CN102114405B - Desulfurizing and adsorption agent containing titanium, preparation method and application thereof - Google Patents

Abstract

An adsorbent for removing sulfur from cracked gasoline and diesel fuel, comprising the following components: 1) cleaved muscovite, 2) titanium dioxide binder, 3) one selected from IIB, VB and VIB One or more metal oxides, 4) at least one metal promoter selected from cobalt, nickel, iron and manganese. The adsorbent has good attrition strength and desulfurization activity, and can be used to remove elemental sulfur and sulfides, such as hydrogen sulfide and organic sulfides, from cracked gasoline and diesel fuels.

Description

A kind of titanium-containing desulfurization adsorbent and its preparation method and application

technical field

The invention relates to an adsorbent for desulfurization from liquid raw materials of 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 GB 17930-2006 "Automotive Gasoline", which further restricts the sulfur content in gasoline, requiring that the sulfur content in gasoline be reduced to 50ppm by December 31, 2009. In this case, FCC gasoline must undergo deep desulfurization to meet the requirements of environmental protection.

In order to ensure the combustion performance of automobile fuel, while reducing the sulfur content of automobile fuel, it should also try to avoid the change of its olefin content so as to reduce its octane number (including ROM and MON). The negative impact on olefin content is generally caused by the removal of thiophenes (including thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes) while simultaneously initiating hydrogenation reactions. In addition, it is also necessary to avoid such conditions that the aromatics of cracked gasoline are also lost through saturation, so the most ideal method is to achieve desulfurization while maintaining its octane number.

On the other hand, both hydrodesulfurization and hydrogenation of unsaturated hydrocarbons need to consume hydrogen, which increases the operating cost of desulfurization. There is therefore a need for a method of desulfurization without large hydrogen consumption, thereby providing a more economical method for cracked gasoline and diesel fuel treatment.

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.

CN 115133A provides a novel absorption composition containing zinc oxide, silicon dioxide, colloidal oxide and accelerator, and provides the preparation method of this 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 US 6150300 is: a granular adsorbent composition comprising a mixture of zinc oxide, silicon oxide, aluminum oxide, reduced valence nickel or cobalt; its preparation method is mainly to use methods such as shearing to convert silicon oxide, oxidized Aluminum and zinc oxide are mixed and passed through a granulator to prepare solid particles, which are dried and calcined and then impregnated with 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.

In CN 1208124C, a promoter metal such as cobalt and nickel is used to impregnate an adsorbent carrier containing zinc oxide, expanded perlite and alumina, and then reduce the promoter at a suitable temperature to prepare an adsorbent for removing sulfide in cracked gasoline. The wear resistance of the adsorbent is improved by adjusting the zinc oxide content and the binder (mainly Condea's Disperal and Vista Dispal's alumina) in the adsorbent. In CN 1627988A, these compounds mainly generated under the reaction conditions are discussed in detail, and the particles prepared by the spray-drying method in this patent are more suitable for fluidized beds in terms of physical and chemical properties. Described in detail in CN 1856359A, CN 1871063A the adsorbent of similar composition and its preparation method.

In these adsorbent preparation methods, the strength of the adsorbent is improved by adding clay, but since the clay itself has no pores, it is easy to make the pore volume of the adsorbent smaller and reduce the activity of the adsorbent. At the same time, alumina binder is used, and zinc aluminate is formed during the preparation process, thereby reducing the desulfurization activity. Accordingly, it would be desirable to provide a new sorbent composition useful for the removal of sulfur from cracked gasoline and diesel fuel, and to provide a method for preparing the sorbent.

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. Compared with existing adsorbents, one of the most notable features of the adsorbent is high activity stability.

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 present invention is based on the discovery that the use of novel material cleaved mica, by forming an adsorbent support comprising zinc oxide, mica and metal oxide binders, can produce a support assembly with very good abrasion resistance points to prolong the service life of the adsorbent; and the use of a new type of titanium dioxide binder can avoid the formation of zinc aluminate, thereby increasing the activity of the adsorbent.

