CN102895945B - Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof - Google Patents
Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a hydrocarbon oil desulphurization adsorbent, and a preparation method and an application thereof. With a total weight of the adsorbent as a standard, The adsorbent provided by the invention at least comprises the components of, by weight: (1) 1-20% of an aluminosilicate molecular sieve with a duodenary-ring pore-channel structure, (2) 3-35% of zirconium dioxide, (3) 5-40% of a silicon oxide source, (4) 10-80% of zinc oxide, and (5) 5-30% of at least one metal accelerating agent selected from cobalt, nickel, iron and manganese. The absorbent provided by the invention adopts a non-aluminum adhesive, such that a zinc oxide is prevented from being partially converted into zinc aluminate. Therefore, activity and stability of the absorbent are greatly improved, and the absorbent has an advantage of a capacity for substantially increasing gasoline octane number.
Description
Technical field
The present invention relates to adsorbent removing sulphur and its preparation method and application from hydrocarbon ils.
Background technology
CN 1355727A provides a kind of novel absorbent composition containing zinc oxide, silica, aluminium oxide and nickel or cobalt, and provides the preparation method of this adsorbent.First the method prepares the carrier containing zinc oxide, silica, aluminium oxide, then introduces nickel by dipping.This adsorbent can be used for removing sulphur from cracking gasoline or diesel fuel.
Promoter metals such as cobalt and nickel dipping is adopted to comprise the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide in CN 1208124C, then reduction accelerator at appropriate temperatures, for the preparation of the adsorbent removing cracking gasoline medium sulphide content.
While 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 reducing sulfur content in hydrocarbon oils, comprises rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By above-mentioned rare earth faujasite and carrier mixture preshaped be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described adsorbent.
CN 101434854A mentions a kind of adsorbent reducing sulfur content of light hydrocarbon oil, comprises P Modification rare earth faujasite, reactive metal oxides and carrier, and wherein carrier comprises aluminium oxide and zinc oxide; By preshaped with carrier mixture after P Modification for above-mentioned rare earth faujasite be porous heat-resistant solid particle, then introduce metal active constituent on this solid particle, prepare described adsorbent.
Although above-mentioned two methods add the type molecular sieve of selecting and are conducive to isomerization and increase octane number, owing to lacking promoter metals and the sulphur storage medium of appropriate level, this adsorbent is caused to lack enough desulphurizing activated.
Summary of the invention
The invention provides a kind of adsorbent that can be used for removing sulphur from hydrocarbon ils, and preparation method and application's method of this adsorbent is provided.
Hydrocarbon ils adsorbent provided by the invention, take total sorbent weight as benchmark, at least comprises following composition:
1) have the Si-Al molecular sieve of twelve-ring pore passage structure, content is 1-20wt%
2) zirconium dioxide, content is 3-35wt%;
3) silica source, content is 5-40wt%;
4) zinc oxide, content is 10-80wt%;
5) at least one is selected from the metallic promoter agent of cobalt, nickel, iron and manganese, and content is 5-30wt%.
Under preferable case, the content with the Si-Al molecular sieve of twelve-ring pore passage structure is 2-15wt%, the content of zirconium dioxide is 5-25wt%, the content of silica source is 10-30wt%, the content of zinc oxide is 25-70wt%, and the content being selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 8-25wt%.
More preferably in situation, the content with the Si-Al molecular sieve of twelve-ring pore passage structure is 2-10wt%, the content of zirconium dioxide is 8-15wt%, the content of silica source is 12-25wt%, the content of zinc oxide is 40-60wt%, and the content being selected from the metallic promoter agent of cobalt, nickel, iron and manganese is 12-20wt%.
There is the Si-Al molecular sieve of twelve-ring pore passage structure, be selected from one or more molecular sieves with crystal structures such as FAU, MOR, MAZ, BEA, the molecular sieve of preferred FAU and/or BEA structure.
Described FAU structure molecular screen is faujasite-type molecular sieve, and the type molecular sieve has three-dimensional twelve-ring duct, and aperture is 7.4A × 7.4A.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 X-type molecular sieve, SiO
2/ Al
2o
3mol ratio be greater than 3.0 for Y zeolite.The skeleton structure of X-type and Y zeolite all belongs to hexagonal crystal system, and space group structure is Fd3m, the cell parameter a=24.86 ~ 25.02A of X-type molecular sieve, the cell parameter a=24.6 ~ 24.85A of Y zeolite.
