CN104549486B

CN104549486B - A kind of method of desulphurization catalyst and its preparation and desulfurization of hydrocarbon oil

Info

Publication number: CN104549486B
Application number: CN201310521602.7A
Authority: CN
Inventors: 王鹏; 田辉平; 孙言; 朱玉霞; 林伟
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-10-29
Filing date: 2013-10-29
Publication date: 2017-06-30
Anticipated expiration: 2033-10-29
Also published as: CN104549486A

Abstract

The invention discloses a kind of desulphurization catalyst, a kind of preparation method of desulphurization catalyst and desulphurization catalyst prepared by this method, and desulfurization of hydrocarbon oil method.The desulphurization catalyst contains SAPO molecular sieve, rare earth oxide, titanium dioxide, silica, zinc oxide and active metal.The desulphurization catalyst has preferably desulphurizing activated and desulfurization stability.

Description

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

Technical field

The present invention relates to a kind of desulphurization catalyst and its method for preparation and desulfurization of hydrocarbon oil, and in particular to a kind of desulfurization catalyst Agent, a kind of preparation method of desulphurization catalyst and desulphurization catalyst prepared by this method, and desulfurization of hydrocarbon oil method.

Background technology

The sulphur compound contained in hydrocarbon ils easily causes the exhaust emission of sulphur in use, especially as vehicle fuel Hydrocarbon ils expands the influence of sulphur pollution with the movement of vehicle.It is used as car for this various countries has formulated strict standard and limited one after another With the sulfur content in the hydrocarbon ils of fuel.

At present, the method for sulphur mainly has catalytic desulfurhydrogenation, catalytic cracking and desulfurizing, oxidation sweetening, solvent in removing hydrocarbon ils Abstraction desulfurization, biological desulphurization, absorption desulfurization, film desulfurization and photocatalysis desulfurization etc..Wherein absorption desulfurization have it is simple, convenient, Quick advantage, one of desulfurization technology of concern is compared as current people.

CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Thing, by zinc oxide, silica, oxidation al and ni constitute, wherein nickel with substantially reduce valence state presence, its amount make it possible to from Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted with the nickeliferous adsorbent composition under desulfurization conditions.The absorption Desulphurizing activated and stability comparatively fresh agent after agent composition is regenerated is decreased obviously.

CN101433821A discloses a kind of adsorbent for reducing sulfur content in hydrocarbon oils, on the basis of total sorbent weight, should Adsorbent includes：The rare earth faujasite of 1-30 weight %, the reactive metal oxides of 5-40 weight % and the load of 30-94 weight % Body, wherein carrier include aluminum oxide and zinc oxide, and rare earth faujasite is tied by faujasite with the duct for being distributed in faujasite Rare earth composition inside structure.The Adsorbent Acidity is strong, and cracking activity is strong, but yield of gasoline and desulphurizing activated and stability are relatively low.

As can be seen here, it is necessary to high and desulphurizing activated and desulfurization stability of developing a kind of yield of gasoline is high and renewable use Hydrocarbon oil desulphurization adsorbing agent.

The content of the invention

The purpose of the present invention is the defect for overcoming above-mentioned desulfuration adsorbent in the prior art to exist, there is provided a kind of desulfurization The method of catalyst and its preparation and desulfurization of hydrocarbon oil.

To achieve these goals, the present invention provides a kind of desulphurization catalyst, the desulphurization catalyst contain SAPO molecular sieve, Rare earth oxide, titanium dioxide, silica, zinc oxide and active metal, it is described on the basis of the gross weight of the desulphurization catalyst The content of SAPO molecular sieve is 1-30 weight %, and the rare earth oxide is with RE₂O₃The content of meter is 0.5-15 weight %, the dioxy The content for changing titanium is 3-35 weight %, and the content of the silica is 5-30 weight %, and the content of the zinc oxide is 10-80 weights Amount %, the content of the active metal is 5-30 weight %.

The present invention also provides a kind of preparation method of desulphurization catalyst, and the method includes：（1）By SAPO molecular sieve and rare earth Metal salt solution contact obtains rare earth modified SAPO molecular sieve；（2）By titania source, zinc oxide, silica source, rare earth modified The slurries that SAPO molecular sieve and water are mixed to form are contacted with acidic liquid and obtain carrier mixture, then through shaping, dry and roasting Obtain carrier；（3）The compound containing active metal is introduced in the carrier, dry, roasting obtains desulphurization catalyst precursor；（4）The desulphurization catalyst precursor is reduced in a hydrogen atmosphere, desulphurization catalyst is obtained.

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

The present invention also provides a kind of preparation method of desulphurization catalyst, and the method includes：（1）By titania source and oxidation The precursor mixing contact of rare earth obtains rare earth-titanium colloidal sol；（2）Zinc oxide, silica source, SAPO molecular sieve and water are mixed into shape Into slurries mix with the rare earth-titanium colloidal sol after, contacted with acidic liquid and obtain carrier mixture, then through shaping, dry and Roasting obtains carrier；（3）The compound containing active metal is introduced in the carrier, before dry, roasting obtains desulphurization catalyst Body；（4）The desulphurization catalyst precursor is reduced in a hydrogen atmosphere, desulphurization catalyst is obtained.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method includes：Hydrocarbon oil containing surphur is connect with desulphurization catalyst Reaction is touched, wherein, the desulphurization catalyst that the desulphurization catalyst is provided for the present invention.

The desulphurization catalyst provided by the present invention, after the desulphurization catalyst can carry out multiple desulfurization regeneration course of reaction Still have preferably desulphurizing activated, desulfurization stability is more preferable.And the desulphurization catalyst carries out desulfurization of hydrocarbon oil reaction and can have less Green coke amount, yield of gasoline is higher.Iso-component is more in the product gasoline composition for obtaining, and sulfur content is lower, product gasoline Octane number improve, product gasoline better quality.The other desulphurization catalyst can obtain more preferable wear resistance.

For example, the desulphurization catalyst A1 obtained in embodiment 1 contains SAPO-11 molecular sieves and cerium, by XRD spectra meter The crystallization reservation degree of the molecular sieve in A1 is calculated for the structure of 99.9%, SAPO-11 molecular sieves does not change, judges that cerium is not entered into In the pore passage structure of SAPO-11 molecular sieves, i.e., content of rare earth is 0 μ g/g in the pore passage structure of SAPO-11 molecular sieves.From XRD The information of middle appearance can be seen that in desulphurization catalyst A1 there is cerium-titanium composite oxide.Therefore, gasoline HDS evaluation is carried out, the The product gasoline sulfur content that six absorption regeneration circulations are obtained is 5 μ g/g, illustrates that desulphurization catalyst A1 has more preferable gasoline desulfurization Activity, stability.Green coke amount is 0.01 weight % in the product slates obtained in gasoline HDS evaluation, and the product gasoline for obtaining is received Rate is 99.96%, and isoparaffin and isomeric olefine content are respectively 39.16 weight % and 23.88 weight %, product gasoline octane number Increase, illustrate that desulphurization catalyst A1 can obtain the product gasoline of better quality.Diesel oil is carried out using desulphurization catalyst A1 in addition Desulfurization performance is evaluated, and sulfur content is 11.4 μ g/g in product diesel oil, and diesel fuel desulfurization rate is 99.69%, and product diesel yield is 99.45%, Cetane number is 36.4.Desulphurization catalyst A1 abrasion index before and after vulcanization are respectively 3.1 and 2.9, there is preferably resistance to Polishing machine.And the desulphurization catalyst B2 in comparative example 2, gasoline HDS evaluation is carried out, what the 6th absorption regeneration circulation was obtained Product gasoline sulfur content is 27 μ g/g, and green coke amount is 0.08 weight % in the product slates for obtaining, and the product gasoline yield for obtaining is 99.7%, isoparaffin and isomeric olefine content are respectively 37.84 weight % and 21.46 weight %.Diesel fuel desulfurization performance is carried out to comment Valency, sulfur content is 58 μ g/g in product diesel oil, and diesel fuel desulfurization rate is 98.44%, and product diesel yield is 98.95%, Cetane number It is 28.5.Desulphurization catalyst B2 abrasion index before and after vulcanization are respectively 6.8 and 6.4.

