CN102343252B - Hydrocarbon oil desulfurization adsorbent and preparation method as well as application thereof - Google Patents

Abstract

The invention provides a hydrocarbon oil desulfurization adsorbent, a preparation method and an application method of the adsorbent. The adsorbent provided by the present invention, based on the total weight of the adsorbent, at least includes the following composition: 1) SAPO molecular sieve, with a content of 1-20wt%; 2) tin dioxide, with a content of 3-35wt%; 3) layered clay , the content is 5-40wt%; 4) zinc oxide, the content is 10-80wt%; 5) at least one metal accelerator selected from cobalt, nickel, iron and manganese, the content is 5-30wt%. The adsorbent of the invention has high desulfurization activity and anti-wear strength, and also has the advantage of obviously increasing the octane number of gasoline, and is applicable to the desulfurization process of catalytic cracking gasoline or diesel engine fuel.

Description

A kind of hydrocarbon oil desulfurization adsorbent and its preparation method and application

technical field

The invention relates to an adsorbent for removing sulfur from hydrocarbon oil, a preparation method and application thereof.

Background technique

CN 1355727A provides a novel absorbent composition containing zinc oxide, silicon oxide, aluminum oxide and nickel or cobalt, and provides the preparation method of this adsorbent. In this method, a carrier containing zinc oxide, silicon oxide and aluminum oxide is prepared first, and then nickel is introduced by impregnation. The adsorbent can be used to remove sulfur from cracked gasoline or diesel fuel.

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.

When the above-mentioned adsorbent removes sulfur from gasoline under hydrogen-facing conditions, the octane number inevitably decreases due to olefin saturation.

CN 101433821A mentions an adsorbent for reducing the sulfur content of hydrocarbon oil, including rare earth faujasite, active metal oxide and carrier, wherein the carrier includes aluminum oxide and zinc oxide; the mixture of the above rare earth faujasite and carrier is preformed into a porous heat-resistant solid particles, and then introduce metal active components on the solid particles to prepare the adsorbent.

CN 101434854A mentions an adsorbent for reducing the sulfur content of light hydrocarbon oil, including phosphorus modified rare earth faujasite, active metal oxide and carrier, wherein the carrier includes aluminum oxide and zinc oxide; the above rare earth faujasite is treated with phosphorus The adsorbent is prepared by pre-shaping the modified porous heat-resistant solid particles with the carrier mixture, and then introducing metal active components on the solid particles.

Although the addition of shape-selective molecular sieves in the above two methods is beneficial to isomerization to increase the octane number of gasoline, the adsorbent lacks sufficient desulfurization activity due to the lack of suitable content of accelerator metals and sulfur storage media.

Contents of the invention

The invention provides an adsorbent which can be used for removing sulfur from hydrocarbon oil, and provides a preparation method and an application method 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) SAPO molecular sieve, the content is 1-20wt%

2) tin dioxide, the content is 3-35wt%;

3) layer pillar clay, content is 5-40wt%;

4) Zinc oxide, the content is 10-80wt%;

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

Preferably, the content of SAPO molecular sieve is 2-15wt%, the content of tin dioxide is 5-25wt%, the content of layered clay is 10-30wt%, the content of zinc oxide is 25-70wt%, selected from cobalt, The metal promoter content of nickel, iron and manganese is 8-25wt%.

More preferably, the content of SAPO molecular sieve is 2-10wt%, the content of tin dioxide is 8-15wt%, the content of layered clay is 12-25wt%, the content of zinc oxide is 40-58wt%, selected from cobalt , nickel, iron and manganese metal accelerator content is 12-20wt%.

孔体积为0.18-0.48cm³/g，SAPO-5、SAPO-11、SAPO-31、SAPO-34和SAPO-20分子筛的孔大小分别为

(12元环)、

(10员环)、

(10员环)、

(8员环)和

(6员环)；孔体积分别为0.31、0.18、0.42、0.42和0.40cm³/g。本申请优选SAPO-11、SAPO-31和SAPO-34。SAPO molecular sieve is a near-body silicoaluminophosphate, which is obtained by introducing silicon into the aluminum phosphate framework, and its framework is composed of PO ₄ ⁺ , AlO ₄ ^- and SiO ₂ tetrahedra. This type of molecular sieve includes 13 three-dimensional microporous framework structures, and its pore size is

The pore volume is 0.18-0.48cm ³ /g, and the pore sizes of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieves are respectively

(12-membered ring),

(10 rings),

(10 rings),

(8 member ring) and

(6-membered ring); pore volumes were 0.31, 0.18, 0.42, 0.42 and 0.40 cm ³ /g, respectively. SAPO-11, SAPO-31 and SAPO-34 are preferred for this application.

