CN102895940A - Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof - Google Patents

Abstract

The invention provides a hydrocarbon oil desulfurization adsorbent, 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 composition: 1) silica-alumina molecular sieve with twelve-membered ring pore structure, the content is 1-20wt%; 2) titanium dioxide, the content is 3-35wt% %; 3) silicon oxide source, 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- 30 wt%. The adsorbent of the present invention adopts a non-aluminum binder, which avoids the formation of zinc aluminate from the zinc oxide part, thereby greatly improving the activity and stability of the adsorbent, and also has the advantage of obviously increasing the octane number of gasoline.

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

3) silicon oxide source, the 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 titanium dioxide is 5-25wt%, the content of silicon oxide source is 10-30wt%, and the content of zinc oxide is 25-25wt%. 70 wt%, and the content of the metal promoter selected from cobalt, nickel, iron and manganese is 8-25 wt%.

More preferably, the content of silica-alumina molecular sieve with twelve-membered ring channel structure is 2-10 wt%, the content of titanium dioxide is 8-15 wt%, the content of silicon oxide source is 12-25 wt%, and the content of zinc oxide is 40 wt%. - 60 wt%, the content of the metal promoter 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 Belonging 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 silicon oxide source can be pure silicon oxide, or natural minerals with a silicon oxide content greater than 45 wt%. Natural minerals may also contain other components such as Al ₂ O ₃ , K ₂ O, CaO, MgO, Fe ₂ O ₃ , TiO ₂ and so on. The silicon oxide source can be selected from one or more of diatomite, expanded perlite, kaolin, siliceous rock, hydrolyzed silica, macroporous silica and silica gel.

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

(1) hydrolyzing the titanium dioxide precursor in an acid solution to form a sol;

(2) The sol is mixed with a silicon oxide source, a silica-alumina molecular sieve having a twelve-membered ring channel structure, and zinc oxide, and formed, dried, and roasted 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 titanium dioxide precursor is a compound that can be hydrolyzed in step (1), and can exist in the form of anatase titanium dioxide after being roasted in step (2), preferably titanium tetrachloride, ethyl titanate , isopropyl titanate, 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 is added to excess acid solution, which can be hydrolyzed and generate a colloidal solution of cohesiveness. 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 0.5-6, preferably 1-4, to form a sol.

In step (2), the sol, silicon oxide source, zinc oxide, and silica-alumina molecular sieve with twelve-membered ring channel structure can be contacted and mixed in any order and manner. For example, the silicon oxide source can be added to the sol first, and then zinc oxide and silicon-alumina molecular sieves with a twelve-membered ring pore structure can be added simultaneously or sequentially, or the three can be added at the same time; the silicon oxide source, 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 (3), 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 metal promoter-introduced carrier is dried at about 50-300°C, preferably at a drying temperature of 100-250°C, and for 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 present invention adopts a non-aluminum binder, which avoids the formation of zinc aluminate from the zinc oxide part, thereby greatly improving the activity and stability of the adsorbent, and also has the advantage of obviously increasing the octane number of gasoline.

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: 2.42 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 3.2 kg of deacidified water, and stirred slowly to avoid the precipitation of titanium oxide crystals. At this time, the solution was colorless The transparent colloidal solution state is called titanium sol. Then add 2.10 kg of expanded perlite (containing 2.06 kg on a dry basis) to the titanium sol and stir to mix evenly.

4.43 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 0.84 kilograms of Beta (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 sieves were obtained Mix the 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 resulting mixture was dried at 180° C. for 4 hours, and dried in an air atmosphere at 635 The adsorbent precursor can be prepared by roasting at ℃ for 1 hour.

The adsorbent can be obtained by reducing the adsorbent precursor in a hydrogen atmosphere at 425° C. for 2 hours, and this adsorbent is designated as adsorbent A1. The chemical composition of the adsorbent A1 is as follows: the content of zinc oxide is 44.3wt.%, the content of expanded perlite is 20.6wt.%, the content of Beta molecular sieve is 7.0wt%, the content of titanium dioxide is 10.0wt.%, and the content of metallic nickel is 18.1wt.%.

Example 2

Get 1.26 kilograms of titanium dioxide (anatase type, containing 1.17 kilograms of titanium dioxide on a dry basis) and join in 2.6 kilograms of 10% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 1 hour to acidify, and now the titanium dioxide is completely dissolved into a colorless Transparent colloidal solution, called titanium sol. Then, 1.54 kg of diatomite (containing 1.50 kg on a dry basis) was added to the above-mentioned titanium sol and mixed 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 the adsorbent A2 is: the content of zinc oxide is 55.2wt.%, the content of titanium dioxide is 11.7wt.%, the content of diatomaceous earth is 15.0wt.%, the content of Beta molecular sieve is 3.0wt%, and the content of nickel is 15.1wt.%. .

