CN104549488B

CN104549488B - A kind of method of desulphurization catalyst and its preparation and desulfurization of hydrocarbon oil

Info

Publication number: CN104549488B
Application number: CN201310522466.3A
Authority: CN
Inventors: 孙言; 林伟; 田辉平; 朱玉霞; 王鹏
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: 2017-03-29
Anticipated expiration: 2033-10-29
Also published as: CN104549488A

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 the method for desulfurization of hydrocarbon oil.The desulphurization catalyst contains SAPO molecular sieve, rare earth oxide, tin ash, silicon oxide, 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 method of desulphurization catalyst and its 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 the method for desulfurization of hydrocarbon oil.

Background technology

The sulphur compound contained in hydrocarbon ils easily causes the exhaust emission of sulfur in use, especially as vehicle fuel The impact of sulphur pollution is expanded by hydrocarbon ils with the movement of vehicle.Strict standard has been formulated one after another for this various countries to limit as car With the sulfur content in the hydrocarbon ils of fuel.

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

CN1355727A discloses a kind of combination of adsorbents suitable for removing sulfur from cracking gasoline and diesel fuel Thing, by Zinc Oxide, silicon oxide, oxidation al and ni constitute, wherein nickel with substantially reduce valence state presence, its amount make it possible to from The cracking gasoline for contacting with the nickeliferous adsorbent composition under desulfurization conditions removes sulfur in diesel fuel stream.The absorption Desulphurizing activated and stability comparatively fresh agent after agent compositionss are 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 load of the reactive metal oxides and 30-94 weight % of 5-40 weight % Body, wherein carrier include aluminium oxide and Zinc Oxide, and rare earth faujasite is by faujasite and the duct knot 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, need to develop a kind of yield of gasoline height, and desulphurizing activated high with desulfurization stability and renewable use Hydrocarbon oil desulphurization adsorbing agent.

The content of the invention

The purpose of the present invention is the defect for overcoming desulfuration adsorbent presence in above-mentioned prior art, 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, tin ash, silicon oxide, Zinc Oxide and active metal, it is on the basis of the gross weight of the desulphurization catalyst, described The content of SAPO molecular sieve is 1-30 weight %, and the rare earth oxide is with RE₂O₃The content of meter be 0.5-15 weight %, the dioxy The content for changing stannum is 3-35 weight %, and the content of the silicon oxide 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 tin ash source, Zinc Oxide, silica source, rare earth modified The serosity that SAPO molecular sieve and water are mixed to form is contacted with acidic liquid and obtains carrier mixture, then Jing molding, drying 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 tin ash source and oxidation The precursor mixing contact of rare earth obtains rare earth-tin oxide sol；（2）Zinc Oxide, silica source, SAPO molecular sieve and water are mixed into shape Into serosity mix with the rare earth-tin oxide sol after, contact with acidic liquid and obtain carrier mixture, then Jing molding, drying 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.In the product gasoline composition for obtaining, iso-component is more, and sulfur content is lower, product gasoline Octane number improve, product gasoline better quality.The desulphurization catalyst can obtain more preferable wear resistance in addition.

For example, the desulphurization catalyst A1 for obtaining in embodiment 1 contains SAPO-11 molecular sieves and cerium, by XRD spectra meter The crystallization reservation degree for calculating the molecular sieve in A1 does not change for the structure of 99.9%, SAPO-11 molecular sieves, judges that cerium is not entered into In the pore passage structure of SAPO-11 molecular sieves, i.e., in the pore passage structure of SAPO-11 molecular sieves, content of rare earth is 0 μ g/g.From XRD figure There is cerium stannum solid solution in can be seen that desulphurization catalyst A1 in the information of middle appearance.Therefore, carry out gasoline HDS evaluation, the 6th time The absorption regeneration product gasoline sulfur content that obtains of circulation is 7 μ g/g, illustrate desulphurization catalyst A1 have more preferable gasoline it is desulphurizing activated, Stability.In the product slates obtained in gasoline HDS evaluation, green coke amount is 0.01 weight %, and the product gasoline yield for obtaining is 99.95%, isoparaffin and isomeric olefine content are respectively 39.01 weight % and 23.68 weight %, and product gasoline octane number increases, Illustrate that desulphurization catalyst A1 can obtain the product gasoline of better quality.Diesel fuel desulfurization is carried out using desulphurization catalyst A1 in addition Can evaluate, in product diesel oil, sulfur content is 11.6 μ g/g, and diesel fuel desulfurization rate is 99.69%, and product diesel yield is 99.40%, ten Six alkane values are 36.0.Desulphurization catalyst A1 abrasion index before and after sulfuration are respectively 3.3 and 3.1, have more preferable abrasion resistance properties. And the desulphurization catalyst B2 in comparative example 2, carry out gasoline HDS evaluation, the product gasoline sulfur that the 6th absorption regeneration circulation is obtained Content is 11 μ g/g, and in the product slates for obtaining, green coke amount is 0.02 weight %, and the product gasoline yield for obtaining is 99.94%, different Structure alkane and isomeric olefine content are respectively 38.19 weight % and 21.46 weight %.Carry out diesel fuel desulfurization performance evaluation, product bavin In oil, sulfur content is 13.6 μ g/g, and diesel fuel desulfurization rate is 99.63%, and product diesel yield is 99.28%, and Cetane number is 29.8. Desulphurization catalyst A4 abrasion index before and after sulfuration are respectively 4.0 and 3.9.

