CN105583002B - A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents

Abstract

The invention discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-30% by weight of heat-resistant inorganic oxide; 2) 5-30% by weight of silicon oxide source; 3) 10-70% by weight of the second 1. Metal oxide; 4) 2-20% by weight of the second metal oxide; 5) 5-30% by weight of metal promoter; 6) 1-20% by weight of rare earth modified aluminum phosphorus molecular sieve. The desulfurization catalyst has better desulfurization activity and activity stability.

Description

A kind of desulfurization catalyst and its preparation method and the method for hydrocarbon oil desulfurization

technical field

The present invention relates to a desulfurization catalyst and a preparation method thereof and a method for desulfurizing hydrocarbon oil, in particular to a desulfurization catalyst, a method for preparing a desulfurization catalyst and a desulfurization catalyst obtained by the method, and using the desulfurization catalyst for desulfurization of hydrocarbon oil Methods.

Background technique

The sulfur oxides produced by the combustion of sulfur in vehicle fuels will inhibit the activity of noble metal catalysts in vehicle exhaust converters and cause irreversible poisoning. As a result, the vehicle exhaust contains unburned non-methane hydrocarbons, nitrogen oxides and carbon monoxide, and these exhaust gases are easily catalyzed by sunlight to form photochemical smog and cause acid rain. At the same time, sulfur oxides in the atmosphere are also the main cause of acid rain. one. As people pay more and more attention to environmental protection, environmental regulations are becoming stricter, and reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures to improve air quality.

my country's current gasoline product standard GB 17930-2011 "Motor Gasoline" requires that by December 31, 2013, the sulfur content in gasoline must be reduced to 50 μg/g; and the gasoline quality standard will be more stringent in the future. In this case, FCC gasoline must undergo deep desulfurization to meet the requirements of environmental protection.

At present, there are mainly two methods for deep desulfurization of oil products: hydrofining and adsorption desulfurization. However, the cost of hydrofining is relatively high in China due to the source of hydrogen. S Zorb adsorption desulfurization belongs to the hydrogen desulfurization technology, which realizes the adsorption and removal of sulfide under certain temperature and pressure conditions. Since this technology has the characteristics of low hydrogen consumption in the removal of sulfur compounds in gasoline, and does not require high purity of hydrogen, this technology has broad application prospects in the removal of sulfur compounds in fuel oil.

Traditionally, fixed bed method is often used for desulfurization from liquid, but this method has obvious disadvantages in reaction uniformity and regeneration. Compared with the fixed bed process, the fluidized bed process has the advantages of better heat transfer and pressure drop, so it has broad application prospects. Fluidized bed reactors generally use granular reactants, but the reactants used are generally not sufficiently abrasive resistant for most reactions. Therefore, it is of great significance to find an adsorbent with good wear resistance and good desulfurization performance.

CN1355727A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein nickel exists in a reduced valence state substantially, and its presence can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the nickel-containing sorbent composition under desulfurization conditions. The composition is obtained by granulating the mixture of zinc oxide, silicon oxide and aluminum oxide to form particles, drying, calcining, impregnating with nickel or a compound containing nickel, drying, calcining and reducing.

CN1382071A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein cobalt exists in a substantially reduced valence state, and its existing amount can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the cobalt-containing sorbent composition under desulfurization conditions. Both CN1355727A and CN1382071A only mentioned the desulfurization activity, and did not introduce the physical and chemical properties (such as wear resistance strength) and stability of the adsorbent.

The adsorbent disclosed in US6150300, CN1130253A and CN1258396A is a granular adsorbent composition comprising a mixture of zinc oxide, silicon oxide, aluminum oxide, reduced valence nickel or cobalt. The preparation method is mainly to mix silicon oxide, aluminum oxide and zinc oxide by shearing and other methods, prepare solid particles through a granulator, and impregnate nickel after drying and roasting to obtain an adsorbent. Although the adsorbents introduced in these patents have good desulfurization performance, their physical and chemical properties, mainly wear strength, are not introduced in the patents.

CN1208124A discloses the use of accelerator metals such as cobalt and nickel to impregnate an adsorbent carrier containing zinc oxide, expanded perlite and alumina, and then reduce the accelerator at a suitable temperature to prepare an adsorbent for removing sulfide in cracked gasoline .

CN1627988A discloses an adsorbent composition suitable for removing elemental sulfur and sulfur compounds from cracked gasoline and diesel fuel, said adsorbent composition comprising: zinc oxide, expanded perlite, aluminate and promoter metals, wherein the promoter metal is present in an amount that will result in desulfurization from the stream of cracked gasoline or diesel fuel when contacting the cracked gasoline or diesel fuel stream therewith under desulfurization conditions, and at least a portion of the promoter metal is at zero valence state exists.

CN1856359A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina and a cocatalyst to form a mixture thereof; b) drying the mixture to form a dried mixture; c) calcining the dried mixture to form a calcined mixture; d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a cocatalyst content having a reduced valence state therein the composition of the product, and e) the recovery composition. The cocatalyst contains various metals selected from nickel and the like.

CN1871063A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, and alumina to form a mixture thereof; b) drying the mixture to form a second a dried mixture; c) calcining said first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto said first calcined mixture to form a promoted mixture; e ) contacting the accelerated mixture with an acid selected from citric acid, tartaric acid, and combinations thereof to form a contacted mixture; f) drying the contacted mixture to form a second dried mixture; g) contacting the second calcining the dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under appropriate conditions to produce a composition comprising reduced valence promoter content therein, and i) The composition is recovered.