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 to constitute the part of specification, with following tool Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is the XRD spectra of the desulphurization catalyst A1 containing cerium and SAPO-11 molecular sieves, wherein 2 θ be 8.01 °, 9.76 °, 12.74 °, 16.02 °, 19.79 °, 21.80 °, 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and mark the peak of " ▲ " It is the characteristic peak of SAPO-11 molecular sieves, 2 θ are 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° and mark "●" Peak is the rhombic characteristic peak of cerium-titanium composite oxide；

Fig. 2 is the XRD spectra of the desulphurization catalyst A2 containing lanthanum and SAPO-34 molecular sieves, wherein 2 θ be 9.58 °, 13.00 °, 16.14 °, 17.82 °, 19.18 ° and 20.78 ° and mark "●" peak be SAPO-34 molecular sieves characteristic peak, 2 θ are 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 ° and mark " ▼ " peak be lanthanum titanium composite oxide rhombic feature Peak；

Fig. 3 is the XRD spectra of the desulphurization catalyst A3 containing neodymium and SAPO-5 molecular sieves, wherein 2 θ be 7.46 °, 13.00 °, 15.15 °, 19.81 °, 20.68 °, 22.29 °, 26.15 ° and 29.05 ° and the peak that marks "●" is SAPO-5 molecular sieves Characteristic peak, 2 θ be 22.7 °, 32.4 °, 46.3 ° and 58.0 ° and mark " ▼ " peak be neodymium titanium composite oxide orthorhombic system Characteristic peak；

Fig. 4 is the Pyridine adsorption IR spectra spectrogram of desulphurization catalyst A4, and wherein wave number is 1445cm^-1It is cerium in SAPO- Absworption peak in 11 molecular sieve pore passages；

Fig. 5 for desulphurization catalyst A4 XRD spectra, wherein 2 θ be 8.01 °, 9.76 °, 12.74 °, 16.02 °, 19.79 °, 21.80 °, 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and mark " ◆ " peak be SAPO-11 molecular sieves characteristic peak, 2 θ are 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° and mark " ■ " peak be titanium dioxide anatase crystal change characteristic peak；

Fig. 6 is the Pyridine adsorption IR spectra spectrogram of desulphurization catalyst B2, and wherein wave number is 1445cm^-1It is cerium in SAPO- Absworption peak in 11 molecular sieve pore passages；

Fig. 7 for desulphurization catalyst B2 XRD spectra, wherein 2 θ be 9.76 °, 12.74 °, 16.02 °, 19.79 °, 21.80 °, 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and mark " ▲ " peak be SAPO-11 molecular sieves characteristic peak, 2 θ be 8.01 °, 28.64 °, 30.92 °, 37.1 °, 59.36 ° and 65.25 ° and mark " ■ " peak be gahnite characteristic peak.

Specific embodiment

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

In the present invention, the composition of the desulphurization catalyst can be with it is further preferred that with the gross weight of the desulphurization catalyst On the basis of amount, the content of the SAPO molecular sieve is 2-25 weight %, and the rare earth oxide is with RE₂O₃The content of meter is 0.5-10 weights Amount %, the content of the titanium dioxide is 5-25 weight %, the content of the silica is 10-20 weight %, and the zinc oxide contains It is 25-70 weight % to measure, and the content of the active metal is 8-25 weight %；More preferably it is with the gross weight of the desulphurization catalyst Benchmark, the content of the SAPO molecular sieve is 2-20 weight %, and the rare earth oxide is with RE₂O₃The content of meter is 1-5 weight %, institute The content of titanium dioxide is stated for 8-15 weight %, the content of the silica is 10-15 weight %, and the content of the zinc oxide is 40-60 weight %, the content of the active metal is 12-20 weight %.

According to the present invention, the SAPO molecular sieve contained in desulphurization catalyst can have makes straight-chain hydrocarbons obtain isomerization, makes vapour Oil product octane number is improved, while ensureing the effect of yield of gasoline higher.Under preferable case, the SAPO molecular sieve be selected from The SAPO-34 of small-bore, 17,18,26,33,34,35,39,42,43,44,47, the SAPO-11 in middle aperture, 31,41 and macropore At least one in the SAPO-5 in footpath, 36,37,40,46.

According to the present invention, the sial atomic molar ratio of the SAPO molecular sieve contained in the desulphurization catalyst is not special Limit, as long as suitable acidity can be provided.Under preferable case, the sial atomic molar ratio of the SAPO molecular sieve is 0.05-1.0：1；Preferably, the sial atomic molar ratio of the SAPO molecular sieve is 0.05-0.75：1；It is highly preferred that described The sial atomic molar ratio of SAPO molecular sieve is 0.1-0.5：1.

According to the present invention, the rare earth oxide can be distributed in inside the duct of SAPO molecular sieve, it is also possible to not in SAPO The duct inside distribution of molecular sieve.Under preferable case, rare earth element in the rare earth oxide be selected from La, Ce, Pr, Nd, Pm, At least one of Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu；It is preferred that rare earth element in the rare earth oxide be La, Ce, At least one in Pr and Nd.

According to the present invention, the active metal is used to promote the absorption and cracking of the sulfur-containing compound in hydrocarbon oil containing surphur.It is excellent In the case of choosing, the active metal is group VIII metal；It is preferred that group VIII metal be selected from cobalt, nickel, iron and manganese at least one Plant, more preferably cobalt and/or nickel.

In a kind of preferred embodiment of the invention, the rare earth oxide is distributed not inside the duct of SAPO molecular sieve, The content of rare earth element is 0 μ g/g in the pore passage structure of i.e. described SAPO molecular sieve；Deposited in the XRD spectra of the desulphurization catalyst In the rhombic characteristic peak of rare earth-titanium composite oxide.

In the present invention, in the desulphurization catalyst content of rare earth oxide and titanium dioxide can advantageously form rare earth- Titanium combined oxidation structure, so as to be more beneficial for improving abrasion resistance properties, the desulphurizing activated and product gasoline quality of desulphurization catalyst.

According to the present invention, there is no rare earth element to be distributed inside the duct of SAPO molecular sieve, the acid intensity of molecular sieve and Distribution carries out desulfurization adsorption reaction more suitable for hydrocarbon ils, it is possible to reduce green coke amount in product form, improves the yield of product gasoline.

According to the present invention it is possible to pass through the polycrystal X ray diffraction approach of desulphurization catalyst（XRD）Spectrogram, calculates molecular sieve Crystallization reservation degree, judges whether rare earth element enters in the pore passage structure of molecular sieve.When rare earth element does not enter into the molecule When in the pore passage structure of sieve, the crystallization reservation degree of molecular sieve is close to 100%, it was demonstrated that in the pore passage structure of the SAPO molecular sieve The content of rare earth element is 0 μ g/g.Conversely, entering when in the pore passage structure of molecular sieve if any rare earth element, the crystallization of molecular sieve Reservation degree can be reduced.In the present invention, during the crystallinity reservation degree of molecular sieve refers to the XRD spectra of desulphurization catalyst, molecular sieve Characteristic peak in the business of content of the peak area of characteristic peak divided by molecular sieve in desulphurization catalyst, with the XRD spectra of pure molecular sieve Peak area ratio（Both with respect to the sample size of Unit Weight）.Characteristic peak such as SAPO-11 molecular sieves is 2 θ=16.02 ° Peak, the characteristic peak of SAPO-34 molecular sieves is the peak of 2 θ=9.58 °, and the characteristic peak of SAPO-5 molecular sieves is 2 θ=7.46 °.

Furthermore it is also possible to judge that rare earth element enters molecular sieve pore passage structure using the infrared spectrum analysis of pyridine adsorption It is interior.Wave number that characteristic peak according to the rare earth element on infrared spectrum occurs judges.Enter the hole of SAPO-11 molecular sieves with cerium As a example by road structure, the characteristic peak of cerium appears in 1445cm^-1Position, show cerium be present in SAPO-11 molecular sieves duct knot In structure, as shown in Figure 4 and Figure 6.

According to the present invention, rare earth oxide can be combined with titanium dioxide, form the crystal knot of rare earth-titanium composite oxide Structure.Under preferable case, as shown in figure 1, when rare earth element is cerium, being in the presence of 2 θ in the XRD spectra of the desulphurization catalyst 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° of diffraction maximum, with standard substance card JCPDS No.01-070- 3939 compared to right, and above-mentioned diffraction maximum is the rhombic characteristic peak of cerium-titanium composite oxide；Be 25.3 ° in the absence of 2 θ, 37.8 °, 48.1 °, 53.9 °, the characteristic peak of the anatase crystal of titanium dioxide at 55.0 °, in the absence of 2 θ be 28.52 ° and The characteristic peak of the cubic crystal of 33.06 ° of cerium oxide.