The molecular sieve with FAU structure also comprises this modified molecular sieve analog, and method of modifying can comprise hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiCl
4vapor phase method) or hydro-thermal combine with chemical treatment, the modified molecular sieve that obtains includes but not limited to super-stable Y molecular sieves (USY), REUSY, REHY, REY containing rare earth element, and phosphorous PUSY, PREHY, PREY etc.
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 mixed crystal of the polymorph A be closely related and B, both have twelve-ring 3 D pore canal system, polymorph A forms a pair 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 direction > and 5.6A in BEA structure molecular screen × 5.6A<001 direction >.
Described silica source can be pure silica, also can be the natural minerals that silica content is greater than 45wt%.Can also containing other component as Al in 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 silica gel.
The invention provides the preparation method of hydrocarbon oil desulphurization adsorbing agent, comprising:
(1) make zirconium dioxide precursor be hydrolyzed in acid solution, form colloidal sol;
(2) make colloidal sol mix with silica source, the Si-Al molecular sieve with twelve-ring pore passage structure and zinc oxide, obtain carrier mixture, and shaping, dry, roasting, obtain the carrier containing active component;
(3) introduce the compound of containing metal promoter in the carrier, obtain adsorbent precursors;
(4) dry, roasting adsorbent precursors;
(5) adsorbent precursors after roasting is reduced in a hydrogen atmosphere, obtain adsorbent.
In step (1), described zirconium dioxide precursor be can hydrolysis in the step (1), one or more with the compound that zirconium dioxide form exists, in preferred zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO), amorphous zirconium dioxide after roasting in step (2).Zirconium dioxide precursor joins in 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 organic acid, and be preferably one or more in hydrochloric acid, nitric acid, phosphoric acid and acetic acid, the consumption of wherein acid is that after making hydrolysis, the pH of solution is 1-6, and preferred 1.5-4, to form colloidal sol.
In 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.Such as, in colloidal sol, first can add silica source, then add zinc oxide successively or simultaneously and there is the Si-Al molecular sieve of twelve-ring pore passage structure, also three can be added simultaneously; Can directly to add in colloidal sol silica source, zinc oxide and or there is the Si-Al molecular sieve powder of twelve-ring pore passage structure, also can add previously prepared good slurries.
In step (2), the carrier mixture obtained is shaped to extrudate, sheet, pill, ball or micro-spherical particle.Such as, described carrier mixture be dough or paste mixture time, described mixture shaping (preferred extrusion molding) can be made to form particle, and preferred diameter is at 1.0-8.0mm, length, at the cylindrical extrudates of 2.0-5.0mm, then makes the extrudate of gained carry out drying, roasting.If gained mixture is wet mixture form, this mixture multiviscosisty can be made, through super-dry aftershaping.More preferably carrier mixture is slurry form, forms the microballoon that granularity is 20-200 micron, reach shaping object by spraying dry.For the ease of spraying dry, before dry, the solid content of 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, such as dry method can be dry, dry, forced air drying.Dry temperature can be room temperature to 400 DEG C, is preferably 100-350 DEG C.
The roasting condition of carrier mixture is also conventionally known to one of skill in the art, and in general, sintering temperature is 400-700 DEG C, and be preferably 450-650 DEG C, roasting time is at least 0.5 hour, is preferably 0.5-100 hour, is more preferably 0.5-10 hour.
In step (3), the described compound containing metal promoter 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 the acetate of metal, carbonate, nitrate, sulfate, rhodanate and oxide, and wherein two or more mixture etc.Preferably containing nickel in described metallic promoter agent.Can adopt and well known to a person skilled in the art that the method for dipping or precipitation introduces metallic promoter agent on carrier.Described dipping method is solution or the carrier of suspension impregnation after roasting of the compound using containing metal promoter; Described intermediate processing is mixed with adsorbing agent carrier the solution of the compound of containing metal promoter or suspension, then adds ammoniacal liquor, by the compound precipitation of metallic promoter agent on carrier.
