CN104549486A

CN104549486A - Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN104549486A
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: 2015-04-29
Anticipated expiration: 2033-10-29
Also published as: CN104549486B

Abstract

The invention discloses a desulfurization catalyst, a method for preparing the desulfurization catalyst, the desulfurization catalyst prepared by the method and a hydrocarbon oil desulfurization method. The desulfurization catalyst contains an SAPO molecular sieve, rare earth oxide, titanium dioxide, silicon oxide, zinc oxide and active metals, and has good desulfurization activity and desulfurization stability.

Description

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

Technical field

The present invention relates to a kind of method of desulfurization catalyst and preparation and desulfurization of hydrocarbon oil, be specifically related to a kind of desulfurization catalyst, a kind of preparation method of desulfurization catalyst and desulfurization catalyst prepared by this method, and the method for desulfurization of hydrocarbon oil.

Background technology

The sulphur compound contained in hydrocarbon ils in use easily causes the exhaust emission of sulphur, and the impact of sulphur pollution, along with the movement of vehicle, expands by the hydrocarbon ils being especially used as vehicle fuel.Various countries to have formulated strict standard one after another and have limited sulphur content in the hydrocarbon ils being used as vehicle fuel for this reason.

At present, the method for sulphur in hydrocarbon ils that removes mainly contains catalytic desulfurhydrogenation, catalytic cracking and desulfurizing, oxidation sweetening, solvent extraction desulfurization, biological desulphurization, adsorption desulfurize, film desulfurization and photochemical catalysis desulfurization etc.Wherein adsorption desulfurize has advantage simply, easily and fast, becomes one of current people's desulfurization technology comparing concern.

CN1355727A discloses a kind of adsorbent composition being applicable to remove sulphur from pressure gasoline and diesel-fuel, be made up of zinc oxide, silicon oxide, oxidation al and ni, wherein nickel is substantially to reduce valence state existence, and its amount makes to remove sulphur from the pressure gasoline contacted with described nickeliferous adsorbent composition under desulfurization conditions or diesel-fuel stream.Desulphurizing activated and stability comparatively fresh agent after this adsorbent composition regenerates obviously declines.

CN101433821A discloses a kind of sorbent material reducing sulfur content in hydrocarbon oils, take total sorbent weight as benchmark, this sorbent material comprises: the rare earth faujasite of 1-30 % by weight, the active metal oxide of 5-40 % by weight and the carrier of 30-94 % by weight, wherein carrier comprises aluminum oxide and zinc oxide, and rare earth faujasite is made up of the rare earth of faujusite with the pore passage structure inside being distributed in faujusite.This Adsorbent Acidity is strong, and cracking activity is strong, but yield of gasoline and desulphurizing activated and stability is lower.

As can be seen here, need to develop a kind of yield of gasoline high, and the high and renewable hydrocarbon oil desulphurization adsorbing agent of desulphurizing activated and desulfurization stability.

Summary of the invention

The object of the invention is to overcome the defect that in above-mentioned prior art, desulfuration adsorbent exists, a kind of method of desulfurization catalyst and preparation and desulfurization of hydrocarbon oil is provided.

To achieve these goals, the invention provides a kind of desulfurization catalyst, this desulfurization catalyst contains SAPO molecular sieve, rare earth oxide, titanium dioxide, silicon oxide, zinc oxide and active metal, with the gross weight of described desulfurization catalyst for benchmark, the content of described SAPO molecular sieve is 1-30 % by weight, and described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-15 % by weight, and the content of described titanium dioxide is 3-35 % by weight, and the content of described silicon oxide is 5-30 % by weight, and the content of described zinc oxide is 10-80 % by weight, and the content of described active metal is 5-30 % by weight.

The present invention also provides a kind of preparation method of desulfurization catalyst, and the method comprises: SAPO molecular sieve contacts with rare earth metal salt solutions and obtains rare earth modified SAPO molecular sieve by (1); (2) slurries titania source, zinc oxide, silica source, rare earth modified SAPO molecular sieve and water are mixed to form contact with acidic liquid and obtain carrier mixture, then obtain carrier through shaping, dry and roasting; (3) in described carrier, introduce the compound containing active metal, dry, roasting obtains desulfurization catalyst precursor; (4) described desulfurization catalyst precursor is reduced in a hydrogen atmosphere, obtain desulfurization catalyst.

Present invention also offers the desulfurization catalyst obtained by preparation method provided by the invention.

The present invention also provides a kind of preparation method of desulfurization catalyst, and the method comprises: titania source contacts with the precursor mixing of rare earth oxide and obtains rare earth-titanium colloidal sol by (1); (2) after the slurries that zinc oxide, silica source, SAPO molecular sieve and water are mixed to form being mixed with described rare earth-titanium colloidal sol, contact with acidic liquid and obtain carrier mixture, then obtain carrier through shaping, dry and roasting; (3) in described carrier, introduce the compound containing active metal, dry, roasting obtains desulfurization catalyst precursor; (4) described desulfurization catalyst precursor is reduced in a hydrogen atmosphere, obtain desulfurization catalyst.

Present invention also offers a kind of method of desulfurization of hydrocarbon oil, the method comprises: hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, and wherein, described desulfurization catalyst is desulfurization catalyst provided by the invention.

By desulfurization catalyst provided by the invention, this desulfurization catalyst still has better desulphurizing activated after can carrying out repeatedly desulfurization regeneration reaction process, desulfurization stability is better.And this desulfurization catalyst carry out desulfurization of hydrocarbon oil reaction can have less green coke amount, yield of gasoline is higher.In the product gasoline composition obtained, iso-component is more, and sulphur content is lower, and the octane value of product gasoline improves, product gasoline better quality.This desulfurization catalyst can obtain better wearability in addition.

Such as, the desulfurization catalyst A1 obtained in embodiment 1 contains SAPO-11 molecular sieve and cerium, the crystallization reservation degree of the molecular sieve calculated in A1 by XRD spectra is 99.9%, the structure of SAPO-11 molecular sieve does not change, judge that cerium does not enter in the pore passage structure of SAPO-11 molecular sieve, i.e. in the pore passage structure of SAPO-11 molecular sieve, content of rare earth is 0 μ g/g.The information going out peak from XRD figure can find out in desulfurization catalyst A1 to there is cerium-titanium composite oxide.Therefore, carry out gasoline desulfur evaluation, the 6th absorption regeneration product gasoline sulphur content obtained that circulates is 5 μ g/g, illustrates that desulfurization catalyst A1 has that better gasoline desulfur is active, stability.In the product slates obtained in gasoline desulfur evaluation, green coke amount is 0.01 % by weight, the product gasoline yield obtained is 99.96%, isoparaffin and isomeric olefine content are respectively 39.16 % by weight and 23.88 % by weight, product gasoline octane value increases, and illustrates that desulfurization catalyst A1 can obtain the product gasoline of more good quality.Adopt desulfurization catalyst A1 to carry out diesel fuel desulfurization performance evaluation in addition, in product diesel oil, sulphur content is 11.4 μ g/g, and diesel fuel desulfurization rate is 99.69%, and product diesel yield is 99.45%, and cetane value is 36.4.Desulfurization catalyst A1 abrasion index before and after sulfuration is respectively 3.1 and 2.9, has better abrasion resistance properties.And the desulfurization catalyst B2 in comparative example 2, carry out gasoline desulfur evaluation, 6th absorption regeneration product gasoline sulphur content obtained that circulates is 27 μ g/g, in the product slates obtained, green coke amount is 0.08 % by weight, the product gasoline yield obtained is 99.7%, and isoparaffin and isomeric olefine content are respectively 37.84 % by weight and 21.46 % by weight.Carry out diesel fuel desulfurization performance evaluation, in product diesel oil, sulphur content is 58 μ g/g, and diesel fuel desulfurization rate is 98.44%, and product diesel yield is 98.95%, and cetane value is 28.5.Desulfurization catalyst B2 abrasion index before and after sulfuration is respectively 6.8 and 6.4.

Other features and advantages of the present invention are described in detail in embodiment part subsequently.

