CN108404945B

CN108404945B - Desulfurization catalyst with regular structure, preparation method thereof and sulfur-containing hydrocarbon desulfurization method

Info

Publication number: CN108404945B
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: 2020-08-18
Anticipated expiration: 2037-02-10
Also published as: CN108404945A

Abstract

The invention discloses a desulfurization catalyst with a regular structure, a preparation method thereof and a desulfurization method for sulfur-containing hydrocarbon, wherein the catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; the matrix comprises 5-35 wt% of non-aluminum binder, 0.5-10 wt% of rare earth oxide and 60-90 wt% of at least one metal oxide selected from IIA and IIB based on the total weight of the matrix. The catalyst has better desulfurization activity and desulfurization stability, and can improve the octane number of desulfurized oil products.

Description

Desulfurization catalyst with regular structure, preparation method thereof and sulfur-containing hydrocarbon desulfurization method

Technical Field

The invention relates to the field of sulfur-containing hydrocarbon desulfurization, in particular to a desulfurization catalyst with a regular structure, a preparation method thereof and a sulfur-containing hydrocarbon desulfurization method.

Background

Sulfur in automotive fuels, after combustion, produces sulfur oxides. The material can inhibit the activity of a noble metal catalyst in an automobile exhaust converter, can cause irreversible poisoning, and can not realize the function of catalyzing and converting toxic gases in automobile exhaust, so that unburned non-methane hydrocarbon, nitrogen oxide and carbon monoxide are contained in the automobile exhaust. The emitted toxic gases are catalyzed by sunlight to easily form photochemical smog, and acid rain is caused. But also sulfur oxides themselves are one of the main causes of acid rain formation.

With the increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing the sulfur content in gasoline and diesel is considered to be one of the most important measures for improving air quality. Taking gasoline as an example, the european union specifies a sulfur content of less than 10 μ g/g in the euro V gasoline standard implemented in 2010. The current gasoline product standard GB 17930-2013 'automotive gasoline' in China requires that the sulfur content in the gasoline must be reduced to 10 mu g/g by 1 month and 1 day in 2018. But also the future gasoline quality standards will be more stringent.

The main method for desulfurization of fuel oil is hydrodesulfurization. However, as the fuel oil standard becomes stricter, the hydrogenation depth increases, and more severe reaction conditions such as higher reaction pressure and the like are required. In addition, for gasoline, since a large amount of olefins are contained, increasing the hydrogenation severity will lead to higher octane number loss, and therefore, some new desulfurization methods are continuously emerging, wherein the adsorption desulfurization is most concerned.

US7427581, US7182918, US6869522 and US6274533 disclose that the adsorbent is used for desulfurizing light sulfur-containing hydrocarbon under the hydrogen condition, and the adsorbent has the characteristics of high desulfurization depth, low hydrogen consumption, low octane number loss and the like, and can produce fuel oil with the sulfur content of below 30 mug/g. The adsorbent is prepared by using a mixture of zinc oxide, silica and alumina as a carrier, wherein the zinc oxide accounts for 10-90 wt%, the silica accounts for 5-85 wt%, and the alumina accounts for 5-30 wt%; the loaded active component is a reduced metal and can be at least one of cobalt, copper, manganese, tungsten, tin, nickel, iron, molybdenum, silver and vanadium. The adsorbent is used at 0.1-10.3 MPa, 37.7-537.7 ℃ and a weight hourly space velocity of 0.5-50 h^-1And under the condition of hydrogen, capturing sulfur in the oil product on the adsorbent, hydrogenating and combining with zinc oxide, and simultaneously, due to the same hydrogenation effect of the transition metal on olefin, the octane number of the gasoline product is reduced. In order to compensate octane number loss caused by olefin reduction, the prior art generally adopts a method of promoting aromatization reaction and increasing aromatic hydrocarbon content, but inevitably leads to increase of benzene content in gasolineAdding; furthermore, saturation of the sulfur bound to the zinc oxide leads to a reduction in the desulfurization activity, and sulfur must be removed by oxidative regeneration. In the frequent oxidation regeneration-reduction process, metals as active components can be aggregated, and the zinc oxide can be converted into zinc silicate and zinc aluminate in the regeneration process, so that the desulfurization activity of the adsorbent in the recycling process is reduced, the deactivation rate of the adsorbent is high, and the implementation effect of sulfur-containing hydrocarbon desulfurization is influenced.

It can be seen that, although deep desulfurization can be well achieved by adsorption desulfurization, the desulfurization activity and desulfurization stability still remain problems in practical applications. Therefore, there is a need to find new sorbents (also known as desulfurization catalysts) that overcome at least one of the above-mentioned drawbacks of the prior art.

Disclosure of Invention

The invention aims to provide a desulfurization catalyst with a regular structure, a preparation method thereof and a sulfur-containing hydrocarbon desulfurization method, so as to improve the desulfurization activity and the desulfurization stability of the catalyst and improve the octane number of a desulfurized oil product.

In order to achieve the above object, according to a first aspect of the present invention, there is provided a desulfurization catalyst of a structured structure comprising a structured carrier and an active component coating layer distributed on an inner surface and/or an outer surface of the structured carrier; the active component coating comprises 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; the matrix comprises 5-35 wt% of non-aluminum binder, 0.5-10 wt% of rare earth oxide and 60-90 wt% of at least one metal oxide selected from IIA and IIB based on the total weight of the matrix.

According to a second aspect of the present invention, there is provided a method for preparing a desulfurization catalyst with a regular structure, comprising the steps of: s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB, a rare earth oxide precursor and a non-aluminum binder precursor to prepare a matrix coating slurry; s2, coating the substrate coating slurry on a regular structure carrier, drying and roasting to form the regular structure on the gaugeForming a substrate coating on the inner surface and/or the outer surface of the whole structure carrier to obtain a catalyst carrier; s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the matrix coating to obtain a catalyst precursor; s4, adding the catalyst precursor into CH₄/H₂And carrying out reduction treatment in the atmosphere to reduce the transition metal oxide to form transition metal carbide, thereby obtaining the desulfurization catalyst with the regular structure.

According to a third aspect of the present invention, there is provided a desulfurization catalyst with a regular structure prepared by the preparation method of the present invention.

According to a fourth aspect of the present invention, there is provided a process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein the catalyst is the catalyst according to the invention.

By applying the desulfurization catalyst with the regular structure, the desulfurization activity and the desulfurization stability of the catalyst can be effectively improved, the content of benzene in a desulfurized oil product is reduced, the content of isomeric hydrocarbon is improved, and the octane number of the desulfurized oil product is improved; the desulfurization catalyst with the regular structure provided by the invention does not need frequent repeated regeneration, can be used for a long period, is not easy to lose and aggregate, improves the desulfurization stability, and reduces the unit consumption of the catalyst.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

In the present invention, the term "structured catalyst" is used to refer to a catalyst comprising a structured carrier and a coating of an active component distributed on the inner and/or outer surface of the carrier; the 'regular structure carrier' is a carrier with a regular structure; the regular structure reactor is a fixed bed reactor filled with a regular structure catalyst as a catalyst bed layer.

The invention provides a desulfurization catalyst with a regular structure, which comprises a regular structure carrier and an active component coating distributed on the inner surface (the surface of pores inside the carrier) and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; the matrix comprises 5-35 wt% of non-aluminum binder, 0.5-10 wt% of rare earth oxide and 60-90 wt% of at least one metal oxide selected from IIA and IIB based on the total weight of the matrix.

The desulfurization catalyst of a regular structure according to the present invention is not particularly limited as long as it contains a transition metal carbide and a matrix having a specific composition therein, and the amount of the active component coating layer distributed on the regular structure support by coating may be not particularly limited. Preferably, the content of the active component coating is 10-50 wt% based on the total weight of the regular structure catalyst; preferably, the content of the organic solvent is 15 to 30% by weight.

