CN105289681B - A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents

Abstract

The invention discloses a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80% by weight of at least one metal oxide selected from group IIB, VB and VIB group elements; 2) 3-35% by weight % of titanium dioxide; 3) 5-40% by weight of silicon nitride; 4) 5-30% by weight of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The hydrocarbon oil desulfurization catalyst has better stability, higher desulfurization activity, better wear resistance and longer service life.

Description

A hydrocarbon oil desulfurization catalyst and its preparation method and method for hydrocarbon oil desulfurization

technical field

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

Background technique

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. Most of the sulfur in my country's gasoline products comes from thermally processed gasoline blending components, such as catalytic cracking gasoline. Therefore, the reduction of sulfur content in thermally processed gasoline will help reduce the sulfur content of gasoline products in my country. my country's current gasoline product standard GB 17930-2011 "Motor Gasoline" requires that by December 31, 2013, the sulfur content in gasoline products must be reduced to 50 μg/g. And the quality standards of gasoline products in the future will be stricter. In this case, FCC gasoline must undergo deep desulfurization to make gasoline products meet environmental protection requirements.

At present, the deep desulfurization methods of oil mainly include selective catalytic hydrodesulfurization and catalytic hydroadsorption desulfurization. Catalytic hydrogenation adsorption desulfurization is to realize the adsorption and removal of sulfide in hydrocarbon oil under certain temperature, pressure and hydrogen exposure conditions. This technology has the characteristics of low hydrogen consumption and low requirements on the purity of hydrogen, making this technology It has broad application prospects in fuel oil desulfurization.

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.

US6150300 discloses a method for preparing an adsorbent, including preparing spherical particles: (a) mixing a composition containing silicon dioxide, a composition containing metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding said first mixture; (b) spherical said first mixture to form particles having a diameter of 10-1000 mm. Wherein step (a) also includes mixing with a metal accelerator.

CN1422177A discloses an adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, expanded perlite, alumina and a promoter metal, wherein the promoter metal is substantially reduced present in the valence state and in an amount capable of removing sulfur from a cracked gasoline or diesel fuel stream when contacted with it under desulfurization conditions.

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.

Although the disclosed adsorbents have a certain desulfurization performance, with the improvement of gasoline quality standards, the requirements for the sulfur content of product gasoline are also becoming stricter. Moreover, such catalysts are prone to wear and tear during use, requiring constant replenishment of catalysts, which increases operating costs. 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 hydrocarbon oil desulfurization catalyst and its preparation method and a method for hydrocarbon oil desulfurization 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 hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80% by weight of at least one selected from IIB, VB and metal oxides of group VIB elements; 2) 3-35% by weight of titanium dioxide; 3) 5-40% by weight of silicon nitride; 4) 5-30% by weight of metal accelerators selected from the group consisting of at least one of cobalt, nickel, iron and manganese.

The present invention also provides a preparation method of the hydrocarbon oil desulfurization catalyst of the present invention, the method comprising: (1) mixing a titanium dioxide binder, water and an acidic liquid to obtain a titanium sol; (2) nitrogenating the titanium sol, Silicon, at least one metal oxide selected from IIB, VB and VIB group elements, and water are mixed, and the mixed carrier slurry is formed, first dried, and first calcined to obtain a carrier; (3) in the carrier Introducing the precursor of the metal promoter into the process, followed by the second drying and the second roasting to obtain the catalyst precursor; (4) reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.

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

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

The composition of the hydrocarbon oil desulfurization catalyst provided by the present invention contains stable silicon nitride, which reduces the correlation with metal oxides such as zinc oxide, and avoids the formation of zinc silicate substances, such as obtained in Example 1 shown in Figure 1 There is no characteristic peak of zinc silicate in the XRD spectrum of hydrocarbon oil desulfurization catalyst A1 after hydrothermal aging. The hydrocarbon oil desulfurization catalyst provided by the present invention has better stability and higher desulfurization activity, and can more effectively adsorb sulfur in hydrocarbon oil onto the hydrocarbon oil desulfurization catalyst in the process of hydrocarbon oil desulfurization, resulting in lower sulfur content hydrocarbon oil. Moreover, the hydrocarbon oil desulfurization catalyst provided by the invention has better wear resistance, lower catalyst loss and longer service life during the desulfurization process.