Accompanying drawing explanation

Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:

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

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

Fig. 3 is the XRD spectra of the desulfurization catalyst A3 containing neodymium and SAPO-5 molecular sieve, wherein 2 θ are 7.46 °, 13.00 °, 15.15 °, 19.81 °, 20.68 °, 22.29 °, 26.15 ° and 29.05 ° and the peak marking "●" is the characteristic peak of SAPO-5 molecular sieve, and 2 θ are 22.7 °, 32.4 °, 46.3 ° and 58.0 ° and the peak marking " ▼ " is the rhombic characteristic peak of neodymium titanium composite oxide;

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

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

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

Fig. 7 is the XRD spectra of desulfurization catalyst B2, wherein 2 θ are 9.76 °, 12.74 °, 16.02 °, 19.79 °, 21.80 °, 23.43 °, 25.67 °, 29.49 ° and 32.56 ° and the peak marking " ▲ " is the characteristic peak of SAPO-11 molecular sieve, and 2 θ are 8.01 °, 28.64 °, 30.92 °, 37.1 °, 59.36 ° and 65.25 ° and the peak marking " ■ " is the characteristic peak of gahnite.

Embodiment

Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.

In the present invention, the composition of described desulfurization catalyst can further preferably, and with the gross weight of described desulfurization catalyst for benchmark, the content of described SAPO molecular sieve is 2-25 % by weight, and described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-10 % by weight, and the content of described titanium dioxide is 5-25 % by weight, and the content of described silicon oxide is 10-20 % by weight, and the content of described zinc oxide is 25-70 % by weight, and the content of described active metal is 8-25 % by weight; More preferably with the gross weight of described desulfurization catalyst for benchmark, the content of described SAPO molecular sieve is 2-20 % by weight, and described rare earth oxide is with RE ₂o ₃the content of meter is 1-5 % by weight, and the content of described titanium dioxide is 8-15 % by weight, and the content of described silicon oxide is 10-15 % by weight, and the content of described zinc oxide is 40-60 % by weight, and the content of described active metal is 12-20 % by weight.

According to the present invention, the SAPO molecular sieve contained in desulfurization catalyst can make straight chain hydrocarbon obtain isomerization, gasoline products octane value is improved, ensures the effect of higher yield of gasoline simultaneously.Under preferable case, described SAPO molecular sieve is the SAPO-34,17,18,26,33,34,35,39,42,43,44,47 being selected from small-bore, the SAPO-11 of mesoporous, 31,41 and wide-aperture SAPO-5,36,37,40,46 at least one.

According to the present invention, the sial atomic molar of the SAPO molecular sieve contained in described desulfurization catalyst is than there is no particular limitation, as long as can provide applicable acidity.Under preferable case, the sial atomic molar of described SAPO molecular sieve is than being 0.05-1.0:1; Preferably, the sial atomic molar of described SAPO molecular sieve is than being 0.05-0.75:1; More preferably, the sial atomic molar of described SAPO molecular sieve is than being 0.1-0.5:1.

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

According to the present invention, described active metal is for promoting absorption and the cracking of the sulfocompound in hydrocarbon oil containing surphur.Under preferable case, described active metal is group VIII metal; Preferred group VIII metal is be selected from least one in cobalt, nickel, iron and manganese, is more preferably cobalt and/or nickel.

In a kind of preferred implementation of the present invention, described rare earth oxide is in the distribution of inside, the duct of SAPO molecular sieve, i.e. in the pore passage structure of described SAPO molecular sieve, the content of rare earth element is 0 μ g/g; The rhombic characteristic peak of rare earth-titanium composite oxide is there is in the XRD spectra of described desulfurization catalyst.

In the present invention, in described desulfurization catalyst, the content of rare earth oxide and titanium dioxide can be conducive to forming rare earth-titanium combined oxidation structure, thus is more conducive to the abrasion resistance properties, the desulphurizing activated and product gasoline quality that improve desulfurization catalyst.

According to the present invention, do not have rare earth element to distribute in the inside, duct of SAPO molecular sieve, the acid intensity of molecular sieve and distribution are more suitable for hydrocarbon ils and carry out desulfurization absorption reaction, can reduce green coke amount in product composition, improve the yield of product gasoline.

According to the present invention, by polycrystal X ray diffraction approach (XRD) spectrogram of desulfurization catalyst, the crystallization reservation degree of molecular sieve can be calculated, judges whether rare earth element enters in the pore passage structure of molecular sieve.When in the pore passage structure that rare earth element does not enter described molecular sieve, the crystallization reservation degree of molecular sieve is close to 100%, and in the pore passage structure confirming described SAPO molecular sieve, the content of rare earth element is 0 μ g/g.On the contrary, time in the pore passage structure entering molecular sieve if any rare earth element, the crystallization reservation degree of molecular sieve can reduce.In the present invention, the degree of crystallinity reservation degree of molecular sieve refers in the XRD spectra of desulfurization catalyst, the peak area of the characteristic peak of molecular sieve divided by the business of the content of molecular sieve in desulfurization catalyst, with the ratio (all relative to the sample size of unit weight) of the peak area of characteristic peak in the XRD spectra of pure molecular sieve.Characteristic peak as SAPO-11 molecular sieve is the peak of 2 θ=16.02 °, and the characteristic peak of SAPO-34 molecular sieve is the peak of 2 θ=9.58 °, and the characteristic peak of SAPO-5 molecular sieve is 2 θ=7.46 °.

In addition, rare earth element enters in molecular sieve pore passage structure the Infrared spectroscopy of pyridine adsorption can also to be utilized to judge.Judge according to the wave number that the characteristic peak of rare earth element on infrared spectrum occurs.Enter in the pore passage structure of SAPO-11 molecular sieve for cerium, the characteristic peak of cerium appears at 1445cm ^-1position, show that cerium is present in the pore passage structure of SAPO-11 molecular sieve, as shown in Figure 4 and Figure 6.

According to the present invention, rare earth oxide can combine with titanium dioxide, forms the crystalline structure of rare earth-titanium composite oxide.Under preferable case, as shown in Figure 1, when rare earth element is cerium, the diffraction peak that 2 θ are 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° is there is in the XRD spectra of described desulfurization catalyst, compare with reference material card JCPDS No.01-070-3939, above-mentioned diffraction peak is the rhombic characteristic peak of cerium-titanium composite oxide; There is not the characteristic peak of anatase crystal that 2 θ are the titanium dioxide at 25.3 °, 37.8 °, 48.1 °, 53.9 °, 55.0 ° places, there is not the characteristic peak that 2 θ are the cubic system of the cerium oxide of 28.52 ° and 33.06 °.

According to the present invention, under preferable case, as shown in Figure 2, when rare earth element is lanthanum, the diffraction peak that 2 θ are 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 ° is there is in the XRD spectra of described desulfurization catalyst, comparing with reference material card JCPDS No.01-073-1686, is the rhombic characteristic peak of lanthanum titanium composite oxide; There is not the characteristic peak that 2 θ are the anatase crystal of the titanium dioxide of 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, there is not the characteristic peak (JCPDS No.24-0554) that 2 θ are the cubic system of the lanthanum trioxide of 25.3 °, 27.8 °, 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 °.

According to the present invention, under preferable case, as shown in Figure 3, when rare earth element is neodymium, the diffraction peak that 2 θ are 22.7 °, 32.4 °, 46.3 ° and 58.0 ° is there is in the XRD spectra of described desulfurization catalyst, comparing with reference material card JCPDS No.01-070-2294, is the rhombic characteristic peak of neodymium titanium composite oxide; There is not the characteristic peak that 2 θ are the anatase crystal of the titanium dioxide of 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, there is not the characteristic peak (JCPDSNo.40-1282) that 2 θ are the cubic system of the Neodymium trioxide of 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 °.

In the present invention, in desulfurization catalyst, form rare earth-titanium composite oxide, desulfurization catalyst tear strength can be overcome and to decline the problem that the life cycle that causes shortens.In addition, the rare earth-titanium composite oxide of formation, can improve gasoline better and diesel fuel desulfurization is active.In described desulfurization catalyst, rare earth element is not had in the duct of SAPO molecular sieve, and the desulfurization catalyst containing rare earth-titanium composite oxide, isomerization product content in the desulfurization product gasoline obtained can also be improved better, improve the octane value of product gasoline.In described desulfurization catalyst, the active phase of zinc oxide can also be increased containing rare earth-titanium composite oxide better, thus improve the desulphurizing activated of desulfurization catalyst better.

In the present invention, in described desulfurization catalyst, titanium dioxide substitutes aluminum oxide can be reduced desulfurization catalyst as binding agent form gahnite in absorption and regeneration process, thus keeps the activity of zinc oxide, improves the desulphurizing activated of desulfurization catalyst.

