CN101934217A - A kind of desulfurization adsorbent and its preparation method and application - Google Patents

Abstract

An adsorbent for removing sulfur from cracked gasoline and diesel fuel, based on the total weight of the adsorbent, comprising the following composition: 1) silicon oxide, with a content of 5-35 wt%, 2) aluminum oxide, with a content of 1 -20wt%, 3) tin oxide, the content is 3-30wt%, 4) at least one metal oxide selected from II B, VB and VIB, the content is 15-75wt%, 5) at least one selected from Metal promoters for cobalt, nickel, iron and manganese, the content is 5-30wt%. The adsorbent has good wear resistance and desulfurization activity.

Description

A kind of desulfurization adsorbent and its preparation method and application

technical field

The invention relates to an adsorbent composition suitable for desulfurization in cracked gasoline and diesel fuel, its preparation method and application.

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, because sulfur in fuel will affect the performance of automotive catalytic converters produce adverse effects. Sulfur oxides present in automobile engine exhaust can inhibit and irreversibly poison precious metal catalysts in converters. Exhaust gases from inefficient or poisoned converters contain unburned non-methane hydrocarbons and oxides of nitrogen and carbon monoxide, which are catalyzed by sunlight to form photochemical smog.

Most of the sulfur in gasoline in my country comes from thermally processed gasoline, mainly catalytic cracked gasoline, so the reduction of sulfur content in cracked gasoline will help reduce the sulfur content of these gasolines. my country's current gasoline product standard is GB17930-2006 "Automotive Gasoline", which further restricts the sulfur content in gasoline, requiring that by December 31, 2009, the sulfur content in gasoline will drop to 50ppm. In this case, FCC gasoline must undergo deep desulfurization to meet the requirements of environmental protection.

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.

In order to prepare an adsorbent with suitable physical and chemical properties, especially to improve the wear resistance of the adsorbent, it is often necessary to add structural components such as alumina binder, clay, and expanded perlite to the adsorbent. The addition of these components is of great help to the physical and chemical properties of the adsorbent, but it also brings some negative effects, that is, these added components are easy to form zinc aluminate with no sulfur storage capacity with zinc oxide in the adsorbent, thus Reduce the desulfurization activity of the adsorbent.

Patents CN 1048418 and CN 1151333 provide a novel absorbent composition containing zinc oxide, silicon dioxide, colloidal oxide and accelerator, and provide a preparation method for the adsorbent. The method adopts the method of pressure molding to prepare fluidizable particles, and at the same time, adds a flammable pore-forming agent to the colloid to increase its pore volume. The particles prepared by this method are relatively large, 100-300 microns, which is not the most favorable for the fluidization process.

The adsorbent introduced in the patent US 6150300, CN 1130253, and CN 1258396 is: a granular adsorbent composition comprising a mixture of zinc oxide, silicon oxide, aluminum oxide, reduced valence nickel or cobalt; its preparation method mainly adopts shearing Mix silicon oxide, aluminum oxide and zinc oxide and prepare solid particles through a granulator, dry and roast and impregnate nickel 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.

Patent CN 1208124 uses accelerator metals such as cobalt and nickel to impregnate the adsorbent carrier containing zinc oxide, expanded perlite and alumina, and then reduces the accelerator at a suitable temperature to prepare an adsorbent for removing sulfide in cracked gasoline . The wear resistance of the adsorbent was improved by adjusting the zinc oxide content and the binder (mainly alumina) in the adsorbent.

The above adsorbent adopts alumina binder, and zinc aluminate is formed during the preparation process, which reduces the desulfurization activity of the adsorbent.

Contents of the invention

The present invention provides an adsorbent for removing sulfur from cracked gasoline and diesel fuel, which adsorbent has good wear resistance and desulfurization activity.

The present invention also provides a preparation method of the above-mentioned adsorbent.

The present invention also provides the use of the above-mentioned adsorbent.

