CN102895944A

CN102895944A - Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof

Info

Publication number: CN102895944A
Application number: CN2011102131846A
Authority: CN
Inventors: 林伟; 田辉平; 王振波; 郭瑶庆; 许明德; 王磊
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2011-07-28
Filing date: 2011-07-28
Publication date: 2013-01-30
Anticipated expiration: 2031-07-28
Also published as: CN102895944B

Abstract

本发明提供一种烃油脱硫吸附剂，并提供该吸附剂的制备方法和应用方法。本发明提供的吸附剂，以吸附剂总重量为基准，至少包括以下组成：1)具有十二元环孔道结构的硅铝分子筛，含量为1-20wt％；2)二氧化锡，含量为3-35wt％；3)氧化硅源，含量为5-40wt％；4)氧化锌，含量为10-80wt％；5)至少一种选自钴、镍、铁和锰的金属促进剂，含量为5-30wt％。本发明吸附剂采用非铝粘结剂，避免了氧化锌部分生成铝酸锌，从而大大提高了吸附剂的活性和稳定性，同时还具有明显的增加汽油辛烷值的优势。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 compositions: 1) a silica-alumina molecular sieve with a twelve-membered ring pore structure, with a content of 1-20 wt%; 2) tin dioxide, 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 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 desulphurization adsorbing agent and its preparation method and application

Technical field

The present invention relates to adsorbent that from hydrocarbon ils, removes sulphur and its preparation method and application.

Background technology

CN 1355727A provides a kind of novel absorbing composition that contains zinc oxide, silica, aluminium oxide and nickel or cobalt, and the preparation method of this adsorbent is provided.The method is at first prepared the carrier that contains zinc oxide, silica, aluminium oxide, then introduces nickel by dipping.This adsorbent can be used for removing sulphur from cracking gasoline or diesel fuel.

Adopt promoter metals such as cobalt and nickel dipping to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide among the CN 1208124C, reduction accelerator under suitable temperature then is for the preparation of the adsorbent that removes the cracking gasoline medium sulphide content.

When above-mentioned adsorbent removes sulfur in gasoline under hydro condition, inevitably because olefin saturated causes octane number to reduce.

CN 101433821A mentions a kind of adsorbent that reduces sulfur content in hydrocarbon oils, comprises rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; With above-mentioned rare earth faujasite and carrier mixture preshaped be the porous heat-resistant solid particle, introduce metal active constituent at this solid particle again, prepare described adsorbent.

CN 101434854A mentions a kind of adsorbent that reduces sulfur content of light hydrocarbon oil, comprises phosphorus modified RE faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; With above-mentioned rare earth faujasite preshaped with carrier mixture after the phosphorus modification be the porous heat-resistant solid particle, introduce metal active constituent at this solid particle again, prepare described adsorbent.

Although above-mentioned two methods add and select the type molecular sieve and be conducive to isomerization and increase octane number, owing to lack promoter metals and the sulphur storage medium of appropriate level, it is enough desulphurizing activated to cause this adsorbent to lack.

Summary of the invention

The invention provides a kind of adsorbent that can be used for from hydrocarbon ils, removing sulphur, and preparation method and application's method of this adsorbent is provided.

Adsorbent provided by the invention take the adsorbent gross weight as benchmark, comprises following composition at least:

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

2) tin ash, 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%.

Under the preferable case, content with Si-Al molecular sieve of twelve-ring pore passage structure is 2-15wt%, the content of tin ash is 5-25wt%, the content of silica source is 10-30wt%, the content of zinc oxide is 25-70wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 8-25wt%.

More preferably in the situation, content with Si-Al molecular sieve of twelve-ring pore passage structure is 2-10wt%, the content of tin ash is 8-15wt%, the content of silica source is 12-25wt%, the content of zinc oxide is 40-60wt%, and the content that is selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.

Si-Al molecular sieve with twelve-ring pore passage structure, be selected from have FAU, one or more molecular sieves of the crystal structures such as MOR, MAZ, BEA, the molecular sieve of preferred FAU and/or BEA structure.