CN101816918A discloses a desulfurization adsorbent, which is composed of rare earth metals, alumina, silicon oxide, promoters and one or more metal oxides selected from IIB, VB and VIB. The adsorbent has good wear resistance and desulfurization activity.

Although the adsorbents prepared by these methods have good desulfurization performance, they also have obvious disadvantages. The above-mentioned adsorbents all use zinc oxide active components. The temperature of zinc oxide absorbing sulfur and oxidation regeneration is relatively high, and it is easy to form zinc silicate and/or aluminate with silicon and aluminum components in the carrier during desulfurization reaction and oxidation regeneration. Zinc, leading to a decrease in the activity of the adsorbent. It can be seen that there is a need to provide a new catalyst with higher desulfurization activity and wear resistance.

Contents of the invention

The object of the present invention is to provide a desulfurization catalyst and its preparation method and a method for desulfurization of hydrocarbon oil in order to overcome the defects of low desulfurization activity, unstable structure and poor wear resistance of the adsorbent in the prior art.

In order to achieve the above object, the present invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-30% by weight of a heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from From at least one of alumina, titania, zirconia and tin dioxide; 2) 5-30% by weight of a silicon oxide source; 3) 10-70% by weight of a first metal oxide, the first metal Oxides are selected from at least one of the metal oxides of IIB, VB and VIB group elements; 4) 2-20% by weight of a second metal oxide selected from lead oxide, antimony oxide and At least one of bismuth oxide; 5) 5-30% by weight of a metal promoter selected from at least one of cobalt, nickel, iron and manganese; 6) 1-20% by weight of rare earth modified Phosphorous aluminum molecular sieves.

The present invention also provides a method for preparing the desulfurization catalyst of the present invention, the method comprising: (1) mixing a rare earth-modified aluminum phosphorus molecular sieve, the first metal oxide, the precursor of the second metal oxide and water to obtain a slurry; (2) mixing a heat-resistant inorganic oxide binder, a silicon oxide source, water and an acidic liquid, and contacting the slurry to form a carrier slurry, and then performing molding, first drying and first roasting on the carrier slurry, Obtain a carrier; (3) introduce the precursor of the metal promoter on the carrier, and carry out the second drying and the second roasting to obtain the catalyst precursor; (4) reduce the catalyst precursor under a hydrogen-containing atmosphere, A desulfurization catalyst is obtained.

The invention also provides the desulfurization catalyst prepared by the method provided by the invention.

The present invention provides a method for desulfurizing hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst provided by the present invention, the contacting temperature is 350-500°C, the contacting The pressure is 0.5-4MPa.

The desulfurization catalyst provided by the present invention contains a mixture of the first metal oxide and the second metal oxide as a sulfur absorbing component, and the second metal oxide can effectively reduce the interaction between the first metal oxide and the silicon and aluminum components in the carrier , reduce the formation of silicates and/or aluminates of the first metal, so that the desulfurization catalyst can absorb sulfur at a lower temperature and still have better desulfurization activity and activity stability after repeated reaction and regeneration processes sex.

The desulfurization catalyst provided by the invention contains the rare earth modified aluminum phosphorus molecular sieve. The unique skeleton structure and acidity of the aluminum phosphorus molecular sieve are beneficial to the isomerization and aromatization reactions of hydrocarbons and increase the octane number of gasoline. By modifying the molecular sieve with rare earth ions, on the one hand, the thermal and hydrothermal stability of the molecular sieve is improved, the life of the catalyst can be extended, and the occurrence of side reactions can be reduced; on the other hand, the acid center strength of the molecular sieve can be reduced, and gasoline cracking and Coke, so that gasoline yield increases.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-30% by weight of a heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from alumina, titanium dioxide , at least one of zirconium dioxide and tin dioxide; 2) 5-30% by weight of a silicon oxide source; 3) 10-70% by weight of a first metal oxide selected from IIB , at least one of the metal oxides of VB and VIB group elements; 4) 2-20% by weight of a second metal oxide, the second metal oxide is selected from at least lead oxide, antimony oxide and bismuth oxide A kind of; 5) 5-30% by weight metal accelerator, described metal accelerator is selected from at least one in cobalt, nickel, iron and manganese; 6) 1-20% by weight of rare earth modified aluminum phosphorus molecular sieve .

Preferably, based on the total weight of the desulfurization catalyst, the content of the heat-resistant inorganic oxide is 10-20% by weight, the content of the silicon oxide source is 10-20% by weight, and the content of the first metal oxide The content of the second metal oxide is 35-54% by weight, the content of the second metal oxide is 5-15% by weight, the content of the metal accelerator is 10-20% by weight, and the content of the rare earth modified aluminum phosphorus molecular sieve It is 2-20% by weight.

According to the present invention, the first metal oxide is a metal oxide with sulfur storage properties, preferably, the first metal oxide is zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, At least one of molybdenum oxide and tungsten oxide; more preferably, the first metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide; most preferably, the first metal oxide is zinc oxide.

According to the present invention, the second metal oxide can prevent the first metal oxide from interacting with the silicon and aluminum components contained in the desulfurization catalyst when it undergoes repeated desulfurization reactions and regeneration reactions at high temperatures, reducing loss of the first metal oxide.

According to the present invention, the heat-resistant inorganic oxide can provide bonding between the components in the desulfurization catalyst. The heat-resistant inorganic oxide is selected from at least one of alumina, titania, zirconia and tin dioxide. Wherein, the alumina can be at least one of γ-alumina, η-alumina, θ-alumina and χ-alumina; preferably, the alumina is γ-alumina; the titanium dioxide can be It is anatase titanium dioxide.