Present invention also offers a kind of preparation method of desulfurization catalyst, the method comprises: SAPO molecular sieve contacts with rare earth metal salt solutions and obtains rare earth modified SAPO molecular sieve by (1); (2) slurries titania source, zinc oxide, silica source, rare earth modified SAPO molecular sieve and water are mixed to form contact with acidic liquid and obtain carrier mixture, then obtain carrier through shaping, dry and roasting; (3) in described carrier, introduce the compound containing active metal, dry, roasting obtains desulfurization catalyst precursor; (4) described desulfurization catalyst precursor is reduced in a hydrogen atmosphere, obtain desulfurization catalyst.

According to the present invention, the rare earth modified SAPO molecular sieve obtained in step (1) can have multiple method, can have method one, comprise: before described contact, SAPO molecular sieve is carried out roasting, and the temperature of roasting is 500-800 DEG C; The condition of described contact comprises: temperature is 80-150 DEG C, and the time of contact is 0.5-6 hour; Described contact is that SAPO molecular sieve and rare earth metal salt solutions are mixed to form slurries, and described slurries carried out filter, wash, dry and roasting; It is 80-120 DEG C that described slurries carry out dry temperature, and the temperature that described slurries carry out roasting is 300-600 DEG C; The concentration of described rare earth metal salt solutions is 0.01-1.5 mol/L.Wherein, before described contact, SAPO molecular sieve is carried out roasting and can remove all or part of template.

Can also have method two, comprise: before described contact, SAPO molecular sieve is carried out roasting, the temperature of roasting is 500-800 DEG C; Described contact is by rare earth metal salt solutions incipient impregnation SAPO molecular sieve, and carries out the drying of 80-120 DEG C and the roasting of 300-600 DEG C.Wherein, before described contact, SAPO molecular sieve is carried out roasting and can remove all or part of template.Described incipient impregnation can be the method that this area catalyst preparing routine adopts, and when can refer to dipping, the volume of rare earth metal salt solutions is equal with the pore volume of impregnated whole SAPO molecular sieves.

According to the present invention, under preferable case, described rare earth metal salt solutions is at least one in the nitrate of rare earth metal, halogenide, acetate and sulfate liquor.

According to the present invention, under preferable case, described titania source is selected from least one in titanium tetrachloride, titanium ethanolate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.

According to the present invention, under preferable case, described silica source can be pure silica, the natural mineral that also can be greater than 45 % by weight for silica content; Preferential oxidation silicon source can be selected from one or more in diatomite, pearlstone, kaolin, silicite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.

According to the present invention, in step (2), the consumption of described acidic liquid can make the pH value of described carrier pulp be 0.5-6, is more preferably 1-4.Described acidic liquid can be selected from water-soluble mineral acid and/or organic acid, such as, can be at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

According to the present invention, in step (2), described carrier mixture can be the forms such as wet mixture, paste mixture, dough or slurries.By described shaping, described carrier mixture can be shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, when described carrier mixture be dough or paste mixture time, described carrier mixture shaping (preferred extrusion moulding) can be made to form particle, and preferred diameter is at 1.0-8.0mm, length, at the cylindrical extrudates of 2.0-5.0mm, then makes the extrudate of gained carry out drying, roasting.If described carrier mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably described carrier mixture is slurry form, forms the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry.For the ease of spraying dry, before dry, the solid content of slurries can be 10-50 % by weight, is preferably 20-50 % by weight.

In the present invention, the drying means of described carrier mixture and condition are conventionally known to one of skill in the art, such as, dry method can be dry, dry, forced air drying.Under preferable case, in step (3), dry temperature can be room temperature to 400 DEG C, is preferably 100-350 DEG C; The time of described drying is at least 0.5 hour, is preferably 0.5-60 hour.

In the present invention, the roasting condition of described carrier mixture also can be conventionally known to one of skill in the art, and in general, the temperature of described roasting is 400-700 DEG C, is preferably 450-650 DEG C; The time of described roasting is at least 0.5 hour, is preferably 0.5-100 hour, is more preferably 0.5-10 hour.

In preparation method provided by the invention, in step (3), in described carrier, the compound introduced containing active metal can pass through accomplished in many ways.Wherein, the described compound containing active metal is selected from least one in the acetate of active metal, carbonate, nitrate, vitriol, thiocyanate-and oxide compound.

In the present invention, the concrete operation method introducing the compound containing active metal in step (3) in described carrier can adopt and well known to a person skilled in the art that dipping method or intermediate processing realize.Described dipping method is with containing carrier described in the solution of compound of active metal or suspension impregnation; Described intermediate processing is mixed with described carrier the solution of the compound containing active metal or suspension, then adds ammoniacal liquor and will contain the compound precipitation of active metal on carrier.Preferred dipping method.

In the present invention, after introducing the compound containing active metal in the carrier, also comprise and carry out drying and roasting.At about 50-300 DEG C, carry out drying, preferably dry temperature is 100-250 DEG C, and the dry time is about 0.5-8 hour, is more preferably 1-5 hour.After drying, roasting is carried out having under oxygen or oxygen-containing gas existent condition at the temperature of about 300-800 DEG C, more preferably 400-750 DEG C, the time of roasting is about 0.5-4 hour, preferred 1-3 hour, until volatile matter is removed and is converted into the oxide compound of active metal containing the compound of active metal, obtain desulfurization catalyst precursor.

According to the present invention, under preferable case, described titania source, zinc oxide, silica source, SAPO molecular sieve, rare earth metal salt solutions and the add-on containing the compound of active metal make in the desulfurization catalyst obtained, with the gross weight of desulfurization catalyst for benchmark, the content of SAPO molecular sieve is that 1-20 % by weight, rare earth oxide are with RE ₂o ₃the content of meter is 0.5-10 % by weight, the content of titanium dioxide is 3-35 % by weight, and the content of silicon oxide is 5-30 % by weight, and the content of zinc oxide is 10-80 % by weight, and the content of active metal is 5-30 % by weight.

In the present invention, the reduction of desulfurization catalyst precursor can be carried out immediately by step (4) after obtained desulfurization catalyst precursor, also can before use (namely for desulfurization absorption before) carry out.Because active metal is easily oxidized, and the active metal in desulfurization catalyst precursor exists in the form of an oxide, and therefore for ease of transport, the reduction of desulfurization catalyst precursor is carried out by preferred steps (4) before carrying out desulfurization absorption.Described being reduced to makes the metal in the oxide compound of active metal substantially exist with reduction-state, obtains desulfurization catalyst of the present invention.Under preferable case, the condition that desulfurization catalyst precursor reduces in a hydrogen atmosphere comprised: hydrogen content is 10-60 volume %, the temperature of reduction is 300-600 DEG C, and the time of reduction is 0.5-6 hour; The temperature of preferred reduction is 400-500 DEG C, and the time of reduction is 1-3 hour.

The present invention also provides the desulfurization catalyst prepared by method provided by the invention.This desulfurization catalyst has composition and the content of aforementioned desulfurization catalyst, does not repeat them here.

In the preferred embodiment of the present invention, additionally provide a kind of preparation method of desulfurization catalyst, the method comprises: titania source contacts with the precursor mixing of rare earth oxide and obtains rare earth-titanium colloidal sol by (1); (2) after the slurries that zinc oxide, silica source, SAPO molecular sieve and water are mixed to form being mixed with described rare earth-titanium colloidal sol, contact with acidic liquid and obtain carrier mixture, then obtain carrier through shaping, dry and roasting; (3) in described carrier, introduce the compound containing active metal, dry, roasting obtains desulfurization catalyst precursor; (4) described desulfurization catalyst precursor is reduced in a hydrogen atmosphere, obtain desulfurization catalyst.

According to the present invention, the step (1) of the preparation method of described desulfurization catalyst, by preparing rare earth-titanium colloidal sol, to form rare earth-titanium composite oxide structure in shaping, dry, the calcination process in step (2), the desulfurization catalyst containing these composite oxides is conducive to realizing object of the present invention.

