CN102895948A - 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 of the present invention is based on the total weight of the adsorbent, and at least includes the following components: 1) a silica-alumina molecular sieve with a twelve-membered ring pore structure, with a content of 1-20 wt%; 2) an alumina binder, with a content of 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 5-30wt%. The adsorbent of the invention has high desulfurization activity, and also has the advantage of obviously increasing the gasoline octane number.

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 hydrocarbon oil desulfurization adsorbent provided by the present invention, based on the total weight of the adsorbent, at least includes the following components:

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

2) alumina binder, 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 alumina is 5-25wt%, the content of silicon oxide source is 10-30wt%, and the content of zinc oxide is 25-70wt% %, the content of the metal accelerator is 8-25wt%.

More preferably, the content of silica-alumina molecular sieve with twelve-membered ring channel structure is 2-10wt%, the content of aluminum oxide is 8-15wt%, the content of silicon oxide source is 12-25wt%, and the content of zinc oxide is 40-60wt%, and the content of the metal accelerator is 12-20wt%.

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 may 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 silica source is selected from one or more of diatomite, expanded perlite, kaolin, siliceous rock, hydrolyzed silica, macroporous silica and silica gel.

The preparation method of described adsorbent comprises:

(1) Make the silica source, the alumina binder precursor and the acidic liquid contact to form a slurry, and age:

(2) mixing the above-mentioned slurry with zinc oxide and a silica-alumina molecular sieve having a twelve-membered ring channel structure 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 alumina binder precursor is preferably hydrated alumina, aluminum sol, boehmite (boehmite), pseudo-boehmite (pseudoboehmite), three One or more of hydrated alumina, amorphous aluminum hydroxide, these different forms of alumina precursors exist in the form of γ-Al ₂ O ₃ after roasting.

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

In the step (2), the slurry in the step (1) is mixed with zinc oxide and a silica-alumina molecular sieve having a twelve-membered ring channel structure. Zinc oxide and silica-alumina molecular sieve powder with twelve-membered ring channel structure can be directly added to the slurry in step (1), or pre-prepared zinc oxide and/or twelve-membered ring channel structure can be added separately or simultaneously. Si-alumina molecular sieve slurry.

The carrier mixture obtained in step (2) can be in the form of wet mixture, dough, paste or slurry, etc., and then the obtained mixture is formed into extrudates, tablets, pellets, spheres or microspheroidal particles. For example, when the carrier mixture is a dough or pasty mixture, the mixture can be molded (preferably extruded) to form granules, preferably cylindrical extrusions with a diameter of 1.0-8.0 mm and a length of 2.0-5.0 mm. The extrudate obtained is then dried and calcined. If the resulting mixture is in the form of a wet mixture, the mixture can be thickened, dried and shaped. More preferably, the carrier mixture is in the form of a slurry, which is spray-dried to form microspheres with a particle size of 20-200 microns to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the slurry before drying is 10-50 wt.%, preferably 20-50 wt.%.

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

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

In step (3), the metal promoter-containing compound 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 containing the metal promoter is precipitated on the support. The compound containing the metal promoter is a material that can be converted into a metal promoter oxide under the roasting condition of step (4), and can be selected from acetates, carbonates, nitrates, sulfates, Thiocyanates and oxides, and mixtures of two or more of them, etc. Nickel is preferably contained in the metal promoter.

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

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

The 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°C to 210°C, derived from the heat of cracking larger hydrocarbon molecules into smaller molecules or products of catalytic processes. Applicable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, etc., and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Accordingly, suitable catalytically cracked gasoline includes, but is not limited to, coker gasoline, thermally cracked gasoline, visbroken gasoline, fluid catalytically cracked gasoline, and heavy oil cracked gasoline, and combinations thereof. In some cases, the cracked gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention. The term "diesel fuel" means a liquid composed of a hydrocarbon mixture or any fraction thereof with a boiling range of 170°C to 450°C. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight-run diesel and hydrotreated diesel, and the like, and combinations thereof.

