CN102463099B - Adsorptive desulfurization adsorbent and preparation method thereof - Google Patents
Adsorptive desulfurization adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN102463099B CN102463099B CN 201110074500 CN201110074500A CN102463099B CN 102463099 B CN102463099 B CN 102463099B CN 201110074500 CN201110074500 CN 201110074500 CN 201110074500 A CN201110074500 A CN 201110074500A CN 102463099 B CN102463099 B CN 102463099B
- Authority
- CN
- China
- Prior art keywords
- weight
- content
- molecular sieve
- nickel
- adsorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to an adsorptive desulfurization adsorbent and a preparation method thereof. An adsorbent composition contains zinc oxide, silicon oxide, aluminium oxide, an AEL-type structured phosphoaluminate molecular sieve and nickel; the nickel basically exists in a reduction state; based on the reference of the weight of the adsorbent composition, the content of the AEL-type structured phosphoaluminate molecular sieve in the adsorbent composition is 1-40% by weight; and in terms of elements, the content of the nickel is 5-50% by weight, the content of the zinc oxide is 10-84% by weight, the content of the silicon oxide is 5-75% by weight, and the content of the aluminium oxide is 5-30% by weight. The adsorbent composition is applied to the adsorptive desulfurization of hydrocarbon oil and has a better desulfurization effect; furthermore, the octane value of cracked gasoline can be increased; and the low-temperature flowing property of diesel can be improved.
Description
Technical field
The present invention relates to a kind of adsorbent composition for desulfurization of hydrocarbon oil.
Background technology
With direct steaming gasoline, with hydrogasoline, compare, the content of FCC sulfur in gasoline, alkene, aromatic hydrocarbons is higher, and stability is poor, easily produces colloid, foul smelling, and corrosion and colour difference, can not directly be used as qualified motor petrol.Simultaneously, along with improving constantly and the continuous change of people's environmental consciousness of environmental requirement, the environmental pollution that the fuel consume that how to reduce increases day by day brings, become the major issue that petroleum refining industry and auto industry sustainable development face, production super-low sulfur, zero-emission fuel become the general trend of petroleum refining industry's development.
A kind of cracking gasoline sulfur method commonly used is hydrodesulfurization.Although yet hydrodesulfurization can be removed the sulfur-containing compound in gasoline, but can make the most of olefin saturated in gasoline, the octane number (organon and motor octane number) of gasoline is significantly descended, and the thiophenes in gasoline is because sterically hindered effect is difficult to remove under conventional hydroconversion condition.
Another gasoline desulfating method commonly used is adsorption desulfurize, for example face hydrogen adsorption desulfurize technology S-Zorb technology [Zhao Xunzhi, Cheng Zhilin. the progress of low-sulfur clean fuel oil production technology. Industrial Catalysis .2007,15 (6): 1-5], there is gasoline desulfur effect preferably, and the decline of octane number (organon and motor octane number) is less.The method needs suitable adsorbent.
CN 1130253 C disclose the granular adsorbent composition of the mixture that comprises zinc oxide, silica, aluminium oxide and basically reduce valence state nickel, for making cracking gasoline or the desulfurization of diesel fuel feed stream at desulfurization zone by the following method, described method comprises: at desulfurization zone, with described feed stream, contact, then the logistics of separating obtained low sulfur content and sulfided sorbent, make isolated adsorbent reactivation and activation, then return to desulfurization zone.
CN 1258396C comprises zinc oxide, silica, aluminium oxide and basically reduces the granular adsorbent composition of mixture of valence state cobalt, for making cracking gasoline or the desulfurization of diesel fuel feed stream at desulfurization zone by the following method, described method comprises: at desulfurization zone, with described feed stream, contact, then the logistics of separating obtained low sulfur content and sulfided sorbent, make isolated adsorbent reactivation and activation, then return to desulfurization zone.Adsorbent comprises zinc oxide, silica, aluminium oxide and metal simple-substance nickel or cobalt.Wherein the CN1130253 C nickeliferous adsorbent of settling sth. according to policy or law can make the sulfur content in cracking gasoline drop to 10ppm or lower by 310ppm, but the motor octane number decline 0.1-0.4 of gasoline.