, according to the invention it is preferred in the case of, as shown in Fig. 2 when rare earth element is lanthanum, the XRD of the desulphurization catalyst There is the diffraction maximum that 2 θ are 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 ° in spectrogram, with standard substance card JCPDS No.01-073-1686, compared to right, is the rhombic characteristic peak of lanthanum titanium composite oxide；Be 25.3 ° in the absence of 2 θ, The characteristic peak of the anatase crystal of 37.8 °, 48.1 °, 53.9 ° and 55.0 ° of titanium dioxide, in the absence of 2 θ be 25.3 °, 27.8 °, The characteristic peak of the cubic crystal of 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 ° of lanthana（JCPDS No.24-0554）.

, according to the invention it is preferred in the case of, as shown in figure 3, when rare earth element is neodymium, the XRD of the desulphurization catalyst There is the diffraction maximum that 2 θ are 22.7 °, 32.4 °, 46.3 ° and 58.0 ° in spectrogram, with standard substance card JCPDS No.01-070- 2294 compared to right, is the rhombic characteristic peak of neodymium titanium composite oxide；In the absence of 2 θ be 25.3 °, 37.8 °, 48.1 °, The characteristic peak of the anatase crystal of 53.9 ° and 55.0 ° of titanium dioxide, in the absence of 2 θ be 26.6 °, 30.0 °, 31.1 °, 40.6 °, The characteristic peak of the cubic crystal of 47.6 °, 53.4 ° and 57.1 ° of neodymia（JCPDSNo.40-1282）.

In the present invention, rare earth-titanium composite oxide is formed in desulphurization catalyst, desulphurization catalyst can be overcome to wear and tear strong Degree declines the problem that caused usage cycles shorten.In addition, rare earth-the titanium composite oxide for being formed, can preferably improve vapour Oil and diesel fuel desulfurization activity.In the desulphurization catalyst, there is no rare earth element in the duct of SAPO molecular sieve, and containing dilute The desulphurization catalyst of soil-titanium composite oxide, isomerization product contains in can also preferably improving the desulfurization product gasoline for obtaining Amount, the octane number for improving product gasoline.Can also preferably increase containing rare earth-titanium composite oxide in the desulphurization catalyst Plus the active phase of zinc oxide, so as to preferably improve the desulphurizing activated of desulphurization catalyst.

In the present invention, in the desulphurization catalyst, titanium dioxide substitutes aluminum oxide and can reduce desulfurization as binding agent Catalyst forms gahnite in absorption and regenerative process, so as to keep the activity of zinc oxide, improves desulphurization catalyst It is desulphurizing activated.

Present invention also offers a kind of preparation method of desulphurization catalyst, the method includes：（1）By SAPO molecular sieve with it is dilute The contact of earth metal salt solution obtains rare earth modified SAPO molecular sieve；（2）Titania source, zinc oxide, silica source, rare earth are changed Property the slurries that are mixed to form of SAPO molecular sieve and water contacted with acidic liquid and obtain carrier mixture, then through shaping, dry and roast Burning obtains carrier；（3）The compound containing active metal is introduced in the carrier, dry, roasting obtains desulphurization catalyst precursor；（4）The desulphurization catalyst precursor is reduced in a hydrogen atmosphere, desulphurization catalyst is obtained.

According to the present invention, step is obtained（1）In rare earth modified SAPO molecular sieve can have various methods, can have method One, including：Before the contact, SAPO molecular sieve is calcined, the temperature of roasting is 500-800 DEG C；The bar of the contact Part includes：Temperature is 80-150 DEG C, and the time of contact is 0.5-6 hours；The contact is SAPO molecular sieve and rare earth metal salt Solution is mixed to form slurries, and the slurries is filtered, is washed, dried and be calcined；The temperature that the slurries are dried It it is 80-120 DEG C, the temperature that the slurries are calcined is 300-600 DEG C；The concentration of the rare earth metal salt solutions is 0.01- 1.5 mol/Ls.Wherein, SAPO molecular sieve being carried out into roasting before the contact can remove all or part of template.

There can also be method two, including：Before the contact, SAPO molecular sieve is calcined, the temperature of roasting is 500-800℃；The contact is, by rare earth metal salt solutions incipient impregnation SAPO molecular sieve, and to carry out 80-120 DEG C of drying Roasting with 300-600 DEG C.Wherein, SAPO molecular sieve being carried out into roasting before the contact can remove all or part of mould Plate agent.The incipient impregnation can be the method that this area catalyst preparation is routinely used, when can refer to dipping, rare earth gold The volume for belonging to salting liquid is equal with the pore volume of impregnated whole SAPO molecular sieves.

, according to the invention it is preferred in the case of, the rare earth metal salt solutions are nitrate, halide, the vinegar of rare earth metal At least one in hydrochlorate and sulfate liquor.

, according to the invention it is preferred in the case of, the titania source be selected from titanium tetrachloride, tetraethyl titanate, isopropyl titanate, At least one in acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.

, according to the invention it is preferred in the case of, the silica source can be pure silica, or silica content is big In the natural minerals of 45 weight %；It is preferred that silica source can be selected from diatomite, expanded perlite, kaolin, silicalite, hydrolysis One or more in silica, macropore silicon oxide and silica gel.

According to the present invention, step（2）In, the consumption of the acidic liquid can cause that the pH value of the carrier pulp is 0.5-6, more preferably 1-4.The acidic liquid can be selected from water-soluble inorganic acid and/or organic acid, for example, can be At least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

According to the present invention, step（2）In, the carrier mixture can be wet mixture, paste mixture, dough or The forms such as slurries.By the shaping, the carrier mixture can be shaped to extrudate, piece, pill, ball or microspheroidal Grain.For example, when the carrier mixture is dough or paste mixture, can be molded the carrier mixture（It is preferred that squeezing Go out shaping）Particle is formed, in 1.0-8.0mm, then length make gained to preferably diameter in the cylindrical extrudates of 2.0-5.0mm Extrudate be dried, be calcined.If the carrier mixture is wet mixture form, can be thickened the mixture, pass through Dry aftershaping.More preferably described carrier mixture is slurry form, and it is 20-200 microns to form granularity by spray drying Microballoon, reaches the purpose of shaping.For the ease of spray drying, the solid content of slurries can be 10-50 weight % before drying, preferably It is 20-50 weight %.

In the present invention, the drying means and condition of the carrier mixture are known to those skilled in the art, for example, dry Dry method can be dry, dry, forced air drying.Under preferable case, step（3）In, dry temperature can be room temperature extremely 400 DEG C, preferably 100-350 DEG C；The dry time is at least 0.5 hour, preferably 0.5-60 hours.

In the present invention, the roasting condition of the carrier mixture can also be known to those skilled in the art, general next Say, the temperature of the roasting is 400-700 DEG C, preferably 450-650 DEG C；The time of the roasting is at least 0.5 hour, preferably It is 0.5-100 hours, more preferably 0.5-10 hours.

In the preparation method that the present invention is provided, step（3）In introduced in the carrier can containing the compound of active metal With by accomplished in many ways.Wherein, the compound containing active metal is selected from acetate, carbonate, the nitre of active metal At least one in hydrochlorate, sulfate, rhodanate and oxide.

In the present invention, step（3）In introduce the concrete operation method of compound containing active metal in the carrier can Realized with using well known to a person skilled in the art dipping method or intermediate processing.The dipping method is with containing active metal Carrier described in the solution or suspension impregnation of compound；The intermediate processing is by the solution of the compound containing active metal or outstanding Supernatant liquid mixes with the carrier, be subsequently adding ammoniacal liquor will contain active metal compound precipitation on carrier.It is preferred that dipping method.

In the present invention, after introducing the compound containing active metal in the carrier, also including being dried and being calcined.About It is dried at 50-300 DEG C, preferably dry temperature is 100-250 DEG C, the dry time is about 0.5-8 hours, more preferably from about It is 1-5 hours.After drying, at about 300-800 DEG C, more preferably 400-750 DEG C under conditions of with the presence of oxygen or oxygen-containing gas At a temperature of be calcined, time of roasting is about 0.5-4 hours, preferably 1-3 hours, until volatile materials be removed and Compound containing active metal is converted into the oxide of active metal, obtains desulphurization catalyst precursor.

, according to the invention it is preferred in the case of, the titania source, zinc oxide, silica source, SAPO molecular sieve, rare earth The addition of metal salt solution and the compound containing active metal is caused in the desulphurization catalyst for obtaining, with the total of desulphurization catalyst On the basis of weight, the content of SAPO molecular sieve is 1-20 weight %, rare earth oxide with RE₂O₃The content of meter is 0.5-10 weight %, two The content of titanium oxide is 3-35 weight %, and the content of silica is 5-30 weight %, and the content of zinc oxide is 10-80 weight %, activity The content of metal is 5-30 weight %.