The adsorbent provided by the present invention, based on the total weight of the adsorbent, at least includes the following compositions:

1) a silicon oxide source containing at least mica in an amount of 5-40 wt%,

2) Titanium dioxide binder, the content is 3-35wt%,

3) at least one metal oxide selected from IIB, VB and VIB, the content is 10-80wt%,

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

Preferably, the content of the silica source containing mica is 10-30wt%, the content of the titanium dioxide binder is 8-25wt%, and the content of at least one metal oxide selected from IIB, VB and VIB is 25-25wt%. 70 wt%, and the content of the promoter metal selected from cobalt, nickel, iron and manganese is 8-25 wt%.

More preferably, the content of the silica source containing mica is 15-27wt%, the content of the titanium dioxide binder is 10-15wt%, and the content of at least one metal oxide selected from IIB, VB and VIB is 40% - 60 wt%, the content of the metal promoter selected from cobalt, nickel, iron and manganese is 12-20 wt%.

The mica is cleaved mica. Mica is a layered silicate, which is a compound silicon-oxygen layer composed of two layers of silicon-oxygen tetrahedron sandwiching a layer of aluminum-oxygen octahedron. Its basic structure is the silicon-oxygen tetrahedral structure of [AlSi ₃ O ₁₀ ]. Si ⁴⁺ is replaced by Al ³⁺ . Completely cleaved mica can be split into extremely thin flakes with a thickness of less than 1 μm. Its chemical structure is:

AB ₂ [AlSi ₃ O ₁₀ ]·(OH) ₂

Wherein A represents K, Na and/or Li; B represents Al and/or Fe.

The mica can be classified into muscovite, phlogopite, pearl mica, phlogopite, biotite, etc. according to the difference in color and shape, and the muscovite after cleavage is preferred in the present invention. Muscovite has the characteristics of small natural particle size, easy processing and ultrafine; its chemical composition, structure, and structure are similar to kaolin, and it also has some characteristics of clay minerals, that is, it has good dispersion and suspension in aqueous media and organic solvents, and is viscous. Etc. Its general chemical composition (mass) is: SiO ₂ content of 44.9-50.3%, Al ₂ O ₃ content of 27.9-39.5%; M ₂ O content of 8.9-10.1% (M is a group IA compound), H ₂ O content It is 4.2-6.2%, and also contains a small or trace amount of Fe ₂ O ₃ , Mn ₂ O ₃ , CaO, etc.

In addition to mica, the adsorbent of the present invention can also contain other silica sources, such as clay (including kaolin, layered clay, etc.), diatomaceous earth, silica sol, silica gel, macroporous silica and expanded perlite, etc. One or more of them, the ratio of the mass of other silicon oxide sources to the mass of mica is no more than 4:1, preferably no more than 2:1, more preferably no more than 1:1.

The oxide of one or more metals selected from IIB, VB and VIB is preferably one or more of vanadium oxide, zinc oxide or molybdenum oxide, most preferably zinc oxide.

The promoter metal may 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, preferably the promoter metal contains nickel.

According to another aspect of the present invention, a kind of preparation method of adsorbent system is provided, comprising:

(1) hydrolyzing the titanium dioxide precursor in an acidic liquid to form a sol;

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

(3) introducing a compound containing a promoter metal into the carrier of (2) to obtain an adsorbent precursor;

(4) drying, roasting the adsorbent precursor in (3);

(5) Reducing the roasted adsorbent precursor in a hydrogen atmosphere to obtain an adsorbent.

In step (1), the titanium dioxide precursor is a compound that can exist in the form of anatase titanium dioxide after being hydrolyzed and roasted in an acidic liquid, preferably titanium tetrachloride, ethyl titanate, isopropyl titanate, One or more of titanium acetate, hydrated titanium oxide and anatase titanium dioxide. Among them, anatase titanium dioxide can still generate anatase titanium dioxide after hydrolysis and roasting. The precursor of titanium dioxide can be hydrolyzed to form a colloidal solution when contacted with excess acid solution.

The acidic liquid can be an acid or an aqueous solution of an acid, and the acid is selected from one or more of water-soluble inorganic acids and/or organic acids, preferably one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid. species or several. The amount of acid used is such that the pH of the slurry is 1-5, preferably 1.5-4.