In the present invention, the described rare earth-titanium colloidal sol obtained in step (1) can have multiple method, can be method one, comprise the following steps: titania source contacts with acid solution and obtains titanium colloidal sol by (a); B described titanium colloidal sol and the precursor of rare earth oxide mix to contact with ammonia soln again and obtain rare earth-titanium colloidal sol by ().Can also be method two, comprise the following steps: titania source contacts with acid solution and obtains titanium colloidal sol by (a); B the aqueous solution of the precursor of described titanium colloidal sol and rare earth oxide is obtained rare earth-titanium colloidal sol by ().Also can be method three, comprise: the precursor of titania source and rare earth oxide be contacted with acid solution and obtains rare earth-titanium colloidal sol.In aforesaid method, described acid solution can be at least one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, and the concentration of described acid solution can be 5-30 % by weight; The concentration of described ammonia soln can be 10-30 % by weight.There is no particular limitation for the consumption of described acid solution or described ammonia soln, as long as can form described rare earth-titanium colloidal sol, consumption that such as can be sour makes the pH value of slurries be 1-5, is preferably 1.5-4.

According to the present invention, in step (1), under preferable case, the add-on of described titania source makes in the desulfurization catalyst obtained, and with the gross weight of desulfurization catalyst for benchmark, the content of titanium dioxide is 3-35 % by weight; The content of preferred titanium dioxide is 5-25 % by weight; More preferably the content of titanium dioxide is 8-15 % by weight.

According to the present invention, in step (1), under preferable case, the add-on of the precursor of described rare earth oxide makes in the desulfurization catalyst obtained, and with the gross weight of desulfurization catalyst for benchmark, described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-15 % by weight; Preferred described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-10 % by weight; More preferably described rare earth oxide is with RE ₂o ₃the content of meter is 1-5 % by weight.

According to the present invention, under preferable case, the precursor of described rare earth oxide is selected from least one in the acetate of the rare earth metal in described rare earth oxide, carbonate, nitrate, vitriol, oxalate, muriate and oxide compound.

According to the present invention, in step (2), under preferable case, the add-on of described silica source makes in the desulfurization catalyst obtained, and with the gross weight of desulfurization catalyst for benchmark, the content of described silicon oxide is 5-30 % by weight; The content of preferred described silicon oxide is 10-20 % by weight; More preferably the content of described silicon oxide is 10-15 % by weight.

According to the present invention, in step (2), under preferable case, the add-on of described zinc oxide and described SAPO molecular sieve makes in the desulfurization catalyst obtained, with the gross weight of desulfurization catalyst for benchmark, the content of described zinc oxide is 10-80 % by weight, and the content of described SAPO molecular sieve is 1-30 % by weight; The content of preferred described zinc oxide is 25-70 % by weight, and the content of described SAPO molecular sieve is 2-25 % by weight; More preferably the content of described zinc oxide is 40-60 % by weight, and the content of described SAPO molecular sieve is 2-20 % by weight.

In the present invention, although containing silica in described SAPO molecular sieve, the amount of the silicon oxide contained in described SAPO molecular sieve still can be regarded as the amount of described SAPO molecular sieve, is not counted in silicon oxide.Namely in the desulfurization catalyst obtained by method provided by the invention, the content of each component calculates according to charging capacity.

According to the present invention, in step (2), the consumption of described acidic liquid and selection as previously mentioned, do not repeat them here.

According to the present invention, in step (2), described carrier mixture is shaping, dry and roasting obtains carrier as previously mentioned, do not repeat them here.

In preparation method provided by the invention, in step (3), in described carrier, the compound introduced containing active metal can pass through accomplished in many ways.Under preferable case, the add-on of the described compound containing active metal makes in the desulfurization catalyst obtained, and with the gross weight of desulfurization catalyst for benchmark, the content of described active metal is 5-30 % by weight; Preferred 8-25 % by weight; More preferably 12-20 % by weight.Wherein, the described compound containing active metal is selected from least one in the acetate of active metal, carbonate, nitrate, vitriol, thiocyanate-and oxide compound.

In the present invention, introduce in described carrier in step (3) containing the compound of active metal concrete operation method and introduce in the carrier contain active metal compound after comprise the drying carried out and roasting as previously mentioned, do not repeat them here.

In the present invention, step (4) by the reduction of desulfurization catalyst precursor as previously mentioned, does not repeat them here.

Present invention also offers the desulfurization catalyst obtained by preparation method provided by the invention.This desulfurization catalyst has composition and the content of aforementioned desulfurization catalyst, does not repeat them here.

According to the present invention, in the method for described desulfurization of hydrocarbon oil, described hydrocarbon oil containing surphur and described desulfurization catalyst can react in a hydrogen atmosphere, and the condition of reaction comprises: the temperature of reaction can be 350-500 DEG C, is preferably 400-450 DEG C; The pressure of reaction can be 0.5-4MPa, is preferably 1-2MPa; The input speed of described hydrocarbon oil containing surphur is weight space velocity 2-10h ^-1, be preferably 3-8h ^-1.

According to the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: regenerated by the desulfurization catalyst through reaction after reaction.The condition of regeneration comprises: regenerate under oxygen atmosphere (oxygen content can be 10-80 volume %); The temperature of regeneration is 450-600 DEG C, is preferably 480-520 DEG C; The pressure of regeneration is normal pressure.

In the present invention, the method for described desulfurization of hydrocarbon oil can also comprise: the desulfurization catalyst after regeneration reduces before reuse.The condition of reduction comprises: reduce under hydrogen atmosphere (hydrogen content can be 30-60 volume %); The temperature of reduction can be 350-500 DEG C, preferred 400-450 DEG C; The pressure of reduction can be 0.2-2MPa, is preferably 0.2-1.5MPa.

The pressure related in the present invention is gauge pressure.

In the present invention, described hydrocarbon ils comprises pressure gasoline and diesel-fuel, and wherein " pressure gasoline " means hydrocarbon or its any cut that boiling range is 40 to 210 DEG C, is the product from making larger crack hydrocarbon molecules become more micromolecular heat or catalytic process.The thermal cracking process be suitable for includes, but are not limited to coking, thermally splitting and viscosity breaking etc. and combination thereof.The example of the catalytic cracking process be suitable for includes but not limited to fluid catalystic cracking and heavy oil fluid catalytic cracking etc. and combination thereof.Therefore, the catalytically cracked gasoline be suitable for includes but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combination thereof.In some cases, be in the methods of the invention used as hydrocarbon-containifluids fluids time can by described pressure gasoline fractionation and/or hydrotreatment before desulfurization.Described " diesel-fuel " means boiling range is the hydrocarbon mixture of 170 DEG C to 450 DEG C or the liquid of its any fractions consisting.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil, catalytic cracking diesel oil and hydroprocessed diesel etc. and combination thereof.

In the present invention, term used " sulphur " represents any type of element sulphur if hydrocarbon-containifluids fluids is as the organosulfur compound existed normal in pressure gasoline or diesel-fuel.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to carbon oxysulfide (COS), dithiocarbonic anhydride (CS ₂), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, thionaphthene, alkylthrophene, alkyl benzothiophenes and methyldibenzothiophene, and the thiophenes that in diesel-fuel, the normal molecular weight existed is larger.

The invention will be further described by the following examples.

In the following Examples and Comparative Examples, the composition of desulfurization catalyst calculates according to feeding intake.

Polycrystal X ray diffraction (XRD) adopts X-ray diffractometer (Siemens company D5005 type) to carry out the structure determination of desulfurization catalyst, Cu target, K α radiation, solid state detector, tube voltage 40kV, tube current 40mA.

Pyridine adsorption IR spectra method adopts the FTS3000 type Fourier infrared spectrograph of BIO-RAD company of the U.S. to measure.Condition is seal in original position pond sample compressing tablet being placed on infrared spectrometer; Under 623K, be evacuated down to 10-3Pa, keep 1h, make the gas molecule desorption of sample surfaces clean, be cooled to room temperature, at 1000-4000cm ^-1wave-number range interscan, records the infrared absorption spectra before sample adsorption pyridine.In original position pond, import the pyridine steam that pressure is 2.67Pa, after balance 30min, be warmed up to 200 DEG C, be again evacuated to 10-3Pa, keep 30min, be chilled to room temperature, at 1400-1700cm ^-1wave-number range interscan, records the infrared absorption spectra of 200 DEG C of pyridine adsorption, observes the characteristic peak of rare earth in molecular sieve pore passage from this spectrogram.

Embodiment 1

The present embodiment is for illustration of the preparation method of desulfurization catalyst of the present invention.