CN 1327988 A disclose a kind of S-Zorb adsorbent, it is to pass through promoter, the adsorbing agent carrier that comprises zinc oxide, expanded perlite and aluminium oxide as the precursor of nickel, nickel oxide or nickel oxide dipping, then make the chemical valence of the promoter metals in the promoter metals adsorbing agent carrier composition of gained reduce, prepare wear-resisting adsorbent composition.Relatively hydrodesulfurization, this adsorbent is applied to after the S-Zorb technology to make sulfur content in cracking gasoline lower than 1ppm, and average octane number Δ (RON+MON)/2 descends and is less than 2.0.
Although use above existing desulfuration adsorbent can reduce the sulfur content in cracking gasoline, can not improve the octane number of gasoline, and may cause the loss of octane number.And when not relating to adsorption desulfurize, prior art reduces the condensation point of diesel oil.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of adsorption-desulfurization sorbent composition that can improve the cracking gasoline octane number and reduce condensation point of diesel oil.
The invention provides a kind of hydrocarbon oil desulphurization adsorbing agent composition, described adsorbent composition comprises:
(1) zinc oxide,
(2) silica,
(3) aluminium oxide,
(4) AEL structure aluminophosphate molecular sieve, and
(5) nickel,
Described nickel exists with reduction-state basically;
The weight of adsorbent composition of take is benchmark, in described adsorbent composition, AEL structure aluminophosphate molecular sieve content is 1～40 % by weight, the content of element nickel of take is 5～50 % by weight, the content of zinc oxide is 10～84 % by weight, the content of silica is 5～75 % by weight, and the content of aluminium oxide is 5～30 % by weight.
The present invention also provides a kind of preparation method of adsorbent provided by the present invention, comprising:
(a) zinc oxide source, silica source, alumina source and AEL structure aluminophosphate molecular sieve are mixed;
(b) step (a) gained compound particles granulation is formed to particle;
(c) by the particle drying of step (b), then roasting;
(d) with the particle after the roasting of nickel compound containing impregnation steps (c) gained;
(e) will after step (d) gained impregnated granules drying, carry out roasting; Then
(f) composition reduction step (e) obtained.
The present invention further provides a kind of hydrocarbon ils desulfurizing method by adsorption, be included in the step under the condition of adsorption desulfurize, hydrocarbon ils contacted with desulfuration adsorbent provided by the invention.
Adsorbent composition provided by the invention, for the hydrocarbon ils adsorption desulfurize, have desulfurized effect preferably; For gasoline absorbing desulfurization, can also improve the octane number of gasoline in sulfur content in reducing hydrocarbon ils; For diesel oil adsorption desulfurizing, not only there is higher desulfurization degree, can also reduce the condensation point of diesel oil, improve the low temperature flowability of diesel oil.
The specific embodiment
In adsorbent composition provided by the invention, described AEL structure aluminophosphate molecular sieve is preferably one or more of AEL structure aluminophosphate molecular sieve that element replaces, and in the AEL structure aluminophosphate molecular sieve that described element replaces, substituted element is one or more in Li, Be, B, Si, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce.Described AEL structure phosphate molecule sieve is preferably one or more in SAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and CoAPO-11.Described AEL structure phosphate molecule sieve can be purchased or according to the preparation of existing method, described existing preparation method for example: [Xu Benjing, etc. the synthetic of. different magnesium source MAPO-11 molecular sieve and characterize. Journal of Molecular Catalysis .2004,18 (6): 409-415; Perhaps originally wait the synthetic and sign of .CoAPO-11 molecular sieve quietly. Industrial Catalysis .2004,12 (10): 38-43; A kind of synthetic method .CN101269822.2008-09-24 with heteroatom substituted AEL cage construction aluminophosphates molecular sieve such as Yan Zifeng].