In step (4), the carrier introducing metal promoter component carries out drying at about 50-300 DEG C, and preferred baking temperature is 100-250 DEG C, and drying time is about 0.5-8 hour, more preferably from about 1-5 hour.After drying, having under oxygen or oxygen-containing gas existent condition, roasting is carried out at the temperature of about 300-800 DEG C, more preferably 450-750 DEG C, time required for roasting general about 0.5-4 hour, preferred 1-3 hour, until volatile materials is removed and metallic promoter agent precursor is converted into metal oxide, obtain adsorbent precursors.
In step (5), adsorbent precursors is reduced under 300-600 DEG C of hydrogeneous atmosphere, metallic promoter agent is existed with reduction-state substantially, obtains adsorbent of the present invention.Preferred reduction temperature is 400-500 DEG C, and hydrogen content is 10-60vol%, recovery time 0.5-6 hour, more preferably 1-3 hour.
The invention provides a kind of desulfurization of hydrocarbon oil method, comprising: hydrocarbon oil containing surphur is fully contacted in a hydrogen atmosphere with adsorbent of the present invention, and temperature and pressure condition is: 350-500 DEG C, 0.5-4MPa; Preferred 400-450 DEG C, 1.0-2.0MPa.Sulphur in the process in hydrocarbon ils is adsorbed on adsorbent, thus obtains the hydrocarbon ils of low sulfur content.
Can reuse after reacted adsorbent reactivation.Regenerative process is carried out under oxygen atmosphere, and regeneration condition is normal pressure, and temperature is 400-700 DEG C, preferred 500-600 DEG C.
After regeneration, adsorbent also needs to reduce in a hydrogen atmosphere before reuse, and the temperature and pressure scope of reduction is: 350-500 DEG C, 0.2-2MPa; Preferred 400-450 DEG C, 0.2-1.5MPa.
Hydrocarbon ils of the present invention comprises cracking gasoline and diesel fuel, and wherein " cracking gasoline " means hydrocarbon or its any cut that boiling range is 40 to 210 DEG C, is the product from making larger crack hydrocarbon molecules become more micromolecular heat or catalytic process.The thermal cracking process be suitable for includes, but are not limited to coking, thermal cracking and visbreaking etc. and combination thereof.The example of the catalytic cracking process be suitable for includes but not limited to fluid catalystic cracking and RFCC etc. and combination thereof.Therefore, the catalytically cracked gasoline be suitable for includes but not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and heavy oil cracked gasoline and combination thereof.In some cases, be in the methods of the invention used as hydrocarbon-containifluids fluids time can by described cracking gasoline fractionation and/or hydrotreatment before desulfurization.It is the hydrocarbon mixture of 170 DEG C to 450 DEG C 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 hydroprocessed diesel etc. and combination thereof.
Term used herein " sulphur " represents any type of element sulphur if hydrocarbon-containifluids fluids is as the organosulfur compound existed normal in cracking gasoline or diesel fuel.The sulphur existed in 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, alkyl benzothiophenes and methyldibenzothiophene, and the thiophenes that in diesel fuel, the normal molecular weight existed is larger.
Adsorbent of the present invention adopts non-al binder, avoids zinc oxide portion and generates zinc aluminate, thus substantially increase activity and the stability of adsorbent, also have the advantage significantly increasing octane number simultaneously.
Detailed description of the invention
The present invention is described further for example below, but therefore do not limit the present invention.
In embodiment, adsorbent composition adopts XRD (X-ray diffraction) to analyze.
Embodiment 1
Adsorbent is prepared as follows: by 1.90 kilograms of zirconium chloride (Beijing Chemical Plant, analyze pure, 99wt.%) slowly join in the salpeter solution of 2.7 kilograms of 5wt.%, and slowly stirring avoids crystal of zirconium oxide to separate out, obtain water white colloidal solution, be called zirconium colloidal sol.Then in above-mentioned zirconium colloidal sol, add the expanded perlite (containing butt 2.06 kilograms) of 2.10 kilograms and be uniformly mixed.
By 4.43 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7wt.%), 0.84 kilogram of Beta molecular sieve (Nanjing catalyst branch company, containing butt 0.70 kilogram) and 4.57 kilograms of deionized water mixing, stir after 30 minutes and obtain zinc oxide and Beta molecular sieve mixed serum.This mixed serum is added in above-mentioned slurries, and obtains the carrier pulp of adsorbent after stirring 1 hour.