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

Description of the drawings

Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with following tool Body embodiment is used for explaining 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 the peak of labelling " ◆ " It is the characteristic peak of SAPO-11 molecular sieves, 2 θ are cerium stannum for the peak of 26.25 °, 33.70 °, 37.85 ° and 51.67 ° and labelling " ▼ " The characteristic peak of the tetragonal crystal system of solid solution；

Fig. 2 is the XRD spectra of the desulphurization catalyst A2 containing lanthanum and SAPO-34 molecular sieves, wherein 2 θ be 9.58 °, The peak of 13.00 °, 16.14 °, 17.82 °, 19.18 ° and 20.78 ° and labelling "●" is the characteristic peak of SAPO-34 molecular sieves, and 2 θ are The peak of 28.88 °, 33.47 °, 48.06 °, 57.04 ° and 59.83 ° and labelling " ▼ " is the rhombic of lanthanum stannum composite oxides Characteristic 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 °, The peak of 13.00 °, 15.15 °, 19.81 °, 20.68 °, 22.29 °, 26.15 ° and 29.05 ° and labelling "●" is SAPO-5 molecular sieves Characteristic peak, it is neodymium stannum combined oxidation that 2 θ are the peak of 29.25 °, 33.90 °, 48.71 °, 57.83 ° and 60.67 ° and labelling " ▼ " The rhombic characteristic peak of thing；

Pyridine adsorption IR spectra spectrograms of the Fig. 4 for desulphurization catalyst A4, wherein wave number are 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 °, The peak of 21.80 °, 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and labelling " ◆ " is the characteristic peak of SAPO-11 molecular sieves, and 2 θ are The peak of 26.60 °, 33.89 °, 37.91 ° and 51.80 ° and labelling " ■ " is the characteristic peak of tin ash；

Pyridine adsorption IR spectra spectrograms of the Fig. 6 for desulphurization catalyst B2, wherein wave number are 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 °, The peak of 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and labelling " ▲ " is the characteristic peak of SAPO-11 molecular sieves, 2 θ are 8.01 °, The peak of 28.64 °, 30.92 °, 37.1 °, 59.36 ° and 65.25 ° and labelling " ■ " is the characteristic peak of gahnite.

Specific embodiment

Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that described herein concrete Embodiment is merely to illustrate and explains the present invention, is not limited to the present 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 tin ash is 5-25 weight %, the content of the silicon oxide is 10-20 weight %, and the Zinc Oxide contains Measure as 25-70 weight %, the content of the active metal is 8-25 weight %；More preferably with the gross weight of the desulphurization catalyst it is Benchmark, the content of the SAPO molecular sieve is 2-20 weight %, and the rare earth oxide is with RE₂O₃The content of meter be 1-5 weight %, institute The content for stating tin ash is 8-15 weight %, and the content of the silicon oxide 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 make straight-chain hydrocarbons obtain isomerization, make gasoline Product octane number is improved, while ensureing the effect of higher yield of gasoline.Under preferable case, the SAPO molecular sieve is selected from little The SAPO-34 in aperture, 17,18,26,33,34,35,39,42,43,44,47, the SAPO-11 in middle aperture, 31,41 and large aperture SAPO-5,36,37,40,46 at least one.

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 It is distributed inside the duct of molecular sieve.Under preferable case, the rare earth element in the rare earth oxide 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 promoting 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 is at least in cobalt, nickel, ferrum and manganese Plant, more preferably cobalt and/or nickel.

In a kind of preferred implementation of the present invention, the rare earth oxide is not distributed inside the duct of SAPO molecular sieve, In the pore passage structure of i.e. described SAPO molecular sieve, the content of rare earth element is 0 μ g/g；Deposit in the XRD spectra of the desulphurization catalyst In the characteristic peak of the cubic system of the tetragonal crystal system or rare earth-stannum composite oxides of rare earth-stannum solid solution.

In the present invention, in the desulphurization catalyst content of rare earth oxide and tin ash can advantageously form rare earth- Stannum solid solution or rare earth-stannum combined oxidation structure, so as to be more beneficial for improving the abrasion resistance properties, desulphurizing activated of desulphurization catalyst With product gasoline quality.