In adsorbent composition provided by the invention, the gross weight of adsorbent composition of take is benchmark, and the content of described AEL structure aluminophosphate molecular sieve is 1～40 % by weight, is preferably 5～30 % by weight, more preferably 8～25 % by weight; Described zinc oxide content is 10～84 % by weight, is preferably 15～60 % by weight, more preferably 45～60 % by weight; The content of silica is 5 to 75 % by weight, preferably 10～60 % by weight; The content of described aluminium oxide is 5～30 % by weight, is preferably 5～15 % by weight; The content of the described nickel of nickel of take is 5～50 % by weight, is preferably 10～40 % by weight.Described nickel exists the chemical valence that refers to most of nickel component in adsorbent composition to be reduced to lower than divalent with reduction-state basically, preferably 0 valency.
Adsorbent composition provided by the invention can mix the major constituent of zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve so that described component is thoroughly mixed to form basically mixture uniformly by any applicable mode in the proper ratio.
In adsorbent composition preparation method provided by the invention, zinc oxide source used can be one or more zinc compounds that there was or can be converted under this paper preparation condition zinc oxide in the zinc oxide form, and the example of described zinc compound includes but not limited to zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.Selected zinc oxide source is preferably powdery zinc oxide.
In adsorbent composition preparation method provided by the invention, silica source used can be silica form or one or more silicon-containing compound forms.The silica of any application type all can be used for adsorbent composition of the present invention, and the example of the silica of application type comprises diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica, preferably diatomite.The compound that in addition, can be converted into silica also can be used as silicic acid, sodium metasilicate, ammonium silicate and ethyl orthosilicate (or methyl esters).Preferential oxidation silicon is the diatomite form.
In adsorbent composition preparation method provided by the invention, described alumina source can be that aluminium oxide form or one or more can be converted into the aluminum contained compound of aluminium oxide, can be Organic Alcohol chemical combination one or more in aluminum nitrate, aluminium chloride, aluminum sulfate, aluminium isopropoxide for example of the inorganic compound aluminium of aluminium and/or aluminium; It can also be any commercially available alumina material, it is including, but not limited to colloidal alumina solution with usually by the alumina cpd of hydrated alumina dehydration production, and for example described alumina source is one or more in aluminium colloidal sol, boehmite, gama-alumina and η-aluminium oxide.
In adsorbent composition preparation method provided by the invention, in step (a), can adopt any applicable device to mix described absorbent component so that described material fully disperses.Described device comprises such as rotary drum, stationary housings or groove, grinder (intermittence or continous way), impact mixer etc.Preferably use grinder in the mixing of zinc oxide source, silica source, alumina source and AEL structure aluminophosphate molecular sieve component.It can be wet mixture, dough, lotion or slurries form that described absorbent component is mixed to form mixture.If the gained mixture is the wet mixture form, can makes described wet mixture multiviscosisty, then in step (b), by granulating, it is granulated, then in step (c) drying and roasting.When described zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve are mixed to form dough or paste mixture, can in step (b), make described mixture moulding make grain, extrudate, sheet, ball, pill or microsphere particle; The cylindrical extrudate of any applicable length of preferred diameter 1/32 to 1/2 in (0.75 to 13mm); Then in step (c) by gained particle drying and roasting.When described mixture is the slurries form, in step (b), by described slurries spray-drying being formed to granularity, for the about microballoon of 20 to 500 μ m, make it granulating, then in step (c), make described microballoon drying and roasting.In step (c), dry described particle temperature is preferably 50 to 180 ℃, and the described particle temperature scope of roasting is preferably 200 to 850 ℃, and roasting time is preferably 0.5 to 6 hour.After described granular mixture drying and roasting, flood the particle of gained by nickel oxide compound or nickel oxide precursor in step (d).