The layered pillar clay is an interlayer mineral crystal, which is composed of two kinds of single-layer mineral clay components regularly arranged alternately, the distance between the bottom surfaces is not less than 1.7nm, and there is a strong peak at 3.4° in the XRD pattern. Examples of the pillar clay include, but are not limited to, rector's clay, dolomite, bentonite, montmorillonite, and montmorillonite, etc., preferably rector's clay.

The invention provides a preparation method of a hydrocarbon oil desulfurization adsorbent, comprising:

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

(2) making the sol contact with layered clay, SAPO molecular sieve and zinc oxide to form a carrier mixture, molding, drying and roasting to obtain the carrier;

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

(4) drying and roasting the adsorbent precursor;

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

In step (1), the precursor of tin dioxide is a compound that can be hydrolyzed in step (1), roasted in step (2), 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 precursor of tin dioxide 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 sol can be contacted and mixed with the layered clay, zinc oxide and SAPO molecular sieve in any manner. For example, layer column clay can be added to the sol first, then zinc oxide and SAPO molecular sieve can be added sequentially or simultaneously, or the three can be added at the same time; layer column clay, zinc oxide and/or SAPO molecular sieve powder can be directly added to the sol, Pre-prepared slurries can also be added.

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 containing the metal promoter component is a substance that can be converted into a metal oxide under calcination conditions. The metal accelerator 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 metal promoter. The metal promoter can be introduced on the support 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 metal promoter; the precipitation method is to mix the solution or suspension of a compound containing a metal promoter with an adsorbent carrier, and then add ammonia water , the compound of the metal promoter is precipitated on the support.

In step (4), the carrier introduced with the metal promoter component 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 metal promoter precursors were converted to metal oxides, yielding the adsorbent precursors.

In step (5), the adsorbent precursor is reduced in a hydrogen-containing atmosphere at 300-600° C., so that the metal promoter 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 invention provides a hydrocarbon oil desulfurization method, comprising: fully contacting the sulfur-containing hydrocarbon oil with the adsorbent of the invention under a hydrogen atmosphere, the temperature and pressure conditions are: 350-500 ° C, 0.5-4 MPa; preferably 400-450 ° C , 1.0-2.0MPa. During this process the sulfur in the hydrocarbon oil is adsorbed onto the adsorbent, resulting in a hydrocarbon oil 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 hydrocarbon oil described in the present invention includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons or any fraction thereof with a boiling range of 40 to 210°C, derived from the heat or heat of cracking larger hydrocarbon molecules into smaller molecules The product of the catalytic process. 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. By "diesel fuel" is meant a liquid consisting of a hydrocarbon mixture or any fraction thereof having a boiling range from 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 of the invention has high desulfurization activity and anti-wear strength, and also has the advantage of obviously increasing the octane number of gasoline, and is applicable to the desulfurization process of catalytic cracking gasoline or diesel engine fuel.

Detailed ways

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

In the examples, the composition of the adsorbent is analyzed by XRD (X-ray diffraction).

Example 1

The adsorbent was prepared as follows: 2.33 kg of crystalline tin tetrachloride (SnCl ₄ .5H ₂ 0, Alfa Aesar, 99 wt.%) was slowly added to 3.2 kg of 3 wt.% hydrochloric acid solution with slow stirring to avoid tin oxide crystals Precipitate to obtain colorless and transparent tin sol. Then add 2.75 kilograms of retort earth (Qilu Catalyst Branch, containing 2.06 kilograms on a dry basis) to the above-mentioned tin sol and stir to mix evenly.

4.43 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 1.00 kilograms of SAPO-31 (Qilu Catalyst Branch Company, containing 0.70 kilograms on a dry basis) and 4.57 kilograms of deionized water were mixed, and after stirring for 30 minutes, zinc oxide and SAPO-31 mixed slurry. The mixed slurry was added to the above slurry and stirred for 1 hour to obtain the carrier slurry of the adsorbent.