According to the present invention, the no rare earth element distribution 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 is entered 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, when entering 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 degree of 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 are 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 analysiss of pyridine adsorption It is interior.Judged according to the wave number of the characteristic peak of the rare earth element on infrared spectrum appearance.The hole of SAPO-11 molecular sieves is entered with cerium As a example by road structure, the characteristic peak of cerium occurs 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 tin ash, form rare earth-stannum solid solution or composite oxides Crystal structure.Under preferable case, as shown in figure 1, when rare earth element is cerium, depositing in the XRD spectra of the desulphurization catalyst In the characteristic peak of the tetragonal crystal system of cerium stannum solid solution（With（《Organizational structure, heating power about Sn, Ce, Ru oxide-based nanomaterial Learn and electrode performance》University of Fuzhou's Master's thesis, Wang little Kang）Document is mutually compared, feature of the features described above peak for cerium stannum solid solution Peak）, with pure SnO₂Standard substance card（JCPDS21-1250）In 26.60 ° of characteristic peak, 33.89 °, 37.91 ° and 51.80 ° have deviation, and this is, as the lattice structure that Ce " has dissolved in " tin ash forms cerium stannum solid solution, to make tin ash Lattice be distorted, so as to be reflected in XRD spectra the generation skew compared with the characteristic peak of pure tin ash.In addition, in 2 θ Characteristic peak for the 28.52 ° and 33.06 ° cubic crystals that there is no cerium oxide also demonstrate that Ce " has dissolved in " tin ash lattice In structure, single cerium oxide structure is there is no longer（Wang little Kang Master's thesis, ibid）.

, 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 cubic system of the lanthanum stannum composite oxides that 2 θ are 28.88 °, 33.47 °, 48.06 °, 57.04 ° and 59.83 ° in spectrogram Characteristic peak；There is no the characteristic peak of the tetragonal crystal of the tin ash that 2 θ are 26.60 °, 33.89 °, 37.91 ° and 51.80 °, no There is the cubic crystal 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 ° The characteristic peak of body（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 cubic system of the neodymium stannum composite oxides that 2 θ are 29.25 °, 33.90 °, 48.71 °, 57.83 ° and 60.67 ° in spectrogram Characteristic peak；There is no the characteristic peak of the tetragonal crystal of the tin ash that 2 θ are 26.60 °, 33.89 °, 37.91 ° and 51.80 °, no There is the characteristic peak of the cubic crystal of the Dineodymium trioxide that 2 θ are 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 ° （JCPDS No.40-1282）.

In the present invention, rare earth-stannum solid solution or rare earth-stannum composite oxides are formed in desulphurization catalyst, can be overcome Desulphurization catalyst tear strength declines, the problem that caused usage cycles shorten.In addition, rare earth-stannum the solid solution or dilute for being formed Soil-stannum composite oxides, can preferably improve gasoline and diesel fuel desulfurization activity.In the desulphurization catalyst, SAPO molecular sieve Duct in no rare earth element exist, and contain rare earth-stannum solid solution or rare earth-stannum composite oxides, can also be preferably Isomerization product content, the octane number of raising product gasoline in the desulfurization product gasoline that raising is obtained.In the desulphurization catalyst In can also preferably increase the active phase of Zinc Oxide containing rare earth-stannum solid solution or rare earth-stannum composite oxides, so as to more preferable Improve the desulphurizing activated of desulphurization catalyst in ground.

In the present invention, in the desulphurization catalyst, tin ash substitutes aluminium oxide and can also be reduced as binding agent Desulphurization catalyst forms the effect of gahnite in absorption with regenerative process, so as to keep the activity of Zinc Oxide, makes desulfurization Catalyst has preferably 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）Tin ash source, Zinc Oxide, silica source, rare earth are changed The serosity that property SAPO molecular sieve and water are mixed to form is contacted with acidic liquid and obtains carrier mixture, then Jing molding, drying and roasting 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 carried out into roasting, 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 serosity, and carries out filtering, wash, be dried and roasting the serosity；The temperature that the serosity is dried For 80-120 DEG C, it is 300-600 DEG C that the serosity carries out the temperature of roasting；The concentration of the rare earth metal salt solutions is 0.01- 1.5 mol/L.Wherein, SAPO molecular sieve is carried out into roasting before the contact and can removes all or part of template.

There can also be method two, including：Before the contact, SAPO molecular sieve is carried out into roasting, 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 With 300-600 DEG C of roasting.Wherein, SAPO molecular sieve is carried out into roasting before the contact and can removes all or part of mould Plate agent.The incipient impregnation can be the method that this area catalyst preparation is routinely adopted, when may refer to dipping, rare earth gold The volume of category saline solution 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 the nitrate of rare earth metal, halogenide, vinegar At least one in hydrochlorate and sulfate liquor.

, according to the invention it is preferred in the case of, the tin ash source selected from butter of tin, four isopropanol stannum, tin acetate and At least one in aqua oxidation stannum.

, 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 kieselguhr, expanded perlite, Kaolin, silicalite, hydrolysis One or more in silicon oxide, macropore silicon oxide and silica gel.