In adsorbent composition preparation method provided by the invention, the solution that in step (d), can contain element state nickel, nickel oxide or nickel compound containing by use (aqueous solution or organic solution) floods described mixture, and element state nickel, nickel oxide or nickel compound containing are added in described granular mixture.Described dipping solution is any aqueous solution that is applicable to flood described zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve mixture, and the amount of this solution is applicable to making providing while being reduced of nickel oxide in final Zinc oxide-base composition to be enough to can from cracking gasoline fluid stream, remove the reduced nickel tenor of sulphur when the adsorbing composition prepared by the inventive method is processed.Generally with described nickel, flood the granular composition that forms zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve and described nickel metal, nickel oxide or nickel oxide precursor, then in step (e) by gained dip composition drying and roasting, dry described particle temperature is preferably 50 to 180 ℃, the described particle temperature scope of roasting is preferably 200 to 850 ℃, roasting time preferably 0.5 to 6 hour.
In adsorbent composition preparation method provided by the invention, step (e) makes the resulting particle drying of step (d), roasting, and dry described particle temperature is preferably 50 to 180 ℃, the described particle temperature scope of roasting is preferably 200 to 850 ℃, roasting time preferably 0.5 to 6 hour.
In adsorbent composition preparation method provided by the invention, the composition reduction that with applicable reducing agent (preferably hydrogen), step (e) is obtained in step (f), Ni is existed with reduction-state basically, be enough to remove the composition of sulphur to produce wherein the nickel content of zeroth order basically from cracking gasoline fluid stream.Particle reduction described reduction makes the roasting of step (e) gained in reducing zone under the valent applicable condition at reduced nickel basically with reducing agent after, can therefrom remove sulfur-containing organic compound while providing the also original cost cobalt metal of such amount so that resulting composition for example to contact with cracking gasoline under S-Zorb adsorption desulfurize condition under the adsorption desulfurize condition.The preferred hydrogen of described reducing agent, the method of reduction can be carried out according to existing method, for example according to the method described in CN 1258396C, reduced, carry out the long enough time to form required reduction valence state nickel component in the scope that the reduction of described nickel is included in the temperature range of 35 to 850 ℃ and reducing agent pressure is 0.1 to 10MPa, general its recovery time is 0.01～20 hour, and the preferred recovery time is 5 minutes～20 hours.
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 ℃, usually from making larger hydrocarbon molecule be cracked into more micromolecular heat and catalytic cracking process product.Applicable thermal cracking process includes but not limited to coking, warmly change and visbreaking and combination thereof.Applicable catalytically cracked gasoline includes but not limited to fluid catalytic cracking and RFCC and combination thereof.In some cases, during in the embodiment of this invention as raw material, can be by described cracking gasoline fractionation hydrotreatment before desulfurization.Described " diesel fuel " means hydrocarbon mixture that boiling range is 150 ℃ to 450 ℃ or the liquid of its any fractional composition.This type of hydrocarbon-containifluids fluids includes but not limited to light cycle oil, kerosene, straight-run diesel oil, coker gas oil and hydrotreatment diesel oil and combination thereof.
Term used herein " sulphur " refers to any type of element sulphur or the sulfur-containing compound usually existed in as cracking gasoline or diesel oil in hydrocarbon-containifluids fluids.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to hydrogen sulfide, carbonyl sulfide (COS) carbon disulfide (CS
2), mercaptan or thiophenes and combination thereof, especially comprise thiophene, benzothiophene, alkylbenzene bithiophene and methyldibenzothiophene, and the normal larger thiophenes of molecular weight existed in diesel fuel.
In hydrocarbon ils desulfurizing method by adsorption provided by the invention, under the condition of adsorption desulfurize, hydrocarbon ils is contacted with adsorbent, the adsorption desulfurize condition comprises: temperature is 250～500 ℃, and pressure is 0.2～8.0Mpa, volume space velocity 0.5～20h
-1, adsorption desulfurize under hydro condition, hydrogen purity is 70 volume %～99 volume %, when raw material is cracking gasoline, hydrogen and hydrocarbon oil feed mol ratio are generally 0.1～10: 1, be preferably 0.2～3.0: 1; When raw material is diesel oil, hydrogen and hydrocarbon oil feed volume ratio (abbreviation hydrogen-oil ratio) are generally 100～2000: 1 (Nm
3/ m
3), be preferably 400～1000: 1.