The desulfurization adsorbent provided by the present invention is based on the total weight of the adsorbent, and comprises the following compositions:

1) silicon oxide, the content is 5-35wt%,

2) Aluminum oxide, the content is 1-20wt%

3) tin oxide, the content is 3-30wt%,

4) an oxide of at least one metal selected from IIB, VB and VIB, the content is 15-75wt%,

5) At least one metal promoter selected from cobalt, nickel, iron and manganese, the content is 5-30wt%.

Preferably, the content of silicon oxide is 6-25wt%, the content of aluminum oxide is 2-15wt%, the content of tin oxide is 5-25wt%, at least one metal oxide selected from II B, VB and VIB The content of the metal accelerator is 35-65wt%, and the content of the metal promoter is 8-25wt%.

More preferably, the content of silicon oxide is 8-18wt%, the content of aluminum oxide is 3-12wt%, the content of tin oxide is 8-18wt%, and at least one metal oxide selected from II B, VB and VIB The content of the compound is 40-58wt%, and the content of the metal accelerator is 12-20wt%.

The at least one metal oxide selected from II B, VB and VIB is a metal oxide with sulfur storage properties, preferably oxides of elements such as vanadium, zinc or molybdenum, most preferably zinc oxide.

The metal promoter can be any metal capable of reducing oxidized sulfur to hydrogen sulfide. The promoter component contains at least one or more metals selected from cobalt, nickel, iron and manganese, and the preferred metal promoter contains nickel.

The preparation method of adsorbent provided by the invention comprises:

(1) make tin dioxide precursor hydrolyze in acidic solution, form sol;

(2) contacting the sol of (1) with a silicon oxide source and one or more metal oxides selected from IIB, VB and VIB to form a carrier mixture;

(3) forming the above mixture, and drying and roasting to form a carrier;

(4) introducing a compound component containing at least one promoter metal selected from cobalt, nickel, iron and manganese on the carrier of (3), and drying and roasting to obtain the adsorbent precursor;

(5) Reducing the adsorbent precursor obtained in (4) in a hydrogen-containing atmosphere, so that the promoter metal basically exists in a reduced state.

In step (1), the precursor of tin dioxide is a compound that can be hydrolyzed in step (1), roasted in step (3), and exists in the form of tin dioxide, preferably tin tetrachloride, tetraisopropyl One or more of tin alkoxide, tin acetate, and hydrated tin oxide. When the tin oxide precursor contacts with excess acid solution, it can be hydrolyzed and generate a colloidal solution with cohesive properties. The acid is selected from one or more of water-soluble inorganic acids and/or organic acids, preferably one or more of hydrochloric acid, nitric acid, phosphoric acid and acetic acid, wherein the amount of acid is such that after hydrolysis The pH of the solution is less than 6.0, preferably less than 4.0, to form a sol.

In step (2), the silicon oxide source may be pure silicon oxide or a natural mineral with a silicon oxide content greater than 45 wt % and an aluminum oxide content greater than 10 wt %. Natural minerals may also contain other components such as K ₂ O, CaO, MgO, Fe ₂ O ₃ , TiO ₂ and so on. The silica source is selected from one or more of pillar clay, diatomaceous earth, expanded perlite, siliceous rock, hydrolyzed silica, macroporous silica and silica gel, preferably pillar clay. The layered pillar clay is an interlayer mineral crystal, which is composed of two kinds of single-layer mineral clay components regularly arranged alternately, and the distance between the bottom surfaces is not less than 1.7nm. Examples of the layered clay include, but are not limited to, rectorite, dolomite, bentonite, montmorillonite, and smectite, etc., preferably rectorite, which is composed of non-expandable mica layers and expandable smectite. A crystalline mineral clay formed by alternating and orderly arrangement of adjacent 2:1 clay layers, characterized in that there is a strong peak at 3.4° in the XRD spectrum of the composition.

The one or more metal oxides selected from IIB, VB and VIB are preferably oxides of elements such as vanadium, zinc or molybdenum.