According to the present invention, step（2）In, the consumption of the acidic liquid can cause the pH value of the carrier pulp to be 0.5-6, more preferably 1-4.The acidic liquid can be selected from water-soluble mineral 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 serosity.By the molding, the carrier mixture can be shaped to into extrudate, piece, pill, ball or microspheroidal Grain.For example, when the carrier mixture is dough or paste mixture, the carrier mixture molding can be made（It is preferred that squeezing Go out molding）Granule is formed, then preferred diameter makes gained in 1.0-8.0mm, cylindrical extrudates of the length in 2.0-5.0mm Extrudate be dried, roasting.If the carrier mixture is wet mixture form, it is thickened can the mixture, passes through It is dried aftershaping.More preferably described carrier mixture is slurry form, forms granularity for 20-200 microns by being spray-dried Microsphere, reaches the purpose of molding.For the ease of being spray-dried, before being dried, the solid content of serosity can be 10-50 weight %, preferably For 20-50 weight %.

In the present invention, the drying meanss and condition of the carrier mixture are known to those skilled in the art, for example, do 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；At least 0.5 hour time of the drying, 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；At least 0.5 hour time of the roasting, preferably For 0.5-100 hours, more preferably 0.5-10 hours.

In the preparation method that the present invention is provided, step（3）In introduce 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 the acetate of active metal, carbonate, nitre 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 To adopt well known to a person skilled in the art dipping method or intermediate processing are realized.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 is mixed with the carrier, be subsequently adding ammonia 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 roasting.About It is dried at 50-300 DEG C, the preferred temperature being dried is 100-250 DEG C, and the dry time is about 0.5-8 hours, more preferably from about For 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 carry out roasting, time of roasting is about 0.5-4 hours, preferred 1-3 hours, until volatile material 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 tin ash source, Zinc Oxide, silica source, SAPO molecular sieve, rare earth During the addition of metal salt solution and the compound containing active metal causes 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 be 0.5-10 weight %, two The content of stannum oxide is 3-35 weight %, and the content of silicon oxide is 5-30 weight %, and the content of Zinc Oxide is 10-80 weight %, active The content of metal is 5-30 weight %.

In the present invention, step（4）The reduction of desulphurization catalyst precursor can be entered after prepared desulphurization catalyst precursor immediately OK, it is also possible to using front（Before being used for desulfurization absorption）Carry out.As 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）Desulphurization catalyst precursor is reduced Carry out before carrying out desulfurization absorption.The metal being reduced to make in the oxide of active metal is substantially present with reduction-state, obtains To the desulphurization catalyst of the present invention.Under preferable case, the condition that desulphurization catalyst precursor is reduced in a hydrogen atmosphere is included：Hydrogen Gas content is 10-60 volumes %, 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 For 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 aforementioned de- The composition and content of sulfur catalyst, will not be described 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 mixing contact of tin ash source and rare earth oxide is obtained into rare earth-tin oxide sol；（2）By Zinc Oxide, oxygen After the serosity that SiClx source, SAPO molecular sieve and water are mixed to form is mixed with the rare earth-tin oxide sol, contact with acidic liquid and obtain Carrier mixture, then Jing molding, drying and roasting obtain carrier；（3）The compound containing active metal is introduced in the carrier, It is dried, roasting obtains desulphurization catalyst precursor；（4）The desulphurization catalyst precursor is reduced in a hydrogen atmosphere, desulfurization is obtained Catalyst.

According to the step of the present invention, the preparation method of the desulphurization catalyst（1）, by preparing rare earth-tin oxide sol, so as to In step（2）In molding, drying, form rare earth-stannum composite oxides structure in calcination process, containing 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-tin oxide sol can have various methods, can be method one, bag Include following steps：（a）Tin ash source is contacted with acid solution and obtains tin oxide sol；（b）By the tin oxide sol and rare earth oxide Precursor mixing is contacted with ammonia spirit again and obtains rare earth-tin oxide sol.Can also be method two, comprise the following steps：（a）By two Stannum oxide source is contacted with acid solution and obtains tin oxide sol；（b）By the tin oxide sol and the aqueous solution of the precursor of rare earth oxide Obtain rare earth-tin oxide sol.Can also be method three, including：The precursor of tin ash source and rare earth oxide and acid solution are connect Touch and obtain rare earth-tin oxide sol.In said method, the acid solution can for hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid, in 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-tin oxide sol can be formed, for example The pH value of serosity can be made as 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 in the tin ash source makes the desulfurization for obtaining In catalyst, on the basis of the gross weight of desulphurization catalyst, the content of tin ash is 3-35 weight %；It is preferred that tin ash Content is 5-25 weight %；More preferably the content of tin ash 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 gold of the rare earth 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 silicon oxide is 5-30 weight %；It is preferred that the silicon oxide Content is 10-20 weight %；The content of more preferably described silicon oxide 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 silicon oxide.Take off obtained in method i.e. provided by the present invention In sulfur catalyst, the content of each component is calculated according to inventory.

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

According to the present invention, step（2）In, the carrier mixture molding, drying and roasting obtain carrier as it was previously stated, This repeats no more.

In the preparation method that the present invention is provided, step（3）In introduce 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 the acetate of active metal, carbonate, nitric acid 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 described here after introducing the compound containing active metal in the carrier.