In the present invention, step（4）The reduction of desulphurization catalyst precursor can immediately be entered after prepared desulphurization catalyst precursor OK, it is also possible to using preceding（Before being used for desulfurization absorption）Carry out.Because active metal is easily aoxidized, and desulphurization catalyst precursor In active metal exist in the form of an oxide, therefore for ease of transport, preferred steps（4）The reduction of desulphurization catalyst precursor is existed Carried out before carrying out desulfurization absorption.The metal for being reduced to make in the oxide of active metal substantially exists with reduction-state, obtains To desulphurization catalyst of the invention.Under preferable case, the condition that desulphurization catalyst precursor is reduced in a hydrogen atmosphere is included：Hydrogen Gas content is 10-60 volume %, and the temperature of reduction is 300-600 DEG C, and the time of reduction is 0.5-6 hours；It is preferred that the temperature for reducing It it is 400-500 DEG C, the time of reduction is 1-3 hours.

The present invention also provides desulphurization catalyst prepared by method provided by the present invention.The desulphurization catalyst has foregoing de- The composition and content of sulfur catalyst, will not be repeated here.

In the preferred embodiment of the present invention, a kind of preparation method of desulphurization catalyst, the method are additionally provided Including：（1）The precursor of titania source and rare earth oxide is mixed into contact and obtains rare earth-titanium colloidal sol；（2）By zinc oxide, oxygen After the slurries that SiClx source, SAPO molecular sieve and water are mixed to form mix with the rare earth-titanium colloidal sol, contacted with acidic liquid and obtained Carrier mixture, then obtain carrier through shaping, dry and roasting；（3）The compound containing active metal is introduced in the carrier, Dry, roasting obtains desulphurization catalyst precursor；（4）The desulphurization catalyst precursor is reduced in a hydrogen atmosphere, desulfurization is obtained Catalyst.

According to the present invention, the step of the preparation method of the desulphurization catalyst（1）, by preparing rare earth-titanium colloidal sol, so as to In step（2）In shaping, drying, calcination process in formed rare earth-titanium composite oxide structure, contain the composite oxides Desulphurization catalyst is advantageously implemented the purpose of the present invention.

In the present invention, step is obtained（1）In the rare earth-titanium colloidal sol can have various methods, can be method one, bag Include following steps：（a）Titania source is contacted with acid solution and obtains titanium colloidal sol；（b）By the titanium colloidal sol and rare earth oxide Precursor mixing contacts with ammonia spirit obtain rare earth-titanium colloidal sol again.Can also be method two, comprise the following steps：（a）By two Titania source is contacted with acid solution and obtains titanium colloidal sol；（b）The titanium colloidal sol is mixed with the aqueous solution of the precursor of rare earth oxide Obtain rare earth-titanium colloidal sol.Can also be method three, including：The precursor of titania source and rare earth oxide and acid solution are connect Touch and obtain rare earth-titanium colloidal sol.In the above method, the acid solution can in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid at least One kind, the concentration of the acid solution can be 5-30 weight %；The concentration of the ammonia spirit can be 10-30 weight %.It is described There is no particular limitation for the consumption of acid solution or the ammonia spirit, as long as the rare earth-titanium colloidal sol can be formed, for example The pH value of slurries can be made to be 1-5 with the consumption of acid, preferably 1.5-4.

According to the present invention, in step（1）In, under preferable case, the addition of the titania source makes the desulfurization for obtaining In catalyst, on the basis of the gross weight of desulphurization catalyst, the content of titanium dioxide is 3-35 weight %；It is preferred that titanium dioxide Content is 5-25 weight %；More preferably the content of titanium dioxide is 8-15 weight %.

According to the present invention, step（1）In, under preferable case, the addition of the precursor of the rare earth oxide makes what is obtained In desulphurization catalyst, on the basis of the gross weight of desulphurization catalyst, the rare earth oxide is with RE₂O₃The content of meter is 0.5-15 weights Amount %；It is preferred that the rare earth oxide is with RE₂O₃The content of meter is 0.5-10 weight %；More preferably described rare earth oxide is with RE₂O₃Meter Content is 1-5 weight %.

, according to the invention it is preferred in the case of, the precursor of the rare earth oxide is selected from the rare earth gold in the rare earth oxide At least one in the acetate of category, carbonate, nitrate, sulfate, oxalates, chloride and oxide.

According to the present invention, step（2）In, under preferable case, the addition of the silica source makes the desulfurization catalyst for obtaining In agent, on the basis of the gross weight of desulphurization catalyst, the content of the silica is 5-30 weight %；It is preferred that the silica Content is 10-20 weight %；The content of more preferably described silica is 10-15 weight %.

According to the present invention, step（2）In, under preferable case, the addition of the zinc oxide and the SAPO molecular sieve makes In the desulphurization catalyst for obtaining, on the basis of the gross weight of desulphurization catalyst, the content of the zinc oxide is 10-80 weight %, institute The content for stating SAPO molecular sieve is 1-30 weight %；It is preferred that the content of the zinc oxide is 25-70 weight %, the SAPO molecular sieve Content be 2-25 weight %；The content of more preferably described zinc oxide is 40-60 weight %, and the content of the SAPO molecular sieve is 2- 20 weight %.

In the present invention, although containing silica, the oxygen contained in the SAPO molecular sieve in the SAPO molecular sieve The amount of SiClx still can be regarded as the amount of the SAPO molecular sieve, be not counted in silica.Taken off obtained in method i.e. provided by the present invention The content of each component is calculated according to inventory in sulfur catalyst.

According to the present invention, step（2）In, the consumption of the acidic liquid and selection are as it was previously stated, will not be repeated here.

According to the present invention, step（2）In, carrier mixture shaping, dry and roasting obtain carrier as it was previously stated, This is repeated no more.

In the preparation method that the present invention is provided, step（3）In introduced in the carrier can containing the compound of active metal With by accomplished in many ways.Under preferable case, the addition of the compound containing active metal makes the desulfurization catalyst for obtaining In agent, on the basis of the gross weight of desulphurization catalyst, the content of the active metal is 5-30 weight %；It is preferred that 8-25 weight %； More preferably 12-20 weight %.Wherein, the compound containing active metal is selected from acetate, carbonate, the nitric acid of active metal At least one in salt, sulfate, rhodanate and oxide.

In the present invention, step（3）In in the carrier introduce containing active metal compound concrete operation method and Include the drying for carrying out and roasting as it was previously stated, will not be repeated here after introducing the compound containing active metal in the carrier.

In the present invention, step（4）By the reduction of desulphurization catalyst precursor as it was previously stated, will not be repeated here.

Present invention also offers the desulphurization catalyst that preparation method provided by the present invention is obtained.The desulphurization catalyst has The composition and content of foregoing desulphurization catalyst, will not be repeated here.

According to the present invention, in the method for the desulfurization of hydrocarbon oil, the hydrocarbon oil containing surphur can be in hydrogen with the desulphurization catalyst Reacted under gas atmosphere, the condition of reaction includes：The temperature of reaction can be 350-500 DEG C, preferably 400-450 DEG C；Reaction Pressure can be 0.5-4MPa, preferably 1-2MPa；The charging rate of the hydrocarbon oil containing surphur is weight space velocity 2-10h^-1, preferably 3-8h^-1。

According to the present invention, the method for the desulfurization of hydrocarbon oil can also include：By by the desulphurization catalyst of reaction after reaction Regenerated.The condition of regeneration includes：In oxygen atmosphere（Oxygen content can be 10-80 volumes %）Under regenerated；Regeneration Temperature is 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 Reduced.The condition of reduction includes：In hydrogen atmosphere（Hydrogen content can be 30-60 volumes %）Under reduced；Reduction Temperature can be 350-500 DEG C, preferably 400-450 DEG C；The pressure of reduction can be 0.2-2MPa, preferably 0.2-1.5MPa.

The pressure being related in the present invention is gauge pressure.

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 the product for making larger hydrocarbon molecule be cracked into the hot or catalytic process compared with small molecule 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 weight 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 and 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 includes 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）Using X-ray diffractometer（Siemens companies D5005 types）Carry out desulphurization catalyst Structure determination, Cu targets, K α radiation, solid probe, tube voltage 40kV, tube current 40mA.