The silicon oxide source, the metal oxide and the sol of the tin oxide precursor may be contacted and mixed in any manner. The metal oxide powder can be directly added to the sol, or a pre-prepared oxide slurry can also be added. The silicon oxide source can be added to the excess acid solution together with the tin oxide precursor in step (1), or can be added to the sol in step (2), or can be added to the metal oxide slurry first.

In step (3), the resulting carrier mixture is shaped into extrudates, tablets, pellets, spheres or microspheroidal particles. For example, when the carrier mixture is a dough or pasty mixture, the mixture can be molded (preferably extruded) to form granules, preferably cylindrical extrusions with a diameter of 1.0-8.0 mm and a length of 2.0-5.0 mm. The extrudate obtained is then 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 carrier mixture is in the form of a slurry, which is 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 slurry before drying is 10-50wt%, preferably 20-50wt%.

The drying method and conditions of the carrier mixture are well known to those skilled in the art, for example, the drying method may be air drying, oven drying, or blow drying. The drying temperature can be from room temperature to 400°C, preferably 100-350°C.

The calcination conditions of the carrier mixture are also well known to those skilled in the art. Generally speaking, the calcination temperature is 400-700°C, preferably 450-650°C, and the calcination time is at least 0.5 hour, preferably 0.5-100 hour, more preferably 0.5-10 hours.

In step (4), the compound component containing the promoter metal is a substance that can be converted into a metal oxide under calcination conditions. The metal promoter compound can be selected from metal acetates, carbonates, nitrates, sulfates, thiocyanates and oxides, and mixtures of two or more thereof. Nickel is preferably contained in the promoter metal. The promoter metals can be introduced on the support by impregnation or precipitation methods known to those skilled in the art. The impregnation method is to impregnate the calcined carrier with a solution or suspension of a compound containing a promoter metal; the precipitation method is to mix the solution or suspension of a compound containing a promoter metal with an adsorbent carrier, and then add ammonia water , the compound of the promoter metal is precipitated on the support.

The carrier introduced with the accelerator is dried at about 50-300°C, preferably at a drying temperature of 100-250°C, and the drying time is about 0.5-8 hours, more preferably about 1-5 hours. After drying, in the presence of oxygen or an oxygen-containing gas, calcining is carried out at a temperature of about 300-800°C, more preferably 450-750°C. The time required for calcining is generally about 0.5-4 hours, preferably 1- 3 hours, until the volatiles were removed and the promoter metal precursor was converted to metal oxide, yielding the adsorbent precursor.

In step (5), the adsorbent precursor is reduced in a hydrogen-containing atmosphere at 300-600°C, so that the promoter metal basically exists in a reduced state, and the adsorbent of the present invention is obtained. The preferred reduction temperature is 400-500°C, the hydrogen content is 10-60vol%, and the reduction time is 0.5-6 hours, more preferably 1-3 hours.

The present invention also provides a desulfurization method for cracked gasoline or diesel engine fuel, comprising fully contacting the sulfur-containing raw material with the adsorbent of the present invention at 350-500°C, preferably 400-450°C, during which the sulfur in the raw material Adsorbed on the adsorbent to obtain a product with low sulfur content. The adsorbent can be reused after the oxidation-reduction regeneration process.

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 adsorbent of the present invention has high wear resistance strength and large pore volume, and can be applied to the adsorption desulfurization process; and due to the use of non-aluminum binders, it is avoided that part of the zinc oxide forms zinc aluminate, thereby greatly improving the adsorption capacity of the adsorbent. activity and stability.

Description of drawings

Fig. 1 is the structural representation of the retort clay adopted in embodiment 1 and embodiment 2, wherein A is the mica layer that cannot expand, B is the smectite layer that can expand, C is the clay layer, and D is the smectite layer The exchangeable cation in E is the fixed cation in the mica layer. The basal spacing (d001) of the retort soil is 1.9-2.9 nm.