Described FAU structure molecular screen is the faujasite-type molecular sieve, and the type molecular sieve has three-dimensional twelve-ring duct, and the aperture is 7.4A * 7.4A.The FAU structure molecular screen is mainly the molecular sieve of X-type and Y type, in general SiO ₂/ Al ₂O ₃Mol ratio be 2.2～3.0 for the X-type molecular sieve, SiO ₂/ Al ₂O ₃Mol ratio greater than 3.0 be Y zeolite.The skeleton structure of X-type and Y zeolite all belongs to hexagonal crystal system, and the space group structure is Fd3m, the cell parameter a=24.86 of X-type molecular sieve～25.02A, the cell parameter a=24.6 of Y zeolite～24.85A.

Molecular sieve with FAU structure also comprises this molecular sieve analog after the modification, and method of modifying can comprise hydro-thermal method, method of chemical treatment (for example mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiCl ₄Vapor phase method) or hydro-thermal combine with chemical treatment, obtain molecular sieve after the modification and include but not limited to super-stable Y molecular sieves (USY), contain REUSY, REHY, the REY of rare earth element, and phosphorous PUSY, PREHY, PREY etc.

The BEA structure molecular screen is mainly beta-molecular sieve, and its structural formula is (Na _n[Al _nSi _64-nO ₁₂₈], n＜7), be different by two structures but the polymorph A that is closely related and the mixed crystal of B both have twelve-ring 3 D pore canal system, polymorph A forms a pair of enantiomer, and space group is P4 ₁22 and P4 ₃22, cell parameter is a=12.5A, b=26.6A; Polymorph B belongs to achirality space group C2/c, cell parameter a=17.6A, b=17.8A, c=14.4A, β=114.5 °.Twelve-ring pore size 7.3A * 6.0A＜100 directions in the BEA structure molecular screen〉and 5.6A * 5.6A＜001 direction.

Described silica source can be pure silica, also can be that silica content is greater than the natural minerals of 45wt%.Can also contain other component such as Al in the natural minerals ₂O ₃, K ₂O, CaO, MgO, Fe ₂O ₃, TiO ₂Deng.Silica source can be selected from one or more in diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and the silica gel.

The invention provides the preparation method of hydrocarbon oil desulphurization adsorbing agent, comprising:

(1) the tin ash 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.

In the step (1), described tin ash precursor is the compound that can be hydrolyzed in step (1), exist with the form of tin ash after the roasting in step (2), one or more in preferred butter of tin, four isopropyl alcohol tin, tin acetate, the aqua oxidation tin.The tin ash precursor joins in the excess acid solution, can be hydrolyzed and generate caking property colloidal solution.Described acid is selected from one or more in water-soluble inorganic acid and/or the organic acid, is preferably in hydrochloric acid, nitric acid, phosphoric acid and the acetic acid one or more, and wherein the consumption of acid is to make the pH value of the rear solution of hydrolysis select 1-4 for 0.5-6, to form colloidal sol.

In the step (2), described colloidal sol and silica source, zinc oxide and the Si-Al molecular sieve with twelve-ring pore passage structure can adopt any order to contact mixing with mode.For example, can add first silica source in colloidal sol, the Si-Al molecular sieve that adds zinc oxide and have the twelve-ring pore passage structure successively or simultaneously more also can add the three simultaneously; Can be 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, also can add the slurries that prepare in advance.

In the step (2), resulting carrier mixture is shaped to extrudate, sheet, pill, ball or micro-spherical particle.For example, when described carrier mixture is dough or paste mixture, can make described mixture moulding (preferred extrusion molding) form particle, preferred diameter is at 1.0-8.0mm, then length make the extrudate of gained carry out drying, roasting at the cylindrical extrudate of 2.0-5.0mm.If the gained mixture is the wet mixture form, can make this mixture multiviscosisty, through the super-dry aftershaping.More preferably carrier mixture is the slurries form, and forming granularity by spray-drying is the microballoon of 20-200 micron, reaches the purpose of moulding.For the ease of spray-drying, the solid content of dry front slurries is 10-50wt%, is preferably 20-50wt%.

