial Application, adsorbent after vulcanizing treatment is also carried out Intensive analysis, specific processing method are：The adsorbent for weighing appropriate mass is positioned in fluid bed, is passed through hydrogen sulfide (50 bodies Product %) and nitrogen (50 volume %) gaseous mixture, and be heated to 400 DEG C of vulcanizing treatment 1h.It the results are shown in Table 1.

Embodiment 5

Desulfurization performance is evaluated.Desulfurization is carried out to desulphurization catalyst A1-A3 and B1-B4 using the micro- anti-experimental provision of fixed bed to comment Valency is tested, and 16 grams of desulphurization catalyst is seated in the fixed bed reactors that internal diameter is 30mm, a length of 1m.Raw material hydrocarbon ils is sulphur Concentration 960ppm catalytically cracked gasoline, reaction pressure 1.38MPa, hydrogen flowing quantity 6.3L/h, gasoline flow 80mL/h, Reaction temperature is 380 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h^-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur.With sulphur in product gasoline Content is weighed desulphurizing activated.Sulfur content is by offline chromatogram analysis method in product gasoline, using the GC6890- of An Jielun companies SCD instruments are measured.In order to which accurate characterization goes out activity of the desulphurization catalyst in industrial actual motion, HDS evaluation has been tested Catalyst after carries out regeneration treatment under 480 DEG C of air atmosphere.Desulphurization catalyst is subjected to HDS evaluation experiment, regeneration Its activity settles out substantially after 6 circulations, is represented and urged with the sulfur content in the product gasoline after the 6th stable circulation of catalyst The activity of agent, sulfur content is as shown in table 1 in product gasoline after stablizing.

Simultaneously product gasoline weigh and calculate its yield.

GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 1.

Embodiment 6

Silicic acid zinc-content determination.By the crystalline phase of desulphurization catalyst A1-A3 and B1-B4 after the 6th circulation in embodiment 5 Composition is analyzed, and determines silicic acid Zn content therein.

Crystal phase analysis using X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans, Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), Rietveld models (the RIQAS rietveld that are corrected Analysis, operation manual, Material Data, Inc., Berkley, CA (1999)), different samples are analyzed, and using plan The method of conjunction calculates the crystalline phase composition of sample.Sent out using the Philips XRG3100 for being equipped with long fine focusing copper X-ray source Raw device (40kV, 30mA drive), the digital goniometers of Philips 3020, Philips 3710MPD control computers and Kevex PSI Peltier cooling silicon detectors carry out all X-ray diffraction measurements.Using the ion pump controllers of Kevex 4601, Kevex4608Peltier power supplys, Kevex4621 detector bias, Kevex4561A pulse processors and Kevex4911-A are mono- Channel analyser operates Kevex detectors.Diffraction pattern is obtained using Philips APD 4.1c versions software.Use Material Data, Inc.Riqas 3.1c versions software (Outokumpu HSC Chemistry for Windows:User's manual, Outokumpo Resarch Oy, Pori, Finland (1999)) carry out all Rietveld and calculate.Different desulphurization catalysts Silicic acid Zn content is as shown in table 1.

Wherein, B2 is carried out into polycrystal X ray diffraction (XRD) to characterize, spectrogram is shown in Fig. 4.In figure 2 θ be 22.1 °, 25.5 °, There is zinc silicate at 31.5 °, 38.8 °, 45.0 °, 47.0 °, 48.9 °, 57.6 °, 59.5 °, 65.6 °, 65.8 ° and 68.7 ° Characteristic peak, but in the absence of the characteristic peak of lanthanum plumbum composite oxide, illustrate not forming lanthanum lead combined oxidation in desulphurization catalyst B2 Thing structure, and form zinc silicate component.

Table 1

	A1	A2	A3	B1	B2	B3	B4
								Zn2SiO4, weight %	0	0	0	3.4	3.0	4.1	0
Abrasion index (before vulcanization)	4.3	4.4	4.4	5.2	4.8	5.3	4.3
								Abrasion index (after vulcanization)	4.0	4.2	4.2	5.0	4.7	5.1	4.0
Yield of gasoline, %	99.8	99.9	99.7	98.9	99.0	98.3	99.8
								Product sulfur content, ppm	4	4	6	24	22	26	6
△RON	0.65	0.61	0.58	0.36	0.45	0.32	0.26
								△MON	0.60	0.60	0.54	0.32	0.40	0.30	0.24
△(RON+MON)/2	0.62	0.60	0.56	0.34	0.42	0.31	0.25

Note：

1st, the sulfur content of feed gasoline is 960ppm, RON 93.7, MON 83.6.

2nd, △ MON represent product MON value added；

3rd, △ RON represent product RON value added；

4th, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.

Desulphurization catalyst provided by the invention is can be seen that with preferably desulphurizing activated and living from the result data of table 1 Property stability.Desulphurization catalyst has more preferable abrasion strength resistance, so that desulphurization catalyst has longer service life.

Claims (19)

1. a kind of desulphurization catalyst, on the basis of the gross weight of the desulphurization catalyst, the desulphurization catalyst contains：

1）3-35 weight % non-aluminum oxide, the non-aluminum oxide be titanium dioxide, zirconium dioxide and tin ash in extremely Few one kind；

2）5-30 weight % silica source；

3）10-80 weight % zinc oxide；

4）2-20 weight % lead oxide；

5）5-30 weight % active metal, the active metal are selected from least one of cobalt, nickel, iron and manganese；

6）The rare-earth oxide of 0.5-15 weight % in terms of rare earth oxide；

7）1-30 weight % molecular sieve, the molecular sieve are at least one of X-type molecular sieve, Y type molecular sieve and beta-molecular sieve；

The characteristic peak of rare earth-plumbum composite oxide in the XRD spectra of the desulphurization catalyst be present.