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

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the XRD spectrum of the hydrocarbon oil desulfurization catalyst A1 obtained in Example 1 before and after hydrothermal aging;

FIG. 2 is the XRD patterns of the hydrocarbon oil desulfurization catalyst B1 obtained in Comparative Example 1 before and after hydrothermal aging.

detailed description

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 present invention provides a hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80% by weight of at least one element selected from group IIB, VB and VIB Metal oxide; 2) 3-35% by weight of titanium dioxide; 3) 5-40% by weight of silicon nitride; 4) 5-30% by weight of a metal promoter selected from cobalt, nickel, iron and at least one of manganese.

Preferably, based on the total weight of the hydrocarbon oil desulfurization catalyst, the content of the metal oxide is 25-70% by weight, the content of titanium dioxide is 6-25% by weight, and the content of silicon nitride is 10-30% by weight , the content of the metal promoter is 8-25% by weight.

More preferably, based on the total weight of the hydrocarbon oil desulfurization catalyst, the content of the metal oxide is 40-60% by weight, the content of titanium dioxide is 8-15% by weight, and the content of silicon nitride is 12-25% by weight %, the content of the metal promoter is 12-20% by weight.

According to the present invention, the silicon nitride is white powder, and the silicon nitride can be α-phase silicon nitride and/or β-phase silicon nitride, and preferably, the silicon nitride is α-phase silicon nitride. The particle size of the silicon nitride powder may preferably be between 2000-500 mesh (ie 6.5-25 μm).

The hydrocarbon oil desulfurization catalyst provided by the invention contains silicon nitride, which can effectively avoid the formation of zinc silicate in the composition of the catalyst during the hydrocarbon oil desulfurization process and ensure better desulfurization activity of the catalyst. Preferably, there is no characteristic peak of zinc silicate at 2θ of 22.0, 25.54, 48.9 and 59.4 in the XRD spectrum of the hydrocarbon oil desulfurization catalyst after hydrothermal aging. The hydrothermal aging is carried out at a temperature of 500-700° C., a water vapor partial pressure of 10-30 kPa, and a treatment time of 10-24 hours.

According to the present invention, the at least one metal oxide selected from group IIB, VB and VIB group elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide. species, preferably, the metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide; preferably, the metal oxide is zinc oxide.

According to the present invention, preferably, the metal promoter is nickel and/or cobalt, and the hydrocarbon oil desulfurization catalyst can have high desulfurization activity and regeneration performance; more preferably, the metal promoter is nickel.

In the present invention, titanium dioxide can provide bonding effect between the components in the hydrocarbon oil desulfurization catalyst, and avoid the formation of aluminum binder and metal oxide when the hydrocarbon oil desulfurization catalyst undergoes desulfurization reaction and regeneration process. The spinel structure degrades the performance of the hydrocarbon oil desulfurization catalyst.

The present invention also provides a preparation method of the hydrocarbon oil desulfurization catalyst of the present invention, the method comprising: (1) mixing a titanium dioxide binder, water and an acidic liquid to obtain a titanium sol; (2) nitrogenating the titanium sol, Silicon, at least one metal oxide selected from IIB, VB and VIB group elements, and water are mixed, and the mixed carrier slurry is formed, first dried, and first calcined to obtain a carrier; (3) in the carrier Introducing the precursor of the metal promoter into the process, followed by the second drying and the second roasting to obtain the catalyst precursor; (4) reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.

In the preparation method step (2) of the hydrocarbon oil desulfurization catalyst provided by the present invention, the addition of the metal oxide may be in the form of powder of the metal oxide, or the metal oxide may be mixed with water to form a slurry Then add in the form of slurry.