Example 3

The adsorbent was prepared as follows: 3.87 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 while stirring, and After stirring for 1 hour, the solution was a light yellow transparent colloidal solution called titanium sol.

With 4.93 kilograms of zinc oxide powder (Headhorse company, purity 99.7%), 1.64 kilograms of diatomite (world mining company, containing dry basis 1.60 kilograms), 0.56 kilograms of USY (Qilu catalyst branch, containing dry basis 0.50 kilograms) and 6.40 One kilogram of deionized water was mixed, and a mixed slurry was obtained after stirring for 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 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.%, titanium dioxide is 13.5wt.%, diatomaceous earth is 16.0wt.%, USY content is 5.0wt%, nickel content is 8.1wt.%, cobalt content It is 8.1wt%.

Example 4

The adsorbent was prepared as follows: 3.36 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 while stirring, and After stirring for 1 hour, the solution was a light yellow transparent colloidal solution called titanium sol.

With 5.52 kilograms of zinc oxide powder (Headhorse company, purity 99.7%), 2.03 kilograms of dekaolin (Suzhou kaolin factory, containing dry basis 1.50 kilograms), 0.36 kilograms of X molecular sieves (Qilu Catalyst Branch Company, containing dry basis 0.30 kilograms) and 6.40 One kilogram of deionized water was mixed, and a mixed slurry was obtained after stirring for 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 the adsorbent A4 is: zinc oxide content is 55.2wt.%, titanium dioxide is 11.7wt.%, kaolin is 15.0wt.%, X molecular sieve content is 3.0wt%, and nickel content is 15.1wt.%.

Example 5

The adsorbent was prepared as follows: 2.42 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 3.2 kg of deacidified water, and stirred slowly to avoid the precipitation of titanium oxide crystals. At this time, the solution was colorless The transparent colloidal solution state is called titanium sol. Then add 2.10 kg of expanded perlite (containing 2.06 kg on a dry basis) to the titanium 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 A4. The chemical composition of the adsorbent A1 is as follows: the content of zinc oxide is 44.3wt.%, the content of expanded perlite is 20.6wt.%, the content of USY molecular sieve is 7.0wt%, the content of titanium dioxide is 10.0wt.%, and the content of metallic nickel is 18.1wt.%.

Comparative example 1

The adsorbent was prepared as follows: 3.31 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99wt.%) was slowly added to 5.0 kg of deacidified water, and stirred slowly to avoid the precipitation of titanium oxide crystals. At this time, the solution was colorless The transparent colloidal solution state is called titanium sol. Then add 2.45 kg of expanded perlite (containing 2.40 kg on a dry basis) to the titanium 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: the content of zinc oxide is 44.3wt.%, the content of expanded perlite is 24.0wt.%, the content of titanium dioxide is 13.6wt.%, and the content of metal nickel is 18.1wt.%.

Comparative example 2

Get 1.26 kilograms of titanium dioxide (anatase type, containing 1.17 kilograms of titanium dioxide on a dry basis) and join in 2.6 kilograms of 10% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) and stir for 1 hour to acidify, and now the titanium dioxide is completely dissolved into a colorless Transparent colloidal solution, called titanium sol. Then add 1.85 kg of diatomaceous earth (containing 1.80 kg on a dry basis) to the above-mentioned titanium 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 titanium dioxide is 11.7wt.%, the content of diatomaceous earth is 18.0wt.%, and the content of nickel is 15.1wt.%.

Comparative example 3

The adsorbent was prepared as follows: 3.87 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 while stirring, and After stirring for 1 hour, the solution was a light yellow transparent colloidal solution called titanium sol.

4.93 kg of zinc oxide powder (Headhorse Company, purity 99.7%), 2.15 kg of diatomaceous earth (World Mining Company, 2.10 kg on a dry basis) and 6.80 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed 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 formed, and the active components nickel and cobalt were introduced to obtain the adsorbent B3. The chemical composition of the adsorbent B3 is: zinc oxide content is 49.3wt.%, titanium dioxide is 13.5wt.%, diatomaceous earth is 21.0wt.%, nickel content is 8.1wt.%, cobalt content is 8.1wt%.

Comparative example 4

The adsorbent was prepared as follows: 3.36 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 while stirring, and After stirring for 1 hour, the solution was a light yellow transparent colloidal solution called titanium sol.