According to the desulfurization catalyst with a regular structure, the active component coating preferably contains 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; preferably, the active component coating contains 10-50 wt% of transition metal carbide and 50-90 wt% of matrix; more preferably, the active component coating layer contains 20 to 50 wt% of transition metal carbide and 50 to 80 wt% of matrix, and particularly preferably, the active component coating layer contains 25 to 50 wt% of transition metal carbide and 50 to 75 wt% of matrix.

According to the desulfurization catalyst with a regular structure of the present invention, preferably, the transition metal in the transition metal carbide is selected from Ti (corresponding carbide is mainly TiC), V (corresponding carbide is mainly VC), and Fe (corresponding carbide is mainly Fe)₃C) Co (the corresponding carbide is mainly Co)₂C) Ni (the corresponding carbide is mainly Ni)₂C) Zr (the corresponding carbide is mainly ZrC)Mn (the corresponding carbide is mainly Mn)₃C) Cu (the corresponding carbide is mainly Cu)₂C) Mo (the carbide corresponding to Mo is mainly₂C) And W (the corresponding carbide is mainly WC), and more preferably one or more selected from Co, Ni, Mo and W.

The structured desulfurization catalyst according to the present invention, wherein the oxide of at least one metal selected from the group consisting of group IIA and group IIB and the optional rare earth oxide are each a metal oxide having a sulfur storage property. Preferably, the oxide of at least one metal selected from the group consisting of group IIA and group IIB is an oxide of at least one metal selected from magnesium, zinc and calcium; preferably zinc oxide; preferably, the rare earth oxide is an oxide of lanthanum and/or cerium and/or neodymium, that is, the rare earth oxide is an oxide of one or more selected from lanthanum, cerium and neodymium.

The desulfurization catalyst with a regular structure according to the present invention, wherein the non-aluminum binder may not be particularly limited, preferably, the non-aluminum binder is at least one selected from the group consisting of zirconium dioxide, titanium dioxide and tin dioxide. The precursor of the non-aluminum binder is zirconium dioxide, titanium dioxide and stannic oxide, or can obtain the zirconium dioxide, the titanium dioxide and the stannic oxide under the roasting condition, for example, the precursor of the non-aluminum binder can be one or more selected from chloride, oxychloride or acetate.

The desulfurization catalyst with a regular structure according to the present invention, wherein the carrier with a regular structure can be used for a catalyst bed provided in a fixed bed reactor. The regular structure carrier can be a whole carrier block, a hollow pore channel structure is formed inside the regular structure carrier, a catalyst coating can be distributed on the inner wall of a pore channel, and the pore channel space can be used as a flowing space of fluid. Preferably, the structured support is selected from monolithic supports having a parallel cell structure with open ends. The regular structure carrier can be a honeycomb type regular carrier (honeycomb carrier for short) with honeycomb-shaped open pores on the cross section.

According to the desulfurization catalyst with a regular structure, the regular structure is preferably supportedThe hole density of the cross section of the body is 40-800 holes/square inch, preferably 100-400 holes/square inch, and the cross section area of each hole in the regular structure carrier is 400-1.8 × 10⁵μm²Preferably 1500 to 22500 μm²The aperture ratio of the carrier surface of the regular structure carrier is 20-80%, preferably 50-80%. The shape of the hole may be one of square, regular triangle, regular hexagon, circle, and wave.

According to the desulfurization catalyst with a regular structure of the present invention, preferably, the carrier with a regular structure may be at least one selected from the group consisting of cordierite honeycomb carrier, mullite honeycomb carrier, diamond honeycomb carrier, corundum honeycomb carrier, zirconia corundum honeycomb carrier, quartz honeycomb carrier, nepheline honeycomb carrier, feldspar honeycomb carrier, alumina honeycomb carrier and metal alloy honeycomb carrier.

Meanwhile, the invention also provides a preparation method of the desulfurization catalyst with the regular structure, which comprises the following steps: s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB, an optional rare earth oxide precursor and a non-aluminum binder precursor to prepare a matrix coating slurry; s2, coating the slurry of the matrix coating on a regular structure carrier, drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier; s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the substrate coating to obtain a catalyst precursor; s4, adding the catalyst precursor into CH₄/H₂And carrying out reduction treatment in the atmosphere to reduce the transition metal oxide to form transition metal carbide, thereby obtaining the desulfurization catalyst with the regular structure.

According to the preparation method of the present invention, preferably, the matrix coating slurry contains, on a dry weight basis (dry weight basis), 5 to 35 wt% of a non-aluminum binder precursor calculated as a non-aluminum binder, 0.5 to 10 wt% of a rare earth oxide precursor calculated as a rare earth oxide, and 60 to 90 wt% of a precursor of an oxide of at least one metal selected from groups IIA and IIB calculated as a metal oxide.

According to the preparation method of the invention, the matrix coating and the transition metal carbide formed on the regular structure carrier are collectively called as an active component coating. Preferably, the total content of the matrix coating layer and the transition metal carbide (i.e. the active component coating layer) is 10 to 50 wt%, preferably 15 to 30 wt%, based on the total weight of the structured desulfurization catalyst; and the content of the transition metal carbide is 5 to 70 wt% and the content of the matrix coating is 30 to 95 wt% based on the total content of the matrix coating and the transition metal carbide (i.e., the active component coating); preferably, the content of the transition metal carbide is 10-50 wt%, and the content of the matrix coating is 50-90 wt%; more preferably, the active component coating contains 20-50 wt% of transition metal carbide and 50-80 wt% of matrix, particularly preferably, the content of the transition metal carbide is 25-50 wt%, and the content of the matrix coating is 50-75 wt%.

According to the preparation method of the invention, no special requirement is required on the solid content of the substrate coating slurry prepared in S1, however, the difficulty of coating the slurry can be increased due to the fact that the solid content of the slurry is too high, and the adhesion amount of each coating can be reduced due to the fact that the solid content of the slurry is too low, so that the coating times are increased. Preferably, the solid content of the substrate coating slurry in the step S1 is 10 to 45 wt%, preferably 20 to 40 wt%.

According to the preparation method of the present invention, preferably, the S1 includes: s11, mixing and grinding a precursor of an oxide of at least one metal selected from IIA and IIB groups with deionized water to obtain slurry A; s12, mixing the rare earth oxide precursor and the non-aluminum binder precursor, and carrying out co-gluing or co-precipitation to prepare slurry B; and S13, mixing the slurry A and the slurry B to prepare the matrix coating slurry.

According to the production method of the present invention, it is preferable that the particle diameter d of the metal oxide in the slurry A obtained by grinding in S11₉₀0.5 to 10 μm; mixture in slurry B formulated in S12Has an average particle diameter of less than 100nm, preferably 40 to 80 nm.

According to the preparation method of the present invention, the step of mixing and co-gumming the rare earth oxide precursor and the non-aluminum binder precursor in S12 may refer to a common method known in the art, and may include, for example, the following steps: (1) according to the gelling condition of the selected non-aluminum binder precursor, the non-aluminum binder precursor is contacted with an acid solution or an alkali solution to react to form a first colloidal solution; for example, when the selected non-aluminum binder precursor is zirconium tetrachloride, mixing the zirconium tetrachloride with an acid solution, and stirring to obtain a first colloidal solution with the pH value of 0.5-6; for another example, when the non-aluminum binder precursor is titanium tetrachloride, zirconium tetrachloride is mixed with an alkaline solution and stirred to obtain a first colloidal solution having a pH greater than 10. (2) And then adding a rare earth oxide precursor into the first colloidal solution, and adding an alkali solution under the stirring condition until the pH is more than 10 (preferably, the mixing temperature is 10-40 ℃, and the mixing time is 0.5-12 h), so as to obtain a second colloidal solution. Preferably, the acid solution is one or more selected from nitric acid, hydrochloric acid, phosphoric acid and acetic acid, and the concentration of the acid solution is preferably 10-75 wt%; preferably, the alkali solution is one or more selected from ammonia water, sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is preferably 20-70 wt%.