Pyridine adsorption IR spectra method is carried out using the FTS3000 types Fourier infrared spectrograph of BIO-RAD companies of the U.S. Determine.Condition is that will be placed in the pond in situ of infrared spectrometer to seal after sample compressing tablet；10-3Pa is evacuated down under 623K, is protected 1h is held, the gas molecule of sample surfaces is desorbed totally, room temperature is cooled to, in 1000-4000cm^-1Scanning in wave-number range, note Infrared absorption spectra before the lower sample adsorption pyridine of record.It is the pyridine steam of 2.67Pa, balance to pressure is imported in pond in situ After 30min, 200 DEG C are warmed up to, 10-3Pa is evacuated to again, keep 30min, be cooled to room temperature, in 1400-1700cm^-1Wave number In the range of scan, record 200 DEG C of infrared absorption spectras of pyridine adsorption, from this spectrogram observe rare earth in molecular sieve pore passage Interior characteristic peak.

Embodiment 1

The present embodiment is used to illustrate the preparation method of desulphurization catalyst of the invention.

（1）Prepare rare earth-titanium colloidal sol.By 2.85 kilograms of titanium tetrachlorides（Beijing Chemical Plant, analyzes pure, 99 weight %）Add To 3.5 kilogram of 5 nitric acid of weight %（Chemistry is pure, and Beijing Chemical Plant produces）In solution and stir 1 hour, obtain water white transparency Colloidal solution, referred to as titanium colloidal sol.By 1.261 kilograms of cerous nitrates（Chemical Reagent Co., Ltd., Sinopharm Group, purity is more than 99.0 weights Amount %）Rear and titanium colloidal sol is mixed to get cerium titanium colloidal sol in being dissolved in 0.2 kilogram of deionized water solution.

（2）Prepare carrier.By 1.33 kilograms of expanded perlite（0.77 kilogram of silicon oxide-containing, 0.13 kilogram of titanium dioxide, 0.07 kilogram of potassium oxide, 0.03 kilogram of sodium oxide molybdena）Heating stirring is after 2 hours in being added to 0.5 kilogram of 2 salpeter solution of weight % Filtering, step is added to after removing the impurity such as potassium, sodium, titanium（1）In the cerium titanium colloidal sol for obtaining, expanded perlite is obtained molten with cerium titanium The mixture of glue.

By 4.00 kilograms of Zinc oxide powders（Headhorse companies, the weight % of purity 99.7）, 2.00 kilograms of SAPO-11 molecules Sieve（Shandong catalyst branch company, containing 1.8 kilograms of butt, sial atomic molar ratio is 0.15：1）It is mixed with 5.25 kilograms of deionized waters Close, stirring obtains zinc oxide and SAPO-11 molecular sieve mixed serums after 30 minutes.The mixed serum is added step（1）Obtain Expanded perlite and cerium titanium colloidal sol mixture in, and obtain carrier mixture after stirring 1 hour.

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, 350 DEG C of drying temperature.The microballoon that spray drying is obtained is calcined 0.5 at 650 DEG C Hour obtains carrier.

（3）Introduce the compound containing active metal.Compound containing active metal is Nickelous nitrate hexahydrate, by step（2） The carrier for obtaining is with 2.79 kilograms of Nickelous nitrate hexahydrates（Beijing chemical reagents corporation, purity is more than 98.5 weight %）With 0.8 kilogram The aqueous impregnation of deionized water, the mixture for obtaining is small in 450 DEG C of roastings 1 of air atmosphere by after 250 DEG C of dryings 5 hours When can be prepared by desulphurization catalyst precursor.

（4）Reduction.By step（3）The desulphurization catalyst precursor for obtaining is reduced 3 hours in 400 DEG C of hydrogen atmosphere Desulphurization catalyst is obtained, desulphurization catalyst A1 is designated as.

The composition of desulphurization catalyst A1 is calculated as by inventory：The weight % of zinc oxide 40.0, the weight % of silica 10.0, The weight % of SAPO-11 molecular sieves 18.0, the weight % of titanium dioxide 15.0, the weight % of cerium oxide 5.0, the weight % of nickel 12.0.

Desulphurization catalyst A1 carries out polycrystal X ray diffraction（XRD）Characterize, spectrogram is shown in Fig. 1.With the characteristic peak that 2 θ are 16.02 ° The crystallization reservation degree of SAPO-11 molecular sieves in desulphurization catalyst A1 is calculated, 1 is the results are shown in Table.

Desulphurization catalyst A1 carry out XRD determining result as shown in figure 1, in spectrogram 2 θ be 11.4 °, 32.6 °, 40.3 °, There is the rhombic characteristic peak of cerium-titanium composite oxide at 46.8 °, 47.0 ° and 58.3 °, 2 θ be 25.3 °, 37.8 °, At 48.1 °, 53.9 ° and 55.0 ° in the absence of titanium dioxide anatase crystal characteristic peak, and 2 θ be 28.52 ° and Do not exist the characteristic peak of the cubic crystal of cerium oxide at 33.06 °.Illustrate that titanium dioxide and cerium oxide are formed in desulphurization catalyst A1 Cerium-titanium composite oxide structure.

Embodiment 2

（1）Prepare rare earth-titanium colloidal sol.By 1.17 kilograms of oxychlorination titaniums（Aldrich, analyzes pure, 98.5 weight %）Plus Enter to 2.0 kilogram of 15 hydrochloric acid of weight %（Chemistry is pure, and Beijing Chemical Plant produces）In solution and stir acidifying 1 hour, formed it is colourless Transparent colloidal solution, referred to as titanium colloidal sol.By 0.1 kilogram of lanthana（Analyze pure, Chinese medicines group）Add in titanium colloidal sol, stirring is mixed Close it is uniform after 25 weight % ammonia spirits are added dropwise until into lanthanum titanium colloidal sol.

（2）Prepare carrier.1.2 kilograms of diatomite（1.00 kilograms of silicon oxide-containing）With 6.00 kilograms of Zinc oxide powders （Headhorse companies, the weight % of purity 99.7）, 0.24 kilogram of SAPO-34 molecular sieve（Nanjing catalyst branch company, containing butt 0.20 kilogram, sial atomic molar ratio is 0.2：1）Diatomite, oxygen are obtained after being mixed 30 minutes with 5.0 kilograms of deionized waters Change the mixed serum of zinc and SAPO-34 molecular sieves.By step（1）The lanthanum titanium colloidal sol for obtaining adds the mixed serum, stirs 1 hour After obtain carrier mixture.

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

（3）Introduce the compound containing active metal.Compound containing active metal is Nickelous nitrate hexahydrate and six hydration nitre Sour cobalt, by step（2）The carrier for obtaining is with 6.93 kilograms of Nickelous nitrate hexahydrates（Beijing chemical reagents corporation, purity is more than 98.5 Weight %）, 2.47 kilograms of cabaltous nitrate hexahydrate and 0.8 kilogram of aqueous impregnation of deionized water, referring next to the step of embodiment 1 （3）The method of middle drying and roasting is obtained desulphurization catalyst precursor.

（4）Reduction.With reference to the step of embodiment 1（4）Method reduction obtain desulphurization catalyst A2.

The composition of desulphurization catalyst A2 is calculated as by inventory：The weight % of zinc oxide 60.0, the weight % of titanium dioxide 8.0, oxygen 10.0 weight %, SAPO-34 molecular sieve of SiClx 2.0 weight %, the weight % of lanthana 1.0, the weight % of nickel 14.0, the weight % of cobalt 5.0.

Desulphurization catalyst A2 carries out polycrystal X ray diffraction（XRD）Characterize, spectrogram is shown in Fig. 2.With the characteristic peak that 2 θ are 9.58 ° The crystallization reservation degree of SAPO-34 molecular sieves in desulphurization catalyst A2 is calculated, 1 is the results are shown in Table.

Desulphurization catalyst A2 carry out XRD determining result as shown in Fig. 2 in spectrogram 2 θ be 25.1 °, 31.9 °, 39.3 °, There is the rhombic characteristic peak of lanthanum titanium composite oxide at 45.7 ° and 57.0 °, 2 θ be 25.3 °, 37.8 °, 48.1 °, At 53.9 ° and 55.0 ° in the absence of titanium dioxide anatase crystal characteristic peak, and 2 θ be 25.3 °, 27.8 °, 28.9 °, Do not exist the characteristic peak of the hexagonal of lanthana at 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 ° （JCPDSNo.24-0554）.Illustrate that titanium dioxide and lanthana form lanthanum titanium composite oxide structure in desulphurization catalyst A2.