(1) rare earth-titanium colloidal sol is prepared.2.85 kilograms of titanium tetrachlorides (Beijing Chemical Plant, analytical pure, 99 % by weight) to be joined in nitric acid (chemical pure, the Beijing Chemical Plant produce) solution of 3.5 kilogram 5 % by weight and to stir 1 hour, obtaining water white colloidal solution, be called titanium colloidal sol.After 1.261 kilograms of cerous nitrates (Chemical Reagent Co., Ltd., Sinopharm Group, purity is greater than 99.0 % by weight) being dissolved in 0.2 kilogram of deionized water solution and titanium colloidal sol be mixed to get cerium titanium colloidal sol.

(2) carrier is prepared.By the pearlstones of 1.33 kilograms (silicon oxide-containing 0.77 kilogram, titanium dioxide 0.13 kilogram, potassium oxide 0.07 kilogram, sodium oxide 0.03 kilogram) join heated and stirred in the salpeter solution of 0.5 kilogram 2 % by weight and filter after 2 hours, join after impurity such as removing potassium, sodium, titanium etc. in the cerium titanium colloidal sol that step (1) obtains, obtain the mixture of pearlstone and cerium titanium colloidal sol.

By 4.00 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), 2.00 kilograms of SAPO-11 molecular sieve (Shandong catalyzer branch officies, containing butt 1.8 kilograms, sial atomic molar is than being 0.15:1) and 5.25 kilograms of deionized water mixing, stir after 30 minutes and obtain zinc oxide and SAPO-11 molecular sieve mixed serum.This mixed serum is added in the mixture of pearlstone that step (1) obtains and cerium titanium colloidal sol, and obtain carrier mixture after stirring 1 hour.

This carrier mixture is adopted Niro Bowen Nozzle Tower ^tMthe spray-drier of model carries out spraying dry, and spraying dry pressure is 8.5-9.5MPa, drying temperature 350 DEG C.The microballoon that spraying dry obtains roasting at 650 DEG C obtains carrier in 0.5 hour.

(3) compound containing active metal is introduced.Compound containing active metal is Nickelous nitrate hexahydrate, the carrier that step (2) is obtained 2.79 kilograms of Nickelous nitrate hexahydrate (Beijing chemical reagents corporations, purity is greater than 98.5 % by weight) and the aqueous impregnation of 0.8 kilogram of deionized water, the mixture obtained after 5 hours, 1 hour can obtain desulfurization catalyst precursor in air atmosphere 450 DEG C of roastings through 250 DEG C of dryings.

(4) reduce.Desulfurization catalyst precursor step (3) obtained reduces in the hydrogen atmosphere of 400 DEG C can obtain desulfurization catalyst in 3 hours, is designated as desulfurization catalyst A1.

The composition of desulfurization catalyst A1 is calculated as by charging capacity: zinc oxide 40.0 % by weight, silicon oxide 10.0 % by weight, SAPO-11 molecular sieve 18.0 % by weight, titanium dioxide 15.0 % by weight, cerium oxide 5.0 % by weight, nickel 12.0 % by weight.

Desulfurization catalyst A1 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 1.The characteristic peak being 16.02 ° with 2 θ calculates the crystallization reservation degree of SAPO-11 molecular sieve in desulfurization catalyst A1, the results are shown in Table 1.

Desulfurization catalyst A1 carries out XRD determining result as shown in Figure 1, be the rhombic characteristic peak that 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 ° of places exist cerium-titanium composite oxide at 2 θ in spectrogram, be that 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° of places do not exist the characteristic peaks of the anatase crystal of titanium dioxide at 2 θ, and be 28.52 ° and the 33.06 ° characteristic peaks locating not exist the cubic system of cerium oxide at 2 θ.Illustrate that in desulfurization catalyst A1, titanium dioxide and cerium oxide define cerium-titanium composite oxide structure.

Embodiment 2

(1) rare earth-titanium colloidal sol is prepared.1.17 kilograms of oxychlorination titaniums (Aldrich company, analytical pure, 98.5 % by weight) to be joined in hydrochloric acid (chemical pure, the Beijing Chemical Plant produce) solution of 2.0 kilogram 15 % by weight and to stir acidifying 1 hour, forming water white colloidal solution, be called titanium colloidal sol.0.1 kilogram of lanthanum trioxide (analytical pure, traditional Chinese medicines group) is added in titanium colloidal sol, is uniformly mixed rear dropping 25 % by weight ammonia soln until become lanthanum titanium colloidal sol.

(2) carrier is prepared.The diatomite of 1.2 kilograms (silicon oxide-containing 1.00 kilograms) and 6.00 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), 0.24 kilogram of SAPO-34 molecular sieve (Nanjing catalyzer branch office, containing butt 0.20 kilogram, sial atomic molar is than for 0.2:1) and 5.0 kilograms of deionized water mix and blends obtain the mixed serum of diatomite, zinc oxide and SAPO-34 molecular sieve after 30 minutes.Lanthanum titanium colloidal sol step (1) obtained adds this mixed serum, stirs and obtains carrier mixture after 1 hour.

The spray drying forming of carrier mixture is carried out and roasting obtains carrier with reference to the method for embodiment 1.

(3) compound containing active metal is introduced.Compound containing active metal is Nickelous nitrate hexahydrate and Cobaltous nitrate hexahydrate, the carrier that step (2) is obtained 6.93 kilograms of Nickelous nitrate hexahydrate (Beijing chemical reagents corporations, purity is greater than 98.5 % by weight), the aqueous impregnation of 2.47 kilograms of Cobaltous nitrate hexahydrates and 0.8 kilogram of deionized water, then obtain desulfurization catalyst precursor with reference to method that is dry in embodiment 1 step (3) and roasting.

(4) reduce.Method reduction with reference to embodiment 1 step (4) obtains desulfurization catalyst A2.

The composition of desulfurization catalyst A2 is calculated as by charging capacity: zinc oxide 60.0 % by weight, titanium dioxide 8.0 % by weight, silicon oxide 10.0 % by weight, SAPO-34 molecular sieve 2.0 % by weight, lanthanum trioxide 1.0 % by weight, nickel 14.0 % by weight, cobalt 5.0 % by weight.

Desulfurization catalyst A2 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 2.The characteristic peak being 9.58 ° with 2 θ calculates the crystallization reservation degree of SAPO-34 molecular sieve in desulfurization catalyst A2, the results are shown in Table 1.

Desulfurization catalyst A2 carries out XRD determining result as shown in Figure 2, be the rhombic characteristic peak that 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 ° of places exist lanthanum titanium composite oxide at 2 θ in spectrogram, be that 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° of places do not exist the characteristic peaks of the anatase crystal of titanium dioxide at 2 θ, and be 25.3 ° at 2 θ, 27.8 °, 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, locate the characteristic peak (JCPDSNo.24-0554) that there is not the hexagonal of lanthanum trioxide for 54 ° and 58.5 °.Illustrate that in desulfurization catalyst A2, titanium dioxide and lanthanum trioxide define lanthanum titanium composite oxide structure.

Embodiment 3

(1) rare earth-titanium colloidal sol is prepared.By 1.90 kilograms of titanium dioxide (Aldrich companies, analytical pure, 99 % by weight) and 0.651 kilogram of six nitric hydrate neodymium (Chemical Reagent Co., Ltd., Sinopharm Group, content is greater than 99.0 % by weight) join the dust technology (chemical pure of 2.7 kilogram 15 % by weight, Beijing Chemical Plant produce) in and stir acidifying 1 hour, obtain transparent colloidal solution, be called neodymium titanium colloidal sol.

(2) carrier is prepared.The pearlstones of 1.66 kilograms (silicon oxide-containing 1.25 kilograms) are joined heated and stirred in the salpeter solution of 0.6 kilogram 2 % by weight filter after 3 hours, with 5.00 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), 1.20 kilograms of SAPO-5(Nanjing catalyzer branch officies, containing butt 1.00 kilograms, sial atomic molar is than being 0.5:1) and 4.65 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide, SAPO-5 and pearlstone after 30 minutes.This mixed serum is added in the neodymium titanium colloidal sol that step (1) obtains, and rapid stirring obtained carrier mixture after 5 minutes.

(3) compound containing active metal and (4) reduction is introduced.The compound and reduction that contain active metal are introduced in the step (3) of reference embodiment 1 and (4), obtain desulfurization catalyst A3.Wherein the compound of active metal is Nickelous nitrate hexahydrate (analytical pure, Beijing chemical reagents corporation), and consumption is 7.43 kilograms.

