CN108404945A

CN108404945A - The method of ordered structure desulphurization catalyst and preparation method thereof and sulfur-bearing hydrocarbon desulfurization

Info

Publication number: CN108404945A
Application number: CN201710073422.5A
Authority: CN
Inventors: 王鹏; 田辉平; 孙言; 宋海涛; 朱玉霞; 任飞
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: 2017-02-10
Filing date: 2017-02-10
Publication date: 2018-08-17
Anticipated expiration: 2037-02-10
Also published as: CN108404945B

Abstract

Method the invention discloses a kind of ordered structure desulphurization catalyst and preparation method thereof with sulfur-bearing hydrocarbon desulfurization, the catalyst include ordered structure carrier and are distributed in the active component coating of the ordered structure inner surface of the carrier and/or outer surface；On the basis of the total weight of the active component coating, the active component coating contains the matrix of the transition metal carbide and 30~95 weight % of 5~70 weight %；On the basis of the total weight of the matrix, the matrix contains the oxide selected from least one of IIA and Group IIB metal of the non-al binder of 5~35 weight %, 0.5~10 weight % rare earth oxides and 60~90 weight %.The catalyst has preferable desulphurizing activated and desulfurization stability, and can improve the octane number of desulfurization oil product.

Description

The method of ordered structure desulphurization catalyst and preparation method thereof and sulfur-bearing hydrocarbon desulfurization

Technical field

The present invention relates to sulfur-bearing hydrocarbon desulfurization fields, and in particular, to a kind of ordered structure desulphurization catalyst and its preparation side The method of method and sulfur-bearing hydrocarbon desulfurization.

Background technology

Sulphur in vehicle fuel generates oxysulfide after burning.The substance can inhibit your gold in vehicle exhaust converter The activity of metal catalyst simultaneously can be allowed to occur irreversibly to be poisoned, and can not achieve the toxic gas in catalyzed conversion vehicle exhaust Effect causes in vehicle exhaust containing unburned non-methane hydrocarbon and nitrogen oxide and carbon monoxide.And these discharges has Poisonous gas is easy to form photochemical fog by hydrophilic dye, causes acid rain.And oxysulfide itself is also the master to form acid rain Want one of reason.

As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces in gasoline and diesel oil Sulfur content is considered as improving one of the most important measure of air quality.By taking gasoline as an example, European Union is in the Europe V vapour of implementation in 2010 Provide that sulfur content is less than 10 μ g/g in oil standard.The existing gasoline products standard GB 17930-2013 in China《Motor petrol》It wants It asks on January 1st, 2018, sulfur content in gasoline must drop to 10 μ g/g.And the gasoline quality standard in future can also be more Strictly.

The main method of the desulfurization of fuel oil is hydrodesulfurization.But increasingly strict with standard of fuel, hydrogenation depth improves, Need for example higher reaction pressure of harsher reaction condition etc..In addition gasoline is improved and is added due to containing a large amount of alkene Hydrogen severity will lead to higher loss of octane number, therefore some new sulfur methods continue to bring out, wherein especially to adsorb desulfurization Most it is concerned by people.

US7427581, US7182918, US6869522 and US6274533 etc. are disclosed using adsorbent in hydro condition Under desulfurization is carried out to lightweight sulfur-bearing hydrocarbon, have the characteristics that desulfurization depth is high, hydrogen consumption is low, loss of octane number lacks, sulphur can be produced and contained Amount is 30 μ g/g fuel oil below.It is sorbent used using zinc oxide, silica and alumina mixture as carrier, wherein zinc oxide Account for 10~90 weight %, silica accounts for 5~85 weight %, aluminium oxide accounts for 5~30 weight %；The active component of load is reduction-state gold Belong to, can be at least one of cobalt, copper, manganese, tungsten, tin, nickel, iron, molybdenum, silver and vanadium.Adsorbent is in 0.1~10.3MPa, 37.7 ~537.7 DEG C, weight (hourly) space velocity (WHSV) be 0.5~50h^-1Under conditions of facing hydrogen, the sulphur in oil product is captured on adsorbent plus after hydrogen It is combined with zinc oxide, at the same time, since transition metal equally exists hydrogenation to alkene, gasoline products octane number can be led to Decline.And in order to make up since alkene reduces caused loss of octane number, prior art generally use promotes aromatization, carries The method of high arene content is realized, but inevitably Determination of Benzene In Gasoline is caused to increase；In addition it combines on zinc oxide Sulphur when reaching saturation, desulphurizing activated decline can be led to, it is necessary to which oxidized regeneration removes sulphur.It is gone back in frequent oxidation regeneration- During original, the metal as active component can be assembled, and zinc oxide can be because being converted into zinc silicate in regenerative process Make desulphurizing activated decline of adsorbent during recycling with zinc aluminate, the deactivation rate of adsorbent is higher, influences sulfur-bearing The implementation result of hydrocarbon desulfurization.

It is desulphurizing activated in practical applications although can be very good to realize deep desulfuration it can be seen that adsorbing desulfurization Problem is still had with desulfurization stability.It is, thus, sought for new adsorbent (also referred to as desulphurization catalyst), at least to overcome One of drawbacks described above present in the prior art.

Invention content

Side the object of the present invention is to provide a kind of ordered structure desulphurization catalyst and preparation method thereof with sulfur-bearing hydrocarbon desulfurization Method to improve the desulphurizing activated and desulfurization stability of catalyst, while improving the octane number of desulfurization oil product.

To achieve the goals above, according to the first aspect of the invention, a kind of ordered structure desulphurization catalyst is provided, The catalyst includes ordered structure carrier and the active component painting for being distributed in the ordered structure inner surface of the carrier and/or outer surface Layer；On the basis of the total weight of the active component coating, the active component coating contains the transition metal of 5~70 weight % The matrix of carbide and 30~95 weight %；On the basis of the total weight of the matrix, the matrix contains 5~35 weight %'s Non- al binder, 0.5~10 weight % rare earth oxides and 60~90 weight % are selected from least one of IIA and Group IIB The oxide of metal.

According to the second aspect of the invention, a kind of preparation method of ordered structure desulphurization catalyst, the preparation are provided Method includes the following steps：S1, by the presoma of the oxide selected from least one of IIA and Group IIB metal, rare-earth oxidation Object presoma and the mixing of non-al binder presoma, prepare matrix coating slurries；S2, the matrix coating slurries are coated in rule On whole structure carrier, drying is simultaneously roasted to form matrix coating in the ordered structure inner surface of the carrier and/or outer surface, is obtained Catalyst base；S3, the catalyst base is in contact with transition metal precursor solution, dry and roast after contact with Transition metal oxide is formed on the matrix coating, obtains catalyst precarsor；S4, by the catalyst precarsor in CH₄/H₂Gas Reduction treatment is carried out under atmosphere, the transition metal oxide is restored to form transition metal carbide, obtains the regular knot Structure desulphurization catalyst.

According to the third aspect of the present invention, regular knot made from a kind of preparation method according to the present invention is provided Structure desulphurization catalyst.

According to the fourth aspect of the present invention, a kind of method of sulfur-bearing hydrocarbon desulfurization is provided, this method includes：By sulfur-bearing hydrocarbon It is contacted with catalyst with hydrogen donor；Wherein, the catalyst is according to catalyst of the present invention.

Using ordered structure desulphurization catalyst provided by the invention, catalyst desulfurizing activity can be effectively improved and desulfurization is steady Qualitative, benzene in reduction desulfurization oil product content improves isomery hydrocarbon content and improves the octane number of desulfurization oil product；And the present invention The ordered structure desulphurization catalyst of offer is not necessarily to frequent repeated regeneration, can be used with long period, not easily run off and assemble, and increases Desulfurization stability, reduces the unit consumption of catalyst.

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

Specific implementation mode

The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

In the present invention, it includes ordered structure carrier and being distributed in table in carrier to refer to using term " ordered structure catalyst " The catalyst of the active component coating in face and/or outer surface；" ordered structure carrier " is the carrier with ordered structure；It is " regular Structural response device " is to have loaded fixed bed reactors of the ordered structure catalyst as catalyst bed.