Embodiment 3

（1）Prepare rare earth-titanium colloidal sol.By 1.90 kilograms of titanium dioxide（Aldrich, analyzes pure, 99 weight %）With 0.651 kilogram of six nitric hydrate neodymium（Chemical Reagent Co., Ltd., Sinopharm Group, content is more than 99.0 weight %）It is added to 2.7 thousand The dust technology of gram 15 weight %（Chemistry is pure, and Beijing Chemical Plant produces）In and stir acidifying 1 hour, obtain transparent colloidal solution, Referred to as neodymium titanium colloidal sol.

（2）Prepare carrier.By 1.66 kilograms of expanded perlite（1.25 kilograms of silicon oxide-containing）It is added to 0.6 kilogram of 2 weight Heating stirring is filtered after 3 hours in measuring the salpeter solution of %, with 5.00 kilograms of Zinc oxide powders（Headhorse companies, purity 99.7 weight %）, 1.20 kilograms of SAPO-5（Nanjing catalyst branch company, containing 1.00 kilograms of butt, sial atomic molar ratio is 0.5：1）With 4.65 kilograms of deionized water mixing, the mixing of zinc oxide, SAPO-5 and expanded perlite is obtained after stirring 30 minutes Slurries.The mixed serum is added step（1）In the neodymium titanium colloidal sol for obtaining, quick stirring obtains carrier mixture after 5 minutes.

（3）Introduce containing active metal compound and（4）Reduction.With reference to the step of embodiment 1（3）With（4）Introduce containing work The compound of property metal and reduction, obtain desulphurization catalyst A3.Wherein the compound of active metal is Nickelous nitrate hexahydrate（Analysis It is pure, Beijing chemical reagents corporation）, consumption is 7.43 kilograms.

The composition of desulphurization catalyst A3 is calculated as by inventory：The weight % of zinc oxide 50.0, the weight % of silica 12.5, The weight % of SAPO-5 molecular sieves 10.0, the weight % of titanium dioxide 10.0, the weight % of neodymium oxide 2.5, the weight % of nickel 15.0.

Desulphurization catalyst A3 carries out polycrystal X ray diffraction（XRD）Characterize, spectrogram is shown in Fig. 3.With the characteristic peak that 2 θ are 7.46 ° The crystallization reservation degree of SAPO-5 in desulphurization catalyst A3 is calculated, 1 is the results are shown in Table.

Desulphurization catalyst A3 carry out XRD determining result as shown in figure 3, in spectrogram 2 θ be 22.7 °, 32.4 °, 46.3 ° and There is the rhombic characteristic peak of neodymium titanium composite oxide at 58.0 °, 2 θ be 25.3 °, 37.8 °, 48.1 °, 53.9 ° and At 55.0 ° in the absence of titanium dioxide anatase crystal characteristic peak, and 2 θ be 26.6 °, 30.0 °, 31.1 °, 40.6 °, Do not exist the characteristic peak of the hexagonal of neodymia at 47.6 °, 53.4 ° and 57.1 °（JCPDS No.40-1282）.Illustrate desulfurization Titanium dioxide and neodymia form neodymium titanium composite oxide structure in catalyst A3.

Embodiment 4

By 3.19 kilograms of acetic acid titaniums（Aldrich, analyzes pure, 99 weight %）3.5 thousand are added in the case of stirring The hydrochloric acid of gram 5 weight %（Chemistry is pure, and Beijing Chemical Plant produces）In solution and stir 1 hour, obtain titanium colloidal sol.

By 1.261 kilogram of six nitric hydrate cerium（Chemical Reagent Co., Ltd., Sinopharm Group, purity is more than 99.0 weight %）It is molten In 0.5 kilogram of deionized water solution, with 2.00 kilograms of SAPO-11 molecular sieves of the cerous nitrate aqueous impregnation（Shandong catalyst Branch company, containing 1.80 kilograms of butt, sial atomic molar ratio is 0.15：1）, dried after dipping, be calcined, obtain cerium modified CeSAPO-11 molecular sieves.

By 4.0 kilograms of Zinc oxide powders（Headhorse companies, the weight % of purity 99.7）, 1.2 kilograms of diatomite（It is oxygen-containing 1.00 kilograms of SiClx）, 2.75 kilograms of CeSAPO-11（Containing 2.30 kilograms of butt）With 6.80 kilograms of deionized water mixing, stirring 30 Mixed serum is obtained after minute.Carrier mixture is obtained during the mixed serum is added above-mentioned titanium colloidal sol, and after stirring 1 hour.

The spray drying forming of carrier mixture, roasting are carried out with reference to the method for embodiment 1, active component nickel is introduced and is gone back Original, obtains desulphurization catalyst A4.Wherein nickel is introduced by adding 2.79 kilograms of Nickelous nitrate hexahydrates.

The composition of desulphurization catalyst A4 is calculated as by inventory：The weight % of zinc oxide 40.0, the weight % of tin ash 15.0, oxygen The weight % of 10.0 weight %, CeSAPO-11 molecular sieve of SiClx 23.0（The weight % of cerium oxide 5.0, the weight % of USY molecular sieve 18.0）, nickel 12.0 weight %.

Desulphurization catalyst A4 is determined through Pyridine adsorption IR spectra, and spectrogram is shown in Fig. 4.In 1445cm in spectrogram^-1Place occurs in that Characterize characteristic peak of the cerium in molecular sieve pore passage.

Desulphurization catalyst A4 carries out polycrystal X ray diffraction（XRD）Characterize, spectrogram is shown in Fig. 5.With the characteristic peak that 2 θ are 16.02 ° The crystallization reservation degree of SAPO-11 molecular sieves in desulphurization catalyst A4 is calculated, 1 is the results are shown in Table.

Analyzed by above-mentioned Pyridine adsorption IR spectra and XRD spectra, illustrate that cerium has entered into SAPO-11 molecular sieves In pore passage structure.

It is 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° in 2 θ shown in Fig. 5, in spectrogram to be answered in the absence of cerium titanium The rhombic characteristic peak of oxide is closed, and there is titanium dioxide for 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° in 2 θ Anatase crystal characteristic peak, although having used titanium dioxide in illustrating A4, cerium in the duct of molecular sieve, titanium dioxide Titanium is distributed in outside molecular sieve, does not have the cerium-titanium composite oxide structure that titanium dioxide is formed with cerium.

Embodiment 5

According to the method for embodiment 4, unlike, with " SAPO-34 molecular sieves（Shandong catalyst branch company, containing butt 1.80 kilograms, sial atomic molar ratio is 0.2：1）", substitute " SAPO-11 molecular sieves（Shandong catalyst branch company, containing butt 1.80 kilograms, sial atomic molar ratio is 0.15：1）”.

The composition for obtaining desulphurization catalyst A5 is calculated as by inventory：The weight % of zinc oxide 40.0, the weight of tin ash 15.0 Amount %, the weight % of 10.0 weight %, CeSAPO-11 molecular sieve of silica 23.0（The weight % of cerium oxide 5.0, the weight of USY molecular sieve 18.0 Amount %）, the weight % of nickel 12.0.

Embodiment 6

According to the method for embodiment 4, unlike, with " SAPO-5 molecular sieves（Shandong catalyst branch company, containing butt 1.80 kilograms, sial atomic molar ratio is 0.5：1）", substitute " SAPO-11 molecular sieves（Shandong catalyst branch company, containing butt 1.80 kilograms, sial atomic molar ratio is 0.15：1）”.

The composition for obtaining desulphurization catalyst A6 is calculated as by inventory：The weight % of zinc oxide 40.0, the weight of tin ash 15.0 Amount %, the weight % of 10.0 weight %, CeSAPO-11 molecular sieve of silica 23.0（The weight % of cerium oxide 5.0, the weight of USY molecular sieve 18.0 Amount %）, the weight % of nickel 12.0.

Comparative example 1

Titanium tetrachloride is crystallized by 3.17 kilograms（ZrCl₄·5H₂O, Alfa Aesar companies, the weight % of purity 99）It is added to In 4.2 kilograms of acid waters, and stir 1 hour, obtain the titanium colloidal sol of water white transparency.Then toward addition 2.45 thousand in above-mentioned titanium colloidal sol Gram expanded perlite（Containing 2.40 kilograms of butt）And be uniformly mixed, obtain mixture.

By 4.50 kilograms of Zinc oxide powders（Headhorse companies, the weight % of purity 99.7）, 2.00 kilograms of SAPO-11 molecules Sieve（Shandong catalyst branch company, containing 1.8 kilograms of butt, sial atomic molar ratio is 0.15：1）It is mixed with 5.25 kilograms of deionized waters Close, stirring obtains the mixed serum of zinc oxide and SAPO-11 molecular sieves after 30 minutes.Add above-mentioned expansion precious the mixed serum Carrier mixture is obtained in the mixture of Zhu Yan and titanium colloidal sol, and after stirring 1 hour.