The drying means of carrier mixture and condition are conventionally known to one of skill in the art, for example dry method can be dry, oven dry, forced air drying.Dry temperature can be room temperature to 400 ℃, is preferably 100-350 ℃.

The roasting condition of carrier mixture also is conventionally known to one of skill in the art, and in general, sintering temperature is 400-700 ℃, is preferably 450-650 ℃, and roasting time is at least 0.5 hour, is preferably 0.5-100 hour, more preferably 0.5-10 hour.

In the step (3), the described compound that contains the metallic promoter agent component is the material that can be converted into metal oxide under roasting condition.The compound of described metallic promoter agent can be selected from acetate, carbonate, nitrate, sulfate, rhodanate and the oxide of metal, and two or more mixture etc. wherein.Preferably contain nickel in the described metallic promoter agent.Can adopt the method that well known to a person skilled in the art dipping or precipitation to introduce metallic promoter agent at carrier.Described dipping method is solution or the carrier of suspension impregnation after roasting with the compound of containing metal promoter; Described intermediate processing is that the solution of the compound of containing metal promoter or suspension are mixed with adsorbing agent carrier, then adds ammoniacal liquor, with the compound precipitation of metallic promoter agent on carrier.

In the step (4), the carrier of introducing the metallic promoter agent component carries out drying under about 50-300 ℃, and preferred baking temperature is 100-250 ℃, is about 0.5-8 hour drying time, more preferably from about 1-5 hour.After the drying, under the condition that has oxygen or oxygen-containing gas to exist, about 300-800 ℃, more preferably carry out roasting under 450-750 ℃ the temperature, general about 0.5-4 hour of needed time of roasting, preferred 1-3 hour, until volatile materials is removed and the metallic promoter agent precursor is converted into metal oxide, obtain the adsorbent precursor.

In the step (5), the adsorbent precursor is reduced under 300-600 ℃ of hydrogeneous atmosphere, metallic promoter agent is existed with reduction-state basically, obtain adsorbent of the present invention.Preferred reduction temperature is 400-500 ℃, and hydrogen content is 10-60vol%, recovery time 0.5-6 hour, and more preferably 1-3 hour.

The invention provides a kind of desulfurization of hydrocarbon oil method, comprising: hydrocarbon oil containing surphur is fully contacted under hydrogen atmosphere with adsorbent of the present invention, and the temperature and pressure condition is: 350-500 ℃, and 0.5-4MPa; Preferred 400-450 ℃, 1.0-2.0MPa.Sulphur in this process in the hydrocarbon ils is adsorbed on the adsorbent, thereby obtains the hydrocarbon ils of low sulfur content.

Can reuse behind the reacted adsorbent reactivation.Regenerative process is carried out under oxygen atmosphere, and regeneration condition is normal pressure, and temperature is 400-700 ℃, preferred 500-600 ℃.

Adsorbent also need to reduce under hydrogen atmosphere before reusing after the regeneration, and the temperature and pressure scope of reduction is: 350-500 ℃, and 0.2-2MPa; Preferred 400-450 ℃, 0.2-1.5MPa.

Hydrocarbon ils of the present invention comprises cracking gasoline and diesel fuel, wherein " cracking gasoline " to mean boiling range be 40 to 210 ℃ hydrocarbon or its any cut, be from making larger hydrocarbon molecule be cracked into the product of more micromolecular heat or catalytic process.Applicable thermal cracking process includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of applicable catalytic cracking process includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, applicable catalytically cracked gasoline includes but not limited to coker gasoline, pressure gasoline, visbreaking gasoline, fluid catalystic cracking gasoline and residual oil cracking gasoline and combination thereof.Can be with described cracking gasoline fractionation and/or hydrotreatment before desulfurization during in some cases, in the methods of the invention as hydrocarbon-containifluids fluids.It is 170 ℃ to 450 ℃ hydrocarbon mixture or the liquid of its any fractional composition that institute's art " diesel fuel " means boiling range.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil and hydrotreatment diesel oil etc. and combination thereof.