2. desulphurization catalyst according to claim 1, wherein, it is described on the basis of the gross weight of the desulphurization catalyst The content of non-aluminum oxide is 5-25 weight %, and the content of the silica source is 10-20 weight %, and the content of zinc oxide is 25- 70 weight %, the content of lead oxide are 2-20 weight %, and the content of the active metal is 8-25 weight %, the rare earth metal oxygen For compound using the content that rare earth oxide is counted as 0.5-10 weight %, the content of the molecular sieve is 2-25 weight %.

3. desulphurization catalyst according to claim 1, wherein, the rare earth element in the rare-earth oxide is selected from At least one of 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 the rare-earth oxide is La, At least one of Ce, Pr and Nd.

5. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth element is lanthanum, and the desulfurization is urged The spy of the cubic system for the lanthanum plumbum composite oxide that 2 θ are 28.3 °, 32.8 °, 47.1 ° and 55.8 ° in the XRD spectra of agent be present Levy peak；In the absence of the feature of the tetragonal crystal system for the lead oxide that 2 θ are 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° Peak, in the absence of the characteristic peak of the cubic system for the lanthana that 2 θ are 27.0 °, 31.4 °, 44.8 ° and 53.2 °.

6. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth element is cerium, and the desulfurization is urged The cubic crystal for the cerium plumbum composite oxide that 2 θ are 28.5 °, 33.1 °, 47.4 °, 56.3 ° and 59.0 ° in the XRD spectra of agent be present The characteristic peak of system；It is the tetragonal crystal system of 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° of lead oxide in the absence of 2 θ Characteristic peak, in the absence of the characteristic peak of the cubic system for the cerium oxide that 2 θ are 28.5 °, 33.1 °, 47.5 ° and 56.3 °.

7. according to the desulphurization catalyst described in any one in claim 1-4, wherein, rare earth element is neodymium, and the desulfurization is urged The cubic crystal for the neodymium plumbum composite oxide that 2 θ are 28.3 °, 32.8 °, 47.0 °, 55.8 ° and 58.5 ° in the XRD spectra of agent be present The characteristic peak of system；It is the tetragonal crystal system of 28.6 °, 31.8 °, 35.7 °, 48.6 °, 54.8 ° and 59.9 ° of lead oxide in the absence of 2 θ Characteristic peak, in the absence of the vertical of the neodymia that 2 θ are 26.8 °, 29.8 °, 30.8 °, 40.5 °, 47.4 °, 53.4 °, 57.0 ° and 57.6 ° The characteristic peak of prismatic crystal system.

8. desulphurization catalyst according to claim 1, wherein, the sial atomic molar ratio of the X-type molecular sieve is 1-3： 1；The sial atomic molar ratio of the Y type molecular sieve is 3-25：1；The sial atomic molar ratio of the beta-molecular sieve is 10-40：1.

9. the preparation method of the desulphurization catalyst in claim 1-8 described in any one, this method include：

（1）The precursor of lead oxide, rare earth compound, water and acidic liquid are mixed to get rare earth-alucol；

（2）Non- al binder, silica source, zinc oxide, molecular sieve, water and acidic liquid are mixed to form slurries, and with it is described Rare earth-alucol contacts to obtain carrier mixture, the carrier mixture is molded, first dry and first roasting, obtain To carrier；

（3）The precursor of active metal is introduced on the carrier, and carries out the second drying and the second roasting, before obtaining catalyst Body；

（4）The catalyst precarsor is reduced in a hydrogen atmosphere, obtains desulphurization catalyst.

10. preparation method according to claim 9, wherein, the precursor of the lead oxide is selected from lead tetrachloride, oxychlorination At least one of lead, lead acetate, aqua oxidation lead and amorphous lead.

11. preparation method according to claim 9, wherein, the rare earth compound is selected from the acetic acid of rare earth metal At least one of salt, carbonate, nitrate, sulfate, oxalates, chloride and oxide.

12. preparation method according to claim 9, wherein, the precursor of the active metal can be selected from the acetic acid of metal At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.

13. preparation method according to claim 9, wherein, the non-al binder is zirconium dioxide, titanium dioxide or two Tin oxide, or the material of zirconium dioxide, titanium dioxide or tin ash can be changed under conditions of being calcined described first.

14. preparation method according to claim 9, wherein, the acidic liquid is acid or the aqueous solution of acid, and the acid selects From water-soluble inorganic acid and/or organic acid.

15. preparation method according to claim 9, wherein, the described first temperature dried is 80-120 DEG C, described first The dry time is 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least 0.5 h。

16. preparation method according to claim 9, wherein, the described second temperature dried is 50-300 DEG C, described second The dry time is 0.5-8 h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4 h。

17. preparation method according to claim 9, wherein, the temperature of the reduction is 300-600 DEG C, the reduction Time is 0.5-6 h, and hydrogen content is 10-60 volumes % in the hydrogen atmosphere.

18. desulphurization catalyst prepared by the method in claim 9-17 described in any one.

19. a kind of method of desulfurization of hydrocarbon oil, this method include：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-8 and 18 Hydrodesulfurization catalyst described in middle any one, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5- 4MPa。