The spray drying forming of carrier mixture, roasting are carried out with reference to the method for embodiment 1, active component nickel is introduced and is gone back Original, obtains desulphurization catalyst B1.Wherein the compound of active metal is Nickelous nitrate hexahydrate, and consumption is 2.79 kilograms.

The composition of desulphurization catalyst B1 is calculated as by inventory：The weight % of zinc oxide 45.0, the weight % of silica 10.0, The weight % of SAPO-11 molecular sieves 18.0, the weight % of titanium dioxide 15.0, the weight % of nickel 12.0.

Rare earth oxide is not used in desulphurization catalyst B1, there is no influence of the rare earth to molecular sieve, also without rare earth-titanium Composite oxides structure is formed.

Comparative example 2

By 2.25 kilograms of boehmites（Shandong Aluminum Plant produces, containing 1.35 kilograms of butt）It is added to 0.32 kilogram of 18 weight Measure the hydrochloric acid of %（Chemistry is pure, and Beijing Chemical Plant produces）In solution and stir 1 hour, obtain alumina gel.

By 1.261 kilogram of six nitric hydrate cerium（Chemical Reagent Co., Ltd., Sinopharm Group, purity is more than 99.0 weight %）It is molten In 0.5 kilogram of deionized water solution, with 2.00 kilograms of SAPO-11 molecular sieves of the cerous nitrate aqueous impregnation（Shandong catalyst Branch company, containing 1.80 kilograms of butt, sial atomic molar ratio is 0.15：1）, to be dried after dipping, roasting obtains cerium modified CeSAPO-11 molecular sieves.

By 4.0 kilograms of Zinc oxide powders（Headhorse companies, the weight % of purity 99.7）, 1.2 kilograms of diatomite（It is oxygen-containing 1.0 kilograms of SiClx）, 2.75 kilograms of CeSAPO-11（Containing 2.30 kilograms of butt）With 6.80 kilograms of deionized water mixing, 30 points are stirred The mixed serum of zinc oxide and CeSAPO-11 molecular sieves is obtained after clock.During the mixed serum is added above-mentioned alumina gel, and Stirring obtains carrier mixture after 1 hour.

The spray drying forming of carrier mixture, roasting are carried out with reference to the method for embodiment 1, active component nickel is introduced and is gone back Original, obtains desulphurization catalyst B2.Wherein nickel is introduced by adding 2.79 kilograms of Nickelous nitrate hexahydrates.

The composition of desulphurization catalyst B2 is calculated as by inventory：The weight % of zinc oxide 40.0, the weight % of tin ash 15.0, oxygen The weight % of 10.0 weight %, CeSAPO-11 molecular sieve of SiClx 23.0（The weight % of cerium oxide 5.0, the weight % of USY molecular sieve 18.0）, nickel 12.0 weight %.

Desulphurization catalyst B2 is determined through Pyridine adsorption IR spectra, and spectrogram is shown in Fig. 6.In 1445cm in spectrogram^-1Place occurs in that Characterize characteristic peak of the cerium in molecular sieve pore passage.

Desulphurization catalyst B2 carries out polycrystal X ray diffraction（XRD）Characterize, spectrogram is shown in Fig. 7.With the characteristic peak that 2 θ are 16.02 ° The crystallization reservation degree of SAPO-11 molecular sieves in desulphurization catalyst B2 is calculated, 1 is the results are shown in Table.

Illustrate that rare-earth element cerium has entered into SAPO-11 molecules by above-mentioned Pyridine adsorption IR spectra and XRD spectra In the pore passage structure of sieve.

Shown in Fig. 7, there is zinc for 8.01 °, 28.64 °, 30.92 °, 37.1 °, 59.36 ° and 65.25 ° in 2 θ in XRD spectra The characteristic peak of aluminate, it is binding agent to illustrate that B2 uses aluminum oxide, and desulfurization can be formed with zinc oxide reaction in roasting process The gahnite structure of poor activity, reduces activated zinc oxide.

Performance test

（1）Abrasion strength resistance is evaluated.Desulphurization catalyst A1-A6 and B1-B2 is evaluated using straight tube abrasion method, method With reference to《Petrochemical Engineering Analysis method（RIPP）Experimental technique》The method of middle RIPP29-90, numerical value is smaller, shows abrasion strength resistance It is higher.In order to more preferably represent activity of the desulphurization catalyst during commercial Application, to the desulfurization catalyst after vulcanizing treatment Agent is also carried out abrasion strength resistance analysis, and specific sulfurizing treatment method is：Desulphurization catalyst is positioned in fluid bed, vulcanization is passed through Hydrogen（50 volume %）And nitrogen（50 volume %）Gaseous mixture, and be heated to 400 DEG C of vulcanizing treatments 1 hour.The results are shown in Table 1.

（2）Desulfurization performance is evaluated.Evaluated using the micro- anti-experimental provision of fixed bed, adsorption reaction raw material uses sulfur content It is the catalytically cracked gasoline of 640 μ g/g.16 grams of desulphurization catalyst A1 is seated in internal diameter for the fixed bed of 30mm, a length of 1m is anti- In answering device, using hydrogen atmosphere, reaction temperature is 410 DEG C, and the charging of adsorption reaction raw material is for weight space velocity for 4h-1 is contained The desulphurization reaction of sulphur hydrocarbon ils.Weigh desulphurizing activated with sulfur content in product gasoline.Sulfur content is by offline chromatogram in product gasoline Analysis method, is measured using the GC6890-SCD instruments of An Jielun companies.The results are shown in Table 2.Equally carry out desulphurization catalyst Using the desulfurization performance evaluation of A2-A6 and B1-B2,2 are the results are shown in Table.

After carrying out 12 hours according to above-mentioned evaluation response, regeneration treatment is carried out, regeneration treatment is the air atmosphere at 550 DEG C Under carry out.6 circulations of reaction-regeneration are so repeated.The desulfurization stability of desulphurization catalyst is evaluated with this.Can be more accurate Symbolize activity of the desulphurization catalyst in industrial actual motion.Terminate the sulfur content result in rear product gasoline per secondary response It is shown in Table 2.Product gasoline is weighed at the end of per secondary response is calculated the yield of product gasoline according to the following formula, the results are shown in Table 3.

Yield of gasoline/%=product gasolines quality/oil inlet quantity × 100%

（3）Investigate product form and product gasoline quality.Table 4 is to carry out the product that the 6th circulation desulfurization catalytic reaction is obtained Product are distributed（Coke content on catalyst is analyzed with carbon sulphur instrument, and gas-phase product is calculated by minusing）.Table 5 is to carry out the 6th The analysis result of the product gasoline composition that secondary circulation desulfurization catalytic reaction is obtained（Method is gas chromatography, is entered with PONA softwares Row is calculated）.Six product gasolines of circulation are mixed, is respectively adopted《GB/T503-1995》With《GB/T5487-1995》Determine The motor octane number of gasoline before and after reaction（MON）And research octane number (RON)（RON）,（MON+RON）/ 2 is anti-knock index.As a result It is shown in Table 6.

（4）Diesel fuel desulfurization performance evaluation

Using（2）In fixed bed micro- anti-experimental provision diesel fuel desulfurization performance is carried out to desulphurization catalyst A1-A6 and B1-B2 Evaluate.It is the catalytic cracking diesel oil of 3718 μ g/g that raw material uses sulfur content.According to（2）In method carry out six times circulation evaluate, After six circulations terminate, using sulfur content in offline chromatography product diesel, and diesel fuel desulfurization rate is calculated, under computing formula is Formula, the results are shown in Table 7.

Diesel fuel desulfurization rate/%=100- diesel products quality × diesel product sulfur content/(feed sulphur content × inlet amount) × 100%

Product diesel oil is weighed, the yield of product diesel oil is calculated according to the following formula, the results are shown in Table 7.Using《GB/T386- 2010 diesel cetane methods》In the Cetane number of CFR (F5) type diesel cetane-number aircraft measurements diesel oil, the results are shown in Table 7。

Diesel yield/%=products diesel quality/oil inlet quantity × 100%

Table 1

Numbering	Crystallization of molecular sieves reservation degree/%	Abrasion index（Before vulcanization）	Abrasion index（After vulcanization）
				A1	99.9	3.1	2.9
A2	100	3.2	3.1
				A3	99.8	3.2	3.1
A4	40.5	3.8	3.6
				A5	48.4	3.7	3.5
A6	47.1	3.8	3.7
				B1	-	5.8	5.9
B2	15.7	7.0	6.5

Table 2

Table 3

Table 4

Table 5

Table 6

Note：

1st, the sulfur content of feed gasoline for 640 μ g/g, RON be that 93.0, MON is 82.7.