According to the preparation method of the present invention, the step of mixing and co-precipitating the rare earth oxide precursor and the non-aluminum binder precursor in step S12 may refer to a common method known in the art, for example: adding a rare earth oxide precursor solution into a non-aluminum binder precursor solution, adding an alkali solution under the stirring condition until the pH value is 10-12 (preferably, the mixing temperature is 10-40 ℃, and the mixing time is 0.5-10 h), and filtering to obtain a filter cake, and washing to remove redundant metal ions. Preferably, the alkali solution is one or more selected from ammonia water, sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is preferably 20-70 wt%. In the case of preparing solution B by coprecipitation, after the coprecipitation treatment to form a filter cake, the method further includes a step of grinding (optionally drying and sintering) the filter cake, and the method and conditions for grinding are well known to those skilled in the art and will not be described herein again.

According to the preparation method of the present invention, it is preferable that the step of adding a dispersant to the base coating slurry is further included in S1, preferably S13, and the addition of the dispersant to the base coating slurry is advantageous for promoting the uniform stabilization of the slurry. In the invention, the dispersant is preferably an organic dispersant, in this case, generally, as the polymerization degree of the dispersant increases, the viscosity of a solution added with the dispersant also increases, which is beneficial to improving the firmness of the slurry after coating, but as the polymerization degree of the dispersant increases, the solubility of the dispersant in water gradually decreases, which is not beneficial to mixing of the dispersant; considering the viscosity of the slurry and the solubility of the dispersant comprehensively, the dispersant is preferably an organic dispersant with the polymerization degree of 500-2500, preferably 1000-2000; preferably, the organic dispersant is one or more selected from polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene.

According to the preparation method of the present invention, the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from group IIA and IIB is preferably greater than 0 and not greater than 0.2, more preferably 0.005 to 0.02: 1; controlling the amount of the dispersant within the range is beneficial to controlling the viscosity of the slurry and prolonging the settling time of the slurry. In view of the small amount of the dispersant, it is preferable in practice to first dissolve the dispersant in water to obtain a dispersant solution and then add the dispersant solution to the substrate coating slurry. In the dispersant solution, the dispersant is preferably used in an amount of 0.5 to 30g, preferably 1 to 20g, more preferably 2 to 10g, particularly preferably 2 to 5g, based on 100mL of water.

According to the preparation method of the present invention, the matrix coating slurry may be distributed on the inner surface and/or the outer surface of the structured support by various coating methods in the S2. The coating method may be a water coating method, a dipping method or a spraying method. The specific operation of coating can be carried out with reference to the method described in CN 1199733C. Preferably, the coating is carried out by a water coating method, namely, a method of coating the carrier by using a dispersion liquid (substrate coating slurry) obtained by beating the substrate coating material and water, wherein one end of the carrier is immersed in the slurry liquid in the coating process, and the other end of the carrier is subjected to vacuum so that the slurry liquid continuously passes through the pore channels of the carrier. The volume of the slurry passing through the carrier pore channel is 2-20 times of the volume of the carrier, the applied vacuum pressure is-0.1 MPa to-0.01 MPa, the coating temperature is 10-70 ℃, and the coating time is 0.1-300 seconds.

The method and conditions for drying and calcining the structured carrier coated with the matrix coating slurry in S2 according to the preparation method of the present invention are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in step S2, the drying temperature is between room temperature and 300 ℃, preferably between 100 and 200 ℃, and the drying time is more than 0.5h, preferably between 1 and 10 h. The roasting temperature is 400-800 ℃, and preferably 500-700 ℃; the roasting time is at least 0.5 hour, and preferably 1-10 hours.

According to the preparation method of the present invention, the transition metal precursor solution in S3 is a mixed solution formed by dissolving a transition metal precursor in a solvent, wherein there is no special requirement for the concentration of the transition metal precursor solution, as long as the transition metal precursor can be completely dissolved, and in actual operation, reasonable matching can be performed according to the solubility of the transition metal precursor. The solvent used therein is not particularly required in the present invention as long as it can dissolve the corresponding transition metal precursor and does not react with the prepared catalyst support. Solvents that may be used include, but are not limited to, one or more of deionized water, distilled water, and decationized water.

According to the production method of the present invention, the method of contacting the catalyst support with the transition metal precursor solution in the step S3 is not particularly required, and any method suitable for contacting a solid with a liquid may be employed. Such as dipping, spraying, etc. In the present invention, the catalyst support is preferably immersed in a transition metal precursor solution, and the immersion conditions are not particularly limited, and the conventional immersion may be carried out at normal temperature and normal pressure.

According to the preparation method of the present invention, preferably, the transition metal in the transition metal precursor solution is one or more selected from Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W, and preferably one or more selected from Co, Ni, Mo and W. The transition metal precursor is a soluble compound capable of obtaining a transition metal oxide under a roasting condition, and preferably, the transition metal precursor is soluble salts of a transition metal such as nitrate, chloride, oxalate, acetate, ammonium salt and the like

The method and conditions for drying and calcining the structured carrier coated with the matrix coating slurry in S3 according to the preparation method of the present invention are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in step S3, the drying temperature is between room temperature and 150 ℃, preferably between 80 and 100 ℃, and the drying time is more than 1 hour, preferably between 2 and 8 hours; the roasting temperature is 200-600 ℃, preferably 200-350 ℃, and the roasting time is more than 1 hour, preferably 2-4 hours.

Preferably, the catalyst precursor obtained in step S3 comprises a regular structure carrier and an active component coating precursor, wherein the active component coating precursor comprises 5.8 to 77.1 wt% of transition metal oxide and 23.9 to 94.2 wt% of matrix, based on the total weight of the catalyst precursor; preferably, the reactive species coating precursor comprises 11.6 to 59.1 wt% of a transition metal oxide and 40.9 to 89.4 wt% of a matrix; preferably, the reactive species coating precursor comprises 22.8 to 59.1 wt% of a transition metal oxide and 40.9 to 77.2 wt% of a matrix; preferably, the reactive species coating precursor comprises 28.3 to 59.1 wt.% transition metal oxide and 40.9 to 72.7 wt.% matrix.

According to the preparation method of the invention, the catalyst precursor is placed in CH in S4₄/H₂Reducing the calcined transition metal oxide to obtain transition metal carbide. The reduction treatment may be carried out immediately after the preparation of the catalyst precursor, or may be carried out before the catalyst is used (i.e., before it is used for desulfurization adsorption). Preferably, the CH₄/H₂Atmosphere with CH₄/H₂The atmosphere contains 5-25 vol% of CH based on 100% of the total volume₄And 75 to 95 vol% of H₂(ii) a Preferably 10 to 20 vol% of CH₄And 80 to 90 vol% of H₂In CH₄/H₂The conditions for reduction under the atmosphere include: the catalyst precursor is placed in CH₄/H₂The conditions for the reduction treatment under the atmosphere include: reducing for 0.5-6 hours at the temperature of 250-550 ℃ and under the pressure of 0.2-5 MPa; preferably, the reduction treatment is carried out for 2 to 4 hours at a temperature of 300 to 450 ℃ and a pressure of 0.5 to 3.5 MPa.

According to the preparation method, the carbide mainly comprises TiC when the transition metal is Ti as can be known by a chemical element analysis method and an X-ray diffraction measurement method; when the transition metal is V, the carbide formed is mainly VC; when the transition metal is Fe, the carbide formed is mainly Fe₃C; when the transition metal is Co, the carbide formed is mainly Co₂C; when the transition metal is Ni, the carbide formed is mainly Ni₂C; when the transition metal is Zr, the carbide mainly comprises ZrC; when the transition metal is Mn, the carbide formed is mainly Mn₃C; when the transition metal is Cu, the carbide formed is mainly Cu₂C; when the transition metal is Mo, the carbide formed is mainly Mo₂C; when the transition metal is W, the carbide formed is mainly WC.