The normal organosulfur compound that exists in term used herein " sulphur " any type of element sulphur of representative such as hydrocarbon-containifluids fluids such as cracking gasoline or the diesel fuel.The sulphur that exists in the hydrocarbon-containifluids fluids of the present invention includes but not limited to carbonyl sulfide (COS), carbon disulfide (CS ₂), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylthrophene, alkylbenzene bithiophene and methyldibenzothiophene, and the normal larger thiophenes of molecular weight that exists in the diesel fuel.

Adsorbent of the present invention adopts non-al binder, has avoided zinc oxide partly to generate zinc aluminate, thereby has greatly improved the active and stable of adsorbent, also has simultaneously the advantage of obvious increase octane number.

The specific embodiment

Following example will the present invention is described further, but not thereby limiting the invention.Among the embodiment, adsorbent forms employing XRD (X-ray diffraction) and analyzes.

Embodiment 1

With 2.33 kilograms of crystallization butter of tin (SnCl ₄.5H ₂O, Alfa Aesar company, purity 99wt.%) slowly join in 3.2 kilograms of acid waters, and slowly stir and avoid the tin oxide crystal to separate out, obtain water white tin oxide sol.Then add 2.10 kilograms expanded perlite (containing 2.06 kilograms of butts) in the above-mentioned tin oxide sol and mix.

With 4.43 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7wt%), 0.84 kilogram Beta molecular sieve (catalyst branch company in Nanjing contains 0.70 kilogram of butt) and 4.57 kilograms of deionized waters are mixed, and stir and obtain zinc oxide and Beta molecular sieve mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir the carrier pulp that obtains adsorbent after 1 hour.

Described carrier pulp adopts Niro Bowen Nozzle Tower ^TMThe spray dryer of model carries out spray-drying, and spray-drying pressure is 8.5 to 9.5MPa, and inlet temperature is below 500 ℃, and outlet temperature is about 150 ℃.First at 180 ℃ times dry 1 hour by the microballoon that spray-drying obtains, then obtained adsorbing agent carrier in 1 hour 635 ℃ of lower roastings.

With 3.2 kilograms adsorbing agent carriers with 3.51 kilograms of Nickelous nitrate hexahydrate (Beijing chemical reagents corporations, purity is greater than 98.5wt%), 0.6 kilogram of deionized water solution dipping, the mixture that obtains after 4 hours, 1 hour can make adsorbent precursor in 635 ℃ of roastings of air atmosphere through 180 ℃ of dryings.

Adsorbent precursor reductase 12 in 425 ℃ hydrogen atmosphere hour can obtain adsorbent, and this adsorbent is designated as adsorbent A 1.The chemical composition of adsorbent A 1 is: zinc oxide content is 44.3wt.%, and expanded perlite content is 20.6wt.%, and the Beta molecular sieve content is 7.0wt%, and tin ash 10.0wt.%, metallic nickel content are 18.1wt.%.

Embodiment 2

Get 1.26 kilograms of Dibutyltin oxide (Aldrich companies, analyze pure, 99wt%) join 2.6 kilogram 10% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) in, and be warming up to 80 ℃ aging 1 hour, this moment, tin oxide was dissolved as water white colloidal solution fully, was called tin oxide sol.Then the diatomite (containing 1.50 kilograms of butts) that adds 1.54 kilograms in the above-mentioned tin oxide sol under agitation mixes.

5.52 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), 0.36 kilogram Beta (catalyst branch company in Nanjing contains 0.30 kilogram of butt) and 5.0 kilograms of deionized water mix and blends obtain zinc oxide and Beta mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 2.The chemical composition of adsorbent A 2 is: zinc oxide content is 55.2wt.%, and tin ash content is 11.7wt.%, and diatomite content is 15.0wt.%, and the Beta molecular sieve content is 3.0wt%, and nickel content is 15.1wt.%.