2nd, △ MON represent the value added of product MON；

3rd, △ RON represent the value added of product RON；

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

Table 7

Note：1st, the sulfur content of raw material diesel oil is 3718 μ g/g, and Cetane number is 26.4.

It can be seen from Table 1 that, the desulphurization catalyst A1-A6 provided using the present invention carries out gasoline desulfurization, gasoline products In isoparaffin and the content of isomeric olefine substantially increase so that the octane number of gasoline products has improvement by a relatively large margin. Meanwhile, the desulphurization catalyst provided using the present invention carries out diesel fuel desulfurization, and Cetane number can be significantly improved.

In the preferred embodiment of the desulphurization catalyst that the present invention is provided, rare earth does not enter into the pore passage structure of molecular sieve Inside, molecular sieve structure is not destroyed, and crystallinity reservation degree is close to 100%.Be can see from the XRD spectra shown in Fig. 1-3, Rare earth is combined with titanium, forms rare earth-titanium composite oxide structure.Desulphurization catalyst A1-A3 is displayed in Table 1 out can wear and tear Index is lower, with more preferable abrasion resistance properties.Desulphurization catalyst A1-A3 has been displayed in Table 2 the sulphur in gasoline can be contained Amount is dropped to below 10 μ g/g, and still has more preferable desulfurized effect after being recycled for multiple times, and illustrate that the desulfurization that the present invention is provided is urged Agent has the desulphurizing activated and desulfurization stability of sulphur in more preferable elimination reaction feed gasoline.Table 3-4 can be seen that desulfurization and urge Agent A1-A3 has product gasoline yield higher, and generation amount of coke is lower.Table 5 shows that desulphurization catalyst A1-A3 is carried out In the gasoline products composition that desulfurization is obtained, the content of isomeric component is higher.Table 6 is as can be seen that what desulphurization catalyst A1-A3 was obtained The octane number of product gasoline is improved.As can be seen here, the desulphurization catalyst that the present invention is provided has more preferable structure, Ke Yigai Enter abrasion resistance properties, there can be preferably desulphurizing activated and desulfurization stability, while producing, yield of gasoline is higher, green coke amount is more It is low, product gasoline better quality.

As can be seen from Table 7, the desulphurization catalyst that the present invention is provided can also have more preferable diesel fuel desulfurization effect, product bavin Sulfur content is lower in oil, and desulfurization degree is higher, desulphurizing activated higher, and desulfurization stability is more preferable；And the product diesel oil 16 for obtaining Alkane value is improved, and yield is higher.

And in comparative example 2, although also contain rare earth, but be distributed across the inside of SAPO-11 molecular sieve pore passages, not only influenceing The crystallization reservation degree of molecular sieve, and then influence the acidity of molecular sieve, the quality of desulfurization reaction product.And made using aluminum oxide It is binding agent in desulfurization of hydrocarbon oil course of reaction, aluminum oxide forms gahnite with zinc oxide, reduces activated zinc oxide Quantity, the desulphurizing activated and stability of final influence desulphurization catalyst.

Claims

1. a kind of desulphurization catalyst, the desulphurization catalyst contains SAPO molecular sieve, rare earth oxide, titanium dioxide, silica, oxidation Zinc and active metal, on the basis of the gross weight of the desulphurization catalyst, the content of the SAPO molecular sieve is 1-30 weight %, The rare earth oxide is with RE₂O₃The content of meter is 0.5-15 weight %, and the content of the titanium dioxide is 3-35 weight %, described The content of silica is 5-30 weight %, and the content of the zinc oxide is 10-80 weight %, and the content of the active metal is 5- 30 weight %；The content of rare earth element is 0 μ g/g in the pore passage structure of the SAPO molecular sieve；The XRD of the desulphurization catalyst There is the rhombic characteristic peak of rare earth-titanium composite oxide in spectrogram.

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 SAPO molecular sieve is 2-25 weight %, and the rare earth oxide is with RE₂O₃The content of meter is 0.5-10 weight %, described two The content of titanium oxide is 5-25 weight %, and the content of the silica is 10-20 weight %, and the content of the zinc oxide is 25- 70 weight %, the content of the active metal is 8-25 weight %.

3. desulphurization catalyst according to claim 1, wherein, the SAPO molecular sieve be selected from small-bore SAPO-34, 17th, 18,26,33,34,35,39,42,43,44,47, the SAPO-5 of the SAPO-11 in middle aperture, 31,41 and large aperture, 36,37, 40th, at least one in 46.

4. the desulphurization catalyst according to any one in claim 1-3, wherein, the sial atom of the SAPO molecular sieve Mol ratio is 0.05-1.0：1.

5. desulphurization catalyst according to claim 1, wherein, the rare earth element in the rare earth oxide be selected from La, Ce, At least one of Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

6. desulphurization catalyst according to claim 5, wherein, rare earth element in the rare earth oxide for La, Ce, Pr and At least one in Nd.

7. desulphurization catalyst according to claim 1, wherein, the active metal is at least in cobalt, nickel, iron and manganese Kind.

8. desulphurization catalyst according to claim 1, wherein, when the rare earth element is cerium, the desulphurization catalyst There is the iris of the cerium-titanium composite oxide that 2 θ are 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° in XRD spectra The characteristic peak of system；In the absence of the spy of the anatase crystal of the titanium dioxide that 2 θ are 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° Peak is levied, in the absence of the characteristic peak of the cubic crystal of the cerium oxide that 2 θ are 28.52 ° and 33.06 °.

9. desulphurization catalyst according to claim 1, wherein, when the rare earth element is lanthanum, the desulphurization catalyst There is the rhombic spy of the lanthanum titanium composite oxide that 2 θ are 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 ° in XRD spectra Levy peak；In the absence of the characteristic peak of the anatase crystal of the titanium dioxide that 2 θ are 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, In the absence of the lanthana that 2 θ are 25.3 °, 27.8 °, 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 ° cube The characteristic peak of crystal.

10. desulphurization catalyst according to claim 1, wherein, when the rare earth element is neodymium, the desulphurization catalyst There is the rhombic characteristic peak of the neodymium titanium composite oxide that 2 θ are 22.7 °, 32.4 °, 46.3 ° and 58.0 ° in XRD spectra； In the absence of the characteristic peak of the anatase crystal of the titanium dioxide that 2 θ are 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, do not exist 2 θ are the characteristic peak of the cubic crystal of 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 ° of neodymia.

The preparation method of the desulphurization catalyst described in a kind of 11. claims 1, the method includes：

(1) precursor of titania source and rare earth oxide is mixed into contact and obtains rare earth-titanium colloidal sol；

(2) after the slurries for being mixed to form zinc oxide, silica source, SAPO molecular sieve and water mix with the rare earth-titanium colloidal sol, Contacted with acidic liquid and obtain carrier mixture, then carrier is obtained through shaping, dry and roasting；

(3) compound containing active metal is introduced in the carrier, dry, roasting obtains desulphurization catalyst precursor；

(4) the desulphurization catalyst precursor is reduced in a hydrogen atmosphere, obtains desulphurization catalyst.

12. methods according to claim 11, wherein, the titania source, zinc oxide, silica source, SAPO molecules The addition of sieve, the precursor of rare earth oxide and the compound containing active metal makes in the desulphurization catalyst for obtaining, and is urged with desulfurization On the basis of the gross weight of agent, the content of SAPO molecular sieve is 1-20 weight %, rare earth oxide with RE₂O₃The content of meter is 0.5- 10 weight %, the content of titanium dioxide are 3-35 weight %, and the content of silica is 5-30 weight %, and the content of zinc oxide is 10-80 weight %, the content of active metal is 5-30 weight %.

13. method according to claim 11 or 12, wherein, the precursor of the rare earth oxide is dilute selected from the oxidation In the acetate of the rare earth metal in soil, carbonate, nitrate, sulfate, oxalates, chloride and oxide at least one Kind.

Desulphurization catalyst prepared by 14. method as described in any one in claim 11-13.

A kind of 15. methods of desulfurization of hydrocarbon oil, the method includes：Hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, its feature exists In desulphurization catalyst of the desulphurization catalyst described in any one in claim 1-10 and 14.