In the present invention, step（4）Desulphurization catalyst precursor is reduced as it was previously stated, will not be described 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 aforementioned desulphurization catalyst, will not be described 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 React 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：The desulphurization catalyst of reaction will be passed through 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, preferred 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 To 210 DEG C of hydrocarbon or its any fraction, it is from the product for making larger hydrocarbon molecule be cracked into the hot or catalytic process compared with small molecule 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 can be before desulfurization by institute during hydrocarbon-containifluids fluids State cracking gasoline fractional distillation 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 including but 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 " sulfur " 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.Present in hydrocarbon-containifluids fluids of the present invention, sulfur includes but is not limited to carbonyl sulfide（COS）、 Carbon bisulfide（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 will to be placed in the pond in situ of infrared spectrometer to seal after sample tabletting；10-3Pa is evacuated down under 623K, is protected 1h is held, is desorbed the gas molecule of sample surfaces clean, is cooled to room temperature, in 1000-4000cm^-1Scanning in wave-number range, note Infrared absorption spectra before the lower sample adsorption pyridine of record.Pyridine steam of the pressure for 2.67Pa, balance are imported in pond in situ After 30min, 200 DEG C are warmed up to, are evacuated to 10-3Pa again, kept 30min, be cooled to room temperature, in 1400-1700cm^-1Wave number In the range of scan, record the infrared absorption spectra of 200 DEG C of pyridine adsorptions, from this spectrogram observe rare earth in molecular sieve pore passage Interior characteristic peak.

Embodiment 1

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

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

（2）Prepare carrier.By 1.33 kilograms of expanded perlite（0.77 kilogram of silicon oxide-containing, 0.13 kilogram of tin ash, 0.07 kilogram of potassium oxide, 0.03 kilogram of sodium oxide）In being added to the salpeter solution of 0.5 kilogram of 2 weight %, heated and stirred is after 2 hours Filter, after removing the impurity such as potassium, sodium, stannum, be added to step（1）In the cerium tin oxide sol for obtaining, expanded perlite is obtained molten with cerium stannum The mixture of glue.

By 4.00 kilograms of Zinc oxide powders（Headhorse companies, 99.7 weight % of purity）, 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 obtained Zinc Oxide and SAPO-11 molecular sieve mixed serums after 30 minutes.The mixed serum is added step（1）Obtain Expanded perlite and cerium tin oxide sol mixture in, and obtain carrier mixture after stirring 1 hour.

The carrier mixture is adopted into Niro Bowen Nozzle Tower^TMThe spray dryer of model carries out spray dried It is dry, spray drying pressure be 8.5-9.5MPa, 350 DEG C of baking temperature.Microsphere roasting 0.5 at 650 DEG C that spray drying is obtained 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 are more than 98.5 weight %）With 0.8 kilogram The aqueous impregnation of deionized water, the mixture for obtaining are after 250 DEG C of dryings 5 hours, little in 450 DEG C of roastings 1 of air atmosphere 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：40.0 weight % of Zinc Oxide, 10.0 weight % of silicon oxide, 18.0 weight % of SAPO-11 molecular sieves, 15.0 weight % of tin ash, 5.0 weight % of cerium oxide, 12.0 weight % of nickel.

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 26.25 °, 33.70 °, 37.85 ° With 51.67 ° at there is the diffraction maximum of tin ash Rutile Type, but with pure SnO₂Standard substance card（JCPDS21- 1250）In 26.60 °, 33.89 °, 37.91 ° and 51.80 ° of the characteristic peak positions of tin ash Rutile Type there is deviation, this It is, as the lattice structure that Ce " has dissolved in " tin ash forms cerium stannum solid solution, to be distorted the lattice of tin ash, from And the generation skew compared with the characteristic peak of pure tin ash is reflected in XRD spectra.In addition, being at 28.52 ° and 33.06 ° in 2 θ The characteristic peak that there is no the cubic crystal of cerium oxide also demonstrate that Ce " has been dissolved in " in tin ash lattice structure, there is no longer individually Cerium oxide structure.Illustrate that tin ash and cerium oxide define cerium stannum solid solution in desulphurization catalyst A1.

Embodiment 2

（1）Prepare rare earth-tin oxide sol.By 1.17 kilograms of oxychlorination stannum（Aldrich, analyzes pure, 98.5 weight %）Plus Enter the hydrochloric acid to 2.0 kilogram of 15 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 tin oxide sol.By 0.1 kilogram of lanthana（Analyze pure, Chinese medicines group）In adding tin oxide sol, stirring is mixed Uniform rear 25 weight % ammonia spirit of Deca is closed until into lanthanum tin oxide sol.

（2）Prepare carrier.1.2 kilograms of kieselguhr（1.00 kilograms of silicon oxide-containing）With 6.00 kilograms of Zinc oxide powders （Headhorse companies, 99.7 weight % of purity）, 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）Kieselguhr, oxygen are obtained after mixing 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 tin oxide 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 are more than 98.5 Weight %）, 2.47 kilograms of cabaltous nitrate hexahydrates and 0.8 kilogram of deionized water aqueous impregnation, referring next to 1 step of embodiment （3）The method of middle drying and roasting is obtained desulphurization catalyst precursor.