Embodiment 3

With 3.19 kilograms of tin acetate (Aldrich companies, analyze pure, 99wt%) in situation about stirring, slowly join in 3.5 kilogram 5% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) solution and stirred the collosol state that this moment, solution was white in color 1 hour.

With 4.93 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), 1.64 diatomite (the Global Mining Industry company of kilogram, contain 1.60 kilograms of butts), 0.56 kilogram USY (Shandong catalyst branch company, contain 0.50 kilogram of butt) and 6.40 kilograms of deionized waters mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel and cobalt with reference to the method for embodiment 1, obtain adsorbent A 3.The chemical composition of adsorbent A 3 is: zinc oxide content is 49.3wt.%, and tin ash is 13.5wt.%, and diatomite is 16.0wt.%, and USY content is 5.0wt%, and nickel content is 8.1wt.%, and cobalt content is 8.1wt%.

Embodiment 4

With 2.64 kilograms of tin acetate (Aldrich companies, analyze pure, 99wt%) in situation about stirring, slowly join in 3.5 kilogram 5% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) solution and stirred the collosol state that this moment, solution was white in color 1 hour.

With 5.52 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), 2.03 kilogram go to kaolin (Kaolin of Suzhou factory, contain 1.50 kilograms of butts), 0.36 kilogram X molecular sieve (Shandong catalyst branch company, contain 0.30 kilogram of butt) and 6.40 kilograms of deionized waters mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 4.The chemical composition of adsorbent A 4 is: zinc oxide content is 55.2wt.%, and tin ash is 11.7wt.%, and kaolin is 15.0wt.%, and X molecular sieve content is 3.0wt%, and nickel content is 15.1wt.%.

Embodiment 5

With 4.43 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7wt%), 0.78 kilogram USY molecular sieve (catalyst branch company in Shandong contains 0.70 kilogram of butt) and 4.57 kilograms of deionized waters are mixed, and stir and obtain zinc oxide and USY molecular sieve mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir the carrier pulp that obtains adsorbent after 1 hour.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent A 5.The chemical composition of adsorbent A 5 is: zinc oxide content is 44.3wt.%, and expanded perlite content is 20.6wt.%, and the USY molecular sieve content is 7.0wt%, and tin ash 10.0wt.%, metallic nickel content are 18.1wt.%.

Comparative Examples 1

With 3.17 kilograms of crystallization butter of tin (SnCl ₄.5H ₂0, Alfa Aesar company, purity 99wt.%) slowly join in 4.2 kilograms of acid waters, and slowly stir and avoid the tin oxide crystal to separate out, obtain water white tin oxide sol.Then add 2.45 kilograms expanded perlite (containing 2.40 kilograms of butts) in the above-mentioned tin oxide sol and mix.

4.43 kilograms of Zinc oxide powders (Headhorse company, purity 99.7wt%) and 4.57 kilograms of deionized waters are mixed, stir and obtain the zinc oxide slurries after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir the carrier pulp that obtains adsorbent after 1 hour.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 1.The chemical composition of adsorbent B 1 is: zinc oxide content is 44.3wt.%, and expanded perlite content is 24.0wt.%, and tin ash 13.6wt.%, metallic nickel content are 18.1wt.%.

Comparative Examples 2

Get 1.26 kilograms of Dibutyltin oxide (Aldrich companies, analyze pure, 99wt%) join 2.6 kilogram 10% hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) in, and be warming up to 80 ℃ aging 1 hour, this moment, tin oxide was dissolved as water white colloidal solution fully, was called tin oxide sol.Then the diatomite (containing 1.80 kilograms of butts) that adds 1.85 kilograms in the above-mentioned tin oxide sol under agitation mixes.

5.52 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%) and 5.0 kilograms of deionized water mix and blends are obtained the zinc oxide slurries after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 2.The chemical composition of adsorbent B 2 is: zinc oxide content is 55.2wt.%, and tin ash content is 11.7wt.%, and diatomite content is 18.0wt.%, and nickel content is 15.1wt.%.