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.

3.2 kg of adsorbent carrier was impregnated with 3.51 kg of nickel nitrate hexahydrate (Beijing Chemical Reagent Company, purity greater than 98.5wt.%), 0.6 kg of deionized aqueous solution, and the obtained mixture was dried at 180°C for 4 hours, and then dried in an air atmosphere at 635°C The adsorbent precursor can be prepared by calcining 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 chemical composition of adsorbent A1 is: zinc oxide content is 44.3wt.%, rector earth content is 20.6wt.%, SAPO-31 content is 7.0wt.%, tin dioxide binder 10.0wt.%, metal nickel The content is 18.1wt.%.

Example 2

Get 1.26 kilograms of dibutyltin oxide (Aldrich Company, analytically pure, 99wt.%) and join in 2.6 kilograms of 10wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant), and heat up to 80 ° C for aging for 1 hour, at this time Tin oxide is completely dissolved into a colorless and transparent colloidal solution, called tin sol. Then add 2.21 kg of montmorillonite (Qilu Catalyst Branch, containing 1.50 kg on a dry basis) to the above-mentioned tin sol and mix under stirring.

5.52 kg of zinc oxide powder (Headhorse company, purity 99.7%), 0.43 kg of SAPO-31 (Qilu Catalyst Branch, containing 0.30 kg on a dry basis) and 5.0 kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide and SAPO-31 Mix the slurry. The mixed slurry was added to the above slurry and stirred 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 A2. The chemical composition of adsorbent A2 is: zinc oxide content is 55.2wt.%, tin dioxide binder content is 11.7wt.%, montmorillonite content is 15.0wt.%, SAPO-31 content is 3.0wt%, nickel The content is 15.1wt.%.

Example 3

The adsorbent was prepared as follows: 3.19 kilograms of tin acetate (Aldrich company, analytically pure, 99wt.%) was slowly added to 3.5 kilograms of 5wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) solution under stirring and After stirring for 1 hour, the solution was in the state of a white sol.

With 4.93 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 2.14 kilograms of retort earth (Qilu Catalyst Branch, containing dry basis 1.60 kilogram), 0.71 kilogram of SAPO-34 (Qilu Catalyst Branch, containing dry basis 0.50 kg) and 6.40 kg of deionized water were mixed, and after stirring for 30 minutes, a mixed slurry was obtained. The mixed slurry was added to the above slurry and stirred for 1 hour to obtain a carrier slurry.

Referring to the method of Example 1, the spray drying of the carrier was carried out and the active components nickel and cobalt were introduced to obtain the adsorbent A3. The chemical composition of adsorbent A3 is: zinc oxide content is 49.3wt.%, tin dioxide binder is 13.5wt.%, rector earth is 16.0wt.%, SAPO-34 content is 5.0wt%, nickel content is 8.1wt.%, the cobalt content is 8.1%.

Example 4

The adsorbent was prepared as follows: 3.19 kilograms of tin acetate (Aldrich company, analytically pure, 99wt.%) was slowly added to 3.5 kilograms of 5wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) solution under stirring and After stirring for 1 hour, the solution was in the state of a white sol.

With 4.93 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 2.09 kilograms of bentonite (Qilu Catalyst Branch, containing 1.60 kilograms of dry basis), 0.72 kilograms of SAPO-11 (Qilu Catalyst Branch, containing 0.50 kilogram of dry basis ) and 6.40 kg of deionized water were mixed and stirred to obtain a mixed slurry after 30 minutes. The mixed slurry was added to the above slurry and stirred 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 A4. The chemical composition of adsorbent A4 is: zinc oxide content is 49.3wt.%, tin dioxide binder is 13.5wt.%, bentonite is 16.0wt.%, SAPO-11 content is 5.0wt.%, nickel content is 16.2 wt.%.

Comparative example 1

The adsorbent was prepared as follows: 4.43 kg of zinc oxide powder (Headhorse Company, purity 99.7%) was mixed with 4.57 kg of deionized water, and stirred for 30 minutes to obtain a zinc oxide slurry.