According to the present invention, the silicon oxide source can provide bonding between the components in the desulfurization catalyst. Preferably, the silica source may be pure silica or natural minerals with a silica content greater than 45% by weight. Preferably, the silica source may be selected from at least one of layered clay, diatomaceous earth, expanded perlite, kaolin, silicalite, hydrolyzed silica, macroporous silica and silica gel. Natural minerals may also contain other components such as Al ₂ O ₃ , K ₂ O, CaO, MgO, Fe ₂ O ₃ , TiO ₂ and so on. In the present invention, the amount of other components contained in the silicon oxide source is still counted as the amount of the silicon oxide source.

According to the present invention, the metal accelerator can be any metal capable of reducing oxidized sulfur to hydrogen sulfide, preferably, the metal accelerator is nickel.

According to the present invention, preferably, the rare earth-modified aluminum phosphorus molecular sieve can be aluminophosphates (aluminophosphates), metalloaluminophosphates (metalloaluminophosphates), metal integrated silicaaluminophosphates (metal integrated silicaaluminophosphates, MeAPSO and ELAPSO) and at least one of silicoaluminophosphates (SAPO). Preferably, the rare earth modified aluminum phosphorus molecular sieve is at least one of SAPO-11, SAPO-31, SAPO-5 and SAPO-34. The SiO ₂ : Al ₂ O ₃ molar ratio of the rare earth modified aluminum phosphorus molecular sieve may be 0.02-3:1.

According to the present invention, the rare earth modification method can be ion exchange method and/or equal volume impregnation method. Preferably, based on the total weight of the rare earth-modified aluminum-phosphorus molecular sieve, the rare-earth-modified aluminum-phosphorus molecular sieve contains 2-15% by weight of rare earths calculated as rare earth oxides.

In the present invention, the rare earth is distributed in the pores of the rare earth modified aluminum phosphorus molecular sieve. Preferably, the rare earth metal can be at least one of carbonate, bicarbonate, nitrate, chloride, formate and acetate of a rare earth metal; preferably, the rare earth metal compound can be carbon of a rare earth metal At least one of acid salts, bicarbonates, formates and acetates. Wherein, the rare earth metal is preferably at least one of lanthanum, cerium and neodymium. Preferably, the rare earth modified aluminum phosphorus molecular sieve can be selected from, for example, La-SAPO-11 molecular sieve (15% by weight of La ₂ O ₃ ), Ce-SAPO-31 molecular sieve (10% by weight of CeO ₂ ), RE- At least one of SAPO-34 molecular sieve (RE is 2.5% by weight of La ₂ O ₃ and 2.5% by weight of CeO ₂ ), Ce-SAPO-5 molecular sieve (5% by weight of CeO ₂ ).

In the present invention, adding the rare earth modified aluminum phosphorus molecular sieve can promote the isomerization of straight-chain hydrocarbons in gasoline while ensuring a higher yield of gasoline, thereby increasing the content of isoparaffins in gasoline and increasing the octane of gasoline products. role or effect of the value.

The present invention also provides a method for preparing the desulfurization catalyst of the present invention, the method comprising: (1) mixing a rare earth-modified aluminum phosphorus molecular sieve, the first metal oxide, the precursor of the second metal oxide and water to obtain a slurry; (2) mixing a heat-resistant inorganic oxide binder, a silicon oxide source, water and an acidic liquid, and contacting the slurry to form a carrier slurry, and then performing molding, first drying and first roasting on the carrier slurry, Obtain a carrier; (3) introduce the precursor of the metal promoter on the carrier, and carry out the second drying and the second roasting to obtain the catalyst precursor; (4) reduce the catalyst precursor under a hydrogen-containing atmosphere, A desulfurization catalyst is obtained.

In the present invention, preferably, the heat-resistant inorganic oxide binder may be a heat-resistant inorganic oxide or a substance that can be transformed into a heat-resistant inorganic oxide under the conditions of the first calcination. Preferably, the heat-resistant inorganic oxide binder is at least one of alumina binder, zirconia binder, titania binder and tin dioxide binder. More preferably, the alumina binder can be hydrated alumina and/or aluminum sol, wherein the hydrated alumina is selected from boehmite (boehmite), pseudoboehmite ( At least one of pseudo-boehmite), trihydrate alumina and amorphous aluminum hydroxide; the zirconium dioxide binder can be zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrated zirconium oxide and At least one of amorphous zirconium dioxide; the tin dioxide binder can be at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide; the The titanium dioxide binder may be at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide.

In the present invention, the silicon oxide source can provide binding effect between components in the desulfurization catalyst. Preferably, the silicon oxide source may be silicon oxide or natural ore with a silicon oxide content greater than 45% by weight. Preferably, the silicon oxide source may be at least one of layered clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica and silica gel. The pillar clay may be at least one of retortite, dolomite, bentonite, montmorillonite and smectite.

It should be noted that although the above-mentioned silica source may contain alumina, the content of alumina in the present invention does not include the amount of alumina contained in the above-mentioned silica source, and the content of alumina only includes amount of alumina. The amount of alumina contained in the silica source is still counted as the amount of the silica source. That is, the content of each component in the desulfurization catalyst prepared by the method provided by the invention is calculated according to the feeding amount.

In the present invention, the precursor of the second metal oxide is the second metal oxide or a substance that can be transformed into the second metal oxide under the conditions of the first calcination; preferably, the The precursor of the second metal oxide is at least one of lead oxide, antimony oxide and bismuth oxide; or at least one of carbonate, nitrate, chloride and hydroxide of metal lead, antimony and bismuth .