The composition of desulfurization catalyst A3 is calculated as by charging capacity: zinc oxide 50.0 % by weight, silicon oxide 12.5 % by weight, SAPO-5 molecular sieve 10.0 % by weight, titanium dioxide 10.0 % by weight, neodymium sesquioxide 2.5 % by weight, nickel 15.0 % by weight.

Desulfurization catalyst A3 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 3.The characteristic peak being 7.46 ° with 2 θ calculates the crystallization reservation degree of SAPO-5 in desulfurization catalyst A3, the results are shown in Table 1.

Desulfurization catalyst A3 carries out XRD determining result as shown in Figure 3, be the rhombic characteristic peak that 22.7 °, 32.4 °, 46.3 ° and 58.0 ° of places exist neodymium titanium composite oxide at 2 θ in spectrogram, be that 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 ° of places do not exist the characteristic peaks of the anatase crystal of titanium dioxide at 2 θ, and be the characteristic peaks (JCPDS No.40-1282) that 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 ° of places do not exist the hexagonal of Neodymium trioxide at 2 θ.Illustrate that in desulfurization catalyst A3, titanium dioxide and Neodymium trioxide define neodymium titanium composite oxide structure.

Embodiment 4

3.19 kilograms of acetic acid titaniums (Aldrich company, analytical pure, 99 % by weight) to be joined when stirring in hydrochloric acid (chemical pure, the Beijing Chemical Plant produce) solution of 3.5 kilogram 5 % by weight and to stir 1 hour, obtaining titanium colloidal sol.

By 1.261 kilogram of six nitric hydrate cerium (Chemical Reagent Co., Ltd., Sinopharm Group, purity is greater than 99.0 % by weight) be dissolved in 0.5 kilogram of deionized water solution, with this cerous nitrate aqueous impregnation 2.00 kilograms of SAPO-11 molecular sieves (Shandong catalyzer branch office, containing butt 1.80 kilograms, sial atomic molar is than being 0.15:1), dipping post-drying, roasting, obtain cerium modified CeSAPO-11 molecular sieve.

By 4.0 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), the diatomite (silicon oxide-containing 1.00 kilograms) of 1.2 kilograms, 2.75 kilograms of CeSAPO-11(are containing butt 2.30 kilograms) and 6.80 kilograms of deionized water mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in above-mentioned titanium colloidal sol, and obtains carrier mixture after stirring 1 hour.

Method with reference to embodiment 1 carries out spray drying forming, the roasting of carrier mixture, introduces active component nickel and reduces, obtaining desulfurization catalyst A4.Wherein nickel is introduced by adding 2.79 kilograms of Nickelous nitrate hexahydrates.

The composition of desulfurization catalyst A4 is calculated as by charging capacity: zinc oxide 40.0 % by weight, tindioxide 15.0 % by weight, silicon oxide 10.0 % by weight, CeSAPO-11 molecular sieve 23.0 % by weight (cerium oxide 5.0 % by weight, USY molecular sieve 18.0 % by weight), nickel 12.0 % by weight.

Desulfurization catalyst A4 measures through Pyridine adsorption IR spectra, and spectrogram is shown in Fig. 4.At 1445cm in spectrogram ^-1place has occurred characterizing the characteristic peak of cerium in molecular sieve pore passage.

Desulfurization catalyst A4 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 5.The characteristic peak being 16.02 ° with 2 θ calculates the crystallization reservation degree of SAPO-11 molecular sieve in desulfurization catalyst A4, the results are shown in Table 1.

By above-mentioned Pyridine adsorption IR spectra and XRD spectra analysis, all illustrate that cerium has entered in the pore passage structure of SAPO-11 molecular sieve.

Shown in Fig. 5, be 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and the 58.3 ° rhombic characteristic peaks that there is not cerium-titanium composite oxide at 2 θ in spectrogram, and be 25.3 °, 37.8 °, 48.1 °, 53.9 ° and the 55.0 ° characteristic peaks that there is the anatase crystal of titanium dioxide at 2 θ, although illustrate in A4 and employ titanium dioxide, but cerium is in the duct of molecular sieve, titanium dioxide is distributed in outside molecular sieve, does not have the cerium-titanium composite oxide structure that titanium dioxide and cerium are formed.

Embodiment 5

According to the method for embodiment 4, unlike, with " SAPO-34 molecular sieve (Shandong catalyzer branch office; containing butt 1.80 kilograms; sial atomic molar is than being 0.2:1) ", substitute " SAPO-11 molecular sieve (Shandong catalyzer branch office, containing butt 1.80 kilograms, sial atomic molar is than being 0.15:1) ".

The composition obtaining desulfurization catalyst A5 is calculated as by charging capacity: zinc oxide 40.0 % by weight, tindioxide 15.0 % by weight, silicon oxide 10.0 % by weight, CeSAPO-11 molecular sieve 23.0 % by weight (cerium oxide 5.0 % by weight, USY molecular sieve 18.0 % by weight), nickel 12.0 % by weight.

Embodiment 6

According to the method for embodiment 4, unlike, with " SAPO-5 molecular sieve (Shandong catalyzer branch office; containing butt 1.80 kilograms; sial atomic molar is than being 0.5:1) ", substitute " SAPO-11 molecular sieve (Shandong catalyzer branch office, containing butt 1.80 kilograms, sial atomic molar is than being 0.15:1) ".

The composition obtaining desulfurization catalyst A6 is calculated as by charging capacity: zinc oxide 40.0 % by weight, tindioxide 15.0 % by weight, silicon oxide 10.0 % by weight, CeSAPO-11 molecular sieve 23.0 % by weight (cerium oxide 5.0 % by weight, USY molecular sieve 18.0 % by weight), nickel 12.0 % by weight.

Comparative example 1

By 3.17 kilograms of crystallization titanium tetrachloride (ZrCl ₄5H ₂o, Alfa Aesar company, purity 99 % by weight) join in 4.2 kilograms of sour waters, and stir 1 hour, obtain water white titanium colloidal sol.Then in above-mentioned titanium colloidal sol, add the pearlstone (containing butt 2.40 kilograms) of 2.45 kilograms and be uniformly mixed, obtaining mixture.

By 4.50 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), 2.00 kilograms of SAPO-11 molecular sieve (Shandong catalyzer branch officies, containing butt 1.8 kilograms, sial atomic molar is than being 0.15:1) and 5.25 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide and SAPO-11 molecular sieve after 30 minutes.This mixed serum is added in the mixture of above-mentioned pearlstone and titanium colloidal sol, and obtain carrier mixture after stirring 1 hour.

Method with reference to embodiment 1 carries out spray drying forming, the roasting of carrier mixture, introduces active component nickel and reduces, obtaining desulfurization catalyst B1.Wherein the compound of active metal is Nickelous nitrate hexahydrate, and consumption is 2.79 kilograms.

The composition of desulfurization catalyst B1 is calculated as by charging capacity: zinc oxide 45.0 % by weight, silicon oxide 10.0 % by weight, SAPO-11 molecular sieve 18.0 % by weight, titanium dioxide 15.0 % by weight, nickel 12.0 % by weight.

Do not use rare earth oxide in desulfurization catalyst B1, there is no rare earth to the impact of molecular sieve, also do not have rare earth-titanium composite oxide structure to be formed.

Comparative example 2

2.25 kilograms of pseudo-boehmites (Shandong Aluminum Plant produce, containing butt 1.35 kilograms) to be joined in hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) solution of 0.32 kilogram 18 % by weight and to stir 1 hour, obtaining alumina gel.

By 1.261 kilogram of six nitric hydrate cerium (Chemical Reagent Co., Ltd., Sinopharm Group, purity is greater than 99.0 % by weight) be dissolved in 0.5 kilogram of deionized water solution, with this cerous nitrate aqueous impregnation 2.00 kilograms of SAPO-11 molecular sieves (Shandong catalyzer branch office, containing butt 1.80 kilograms, sial atomic molar is than being 0.15:1), dipping post-drying, roasting, obtains cerium modified CeSAPO-11 molecular sieve.

By 4.0 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7 % by weight), the diatomite (silicon oxide-containing 1.0 kilograms) of 1.2 kilograms, 2.75 kilograms of CeSAPO-11(are containing butt 2.30 kilograms) and 6.80 kilograms of deionized water mixing, stir the mixed serum obtaining zinc oxide and CeSAPO-11 molecular sieve after 30 minutes.This mixed serum is added in above-mentioned alumina gel, and obtains carrier mixture after stirring 1 hour.