Take 1.87 kg of alumina (produced by Shandong Aluminum Plant, containing 1.36 kg on a dry basis) and 3.20 kg of retort earth (including 2.40 kg on a dry basis) and mix them under stirring, then add 4.6 kg of deionized water and mix well, then add 360 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. Zinc oxide slurry was added and stirred 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 chemical composition of the adsorbent B1 is 44.3wt.% of zinc oxide, 13.6wt.% of alumina binder, 24.0wt.% of rector earth and 18.1wt.% of nickel.

Comparative example 2

Get 1.61 kilograms of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.17 kilograms on a dry basis) and 2.65 kilograms of montmorillonite (containing 1.80 kilograms on a dry basis) and mix under stirring, then add 8.2 kilograms of deionized water and mix well, Add 260 milliliters of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) and stir for acidification for 1 hour, then raise the temperature to 80° C. and age for 2 hours. After the temperature dropped, 5.52 kg of zinc oxide powder (Headhorse Company, purity 99.7%) was added and stirred 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 B2. The chemical composition of the adsorbent B2 is: the content of zinc oxide is 55.2wt.%, the content of alumina binder is 11.7wt.%, the content of montmorillonite is 18.0wt.%, and the content of nickel is 15.1wt.%.

Comparative example 3

The adsorbent was prepared as follows: 4.93 kg of zinc oxide powder (Headhorse Company, purity 99.7%) was mixed with 5.57 kg of deionized water, and stirred for 30 minutes to obtain a zinc oxide slurry.

Get 1.85 kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35 kg on dry basis) and 2.81 kg of rectorite (Qilu Catalyst Branch, containing 2.10 kg on dry basis) and mix them under stirring, then add 4.6 kg of deionized water After the kilogram is mixed evenly, add 300 milliliters of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) to make the slurry pH value 2.5, stir and acidify for 1 hour, then heat up to 80° C. and age for 2 hours. Zinc oxide slurry was added and stirred for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and formed, and the active components nickel and cobalt were introduced to obtain the adsorbent B3. The chemical composition of adsorbent B3 is: zinc oxide content is 49.3wt.%, alumina binder is 13.5wt.%, rector earth is 21.0wt.%, nickel content is 8.1wt.%, cobalt content is 8.1% .

Comparative example 4

The adsorbent was prepared as follows: 4.93 kg of zinc oxide powder (Headhorse Company, purity 99.7%) was mixed with 5.57 kg of deionized water, and stirred for 30 minutes to obtain a zinc oxide slurry.

Get 1.86 kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35 kg on dry basis) and 2.74 kg of bentonite (Qilu Catalyst Branch, containing 2.10 kg on dry basis) and mix under stirring, then add 3.6 kg of deionized water to mix After uniformity, 300 ml of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) was added to make the pH value of the slurry 2.5, stirred and acidified for 1 hour, then heated to 80°C for 2 hours of aging. Zinc oxide slurry was added and stirred 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 B4. The chemical composition of the adsorbent B4 is: the content of zinc oxide is 49.3wt.%, the content of alumina binder is 13.5wt.%, the content of bentonite is 21.0wt.%, and the content of nickel is 16.2wt.%.

Example 5

Three indicators of wear resistance strength, desulfurization performance and octane number 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 wear index, the higher the wear resistance. The wear evaluation results of different adsorbents are shown in Table 1.

The desulfurization performance is measured by the sulfur content of the product. The sulfur content in the product is analyzed by off-line chromatography and evaluated by a fixed-bed micro-reactor experimental device. The raw material for the adsorption reaction is 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 1.

GB/T 503-1995 and GB/T 5487-1995 were used to measure the motor octane number (MON) and research octane number (RON) of gasoline before and after the reaction, and the results are shown in Table 1. It can be seen from Table 1 that after the reaction of the adsorbent containing SAPO molecular sieve, the octane number of the product gasoline increases to varying degrees.

Table 1 Performance of different adsorbents

Adsorbent A1 A2 A3 A4 B1 B2 B3 B4 wear index 4.6 6.5 5.8 5.9 4.9 6.8 6.0 6.0 Sulfur content in product gasoline/ppm 8 5 11 15 20 13 twenty three 38 △MON 0.45 0.10 0.20 0.10 -0.55 -0.45 -0.35 -0.40 △RON 0.55 0.20 0.30 0.20 -0.45 -0.35 -0.45 -0.40 △(RON+MON)/2 0.50 0.15 0.25 0.15 -0.50 -0.40 -0.40 -0.40

Note:

1. The sulfur content of raw gasoline is 1080ppm, RON is 93.1, 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.

Claims (18)

1. a hydrocarbon oil desulphurization adsorbing agent is benchmark with the adsorbent gross weight, comprises following composition at least:

1) SAPO molecular sieve, content are 1-20wt%;

2) tin ash, content are 3-35wt%;

3) laminated clay column, content are 5-40wt%;

4) zinc oxide, content are 10-80wt%;

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, wherein, the content of SAPO molecular sieve is 2-15wt%, the content of tin ash is 5-25wt%, the content of laminated clay column is 10-30wt%, the content of zinc oxide is 25-70wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 8-25wt%.