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

The composition of desulphurization catalyst A2 is calculated as by inventory：60.0 weight % of Zinc Oxide, 8.0 weight % of tin ash, oxygen 10.0 weight % of SiClx, 2.0 weight % of SAPO-34 molecular sieves, 1.0 weight % of lanthana, 14.0 weight % of nickel, 5.0 weight % of cobalt.

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 28.88 °, 33.47 °, There is the characteristic peak of the cubic system of lanthanum stannum composite oxides at 48.06 °, 57.04 ° and 59.83 °, 2 θ be 26.60 °, There is no the characteristic peak of tin ash tetragonal crystal at 33.89 °, 37.91 ° and 51.80 °, 2 θ be 25.3 °, 27.8 °, There is no the characteristic peak of the hexagonal of lanthana at 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 ° （JCPDSNo.24-0554）.Illustrate that tin ash and lanthana define lanthanum stannum composite oxides structure in desulphurization catalyst A2.

Embodiment 3

（1）Prepare rare earth-tin oxide sol.By 1.90 kilograms of tin ash（Aldrich, analyzes pure, 99 weight %）With 0.651 kilogram of six nitric hydrate neodymium（Chemical Reagent Co., Ltd., Sinopharm Group, content are 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 tin oxide 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 In the salpeter solution of amount %, heated and stirred was filtered after 3 hours, 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 after stirring 30 minutes, is obtained Serosity.The mixed serum is added step（1）In the neodymium tin oxide sol for obtaining, quick stirring obtained 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：50.0 weight % of Zinc Oxide, 12.5 weight % of silicon oxide, 10.0 weight % of SAPO-5 molecular sieves, 10.0 weight % of tin ash, 2.5 weight % of neodymium oxide, 15.0 weight % of nickel.

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 29.25 °, 33.90 °, There is the characteristic peak of the cubic system of neodymium stannum composite oxides at 48.71 °, 57.83 ° and 60.67 °, 2 θ be 26.60 °, There is no the characteristic peak of the tetragonal crystal of tin ash at 33.89 °, 37.91 ° and 51.80 °, 2 θ be 26.6 °, 30.0 °, There is no the characteristic peak of the hexagonal of Dineodymium trioxide at 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 °（JCPDS No.40- 1282）.Illustrate that tin ash and Dineodymium trioxide define neodymium stannum composite oxides structure in desulphurization catalyst A3.

Embodiment 4

By 3.19 kilograms of tin acetates（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 tin oxide sol.

By 1.261 kilogram of six nitric hydrate cerium（Chemical Reagent Co., Ltd., Sinopharm Group, purity are 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）, dipping post-drying, roasting obtain cerium modified CeSAPO-11 molecular sieves.

By 4.0 kilograms of Zinc oxide powders（Headhorse companies, 99.7 weight % of purity）, 1.2 kilograms of kieselguhr（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.The mixed serum is added in above-mentioned tin oxide sol, and carrier mixture is obtained 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：40.0 weight % of Zinc Oxide, 15.0 weight % of tin ash, oxygen 10.0 weight % of SiClx, 23.0 weight % of CeSAPO-11 molecular sieves（5.0 weight % of cerium oxide, 18.0 weight % of USY molecular sieve）, nickel 12.0 weight %.

Desulphurization catalyst A4 Jing Pyridine adsorption IR spectras are determined, 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.

Shown in Fig. 5, in spectrogram 2 θ be 26.60 °, 33.89 °, 37.91 ° and 51.80 ° presence characteristic peaks be pure dioxy Change the characteristic peak of the tetragonal crystal of stannum, characteristic peak does not shift, although having used tin ash, cerium to exist in illustrating A4 In the duct of molecular sieve, tin ash is distributed in outside molecular sieve, does not have cerium to enter into the lattice structure of stannum oxide, no titanium dioxide Stannum forms cerium stannum solid solution structure with cerium.

Embodiment 5

According to the method for embodiment 4, except for the difference that, " SAPO-34 molecular sieves are used（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：40.0 weight % of Zinc Oxide, 15.0 weight of tin ash Amount %, 10.0 weight % of silicon oxide, 23.0 weight % of CeSAPO-11 molecular sieves（5.0 weight % of cerium oxide, 18.0 weight of USY molecular sieve Amount %）, 12.0 weight % of nickel.

Embodiment 6

According to the method for embodiment 4, except for the difference that, " SAPO-5 molecular sieves are used（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：40.0 weight % of Zinc Oxide, 15.0 weight of tin ash Amount %, 10.0 weight % of silicon oxide, 23.0 weight % of CeSAPO-11 molecular sieves（5.0 weight % of cerium oxide, 18.0 weight of USY molecular sieve Amount %）, 12.0 weight % of nickel.

Comparative example 1

By 3.17 kilograms of stannic chloride pentahydrates（ZrCl₄·5H₂O, Alfa Aesar companies, 99 weight % of purity）It is added to In 4.2 kilograms of acid waters, and stir 1 hour, obtain water white tin oxide sol.Then the addition 2.45 thousand toward above-mentioned tin oxide 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, 99.7 weight % of purity）, 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, after stirring 30 minutes, obtain the mixed serum of Zinc Oxide and SAPO11 molecular sieves.Add above-mentioned expansion precious the mixed serum In the mixture of Zhu Yan and tin oxide sol, and carrier mixture is obtained 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：45.0 weight % of Zinc Oxide, 10.0 weight % of silicon oxide, 18.0 weight % of SAPO-11 molecular sieves, 15.0 weight % of tin ash, 12.0 weight % of nickel.