Method with reference to embodiment 1 carries out spray drying forming, the roasting of carrier mixture, introduces active component nickel and reduces, obtaining desulfurization catalyst B2.Wherein nickel is introduced by adding 2.79 kilograms of Nickelous nitrate hexahydrates.

The composition of desulfurization catalyst B2 is calculated as by charging capacity: zinc oxide 40.0 % by weight, tindioxide 15.0 % by weight, silicon oxide 10.0 % by weight, CeSAPO-11 molecular sieve 23.0 % by weight (cerium oxide 5.0 % by weight, USY molecular sieve 18.0 % by weight), nickel 12.0 % by weight.

Desulfurization catalyst B2 measures through Pyridine adsorption IR spectra, and spectrogram is shown in Fig. 6.At 1445cm in spectrogram ^-1place has occurred characterizing the characteristic peak of cerium in molecular sieve pore passage.

Desulfurization catalyst B2 carries out polycrystal X ray diffraction (XRD) and characterizes, and spectrogram is shown in Fig. 7.The characteristic peak being 16.02 ° with 2 θ calculates the crystallization reservation degree of SAPO-11 molecular sieve in desulfurization catalyst B2, the results are shown in Table 1.

All illustrate that rare-earth element cerium has entered in the pore passage structure of SAPO-11 molecular sieve by above-mentioned Pyridine adsorption IR spectra and XRD spectra.

Shown in Fig. 7, it is 8.01 °, 28.64 °, 30.92 ° at 2 θ in XRD spectra, 37.1 °, 59.36 ° and the 65.25 ° characteristic peaks that there is gahnite, illustrate that B2 uses aluminum oxide to be binding agent, can react with zinc oxide in roasting process, form the gahnite structure of desulphurizing activated difference, active zinc flower is reduced.

Performance test

(1) abrasion strength resistance evaluation.Adopt straight tube wearing and tearing method to evaluate to desulfurization catalyst A1-A6 and B1-B2, method is with reference to the method for RIPP29-90 in " Petrochemical Engineering Analysis method (RIPP) experimental technique ", and numerical value is less, shows that abrasion strength resistance is higher.In order to the activity of desulfurization catalyst in industrial application process better can be represented, also abrasion strength resistance analysis is carried out to the desulfurization catalyst after sulfidizing, concrete sulfurizing treatment method is: be positioned over by desulfurization catalyst in fluidized-bed, pass into the gas mixture of hydrogen sulfide (50 volume %) and nitrogen (50 volume %), and be heated to 400 DEG C of sulfidizing 1 hour.The results are shown in Table 1.

(2) desulfurization performance evaluation.Adopt the micro-anti-experimental installation of fixed bed to evaluate, absorption reaction raw material employing sulphur content is the catalytically cracked gasoline of 640 μ g/g.The desulfurization catalyst A1 of 16 grams being seated in internal diameter is that in 30mm, the long fixed-bed reactor for 1m, adopt hydrogen atmosphere, temperature of reaction is 410 DEG C, and the charging of absorption reaction raw material is weight space velocity is the desulphurization reaction that 4h-1 carries out hydrocarbon oil containing surphur.Weigh desulphurizing activated with sulphur content in product gasoline.In product gasoline, sulphur content is by off-line chromatogram analysis method, adopts the GC6890-SCD instrument of An Jielun company to measure.The results are shown in Table 2.Carry out the desulfurization performance evaluation that desulfurization catalyst adopts A2-A6 and B1-B2 equally, the results are shown in Table 2.

After carrying out 12 hours according to above-mentioned evaluation response, carry out manipulation of regeneration, manipulation of regeneration is carried out under the air atmosphere of 550 DEG C.So repeatedly carry out reacting-regenerate 6 circulations.The desulfurization stability of desulfurization catalyst is evaluated with this.The activity of desulfurization catalyst in industrial actual motion can be symbolized more accurately.The sulphur content that every secondary response terminates in rear product gasoline the results are shown in Table 2.At the end of every secondary response, product gasoline to be weighed the yield of counting yield gasoline according to the following formula, the results are shown in Table 3.

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

(3) product composition and product gasoline quality is investigated.Table 4 carries out the product slates (the coke content carbon sulphur instrument on catalyzer is analyzed, and gas-phase product is calculated by minusing) that the 6th time circulation desulfurization catalyzed reaction obtains.Table 5 is the analytical resultss (method is vapor-phase chromatography, calculates with PONA software) carrying out the product gasoline composition that the 6th time circulation desulfurization catalyzed reaction obtains.The product gasoline mixing circulated six times, adopt motor-method octane number (MON) and the research octane number (RON) (RON) of gasoline before and after " GB/T503-1995 " and " GB/T5487-1995 " assaying reaction respectively, (MON+RON)/2 are anti-knock index.The results are shown in Table 6.

(4) diesel fuel desulfurization performance evaluation

The micro-anti-experimental installation of fixed bed in (2) is adopted to carry out diesel fuel desulfurization performance evaluation to desulfurization catalyst A1-A6 and B1-B2.Raw material employing sulphur content is the catalytic cracking diesel oil of 3718 μ g/g.Carry out six circulations according to the method in (2) to evaluate, after six loop ends, adopt sulphur content in off-line stratographic analysis product diesel, and calculate diesel fuel desulfurization rate, calculation formula is following formula, the results are shown in Table 7.

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

Weigh to product diesel oil, the yield of counting yield diesel oil, the results are shown in Table 7 according to the following formula.Adopt " GB/T386-2010 diesel cetane method " at CFR (F5) type diesel cetane-number aircraft measurements diesel-fuel cetane number, the results are shown in Table 7.

Diesel yield/%=product 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	3.1	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:

1, the sulphur content of feed gasoline is 640 μ g/g, RON be 93.0, MON is 82.7.

2, △ MON represents the increased value of product MON;

3, △ RON represents the increased value of product RON;

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

Table 7

Note: 1, the sulphur content of raw material diesel oil is 3718 μ g/g, and cetane value is 26.4.

Can be found out by table 1, adopt desulfurization catalyst A1-A6 provided by the invention to carry out gasoline desulfur, the isoparaffin in gasoline products and the content of isomeric olefine obviously increase, thus make the octane value of gasoline products have improvement by a relatively large margin.Meanwhile, adopt desulfurization catalyst provided by the invention to carry out diesel fuel desulfurization, cetane value can be significantly improved.

In the preferred implementation of desulfurization catalyst provided by the invention, the pore passage structure that rare earth does not enter molecular sieve is inner, and molecular sieve structure does not destroy, and degree of crystallinity reservation degree is close to 100%.Can see from the XRD spectra shown in Fig. 1-3, rare earth combines with titanium, forms rare earth-titanium composite oxide structure.Displayed in Table 1 go out desulfurization catalyst A1-A3 can abrasion index lower, there is better abrasion resistance properties.Sulphur content in gasoline can be dropped to 10 below μ g/g by desulfurization catalyst A1-A3 displayed in Table 2, and still have better sweetening effectiveness after repeatedly recycling, illustrate that desulfurization catalyst provided by the invention has and better remove the desulphurizing activated of reaction raw materials sulfur in gasoline and desulfurization stability.Table 3-4 can find out, desulfurization catalyst A1-A3 has higher product gasoline yield, and it is lower to generate amount of coke.Table 5 shows desulfurization catalyst A1-A3 to carry out in the gasoline products composition of desulfurization acquisition, and the content of isomeric component is higher.Table 6 can be found out, the octane value of the product gasoline that desulfurization catalyst A1-A3 obtains is improved.As can be seen here, desulfurization catalyst provided by the invention has better structure, can improve abrasion resistance properties, can have better desulphurizing activated and desulfurization stability, and produce yield of gasoline higher, green coke amount is lower, product gasoline better quality simultaneously.

As can be seen from Table 7, desulfurization catalyst provided by the invention can also have better diesel fuel desulfurization effect, and in product diesel oil, sulphur content is lower, and desulfurization degree is higher, desulphurizing activated higher, and desulfurization stability is better; And the product diesel cetane-number obtained improves, and yield is higher.