Adsorbent of the present invention is applicable to the hydrocarbon ils adsorption desulfurize, for example, for the S-Zorb process for adsorption desulfuration.Hydrocarbon ils desulfurizing method by adsorption provided by the invention can be used for producing the vehicle fuel oil of low sulfur content.
The present invention is further described for following embodiment.In embodiment, AEL structure molecular screen used is that the inventor makes by oneself according to existing method.For example, (Si: Al: P mol ratio=1: 9: 10) the Zeolite synthesis step is as follows: first by the aluminium isopropoxide of 18.6 kilograms, water and phosphoric acid solution mix and blend 2 hours, then add the Ludox of 0.78 kilogram, stir 1 hour for described SAPO-11; Add di-n-propylamine that mass ratio is 1: 1 and the mixture of diisopropylamine, then, after stirring 2 hours, the pH value is transferred to 5.5～6.5; Then reactant mixture is transferred in autoclave, 180 ℃ of lower thermostatic crystallizations take out cooling after 36 hours, then use the deionized water filtering and washing constant to pH, under 100 ℃, drying is 24 hours, obtain molecular screen primary powder, finally in 500-600 ℃ of lower roasting (to remove template), within 2 hours, obtain molecular sieve.Replace silicon with other substituted element, and corresponding adjustment proportioning, the AEL structure molecular screen that other element replaces can be obtained.Can be with reference to CN101269822A.
Embodiment 1
By 6.2 kilograms of diatomite (SiO
2content 87.6 % by weight, Qingdao Samsung diatomite Co., Ltd product), 15.3 kilogram zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 3.1 kilograms of SAPO-11 (Si: Al: P=1: 9: 10 mol ratios) molecular sieve is put into grinding machine for grinding and within 15 minutes, is formed mixture, this mixture is mixed and pulled an oar with deionized water, the solid content slurries that are 30 % by weight, and then (alumina content is 21.2 % by weight to add 14.6 kg aluminium colloidal sols, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), the hydrochloric acid adjust pH that is 31 % by weight by concentration is 3, then in 75 ℃, stir 2.5 hours, be cooled to 60 ℃, spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter (diameter) is 40～200 μ m, be designated as carrier granular A.By 16.1 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.8 kilograms of heat (temperature is 90 ℃) deionized water and make maceration extract; 24.8 kilograms of described carrier granular A are flooded with above-mentioned maceration extract, produce the granulate mixture after flooding.Granulate mixture after described dipping, 150 ℃ of dryings 2 hours, then, in 600 ℃ of lower roastings 2 hours, is obtained to particulate composition, be designated as particle B.By the particulate composition of above preparation (particle B) under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition.The nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.The gained adsorbent composition consist of SiO
2: Al
2o
3: ZnO: SAPO-11: Ni=1: 1: 6: 1: 1 (weight ratio, lower same).
Embodiment 2
Take Ludox, gama-alumina, zinc oxide, CoAPO-11 (Co: Al: P=1: 10: 10) and nickel nitrate is raw material.Its preparation method: zinc oxide and CoAPO-11 (Co: Al: P=1: 10: 10) molecular sieve are obtained to mixture in 15 minutes in grinding machine for grinding, then described mixture is mixed to making beating with deionized water, obtaining solid content is the first slurries of 40 % by weight, add Ludox in described the first slurries, gama-alumina and deionized water, be warming up to 60 ℃, stir 2 hours, obtaining solid content is the second slurries of 30 % by weight, by the second slurries spray-drying, obtain the adsorbent composition particle, then the hot zinc nitrate solution of preparation method according to embodiment 1 floods, dry, roasting and reduction.The consumption of each component makes the SiO that consists of of resulting adsorbent composition
2: Al
2o
3: ZnO: CoAPO-11: Ni=10: 2: 8: 5: 3 (weight ratios, lower same).