The present invention provides a kind of ordered structure desulphurization catalyst, which includes ordered structure carrier and is distributed in institute State the active component coating of ordered structure inner surface of the carrier (carrier inside pore surface) and/or outer surface；With the activearm Divide on the basis of the total weight of coating, the active component coating contains the transition metal carbide and 30~95 of 5~70 weight % The matrix of weight %；On the basis of the total weight of the matrix, the matrix contains the non-al binder of 5~35 weight %, 0.5 The oxide selected from least one of IIA and Group IIB metal of~10 weight % rare earth oxides and 60~90 weight %.

Ordered structure desulphurization catalyst according to the present invention, as long as wherein containing transition metal carbide and there is specific group The matrix divided, can not have the amount by the active component coating being distributed on ordered structure carrier with coating method It is special to limit.Under preferable case, on the basis of the total weight of the ordered structure catalyst, the active component coating contains Amount is 10~50 weight %；It is preferred that can be 15~30 weight %.

Ordered structure desulphurization catalyst according to the present invention, under preferable case, with the total weight of the active component coating On the basis of, the active component coating contains the matrix of the transition metal carbide and 30~95 weight % of 5~70 weight %；It is excellent Select the matrix for the transition metal carbide and 50~90 weight % that the active component coating contains 10~50 weight %；More preferably The active component coating contains the matrix of the transition metal carbide and 50~80 weight % of 20~50 weight %, particularly preferably The active component coating contains the matrix of the transition metal carbide and 50~75 weight % of 25~50 weight %.

Ordered structure desulphurization catalyst according to the present invention, under preferable case, the transition in the transition metal carbide Metal is selected from Ti (corresponding carbide is mainly TiC), V (corresponding carbide is mainly VC), Fe (corresponding carbon Compound is mainly Fe₃C), (corresponding carbide is mainly Co to Co₂C), (corresponding carbide is mainly Ni to Ni₂C)、Zr (corresponding carbide is mainly Mn by (corresponding carbide is mainly ZrC), Mn₃C), (corresponding carbide is main by Cu For Cu₂C), (corresponding carbide is mainly Mo to Mo₂C) and one or more of W (corresponding carbide is mainly WC), More preferably it is selected from one or more of Co, Ni, Mo and W.

Ordered structure desulphurization catalyst according to the present invention, wherein described be selected from least one of IIA and Group IIB metal Oxide and optional rare earth oxide be with storage sulphur performance metal oxide.It is described to be selected from IIA under preferable case Oxide at least one of Group IIB metal is the oxide selected from least one of magnesium, zinc and calcium metal；Preferably oxygen Change zinc；Under preferable case, the rare earth oxide is the oxide of lanthanum and/or cerium and/or neodymium, i.e., the described rare earth oxide is Oxide selected from one or more of lanthanum, cerium and neodymium.

Ordered structure desulphurization catalyst according to the present invention, wherein can not limited particularly for the non-al binder Fixed, under preferable case, the non-al binder is selected from least one of zirconium dioxide, titanium dioxide and stannic oxide.Institute The presoma for stating non-al binder is zirconium dioxide, titanium dioxide and stannic oxide, or can obtain two under the roasting condition The substance of zirconium oxide, titanium dioxide and stannic oxide, such as the presoma of non-al binder can be selective chlorination object, oxychlorination One or more of object or acetate.

Ordered structure desulphurization catalyst according to the present invention, wherein ordered structure carrier can be used in fixed bed reactors The catalyst bed of offer.The ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, duct Inner wall on can be distributed catalyst coat, duct space may be used as the flowing space of fluid.It is described regular under preferable case Structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open.The ordered structure carrier can be section The regular carrier (abbreviation honeycomb substrate) of honeycomb fashion with cellular trepanning.

Ordered structure desulphurization catalyst according to the present invention, under preferable case, the hole in the section of the ordered structure carrier Density is 40~800 holes/square inch, preferably 100~400 holes/square inch；The cross in each hole in the ordered structure carrier Sectional area is 400~1.8 × 10⁵μm², preferably 1500~22500 μm², the percent opening of the section of the ordered structure carrier is 20~80%, preferably 50~80%.The shape in hole can be square, equilateral triangle, regular hexagon, circle and it is corrugated in One kind.

Ordered structure desulphurization catalyst according to the present invention, under preferable case, the ordered structure carrier can be selected from violet Green stone honeycomb substrate, mullite honeycomb substrate, diamond honeycomb substrate, corundum honeycomb substrate, fused alumina zirconia honeycomb substrate, quartzy bee At least one in nest carrier, nepheline honeycomb substrate, feldspar honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate Kind.

Meanwhile a kind of preparation method of ordered structure desulphurization catalyst, the preparation method packet are additionally provided in the present invention Include following steps：S1, by the presoma of the oxide selected from least one of IIA and Group IIB metal, optional rare-earth oxidation Object presoma and the mixing of non-al binder presoma, prepare matrix coating slurries；S2, the matrix coating slurries are coated in rule On whole structure carrier, drying is simultaneously roasted to form matrix coating in the ordered structure inner surface of the carrier and/or outer surface, is obtained Catalyst base；S3, the catalyst base is in contact with transition metal precursor solution, and dries and roasts after contact To form transition metal oxide on the matrix coating, catalyst precarsor is obtained；S4, by the catalyst precarsor in CH₄/ H₂Reduction treatment is carried out under atmosphere, the transition metal oxide is restored to form transition metal carbide, obtains the rule Whole structure desulphurization catalyst.

Preparation in accordance with the present invention, under preferable case, the matrix coating slurries in terms of its dry weight (dry weight), The non-al binder presoma in terms of non-al binder, in terms of rare earth oxide 0.5~10 weight % containing 5~35 weight % Rare earth oxide presoma and in terms of metal oxide 60~90 weight % selected from least one of IIA and Group IIB it is golden The presoma of the oxide of category.

Preparation in accordance with the present invention is formed by matrix coating and transition metal carbide on ordered structure carrier It is referred to as active component coating.In the preferred case, on the basis of the total weight of the ordered structure desulphurization catalyst, the base The total content of matter coating and the transition metal carbide (i.e. the active component coating) is 10~50 weight %, preferably 15~30 weight %；And always containing with the matrix coating and the transition metal carbide (i.e. the active component coating) On the basis of amount, the content of the transition metal carbide is 5~70 weight %, and the content of the matrix coating is 30~95 weights Measure %；It is preferred that the content of the transition metal carbide is 10~50 weight %, the content of the matrix coating is 50~90 weights Measure %；The more preferable active component coating contains the base of the transition metal carbide and 50~80 weight % of 20~50 weight % The content of matter, the particularly preferred transition metal carbide is 25~50 weight %, and the content of the matrix coating is 50~75 Weight %.

Preparation in accordance with the present invention wants the solid content of prepared matrix coating slurries in S1 there is no special It asks, however the excessively high difficulty that may increase slurry coating of the solid content of slurries, and the solid content of slurry is too low, may reduce The adhesion amount coated every time, and then increase coating number.Under preferable case, the solid content of the step S1 mesostroma coating slurries For 10~45 weight %, preferably 20~40 weight %.

Preparation in accordance with the present invention, under preferable case, the S1 includes：S11, by IIA and Group IIB extremely The presoma and deionized water of a kind of few oxide of metal are mixed and are ground, and obtain slurries A；S12, by rare earth oxide forerunner Body and the mixing of non-al binder presoma, altogether glue or co-precipitation, preparation obtain slurries B；S13, the slurries A and slurries B are mixed It closes, prepares the matrix coating slurries.

Preparation in accordance with the present invention, under preferable case, the metal oxide in the ground obtained slurries A of S11 Grain diameter d₉₀It is 0.5~10 μm；The average grain diameter of mixture is less than 100nm in prepared slurries B in S12, preferably For 40~80nm.