The preparation process according to the invention, in which the carriers of structured structure used have been described in the foregoing, is described in detail with reference to the foregoing description.

The preparation method according to the present invention, wherein the precursor of the oxide of at least one metal selected from groups IIA and IIB is a substance capable of obtaining an oxide of at least one metal selected from groups IIA and IIB under the calcination condition, for example, one or more of nitrate, acetate, carbonate, sulfate, oxalate, chloride and oxide of at least one metal selected from groups IIA and IIB. Wherein the oxide of at least one metal selected from the group consisting of group IIA and group IIB is an oxide of at least one metal selected from the group consisting of magnesium, zinc and calcium, and more preferably zinc oxide.

The preparation method according to the present invention, wherein the rare earth in the rare earth oxide precursor is at least one selected from lanthanum, cerium and neodymium; the precursor of the rare earth oxide is rare earth oxide or a substance capable of obtaining the rare earth oxide under the roasting condition, such as one or more of nitrate, acetate, carbonate, sulfate, oxalate, chloride and oxide of rare earth.

The preparation method according to the present invention, wherein the non-aluminum binder in the non-aluminum binder precursor is at least one selected from zirconium dioxide, titanium dioxide and tin dioxide, and the non-aluminum binder precursor is zirconium dioxide, titanium dioxide or tin dioxide, or a substance capable of obtaining zirconium dioxide, titanium dioxide or tin dioxide under the baking condition, such as one or more of chloride, oxychloride, acetate and oxide. Specifically, the zirconia binder may be at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconia, and amorphous zirconia; the tin dioxide binder can be at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide; the precursor of titanium dioxide may be a substance that is converted into anatase titanium dioxide under the condition of the first firing, and the titanium dioxide binder may be at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrous titanium oxide, and anatase titanium dioxide. Wherein the anatase titanium dioxide is still capable of producing anatase titanium dioxide after hydrolysis and first calcination.

Furthermore, according to the desulfurization catalyst with a regular structure of the present invention, it can be obtained by: s1, mixing and pulping the components of the matrix with water, drying and roasting the pulp to obtain the matrix (preferably, the matrix coating pulp is prepared according to the method in S11-S13, and then the matrix coating pulp is dried and roasted to obtain the matrix) (ii) a S2, impregnating the substrate with a solution or suspension containing a transition metal compound, introducing the transition metal compound into the substrate, drying, calcining, and dissolving in CH₄/H₂Carrying out reduction treatment in the atmosphere to form transition metal carbide to obtain an active component; s3, grinding the obtained active component and a water-containing solvent into slurry to obtain active component coating slurry, wherein the active component coating slurry contains transition metal carbide; s4, coating the regular structure carrier with the active component slurry by a coating method, drying and roasting to obtain the desulfurization catalyst with the regular structure. The raw materials, raw material components and process methods involved in the preparation method can all refer to the related description in the preparation method of the desulfurization catalyst with the regular structure.

In addition, the invention also provides a desulfurization catalyst with a regular structure prepared by the preparation method. The catalyst comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; the matrix comprises 5-35 wt% of non-aluminum binder, 0.5-10 wt% of rare earth oxide and 60-90 wt% of at least one metal oxide selected from IIA and IIB based on the total weight of the matrix. The desulfurization catalyst with a regular structure prepared by the preparation method has the same technical characteristics as the desulfurization catalyst with a regular structure claimed in the invention, and the specific content refers to the previous description of the desulfurization catalyst with a regular structure.

Also provided in the present invention is a process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein, the catalyst is the desulfurization catalyst with the regular structure. Preferably, the structured desulfurization catalyst is present in the form of a catalyst bed.

In the desulfurization method for sulfur-containing hydrocarbon provided by the invention, the desulfurization catalyst with a regular structure can be used in a desulfurization reactor for sulfur-containing hydrocarbon as a fixed catalyst bed layer, and flowing sulfur-containing hydrocarbon and hydrogen donor can flow through the catalyst bed layer with the regular structure, namely can flow through the pore channels in the carrier with the regular structure and react with the active component coating distributed on the wall of the pore channel under the desulfurization reaction condition for sulfur-containing hydrocarbon. The sulfur-containing hydrocarbon desulfurization reactor may be a conventional reactor, and may be, for example, a fixed bed reactor in which the desulfurization catalyst of the regular structure of the present invention is packed when a fixed bed reactor is used as the reactor.

In the method for desulfurizing the sulfur-containing hydrocarbon, the desulfurization catalyst with the regular structure containing the transition metal carbide only needs to be operated under the condition of the sulfur-containing hydrocarbon desulfurization reaction. The desulfurization catalyst with the regular structure can be regenerated at intervals after the desulfurization effect of the sulfur-containing hydrocarbon does not meet the requirement; and active metal can be aggregated without repeatedly undergoing oxidation regeneration-reduction, which is beneficial to improving the desulfurization activity of the catalyst and the stability of the desulfurization process of the sulfur-containing hydrocarbon.

According to the method for desulfurizing sulfur-containing hydrocarbon of the present invention, the reaction conditions for desulfurizing sulfur-containing hydrocarbon can adopt the reaction conditions for desulfurizing sulfur-containing hydrocarbon conventionally used in the field, and can also combine the use conditions of the desulfurization catalyst with a regular structure, and preferably, the reaction conditions for desulfurizing sulfur-containing hydrocarbon can include: the reaction temperature is 200-450 ℃, the reaction pressure is 0.5-5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 0.1-100 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01 to 1000. The preferable reaction temperature is 350-400 ℃, the reaction pressure is 1-3.5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 1-10 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500. The reaction conditions can be more favorable for the desulfurization reaction of the sulfur-containing hydrocarbon, and the occurrence of adverse side reactions is reduced.

In the present invention, the sulfur-containing hydrocarbon feed weight hourly space velocity refers to the weight of sulfur-containing hydrocarbon feed per hour to the loading weight of the active component coating in the structured desulfurization catalyst.

According to the present invention, the sulfur-containing hydrocarbon may be selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil, preferably gasoline and/or diesel oil. The above gasoline, kerosene, diesel oil and gas oil fractions are full fractions thereof and/or partially narrow fractions thereof. The sulfur content of the sulfur-containing hydrocarbon is above 50 micrograms/gram, preferably above 100 micrograms/gram. For example, the sulfur content of the sulfur-containing hydrocarbon can be 100 to 1500 micrograms/gram.

According to the present invention, the hydrogen donor is one or a mixture of two or more selected from hydrogen gas, a hydrogen-containing gas, and a hydrogen donor. The hydrogen refers to hydrogen with various purities, and the hydrogen-containing gas is preferably one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas. The volume content of hydrogen in the hydrogen-containing gas is more than 30 volume percent, and the hydrogen donor is selected from at least one of tetrahydronaphthalene, decahydronaphthalene and indane.

In the present invention, the pressures involved are all expressed as gauge pressures.

The desulfurization catalyst with a regular structure and the preparation method thereof and the desulfurization method of sulfur-containing hydrocarbon according to the present invention will be described in detail by way of examples.

The sulfur content was measured in the following examples and comparative examples by off-line chromatographic analysis using a GC6890-SCD instrument from the company agilent. Motor Octane Number (MON) and Research Octane Number (RON) of the reaction raw material catalytically cracked gasoline and the product gasoline after the desulfurization catalyst is stabilized were measured by GB/T503-1995 and GB/T5487-1995.