In the present invention, the precursor of the metal promoter may be a substance that can be transformed into an oxide of the metal promoter under the conditions of the second calcination. Preferably, the precursor of the metal promoter may be at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal promoter. Wherein the metal accelerator is selected from at least one of cobalt, nickel, iron and manganese.

In the present invention, the first metal oxide and the rare earth-modified aluminum phosphorus molecular sieve are as described above, and will not be repeated one by one.

The steps (1) and (2) of the preparation method of the desulfurization catalyst provided by the present invention are used to prepare the carrier.

In step (1) of the present invention, the addition of the first metal oxide may be in the form of oxide powder, or the first metal oxide may be prepared as a slurry and then used in the form of slurry.

In the present invention, adding the precursor of the second metal oxide may directly add powder of at least one of lead oxide, antimony oxide and bismuth oxide, or add the powder that can be transformed into the The substance of the second metal oxide, such as at least one of carbonate, nitrate, chloride and hydroxide of metal lead, antimony and bismuth; also at least one of lead oxide, antimony oxide and bismuth oxide One is prepared as a slurry and then used in slurry form.

In the present invention, the solid content of the slurry in step (1) may be 15-30% by weight.

In step (2) of the present invention, the feed weight ratio of the silicon oxide source to the heat-resistant inorganic oxide binder is 0.4-2:1, preferably 0.6-1.5:1. This can provide better cohesiveness between components of the desulfurization catalyst.

In the step (2) of the present invention, the mixing may be: after acidifying the heat-resistant inorganic oxide binder and the silicon oxide source with water and an acidic liquid, respectively, mixing the obtained mixtures into an acidifying slurry; wherein , when the heat-resistant inorganic oxide binder is a non-aluminum binder, the obtained mixture is a sol. In addition, when the heat-resistant inorganic oxide binder is an alumina binder, the mixing may also be: mixing and aging water, acidic liquid, alumina binder and silica source to form an acidified slurry . Preferably, the pH value of the acidified slurry is 1-5, preferably 1.5-4; the solid content of the acidified slurry is 15-30% by weight.

In the present invention, the acidic liquid is an acid or an aqueous solution of an acid, and the acid can be selected from water-soluble inorganic acids and/or organic acids, such as at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

In the present invention, the shaping in step (2) can shape the slurry into extrudates, tablets, pellets, spheres or microspherical particles. For example, when the slurry is a dough or pasty mixture, the mixture can be shaped (preferably extruded) to form granules, preferably cylindrical extrudates with a diameter of 1-8 mm and a length of 2-5 mm, and then The extrudate obtained is dried and calcined. If the resulting mixture is in the form of a wet mixture, the mixture can be thickened, dried and shaped. More preferably, the slurry is in the form of a slurry, and microspheres with a particle size of 20-200 microns are formed by spray drying to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the carrier slurry before drying is 10-40% by weight, preferably 20-35% by weight. The process of obtaining the carrier slurry in step (2) may also include adding water, and the amount of water added is not particularly limited, as long as the obtained carrier slurry satisfies the solid content of the above-mentioned carrier slurry.

In the present invention, the conditions of the first drying and the first calcination can be known to those skilled in the art. Preferably, the temperature of the first drying is 80-150° C., and the time of the first drying is 0.5 -24h; the temperature of the first calcination is 300-700°C, and the time of the first calcination is at least 0.5h. Preferably, the temperature of the first calcination is 400-500°C, the time of the first calcination is 0.5-100h, more preferably the time of the first calcination is 0.5-10h.

According to the present invention, step (3) is used to add metal promoters. The precursor of the metal promoter is a material that can be converted into an oxide of the metal promoter under the second calcination condition; preferably, the precursor of the metal promoter can be selected from the acetate of the metal promoter, At least one of carbonates, nitrates, sulfates, thiocyanates and oxides.

According to the present invention, preferably, the method of introducing the precursor of the metal promoter on the carrier is impregnation or precipitation. The impregnation may be to impregnate the carrier with a solution or suspension of the precursor of the metal accelerator; the precipitation may be to mix the solution or suspension of the precursor of the metal accelerator with the carrier, and then add ammonia to dissolve the precursor of the metal accelerator. body deposited on the carrier.

In the present invention, the conditions of the second drying and the second calcination can be known to those skilled in the art. Preferably, the temperature of the second drying is 50-300° C., and the time of the second drying is 0.5 -8h; the temperature of the second calcination is 300-700°C, and the time of the second calcination is 0.5-4h; preferably, the temperature of the second drying is 100-250°C, and the second drying The time is 1-5h; the temperature of the second calcination is 400-500°C, and the time of the second calcination is 1-3h. The second calcination may be carried out in the presence of oxygen or an oxygen-containing gas until the volatile substances are removed and the metal promoter is converted to the form of metal oxide, resulting in a catalyst precursor.

According to the present invention, in step (4), the oxide of the metal promoter in the catalyst precursor is converted into a metal element, and the catalyst precursor can be reduced under a hydrogen-containing atmosphere, so that the metal promoter is basically In the reduced state, the catalyst of the present invention is obtained. The reducing conditions only convert the oxides of the metal promoters in the catalyst precursor into simple metals, but the metal oxides in the support will not be converted. Preferably, the reduction temperature is 300-600°C, the reduction time is 0.5-6h, and the hydrogen content in the hydrogen-containing atmosphere is 10-60% by volume; preferably, the reduction temperature is 350 -450°C, the reduction time is 1-3h.