The preparation process of following examples 3～9 is similar to embodiment 1, and Main change is raw material and proportioning difference thereof used.Only list the proportioning of raw material wherein used and each component of gained adsorbent composition in following embodiment.
Embodiment 3
Take silica gel, aluminium colloidal sol, zinc oxide, ZrAPO-11 (Zr: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: ZrAPO-11: Ni=4: 3: 8: 4: 5.
Embodiment 4
Take ethyl orthosilicate, aluminium isopropoxide, zinc oxide, TAPO-11 (Ti: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: TAPO-11: Ni=3: 2: 7: 3: 2.
Embodiment 5
Take rectorite, acidic silicasol, zinc oxide, VAPO-11 (V: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: VAPO-11: Ni=3: 2: 5: 2: 2.
Embodiment 6
Take ammonium silicate, aluminium Ludox, zinc oxide, ZnAPO-11 (Zn: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is Al
2o
3: SiO
2: ZnO: ZnAPO-11: Ni=2: 4: 6: 2: 3.
Embodiment 7
Take sodium metasilicate, aluminum sulfate, zinc oxide, CuAPO-11 (Cu: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: CuAPO-11: Ni=6: 2: 8: 4: 3.
Embodiment 8
Take expanded perlite, aluminium colloidal sol, zinc oxide, MgAPO-11 (Mg: Al: P=1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: MgAPO-11: Ni=2: 3: 9: 3: 4.
Embodiment 9
Take diatomite, aluminium isopropoxide, zinc oxide, CoAPSO-11 (Co: Si: Al: P=1: 1: 10: 10) and nickel nitrate is raw material, and resulting adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: CoAPSO-11: Ni=10: 14: 6: 5.
Embodiment 10
By 6.2 kilograms of diatomite (SiO
2content 87.6 % by weight, Qingdao Samsung diatomite Co., Ltd product) and 15.3 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) put into the grinder rear formation mixture of being pulverized, this mixture is mixed to making beating with deionized water, the solid content slurries that are 30 % by weight, and then (alumina content is 21.2 % by weight to add 14.6 kg aluminium colloidal sols, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product), the hydrochloric acid adjust pH that is 31 % by weight by concentration is 3, then in 75 ℃, stir 2.5 hours, be cooled to 60 ℃, spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as particle D.By nickel nitrate solution dipping (16.1 kilogram of six water nickel nitrate is dissolved in 4.8 kilograms of heat (90 ℃) deionized water and makes) dipping for 21.7 kilograms of described carrier granulars (particle D), produce the granulate mixture after flooding.Granulate mixture after described dipping, 150 ℃ of dryings 2 hours, then, in 600 ℃ of lower roastings 2 hours, is obtained to particulate composition, be designated as particle E.The particulate composition of above preparation (particle E) is obtained to particle F in 1 hour with hydrogen reducing under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa, and by this particle F and the 3.1 kilograms of SAPO-11 that are 40～200 μ m through the moulding particle diameter, (Si: Al: P=1: 9: 10 mol ratios) molecular sieve is mixed to get adsorbent composition.The nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.Consisting of of gained adsorbent composition: SiO
2: Al
2o
3: ZnO: SAPO-11: Ni=1: 1: 6: 1: 1 (weight ratio).
Comparative Examples 1
Take diatomite, aluminium colloidal sol, zinc oxide and nickel nitrate prepares material ratio as SiO as raw material
2: Al
2o
3: ZnO: Ni=2: the adsorbent of 1: 5: 1 (weight ratio).
Comparative Examples 2
(Si: Al: P mol ratio=1: 9: 10) molecular sieve prepares material ratio as SiO as raw material to take diatomite, aluminium colloidal sol and SAPO-11
2: Al
2o
3: SAPO-11=5: the adsorbent of 4: 1.