Preparation in accordance with the present invention, mix rare earth oxide presoma and non-al binder presoma in S12, The step of glue is referred to common method known in the field altogether, such as may comprise steps of：(1) according to selected Non- al binder presoma and acid solution or aqueous slkali haptoreaction are formed first by the Gelation Conditions of non-al binder presoma Colloidal solution；Such as selected non-al binder presoma be zirconium chloride when, zirconium chloride is mixed with acid solution, Stir to get the first colloidal solution that pH value is 0.5~6；In another example selected non-al binder presoma is titanium tetrachloride When, zirconium chloride is mixed with aqueous slkali, stirs to get the first colloidal solution that pH value is more than 10.(2) then to described first Rare earth oxide presoma is added in colloidal solution, and aqueous slkali is added under agitation, until pH is more than 10 (preferably mixing temperature Degree is 10~40 DEG C, and incorporation time is 0.5~12h), obtain the second colloidal solution.Preferably, the acid solution is selected from nitre One or more of acid, hydrochloric acid, phosphoric acid and acetic acid, a concentration of 10~75wt% of the preferably described acid solution；Preferably, described Aqueous slkali be selected from selected from one or more of ammonium hydroxide, sodium hydroxide and potassium hydroxide, the preferably described aqueous slkali it is a concentration of 20~70wt%.

Preparation in accordance with the present invention, in step s 12 by rare earth oxide presoma and non-al binder presoma The step of mixing, co-precipitation, is referred to common method known in the field, such as：It will be in non-al binder precursor solution Rare earth oxide precursor solution is added, and aqueous slkali is added under agitation, until (preferably mixing temperature is for pH=10~12 10~40 DEG C, incorporation time is 0.5~10h), filter cake is obtained after filtering carries out the extra metal ion of washing removing.Preferably, The aqueous slkali be selected from one or more of ammonium hydroxide, sodium hydroxide and potassium hydroxide, the preferably described aqueous slkali it is a concentration of 20~70wt%.In the case of preparing solution B for the method using co-precipitation, after forming filter cake through co-precipitation processing, also The step of further comprising carrying out (optional dry, sintering) milled processed to filter cake, the method and condition being ground is this Well known to field technology personnel, details are not described herein.

Preparation in accordance with the present invention further includes being starched in matrix coating in S1, preferably in S13 under preferable case The step of dispersant is added in liquid, by adding dispersant into matrix coating slurries, is conducive to promote slurries uniform and stable. The preferred dispersant is organic dispersing agent in the present invention, at this time usually as the degree of polymerization of dispersant increases, added with dispersion The viscosity of the solution of agent also will increase, and be conducive to improve the firmness after slurries coating, however as the increasing of the dispersant degree of polymerization Greatly, solubility can be gradually reduced dispersant in water, be unfavorable for the mixing of dispersant；Consider the viscosity and dispersant of slurries Dissolubility, under preferable case, the dispersant is the degree of polymerization in 500~2500 ranges, preferably in 1000~2000 ranges Interior organic dispersing agent；It is preferred that the organic dispersing agent in polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene one Kind is several.

Preparation in accordance with the present invention, under preferable case, the dispersant and at least one in IIA and Group IIB The weight ratio of the presoma of the oxide of kind metal is more than 0 and is less than or equal to 0.2, preferably 0.005~0.02：1；It will dispersion The dosage control of agent in the range, is conducive to control the viscosity of slurries and extends its sedimentation time.In view of the use of the dispersant It measures less, the dispersant first preferably is dissolved in water to obtain dispersant solution in practical operation, then by the dispersant solution It is added in matrix coating slurries.In the dispersant solution, the dosage of the water based on 100mL, the preferably described dispersant is 0.5-30g, preferably 1-20g, more preferably 2-10g, particularly preferably 2-5g.

Preparation in accordance with the present invention, can be by various painting methods by the matrix coating slurries point in the S2 On cloth to the inner surface of ordered structure carrier and/or outer surface.The method of the coating can be water coating, infusion process or spray Method.The concrete operations of coating are referred to the progress of the method described in CN1199733C.In the preferred case, the coating uses Water coating, i.e., the side that the dispersion liquid (matrix coating slurry) being beaten with matrix coating material and water coats carrier Formula, carrier one end is immersed in slurries in coating procedure, and other end applying vacuum makes slurries continue through the duct of carrier.Institute State by 2~20 times that the slurry volume in carrier duct is carrier bulk, the vacuum pressure of application be -0.1MPa (megapascal) to - 0.01MPa (megapascal), application temperature are 10~70 DEG C, and coating time is 0.1~300 second.

Preparation in accordance with the present invention, in the S2 by the ordered structure carrier of the good matrix coating slurries of coating into The method and condition of row drying and roasting is known to those skilled in the art.For example, dry method can be dried, dry Dry, forced air drying；The method of roasting can also be method known in the field.Under preferable case, in step S2, dry temperature It spends for room temperature to 300 DEG C, preferably 100~200 DEG C, drying time is in 0.5h or more, preferably 1~10h.The temperature of the roasting Degree is 400~800 DEG C, preferably 500~700 DEG C；The time of the roasting is at least 0.5 hour, preferably 1~10 hour.

Preparation in accordance with the present invention, transition metal precursor solution is to dissolve transition metal precursor in the S3 Be formed by mixed solution in a solvent, wherein for the transition metal precursor solution concentration there is no particular/special requirement, only It wants transition metal precursor can be completely dissolved, it can be according to the solubility of transition metal precursor in practical operation Carry out Proper Match.For wherein used solvent, there is no particular/special requirements in the present invention, as long as it can be dissolved accordingly Transition metal precursor, and do not react with prepared catalyst base.The solvent that can be used include but It is not limited to one or more of deionized water, distilled water and decationized Y sieve water.

Preparation in accordance with the present invention, for by the catalyst base and transition metal precursor in the step S3 The arbitrary method to contact with each other with liquid suitable for solid may be used there is no particular/special requirement in the method for solution contact.Example It such as impregnates, spray.Preferably the catalyst base is immersed in transition metal precursor solution in the present invention, wherein right In dipping condition there is no particular/special requirement, conventional dipping can be carried out under room temperature, normal pressure.

Preparation in accordance with the present invention, under preferable case, transition metal is choosing in the transition metal precursor solution From one or more of Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W, one kind for being preferably selected from Co, Ni, Mo and W or It is several.The transition metal precursor is the soluble compound that can obtain transition metal oxide under the roasting condition, excellent Selection of land, the transition metal precursor are the soluble-salts such as nitrate, chloride, oxalates, acetate, the ammonium salt of transition metal Class

Preparation in accordance with the present invention, in the S3 by the ordered structure carrier of the good matrix coating slurries of coating into The method and condition of row drying and roasting is known to those skilled in the art.For example, dry method can be dried, dry Dry, forced air drying；The method of roasting can also be method known in the field.Under preferable case, in step S3, dry temperature It spends for room temperature to 150 DEG C, preferably 80~100 DEG C, drying time is in 1h or more, preferably 2~8h；The temperature of roasting is 200 ~600 DEG C, preferably 200~350 DEG C, the time of roasting is in 1h or more, preferably 2~4h.

Under preferable case, in the catalyst precarsor that step S3 is obtained, including before ordered structure carrier and active component coating Body, on the basis of the total weight of the catalyst precarsor, the active component coating precursor contains the mistake of 5.8~77.1 weight % Cross the matrix of metal oxide and 23.9~94.2 weight %；It is preferred that the active component coating precursor contains 11.6~59.1 weights Measure the matrix of the transition metal oxide and 40.9~89.4 weight % of %；It is preferred that the active component coating precursor contains 22.8 The matrix of the transition metal oxide of~59.1 weight % and 40.9~77.2 weight %；It is preferred that the active component coating precursor The matrix of transition metal oxide containing 28.3~59.1 weight % and 40.9~72.7 weight %.

Preparation in accordance with the present invention, by the catalyst precarsor in CH in the S4₄/H₂Reduction treatment under atmosphere, makes The transition metal oxide for obtaining fired formation restores to obtain transition metal carbide.The reduction treatment can be made described It carries out, can also be carried out (before being used for desulfurization absorption) before catalyst use immediately after catalyst precarsor.Under preferable case, institute State CH₄/H₂Atmosphere is with CH₄/H₂The total volume 100% of atmosphere is counted, the CH containing 5~25 volume %₄With the H of 75~95 volume %₂； Preferably comprise the CH of 10~20 volume %₄With the H of 80~90 volume %₂, in CH₄/H₂The condition restored under atmosphere includes：By institute Catalyst precarsor is stated in CH₄/H₂The condition of progress reduction treatment includes under atmosphere：It is 250~550 DEG C in temperature, pressure 0.2 Under the conditions of~5MPa, reduction treatment 0.5~6 hour；It is preferred that being 300~450 DEG C in temperature, pressure is 0.5~3.5MPa conditions Under, reduction treatment 2~4 hours.