According to the present invention, preferably, the titanium dioxide binder may be a substance that is hydrolyzed in an acidic liquid and transformed into anatase titanium dioxide under the conditions of the first calcination. Preferably, the titanium dioxide binder is at least one selected from titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide. Titanium dioxide binder can be hydrolyzed to form a colloidal solution of cohesiveness when contacted with excess acid solution.

In the present invention, the at least one metal oxide selected from group IIB, VB and VIB elements, silicon nitride and metal accelerator are as described above, and will not be repeated here.

According to the present invention, the acidic liquid may be an acid or an aqueous acid solution, the acid may be selected from water-soluble inorganic acids and/or organic acids, preferably the acid may be hydrochloric acid, nitric acid, phosphoric acid and acetic acid at least one of .

According to the present invention, during the mixing process in step (1), preferably, the acidic liquid is used in an amount such that the pH of the titanium sol is 1-5, preferably 1.5-4.

In the present invention, the amount of water added in step (1) is not particularly limited, as long as the titanium sol can be obtained. For example, the weight ratio of the amount of water added to the titanium dioxide binder is 5-10:1.

In the present invention, the carrier slurry obtained in step (2) may be in the form of paste or slurry. The carrier slurry can be thickened and then dried and reshaped. More preferably, the carrier slurry is in the form of a slurry, which can be spray-dried to form microspheres with a particle size of 20-200 microns to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the carrier slurry before drying is 10-50% by weight, preferably 20-50% by weight. The amount of water added in step (2) is not particularly limited, as long as the obtained carrier slurry satisfies the above-mentioned solid content.

In the present invention, the first drying method and conditions of the carrier slurry in step (2) are well known to those skilled in the art, for example, the drying method may be air drying, oven drying, or blast drying. Preferably, the temperature of the first drying can be from room temperature to 400°C, preferably 100-350°C; the time of the first calcination is more than 0.5h, preferably 0.5-100h, more preferably 2-20h.

In the present invention, the first calcination condition of the carrier slurry in step (2) is also well known to those skilled in the art, preferably, the temperature of the first calcination is 400-700°C, preferably 450-650°C; The time for the first calcination is at least 0.5h, preferably 0.5-100h, more preferably 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.

According to the present invention, preferably, the second drying temperature is 50-300°C, and the second drying time is 0.5-8h; preferably, the second drying temperature is 100-250°C, so The time for the second drying is 1-5h; the temperature for the second calcination is 300-800°C, and the time for the second calcination is more than 0.5h; preferably, the temperature for the second calcination is 450-750°C °C, the time for 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 precursor of the metal promoter is converted to the oxide form of the metal promoter, 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 400°C -500°C, preferably 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 present invention, preferably, the addition amount of the precursor of the titanium dioxide binder, silicon nitride, the metal oxide and the metal promoter makes the hydrocarbon oil desulfurization catalyst obtained contain the hydrocarbon oil Based on the total weight of the desulfurization catalyst, it contains 10-80% by weight of the metal oxide, 3-35% by weight of titanium dioxide, 5-40% by weight of silicon nitride, and 5-30% by weight of the metal promoter ; Preferably, containing 25-70% by weight of the metal oxide, 6-25% by weight of titanium dioxide, 10-30% by weight of silicon nitride, 8-25% by weight of the metal promoter; more preferably , containing 40-60% by weight of the metal oxide, 8-15% by weight of titanium dioxide, 12-25% by weight of silicon nitride, and 12-20% by weight of the metal accelerator.

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

The invention provides a method for desulfurizing hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the hydrocarbon oil desulfurization catalyst provided by the invention, the temperature of the contact is 350-500°C, the The contact pressure is 0.5-4 MPa; preferably, the contact temperature is 400-450° C., and the contact pressure is 1.0-2.0 MPa. During this process, the sulfur in the hydrocarbon oil is adsorbed onto the catalyst, resulting in a hydrocarbon oil with low sulfur content.

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.

In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons with a boiling range of 40°C to 210°C or any fraction thereof, which is derived from cracking larger hydrocarbon molecules into smaller molecules products of thermal or catalytic processes. 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" means a liquid composed of a hydrocarbon mixture or any fraction thereof with a boiling range of 170°C 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 (CS2), mercaptans, or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, alkane Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often present in diesel fuel.