In the following examples and comparative examples, the method for coating the substrate slurry on the regular structure carrier is a water coating method, and the specific process method comprises the following steps: in each coating process, one end of the regular structure carrier is immersed in the matrix coating slurry, and the other end of the regular structure carrier is vacuumized to enable the slurry to continuously pass through the pore channel of the carrier; wherein the volume of the slurry passing through the carrier pore channel is 2.5 times of the volume of the carrier, the applied vacuum pressure is-0.03 MPa (MPa), the coating temperature is 35 ℃, and the coating time is 60-120 seconds.

Example 1

This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.

(1) Preparation of matrix coating slurry:

1.01kg of nano zinc oxide powder(Beijing chemical plant, containing zinc oxide dry basis 1.0kg) and 1L deionized water, and wet ball milling to obtain slurry A (particle diameter d of mixture particles)₉₀8 μm); slowly adding 0.356kg of zirconium tetrachloride (0.188 kg of zirconium oxide in Beijing chemical plant, analytically pure) into 3.1kg of 10 wt% nitric acid solution until the pH value of the solution is 2, and slowly stirring to avoid the precipitation of zirconium oxide crystals to obtain colorless and transparent zirconium sol; adding 0.0625kg of lanthanum oxide (0.062 kg of dry basis, analytically pure, by national pharmaceutical group) into the zirconium sol, stirring and mixing uniformly, and then dropwise adding 25 wt% of ammonia water solution until the pH value is 12 to form lanthanum zirconium sol, thereby obtaining slurry B; the slurry A and the slurry B obtained above were mixed and stirred for 20 minutes to prepare a substrate coating slurry having a solid content of 30% by weight.

(2) Preparation of catalyst carrier:

the substrate coating slurry thus obtained was applied to 1.18kg of a cylindrical honeycomb cordierite carrier (available from Jiangsu Yixing non-metallic chemical mechanical works Co., Ltd., size: 1.18 kg)

The open porosity was 70%, the cell density of the cross section was 200 cells/square inch, and the cross sectional area of the cells was 5625 μm²The same applies hereinafter), followed by drying the coated carrier at 120 ℃ for 120min and then calcining at 650 ℃ for 60min, and repeating the above coating, drying and calcining processes to obtain 1.52kg of a catalyst support.

(3) Preparation of the catalyst precursor:

1.01kg of ammonium paramolybdate tetrahydrate (NH)₄)₆Mo₇O₂₄·4H₂O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. The prepared catalyst carrier is immersed in an ammonium molybdate aqueous solution for 5min, taken out and dried at 100 ℃ for 120min, calcined at 300 ℃ for 120min, and the immersion, drying and calcination procedures are repeated to obtain 1.76kg of catalyst precursor.

(4) Reduction treatment:

the catalyst precursor was added at 10 vol% CH₄90% by volume of H₂Under the atmosphereAnd reducing for 4h at the temperature of 300 ℃ and under the pressure of 2MPa to obtain 1.69kg of desulfurization catalyst A1 with a regular structure.

(5) Composition of desulfurization catalyst a1 with regular structure:

the desulfurization catalyst of a regular structure a1 contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of molybdenum carbide.

Example 2

(1) Preparation of matrix coating slurry:

1.01kg of nano zinc oxide powder (Beijing chemical plant, containing 1.0kg of zinc oxide dry basis) and 1L of deionized water were mixed uniformly and ball-milled by a wet method (particle size d of the mixture₉₀8 μm) to give slurry a; slowly adding 1.19kg of titanium tetrachloride (0.5 kg of analytically pure titanium oxide in Beijing chemical plant) into 0.76kg of 25 wt% ammonia water solution until the pH value of the solution is more than 10, and slowly stirring to avoid the precipitation of titanium oxide crystals to obtain colorless and transparent titanium sol; adding 0.322kg of cerium nitrate (0.17 kg calculated by cerium oxide in Beijing chemical plant, analytically pure) into the titanium sol, uniformly stirring and mixing, and then dropwise adding 25 wt% ammonia water solution until the pH value is more than 10 to form cerium-titanium sol, thereby obtaining slurry B; the slurry A and the slurry B obtained above were mixed and stirred for 20 minutes to prepare a substrate coating slurry having a solid content of 30% by weight.

(2) Preparation of catalyst carrier:

the substrate coating slurry prepared as described above was coated on 1.18kg of a cylindrical honeycomb-shaped cordierite carrier, and then the coated carrier was dried at 100 ℃ for 150min and then calcined at 500 ℃ for 240min, and the above coating, drying and calcining steps were repeated to obtain 1.33kg of a catalyst support.

(3) Preparation of the catalyst precursor:

mixing a cobalt nitrate solution, 3.65kg of nickel nitrate hexahydrate (the molar ratio of Co to Ni is 1: 5) and 2L of deionized water to form a Co-Ni aqueous solution, soaking the prepared catalyst support in the Co-Ni aqueous solution for 2min, taking out, drying at 80 ℃ for 120min, roasting at 350 ℃ for 60min, and repeating the steps of soaking, drying and roasting to obtain 1.51kg of a catalyst precursor;

(4) reduction treatment:

the catalyst precursor was added at 10 vol% CH₄90% by volume of H₂And reducing for 2h at 425 ℃ and 1MPa in the atmosphere to obtain 1.48kg of desulfurization catalyst A2 with a regular structure.

(5) Composition of desulfurization catalyst a2 with regular structure:

the desulfurization catalyst a2 having a regular structure contained 80 wt% of cordierite, 6 wt% of zinc oxide, 3 wt% of titania (non-aluminum binder), 1 wt% of cerium oxide (rare earth oxide), 1.67 wt% of cobalt carbide, and 8.33 wt% of nickel carbide, based on the dry weight of the catalyst.

Example 3

(1) Preparation of matrix coating slurry:

1.01kg of nano zinc oxide powder (Beijing chemical plant, containing 1kg of zinc oxide dry basis) and 1L of deionized water were mixed uniformly and ball-milled by a wet method (particle size d of the mixture₉₀8 μm) to give slurry a; slowly adding 0.63kg of zirconium tetrachloride (0.33 kg of zirconium oxide in Beijing chemical plant, analytically pure) into 3.1kg of nitric acid solution with the concentration of 15 wt% until the pH value of the solution is 2, and slowly stirring to avoid the precipitation of zirconium oxide crystals to obtain colorless and transparent zirconium sol; adding 0.11kg of lanthanum oxide (national drug group, analytically pure) into the zirconium sol, stirring and mixing uniformly, and then dropwise adding 25 wt% of ammonia water solution until the pH value is more than 12 to form lanthanum-zirconium sol, thereby obtaining slurry B; the slurry A and the slurry B obtained above were mixed and stirred for 20 minutes to prepare a substrate coating slurry having a solid content of 30% by weight.

(2) Preparation of catalyst carrier:

the substrate coating slurry prepared as described above was coated on a 1.18kg cylindrical honeycomb cordierite carrier, and the coated carrier was dried at 200 ℃ for 60min and then calcined at 700 ℃ for 120min, and the above coating, drying and calcining processes were repeated to obtain 1.32kg of a catalyst carrier.

(3) Preparation of the catalyst precursor:

393.12g of ammonium paratungstate (product of national chemical group, Beijing Co., Ltd., molecular weight 1419.57, analytical purity) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium paratungstate. The prepared catalyst carrier is immersed in an ammonium paratungstate aqueous solution for 5min, taken out, dried at 100 ℃ for 120min, roasted at 300 ℃ for 120min, and the immersion, drying and roasting processes are repeated to obtain 1.40kg of catalyst precursor.

(4) Reduction treatment:

the catalyst precursor was added at 20% by volume CH₄80% by volume H₂The reaction mixture was reduced at 425 ℃ and 1MPa for 3 hours under an atmosphere to obtain 1.39kg of desulfurization catalyst A3 with a regular structure.