In step (2), the sol in step (1) is mixed with a silicon oxide source containing at least mica and one or more metal oxides selected from IIB, VB and VIB. The silicon oxide source and the metal oxide powder can be directly added to the sol, or the pre-prepared slurry containing the silicon oxide source and the metal oxide can be added separately or simultaneously.

The carrier mixture obtained in step (2) can be in the form of wet mixture, dough, paste or slurry, etc., and then the obtained mixture is formed 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 10-50 wt.%, preferably 20-50 wt.%.

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 (3), the metal promoter can be introduced on the carrier by means of impregnation or precipitation 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 promoter metal-containing compound is precipitated on the support. The promoter metal-containing compound is a substance which can be converted into a promoter metal oxide under calcination conditions and may be selected from the group consisting of promoter metal acetates, carbonates, nitrates, sulfates, thiocyanates and oxides, and mixtures of two or more of them. The promoter metal preferably contains nickel.

In step (4), the carrier introduced with the accelerator component is dried at about 50-300°C, preferably at 100-250°C, and the drying time is about 0.5-8 hours, more preferably about 1-5 hours. After drying, roasting is carried out at a temperature of about 300-800°C, more preferably 450-750°C, in the presence of oxygen or an oxygen-containing gas. The time required for roasting is generally about 0.5-4 hours, preferably 1-3 hours. hours until the volatile species are removed and the promoter metal is converted to a 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°C-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 in a hydrogen atmosphere, and the temperature and pressure conditions are: 350-500 ° C, 0.5-4 MPa; preferably 400-450°C, 1.0-2.0MPa. In this process, the sulfur in the feedstock is adsorbed onto the adsorbent, resulting in gasoline or diesel fuel with low sulfur content.

The reacted adsorbent can be reused after regeneration. The regeneration process is carried out under an oxygen atmosphere, the regeneration condition is normal pressure, and the temperature is 400-700°C, preferably 500-600°C.

After regeneration, the adsorbent needs to be reduced under hydrogen atmosphere before being reused. The range of temperature and pressure for reduction is: 350-500°C, 0.2-2MPa; preferably 400-450°C, 0.2-1.5MPa.

The term "cracked gasoline" as used herein means a hydrocarbon or any fraction thereof having a boiling range of 40°C 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 in the present invention means a liquid composed of a hydrocarbon mixture or any fraction thereof having 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 (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 provided by the present invention has high wear resistance strength and large pore volume, and what is even rarer is that the adsorbent maintains high activity stability during use, and is very suitable for use in fluidized bed reactors. Adsorption desulfurization process, and has a very good service life.

Description of drawings

Figure 1 is a schematic diagram of the crystal structure of muscovite. It consists of two identical silicon-oxygen tetrahedral [(Si, Al)O4] network layers sandwiching an octahedrally coordinated cation layer (Al ³⁺ for muscovite), and the top of each tetrahedron The corner oxygen shares oxygen with the vertices of the adjacent three octahedrons. Since Al ³⁺ only occupies two of the three octahedral gaps, it is a dioctahedral mica. This constitutes a structural layer consisting of two hexagonal mesh layers sandwiched between a layer of octahedrons. A quarter of Si ⁴⁺ in the hexagonal network layer of muscovite is replaced by Al ³⁺ , and residual charges appear in the entire mica structure layer, so there are larger cations (K ⁺ ) between the mica structure layers to balance the charge .

Fig. 2 is the X-ray diffraction diagram of muscovite, and the crystalline phase peak of muscovite has stronger peak (characteristic peak) at 9 ° and 27 °, can be used for distinguishing this system adsorbent. 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 pattern of the adsorbent A1 precursor prepared in Example 1. It can be seen from Fig. 3 that the crystal phase of the precursor of the adsorbent A1 is mainly composed of zinc oxide, nickel oxide, muscovite and titanium dioxide. The corresponding relationship of each component on the XRD pattern is 1: Muscovite; 2: TiO 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. The sulfur content in the product is analyzed by off-line chromatography, and the composition of the adsorbent is analyzed by X-ray diffraction (XRD).