The composition of the hydrocarbon oil desulfurization catalyst provided by the present invention contains a silicon nitride component, which is not easy to react with the zinc oxide component during the multiple reactions and regeneration processes of the catalyst, and will not produce zinc silicate substances to make the catalyst Hydrocarbon oil desulfurization catalyst reduces desulfurization activity due to loss of zinc oxide. The catalyst of the invention has high desulfurization activity, and at the same time has the property of obviously increasing the wear resistance of the catalyst, and is applicable to the desulfurization process of repeated reaction and regeneration of catalytic cracking gasoline or diesel engine fuel.

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

The hydrocarbon oil desulfurization catalyst obtained in Examples and Comparative Examples was obtained by X-ray diffractometer (Siemens D5005 type) to obtain XRD spectrum for structural determination, Cu target, Kα radiation, solid detector, tube voltage 40kV, tube current 40mA.

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

Example 1

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

(1) Prepare the carrier. 3.25kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99% by weight) was slowly added to 4.6kg of 5% by weight of dilute hydrochloric acid, stirred slowly to avoid the precipitation of titanium oxide crystals, and obtained a light yellow transparent titanium sol pH=2.0 ;

4.43kg of zinc oxide powder (Headhorse company, purity 99.7% by weight), 2.40kg of silicon nitride (purity>99.0% by weight, Qinhuangdao Yinuo High-tech Material Development Co., Ltd.) and 6.57kg of deionized water were mixed and stirred for 30 Minutes later, a mixed slurry of zinc oxide and silicon nitride was obtained; then the above-mentioned titanium sol was added, mixed and stirred for 1 hour to obtain a 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 180°C for 1h, and then calcined at 635°C for 1h to obtain the carrier;

(2) Preparation of catalyst precursor. The carrier of 3.2kg was impregnated with 3.51kg of nickel nitrate hexahydrate (Beijing Chemical Reagent Company, purity > 98.5% by weight) and 0.6kg of deionized aqueous solution. Roasting 1h, makes catalyst precursor;

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

The chemical composition of A1 is: the content of zinc oxide is 44.3% by weight, the content of silicon nitride is 24.0% by weight, the content of titanium dioxide is 13.6% by weight, and the content of nickel is 18.1% by weight.

Example 2

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

Get 1.25kg of titanium dioxide (anatase type, containing 1.17kg on a dry basis) and add it to 1.8kg of deionized water and 1.0kg of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant), pH=1.9, and stir to react 1h, a light yellow transparent titanium sol was obtained;

Mix 1.80 kg of silicon nitride, 5.52 kg of zinc oxide powder and 10.0 kg of deionized water under stirring to obtain a mixed slurry of zinc oxide and silicon nitride, then add the above titanium sol and stir for 1 h 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 hydrocarbon oil desulfurization catalyst A2 was obtained after reduction.

The chemical composition of A2 is: the content of zinc oxide is 55.2% by weight, the content of silicon nitride is 18.0% by weight, the content of titanium dioxide is 11.7% by weight, and the content of nickel is 15.1% by weight.

Example 3

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

Take 3.90kg of ethyl titanate (Aldrich company, analytically pure, 99% by weight) and 1.6kg of deionized water and slowly add it to 3.8kg of 10% by weight of nitric acid (analytically pure, produced by Beijing Chemical Plant) under the condition of stirring. In the solution, pH = 2.3, and stirred for 1 h to obtain a light yellow transparent titanium sol;

Mix 4.93 kg of zinc oxide powder, 2.1 kg of silicon nitride and 8.8 kg of deionized water, stir for 30 minutes to obtain a mixed slurry of zinc oxide and silicon nitride, then add titanium sol and stir for 1 hour to obtain a carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and formed.