The term "sulfur" as used herein denotes any form of elemental sulfur such as organic sulfur compounds commonly present in hydrocarbon-containing fluids such as cracked gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluids of the present invention includes, but is not limited to, carbon oxysulfide (COS), carbon disulfide (CS ₂ ), mercaptans or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often found in diesel fuel.

The adsorbent of the invention has high desulfurization activity, 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

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

Example 1

4.43 kilograms of zinc oxide powder (Headhorse company, purity 99.7wt.%), 0.84 kilograms of β 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 β Molecular sieve mixed slurry.

Take 1.37 kg of alumina (produced by Shandong Aluminum Factory, containing 1.00 kg on a dry basis) and 2.10 kg of expanded perlite (including 2.06 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 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was stirred and acidified for 1 hour, then heated to 80° C. and aged for 2 hours, then added zinc oxide and Beta molecular sieve slurry, mixed and stirred for 1 hour to obtain carrier slurry.

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

3.2 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: the zinc oxide content is 44.3wt.%, the expanded perlite content is 20.6wt.%, the β molecular sieve content is 7.0wt.%, the alumina binder is 10.0wt.%, and the metal nickel content is 18.1 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 2.46 kg of expanded perlite (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 expanded perlite, and 18.1wt.% of nickel.

Example 2

Get 1.61 kilograms of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.17 kilograms on a dry basis) and 1.54 kilograms of diatomite (containing 1.50 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%) and 0.36 kg of β molecular sieve (Nanjing Catalyst Branch, containing 0.30 kg on a dry basis) were 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 A2. The chemical composition of the adsorbent A2 is: the content of zinc oxide is 55.2wt.%, the content of alumina binder is 11.7wt.%, the content of diatomaceous earth is 15.0wt.%, the content of β molecular sieve is 3.0wt.%, and the content of nickel It is 15.1wt.%.

Comparative example 2

Get 1.61 kilograms of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.17 kilograms on a dry basis) and 1.85 kilograms of diatomite (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 diatomite is 18.0wt.%, and the content of nickel is 15.1wt.%.

Example 3

The adsorbent was prepared as follows: 4.93 kg of zinc oxide powder (Headhorse Company, purity 99.7%), 0.56 kg of USY (Qilu Catalyst Branch, containing 0.50 kg on a dry basis) and 5.57 kg of deionized water were mixed and stirred for 30 minutes to obtain Mixed slurry of zinc oxide and USY.

Take 1.85 kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35 kg on a dry basis) and 1.64 kg of diatomite (world mining company, containing 1.60 kg on a dry basis) and mix them under stirring, then add 4.6 kg of deionized water After mixing evenly, add 300 ml of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Factory) to make the pH value of the slurry 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 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.%, alumina binder is 13.5wt.%, diatomaceous earth is 16.0wt.%, USY content is 5.0wt.%, nickel content is 8.1wt. .%, the cobalt content is 8.1wt.%.

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.

Take 1.85 kg of pseudo-boehmite (produced by Shandong Aluminum Factory, containing 1.35 kg on a dry basis) and 2.16 kg of de-diatomite (world mining company, containing 2.10 kg on a 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.%, diatomaceous earth is 21.0wt.%, nickel content is 8.1wt.%, cobalt content is 8.1wt. .%.

Example 4

The adsorbent was prepared as follows: 5.52 kilograms of zinc oxide powder (Headhorse company, purity 99.7%), 0.36 kilograms of X molecular sieves (Qilu catalyst branch, containing 0.30 kilograms on a dry basis) and 5.57 kilograms of deionized water were mixed, and after stirring for 30 minutes A mixed slurry of zinc oxide and X molecular sieve was obtained.

Take 1.61 kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.17 kg on a dry basis) and 2.03 kg of dekaolin (Suzhou Kaolin Factory, containing 1.50 kg on a dry basis) and mix them under stirring, then add 4.6 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. Then add zinc oxide and X molecular sieve slurry, mix and stir for 1 hour to obtain carrier slurry.

Referring to the method of Example 1, the carrier was spray-dried and molded and the active component nickel was introduced to obtain the adsorbent A4. The chemical composition of adsorbent A4 is: zinc oxide content is 55.2wt.%, alumina binder is 11.7wt.%, kaolin is 15.0wt.%, X molecular sieve content is 3.0wt.%, nickel content is 15.1wt. %.