Described carrier pulp adopts Niro Bowen Nozzle Tower
tMthe spray dryer of model carries out spraying dry, and spraying dry pressure is 8.5 to 9.5MPa, and inlet temperature less than 500 DEG C, outlet temperature is about 150 DEG C.The microballoon that obtained by spraying dry first at 180 DEG C dry 1 hour, then at 635 DEG C, roasting obtains adsorbing agent carrier in 1 hour.
By the adsorbing agent carrier of 3.2 kilograms 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 obtained after 4 hours, 1 hour can obtain adsorbent precursors in air atmosphere 635 DEG C of roastings through 180 DEG C of dryings.
Adsorbent precursors reductase 12 hour in the hydrogen atmosphere of 425 DEG C 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.%, Beta molecular sieve content is 7.0wt.%, zirconium dioxide binding agent 10.0wt.%, and metallic nickel content is 18.1wt.%.
Embodiment 2
By 1.71 kilograms of zirconium oxychloride (Aldrich companies, analyze pure, hydrochloric acid (the chemical pure of 3.2 kilograms of 15wt.% 98.5wt.%) is slowly joined when stirring, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now solution is water white colloidal solution, is called zirconium colloidal sol.Then the diatomite (containing butt 1.50 kilograms) adding 1.54 kilograms in above-mentioned zirconium colloidal sol under agitation mixes.
5.52 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), 0.36 kilogram of Beta molecular sieve (Nanjing catalyst branch company, containing butt 0.30 kilogram) and 5.0 kilograms of deionized water mix and blends obtain zinc oxide and Beta molecular sieve mixed serum after 30 minutes.This mixed serum is added in above-mentioned slurries, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains adsorbent A 2.The chemical composition of adsorbent A 2 is: zinc oxide content is 55.2wt.%, and zirconium dioxide binder content is 11.7wt.%, and diatomite content is 15.0wt.%, Beta molecular sieve content is 3.0wt.%, and nickel content is 15.1wt.%.
Embodiment 3
Adsorbent is prepared as follows: by 1.76 kg of hydrogen zirconia (Aldrich companies, analyze pure, 99wt.%) join the hydrochloric acid (chemical pure of 3.1 kilograms of 30wt.%, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now obtain transparent colloidal solution, be called zirconium colloidal sol.
By 4.93 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), diatomite (the Global Mining Industry company of 1.64 kilograms, containing butt 1.60 kilograms), 0.56 kilogram of USY (Shandong catalyst branch company, containing butt 0.50 kilogram) and 6.40 kilograms of deionized water mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in above-mentioned zirconium colloidal sol, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel and cobalt, obtains adsorbent A 3.The chemical composition of adsorbent A 3 is: zinc oxide content is 49.3wt.%, and zirconium dioxide binding agent is 13.5wt.%, and diatomite is 16.0wt.%, USY content is 5.0wt.%, and nickel content is 8.1wt.%, and cobalt content is 8.1wt%.
Embodiment 4
Adsorbent is prepared as follows: by 1.53 kg of hydrogen zirconia (Aldrich companies, analyze pure, 99wt.%) join the hydrochloric acid (chemical pure of 3.1 kilograms of 30wt.%, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now obtain transparent colloidal solution, be called zirconium colloidal sol.
By 5.52 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), 2.03 kilograms go to kaolin (Kaolin of Suzhou factory, containing butt 1.50 kilograms), 0.36 kilogram of X molecular sieve (Shandong catalyst branch company, containing butt 0.30 kilogram) and 7.40 kilograms of deionized water mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in above-mentioned zirconium colloidal sol, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains adsorbent A 4.The chemical composition of adsorbent A 4 is: zinc oxide content is 55.2wt.%, and zirconium dioxide binding agent is 11.7wt.%, and kaolin is 15.0wt.%, and X molecular sieve content is 3.0wt.%, and nickel content is 15.1wt.%.
Embodiment 5
Adsorbent is prepared as follows: by 1.90 kilograms of zirconium chloride (Beijing Chemical Plant, analyze pure, 99wt.%) slowly join in the salpeter solution of 2.7 kilograms of 5wt.%, and slowly stirring avoids crystal of zirconium oxide to separate out, obtain water white colloidal solution, be called zirconium colloidal sol.Then in above-mentioned zirconium colloidal sol, add the expanded perlite (containing butt 2.06 kilograms) of 2.10 kilograms and be uniformly mixed.