The catalyst precursor and catalyst were prepared with reference to the method of Example 1, except that nickel nitrate and cobalt nitrate solutions were used instead of nickel nitrate hexahydrate to impregnate the carrier, and the active components nickel and cobalt were introduced, and hydrocarbon oil desulfurization catalyst A3 was obtained after reduction.

The chemical composition of A3 is: 49.3% by weight of zinc oxide, 21.0% by weight of silicon nitride, 13.5% by weight of titanium dioxide, 8.1% by weight of nickel, and 8.1% by weight of cobalt.

Example 4

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

Take 3.90kg of ethyl titanate (Aldrich company, analytically pure, 99% by weight) and 1.6kg of deionized water and slowly add it to 3.8kg of 10% by weight of nitric acid (analytically pure, produced by Beijing Chemical Plant) under the condition of stirring. In the solution, pH = 2.3, and stirred for 1 h to obtain a light yellow transparent titanium sol;

Mix 4.93kg of zinc oxide powder, 2.1kg of silicon nitride and 8.8kg of deionized water, and stir for 30 minutes to obtain a mixed slurry of zinc oxide and silicon nitride; then add titanium sol and stir 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 hydrocarbon oil desulfurization catalyst A4 was obtained after reduction.

The chemical composition of A4 is: the content of zinc oxide is 49.3% by weight, the content of silicon nitride is 21.0% by weight, the content of titanium dioxide is 13.5% by weight, and the content of nickel is 16.2% by weight.

Comparative example 1

4.43kg of zinc oxide powder and 6.57kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry;

Get pseudo-boehmite 1.81kg (catalyst Nanjing branch, containing dry basis 1.36kg) and 2.46kg of expanded perlite (catalyst Nanjing branch, containing dry basis 2.40kg) and stir and mix, then add deionized water 4.6kg to mix Uniformly, then add 360ml of 30% by weight hydrochloric acid pH = 2.1, stir for 1 hour to acidify, heat up to 80°C for aging for 2 hours, then add zinc oxide slurry, mix and stir for 1 hour to obtain carrier slurry;

Referring to the method of Example 1, carry out the spray drying of the carrier slurry and introduce the active component nickel, and obtain the hydrocarbon oil desulfurization catalyst B1 after reduction;

The chemical composition of B1 is: 44.3% by weight of zinc oxide, 24.0% by weight of expanded perlite, 13.6% by weight of alumina binder, and 18.1% by weight of nickel.

Comparative example 2

Take 1.56kg of pseudo-boehmite (produced by Shandong Aluminum Factory, containing 1.17kg on dry basis) and 1.85kg of diatomite (including 1.80kg on dry basis) and stir and mix, then add 8.2kg of deionized water and mix evenly, then add 260ml 30% by weight of hydrochloric acid pH = 1.9, stirred and acidified for 1 hour, then heated to 80° C. for 2 hours of aging. After the temperature drops, add 5.52kg of zinc oxide powder and stir for 1 hour to obtain a carrier slurry;

Referring to the method of Example 1, carry out the spray-drying and molding of the carrier slurry and introduce the active component nickel, and obtain the hydrocarbon oil desulfurization catalyst B2 after reduction;

The chemical composition of B2 is as follows: the content of zinc oxide is 55.2% by weight, the content of diatomite is 18.0% by weight, the content of alumina binder is 11.7% by weight, and the content of nickel is 15.1% by weight.

Comparative example 3

4.93kg of zinc oxide powder and 5.57kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry;

Take 1.80kg of pseudo-boehmite (produced by Shandong Aluminum Factory, containing 1.35kg on a dry basis) and 2.16kg of de-diatomite (World Mining Company, containing 2.10kg on a dry basis) and stir and mix, then add 4.6kg of deionized water to mix After uniformity, 300 ml of 30% by weight hydrochloric acid was added to make the pH of the slurry = 2.5, stirred and acidified for 1 hour, and then heated to 80° C. for 2 hours of aging. Then add the zinc oxide slurry and stir for 1 hour to obtain the carrier slurry;

Referring to the method of Example 3, the carrier slurry was spray-dried and formed, and the active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst B3 was obtained after reduction;

The chemical composition of B3 is: 49.3% by weight of zinc oxide, 21.0% by weight of diatomaceous earth, 13.5% by weight of alumina binder, 8.1% by weight of nickel, and 8.1% by weight of cobalt.