Preparation in accordance with the present invention, through analysis of chemical elements method and X-ray diffraction measurement method it is found that transition metal is When Ti, it is mainly TiC to be formed by carbide；When transition metal is V, it is mainly VC to be formed by carbide；Transition metal is When Fe, it is mainly Fe to be formed by carbide₃C；When transition metal is Co, it is mainly Co to be formed by carbide₂C；Transition metal For Ni when, it is mainly Ni to be formed by carbide₂C；When transition metal is Zr, it is mainly ZrC to be formed by carbide；Transition gold When category is Mn, it is mainly Mn to be formed by carbide₃C；When transition metal is Cu, it is mainly Cu to be formed by carbide₂C；Transition When metal is Mo, it is mainly Mo to be formed by carbide₂C；When transition metal is W, it is mainly WC to be formed by carbide.

Preparation in accordance with the present invention, wherein the carrier of used ordered structure is retouched in foregoing teachings It states, illustrates with reference to preceding description.

Preparation in accordance with the present invention, wherein the oxide selected from least one of IIA and Group IIB metal Presoma is the substance that can obtain being selected from the oxide of at least one of IIA and Group IIB metal under the roasting condition, such as Nitrate, acetate, carbonate, sulfate, oxalates, the chloride selected from least one of IIA and Group IIB metal One or more of with oxide.Wherein, the oxide selected from least one of IIA and Group IIB metal be selected from The oxide of at least one of magnesium, zinc and calcium metal, more preferably zinc oxide.

Preparation in accordance with the present invention, wherein the rare earth oxide presoma middle rare earth is in lanthanum, cerium and neodymium At least one；The rare earth oxide presoma is rare earth oxide or can obtain rare earth oxide under the roasting condition Substance, such as one kind in the nitrate of rare earth, acetate, carbonate, sulfate, oxalates, chloride and oxide or It is several.

Preparation in accordance with the present invention, wherein non-al binder is selected from titanium dioxide in the non-aluminum binder presoma At least one of zirconium, titanium dioxide and stannic oxide, the non-al binder presoma are zirconium dioxide, titanium dioxide or dioxy Change tin, or the substance of zirconium dioxide, titanium dioxide or stannic oxide, such as chloride, oxygen can be obtained under the roasting condition One or more of chloride, acetate, oxide.Specifically, the zirconium dioxide binder can be zirconium chloride, oxygen At least one of zirconium chloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide；The stannic oxide binder can be At least one of butter of tin, four isopropanol tin, tin acetate, aqua oxidation tin and stannic oxide；Before the titanium dioxide Body object can be the substance for being changed into anatase titanium dioxide under conditions of first roasting, and the titanium dioxide bonds Agent can be in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide It is at least one.Wherein anatase titanium dioxide remains able to generate anatase titanium dioxide after hydrolyzing and first roasts.

In addition, ordered structure desulphurization catalyst according to the present invention, can also obtain by the following method：S1, by group It is mixed with beating, and the slurries is dried and roasting obtains matrix (preferably according to aforementioned at each component and water of the matrix Dry, roasting obtains matrix after method prepares matrix coating slurry in S11-S13)；S2, with the solution containing transistion metal compound Or matrix described in suspension impregnation, transistion metal compound is introduced into matrix, then by drying, roasting and in CH₄/H₂Gas Reduction treatment is carried out under atmosphere, is formed transition metal carbide, is obtained active component；S3, by obtained active component with containing water-soluble Agent is ground into slurries to get to the active component coating slurries, which contains transition metal carbide； S4, it the ordered structure carrier is coated by cladding process with above-mentioned active component slurries is made, the present invention is obtained through drying, roasting Ordered structure desulphurization catalyst.Before involved raw material, raw material components and process can refer in the preparation method State the associated description in the preparation method of ordered structure desulphurization catalyst.

In addition, additionally providing a kind of ordered structure desulfurization catalyst made from the above-mentioned preparation method of the present invention in the present invention Agent.The catalyst includes ordered structure carrier and is distributed in the ordered structure inner surface of the carrier and/or the activearm of outer surface Divide coating；On the basis of the total weight of the active component coating, the active component coating contains the transition of 5~70 weight % The matrix of metal carbides and 30~95 weight %；On the basis of the total weight of the matrix, the matrix contains 5~35 weights Measure the non-al binder of %, 0.5~10 weight % rare earth oxides and 60~90 weight % in IIA and Group IIB extremely A kind of few oxide of metal.Ordered structure desulphurization catalyst obtained by the above-mentioned preparation method of the present invention and institute of the present invention Claimed ordered structure desulphurization catalyst technical characteristic having the same, particular content is previously with regard to regular with reference to the present invention The explanation of structure desulphurization catalyst.

A kind of method of sulfur-bearing hydrocarbon desulfurization is additionally provided in the present invention, and this method includes：By sulfur-bearing hydrocarbon and hydrogen donor with Catalyst contacts；Wherein, the catalyst is the aforementioned ordered structure desulphurization catalyst of the present invention.Under preferable case, the regular knot Structure desulphurization catalyst exists in the form of catalyst bed.

In sulfur-bearing hydrocarbon desulfurization method provided by the invention, ordered structure desulphurization catalyst can be used for sulfur-bearing hydrocarbon desulfurization reaction It is used as fixed catalyst bed, the sulfur-bearing hydrocarbon and hydrogen donor of flowing that can flow through ordered structure catalyst bed in device, The duct in ordered structure carrier can be flowed through, it is anti-in sulfur-bearing hydrocarbon desulfurization with the active component coating that is distributed in cell walls It reacts under the conditions of answering.Sulfur-bearing hydrocarbon desulfurization reactor can be the reactor of routine, such as can be fixed bed reactors, Middle when using fixed bed reactors as reactor, ordered structure desulphurization catalyst of the invention is seated in fixed bed reactors In.

In the method for sulfur-bearing hydrocarbon desulfurization provided by the invention, the ordered structure desulphurization catalyst containing transition metal carbide It need to only be operated under sulfur-bearing hydrocarbon desulfurization reaction condition.Wherein ordered structure desulphurization catalyst can at interval of a period of time, After the desulfurization effect of sulfur-bearing hydrocarbon is unsatisfactory for requirement, then regenerated；It can make without undergoing oxidation regeneration-reduction repeatedly Active metal is assembled, and the stability for improving catalyst desulfurizing activity and sulfur-bearing hydrocarbon desulfurization process is conducive to.

According to the method for sulfur-bearing hydrocarbon desulfurization of the present invention, this field, which may be used, in the sulfur-bearing hydrocarbon desulfurization reaction condition routinely makes The condition of sulfur-bearing hydrocarbon desulfurization reaction, can also be in conjunction with the use condition of ordered structure desulphurization catalyst, under preferable case, institute Stating sulfur-bearing hydrocarbon desulfurization reaction condition may include：Reaction temperature is 200~450 DEG C, and reaction pressure is 0.5~5MPa, sulfur-bearing hydrocarbon Charging weight (hourly) space velocity (WHSV) is 0.1~100h^-1, the volume ratio of hydrogen donor and sulfur-bearing hydrocarbon is 0.01~1000.Preferable reaction temperature is 350 ~400 DEG C, reaction pressure is 1~3.5MPa, and sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) is 1~10h^-1, the volume of hydrogen donor and sulfur-bearing hydrocarbon Than being 0.05~500.Above-mentioned reaction condition can be more advantageous to sulfur-bearing hydrocarbon desulfurization reaction and carry out, and reduce the hair of unfavorable side reaction It is raw.

In the present invention, sulfur-bearing hydrocarbon charging weight (hourly) space velocity (WHSV) refers to that the weight of the charging of sulfur-bearing hydrocarbon per hour and ordered structure are de- The charge weitght ratio of active component coating in sulfur catalyst.

According to the present invention, the sulfur-bearing hydrocarbon can be selected from natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas It is one or more in oil, preferably gasoline and/or diesel oil.Above-mentioned gasoline, kerosene, diesel oil and gas oil fraction are its full fraction And/or its part narrow fraction.The sulfur content of the sulfur-bearing hydrocarbon is more than 50 micro- gram grams, preferably more than 100 micro- gram grams.Such as The sulfur content of the sulfur-bearing hydrocarbon can be in 100~1500 micro- gram grams.