By 4.43 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7wt.%), 0.78 kilogram of USY molecular sieve (Shandong catalyst branch company, containing butt 0.70 kilogram) and 4.57 kilograms of deionized water mixing, stir and obtain zinc oxide and USY molecular sieve mixed serum after 30 minutes.This mixed serum is added in above-mentioned slurries, and obtains the carrier pulp of adsorbent after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains 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 USY molecular sieve content is 7.0wt.%, zirconium dioxide binding agent 10.0wt.%, and metallic nickel content is 18.1wt.%.
Comparative example 1
Adsorbent is prepared as follows: by 2.58 kilograms of zirconium chloride (Beijing Chemical Plant, analyze pure, 99wt.%) slowly join in the salpeter solution of 4.2 kilograms of 5wt.%, and slowly stirring avoids crystal of zirconium oxide to separate out, obtain water white colloidal solution, be called zirconium colloidal sol.Then in above-mentioned zirconium colloidal sol, add the expanded perlite (containing butt 2.40 kilograms) of 2.45 kilograms and be uniformly mixed.
By 4.43 kilograms of Zinc oxide powders (Headhorse company, purity 99.7wt.%) and 4.57 kilograms of deionized water mixing, stir and obtain zinc oxide slurries after 30 minutes.This mixed serum is added in above-mentioned slurries, and obtains the carrier pulp of adsorbent after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains adsorbent B 1.The chemical composition of adsorbent B 1 is: zinc oxide content is 44.3wt.%, and expanded perlite content is 24.0wt.%, zirconium dioxide binding agent 13.6wt.%, and metallic nickel content is 18.1wt.%.
Comparative example 2
By 1.71 kilograms of zirconium oxychloride (Aldrich companies, analyze pure, hydrochloric acid (the chemical pure of 3.2 kilograms of 15wt.% 98.5wt.%) is slowly joined when stirring, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now solution is water white colloidal solution, is called zirconium colloidal sol.Then the diatomite (containing butt 1.80 kilograms) adding 1.85 kilograms in above-mentioned zirconium colloidal 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 were obtained zinc oxide slurries after 30 minutes.This mixed serum is added in above-mentioned slurries, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains adsorbent B 2.The chemical composition of adsorbent B 2 is: zinc oxide content is 55.2wt.%, and zirconium dioxide binder content is 11.7wt.%, and diatomite content is 18.0wt.%, and nickel content is 15.1wt.%.
Comparative example 3
Adsorbent is prepared as follows: by 1.76 kg of hydrogen zirconia (Aldrich companies, analyze pure, 99wt.%) join the hydrochloric acid (chemical pure of 3.1 kilograms of 30wt.%, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now obtain transparent colloidal solution, be called zirconium colloidal sol.
By 4.93 kilograms of Zinc oxide powders (Headhorse company, purity 99.7%), the diatomite (Global Mining Industry company, containing butt 2.10 kilograms) of 2.15 kilograms and 6.90 kilograms of deionized water mixing, stir and obtain mixed serum after 30 minutes.This mixed serum is added in above-mentioned zirconium colloidal sol, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel and cobalt, obtains adsorbent B 3.The chemical composition of adsorbent B 3 is: zinc oxide content is 49.3wt.%, and zirconium dioxide binding agent is 13.5wt.%, and diatomite is 21.0wt.%, and nickel content is 8.1wt.%, and cobalt content is 8.1wt%.
Comparative example 4
Adsorbent is prepared as follows: by 1.53 kg of hydrogen zirconia (Aldrich companies, analyze pure, 99wt.%) join the hydrochloric acid (chemical pure of 3.1 kilograms of 30wt.%, Beijing Chemical Plant produce) in and stir acidifying 1 hour, now obtain transparent colloidal solution, be called zirconium colloidal sol.
By 5.52 kilograms of Zinc oxide powder (Headhorse companies, purity 99.7%), go kaolin (Kaolin of Suzhou factory, containing butt 1.80 kilograms) and 7.40 kilograms of deionized waters of 2.44 kilograms mix, and stir and obtain mixed serum after 30 minutes.This mixed serum is added in above-mentioned zirconium colloidal sol, and obtains carrier pulp after stirring 1 hour.