The chemical composition expression of the retort soil is:

{(Na _0.72 K _0.02 Ca _0.05 )(Ca _0.24 Na _0.07 )}(Al _4.00 Mg _0.02 )[Si _6.58 Al _1.62 ]O ₂₂

Among them, the (Na _0.72 K _0.02 Ca _0.05 ) part represents the interlayer fixed cation; the (Ca _0.24 Na _0.07 ) part represents the interlayer exchangeable cation; the (Al _4.00 Mg _0.02 ) part represents the hexacoordinated ion; the [Si _6.58 Al _1.62 ] part Indicates a tetracoordinated ion.

Figure 2 is the X-ray diffraction pattern of rector soil, which is characterized by a strong peak (characteristic peak) at 3.4°, which is associated with the height of the layer column. The XRD test was carried out on a D5005 X-ray diffractometer from Siemens, Germany, with a Cu target, K _α radiation, a solid-state detector, a tube voltage of 40kV, and a tube current of 40mA.

Fig. 3 is the XRD spectrum of the adsorbent A1 in Example 1. It can be seen from Fig. 1 that the crystal phase of the adsorbent A1 is mainly composed of zinc oxide, nickel oxide, rector earth and tin dioxide. The corresponding relationship of each component on the XRD pattern is 1: rector earth; 2: SnO ₂ ; 3: ZnO; 4: NiO.

Detailed ways

The following examples will further illustrate the present invention, but do not thereby limit the present invention.

The desulfurization effect is measured by the sulfur content of the product, and the sulfur content in the product is analyzed by off-line chromatography; the composition of the adsorbent is analyzed by X-ray fluorescence (XRF) analysis method.

Example 1

Slowly add 3.29 kg of crystalline tin tetrachloride (SnCl ₄ .5H ₂ O, Alfa Aesar, 99%) into 3.2 kg of acidic water, and stir slowly to avoid the precipitation of tin oxide crystals. At this time, the solution is a colorless and transparent gel solution, known as tin sol.

5.55 kilograms of zinc oxide powder (produced by Beijing Chemical Plant, containing 5.38 kilograms on a dry basis) and 10.8 kilograms of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry; Base 1.84 kg, silicon oxide content 50wt%, aluminum oxide content _43wt .%, the rest are impurities such as CaO, _Fe2O3 , MgO, _K2O ), and stirred for 15 minutes. Then add the above tin sol, mix and stir for 1 hour to obtain carrier slurry.

The carrier slurry is spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray-drying pressure is 8.5 to 9.5 MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 180°C for 1 hour, and then calcined at 635°C for 1 hour to obtain the adsorbent carrier.

3.24 kg of adsorbent carrier (3.0 kg on a dry basis) was impregnated with 2.42 kg of nickel nitrate hexahydrate (Yixing Xuchi Chemical Factory) and 1.2 kg of deionized aqueous solution. The adsorbent precursor can be prepared by roasting at ℃ for 1 hour. The adsorbent can be obtained by reducing the adsorbent precursor in a hydrogen atmosphere at 425° C. for 2 hours, and this adsorbent is designated as adsorbent A1.

The main chemical composition of adsorbent A1 is: the content of zinc oxide is 53.8wt%, the content of tin dioxide is 14.0wt%, the content of aluminum oxide is 7.9wt%, the content of silicon oxide is 9.2wt%, nickel (calculated as metallic nickel) It is 13.8wt%.

Example 2

2.54 kg of tin acetate (Aldrich company, analytically pure, 99%) was slowly added to 3.2 kg of 5% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) solution under stirring and stirred for 1 hour. Yellow transparent colloidal solution, called tin sol.