And in comparative example 2, although also containing rare earth, be distributed in the inside of SAPO-11 molecular sieve pore passage, not only have impact on the crystallization reservation degree of molecular sieve, and then affect the acidity of molecular sieve, the quality of desulfurization reaction product.And using aluminum oxide as binding agent in desulfurization of hydrocarbon oil reaction process, aluminum oxide and zinc oxide form gahnite, decrease the quantity of active zinc flower, finally affect the desulphurizing activated of desulfurization catalyst and stability.

Claims

1. a desulfurization catalyst, this desulfurization catalyst contains SAPO molecular sieve, rare earth oxide, titanium dioxide, silicon oxide, zinc oxide and active metal, with the gross weight of described desulfurization catalyst for benchmark, the content of described SAPO molecular sieve is 1-30 % by weight, and described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-15 % by weight, and the content of described titanium dioxide is 3-35 % by weight, and the content of described silicon oxide is 5-30 % by weight, and the content of described zinc oxide is 10-80 % by weight, and the content of described active metal is 5-30 % by weight.

2. desulfurization catalyst according to claim 1, wherein, with the gross weight of described desulfurization catalyst for benchmark, the content of described SAPO molecular sieve is 2-25 % by weight, and described rare earth oxide is with RE ₂o ₃the content of meter is 0.5-10 % by weight, and the content of described titanium dioxide is 5-25 % by weight, and the content of described silicon oxide is 10-20 % by weight, and the content of described zinc oxide is 25-70 % by weight, and the content of described active metal is 8-25 % by weight.

3. desulfurization catalyst according to claim 1, wherein, described SAPO molecular sieve is the SAPO-34,17,18,26,33,34,35,39,42,43,44,47 being selected from small-bore, the SAPO-11 of mesoporous, 31,41 and wide-aperture SAPO-5,36,37,40,46 at least one.

4. according to the desulfurization catalyst in claim 1-3 described in any one, wherein, the sial atomic molar of described SAPO molecular sieve is than being 0.05-1.0:1.

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

6. desulfurization catalyst according to claim 5, wherein, the rare earth element in described rare earth oxide is at least one in La, Ce, Pr and Nd.

7. desulfurization catalyst according to claim 1, wherein, described active metal is at least one in cobalt, nickel, iron and manganese.

8. in the pore passage structure of according to the desulfurization catalyst in claim 1-7 described in any one, wherein, described SAPO molecular sieve, the content of rare earth element is 0 μ g/g; The rhombic characteristic peak of rare earth-titanium composite oxide is there is in the XRD spectra of described desulfurization catalyst.

9. desulfurization catalyst according to claim 8, wherein, when described rare earth element is cerium, in the XRD spectra of described desulfurization catalyst, there is the rhombic characteristic peak that 2 θ are the cerium-titanium composite oxide of 11.4 °, 32.6 °, 40.3 °, 46.8 °, 47.0 ° and 58.3 °; There is not the characteristic peak that 2 θ are the anatase crystal of the titanium dioxide of 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, there is not the characteristic peak that 2 θ are the cubic system of the cerium oxide of 28.52 ° and 33.06 °.

10. desulfurization catalyst according to claim 8, wherein, when described rare earth element is lanthanum, in the XRD spectra of described desulfurization catalyst, there is the rhombic characteristic peak that 2 θ are the lanthanum titanium composite oxide of 25.1 °, 31.9 °, 39.3 °, 45.7 ° and 57.0 °; There is not the characteristic peak that 2 θ are the anatase crystal of the titanium dioxide of 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, there is not the characteristic peak that 2 θ are the cubic system of the lanthanum trioxide of 25.3 °, 27.8 °, 28.9 °, 37.9 °, 44.6 °, 49.8 °, 53.5 °, 54 ° and 58.5 °.

, wherein, when described rare earth element is neodymium, in the XRD spectra of described desulfurization catalyst, there is the rhombic characteristic peak that 2 θ are the neodymium titanium composite oxide of 22.7 °, 32.4 °, 46.3 ° and 58.0 ° in 11. desulfurization catalysts according to claim 8; There is not the characteristic peak that 2 θ are the anatase crystal of the titanium dioxide of 25.3 °, 37.8 °, 48.1 °, 53.9 ° and 55.0 °, there is not the characteristic peak that 2 θ are the cubic system of the Neodymium trioxide of 26.6 °, 30.0 °, 31.1 °, 40.6 °, 47.6 °, 53.4 ° and 57.1 °.

The preparation method of 12. 1 kinds of desulfurization catalysts, the method comprises:

(1) SAPO molecular sieve is contacted with rare earth metal salt solutions obtain rare earth modified SAPO molecular sieve;

(2) slurries titania source, zinc oxide, silica source, rare earth modified SAPO molecular sieve and water are mixed to form contact with acidic liquid and obtain carrier mixture, then obtain carrier through shaping, dry and roasting;

(3) in described carrier, introduce the compound containing active metal, dry, roasting obtains desulfurization catalyst precursor;

(4) described desulfurization catalyst precursor is reduced in a hydrogen atmosphere, obtain desulfurization catalyst.

13. methods according to claim 12, wherein, before step (1) is included in described contact, carry out roasting by SAPO molecular sieve, and the temperature of roasting is 500-800 DEG C; The condition of described contact comprises: temperature is 80-150 DEG C, and the time of contact is 0.5-6 hour; Described contact is that SAPO molecular sieve and rare earth metal salt solutions are mixed to form slurries, and described slurries carried out filter, wash, dry and roasting; It is 80-120 DEG C that described slurries carry out dry temperature, and the temperature that described slurries carry out roasting is 300-600 DEG C; The concentration of described rare earth metal salt solutions is 0.01-1.5 mol/L.

14. methods according to claim 12, wherein, before step (1) is included in described contact, carry out roasting by SAPO molecular sieve, and the temperature of roasting is 500-800 DEG C; Described contact is by rare earth metal salt solutions incipient impregnation SAPO molecular sieve, and carries out the drying of 80-120 DEG C and the roasting of 300-600 DEG C.

15. according to the method in claim 12-14 described in any one, and wherein, described rare earth metal salt solutions is at least one in the nitrate of rare earth metal, halogenide, acetate and sulfate liquor.

16. according to the method in claim 12-14 described in any one, wherein, described titania source, zinc oxide, silica source, SAPO molecular sieve, rare earth metal salt solutions and the add-on containing the compound of active metal make in the desulfurization catalyst obtained, with the gross weight of desulfurization catalyst for benchmark, the content of SAPO molecular sieve is that 1-20 % by weight, rare earth oxide are with RE ₂o ₃the content of meter is 0.5-10 % by weight, the content of titanium dioxide is 3-35 % by weight, and the content of silicon oxide is 5-30 % by weight, and the content of zinc oxide is 10-80 % by weight, and the content of active metal is 5-30 % by weight.

17. methods according to claim 12, wherein, described titania source is selected from least one in titanium tetrachloride, titanium ethanolate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.

18. desulfurization catalysts prepared by the method in claim 12-17 described in any one.

The preparation method of 19. 1 kinds of desulfurization catalysts, the method comprises:

(1) mixing of the precursor of titania source and rare earth oxide is contacted obtain rare earth-titanium colloidal sol;

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

20. methods according to claim 19, wherein, the precursor of described titania source, zinc oxide, silica source, SAPO molecular sieve, rare earth oxide and make in the desulfurization catalyst obtained containing the add-on of the compound of active metal, with the gross weight of desulfurization catalyst for benchmark, the content of SAPO molecular sieve is that 1-20 % by weight, rare earth oxide are with RE ₂o ₃the content of meter is 0.5-10 % by weight, the content of titanium dioxide is 3-35 % by weight, and the content of silicon oxide is 5-30 % by weight, and the content of zinc oxide is 10-80 % by weight, and the content of active metal is 5-30 % by weight.

21. methods according to claim 19 or 20, wherein, the precursor of described rare earth oxide is at least one in the acetate of the rare earth metal be selected from described rare earth oxide, carbonate, nitrate, vitriol, oxalate, muriate and oxide compound.

22. desulfurization catalysts prepared by the method in claim 19-21 described in any one.

The method of 23. 1 kinds of desulfurization of hydrocarbon oil, the method comprises: hydrocarbon oil containing surphur and hydrodesulfurization catalyst are reacted, it is characterized in that, described desulfurization catalyst is claim 1-11, desulfurization catalyst in 18 and 22 described in any one.