(5) Composition of desulfurization catalyst a3 with regular structure:

the desulfurization catalyst a3 having a regular structure contained 85 wt% of cordierite, 6.94 wt% of zinc oxide, 2.3 wt% of zirconia (non-aluminum binder), 0.76 wt% of lanthanum oxide (rare earth oxide), and 5 wt% of tungsten carbide, based on the dry weight of the catalyst.

Example 4

(1) Preparation of matrix coating slurry: referring to example 1, except that 1.01kg of magnesium oxide (manufactured by Beijing chemical plant, average particle diameter 500 nm; containing 1.0kg of dry basis) was used in place of the zinc oxide powder to prepare a substrate coating slurry;

(2) preparation of catalyst carrier: referring to example 1, except for using the matrix coating slurry prepared in the foregoing step (1) instead of the matrix coating slurry prepared in step (1) of example 1, 1.52kg of a catalyst support was obtained;

(3) preparation of the catalyst precursor: referring to example 1, except that the catalyst support obtained in the foregoing step (2) was used in place of the catalyst support prepared in the step (2) of example 1, 1.76kg of a catalyst precursor was obtained;

(4) reduction treatment: referring to example 1, except for using the catalyst precursor obtained in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A4 of a regular structure was obtained.

(5) Composition of desulfurization catalyst a4 with regular structure:

the desulfurization catalyst A4 having a regular structure contained cordierite 70 wt%, magnesia 16 wt%, zirconia (non-aluminum binder) 3 wt%, lanthanum oxide (rare earth oxide) 1 wt%, and molybdenum carbide 10 wt% based on the dry weight of the catalyst.

Example 5

(1) Preparation of matrix coating slurry: referring to example 1, except that 1.08kg of calcium oxide (available from Beijing chemical plant, average particle diameter 200 nm; containing 1.0kg of dry basis) was used in place of the zinc oxide powder to prepare a substrate coating slurry;

(4) reduction treatment: referring to example 1, except for using the catalyst precursor obtained in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A5 of a regular structure was obtained.

(5) Composition of desulfurization catalyst a5 with regular structure:

the desulfurization catalyst A5 having a regular structure contained cordierite 70 wt%, calcium oxide 16 wt%, zirconia (non-aluminum binder) 3 wt%, lanthanum oxide (rare earth oxide) 1 wt%, and molybdenum carbide 10 wt% based on the dry weight of the catalyst.

Example 6

(1) Preparation of matrix coating slurry: the same as example 1;

(2) preparation of catalyst carrier: the same as example 1;

(3) preparation of the catalyst precursor:

1.08kg of ammonium metavanadate (manufactured by national drug group, molecular weight 116.98, analytical purity) was dissolved in 2L of deionized water to obtain an ammonium metavanadate aqueous solution. Soaking the prepared catalyst carrier in ammonium metavanadate aqueous solution for 5min, taking out, drying at 95 ℃ for 120min, roasting at 320 ℃ for 120min, and repeating the soaking, drying and roasting procedures to obtain 1.76kg of catalyst precursor.

(4) Reduction treatment:

the catalyst precursor was added at 20% by volume CH₄80% by volume H₂The reaction mixture was reduced at 425 ℃ and 1MPa for 3 hours under an atmosphere to obtain 1.69kg of desulfurization catalyst A6 with a regular structure.

(5) Composition of desulfurization catalyst a6 with regular structure:

the desulfurization catalyst A6 having a regular structure contained cordierite 70 wt%, calcium oxide 16 wt%, zirconia (non-aluminum binder) 3 wt%, lanthanum oxide (rare earth oxide) 1 wt%, and vanadium carbide 10 wt% based on the dry weight of the catalyst.

Example 7

(1) Preparation of a matrix coating slurry (adding a dispersant to the matrix material): referring to example 1, the difference is that while slurry A and slurry B (1.0 kg dry basis of zinc oxide) were mixed, 1000mL of an aqueous polyethylene glycol solution (prepared by adding 2g of polyethylene glycol per 100mL of water dissolved therein, wherein polyethylene glycol is available from Aladdin reagent, having a polymerization degree of 1700, analytically pure, the same applies hereinafter) was added and mixed, and the mixture was stirred for 20 minutes to prepare a substrate coating slurry having a solid content of 30 wt%.

(2) Preparation of catalyst carrier: referring to example 1, except for using the matrix coating slurry prepared in the foregoing step (1) instead of the matrix coating slurry prepared in step (1) of example 1, 1.52kg of the catalyst support was obtained;

(3) preparation of the catalyst precursor: referring to example 1, except for using the catalyst support prepared in the foregoing step (2) instead of the catalyst support prepared in the step (2) of example 1, 1.76kg of the catalyst precursor was obtained;

(4) reduction treatment: referring to example 1, except for using the catalyst precursor prepared in the foregoing step (3) in place of the catalyst precursor prepared in the step (3) of example 1, 1.69kg of desulfurization catalyst A7 of a regular structure was obtained.

(5) Composition of desulfurization catalyst a7 with regular structure:

the desulfurization catalyst of a regular structure a7 contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of molybdenum carbide.

Example 8

(1) Preparation of a matrix coating slurry (adding a dispersant to the matrix material): referring to example 1, the difference is that while slurry A and slurry B (1.0 kg dry basis of zinc oxide) were mixed, 1000mL of an aqueous polyethylene glycol solution (prepared by adding 20g of polyethylene glycol per 100mL of water dissolved therein, wherein polyethylene glycol is available from Aladdin reagent, having a polymerization degree of 1700, analytically pure, the same applies hereinafter) was added and mixed, and the mixture was stirred for 20 minutes to prepare a substrate coating slurry having a solid content of 30 wt%.

(4) reduction treatment: referring to example 1, except for using the catalyst precursor prepared in the foregoing step (3) instead of the catalyst precursor prepared in step (2) of example 1, 1.69kg of desulfurization catalyst A8 of a regular structure was obtained.

(5) Composition of desulfurization catalyst A8 with regular structure:

the desulfurization catalyst of a regular structure A8 contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of molybdenum carbide.

Example 9

(1) Preparing a matrix coating slurry: referring to example 1, except that the preparation method of slurry B includes: 0.356kg of zirconium tetrachloride (0.188 kg in terms of zirconium oxide, analytically pure, Beijing chemical plant) was dissolved in 800mL of deionized water, 0.166kg of lanthanum nitrate hexahydrate (0.062 kg in terms of lanthanum oxide, analytically pure, national drug group) was dissolved in 200mL of deionized water, the two aqueous solutions were mixed and 30 wt% aqueous ammonia was added with stirring until the pH of the solution became 11 (mixing temperature 30 ℃ C., mixing time 4h), and the filtrate was filtered to obtain a filter cake which was washed to remove excess metal ions. Drying the obtained filter cake at 120 ℃ for 120min, and roasting at 550 ℃ for 180min to obtain a dried substance; adding the dried substance into water, pulping, and wet-milling with ball mill for 5 hr (the ball-milling solution is distilled water, and the mixture granule d₉₀8 μm) to prepare slurry B. Then, referring to example 1, slurry B prepared as described above was mixed with slurry a instead of slurry B in step (1) of example 1 to obtain a base coating slurry;

(4) reduction treatment: referring to example 1, except for using the catalyst precursor prepared in the foregoing step (3) instead of the catalyst precursor prepared in step (2) of example 1, 1.69kg of desulfurization catalyst A9 of a regular structure was obtained.

(5) Composition of desulfurization catalyst a9 with regular structure:

the desulfurization catalyst of a regular structure a9 contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of molybdenum carbide.

