CN102895946A - Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof - Google Patents

Abstract

The invention provides a hydrocarbon oil desulphurization adsorbent, and a preparation method and an application thereof. With a total weight of the adsorbent as a standard, The adsorbent provided by the invention at least comprises the components of, by weight: (1) 1-20% of an aluminosilicate molecular sieve with a duodenary-ring pore-channel structure, (2) 3-35% of zirconium dioxide, (3) 5-40% of pillared interlayer clay, (4) 10-80% of zinc oxide, and (5) 5-30% of at least one metal accelerating agent selected from cobalt, nickel, iron and manganese. The absorbent provided by the invention has high desulphurization activity and abrasion resistance, and has an advantage of a capacity for substantially increasing gasoline octane number. The absorbent can be used in catalytic cracking gasoline or diesel fuel desulphurization processes.

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) A silica-alumina molecular sieve with a twelve-membered ring channel structure, the content of which is 1-20wt%

2) zirconium 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 silica-alumina molecular sieve with twelve-membered ring channel structure is 2-15wt%, the content of zirconium dioxide is 5-25wt%, the content of layered clay is 10-30wt%, and the content of zinc oxide is 25-70wt%, and the content of the metal accelerator selected from cobalt, nickel, iron and manganese is 8-25wt%.

More preferably, the content of silica-alumina molecular sieve with twelve-membered ring channel structure is 2-10wt%, the content of zirconium dioxide is 8-15wt%, the content of layered clay is 12-25wt%, and the content of zinc oxide The content of the metal accelerator selected from cobalt, nickel, iron and manganese is 12-20 wt%.

The silica-alumina molecular sieve with twelve-membered ring channel structure is selected from one or more molecular sieves with crystal structures such as FAU, MOR, MAZ, BEA, etc., preferably molecular sieves with FAU and/or BEA structures.

The molecular sieve with FAU structure is a faujasite type molecular sieve, and this type of molecular sieve has three-dimensional twelve-membered ring channels with a pore diameter of 7.4A×7.4A. Molecular sieves with FAU structure are mainly X-type and Y-type molecular sieves. Generally speaking, those with a SiO ₂ /Al ₂ O ₃ molar ratio of 2.2 to 3.0 are X-type molecular sieves, and those with a SiO ₂ /Al ₂ O ₃ molar ratio greater than 3.0 are Y-type molecular sieves. Molecular sieve. The framework structures of X-type and Y-type molecular sieves belong to the hexagonal crystal system, and the space group structure is Fd3m. The unit cell parameters of X-type molecular sieves are a=24.86-25.02A, and the unit-cell parameters of Y-type molecular sieves are a=24.6-24.85A.

Molecular sieves with a FAU structure also include modified molecular sieves of this type, and the modification methods may include hydrothermal methods, chemical treatment methods (such as inorganic acid treatment methods, fluosilicic acid extraction of aluminum and silicon supplementation methods, and SiCl _gas phase method) or water Combining heat and chemical treatment, molecular sieves obtained after modification include but are not limited to ultra-stable Y-type molecular sieves (USY), REUSY, REHY, REY containing rare earth elements, and PUSY, PREHY, PREY containing phosphorus, etc.

The BEA structure molecular sieve is mainly β molecular sieve, and its structural formula is (Na _n [Al _n Si _64-n O ₁₂₈ ], n<7), which is a mixed crystal of two closely related polymorphs A and B with different structures. Both have a twelve-membered ring three-dimensional channel system, polymorph A forms a pair of enantiomers, the space group is P4 ₁ 22 and P4 ₃ 22, and the unit cell parameters are a=12.5A, b=26.6A; polymorph B Belongs to the achiral space group C2/c, unit cell parameters a=17.6A, b=17.8A, c=14.4A, β=114.5. The twelve-membered ring channel size in the BEA molecular sieve is 7.3A×6.0A<100 direction> and 5.6A×5.6A<001 direction>.

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 spectrum. 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) hydrolyzing the zirconium dioxide precursor in an acid solution to form a sol;

(2) mixing the sol with layered clay, silica-alumina molecular sieve with a twelve-membered ring channel structure and zinc oxide to obtain a carrier mixture, and forming, drying, and roasting to obtain a carrier containing an active component;

(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 zirconium dioxide precursor is a compound that can be hydrolyzed in step (1), and can exist in the form of zirconium dioxide after being roasted in step (2), preferably zirconium tetrachloride, zirconium oxychloride , zirconium acetate, hydrated zirconia, amorphous zirconia or one or more. The precursor of zirconium dioxide can be hydrolyzed and generate a cohesive colloidal solution in contact with excess acid solution. 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 1-6, preferably 1.5-4, to form a sol.