Method with reference to embodiment 1 is carried out the spray drying forming of carrier and introduces active component nickel, obtains adsorbent B 4.The chemical composition of adsorbent B 4 is: zinc oxide content is 55.2wt.%, and zirconium dioxide binding agent is 11.7wt.%, and kaolin is 18.0wt.%, and nickel content is 15.1wt.%.
Embodiment 6
Desulfurization performance and octane number two indexs are investigated to the adsorbent that distinct methods is prepared.Desulfurization performance is weighed with product sulfur levels, and in product, sulfur content adopts off-line chromatography, and adopt the micro-anti-experimental provision of fixed bed to evaluate, adsorption reaction raw material adopts sulphur concentration to be the catalytically cracked gasoline of 640ppm.Absorption test process adopts hydrogen atmosphere, and reaction temperature is 410 DEG C, and adsorption reaction weight space velocity is 4h
-1, in order to accurate characterization goes out the activity of adsorbent in industrial actual motion, reacted rear adsorbent and carried out regeneration process, regeneration process is what to carry out under the air atmosphere of 550 DEG C.After adsorbent carries out reaction regeneration 6 circulation, its activity settles out substantially, and represent the activity of adsorbent with the adsorbent sulfur content stablized in rear product gasoline, after stable, in product gasoline, sulfur content is as shown in table 1.Product gasoline is weighed simultaneously and calculate its yield.
Adopt GB/T 503-1995 and GB/T 5487-1995 to measure motor octane number (MON) and the research octane number (RON) (RON) of gasoline before and after reaction respectively, the results are shown in Table 1.Can be found out by table 1, after sorbent reactions of the present invention, the octane number of product gasoline all has increase in various degree.
The desulfurization performance of the different adsorbent of table 1 and octane number
Note:
1, the sulfur content of feed gasoline is 640ppm, RON be 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 difference of product anti-knock index and raw material anti-knock index.
Claims (19)
1. a cracking gasoline desulfuration adsorbent, is benchmark with total sorbent weight, comprises following component:
1) have the Si-Al molecular sieve of twelve-ring pore passage structure, content is 1-20wt%;
2) zirconium dioxide, content is 3-35wt%;
3) silica source, content is 5-40wt%;
4) zinc oxide, content is 10-80wt%;
5) at least one is selected from the metallic promoter agent of cobalt, nickel, iron and manganese, and content is 5-30wt%.
2. according to adsorbent according to claim 1, wherein each constituent content is: the content with the Si-Al molecular sieve of twelve-ring pore passage structure is 2-15wt%, zirconium dioxide content 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 according to claim 1, the content wherein with the Si-Al molecular sieve of twelve-ring pore passage structure is 2-10wt%, the content of zirconium 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 according to claim 1, the Si-Al molecular sieve wherein with twelve-ring pore passage structure is selected from one or more molecular sieves with FAU, MOR, MAZ, BEA crystal structure.
5., according to adsorbent according to claim 4, wherein said FAU structure molecular screen is X-type and/or Y zeolite.
6. according to adsorbent according to claim 4, the molecular sieve wherein with FAU structure also comprises this modified molecular sieve analog, include but not limited to USY, REUSY, REHY, REY containing rare earth element, and one or more in phosphorous PUSY, PREHY, PREY.
7., according to adsorbent according to claim 4, wherein BEA structure molecular screen is beta-molecular sieve.
8., according to adsorbent according to claim 1, wherein said silica source is selected from the natural minerals that pure silica or silica content are greater than 45wt%.
9., according to adsorbent according to claim 1, wherein silica source is selected from one or more in diatomite, expanded perlite, kaolin, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silica gel.
10. the preparation method of the adsorbent that one of claim 1 ~ 9 is described, comprising:
(1) make zirconium dioxide precursor be hydrolyzed in acid solution, form colloidal sol;
(2) colloidal sol is made to mix with silica source, the Si-Al molecular sieve with twelve-ring pore passage structure and zinc oxide, and shaping, dry, roasting, obtain the carrier containing active component;
(3) introduce the compound of containing metal promoter in the carrier, obtain adsorbent precursors;
(4) dry, roasting adsorbent precursors;
(5) adsorbent precursors after roasting is reduced in a hydrogen atmosphere, obtain adsorbent.