Example 10

(1) Preparation of the matrix material: referring to step (1) of example 1, except that the prepared matrix coating slurry was dried at 120 ℃ for 120min and then baked at 550 ℃ for 180min to obtain a matrix material;

(2) preparation of active ingredients:

1.01g of ammonium paramolybdate tetrahydrate (NH)₄)₆Mo₇O₂₄·4H₂O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. Soaking 1.01kg of the matrix material in ammonium molybdate aqueous solution for 5min, taking out, drying at 100 ℃ for 120min, roasting at 300 ℃ for 120min, and repeating the soaking, drying and roasting procedures to obtain 1.72kg of the active component;

(3) preparation of the catalyst precursor:

wet-milling the active components with a ball mill for 5h to prepare slurry with a solid content of 30 wt%, coating the slurry on a cylindrical honeycomb cordierite carrier, drying the slurry at 120 ℃ for 120min, calcining the dried slurry at 550 ℃ for 180min, and repeating the coating twice, so that the weight of the active component coating reaches a target weight (30 wt% of the total weight of the finally prepared desulfurization catalyst with a regular structure (catalyst A11 described below)), and obtaining 1.76kg of catalyst precursor.

(4) Reduction treatment:

the catalyst precursor was added at 10 vol% CH₄90% by volume of H₂And reducing for 4h at the temperature of 300 ℃ and under the pressure of 2MPa in the atmosphere to obtain 1.69kg of desulfurization catalyst A10 with a regular structure.

(5) Composition of desulfurization catalyst a10 with regular structure:

the desulfurization catalyst of a regular structure a10 contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of molybdenum carbide.

Comparative example 1

This comparative example is used for comparative illustration of the desulfurization catalyst of regular structure of the present invention and the preparation method thereof.

(1) Preparation of matrix coating slurry: the same as in example 1.

(2) Preparation of catalyst carrier: the same as in example 1.

(3) Preparation of the catalyst precursor:

1.01kg of ammonium paramolybdate tetrahydrate (NH)₄)₆Mo₇O24·4H₂O (molecular weight 1235.86, analytical grade) was dissolved in 2L of deionized water to obtain an aqueous solution of ammonium molybdate. The prepared catalyst carrier is immersed in an ammonium molybdate aqueous solution for 5min, taken out and dried at 100 ℃ for 120min, calcined at 300 ℃ for 120min, the immersion process is repeated twice, and the immersion, drying and calcination processes are repeated to obtain 1.78kg of catalyst precursor.

(4) Reduction treatment:

the foregoing catalyst precursor was reduced with a gas containing 96 vol% hydrogen at a temperature of 300 ℃ and a pressure of 2MPa for 4 hours to obtain 1.69kg of desulfurization catalyst B of a regular structure.

(5) Composition of desulfurization catalyst B with a regular structure:

the desulfurization catalyst B of a regular structure contained, by dry weight, 70% by weight of cordierite, 16% by weight of zinc oxide, 3% by weight of zirconium dioxide (non-aluminum binder), 1% by weight of lanthanum oxide (rare earth oxide), and 10% by weight of metallic molybdenum.

Application example

Desulfurization evaluation experiments were performed on the desulfurization catalysts a1-a10 and B of the regular structures prepared according to examples 1 to 10 and comparative example 1 of the present invention using a fixed bed micro-reaction experimental apparatus, specifically including: 16g of a desulfurization catalyst was packed in a fixed bed reactor having an inner diameter of 30 mm. Hydrogen is used as a hydrogen supply medium, the reaction temperature is 400 ℃, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, and the weight space velocity of the raw material hydrocarbon oil is 4h^-1The desulfurization reaction of sulfur-containing hydrocarbon oil (gasoline) was carried out under the desulfurization reaction conditions of sulfur-containing hydrocarbon, and the composition of the gasoline is shown in table 1.

Evaluation of desulfurization Performance:

(1) measuring the composition of the product gasoline by adopting a gas chromatography POINA method, and recording corresponding data in tables 2 and 3;

(2) calculating the yield of the product gasoline by a weighing method, and recording corresponding data in tables 2 and 3;

(3) motor Octane Number (MON) and Research Octane Number (RON) of the pre-reaction and post-reaction mixed gasoline were measured using GB/T503-;

(4) the sulfur content in the product gasoline was measured using the total sulfur assay (coulometry) in the petrochemical industry standard SH/T0253-1992 light petroleum products, and the change in sulfur content in the product gasoline with reaction time was recorded in tables 2 and 3.

TABLE 1

Item	Analyzing data	Item	Analyzing data
				Density (20 ℃ C.) (kg.m)^-3)	727.3	Induction phase (min)	922
Actual gum (mg/mL)	0.34	Distillation range (. degree.C.)
				Refractive index (20 ℃ C.)	1.4143	Initial boiling point	38.5
Sulfur content (ng./. mu.L)	960.48	5％	49.0
				Mercaptan sulfur content (ng/. mu.L)	10.2	10％	55.5
Hydrogen sulfide content (ng/. mu.L)	0	30％	74.7
				Octane number (RON/MON)	93.7/83.6	50％	97.2
Group composition volume (%)		70％	124.2
				Saturated hydrocarbons	44.0	90％	155.2
Olefins	41.2	95％	165.2
				Aromatic hydrocarbons	14.8	End point of distillation	185.0
Isomeric hydrocarbons	35.1
				Benzene and its derivatives	1.16

Table 2.

Table 3.

Note:

1. the feed gasoline had a sulfur content of 960ppm, a RON of 93.7 and a MON of 83.6.

2.Δ MON represents the increase in product gasoline MON compared to the gasoline feedstock;

3.Δ RON represents the increase in the RON of the product gasoline compared to the gasoline feedstock;

4. and delta (RON + MON)/2 represents the difference between the antiknock index of the product gasoline and the antiknock index of the raw gasoline.

As can be seen from the result data in tables 2 and 3, after the gasoline desulfurization treatment is performed by using the catalyst B prepared in comparative example 1, the sulfur content in the gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial stage of the reaction, and gradually increases with the progress of the reaction time, but after the reaction for 24h to 96h, the sulfur content in the gasoline product reaches 12.6ppm, which is close to the marginal requirement (10ppm) of the sulfur content in the gasoline product, and the catalyst needs to be regenerated. Moreover, the gasoline product produced in the process had a saturated hydrocarbon content of 62 wt%, an iso-hydrocarbon content of 35 wt%, a benzene content of 0.83 wt%, and an octane number loss of 0.36 units.

After the desulfurization catalysts A1-A10 with the regular structures prepared in the embodiments 1-10 are used as catalysts to carry out gasoline desulfurization treatment, the sulfur content in a gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial reaction stage, the sulfur content in the product gradually increases along with the reaction time, but the sulfur content in the gasoline product is only 7.1ppm at most after 24-96 hours of reaction; at the same time, the resulting gasoline product has a saturated hydrocarbon content in the range of 51 to 56 wt.% (reduced relative to comparative example 1), an iso-hydrocarbon content in the range of 40 to 48 wt.% (increased relative to comparative example 1), and a benzene content in the range of 0.38 to 0.57 wt.% (reduced relative to comparative example 1); and the octane number of the resulting gasoline product is increased by at least 0.11 units (relative to the increase of comparative example 1).

In conclusion, the desulfurization catalyst with the regular structure provided by the invention has better desulfurization activity and activity stability. Moreover, compared with the prior desulfurization technology, the desulfurization catalyst with the regular structure provided by the invention can reduce the content of saturated hydrocarbon and benzene in the desulfurized oil product, improve the content of isomeric hydrocarbon and improve the octane number of the desulfurized oil product (namely the octane number loss is obviously reduced).

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A desulfurization catalyst with a regular structure comprises a regular structure carrier and an active component coating distributed on the inner surface and/or the outer surface of the regular structure carrier; the active component coating comprises 5-70 wt% of transition metal carbide and 30-95 wt% of matrix based on the total weight of the active component coating; the matrix comprises 5-35 wt% of non-aluminum binder, 0.5-10 wt% of rare earth oxide and 60-90 wt% of at least one metal oxide selected from IIA and IIB based on the total weight of the matrix;

wherein the transition metal is one or more selected from Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W.