In step (2), the sol can be contacted and mixed with the columnar clay, zinc oxide and the silica-alumina molecular sieve having a twelve-membered ring channel structure in any order or manner. For example, layer pillar clay can be added to the sol first, then zinc oxide and silica-alumina molecular sieve with twelve-membered ring pore structure can be added sequentially or simultaneously, or the three can be added at the same time; layer pillar clay, Zinc oxide and/or silica-alumina molecular sieve powder with twelve-membered ring channel structure can also be added to the pre-prepared slurry.

In step (2), 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: 1.90 kilograms of zirconium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 2.7 kilograms of 5wt.% nitric acid solution, and stirred slowly to avoid the precipitation of zirconia crystals, and obtained no The transparent colloidal solution is called zirconium sol. Then add 2.75 kilograms of retort earth (Qilu Catalyst Branch, containing 2.06 kilograms on a dry basis) to the above zirconium sol and stir to mix evenly.

4.43 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 0.84 kilograms of Beta molecular sieves (Nanjing Catalyst Branch, 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 Beta Molecular sieve 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 98.5%) and 0.6 kg of deionized aqueous solution, and the resulting mixture was dried at 180°C for 4 hours, and then calcined at 635°C in an air atmosphere The adsorbent precursor can be prepared in 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 the adsorbent A1 is: zinc oxide content is 44.3wt.%, rector earth content is 20.6wt.%, Beta molecular sieve content is 7.0wt.%, zirconia binder 10.0wt.%, metal nickel content It is 18.1wt.%.

Example 2

The adsorbent is prepared as follows: 1.71 kg of zirconium oxychloride (Aldrich company, analytically pure, 98.5wt.%) is slowly added to 3.2 kg of 15wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) under stirring Neutralize and stir for 1 hour to acidify. At this time, the solution is a colorless and transparent colloidal solution, called zirconium sol. Then add 2.21 kg of montmorillonite (Qilu Catalyst Branch, containing 1.50 kg on a dry basis) to the above-mentioned zirconium sol and mix under stirring.

5.52 kg of zinc oxide powder (Headhorse company, purity 99.7%), 0.36 kg of Beta molecular sieve (Nanjing 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 a mixed slurry of zinc oxide and Beta molecular sieve . 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.%, zirconium dioxide binder content is 11.7wt.%, montmorillonite content is 15.0wt.%, Beta molecular sieve content is 3.0wt.%, nickel The content is 15.1wt.%.

Example 3

The adsorbent was prepared as follows: 1.76 kilograms of zirconium hydroxide (Aldrich company, analytically pure, 99wt.%) was added to 3.1 kilograms of 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stirred and acidified for 1 hour. When a transparent colloidal solution is obtained, it is called zirconium sol.

With 4.93 kilograms of zinc oxide powder (Headhorse company, purity 99.7%), 2.14 kilograms of rector's earth (Qilu Catalyst Branch, containing dry basis 1.60 kilogram), 0.56 kilogram of USY (Qilu Catalyst Branch, containing dry basis 0.50 kilogram) 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.%, zirconium dioxide binder is 13.5wt.%, rector earth is 16.0wt.%, USY content is 5.0wt.%, nickel content is 8.1 wt.%, the cobalt content is 8.1%.

Example 4

The adsorbent was prepared as follows: 1.53 kilograms of zirconium hydroxide (Aldrich company, analytically pure, 99wt.%) was added to 3.1 kilograms of 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and acidified with stirring for 1 hour. When a transparent colloidal solution is obtained, it is called zirconium sol.

With 5.52 kilograms of zinc oxide powders (Headhorse company, purity 99.7%), 1.96 kilograms of debentonite (Qilu Catalyst Branch, containing 1.50 kilograms on a dry basis), 0.36 kilograms of X molecular sieves (Qilu Catalyst Branch, containing 0.30 kilograms on a dry basis) and 7.40 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed slurry. The mixed slurry was added to the above zirconium sol, 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 55.2wt.%, zirconium dioxide binder is 11.7wt.%, bentonite is 15.0wt.%, X molecular sieve content is 3.0wt.%, nickel content is 15.1wt. .%.