4.88 kilograms of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.73 kilograms on a dry basis) and 3.50 kilograms of retort earth (containing 2.62 kilograms on a dry basis, with a silicon oxide content of 50wt%, an aluminum oxide content of 43wt.%, and the rest being CaO, Fe ₂ O ₃ , MgO, K ₂ O and other impurities) were added into 10.8 kg of deionized water, and stirred for 30 minutes. Then add the above-mentioned hydrolyzed tin sol, mix and stir for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent A2. The main chemical composition of adsorbent A2 is: zinc oxide content is 47.3wt%, the content of tin dioxide is 10.7wt%, aluminum oxide content is 11.3wt%, silicon oxide content is 13.1wt%, nickel (calculated as metal nickel) It is 15.8wt%.

Example 3

3.32 kilograms of tin tetraisopropoxide (Aldrich company, analytically pure, 99%) were slowly added to 3.2 kilograms of 5% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) solution under stirring and stirred for 1 hour, at this time The solution is light yellow transparent colloidal solution, called tin sol.

5.55 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 5.38 kg on a dry basis) and 1.89 kg of expanded perlite (containing 1.84 kg on a dry basis, with a silicon oxide content of 72wt%, an alumina content of 19wt.%, and the rest being CaO, Fe ₂ O ₃ , MgO and other impurities) were added into 10.8 kg of deionized water, and stirred for 30 minutes. Then add the above-mentioned hydrolyzed tin sol, mix and stir for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent A3. The main chemical composition of adsorbent A3 is: zinc oxide content is 53.8wt%, the content of tin dioxide is 14.0wt%, aluminum oxide content is 3.5wt%, silicon oxide content is 13.2wt%, nickel (calculated as metallic nickel) It is 13.8wt%.

Comparative example 1

In this comparative example, aluminum oxide was used as the binder.

5.55 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 5.38 kg on a dry basis) and 10.8 kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry.

Take 1.91 kg of alumina (produced by Shandong Aluminum Works, containing 1.4 kg on a dry basis) and 2.46 kg of retort earth (including 1.84 kg on a dry basis) and mix them under stirring, then add 4.0 kg of deionized water and mix well, then add 400 ml 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was stirred and acidified for 1 hour, and then heated to 80° C. for 2 hours of aging. Then add the above zinc oxide slurry, mix and stir for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent B1. The main chemical composition of the adsorbent B1 is as follows: zinc oxide content is 53.8wt%, aluminum oxide content is 21.9wt%, silicon oxide content is 9.2wt%, nickel (calculated as metal nickel) is 13.8wt%.

Comparative example 2

In this comparative example, aluminum oxide was used as the binder.

4.88 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.73 kg on a dry basis) and 3.50 kg of retort earth (containing 2.62 kg on a dry basis) were added to 11.8 kg of deionized water, and stirred and mixed for 30 minutes to obtain a mixed slurry.

Take 1.46 kg of alumina monohydrate (SB powder, containing 1.07 kg on a dry basis) and add it to 3.6 kg of deionized water, and stir for 10 minutes; then add 350 ml of 30% nitric acid (chemically pure, produced by Beijing Chemical Factory) and stir to acidify 1 hour. Then add the zinc oxide and retort earth slurry, mix and stir for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent B2. The main chemical composition of the adsorbent B2 is: zinc oxide content 47.3wt%, aluminum oxide content 22.0wt%, silicon oxide content 13.1wt%, nickel (calculated as metal nickel) 15.8wt%.

Comparative example 3

Get 1.91 kg of alumina (produced by Shandong Aluminum Plant, containing 1.4 kg on a dry basis) and 4.0 kg of ionized water, mix evenly, add 360 ml of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for acidification for 1 hour, then heat up to 80 After aging at ℃ for 2 hours, it was cooled to room temperature.

5.55 kilograms of zinc oxide powder (produced by Beijing Chemical Plant, containing 5.38 kilograms on a dry basis) and 1.89 kilograms of expanded perlite (containing 1.84 kilograms on a dry basis, with a silicon oxide content of 72wt%, an aluminum oxide content of 19wt.%, and the rest being GaO, Fe ₂ O ₃ , MgO and other impurities) were added into 10.8 kg of deionized water, and stirred for 30 minutes. Then add the above-mentioned alumina sol, mix and stir for 1 hour to obtain a carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent B3. The main chemical composition of the adsorbent B3 is: zinc oxide content is 53.8wt%, aluminum oxide content is 17.5wt%, silicon oxide content is 13.2wt%, nickel (calculated as metal nickel) is 13.8wt%.