According to the present invention, the hydrogen donor is selected from the mixed of one or more of hydrogen, hydrogen-containing gas and hydrogen supply agent Close object.Hydrogen refers to the hydrogen of various purity, the cracking of hydrogen-containing gas preferred catalytic (FCC) dry gas, coking dry gas, thermal cracking dry gas One or more of.For the volume content of hydrogen more than 30 volume %, hydrogen supply agent is selected from naphthane, decahydronaphthalene in hydrogen-containing gas At least one of with indane.

In the present invention, the pressure being related to is indicated with gauge pressure.

A kind of ordered structure desulphurization catalyst of the present invention and preparation method thereof will be taken off with sulfur-bearing hydrocarbon by embodiment below The method of sulphur is described in detail.

Sulfur content is measured using offline chromatogram analysis method in following embodiment and comparative example, using An Jielun companies GC6890-SCD instruments are measured.Reaction raw materials catalytic cracking is measured using GB/T 503-1995 and GB/T 5487-1995 The motor octane number (MON) and research octane number (RON) (RON) of product gasoline after gasoline and desulphurization catalyst are stablized.

It is water coating, specific work that following embodiment and comparative example mesostroma slurry, which are coated in the method on ordered structure carrier, Process includes：In each coating procedure, ordered structure carrier one end is immersed in matrix coating slurries, the other end applies true Sky makes slurries continue through the duct of carrier；Wherein by 2.5 times that the slurry volume in carrier duct is carrier bulk, apply Vacuum pressure be -0.03MPa (megapascal), 35 DEG C of the temperature of coating, coating time be 60~120 seconds.

Embodiment 1

The embodiment is used to illustrate the regular texture desulphurization catalyst and preparation method thereof of the present invention.

(1) preparation of matrix coating slurry：

The nano-zinc oxide powder (Beijing Chemical Plant, the butt 1.0kg containing zinc oxide) and 1L deionized waters of 1.01kg is mixed It closes uniformly, wet ball grinding obtains slurries A (compound particles grain size d₉₀It it is 8 μm)；By zirconium chloride (Beijing chemical industry of 0.356kg Factory, analysis is pure, and 0.188kg is calculated as with zirconium oxide) in the salpeter solution of the 10 weight % of concentration that is slowly added into 3.1kg to solution PH value is 2, and is slowly stirred and crystal of zirconium oxide is avoided to be precipitated, and obtains the zirconium colloidal sol of water white transparency；By the lanthana of 0.0625kg (Chinese medicines group, analysis is pure, contains butt 0.062kg) is added in aforementioned zirconium colloidal sol, and 25 weight % ammonia are added dropwise after being uniformly mixed For aqueous solution until pH value is 12, formation lanthanum zirconium colloidal sol obtains slurries B；Aforementioned obtained slurries A and slurries B are mixed, stirring 20 Minute prepares the matrix coating slurries that solid content is 30wt%.

(2) preparation of catalyst base：

By the carrier of the aforementioned cordierite for obtaining cylindrical honeycomb of the matrix coating slurry coated on 1.18kg, (Jiangsu is suitable Emerging Co., Ltd of non-metal chemical mechinery works produces, and size isPercent opening is 70%, and the hole density in section is The cross-sectional area in 200 holes/square inch, hole is 5625 μm², similarly hereinafter) on, then by the carrier after coating in 120 DEG C of dryings After 120min, 60min is roasted at 650 DEG C, is repeated above-mentioned coating, drying and calcining process, is obtained the catalyst base of 1.52kg.

(3) preparation of catalyst precarsor：

1.01kg tetra- is hydrated ammonium paramolybdate (NH₄)₆Mo₇O₂₄·4H₂O (Chinese medicines group is produced, molecular weight 1235.86, point Analyse pure) it is dissolved in 2L deionized waters and obtains ammonium molybdate aqueous solution.By the above-mentioned catalyst base prepared in ammonium molybdate aqueous solution Middle dipping 5min roasts 120min at 300 DEG C in 100 DEG C of dry 120min after taking-up, repeats above-mentioned dipping, drying and roasting Process obtains 1.76kg catalyst precarsors.

(4) reduction treatment：

By aforementioned catalytic agent precursor in 10 volume %CH₄/ 90 volume %H₂Under atmosphere and 300 DEG C of temperature, the pressure of 2MPa 4h is restored under power, obtains 1.69kg ordered structure desulphurization catalysts A1.

(5) composition of ordered structure desulphurization catalyst A1：

The ordered structure desulphurization catalyst A1 in terms of its dry weight, containing 70 weight % of cordierite, 16 weight % of zinc oxide, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 2

(1) preparation of matrix coating slurry：

The nano-zinc oxide powder (Beijing Chemical Plant, the butt 1.0kg containing zinc oxide) and 1L deionized waters of 1.01kg is mixed Close uniform, wet ball grinding (compound particles grain size d₉₀It is 8 μm), obtain slurries A；By titanium tetrachloride (Beijing chemical industry of 1.19kg Factory, analysis is pure, and 0.5kg is calculated as with titanium oxide) in the ammonia spirit of the 25 weight % of concentration that is slowly added into 0.76kg to solution PH value is more than 10, and is slowly stirred and oxidation titanium crystal is avoided to be precipitated, and obtains the titanium colloidal sol of water white transparency；By the nitric acid of 0.322kg Cerium (Beijing Chemical Plant, analysis is pure, and 0.17kg is calculated as with cerium oxide) is added in aforementioned titanium colloidal sol, and 25 are added dropwise after being uniformly mixed Weight % ammonia spirits form cerium titanium colloidal sol until pH value is more than 10, obtain slurries B；Aforementioned obtained slurries A and slurries B is mixed It closes, stirs the matrix coating slurries for preparing that solid content is 30 weight % for 20 minutes.

(2) preparation of catalyst base：

By on the carrier of the cordierite of cylindrical honeycomb of the matrix coating slurries of aforementioned preparation coated on 1.18kg, connect It by the carrier after coating after 100 DEG C of dry 150min, 240min is roasted at 500 DEG C, repeat above-mentioned coating, drying and roasting The step of, obtain the catalyst base of 1.33kg.

(3) preparation of catalyst precarsor：

By the Nickelous nitrate hexahydrate of cobalt nitrate solution and 3.65kg, (molar ratio of Co and Ni are 1：And the deionized water of 2L 5) It is mixed to form in Co-Ni aqueous solutions, the above-mentioned catalyst base prepared is impregnated into 2min in Co-Ni aqueous solutions, after taking-up In 80 DEG C of dry 120min, 60min is roasted at 350 DEG C, is repeated above-mentioned dipping, drying and calcination steps, is obtained urging for 1.51kg Agent precursor；

(4) reduction treatment：

By aforementioned catalytic agent precursor in 10 volume %CH₄/ 90 volume %H₂Under atmosphere and 425 DEG C of temperature, the pressure of 1MPa Reductase 12 h under power obtains the ordered structure desulphurization catalyst A2 of 1.48kg.

(5) composition of ordered structure desulphurization catalyst A2：

In terms of the dry weight of the ordered structure desulphurization catalyst A2, wherein containing 80 weight % of cordierite, 6 weight of zinc oxide Measure %, 3 weight % of titanium dioxide (non-al binder), 1 weight % of cerium oxide (rare earth oxide), 1.67 weight % of cobalt carbide and Be carbonized 8.33 weight % of nickel.

Embodiment 3

(1) preparation of matrix coating slurry：

The nano-zinc oxide powder (Beijing Chemical Plant, the butt 1kg containing zinc oxide) and 1L deionized waters of 1.01kg are mixed Uniformly, wet ball grinding (compound particles grain size d₉₀It is 8 μm), obtain slurries A；By the zirconium chloride of 0.63kg (Beijing Chemical Plant, Analyze pure, the 0.33kg in terms of zirconium oxide) be to solution ph in the salpeter solution of the 15 weight % of concentration that is slowly added into 3.1kg 2, and be slowly stirred and crystal of zirconium oxide is avoided to be precipitated, obtain the zirconium colloidal sol of water white transparency；By lanthana (the traditional Chinese medicines collection of 0.11kg Group, analysis are pure) it is added in aforementioned zirconium colloidal sol, 25 weight % ammonia spirits are added dropwise after being uniformly mixed until pH value is more than 12 shapes At lanthanum zirconium colloidal sol, slurries B is obtained；Aforementioned obtained slurries A and slurries B are mixed, it is 30 weights to stir and prepare within 20 minutes solid content Measure the matrix coating slurries of %.