Comparative example 4

4.93kg of zinc oxide powder and 5.57kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry;

Get 1.80kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35kg on a dry basis) and 2.84kg of kaolin (Suzhou Kaolin Factory, containing 2.10kg on a dry basis) and stir and mix, then add 3.6kg of deionized water and mix evenly, then Add 300 ml of 30% by weight hydrochloric acid to make the pH of the slurry = 2.5, stir and acidify for 1 hour, then raise the temperature to 80° C. and age for 2 hours. Then add the zinc oxide slurry and stir for 1 hour to obtain the carrier slurry;

Referring to the method of Example 1, carry out the spray-drying and molding of the carrier slurry and introduce the active component nickel, and obtain the hydrocarbon oil desulfurization catalyst B4 after reduction;

The chemical composition of B4 is: the content of zinc oxide is 49.3% by weight, the content of kaolin is 21.0% by weight, the content of alumina binder is 13.5% by weight, and the content of nickel is 16.2% by weight.

Example 5

(1) Evaluation of abrasion resistance. The abrasion resistance strength test was carried out on the hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4. The straight pipe wear method is adopted, and the method refers to RIPP 29-90 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.

(2) Evaluation of desulfurization performance. The desulfurization evaluation experiment of hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 was carried out using a fixed bed micro-reactor experimental device. 16 grams of hydrocarbon oil 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 780ppm, 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 410°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 hydrocarbon oil desulfurization catalyst in actual industrial operation, the catalyst after the completion of the desulfurization evaluation experiment was regenerated in an air atmosphere at 550 °C. The hydrocarbon oil desulfurization catalyst was subjected to a desulfurization evaluation experiment. After 6 cycles of regeneration, its activity was basically stabilized. 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 the table 1.

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 .

Table 1

catalyst A1 A2 A3 A4 B1 B2 B3 B4 wear index 2.2 2.8 2.6 2.6 7.0 7.8 7.4 7.4 Product gasoline sulfur content/ppm 5 2 4 3 10 5 8 7 △MON -0.50 -0.40 -0.45 -0.45 -0.50 -0.45 -0.50 -0.45 △RON -0.45 -0.30 -0.45 -0.40 -0.45 -0.35 -0.40 -0.45 △(RON+MON)/2 -0.48 -0.40 -0.45 -0.43 -0.48 -0.40 -0.45 -0.45

Note:

1. The sulfur content of raw gasoline is 780ppm, RON is 93.0, and MON is 82.7.

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 hydrocarbon oil desulfurization catalyst provided by the present invention contains silicon nitride components, and the hydrocarbon oil desulfurization catalyst 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.

Example 6

Aging of hydrocarbon oil desulfurization catalysts A1-A4 and B1-B4 is carried out under the following conditions: placing the catalysts in an atmosphere of 600° C. and a water vapor partial pressure of 20 kPa for 16 hours.

The XRD patterns of A1-A4 and B1-B4 before and after aging were analyzed. Figure 1 is the XRD patterns of A1 before and after hydrothermal aging, and Fig. 2 is the XRD patterns of B1 before and after hydrothermal aging. A2-A4 have similar XRD patterns to A1, not shown; B2-B4 have similar XRD patterns to B1, not shown. In Figure 1, the characteristic peaks of 2θ=22.0, 25.54, 48.9 and 59.4 of zinc silicate do not appear in the XRD spectrum of A1 after hydrothermal aging; in Figure 2, the XRD spectrum of B1 after hydrothermal aging appears The above characteristic peaks of zinc silicate were obtained. The zinc silicate content in the XRD spectrum of B1-B4 was quantitatively analyzed by using the crystal phase content, and the results are shown in Table 2.

The desulfurization performance of A1-A4 and B1-B4 after aging was evaluated by the same evaluation method as in Example 5, and the results are shown in Table 2.