5.52 kg of zinc oxide powder (Headhorse Company, purity 99.7%), 2.44 kg of dekaolin (Suzhou Kaolin Factory, containing 1.80 kg on a dry basis) and 7.00 kg of deionized water were mixed and stirred for 30 minutes to obtain a mixed 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 B4. The chemical composition of the adsorbent B4 is: the content of zinc oxide is 55.2wt.%, the content of titanium oxide is 11.7wt.%, the content of kaolin is 18.0wt.%, and the content of nickel is 15.1wt.%.

Example 6

The desulfurization performance and octane number of the adsorbents prepared by different methods were investigated. 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 Desulfurization performance and octane number 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. hydrocarbon oil desulphurization adsorbing agent take the adsorbent gross weight as benchmark, comprises following component:

1) have the Si-Al molecular sieve of twelve-ring pore passage structure, content is 1-20wt%;

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

3) silica source, 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 adsorbent claimed in claim 1, wherein each constituent content is: the content with Si-Al molecular sieve of twelve-ring pore passage structure is 2-15wt%, content of titanium dioxide is 5-25wt%, the content of silica source is 10-30wt%, zinc oxide content is 25-70wt%, and the content of metallic promoter agent is 8-25wt%.

3. according to adsorbent claimed in claim 1, the content that wherein has the Si-Al molecular sieve of twelve-ring pore passage structure is 2-10wt%, the content of titanium dioxide is 8-15wt%, the content of silica source is 12-25wt%, the content of zinc oxide is 40-60wt%, and the content of metallic promoter agent is 12-20wt%.

4. according to adsorbent claimed in claim 1, the Si-Al molecular sieve that wherein has the twelve-ring pore passage structure be selected from have FAU, one or more molecular sieves of MOR, MAZ, BEA crystal structure.

5. according to adsorbent claimed in claim 4, wherein said FAU structure molecular screen is X-type and/or Y zeolite.

6. according to adsorbent claimed in claim 4, the molecular sieve that wherein has a FAU structure also comprises this molecular sieve analog after the modification, include but not limited to USY, contain REUSY, REHY, the REY of rare earth element, and among phosphorous PUSY, PREHY, the PREY one or more.

7. according to adsorbent claimed in claim 4, wherein the BEA structure molecular screen is beta-molecular sieve.

8. according to adsorbent claimed in claim 1, wherein said silica source is selected from pure silica or silica content greater than the natural minerals of 45wt%.

9. according to adsorbent claimed in claim 1, wherein silica source is selected from one or more in diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and the silica gel.

10. the preparation method of the described adsorbent of one of claim 1～9 comprises:

(1) the titanium dioxide precursor is hydrolyzed in acid solution, forms colloidal sol;

(2) colloidal sol is mixed with silica source, the Si-Al molecular sieve with twelve-ring pore passage structure and zinc oxide, and moulding, drying, roasting, obtain containing the carrier of active component;

(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.

11. according to preparation method claimed in claim 10, wherein in the step (1), described titanium dioxide precursor is selected from one or more in titanium tetrachloride, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and the anatase titanium dioxide.

12. according to preparation method claimed in claim 10, said acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, the consumption of acid is to make the pH value of the rear solution of hydrolysis be 0.5-6.

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 the acetic acid, the consumption of acid makes the pH value of the rear solution of hydrolysis be 1-4.

14. according to preparation method claimed in claim 10, in the step (2), in colloidal sol, add first silica source, the Si-Al molecular sieve that adds zinc oxide and have the twelve-ring pore passage structure successively or simultaneously again, or the three added colloidal sol simultaneously; Directly add in the colloidal sol silica source, zinc oxide and or have the Si-Al molecular sieve powder of twelve-ring pore passage structure, or add the slurries that prepare in advance.

15. according to preparation method claimed in claim 10, dry temperature is room temperature to 400 ℃, sintering temperature is 400-700 ℃.

16. according to preparation method claimed in claim 10, in the step (3), the compound of described containing metal promoter is selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metallic promoter agent, and two or more mixture wherein.

17. according to preparation method claimed in claim 10, in the step (4), the carrier of introducing promoter component is lower dry at about 50-300 ℃, under the condition that has oxygen or oxygen-containing gas to exist, under about 300-800 ℃ temperature, carry out roasting, until volatile materials is removed and metallic promoter agent is converted into metal oxide, obtain the adsorbent precursor.

18. according to preparation method claimed in claim 10, in the step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, metallic promoter agent is existed with reduction-state basically.

19. desulfurization of hydrocarbon oil method, comprise: the described adsorbent of hydrocarbon oil containing surphur and one of claim 1～9 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.