In the present invention, the reduction of the catalyst precursor in step (4) can be carried out immediately after the catalyst precursor is prepared, or can be carried out before use (that is, before being used for desulfurization and adsorption). Since the metal promoter is easy to oxidize, and the metal promoter in the catalyst precursor exists in the form of oxide, so for the convenience of transportation, it is preferable to carry out the reduction of the catalyst precursor in step (4) before the desulfurization adsorption. The reduction is to make the metal in the oxide of the metal promoter basically exist in a reduced state, so as to obtain the desulfurization catalyst of the present invention.

According to the preparation method provided by the present invention, the heat-resistant inorganic oxide binder, silicon oxide source, first metal oxide, precursor of the second metal oxide, rare earth modified aluminum phosphorus molecular sieve and metal accelerator The amount of the precursor added is such that the obtained desulfurization catalyst contains 5-35% by weight of heat-resistant inorganic oxide, 5-35% by weight of silicon oxide source, 10-70% by weight of the desulfurization catalyst based on the total weight of the desulfurization catalyst % of the first metal oxide, 2-20% by weight of the second metal oxide, 3-30% by weight of the metal promoter and 0.5-10% by weight of the rare earth modified aluminum phosphorus molecular sieve.

Preferably, based on the total weight of the desulfurization catalyst, the content of the heat-resistant inorganic oxide is 10-25% by weight, the content of the silicon oxide source is 10-25% by weight, and the content of the first metal oxide The content of the second metal oxide is 35-54% by weight, the content of the second metal oxide is 5-15% by weight, the content of the metal accelerator is 10-20% by weight, and the content of the rare earth modified aluminum phosphorus molecular sieve It is 1-5% by weight.

The invention also provides the desulfurization catalyst prepared by the method provided by the invention. The composition of the desulfurization catalyst is as described above, and will not be repeated here.

The present invention provides a method for desulfurizing hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst provided by the present invention, the contacting temperature is 350-500°C, the contacting The pressure is 0.5-4MPa; preferably, the contacting temperature is 400-450°C, and the contacting pressure is 1-2MPa. During this process, the sulfur in the hydrocarbon oil is adsorbed onto the catalyst, resulting in a hydrocarbon oil with low sulfur content.

The method for desulfurizing hydrocarbon oil provided by the present invention is preferably carried out in a fluidized bed reactor, that is, the contacting is preferably carried out in a fluidized bed reactor.

In the present invention, the reacted catalyst can be reused after being regenerated. The regeneration is carried out under an oxygen atmosphere, and the regeneration conditions include: the regeneration pressure is normal pressure, and the regeneration temperature is 400-700°C, preferably 500-600°C.

In the present invention, the regenerated catalyst needs to be reduced in a hydrogen-containing atmosphere before re-desulfurizing the hydrocarbon oil. The reduction conditions of the regenerated catalyst include: a temperature of 350-500°C, preferably 400-450°C; a pressure of 0.2-2MPa, preferably 0.2-1.5MPa.

The term "cracked gasoline" as used herein means a hydrocarbon or any fraction thereof having a boiling range of 40 to 210°C, the product from a thermal or catalytic process of cracking larger hydrocarbon molecules into smaller molecules. Applicable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, etc., and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Accordingly, suitable catalytically cracked gasoline includes, but is not limited to, coker gasoline, thermally cracked gasoline, visbroken gasoline, fluid catalytically cracked gasoline, and heavy oil cracked gasoline, and combinations thereof. In some cases, the cracked gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention.

The term "diesel fuel" as used herein means a liquid consisting of a hydrocarbon mixture or any fraction thereof having a boiling range of 170 to 450°C. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight-run diesel and hydrotreated diesel, and the like, and combinations thereof.

The term "sulfur" as used herein denotes any form of elemental sulfur such as organic sulfur compounds commonly present in hydrocarbon-containing fluids such as cracked gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluids of the present invention includes, but is not limited to, carbon oxysulfide (COS), carbon disulfide (CS ₂ ), mercaptans or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often found in diesel fuel.

The desulfurization catalyst provided by the invention has good wear resistance strength and desulfurization activity, can greatly prolong the service life, and is suitable for the process of adsorption desulfurization.

The present invention will be described in detail below by way of examples.

In the following examples and comparative examples, the composition of the desulfurization catalyst is calculated according to the feed.

Example 1

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

(1) Prepare the carrier. 4.05kg of zinc oxide powder (Beijing Chemical Plant, containing 4.0kg on a dry basis), 0.50kg of lead oxide powder (Sinopharm Chemical Reagent Company, analytically pure), 1.0kg of 15% by weight La ₂ O ₃ modified SAPO- 11 molecular sieves (containing 0.7kg on a dry basis, SiO ₂ :Al ₂ O ₃ molar ratio=1:1, denoted as La-SAPO-11) mixed with 6.9kg of deionized water, stirred for 30 minutes to obtain a solution containing zinc oxide, Slurry of lead oxide and La-SAPO-11 molecular sieve;

Mix 1.60kg of alumina (Shandong Aluminum Plant, containing 1.20kg on dry basis) and 2.16kg of kaolin (catalyst Nanjing branch, containing 1.80kg on dry basis) under stirring, then add 3.6kg of deionized water and mix evenly, Add 300ml of 30% by weight hydrochloric acid (Beijing Chemical Plant, chemically pure) and stir to make the pH = 1.8, acidify for 1 hour, then heat up to 80° C. for aging for 2 hours. Then add the above slurry and mix and stir for 1 h to obtain the carrier slurry;

The carrier slurry was spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray drying pressure was 8.5 to 9.5 MPa, the inlet temperature was below 500°C, and the outlet temperature was about 150°C. The microspheres obtained by spray drying were first dried at 150°C for 1h, and then calcined at 480°C for 1h to obtain the carrier;

(2) The 8.2kg carrier was impregnated twice with an aqueous solution formed by 8.91kg nickel nitrate hexahydrate and 1.10kg deionized, and the resulting mixture was dried at 150°C for 4h and then calcined at 480°C for 1h to obtain a catalyst precursor ;

(3) Reduction. The catalyst precursor was reduced in a hydrogen atmosphere at 425° C. for 2 hours to obtain desulfurization catalyst A1.