Comparative Examples 3

With 4.93 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%), 2.15 kilograms diatomite (Global Mining Industry company contains 2.10 kilograms of butts) and 6.80 kilograms of deionized waters are mixed, and stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel and cobalt with reference to the method for embodiment 1, obtain adsorbent B 3.The chemical composition of adsorbent B 3 is: zinc oxide content is 49.3wt.%, and tin ash is 13.5wt.%, and diatomite is 21.0wt.%, and nickel content is 8.1wt.%, and cobalt content is 8.1wt%.

Comparative Examples 4

With 5.52 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%), go kaolin (Kaolin of Suzhou factory contains 1.80 kilograms of butts) and 6.80 kilograms of deionized waters of 2.44 kilograms are mixed, and stir and obtain mixed serum after 30 minutes.This mixed serum is added in the above-mentioned slurries, and stir after 1 hour and obtain carrier pulp.

Carry out the spray drying forming of carrier and introduce active component nickel with reference to the method for embodiment 1, obtain adsorbent B 4.The chemical composition of adsorbent B 4 is: zinc oxide content is 55.2wt.%, and tin ash is 11.7wt.%, and kaolin is 18.0wt.%, and nickel content is 15.1wt.%.

Embodiment 6

The adsorbent that distinct methods is prepared is investigated desulfurization performance and two indexs of octane number.Desulfurization performance is weighed with the product sulfur content, and sulfur content adopts the off-line chromatography in the product, adopts the little anti-experimental provision of fixed bed to estimate, and it is the catalytically cracked gasoline of 640ppm that the adsorption reaction raw material adopts sulphur concentration.The absorption test process adopts hydrogen atmosphere, and reaction temperature is 410 ℃, and the adsorption reaction weight space velocity is 4h ^-1, in order accurately to characterize out the activity of adsorbent in industrial actual motion, adsorbent processings of regenerating after reaction is finished, the regeneration processing is what to carry out under 550 ℃ air atmosphere.Its activity settled out substantially after adsorbent carried out 6 circulations of reaction regeneration, and the sulfur content after stablizing with adsorbent in the product gasoline represents the activity of adsorbent, and sulfur content is as shown in table 1 in the stable rear product gasoline.Simultaneously product gasoline is weighed and calculate its yield.

Adopt respectively GB/T 503-1995 and GB/T 5487-1995 to measure motor octane number (MON) and the research octane number (RON) (RON) of reaction front and back gasoline, the results are shown in Table 1.Can find out by table 1, contain the sorbent reactions of BEA or FAU structure molecular screen after, the octane number of product gasoline all has increase in various degree.

The desulfurization performance of the different adsorbents of table 1 and octane number

Annotate:

1, the sulfur content of feed gasoline is 640ppm, and RON is that 93.0, MON is 82.7.

2, Δ MON represents the value added of product MON;

3, Δ RON represents the value added of product RON;

4, Δ (RON+MON)/2 is the poor of product anti-knock index and raw material anti-knock index.

Claims

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) tin 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%.

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 tin dioxide content is 5-25wt%, and the silica The content of the source is 10-30wt%, the content of the zinc oxide is 25-70wt%, and the content of the metal promoter 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 tin dioxide is 8-15wt%, and the content of silicon oxide source 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. 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 tin dioxide precursor hydrolyze in acid solution, form 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.

11. according to the described preparation method of claim 10, wherein in step (1), described tin dioxide precursor is selected from the one in tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide or Several kinds.

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

14. according to the preparation method described in claim 10, in step (2), in sol, add silicon oxide source earlier, then add zinc oxide and the silicon-alumina molecular sieve with 12-membered ring channel structure successively or simultaneously, or three Or add the sol at the same time; directly add the silicon oxide source, zinc oxide and/or silicon-aluminum molecular sieve powder with twelve-membered ring channel structure to the sol, or add the 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 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.