(2) preparation of catalyst base：

The matrix coating slurries of aforementioned preparation are coated on the carrier of the cordierite of the cylindrical honeycomb of 1.18kg, and After the dry 60min of 200 DEG C of carrier after coating, 120min is roasted at 700 DEG C, repeat the work of above-mentioned coating, drying and roasting Sequence obtains the catalyst base of 1.32kg.

(3) preparation of catalyst precarsor：

By 393.12g ammonium paratungstates, (Chinese medicines group chemical reagent Beijing Co., Ltd produces, molecular weight 1419.57, analysis It is pure) it is dissolved in 2L deionized waters and obtains ammonium paratungstate aqueous solution.The above-mentioned catalyst base prepared is water-soluble in ammonium paratungstate 5min is impregnated in liquid, and in 100 DEG C of dry 120min after taking-up, 120min is roasted at 300 DEG C, repeats above-mentioned dipping, drying and roasting Process is burnt, 1.40kg catalyst precarsors are obtained.

(4) reduction treatment：

By aforementioned catalytic agent precursor in 20 volume %CH₄/ 80 volume %H₂Under atmosphere and 425 DEG C of temperature, the pressure of 1MPa 3h is restored under power, obtains the ordered structure desulphurization catalyst A3 of 1.39kg.

(5) composition of ordered structure desulphurization catalyst A3：

In terms of the dry weight of the ordered structure desulphurization catalyst A3, wherein containing 85 weight % of cordierite, zinc oxide 6.94 Weight %, 2.3 weight % of zirconium oxide (non-al binder), 0.76 weight % of lanthana (rare earth oxide) and 5 weight of tungsten carbide Measure %.

Embodiment 4

(1) preparation of matrix coating slurry：With reference to embodiment 1, difference lies in using 1.01kg magnesia (Beijing Chemical Plant It produces, average grain diameter 500nm；Containing butt 1.0kg) replace the Zinc oxide powder to prepare matrix coating slurry；

(2) preparation of catalyst base：With reference to embodiment 1, difference lies in using the matrix painting prepared in abovementioned steps (1) Layer slurry replaces the matrix coating slurry prepared in 1 step of embodiment (1), obtains the catalyst base of 1.52kg；

(3) preparation of catalyst precarsor：With reference to embodiment 1, difference lies in using the catalysis obtained in abovementioned steps (2) Agent carrier replaces the catalyst base prepared in 1 step of embodiment (2), obtains the catalyst precarsor of 1.76kg；

(4) reduction treatment：With reference to embodiment 1, difference lies in using the catalyst precarsor generation obtained in abovementioned steps (3) For the catalyst precarsor prepared in 1 step of embodiment (3), the ordered structure desulphurization catalyst A4 of 1.69kg is obtained.

(5) composition of ordered structure desulphurization catalyst A4：

In terms of the dry weight of the ordered structure desulphurization catalyst A4, wherein containing 70 weight % of cordierite, 16 weight of magnesia Measure %, 3 weight % of zirconium oxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 5

(1) preparation of matrix coating slurry：With reference to embodiment 1, difference lies in using 1.08kg calcium oxide (Beijing chemical industry Factory produces, average grain diameter 200nm；Containing butt 1.0kg) replace the Zinc oxide powder to prepare matrix coating slurry；

(4) reduction treatment：With reference to embodiment 1, difference lies in using the catalyst precarsor generation obtained in abovementioned steps (3) For the catalyst precarsor prepared in 1 step of embodiment (3), the ordered structure desulphurization catalyst A5 of 1.69kg is obtained.

(5) composition of ordered structure desulphurization catalyst A5：

In terms of the dry weight of the ordered structure desulphurization catalyst A5, wherein containing 70 weight % of cordierite, 16 weight of calcium oxide Measure %, 3 weight % of zirconium oxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 6

(1) preparation of matrix coating slurry：With embodiment 1；

(2) preparation of catalyst base：With embodiment 1；

(3) preparation of catalyst precarsor：

1.08kg ammonium metavanadates (Chinese medicines group is produced, molecular weight 116.98, and analysis is pure) are dissolved in 2L deionized waters and are obtained To ammonium metavanadate aqueous solution.The above-mentioned catalyst base prepared is impregnated into 5min in ammonium metavanadate aqueous solution, after taking-up 95 DEG C of dry 120min roast 120min at 320 DEG C, and repeated impregnations, drying and calcining process obtain 1.76kg catalyst precarsors.

(4) reduction treatment：

By aforementioned catalytic agent precursor in 20 volume %CH₄/ 80 volume %H₂Under atmosphere and 425 DEG C of temperature, the pressure of 1MPa 3h is restored under power, obtains the ordered structure desulphurization catalyst A6 of 1.69kg.

(5) composition of ordered structure desulphurization catalyst A6：

In terms of the dry weight of the ordered structure desulphurization catalyst A6, wherein containing 70 weight % of cordierite, 16 weight of calcium oxide Measure %, 3 weight % of zirconium oxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and vanadium carbide.

Embodiment 7

(1) preparation (increasing dispersant in host material) of matrix coating slurry：With reference to embodiment 1, difference lies in inciting somebody to action While slurries A and slurries B (butt of zinc oxide is 1.0kg) are mixed, 1000mL Aqueous Solutions of Polyethylene Glycol is added (based on every The water dissolution addition 2g polyethylene glycol of 100mL configures, and wherein polyethylene glycol is produced for Aladdin Reagent Company, and the degree of polymerization is 1700, analysis is pure, similarly hereinafter) mixing, stir the matrix coating slurries for preparing that solid content is 30 weight % for 20 minutes.

(3) preparation of catalyst precarsor：With reference to embodiment 1, difference lies in using the catalyst prepared in abovementioned steps (2) Carrier replaces the catalyst base prepared in 1 step of embodiment (2), obtains the catalyst precarsor of 1.76kg；

(4) reduction treatment：With reference to embodiment 1, difference lies in using the catalyst precarsor replacement prepared in abovementioned steps (3) The catalyst precarsor prepared in 1 step of embodiment (3), obtains the ordered structure desulphurization catalyst A7 of 1.69kg.

(5) composition of ordered structure desulphurization catalyst A7：

The ordered structure desulphurization catalyst A7 in terms of its dry weight, containing 70 weight % of cordierite, 16 weight % of zinc oxide, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 8

(1) preparation (increasing dispersant in host material) of matrix coating slurry：With reference to embodiment 1, difference lies in inciting somebody to action While slurries A and slurries B (butt of zinc oxide is 1.0kg) are mixed, 1000mL Aqueous Solutions of Polyethylene Glycol is added (based on every The water dissolution addition 20g polyethylene glycol of 100mL configures, and wherein polyethylene glycol is produced for Aladdin Reagent Company, the degree of polymerization It is 1700, analysis is pure, similarly hereinafter) mixing, stir the matrix coating slurries for preparing that solid content is 30 weight % for 20 minutes.

(4) reduction treatment：With reference to embodiment 1, difference lies in using the catalyst precarsor replacement prepared in abovementioned steps (3) The catalyst precarsor prepared in 1 step of embodiment (2), obtains the ordered structure desulphurization catalyst A8 of 1.69kg.