Example 4

Two indicators of wear resistance strength and desulfurization performance were investigated for the adsorbents prepared by different methods. The strength of the adsorbent is evaluated by the straight tube wear method. The evaluation method refers to the method of RIPP 29-90 in the "Petrochemical Analysis Method (RIPP) Experimental Method". The smaller the value, the higher the wear resistance. The wear evaluation results of different adsorbents are shown in Table 1.

In order to investigate the performance of the adsorbent, the crystal phase composition of A1-A3 and B1-B3 was analyzed. 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 equipped with a long fine-focus copper X-ray source driven at 40kV, 30mA; a Philips 3020 digital goniometer and a Philips 3710 MPD 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 adsorbents are shown in Table 1.

At the same time, the following methods were used to evaluate the desulfurization performance of these adsorbents. The desulfurization effect is measured by the sulfur content of the product, and the sulfur content in the product is analyzed by off-line chromatography. The desulfurization performance of the adsorbent was evaluated using a fixed-bed micro-reactor experimental device, and the raw material for the adsorption reaction was FCC gasoline with a sulfur concentration of 1080ppm. The adsorption test process adopts a hydrogen atmosphere, the reaction temperature is 410°C, and the weight space velocity of the adsorption reaction is 4h ^-1 . In order to accurately characterize the activity of the adsorbent in the actual industrial operation, the adsorbent is regenerated after the reaction is completed. Carried out in an air atmosphere at 550°C. The activity of the adsorbent is basically stabilized after 6 cycles of reaction and regeneration. The sulfur content in the product gasoline after the adsorption is stabilized represents the activity of the adsorbent. The sulfur content in the product gasoline after stabilization is shown in Table 2. At the same time, the sulfur content of the reacted adsorbent was analyzed, and the results are shown in Table 2.

Table 1 Abrasion strength and zinc aluminate content of different adsorbents

Adsorbent A1 A2 A3 B1 B2 B3 wear index 6.8 5.0 8.4 6.8 5.1 8.6 ZnAl2O4, wt% 0 0 0 10.5 8.7 9.2

Table 2 Adsorption and desulfurization performance of different adsorbents

Adsorbent A1 A2 A3 B1 B2 B3 Sulfur content in product gasoline/ppm 39 36 40 76 68 78 RON 93.1 93.0 93.0 93.0 93.0 93.0 MON 82.0 81.9 81.9 82.0 81.8 81.9

Δ(RON+MON)/2 0.35 0.45 0.45 0.4 0.5 0.45

Note: The sulfur content of raw gasoline is 1080ppm, RON is 93.1, and MON is 82.7.

Claims (21)

1. a desulfuration adsorbent is a benchmark with the adsorbent gross weight, comprises following composition:

1) silica, content are 5-35wt%,

2) aluminium oxide, content are 1-20wt%,

3) tin oxide, content are 3-30wt%,

4) be selected from the oxide of at least a metal among IIB, VB and the VIB, content is 15-75wt%,

5) at least a metallic promoter agent that is selected from cobalt, nickel, iron and manganese, content is 5-30wt%.

2. according to the described adsorbent of claim 1, it is characterized in that the content of silica is 6-25wt%, the content of aluminium oxide is 2-15wt%, the content of tin oxide is 5-25wt%, and the content of metal oxide is 35-65wt%, and the content of metallic promoter agent is 8-25wt%.

3. according to the described adsorbent of claim 1, it is characterized in that the content of silica is 8-18wt%, the content of aluminium oxide is 3-12wt%, the content of tin oxide is 8-18wt%, and the content of metal oxide is 40-58wt%, and the content of metallic promoter agent is 12-20wt%.