3. according to the described adsorbent of claim 1, wherein, the content of SAPO molecular sieve is 2-10wt%, the content of tin ash is 8-15wt%, the content of laminated clay column is 12-25wt%, the content of zinc oxide is 40-58wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.

4. according to the described adsorbent of one of claim 1～3, wherein, the SAPO molecular sieve is one or more among SAPO-11, SAPO-31 and the SAPO-34.

5. according to the described adsorbent of claim 1, wherein, described laminated clay column is the interbed mineral crystal, is alternately to be rearranged by two kinds of individual layer mineral clay component rules, and its basal spacing is not less than 1.7nm, at 3.4 ° a stronger peak is arranged in its XRD collection of illustrative plates.

6. according to the described adsorbent of claim 1, wherein, described laminated clay column is selected from one or more in rectorite, Yun Mengshi, bentonite, imvite and the smectite.

7. the preparation method of the described hydrocarbon oil desulphurization adsorbing agent of one of claim 1～6 comprises:

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

(2) colloidal sol is contacted with laminated clay column, SAPO molecular sieve with zinc oxide, form carrier mixture, moulding, drying, roasting obtain carrier;

(3) compound of introducing containing metal promoter in carrier obtains the adsorbent precursor;

(4) dry, roasting adsorbent precursor;

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

8. according to the described preparation method of claim 7, the compound that in the step (1), described tin ash precursor is can hydrolysis in step (1), exist with the form of tin ash after the roasting in step (2).

9. according to the described preparation method of claim 7, in the step (1), described tin ash precursor is selected from one or more in butter of tin, four isopropyl alcohol tin, tin acetate, the aqua oxidation tin.

10. according to the described preparation method of claim 7, wherein, in the step (1), described acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, and the consumption of acid is to make the pH value of solution after the hydrolysis less than 6.0.

11. according to the described preparation method of claim 7, wherein, in the step (1), described acid is selected from one or more in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid, wherein Suan consumption is to make the pH value of solution after the hydrolysis less than 4.0.

12. according to the described preparation method of claim 7, in the step (2), add laminated clay column in the colloidal sol earlier, more simultaneously or add zinc oxide and SAPO molecular sieve successively, or the three added simultaneously.

13. according to the described preparation method of claim 7, in the step (2), the temperature of carrier mixture drying is room temperature to 400 ℃, sintering temperature is 400-700 ℃, and roasting time was at least 0.5 hour.

14. according to the described preparation method of claim 7, in the step (3), adopt the method for dipping or precipitation to introduce the compound of containing metal promoter at carrier.

15. according to the described preparation method of claim 7, the compound of described containing metal promoter is selected from the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide, and two or more mixture wherein.

16. according to the described preparation method of claim 7, in the step (4), introduce the carrier of promoter component under 50-300 ℃, dry 0.5-8 hour, after the drying, under the condition that has oxygen or oxygen-containing gas to exist, 300-800 ℃ of following roasting, be removed and metallic promoter agent is converted into metal oxide until volatile materials, obtain the adsorbent precursor after the roasting.

17. according to the described preparation method of claim 7, in the step (5), the adsorbent precursor after the roasting is reduced under 300-600 ℃ of hydrogeneous atmosphere, metallic promoter agent is existed to go back ortho states basically.

18. desulfurization of hydrocarbon oil method, comprise: the described adsorbent of hydrocarbon oil containing surphur and one of claim 1～6 is fully contacted under hydrogen atmosphere, the temperature and pressure condition is: 350-500 ℃, 0.5-4MPa, sulphur in this process in the hydrocarbon ils is adsorbed on the adsorbent, thereby obtains the hydrocarbon ils of low sulfur content.