The chemical composition of A1 is: 40.0% by weight of zinc oxide, 5.0% by weight of lead oxide, 12.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of La-SAPO-11 molecular sieve, nickel The content is 18.0% by weight.

Example 2

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

With 3.84kg of zinc oxide powder (Beijing chemical plant, containing dry basis 3.8kg), 1.21kg of bismuth oxide powder (Sinopharm Chemical Reagent Company, analytically pure), 0.43kg of 10% by weight _CeO Modified SAPO-31 molecular sieve (Contain dry basis 0.30kg, the molar ratio of SiO ₂ :Al ₂ O ₃ =0.5:1, denoted as Ce-SAPO-31) and 7.8kg deionized water are mixed, after stirring for 30 minutes, obtain zinc oxide, bismuth oxide And the slurry of Ce-SAPO-31 molecular sieve;

3.42kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 4.65kg of 5% by weight nitric acid solution to make pH=2.0, and slowly stirred to avoid the precipitation of zirconia crystals to obtain colorless and transparent zirconium Sol;

Take 1.85kg of retort earth (Qilu Petrochemical Catalyst Factory, containing 1.50kg on a dry basis), add 1.5kg of deionized water and mix evenly, add 95ml of 30% by weight hydrochloric acid and stir to make pH = 2.0, acidify for 1h and then heat up to 80°C Aging for 2 hours to obtain a mixture containing retort earth; then adding the above slurry and zirconium sol and mixing and stirring for 1 hour to obtain a carrier slurry.

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the desulfurization catalyst A2 was obtained after reduction.

The chemical composition of A2 is: the content of zinc oxide is 38.0% by weight, the content of bismuth oxide is 12.0% by weight, the content of zirconia is 18.0% by weight, the content of Ce-SAPO-31 is 3.0% by weight, and the content of rector earth is 15.0% by weight, The nickel content was 14.0% by weight.

Example 3

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

5.06kg of zinc oxide powder (Beijing Chemical Plant, containing 5.0kg on a dry basis), 1.05kg of lead nitrate (Sinopharm Chemical Reagent Company, analytically pure), 0.6kg of mixed rare earths (2.5% by weight La ₂ O ₃ and 2.5 Weight % CeO ₂ ) modified SAPO-34 molecular sieve (catalyst Nanjing Branch, containing 0.5kg dry basis, SiO ₂ : Al ₂ O ₃ molar ratio=0.25:1, denoted as RE-SAPO-34) and 7.8 kg of deionized water was mixed, and after stirring for 30 minutes, a slurry containing zinc oxide, lead oxide and RE-SAPO-34 molecular sieve was obtained;

Mix 1.03kg of diatomaceous earth (Catalyst Nanjing Branch, containing 1.0kg on a dry basis) in 4.8kg of deionized water, add 275ml of 30% by weight hydrochloric acid and stir to make pH = 1.5, acidify for 1h to obtain treated diatoms earth;

After mixing 2.13kg of alumina (Shandong Aluminum Plant, including 1.6kg on a dry basis) and 9.0kg of deionized water under stirring, add 170g of concentrated nitric acid and stir to make the pH = 2.0 and heat up to 60°C for acidification for 1h. When the temperature drops below 40° C., the above slurry is added for mixing and then stirred for 1 h to obtain carrier slurry.

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the desulfurization catalyst A3 was obtained after reduction.

The chemical composition of A3 is: 50.0% by weight of zinc oxide, 7.0% by weight of lead oxide, 16.0% by weight of aluminum oxide, 10.0% by weight of diatomaceous earth, and 5.0% by weight of RE-SAPO-34 molecular sieve , the nickel content is 12.0% by weight.

Example 4

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

With 3.84kg of zinc oxide powder (Beijing chemical plant, containing 3.8kg on a dry basis), 0.90kg of antimony oxide powder and 0.43kg of 5% by weight CeO ₂ modified SAPO-5 molecular sieves (containing 0.30kg on a dry basis, SiO ₂ : Al ₂ O ₃ molar ratio=0.8:1, denoted as Ce-SAPO-5) mixed in the deionized water of 8.3kg, after stirring for 30 minutes, obtain the slurry of zinc oxide, antimony oxide and Ce-SAPO-5 molecular sieve;

4.36 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure) was slowly added to 5.76 kg of deionized water, and slowly stirred to avoid the precipitation of titanium oxide crystals, to obtain a light yellow transparent titanium sol, pH=1.0;

Take 2.22 kg of rector earth (Qilu Petrochemical Catalyst Factory, containing 1.80 kg on a dry basis), add 3.0 kg of deionized water and mix evenly, add 90 ml of 30% by weight hydrochloric acid and stir to make pH = 1.5, acidify for 1 hour and then heat up to 80 Aging at ℃ for 2 hours to obtain a mixture containing retort earth; then adding the above slurry and titanium sol to mix together and stirring for 1 hour to obtain a carrier slurry.