(5) composition of ordered structure desulphurization catalyst A8：

The ordered structure desulphurization catalyst A8 in terms of its dry weight, containing 70 weight % of cordierite, 16 weight % of zinc oxide, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 9

(1) prepared by matrix coating slurry：With reference to embodiment 1, difference lies in the preparation method of slurry B includes：It will 0.356kg zirconium chlorides (Beijing Chemical Plant analyzes pure, the 0.188kg in terms of zirconium oxide) are dissolved in 800mL deionized waters, will 0.166kg lanthanum nitrate hexahydrates (Chinese medicines group analyzes pure, the 0.062kg in terms of lanthana) are dissolved in 200mL deionized waters, will Two kinds of aqueous solutions mix and the ammonium hydroxide of a concentration of 30 weight % are added under agitation to the pH=11 (mixing temperatures 30 of solution DEG C, incorporation time 4h), filter cake is obtained after filtering carries out the extra metal ion of washing removing.By obtained filter cake at 120 DEG C After dry 120min, 180min is roasted at 550 DEG C, obtains dried object；The dried object is added to the water mashing, then uses ball mill (ball milling liquid is distilled water, compound particles d to wet-milling 5h₉₀It is 8 μm) prepare slurries B.Referring next to embodiment 1, by aforementioned preparation Slurries B replace slurries B and the slurries A in 1 step of embodiment (1) to be mixed to get matrix coating slurry；

(4) reduction treatment：With reference to embodiment 1, difference lies in using the catalyst precarsor replacement prepared in abovementioned steps (3) The catalyst precarsor prepared in 1 step of embodiment (2), obtains the ordered structure desulphurization catalyst A9 of 1.69kg.

(5) composition of ordered structure desulphurization catalyst A9：

The ordered structure desulphurization catalyst A9 in terms of its dry weight, containing 70 weight % of cordierite, 16 weight % of zinc oxide, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Embodiment 10

(1) preparation of host material：With reference to step (1) in embodiment 1, difference lies in by prepared matrix coating slurry After 120 DEG C of dry 120min, 180min is roasted at 550 DEG C, obtains host material；

(2) preparation of active component：

1.01g tetra- is hydrated ammonium paramolybdate (NH₄)₆Mo₇O₂₄·4H₂O (produce, molecular weight 1235.86, analysis by Chinese medicines group It is pure) it is dissolved in 2L deionized waters and obtains ammonium molybdate aqueous solution.The above-mentioned host material of 1.01kg is impregnated into ammonium molybdate aqueous solution Middle 5min roasts 120min at 300 DEG C in 100 DEG C of dry 120min after taking-up, repeats above-mentioned dipping, drying and calcining process, Obtain the active component of 1.72kg；

(3) preparation of catalyst precarsor：

Foregoing active component ball mill wet-milling 5h is prepared into the slurry that solid content is 30 weight %, is coated in cylinder On the carrier of cellular cordierite, after 120 DEG C of dry 120min, 180min is roasted at 550 DEG C, repetitive coatings twice, make The weight of active component coating reaches target weight and (accounts for ordered structure desulphurization catalyst (the following catalyst finally prepared A11) the 30wt% of total weight), obtain the catalyst precarsor of 1.76kg.

(4) reduction treatment：

By aforementioned catalytic agent precursor in 10 volume %CH₄/ 90 volume %H₂Under atmosphere and 300 DEG C of temperature, the pressure of 2MPa 4h is restored under power, obtains the ordered structure desulphurization catalyst A10 of 1.69kg.

(5) composition of ordered structure desulphurization catalyst A10：

The ordered structure desulphurization catalyst A10 contains 70 weight % of cordierite, 16 weight of zinc oxide in terms of its dry weight Measure %, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and molybdenum carbide.

Comparative example 1

The comparative example is used for the regular texture desulphurization catalyst and preparation method thereof of the comparative illustration present invention.

(1) preparation of matrix coating slurry：With embodiment 1.

(2) preparation of catalyst base：With embodiment 1.

(3) preparation of catalyst precarsor：

1.01kg tetra- is hydrated ammonium paramolybdate (NH₄)₆Mo₇O24·4H₂O (Chinese medicines group is produced, molecular weight 1235.86, point Analyse pure) it is dissolved in 2L deionized waters and obtains ammonium molybdate aqueous solution.By the above-mentioned catalyst base prepared in ammonium molybdate aqueous solution Middle dipping 5min roasts 120min at 300 DEG C in 100 DEG C of dry 120min after taking-up, repeated impregnations process twice, in repetition Dipping, drying and calcining process are stated, the catalyst precarsor of 1.78kg is obtained.

(4) reduction treatment：

Aforementioned catalytic agent precursor is restored into 4h with the gas containing 96 volume % hydrogen under 300 DEG C of temperature, the pressure of 2MPa, Obtain the ordered structure desulphurization catalyst B of 1.69kg.

(5) composition of ordered structure desulphurization catalyst B：

The ordered structure desulphurization catalyst B in terms of its dry weight, containing 70 weight % of cordierite, 16 weight % of zinc oxide, 3 weight % of zirconium dioxide (non-al binder), 10 weight % of 1 weight % of lanthana (rare earth oxide) and metal molybdenum.

Application examples

To ordered structure the desulphurization catalyst A1-A10 and B prepared by 1-10 according to an embodiment of the invention and comparative example 1 HDS evaluation experiment is carried out using the micro- anti-experimental provision of fixed bed, specific method includes：The desulphurization catalyst of 16g is seated in interior Diameter is in the fixed bed reactors of 30mm.It is 400 DEG C in reaction temperature, reaction pressure is as hydrogen medium to use hydrogen The weight space velocity of 1.38MPa, hydrogen flowing quantity 6.3L/h, gasoline flow 80mL/h, raw material hydrocarbon ils are 4h^-1Sulfur-bearing hydrocarbon desulfurization Under reaction condition, the desulphurization reaction of hydrocarbon oil containing surphur (gasoline) is carried out, the gasoline composition is shown in Table 1.

Desulfurization performance is evaluated：

(1) gas-chromatography POINA methods are used to measure the composition of product gasoline, and by respective data record in table 2 and table 3 In；

(2) yield of product gasoline is calculated by weight method, and by respective data record in table 2 and table 3；

(3) GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and blend gasoline after reaction Motor octane number (MON) and research octane number (RON) (RON), and by respective data record in table 2 and table 3；

(4) total sulfur content measuring method (electricity in petroleum chemical industry standard SH/T 0253-1992 oils is used Amount method) measure product gasoline in sulfur content, and in table 2 and table 3 record product sulfur content in gasoline with the reaction time change Change.

Table 1

Project	Analyze data	Project	Analyze data
				Density (20 DEG C) (kg.m^-3)	727.3	Induction period (min)	922
Existent gum (mg/mL)	0.34	Boiling range (DEG C)
				Refraction index (20 DEG C)	1.4143	Initial boiling point	38.5
Sulfur content (ng./μ L)	960.48	5%	49.0
				Mercaptan sulfur content (ng/ μ L)	10.2	10%	55.5
Hydrogen sulfide content (ng/ μ L)	0	30%	74.7
				Octane number (RON/MON)	93.7/83.6	50%	97.2
Race forms volume (%)		70%	124.2
				Saturated hydrocarbons	44.0	90%	155.2
Alkene	41.2	95%	165.2
				Aromatic hydrocarbons	14.8	The end point of distillation	185.0
Isohydrocarbon	35.1
				Benzene	1.16

Table 2.

Table 3.

Note：

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

2, △ MON indicate the value added of the product gasoline MON compared with gasoline stocks；

3, △ RON indicate the value added of the product gasoline RON compared with gasoline stocks；

4, △ (RON+MON)/2 indicates the difference of product gasoline anti-knock index and feed gasoline anti-knock index.

It can be seen that from the result data of table 2 and table 3 and gasoline desulfurization place carried out using the catalyst B prepared by comparative example 1 After reason, sulfur content is less than 0.5ppm (chromatographic detectability) in initial reaction stage in gasoline products, with the progress in reaction time, product Middle sulfur content gradually rises, but by for 24 hours~96h reaction after, the sulfur content of gasoline products reaches 12.6ppm, has connect The close edge requirements (10ppm) of the sulfur content of gasoline products, need to carry out regeneration treatment to wherein catalyst.And the process In in generated gasoline products saturated hydrocarbon content be 62 weight %, isomery hydrocarbon content is 35 weight %, and benzene content is 0.83 weight Measure %, 0.36 unit of loss of octane number.