Example 5

The adsorbent was prepared as follows: 1.90 kilograms of zirconium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 2.7 kilograms of 5wt.% nitric acid solution, and stirred slowly to avoid the precipitation of zirconia crystals, and obtained no The transparent colloidal solution is called zirconium sol. Then add 2.75 kilograms of retort earth (Qilu Catalyst Branch, containing 2.06 kilograms on a dry basis) to the above zirconium sol and stir to mix evenly.

4.43 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 0.78 kilograms of USY molecular sieves (Qilu Catalyst Branch, 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 USY were obtained. Molecular sieve mixed slurry. The mixed slurry was added to the above slurry and stirred for 1 hour to obtain the carrier slurry of the adsorbent.

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 A5. The chemical composition of the adsorbent A5 is: zinc oxide content is 44.3wt.%, rector earth content is 20.6wt.%, USY molecular sieve content is 7.0wt.%, zirconia binder 10.0wt.%, metal nickel content It is 18.1wt.%.

Comparative example 1

The adsorbent was prepared as follows: 2.58 kilograms of zirconium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 4.2 kilograms of 5wt.% nitric acid solution, and stirred slowly to avoid the precipitation of zirconia crystals, and obtained no The transparent colloidal solution is called zirconium sol. Then add 3.20 kg of retort earth (Qilu Catalyst Branch, containing 2.40 kg on a dry basis) to the zirconium sol and stir to mix evenly.

4.43 kg of zinc oxide powder (Headhorse Company, purity 99.7 wt.%) was mixed with 4.57 kg of deionized water, and stirred for 30 minutes to obtain a zinc oxide slurry. The mixed slurry was added to the above slurry and stirred for 1 hour to obtain the carrier slurry of the adsorbent.

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 as follows: the content of zinc oxide is 44.3wt.%, the content of rector earth is 24.0wt.%, the content of zirconium dioxide binder is 13.6wt.%, and the content of metal nickel is 18.1wt.%.

Comparative example 2

1.71 kg of zirconium oxychloride (Aldrich company, analytically pure, 98.5wt.%) was slowly added to 3.2 kg of 15wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) under stirring and acidified with stirring for 1 hour, At this time, the solution is a colorless and transparent colloidal solution, called zirconium sol. Then add 2.65 kg of montmorillonite (Qilu Catalyst Branch, containing 1.80 kg on a dry basis) to the above-mentioned zirconium sol and mix under stirring.

5.52 kg of zinc oxide powder (Headhorse Company, purity 99.7%) and 5.0 kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide 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 B2. The chemical composition of the adsorbent B2 is: the content of zinc oxide is 55.2wt.%, the content of zirconium dioxide 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: 1.76 kilograms of zirconium hydroxide (Aldrich company, analytically pure, 99wt.%) was added to 3.1 kilograms of 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stirred and acidified for 1 hour. When a transparent colloidal solution is obtained, it is called zirconium sol.

4.93 kg of zinc oxide powder (Headhorse company, purity 99.7%), 2.81 kg of rector earth (Qilu Catalyst Branch, 2.10 kg on a dry basis) and 6.90 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed slurry. The mixed slurry was added to the above zirconium sol, and stirred for 1 hour to obtain a 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.%, zirconium dioxide 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: 1.53 kilograms of zirconium hydroxide (Aldrich company, analytically pure, 99wt.%) was added to 3.1 kilograms of 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and acidified with stirring for 1 hour. When a transparent colloidal solution is obtained, it is called zirconium sol.

5.52 kg of zinc oxide powder (Headhorse company, purity 99.7%), 2.35 kg of bentonite (Qilu Catalyst Branch, containing 1.80 kg on a dry basis) and 7.40 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed slurry. The mixed slurry was added to the above zirconium sol, 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 B4. The chemical composition of the adsorbent B4 is: zinc oxide content 55.2wt.%, zirconium dioxide binder 11.7wt.%, bentonite 18.0wt.%, nickel content 15.1wt.%.

Example 6

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 catalytic cracked gasoline with a sulfur concentration of 640ppm. 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. At the same time, the product gasoline is weighed to calculate its yield.

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 adsorbents containing molecular sieves with BEA or FAU structure, the octane number of product gasoline increases to varying degrees.