Referring to the method of Example 1, the carrier slurry was spray-dried and formed, and the active component nickel was introduced, and the desulfurization catalyst A4 was obtained after reduction.

The chemical composition of A4 is: zinc oxide content 38.0 wt%, antimony oxide content 9.0 wt%, titanium dioxide content 18.0 wt%, rector earth content 18.0 wt%, nickel content 14.0 wt%, Ce-SAPO-5 The molecular sieve content was 3.0% by weight.

Comparative example 1

Mix 4.05kg of zinc oxide powder, 1.0kg of 15% by weight La-SAPO-11 molecular sieve (containing _0.7kg on a dry basis, molar ratio of _SiO2 : _Al2O3 =1:1) and 6.9kg of deionized water After stirring for 30 minutes, a slurry containing zinc oxide and La-SAPO-11 molecular sieves was obtained;

2.27kg of alumina (Shandong Aluminum Works, containing 1.70kg on a dry basis) and 2.16kg of kaolin were mixed under stirring, then 4.0kg of deionized water was added and after mixing evenly, 400ml of 30% by weight hydrochloric acid was added and stirred to make the pH = 1.8, Acidify for 1 hour and then heat up to 80°C for 2 hours of aging. Then add the above slurry and mix and stir for 1 h to obtain the carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the desulfurization catalyst B1 was obtained after reduction.

The chemical composition of B1 is: 40.0% by weight of zinc oxide, 17.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of La-SAPO-11 molecular sieve, and 18.0% by weight of nickel.

Comparative example 2

Mix 4.05kg of zinc oxide powder, 0.50kg of lead oxide powder and 6.9kg of deionized water, and stir for 30 minutes to obtain a slurry containing zinc oxide and lead oxide;

2.53kg of alumina (Shandong Aluminum Works, containing 1.90kg on a dry basis) and 2.16kg of kaolin were mixed under stirring, then 3.6kg of deionized water was added and after mixing evenly, 450ml of 30% by weight hydrochloric acid was added and stirred to make the pH = 1.8, Acidify for 1 hour and then heat up to 80°C for 2 hours of aging. Then add the above slurry and mix and stir for 1 h to obtain the carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and formed, and the active component nickel was introduced, and the desulfurization catalyst B2 was obtained after reduction.

The chemical composition of B2 is: 40.0% by weight of zinc oxide, 5.0% by weight of lead oxide, 19.0% by weight of aluminum oxide, 18.0% by weight of kaolin, and 18.0% by weight of nickel.

Example 5

Abrasion Strength Evaluation. The abrasion resistance strength test was carried out on the desulfurization catalysts A1-A4 and B1-B2. The straight pipe wear method is adopted, and the method refers to RIPP29-90 in the "Petrochemical Analysis Method (RIPP) Experimental Method", and the results are shown in Table 1. The smaller the value obtained in the test, the higher the wear resistance. The wear index in Table 1 corresponds to the percentage of fine powder generated when worn under certain conditions.

In order to better represent the activity of the adsorbent in the process of industrial application, the strength analysis of the adsorbent after sulfidation treatment is also carried out. The specific treatment method is: weigh an appropriate mass of adsorbent and place it in a fluidized bed, and feed hydrogen sulfide ( 50% by volume) and nitrogen (50% by volume), and heated to 400°C for sulfidation treatment for 1h. The results are shown in Table 1.

Example 6

Evaluation of desulfurization performance. Desulfurization evaluation experiments were carried out on desulfurization catalysts A1-A4 and B1-B2 using a fixed-bed micro-reactor experimental device, and 16 g of desulfurization catalysts were loaded into a fixed-bed reactor with an inner diameter of 30 mm and a length of 1 m. The raw material hydrocarbon oil is FCC gasoline with a sulfur concentration of 960ppm, the reaction pressure is 1.38MPa, the hydrogen flow rate is 6.3L/h, the gasoline flow rate is 80mL/h, the reaction temperature is 380°C, and the weight space velocity of the raw material hydrocarbon oil is 4h ^-1 , to carry out the desulfurization reaction of sulfur-containing hydrocarbon oil. The desulfurization activity is measured by the sulfur content in the product gasoline. The sulfur content in the product gasoline was determined by off-line chromatographic analysis method using Agilent's GC6890-SCD instrument. In order to accurately characterize the activity of the desulfurization catalyst in actual industrial operation, the catalyst after the completion of the desulfurization evaluation experiment was regenerated in an air atmosphere at 480 °C. The desulfurization catalyst was subjected to a desulfurization evaluation experiment, and its activity was basically stabilized after 6 cycles of regeneration. The catalyst activity was represented by the sulfur content in the product gasoline after the 6th cycle of the catalyst was stabilized. The sulfur content in the product gasoline after stabilization was shown in Table 1. Show.

At the same time, the product gasoline is weighed to calculate its yield.

Using GB/T 503-1995 and GB/T 5487-1995 to measure the motor octane number (MON) and research octane number (RON) of gasoline before the reaction and after the sixth cycle of stabilization, the results are shown in Table 1 .

Example 7

Determination of zinc aluminate content. The crystal phase composition of the desulfurization catalysts A1-A4 and B1-B2 after the sixth cycle in Example 6 was analyzed, and the content of zinc aluminate therein was determined.