Table 2

catalyst A1 A2 A3 A4 B1 B2 B3 B4 Zinc silicate content/wt% 0 0 0 0 23.4 18.6 19.2 20.1 Product gasoline sulfur content/ppm 13 7 10 9 50 36 44 44 △MON -0.45 -0.35 -0.35 -0.40 -0.45 -0.40 -0.40 -0.45 △RON -0.40 -0.30 -0.35 -0.40 -0.40 -0.35 -0.40 -0.35 △(RON+MON)/2 -0.43 -0.33 -0.35 -0.40 -0.43 -0.38 -0.40 -0.40

As can be seen from the results in Table 2, after the aging process, zinc silicate is not generated in the hydrocarbon oil desulfurization catalyst of the embodiment, while the catalyst in the comparative example, zinc oxide can generate zinc silicate with the material containing silicon oxide, thereby Decrease the desulfurization activity of the catalyst.

Claims (14)

1. A hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80% by weight of zinc oxide; 2) 3-35% by weight of titanium dioxide; 3) 5-40% by weight of silicon nitride; 4) 5-30% by weight of metal promoter, said metal promoter is selected from at least one of cobalt, nickel, iron and manganese. 2. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein, based on the total weight of the hydrocarbon oil desulfurization catalyst, the content of zinc oxide is 40-60% by weight, and the content of titanium dioxide is 8-15% by weight , the content of silicon nitride is 12-25% by weight, and the content of the metal promoter is 12-20% by weight. 3. The hydrocarbon oil desulfurization catalyst according to claim 1 or 2, wherein the silicon nitride is α-phase silicon nitride. 4. The preparation method of the hydrocarbon oil desulfurization catalyst described in any one of claims 1-3, the method comprising: (1) mixing titanium dioxide binder, water and acidic liquid to obtain titanium sol; (2) mixing the titanium sol, silicon nitride, zinc oxide and water, and forming the carrier slurry obtained by mixing, first drying, and first roasting to obtain a carrier; (3) introducing the precursor of the metal promoter in the carrier, then carrying out the second drying and the second roasting to obtain the catalyst precursor; (4) Reducing the catalyst precursor in a hydrogen atmosphere to obtain a hydrocarbon oil desulfurization catalyst. 5. The preparation method according to claim 4, wherein the titanium dioxide binder is a substance that is hydrolyzed in the acidic liquid and transformed into anatase titanium dioxide under the first calcination conditions. 6. The preparation method according to claim 5, wherein the titanium dioxide binder is at least one selected from titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, and hydrated titanium oxide . 7. The preparation method according to claim 4, wherein the precursor of the metal accelerator is selected from acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal accelerator at least one of . 8. The preparation method according to claim 4, wherein the method of introducing the precursor of the metal promoter on the carrier is impregnation or precipitation. 9. The preparation method according to any one of claims 4-8, wherein the acidic liquid is an acid or an acid aqueous solution, and the acid is selected from water-soluble inorganic acids and/or organic acids; The amount of the acidic liquid makes the pH of the titanium sol 1-5. 10. The preparation method according to claim 4, wherein, the temperature of the first drying is room temperature-400°C, the time of the first drying is 0.5-8h; the temperature of the first calcination is 400-700°C °C, the time for the first calcination is more than 0.5h. 11. The preparation method according to claim 4, wherein, the temperature of the second drying is 50-300°C, the time of the second drying is 0.5-8h; the temperature of the second calcination is 300-800°C °C, the time for the second calcination is 0.5-4h. 12. The preparation method according to claim 4, wherein the reduction temperature is 300-600°C, the reduction time is 0.5-6h, and the hydrogen content in the hydrogen atmosphere is 10-60% by volume. 13. The hydrocarbon oil desulfurization catalyst prepared by the preparation method described in any one of claims 4-12. 14. A method for hydrocarbon oil desulfurization, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the hydrocarbon oil desulfurization catalyst described in any one of claims 1-3 and 13, the contact temperature 350-500°C, and the contact pressure is 0.5-4MPa.