Rare earth oxide is not used in desulphurization catalyst B1, there is no impact of the rare earth to molecular sieve, no rare earth-stannum yet 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 The hydrochloric acid of amount %（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 are 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）, post-drying is impregnated, roasting obtains cerium modified CeSAPO-11 molecular sieves.

By 4.0 kilograms of Zinc oxide powders（Headhorse companies, 99.7 weight % of purity）, 1.2 kilograms of kieselguhr（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.The mixed serum is added in above-mentioned alumina gel, and Stirring obtained 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：40.0 weight % of Zinc Oxide, 15.0 weight % of aluminium oxide, oxidation 10.0 weight % of silicon, 23.0 weight % of CeSAPO-11 molecular sieves（5.0 weight % of cerium oxide, 18.0 weight % of SAPO-11 molecular sieves）, 12.0 weight % of nickel.

Desulphurization catalyst B2 Jing Pyridine adsorption IR spectras are determined, 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, in XRD spectra, there is zinc for 8.01 °, 28.64 °, 30.92 °, 37.1 °, 59.36 ° and 65.25 ° in 2 θ The characteristic peak of aluminate, it is binding agent to illustrate that B2 uses aluminium oxide, can react with Zinc Oxide, form desulfurization 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 are less, show 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 concrete sulfurizing treatment method is：Desulphurization catalyst is positioned in fluid bed, sulfuration is passed through Hydrogen（50 volumes %）And nitrogen（50 volumes %）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 adopts sulfur content For the catalytically cracked gasoline of 640 μ g/g.By 16 grams of desulphurization catalyst A1 be seated in internal diameter for 30mm, a length of 1m fixed bed it is anti- In answering device, using hydrogen atmosphere, reaction temperature is 410 DEG C, and the charging of adsorption reaction raw material is that weight space velocity is 4h^-1Carry out sulfur-bearing The desulphurization reaction of hydrocarbon ils.Weigh desulphurizing activated with sulfur content in product gasoline.In product gasoline, sulfur content is by offline chromatograph point 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 to adopt With the desulfurization performance evaluation of A2-A6 and B1-B2,2 are the results are shown in Table.

Carry out after 12 hours according to above-mentioned evaluation response, carry out Regeneration Treatment, Regeneration Treatment is the air atmosphere at 550 DEG C Under carry out.6 circulations of reaction-regeneration are repeated so.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 and 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 sulfur 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）.By the product gasoline mixing of six circulations, it 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.Raw material adopts sulfur content for the catalytic cracking diesel oil of 3718 μ g/g.According to（2）In method carry out six times circulation evaluate, After six loop ends, 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, is calculated the yield of product diesel oil according to the following formula, be the results are shown in Table 7.Using《GB/T386- 2010 diesel cetane methods》In CFR (F5) type diesel cetane-number aircraft measurements diesel-fuel cetane number, 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 sulfuration）	Abrasion index（After sulfuration）
				A1	99.9	3.3	3.1
A2	100	3.3	3.2
				A3	99.8	3.4	3.2
A4	39.7	4.1	3.9
				A5	47.0	4.2	4.1
A6	45.2	4.3	4.1
				B1	-	5.7	5.8
B2	15.7	6.8	6.4

Table 2

Table 3

Table 4

Table 5

Table 6

Note：

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

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 implementation 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 are not destroyed, and degree of crystallinity reservation degree is close to 100%.Can see from the XRD spectra shown in Fig. 1-3, Rare earth is combined with stannum, forms rare earth-stannum solid solution or rare earth-stannum composite oxides structure.It is displayed in Table 1 go out desulfurization catalyst Agent A1-A3 can be lower with abrasion index, with more preferable abrasion resistance properties.Desulphurization catalyst A1-A3 displayed in Table 2 can be with Sulfur content in gasoline is dropped to into below 10 μ g/g, and after being recycled for multiple times, still has more preferable desulfurized effect, illustrate this The desulphurization catalyst of bright offer has the desulphurizing activated and desulfurization stability of sulfur in more preferable elimination reaction feed gasoline.Table 3-4 As can be seen that desulphurization catalyst A1-A3 has higher product gasoline yield, and it is lower to generate amount of coke.Table 5 shows desulfurization Catalyst A1-A3 is carried out in the gasoline products composition of desulfurization acquisition, and the content of isomeric component is higher.Table 6 is as can be seen that desulfurization is urged The octane number of the product gasoline that agent A1-A3 is obtained is improved.As can be seen here, the desulphurization catalyst that the present invention is provided has more Good structure, can improve abrasion resistance properties, can have preferably desulphurizing activated and desulfurization stability, while producing yield of gasoline Higher, green coke amount is lower, 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 In oil, sulfur content is lower, 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 affecting The crystallization reservation degree of molecular sieve, and then affect the acidity of molecular sieve, the quality of desulfurization reaction product.And made using aluminium oxide It is binding agent in desulfurization of hydrocarbon oil course of reaction, aluminium oxide forms gahnite with Zinc Oxide, reduces activated zinc oxide Quantity, the final desulphurizing activated and stability for affecting desulphurization catalyst.