Crystal phase analysis using X-ray diffraction and phase filtering (R. V. Siriwardane, J. A. Poston, G. Evans, Jr. Ind. Eng. Chem. Res. 33 (1994) 2810-2818), the modified Rietveld model (RIQAS rietveld Analysis , Operation Manual, Material Data, Inc., Berkley, CA (1999)), analyze different samples, and use the fitting method to calculate the crystal phase composition of the samples. All X-ray diffraction measurements were performed using a Philips XRG3100 generator (40kV, 30mA drive) equipped with a long fine-focus copper X-ray source, a Philips 3020 digital goniometer, a Philips 3710MPD control computer and a Kevex PSI Peltier cooled silicon detector . The Kevex detector was operated with a Kevex 4601 ion pump controller, Kevex4608 Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer. Diffraction patterns were acquired using Philips APD version 4.1c software. All Rietveld calculations were performed using Material Data, Inc. Riqas version 3.1c software (Outokumpu HSCChemistry for Windows: User Manual, Outokumpo Research Oy, Pori, Finland (1999)). The zinc aluminate contents of different desulfurization catalysts are shown in Table 1.

Table 1

A1 A2 A3 A4 B1 B2 ZnAl ₂ O ₄ , wt% 0 0 0 0 7.6 5.5 wear index 3.0 3.8 3.8 3.2 7.6 5.0 Gasoline yield, % 99.8 99.9 99.7 99.8 98.4 98.8 Product sulfur content, ppm 6 9 10 7 15 35 △RON 0.65 0.45 0.48 0.52 -0.32 -0.63 △MON 0.60 0.42 0.44 0.50 -0.31 -0.55 △(RON+MON)/2 0.63 0.43 0.46 0.51 -0.31 -0.59

Note:

1. The sulfur content of raw gasoline is 960ppm, RON is 93.7, and MON is 83.6.

2. △MON represents the added value of product MON;

3. △RON represents the added value of the product RON;

4. △(RON+MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.

It can be seen from the result data in Table 1 that the desulfurization catalyst provided by the present invention has better desulfurization activity and activity stability. The desulfurization catalyst has better wear resistance strength, so that the desulfurization catalyst has a longer service life.

Claims (15)

1. a kind of desulphurization catalyst, on the basis of the total weight of the desulphurization catalyst, which contains：

1) aluminium oxide of 5-30 weight %；

2) kaolin of 5-30 weight %；

3) the first metal oxide of 10-70 weight %, first metal oxide in IIB, VB and group vib metal extremely A kind of few oxide；

4) lead oxide of 2-20 weight %；

5) metallic promoter agent of 5-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；

6) the rare earth modified phosphate aluminium molecular sieve of 1-20 weight %.

2. desulphurization catalyst according to claim 1, wherein, on the basis of the total weight of the desulphurization catalyst, aluminium oxide Content for 10-20 weight %, kaolinic content is 10-20 weight %, and the content of first metal oxide is 35-54 Weight %, the content of lead oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-20 weight %, and the rare earth changes Property phosphate aluminium molecular sieve content be 2-20 weight %.

3. desulphurization catalyst according to claim 1, wherein, the rare earth modified phosphate aluminium molecular sieve is aluminate or phosphate, At least one of silicoaluminophosphate and silicoaluminophosphate that metalloaluminophosphate, metal combine.

4. according to the desulphurization catalyst described in any one in claim 1-3, wherein, with the rare earth modified phosphorus aluminium molecule On the basis of the total weight of sieve, the rare earth modified phosphate aluminium molecular sieve contains rare earths of the 5-15 weight % in terms of rare earth oxide.

5. desulphurization catalyst according to claim 1, wherein, first metal oxide is zinc oxide, cadmium oxide, oxygen Change at least one of vanadium, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide.

6. the preparation method of the desulphurization catalyst in claim 1-5 described in any one, this method include：

(1) rare earth modified phosphate aluminium molecular sieve, the first metal oxide, the precursor of lead oxide and water are mixed to get slurries；

(2) alumina binder, kaolin, water with acidic liquid are mixed, and carrier pulp is formed with the slurry liquid contacts, then The carrier pulp is molded, first drying and first roasting, obtain carrier；

(3) precursor of metallic promoter agent is introduced on the carrier, and carries out the second drying and the second roasting, before obtaining catalyst Body；

(4) catalyst precarsor under hydrogen atmosphere is reduced, obtains desulphurization catalyst.

7. according to the method described in claim 6, wherein, the precursor of the lead oxide is lead oxide or the carbonic acid of metallic lead At least one of salt, nitrate, chloride and hydroxide.

8. according to the method described in claim 6, wherein, the alumina binder is for aluminium oxide or in the described first roasting Under conditions of can be changed into the substance of aluminium oxide.

9. according to the method described in claim 6, wherein, the precursor of the metallic promoter agent for metallic promoter agent acetate, At least one of carbonate, nitrate, sulfate, rhodanate and oxide.

10. according to the method described in claim 6, wherein, the method that the precursor of the metallic promoter agent is introduced on carrier is Dipping or precipitation.

11. according to the method described in claim 6, wherein, the temperature of first drying is 80-120 DEG C, and described first dries Time be 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least 0.5h.

12. according to the method described in claim 6, wherein, the temperature of second drying is 50-300 DEG C, and described second dries Time be 0.5-8h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4h.

13. according to the method described in claim 6, wherein, the temperature of the reduction is 300-600 DEG C, the time of the reduction For 0.5-6h, hydrogen content is 10-60 volumes % in the hydrogen atmosphere.

14. desulphurization catalyst made from the preparation method in claim 6-13 described in any one.

15. a kind of method of desulfurization of hydrocarbon oil, this method include：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-5 and 14 Hydrodesulfurization catalyst described in middle any one, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5- 4MPa。