Comparative example 4

The adsorbent was prepared as follows: 5.52 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.

Take 1.61 kg of pseudo-boehmite (produced by Shandong Aluminum Factory, containing 1.17 kg on a dry basis) and 2.44 kg of kaolin (Suzhou Kaolin Factory, containing 1.80 kg on a dry basis) and mix them under stirring, then add 3.6 kg of deionized water and mix well Finally, 300 milliliters of 30% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was added to make the pH value of the slurry 2.5, stirred and acidified for 1 hour, and then heated to 80° C. for aging 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 molded and the active component nickel was introduced to obtain the adsorbent B4. The chemical composition of the adsorbent B4 is as follows: the zinc oxide content is 55.2wt.%, the alumina binder is 11.7wt.%, the kaolin is 18.0wt.%, and the nickel content is 15.1wt.%.

Example 5

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.

Take 1.37 kg of alumina (produced by Shandong Aluminum Factory, containing 1.00 kg on a dry basis) and 2.10 kg of expanded perlite (including 2.06 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 30wt.% hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) was stirred and acidified for 1 hour, then heated to 80° C. for 2 hours of aging, then added zinc oxide and USY molecular sieve slurry, mixed 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 A5. The chemical composition of adsorbent A5 is: zinc oxide content is 44.3wt.%, expanded perlite content is 20.6wt.%, USY molecular sieve content is 7.0wt.%, alumina binder is 10.0wt.%, metal nickel content is 18.1 wt.%.

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 uses 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. The regeneration process is in 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 the adsorbent of the present invention, the octane number of the 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) alumina binder, 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%. 2. The adsorbent according to claim 1, wherein the content of each component is: the content of the silica-alumina molecular sieve with twelve-membered ring pore structure is 2-15wt%, the alumina content is 5-25wt%, and the silica source The content of zinc oxide 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 aluminum oxide is 8-15wt%, and the content of silicon oxide source is 12-10wt%. 25 wt%, the content of zinc oxide is 40-60 wt%, and the content of metal accelerator is 12-20 wt%. 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 structured molecular sieve is a beta molecular sieve. 8. The adsorbent according to claim 1, wherein said source of silica is selected from pure silica or natural minerals having a silica content greater than 45 wt%. 9. The adsorbent according to claim 1, wherein the silica source is selected from one or more of diatomite, expanded perlite, kaolin, siliceous rock, hydrolyzed silica, macroporous silica and silica gel. 10. The preparation method of the adsorbent according to any one of claims 1 to 9, comprising: (1) Make the silica source, the alumina binder precursor and the acidic liquid contact to form a slurry, and age: (2) mixing the above-mentioned slurry with zinc oxide and a silicon-aluminum molecular sieve having a twelve-membered ring channel structure to obtain a carrier mixture containing the active component zinc oxide, molding, drying, and roasting to obtain a carrier containing the active component zinc oxide; (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 an adsorbent. 11. The preparation method according to claim 10, wherein in the step (1), the alumina binder precursor is selected from the group consisting of hydrated alumina, aluminum sol, boehmite, pseudo-boehmite, One or more of aluminum oxide trihydrate and amorphous aluminum hydroxide. 12. according to the described preparation method of claim 10, wherein said acidic liquid is the aqueous solution of acid or acid, said acid is selected from one or more in water-soluble inorganic acid and/or organic acid, The amount of acid used is such that the pH of the slurry is 1-5. 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, and the consumption of acid makes the pH value of slurry be 1.5-4. 14. according to the preparation method described in claim 10, in step (2), in the slurry of step (1), directly add zinc oxide and the silica-alumina molecular sieve powder that has 12-membered ring channel, or separately or simultaneously add pre-prepared Good slurries contain zinc oxide and/or silica-alumina molecular sieves with twelve-membered ring channels. 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 to 9 under a hydrogen atmosphere, the temperature and pressure conditions are: 350-500 ° C, 0.5-4 MPa, During this process the sulfur in the hydrocarbon oil is adsorbed onto the adsorbent, resulting in a hydrocarbon oil with low sulfur content.