Claims

1. a kind of desulphurization catalyst, the desulphurization catalyst contain SAPO molecular sieve, rare earth oxide, tin ash, silicon oxide, 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 tin ash is 3-35 weight %, described The content of silicon oxide 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 %；In the pore passage structure of the SAPO molecular sieve, the content of rare earth element is 0 μ g/g；The XRD of the desulphurization catalyst There is the characteristic peak of the cubic system of the tetragonal crystal system or rare earth of rare earth-stannum solid solution-stannum composite oxides in spectrogram；

The active metal is at least one in cobalt, nickel, ferrum and manganese.

2. desulphurization catalyst according to claim 1, wherein, it is on the basis of the gross weight of the desulphurization catalyst, described The content of SAPO molecular sieve is 2-25 weight %, and the rare earth oxide is with RE₂O₃The content of meter be 0.5-10 weight %, described two The content of stannum oxide is 5-25 weight %, and the content of the silicon oxide 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-11 in middle aperture, 31,41 and wide-aperture SAPO-5,36,37, 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 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, the rare earth element in the rare earth oxide be La, Ce, Pr and At least one in Nd.

7. desulphurization catalyst according to claim 1, wherein, it is when the rare earth element in the rare earth oxide is cerium, described There is the characteristic peak of the tetragonal crystal system of cerium stannum solid solution in the XRD spectra of desulphurization catalyst, there are no 2 θ for 28.52 ° and The characteristic peak of the cubic crystal of 33.06 ° of cerium oxide.

8. desulphurization catalyst according to claim 1, wherein, it is when the rare earth element in the rare earth oxide is lanthanum, described There is the lanthanum stannum composite oxygen that 2 θ are 28.88 °, 33.47 °, 48.06 °, 57.04 ° and 59.83 ° in the XRD spectra of desulphurization catalyst The characteristic peak of the cubic system of compound；There is no the four directions of the tin ash that 2 θ are 26.60 °, 33.89 °, 37.91 ° and 51.80 ° The characteristic peak of crystal, there are no 2 θ is 25.3 °, 27.8 °, 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 ° The characteristic peak of the cubic crystal of lanthana.

9. desulphurization catalyst according to claim 1, wherein, it is when the rare earth element in the rare earth oxide is neodymium, described There is the neodymium stannum composite oxygen that 2 θ are 29.25 °, 33.90 °, 48.71 °, 57.83 ° and 60.67 ° in the XRD spectra of desulphurization catalyst The characteristic peak of the cubic system of compound；There is no the four directions of the tin ash that 2 θ are 26.60 °, 33.89 °, 37.91 ° and 51.80 ° , there is no the vertical of the Dineodymium trioxide that 2 θ are 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 ° in the characteristic peak of crystal The characteristic peak of square crystal.

10. a kind of preparation method of desulphurization catalyst, the method include：

(1) the precursor mixing contact of tin ash source and rare earth oxide is obtained into rare earth-tin oxide sol；

(2) after the serosity for being mixed to form Zinc Oxide, silica source, SAPO molecular sieve and water is mixed with the rare earth-tin oxide sol, Contact with acidic liquid and obtain carrier mixture, then Jing molding, drying and roasting obtain carrier；

(3) compound of the introducing containing active metal in the carrier, dry, roasting obtain desulphurization catalyst precursor；

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

Wherein, the tin ash source, Zinc Oxide, silica source, SAPO molecular sieve, the precursor of rare earth oxide and gold containing activity During the addition of the compound of category makes the desulphurization catalyst for obtaining, on the basis of the gross weight of desulphurization catalyst, SAPO molecular sieve Content be 1-20 weight %, rare earth oxide with RE₂O₃The content of meter is 0.5-10 weight %, the content of tin ash is 3-35 Weight %, the content of silicon oxide is 5-30 weight %, and the content of Zinc Oxide is 10-80 weight %, and the content of active metal is 5- 30 weight %；

The temperature of roasting described in step (2) is 400-700 DEG C, and the time of the roasting is at least 0.5 hour；

At least one of the active metal in cobalt, nickel, ferrum and manganese.

11. methods according to claim 10, wherein, the precursor of the rare earth oxide is in the rare earth oxide The acetate of rare earth metal, carbonate, nitrate, sulfate, oxalates, at least one in chloride and oxide.

Desulphurization catalyst prepared by 12. methods by described in claim 10 or 11.

A kind of 13. methods of desulfurization of hydrocarbon oil, the method include：Hydrocarbon oil containing surphur is reacted with hydrodesulfurization catalyst, its feature exists In the desulphurization catalyst is the desulphurization catalyst in claim 1-9 and 12 described in any one.