Table 1 Performance of different adsorbents

Note:

1. The sulfur content of raw gasoline is 640ppm, RON is 93.0, and MON is 82.7.

2. ΔMON represents the added value of product MON;

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

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

Claims (19)

1. A hydrocarbon oil desulfurization adsorbent, based on the total weight of the adsorbent, comprising the following components: 1) A silica-alumina molecular sieve with a twelve-membered ring channel structure, the content of which is 1-20wt%; 2) zirconium 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%. 2. The adsorbent according to claim 1, wherein the content of each component is: the content of the silica-alumina molecular sieve with the twelve-membered ring pore structure is 2-15wt%, the content of zirconium dioxide is 5-25wt%, and the layer column The content of clay is 10-30wt%, the content of zinc oxide is 25-70wt%, and the content of metal accelerator is 8-25wt%. 3. The adsorbent according to claim 1, wherein the content of the silica-alumina molecular sieve with twelve-membered ring pore structure is 2-10wt%, the content of zirconium dioxide is 8-15wt%, and the content of layered clay is 12 -25wt%, the content of zinc oxide is 40-60wt%, and the content of metal accelerator is 12-20wt%. 4. The adsorbent according to claim 1, wherein the silica-alumina molecules with a twelve-membered ring pore structure are screened from one or more molecular sieves with crystal structures of FAU, MOR, MAZ, and BEA. 5. The adsorbent according to claim 4, wherein the molecular sieve with FAU structure is X-type and/or Y-type molecular sieve. 6. The adsorbent according to claim 4, wherein the molecular sieve with FAU structure also includes modified molecular sieves, including but not limited to USY, REUSY, REHY, REY containing rare earth elements, and phosphorus-containing PUSY, One or more of PREHY and PREY. 7. The adsorbent according to claim 4, wherein the BEA structure molecular sieve is a beta molecular sieve. 8. according to the described adsorbent of claim 1, wherein said layer pillar clay is made up of two kinds of single-layer mineral clay components regularly arranged alternately, and its basal surface distance is not less than 1.7nm, and in its XRD collection of illustrative plates there is a relatively large one at 3.4°. strong peak. 9. The adsorbent according to claim 1, wherein the layered clay is selected from one or more of retortite, dolomite, bentonite, montmorillonite and smectite. 10. The preparation method of the adsorbent described in one of claims 1-9, comprising: (1) hydrolyzing the zirconium dioxide precursor in an acid solution to form a sol; (2) mixing the sol with layered clay, silica-alumina molecular sieve with twelve-membered ring channel structure and zinc oxide, forming, drying, and roasting to obtain a carrier containing the active component; (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. 11. according to the described preparation method of claim 10, wherein in step (1), described zirconium dioxide precursor is selected from zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconium oxide, amorphous zirconium dioxide one or more of them. 12. according to the described preparation method of claim 10, said acid is selected from one or more in water-soluble inorganic acid and/or organic acid, and the consumption of acid is to make the pH value of solution after hydrolysis be 1-6. 13. according to the described preparation method of claim 12, wherein said acid is one or more in hydrochloric acid, nitric acid, phosphoric acid and acetic acid, the consumption of acid makes the pH value of solution after hydrolysis be 1.5-4. 14. according to the preparation method described in claim 10, in the step (2), in the sol, first add layer pillar clay, then add zinc oxide and the silica-alumina molecular sieve with twelve-membered ring channel structure successively or simultaneously, or three Or add the sol at the same time; directly add layered clay, zinc oxide and/or silicon-aluminum molecular sieve powder with a twelve-membered ring channel structure to the sol, or add a pre-prepared slurry. 15. The preparation method according to claim 10, wherein the drying temperature is from room temperature to 400°C, and the calcination temperature is 400-700°C. 16. according to the preparation method described in claim 10, in step (3), the compound containing metal accelerator is selected from acetate, carbonate, nitrate, sulfate, thiocyanate of metal accelerator and oxides, and mixtures of two or more of them. 17. according to the described preparation method of claim 10, in step (4), the carrier that introduces accelerator component is dried at about 50-300 ℃, under the condition that oxygen or oxygen-containing gas exist, at about 300-800 Calcination is carried out at a temperature of 10 °C until the volatile substances are removed and the metal promoter is converted to a metal oxide to obtain the adsorbent precursor. 18. The preparation method according to claim 10, 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. 19. A hydrocarbon oil desulfurization method, comprising: fully contacting the sulfur-containing hydrocarbon oil with the adsorbent described in any one of claims 1-9 under a hydrogen atmosphere, the temperature and pressure conditions are: 350-500°C, 0.5-4MPa, During this process the sulfur in the hydrocarbon oil is adsorbed onto the adsorbent, resulting in a hydrocarbon oil with low sulfur content.