Gasoline is carried out as catalyst using ordered structure desulphurization catalyst A1~A10 prepared in Examples 1 to 10 After desulfurization process, in gasoline products sulfur content initial reaction stage be less than 0.5ppm (chromatographic detectability), with the reaction time into Row, sulfur content gradually rises in product, but by for 24 hours~96h reactions after, the sulfur content highest of gasoline products only has 7.1ppm；At the same time, it is (opposite within the scope of 51 weight % to 56 weight % to embezzle the content for closing hydrocarbon for obtained gasoline products Reduced in comparative example 1), the content of isohydrocarbon (increases) within the scope of 40 weight % to 48 weight % relative to comparative example 1, and benzene contains Amount (reduces) within the scope of 0.38 weight % to 0.57 weight % relative to comparative example 1；And obtained gasoline products octane Value increases at least 0.11 unit (being increased relative to comparative example 1).

In conclusion being had according to ordered structure desulphurization catalyst provided by the present invention preferably desulphurizing activated and active Stability.Moreover, compared with existing desulfurization technology, it, can using this ordered structure desulphurization catalyst provided by the present invention It reduces desulfurization oil product and embezzles the content for closing hydrocarbon and benzene, raising isomery hydrocarbon content and octane number (the i.e. octane number for improving desulfurization oil product Loss is substantially reduced).

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of ordered structure desulphurization catalyst, which includes ordered structure carrier and is distributed in the ordered structure carrier Inner surface and/or the active component coating of outer surface；On the basis of the total weight of the active component coating, the active component Coating contains the matrix of the transition metal carbide and 30~95 weight % of 5~70 weight %；Total weight with the matrix is Benchmark, the matrix contain the non-al binder of 5~35 weight %, 0.5~10 weight % rare earth oxides and 60~90 weights Measure the oxide selected from least one of IIA and Group IIB metal of %.

2. catalyst according to claim 1, wherein on the basis of the total weight of the ordered structure desulphurization catalyst, The content of the active component coating is 10~50 weight %, preferably 15~30 weight %；

Preferably, on the basis of the total weight of the active component coating, the active component coating contains 10~50 weight % Transition metal carbide and 50~90 weight % matrix, the preferably described active component coating contains the mistake of 20~50 weight % The matrix of metal carbides and 50~80 weight % is crossed, the more preferable active component coating contains the transition of 25~50 weight % The matrix of metal carbides and 50~75 weight %.

3. catalyst according to claim 1 or 2, wherein

The transition metal is selected from one or more of Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W；

The oxide selected from least one of IIA and Group IIB metal is selected from least one of magnesium, zinc and calcium metal Oxide；

The rare earth oxide is the oxide selected from least one of lanthanum, cerium and neodymium rare earth metal；

The non-al binder is selected from least one of zirconium dioxide, titanium dioxide and stannic oxide；

The ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open；It is preferred that the regular knot The hole density in the section of structure carrier is 40~800 holes/square inch, and the cross-sectional area in each hole is in the ordered structure carrier 400~1.8 × 10⁵μm²；It is preferred that the ordered structure carrier is selected from cordierite honeycomb carrier, mullite honeycomb substrate, diamond Honeycomb substrate, corundum honeycomb substrate, fused alumina zirconia honeycomb substrate, quartzy honeycomb substrate, nepheline honeycomb substrate, feldspar honeycomb substrate, At least one of cellular alumina carrier and metal alloy honeycomb substrate.

4. a kind of preparation method of ordered structure desulphurization catalyst, which is characterized in that the preparation method comprises the following steps：

S1, by the presoma of the oxide selected from least one of IIA and Group IIB metal, rare earth oxide presoma and non- Al binder presoma mixes, and prepares matrix coating slurries；

S2, the matrix coating slurries are coated on ordered structure carrier, drying is simultaneously roasted in the ordered structure carrier Inner surface and/or outer surface form matrix coating, obtain catalyst base；

S3, the catalyst base is in contact with transition metal precursor solution, dries and roast after contact in the base Transition metal oxide is formed on matter coating, obtains catalyst precarsor；

S4, by the catalyst precarsor in CH₄/H₂Reduction treatment is carried out under atmosphere, by the transition metal oxide also original shape At transition metal carbide, the ordered structure desulphurization catalyst is obtained.

5. according to the method described in claim 4, wherein, on the basis of the total weight of the ordered structure desulphurization catalyst, institute The total content for stating matrix coating and the transition metal carbide is 10~50 weight %, preferably 15~30 weight %；

Preferably, on the basis of the total content of the matrix coating and the transition metal carbide, the transition metal carbonization The content of object is 5~70 weight %, and the content of the matrix coating is 30~95 weight %；The more preferably described transition metal carbonization The content of object is 10~50 weight %, and the content of the matrix coating is 50~90 weight %, the particularly preferred active component Coating contains the matrix of the transition metal carbide and 50~80 weight % of 20~50 weight %, especially the particularly preferably transition The content of metal carbides is 25~50 weight %, and the content of the matrix coating is 50~75 weight %；

Preferably, in terms of its dry weight, the non-aluminum containing in terms of non-al binder 5~35 weight % bonds the matrix coating slurries Agent presoma, the rare earth oxide presoma of in terms of rare earth oxide 0.5~10 weight % and in terms of metal oxide 60~90 The presoma of the oxide selected from least one of IIA and Group IIB metal of weight %.

6. method according to claim 4 or 5, wherein further include adding dispersion in matrix coating slurries in the S1 The step of agent, the preferably described dispersant be the degree of polymerization in 500~2500 ranges, preferably the degree of polymerization is in 1000~2000 ranges Interior organic dispersing agent, the preferably described dispersant are one kind or several in polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene Kind；

Preferably, the weight ratio of the dispersant and the presoma of the oxide selected from least one of IIA and Group IIB metal More than 0 and it is less than or equal to 0.2, preferably 0.005~0.02：1.

7. method according to claim 4 or 5, wherein

Dry temperature is room temperature to 300 DEG C in the S2, preferably 100~200 DEG C, drying time in 0.5h or more, preferably For 1~10h；The temperature of roasting is 400~800 DEG C, and preferably 500~700 DEG C, the time of roasting is in 0.5h or more, preferably 1 ~10h；

Dry temperature is room temperature to 150 DEG C in the S3, and preferably 80~100 DEG C, drying time is in 1h or more, preferably 2 ~8h；The temperature of roasting is 200~600 DEG C, and preferably 200~350 DEG C, the time of roasting is in 1h or more, preferably 2~4h.

8. method according to claim 4 or 5, wherein the condition of reduction treatment includes in the S4：It is 250 in temperature ~550 DEG C, under the conditions of pressure is 0.2~5MPa, reduction treatment 0.5~6 hour；It is preferred that be 300~450 DEG C in temperature, pressure Under the conditions of 0.5~3.5MPa, reduction treatment 2~4 hours；

Preferably, CH in the step S4₄/H₂Atmosphere is on the basis of its total volume, the CH containing 5~25 volume %₄With 75~95 The H of volume %₂；Preferably comprise the CH of 10~20 volume %₄With the H of 80~90 volume %₂。

9. method according to claim 4 or 5, wherein

The rare earth oxide presoma middle rare earth is selected from least one of lanthanum, cerium and neodymium；

The non-al binder presoma is zirconium dioxide, titanium dioxide or stannic oxide, or can be obtained under the roasting condition To the substance of zirconium dioxide, titanium dioxide or stannic oxide；

Transition metal is one in Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W in the transition metal precursor solution Kind is several, and transition metal precursor is nitrate, chloride, oxalates, acetate or the ammonium salt of transition metal；

The ordered structure carrier is selected from the monolithic substrate of the parallel channels structure with both ends open, the preferably described regular knot The hole density in the section of structure carrier is 40~800 holes/square inch, and the cross-sectional area in each hole is in the ordered structure carrier 400~1.8 × 10⁵μm², the preferably described ordered structure carrier is selected from cordierite honeycomb carrier, mullite honeycomb substrate, diamond Honeycomb substrate, corundum honeycomb substrate, fused alumina zirconia honeycomb substrate, quartzy honeycomb substrate, nepheline honeycomb substrate, feldspar honeycomb substrate, At least one of cellular alumina carrier and metal alloy honeycomb substrate.

10. ordered structure desulphurization catalyst made from a kind of method by described in any one of claim 4 to 9.

11. a kind of method of sulfur-bearing hydrocarbon desulfurization, this method include：Sulfur-bearing hydrocarbon and hydrogen donor are contacted with catalyst；Wherein, described Catalyst is the ordered structure desulphurization catalyst described in any one of claims 1 to 3 and 10.