2. The catalyst according to claim 1, wherein the active component coating layer is contained in an amount of 10 to 50 wt% based on the total weight of the structured desulfurization catalyst.

3. The catalyst according to claim 1, wherein the active component coating layer is contained in an amount of 15 to 30 wt% based on the total weight of the structured desulfurization catalyst.

4. The catalyst according to any one of claims 1 to 3, wherein the active component coating layer comprises 10 to 50 wt% of the transition metal carbide and 50 to 90 wt% of the matrix, based on the total weight of the active component coating layer.

5. The catalyst according to claim 4, wherein the active component coating layer comprises 20 to 50 wt% of the transition metal carbide and 50 to 80 wt% of the matrix.

6. The catalyst according to claim 5, wherein the active component coating layer comprises 25 to 50 wt% of the transition metal carbide and 50 to 75 wt% of the matrix.

7. The catalyst according to any one of claims 1 to 3,

the oxide of at least one metal selected from IIA and IIB is an oxide of at least one metal selected from magnesium, zinc and calcium;

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

the non-aluminum binder is at least one selected from zirconium dioxide, titanium dioxide and tin dioxide;

the regular structure carrier is selected from a monolithic carrier with a parallel pore channel structure with two open ends.

8. According to claimThe catalyst according to claim 7, wherein the pore density of the cross section of the regular structure carrier is 40 to 800 pores per square inch, and the cross sectional area of each pore in the regular structure carrier is 400 to 1.8 × 10⁵μm²。

9. The catalyst of claim 8, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zircon corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.

10. A preparation method of a desulfurization catalyst with a regular structure is characterized by comprising the following steps:

s1, mixing a precursor of an oxide of at least one metal selected from IIA and IIB, a rare earth oxide precursor and a non-aluminum binder precursor to prepare a matrix coating slurry;

s2, coating the slurry of the matrix coating on a regular structure carrier, drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier;

s3, contacting the catalyst supporter with a transition metal precursor solution, drying and roasting after the contact to form a transition metal oxide on the matrix coating to obtain a catalyst precursor;

s4, adding the catalyst precursor into CH₄/H₂Carrying out reduction treatment under the atmosphere to reduce the transition metal oxide to form transition metal carbide to obtain the desulfurization catalyst with the regular structure;

wherein the transition metal in the transition metal precursor solution is one or more selected from Ti, V, Fe, Co, Ni, Zr, Mn, Cu, Mo and W, and the transition metal precursor is nitrate, chloride, oxalate, acetate or ammonium salt of the transition metal;

wherein the total content of the matrix coating and the transition metal carbide is 10-50 wt% based on the total weight of the desulfurization catalyst with the regular structure;

based on the total content of the matrix coating and the transition metal carbide, the content of the transition metal carbide is 5-70 wt%, and the content of the matrix coating is 30-95 wt%;

the matrix coating slurry contains, by dry weight, 5 to 35 wt% of a non-aluminum binder precursor in terms of a non-aluminum binder, 0.5 to 10 wt% of a rare earth oxide precursor in terms of a rare earth oxide, and 60 to 90 wt% of a precursor of an oxide of at least one metal selected from groups IIA and IIB in terms of a metal oxide.

11. The method of claim 10, wherein the matrix coating layer and the transition metal carbide are present in a total amount of 15 to 30 wt.%, based on the total weight of the structured desulfurization catalyst.

12. The method of claim 10, wherein the transition metal carbide is present in an amount of 10 to 50 wt% and the matrix coating is present in an amount of 50 to 90 wt%, based on the total amount of the matrix coating and the transition metal carbide.

13. The method of claim 10, wherein the transition metal carbide is present in an amount of 20 to 50 wt% and the matrix coating is present in an amount of 50 to 80 wt%, based on the total amount of the matrix coating and the transition metal carbide.

14. The method of claim 10, wherein the transition metal carbide is present in an amount of 25 to 50 wt.% and the matrix coating is present in an amount of 50 to 75 wt.%, based on the total amount of the matrix coating and the transition metal carbide.

15. The method of any of claims 10-14, wherein S1 further comprises adding a dispersant to the matrix coating slurry.

16. The method according to claim 15, wherein the dispersant is an organic dispersant having a degree of polymerization in the range of 500 to 2500.

17. The method according to claim 15, wherein the dispersant is an organic dispersant having a degree of polymerization in the range of 1000 to 2000.

18. The method of claim 15, wherein the dispersant is one or more of polyethylene glycol, polyglycerol, polyvinyl alcohol and polypropylene.

19. The method as claimed in claim 15, wherein the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from groups IIA and IIB is greater than 0 and equal to or less than 0.2.

20. The method as claimed in claim 15, wherein the weight ratio of the dispersant to the precursor of the oxide of at least one metal selected from groups IIA and IIB is 0.005 to 0.02: 1.

21. the method of any one of claims 10-14,

the drying temperature in the S2 is between room temperature and 300 ℃, and the drying time is more than 0.5 h; the roasting temperature is 400-800 ℃, and the roasting time is more than 0.5 h;

the drying temperature in the S3 is between room temperature and 150 ℃, and the drying time is more than 1 h; the roasting temperature is 200-600 ℃, and the roasting time is more than 1 h.

22. The method according to claim 21, wherein the temperature for drying in S2 is 100-200 ℃.

23. The method according to claim 21, wherein the drying time in S2 is 1-10 h.

24. The method as claimed in claim 21, wherein the temperature of the calcination in S2 is 500-700 ℃.

25. The method as claimed in claim 21, wherein the roasting time in S2 is 1-10 h.

26. The method according to claim 21, wherein the temperature of the drying in S3 is 80-100 ℃.

27. The method according to claim 21, wherein the drying time in S3 is 2-8 h.

28. The method as claimed in claim 21, wherein the temperature of the calcination in S3 is 200-350 ℃.

29. The method as claimed in claim 21, wherein the roasting time in S3 is 2-4 h.

30. The method according to any one of claims 10 to 14, wherein the conditions of the reduction treatment in S4 include: reducing for 0.5-6 hours at 250-550 ℃ and 0.2-5 MPa.

31. The method as claimed in claim 30, wherein the conditions of the reduction treatment in S4 include: reducing for 2-4 hours at the temperature of 300-450 ℃ and under the pressure of 0.5-3.5 MPa.

32. The method according to any of claims 10-14, wherein CH in step S4₄/H₂The atmosphere contains 5 to 25 vol% of CH based on the total volume of the atmosphere₄And 75 to 95 vol% of H₂。

33. The method of claim 32, wherein the step S4Middle CH₄/H₂The atmosphere contains 10 to 20 vol% of CH based on the total volume of the atmosphere₄And 80 to 90 vol% of H₂。

34. The method of any one of claims 10-14,

the rare earth in the rare earth oxide precursor is at least one selected from lanthanum, cerium and neodymium;

the non-aluminum binder precursor is zirconium dioxide, titanium dioxide or stannic oxide, or a substance capable of obtaining zirconium dioxide, titanium dioxide or stannic oxide under the roasting condition;

35. The method as claimed in any one of claims 10 to 14, wherein the structured carrier has a cross-section having a pore density of 40 to 800 pores per square inch and a cross-sectional area of 400 to 1.8 × 10 for each pore in the structured carrier⁵μm²。

36. The method of any of claims 10-14, wherein the structured carrier is selected from at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier, and a metal alloy honeycomb carrier.

37. A structured desulfurization catalyst made by the method of any one of claims 10 to 36.

38. A process for the desulfurization of sulfur-containing hydrocarbons, the process comprising: contacting a sulfur-containing hydrocarbon and a hydrogen donor with a catalyst; wherein the catalyst is the desulfurization catalyst with a regular structure as set forth in any one of claims 1 to 9 and 37.