11. according to preparation method according to claim 10, and wherein in step (1), described zirconium dioxide precursor is selected from one or more in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO), amorphous zirconium dioxide.
12. according to preparation method according to claim 10, and said acid is selected from one or more in water-soluble inorganic acid and/or organic acid, and the consumption of acid is that after making hydrolysis, the pH value of solution is 1-6.
13. according to preparation method according to claim 12, and wherein said acid is one or more in hydrochloric acid, nitric acid, phosphoric acid and acetic acid, and after sour consumption makes hydrolysis, the pH value of solution is 1.5-4.
14. according to preparation method according to claim 10, in step (2), in colloidal sol, first adds silica source, then adds zinc oxide successively or simultaneously and have the Si-Al molecular sieve of twelve-ring pore passage structure, or three is added colloidal sol simultaneously; Directly to add in colloidal sol silica source, zinc oxide and or there is the Si-Al molecular sieve powder of twelve-ring pore passage structure, or add previously prepared good slurries.
15. according to preparation method according to claim 10, and dry temperature is room temperature to 400 DEG C, and sintering temperature is 400-700 DEG C.
16. according to preparation method according to claim 10, in step (3), the compound of described containing metal promoter is selected from the acetate of metallic promoter agent, carbonate, nitrate, sulfate, rhodanate and oxide, and wherein two or more mixture.
17. according to preparation method according to claim 10, in step (4), the carrier introducing promoter component is dry at 50-300 DEG C, roasting is carried out having under oxygen or oxygen-containing gas existent condition at the temperature of about 300-800 DEG C, until volatile materials is removed and metallic promoter agent is converted into metal oxide, obtain adsorbent precursors.
18. according to preparation method according to claim 10, in step (5), is reduced by adsorbent precursors under 300-600 DEG C of hydrogeneous atmosphere, and metallic promoter agent is existed with reduction-state substantially.
19. 1 kinds of cracking gasoline sulfur methods, comprise: make fully to contact in a hydrogen atmosphere with the described adsorbent of one of claim 1 ~ 9 containing cracked-gasoline, temperature and pressure condition is 350-500 DEG C, 0.5-4MPa, sulphur in the process in cracking gasoline is adsorbed on adsorbent, thus obtains the cracking gasoline of low sulfur content.
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| CN201110213242.5A CN102895945B (en) | 2011-07-28 | 2011-07-28 | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof |
| BR112014002046-9A BR112014002046B1 (en) | 2011-07-28 | 2012-07-27 | hydrocarbon oil desulfurization absorbing agent, its production and use |
| PCT/CN2012/001004 WO2013013507A1 (en) | 2011-07-28 | 2012-07-27 | Desulfurization absorbent for hydrocarbon oil, preparing method and use thereof |
| US14/235,124 US9446381B2 (en) | 2011-07-28 | 2012-07-27 | Hydrocarbon oil desulfurization adsorbing agent, production and use thereof |
| BR112014001997-5A BR112014001997B1 (en) | 2011-07-28 | 2012-07-27 | desulphurization adsorbent for hydrocarbon oil, production and use thereof |
| US14/235,037 US9511347B2 (en) | 2011-07-28 | 2012-07-27 | Hydrocarbon oil desulfurization adsorbing agent, production and use thereof |
| RU2014107736/05A RU2587444C2 (en) | 2011-07-28 | 2012-07-27 | Adsorbent for desulphuration of hydrocarbon oil, production and use thereof |
| RU2014107487/05A RU2585633C2 (en) | 2011-07-28 | 2012-07-27 | Adsorbing substance for desulphuration of hydrocarbon oil, production and use thereof |
| PCT/CN2012/001005 WO2013013508A1 (en) | 2011-07-28 | 2012-07-27 | Adsorbent for desulfurization of hydrocarbon oils, preparation method therefor and use thereof |
| TW101127301A TWI549746B (en) | 2011-07-28 | 2012-07-27 | A hydrocarbon oil desulfurization adsorbent, its preparation method and its application |
| TW101127302A TWI549747B (en) | 2011-07-28 | 2012-07-27 | A hydrocarbon oil desulfurization adsorbent, its preparation method and its application |
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| CN104415775B (en) * | 2013-08-21 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation and application thereof |
| CN104549487B (en) * | 2013-10-29 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and its method for preparation and desulfurization of hydrocarbon oil |
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