Example 1

3.36 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99%) was slowly added to 3.2 kg of deionized water, and slowly stirred to avoid the precipitation of titanium oxide crystals. At this time, the solution was a colorless and transparent colloidal solution state, called For titanium sol.

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; 2.11 kg of mica (containing a dry basis of 1.84 kg) was added to the zinc oxide slurry. kg), and stirred for 15 minutes. Then it was added into the above titanium sol and stirred for 1 hour to obtain a carrier mixture 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 2.38 kg of nickel nitrate hexahydrate and 1.2 kg of deionized aqueous solution, and the resulting mixture was dried at 180°C for 4 hours, and then calcined at 635°C for 1 hour in an air atmosphere. to obtain the adsorbent precursor. The adsorbent precursor can be obtained by reducing the adsorbent precursor in a hydrogen atmosphere at 425° C. for 2 hours. At this time, the nickel oxide in the precursor is reduced to metallic nickel. This adsorbent is denoted as adsorbent A1.

The main chemical composition of the adsorbent A1 is: zinc oxide content is 53.8wt%, titanium dioxide content is 14.0wt%, muscovite content is 18.4wt%, nickel (calculated as metallic nickel) is 13.8wt%.

Example 2

3.09 kg of ethyl titanate (Aldrich company, analytically pure, 99%) was slowly added to 3.2 kg of 10% nitric acid (chemically pure, produced by Beijing Chemical Plant) solution under stirring and stirred for 1 hour, at this time the solution It is a light yellow transparent colloidal solution called titanium sol.

4.88 kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.73 kg on a dry basis) and 3.01 kg of mica (containing a dry basis of 2.62 kg) were added to 10.8 kg of deionized water, and stirred for 30 minutes. Then, the hydrolyzed ethyl titanate was added, mixed and then stirred for 1 hour to obtain a carrier mixture 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 the adsorbent A2 is as follows: the content of zinc oxide is 47.3wt%, the content of titanium dioxide is 10.7wt%, the content of muscovite is 26.2wt%, and nickel (calculated as metal nickel) is 15.8wt%.

Example 3

1.51 kg of titanium dioxide (anatase type, containing 1.40 kg of titanium dioxide on a dry basis) was added to 3.6 kg of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stirred for 1 hour to acidify. At this time, the titanium dioxide was completely dissolved into a colorless Transparent colloidal solution, called titanium sol.

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; 1.38 kg of muscovite (containing a dry basis) was added to the zinc oxide slurry. 1.20 kg) and 0.67 kg of expanded perlite (containing 0.64 kg on a dry basis), and stirred for 15 minutes. Then add the above-mentioned titanium sol, mix and stir for 1 hour to obtain a carrier mixture 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%, and the content of titanium dioxide is 14.0wt%, and muscovite content is 12.0wt%, and expanded perlite content is 6.4wt%, and nickel (calculated as metallic nickel) is 13.8 wt%.

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: zinc oxide content 53.8wt%, alumina binder content 14.0wt%, rector earth content 18.4wt%, nickel (calculated as metallic nickel) 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.

Get 1.46 kilograms of alumina monohydrate (SB powder, containing 1.07 kilograms on a dry basis) and join in 3.6 kilograms of deionized water, and stir for 10 minutes; 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: the content of zinc oxide is 47.3wt%, the content of alumina binder is 10.7wt%, the content of rector earth is 26.2wt%, and nickel (calculated as metal nickel) is 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 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 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%, alumina binder content is 14.0wt%, expanded perlite content is 18.4wt%, 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, A2, 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 40 kV, 30 mA; 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 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 6.4 4.9 7.9 6.8 5.1 8.6 ZnAl ₂ O ₄ % 0 0 0 10.5 8.7 9.2

Table 2 Strength and adsorption desulfurization performance of different adsorbents

A1 A2 A3 B1 B2 B3 Sulfur content in product gasoline/ppm 30 31 34 76 78 78 Δ(RON+MON)/2 0.35 0.5 0.4 0.4 0.5 0.45

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

It can be seen from Tables 1 and 2 that the adsorbent of the present invention has both good abrasion strength and desulfurization activity.