4. according to the described adsorbent of claim 1, it is characterized in that described metal oxide is selected from the oxide of elements such as at least a vanadium, zinc or molybdenum.

5. according to the described adsorbent of claim 1, it is characterized in that, contain nickel in the metallic promoter agent.

6. the described preparation of adsorbent method of claim 1 comprises:

(1) makes the hydrolysis in acid solution of tin ash precursor, form colloidal sol;

(2) colloidal sol that makes (1) and silica source be selected from IIB, VB and contact with one or more metal oxides among the VIB, form carrier mixture;

(3) make the said mixture moulding, and drying and roasting, carrier formed;

(4) introducing contains at least a compound component that is selected from the promoter metals of cobalt, nickel, iron and manganese on the carrier of (3), and drying and roasting, obtains the adsorbent precursor;

(5) the adsorbent precursor that (4) are obtained reduces under hydrogeneous atmosphere, and promoter metals is existed to go back ortho states basically.

7. according to the described preparation method of claim 6, it is characterized in that, in the step (1), one or more in the preferred butter of tin of described tin ash precursor, four isopropyl alcohol tin, tin acetate, the stannic hydroxide.

8. according to the described preparation method of claim 6, it is characterized in that in the step (1), described acid is selected from one or more in water-soluble inorganic acid and/or the organic acid.

9. according to the described preparation method of claim 6, it is characterized in that in the step (1), described acid is selected from one or more in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid.

10. according to the described preparation method of claim 6, it is characterized in that in the step (1), the consumption of described acid is to make the pH value of solution after the hydrolysis less than 6.0.

11., it is characterized in that in the step (1), the consumption of described acid is to make the pH value of solution after the hydrolysis less than 4.0 according to the described preparation method of claim 6.

12. according to the described preparation method of claim 6, it is characterized in that, in the step (2), described silica source be pure silica or silica content greater than 45wt%, alumina content is greater than the natural minerals of 10wt%.

13., it is characterized in that in the step (2), silica source is selected from one or more in laminated clay column, diatomite, expanded perlite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and the silica gel according to the described preparation method of claim 6.

14., it is characterized in that described laminated clay column is alternately to be rearranged by two kinds of individual layer mineral clay component rules according to the described preparation method of claim 13, its basal spacing is not less than 1.7nm.

15., it is characterized in that described laminated clay column includes but not limited to rectorite, Yun Mengshi, bentonite, imvite and smectite etc. according to the described preparation method of claim 14.

16., it is characterized in that in the step (2), one or more metal oxides among the described IIB of being selected from, VB and the VIB are selected from the oxide of elements such as vanadium, zinc or molybdenum according to the described preparation method of claim 6.

17., it is characterized in that in the step (3), the baking temperature of carrier mixture is a room temperature to 400 ℃ according to the described preparation method of claim 6, the sintering temperature of carrier mixture is 400-700 ℃.

18. according to the described preparation method of claim 6, it is characterized in that, in the step (4), the compound of described promoter metals is selected from the acetate of metal, carbonate, nitrate, sulfate, rhodanate and oxide, and two or more mixture wherein.

19., it is characterized in that in the step (4), the carrier of introducing promoter carries out drying under about 50-300 ℃, under the condition that has oxygen or oxygen-containing gas to exist, carries out roasting under about 300-800 ℃ temperature according to the described preparation method of claim 6.

20. according to the described preparation method of claim 6, it is characterized in that, in the step (5), the adsorbent precursor reduced under 300-600 ℃ of hydrogeneous atmosphere.

21. the sulfur method of cracking gasoline or diesel fuel, be included in the sulfur-bearing raw material is fully contacted with the described adsorbent of one of claim 1-5, sulphur in this process in the raw material is adsorbed on the adsorbent, thereby obtains the gasoline or the diesel fuel of low sulfur content.

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