Claims (17)

1. desulfuration adsorbent take the adsorbent gross weight as benchmark, comprises following composition at least:

1) contain at least the silica source of mica, content is 5-40wt%,

2) titanium dioxide binding agent, content are 3-35wt%,

3) at least a oxide that is selected from the metal in IIB, VB and VIB, content is 10-80wt%,

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

2. according to adsorbent claimed in claim 1, it is characterized in that, the content that contains the silica source of mica is 10-30wt%, the content of titanium dioxide binding agent is 8-25wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 25-70wt%, and the content that is selected from the promoter metals of cobalt, nickel, iron and manganese is 8-25wt%.

3. according to adsorbent claimed in claim 1, it is characterized in that, the content that contains the silica source of mica is 15-27wt%, the content of titanium dioxide binding agent is 10-15wt%, the content that is selected from least a metal oxide in IIB, VB and VIB is 40-60wt%, and the content that is selected from the promoter metals of cobalt, nickel, iron and manganese is 12-20wt%.

4. according to adsorbent claimed in claim 1, it is characterized in that, described mica is the muscovite after cleavage.

5. according to adsorbent claimed in claim 1, it is characterized in that, in silica source except mica, contain one or more other silica source that are selected from clay, diatomite, Ludox, silicon gel, macropore silicon oxide and expanded perlite, the quality of other silica source is no more than 4: 1 with the ratio of mica quality.

6. according to adsorbent claimed in claim 1, it is characterized in that, the oxide of the metal in the described IIB of being selected from, VB and VIB is one or more in vanadium oxide, zinc oxide or molybdenum oxide.

7. according to adsorbent claimed in claim 1, it is characterized in that, contain nickel in described promoter metals.

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

(1) the titanium dioxide precursor is hydrolyzed in acidic liquid, forms colloidal sol;

(2) make the colloidal sol of (1) and the silica source that contains at least mica and be selected from IIB, VB and contact with one or more metal oxides in VIB, form carrier mixture; Dry, roasting obtain carrier;

(3) introduce the compound that contains promoter metals in the carrier of (2), obtain the adsorbent precursor;

(4) the adsorbent precursor in drying, roasting (3);

(5) the adsorbent precursor after roasting is reduced under hydrogen atmosphere, obtain adsorbent.

9. according to preparation method claimed in claim 8, it is characterized in that, in step (1), described titanium dioxide precursor is the compound that can exist with the anatase titanium dioxide form after hydrolysis, roasting in acidic liquid.

10. according to preparation method claimed in claim 8, it is characterized in that, described titanium dioxide precursor is selected from one or more in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.

11. according to preparation method claimed in claim 8, it is characterized in that, in step (1), the consumption of acid makes the pH value of colloidal sol be 1-5.

12. according to preparation method claimed in claim 8, it is characterized in that, in step (2), dry temperature is room temperature to 400 ℃, sintering temperature is 400-700 ℃, and roasting time is at least 0.5 hour.

13. according to preparation method claimed in claim 8, it is characterized in that, in step (3), adopt the method for dipping or precipitation to introduce the compound that contains promoter metals on carrier.

14. according to the described preparation method of claim 13, it is characterized in that, the described compound that contains promoter metals is selected from one or more in acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of promoter metals.

15. according to preparation method claimed in claim 8, it is characterized in that, in step (4), introduce the carrier of promoter component after drying under 50-300 ℃, carry out roasting at 300-800 ℃ of temperature under the condition that oxygen-containing gas exists.

16. according to preparation method claimed in claim 8, it is characterized in that, in step (5), the adsorbent precursor reduced under 300-600 ℃ of hydrogeneous atmosphere.

17. the sulfur method of a cracking gasoline or diesel fuel, comprise: make one of sulfur-bearing raw material and claim 1-7 described adsorbent under hydrogen atmosphere, 350-500 ℃ with the 0.5-4MPa condition under fully contact, obtain gasoline or the diesel fuel of low sulfur content.

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