It is the stainless steel tube of 13mm that the absorbent particles (100～350 order) that the adsorbent composition that 10g is made as above embodiment 1～10 and Comparative Examples 1～2 make is placed in respectively diameter (interior warp), the length of described stainless steel tube is 30.5cm, and bottom is placed with quartz sand (100～350 order) more than 1/3, in order to be the adsorbent bed inert carrier that provides, and adsorbent bed in quartz ampoule, be positioned at quartz sand above.The sulphur (weight content of the sulfur-containing compound based on described gaseous state cracking gasoline weight) that catalytically cracked gasoline (40～210 ℃ of the boiling ranges) raw material that evaluation adopts contains 1400 μ g/g, weight based on sulfur-containing compound has 95% thiophenes (thiophene, benzothiophene, alkylthrophene and alkylbenzene bithiophene), octane number RON is that 92.9, MON is 80.6.Appreciation condition is: 410 ℃ of temperature, and gross pressure 1.4MPa, (hydrogen used is plant hydrogen to hydrogen partial pressure 0.6MPa, certified products, H
2content is 99 volume %), gasoline volume space velocity 5h
-1, adsorption time is 4 hours, evaluation result is in Table 1.
Table 1
In table 1:
After octane number variation=desulfurization, (MON+RON)/2 of gasoline deduct (MON+RON)/2 of gasoline stocks
+ mean that octane number increases ,-mean that octane number reduces;
Wherein except the sulfur content in the percentage of desulfuration=(sulfur content in the gasoline after the sulfur content-desulfurization in raw material)/raw material * 100%.
The absorbent particles that the adsorbent composition that 10g embodiment 1～10 is made and Comparative Examples 1～2 make (100～350 order) is placed in respectively the stainless steel tube that diameter is 13mm, the length of described stainless steel tube is 30.5cm, and bottom is placed with quartz sand (100～350 order) more than 1/3, in order to be the adsorbent bed inert carrier that provides, and adsorbent bed in quartz ampoule, be positioned at quartz sand above.The sulphur (weight content of the sulfur-containing compound based on described gaseous state straight-run diesel oil weight) that straight-run diesel oil (230～350 ℃ of the boiling ranges) raw material that evaluation adopts contains 1400 μ g/g, weight based on sulfur-containing compound has 95% thiophenes (thiophene, benzothiophene, alkylthrophene and alkylbenzene bithiophene), 9.6 ℃ of condensation points, Cetane number is 58.0.Appreciation condition is: 370 ℃ of temperature, pressure 6.0MPa, diesel oil volume space velocity 1h
-1, hydrogen-oil ratio (hydrogen and hydrocarbon oil feed volume ratio) is 800 (Nm
3/ m
3), adsorption time is 4 hours, evaluation result is in Table 2.
Table 2
In table 2, except the sulfur content in the percentage of desulfuration=(sulfur content in the diesel oil after the sulfur content-desulfurization in raw material)/raw material * 100%.
From table 2, adsorption-desulfurization sorbent composition provided by the invention, can reduce the condensation point of straight-run diesel oil and improve its Cetane number, get unexpected effect, and there is good desulfurized effect, its desulfurization degree is higher, can reach more than 98%, even can surpass 99.5%.
Claims (9)
1. a hydrocarbon oil desulphurization adsorbing agent composition, described adsorbent composition comprises:
(1) zinc oxide,
(2) silica,
(3) aluminium oxide,
(4) AEL structure aluminophosphate molecular sieve, and
(5) nickel;
Described nickel exists with reduction-state basically;
The weight of adsorbent composition of take is benchmark, and in described adsorbent composition, AEL structure aluminophosphate molecular sieve content is 1～40 % by weight, and the content of element nickel of take is 5～50 % by weight; The content of zinc oxide is 10～84 % by weight; The content of silica is 5～75 % by weight; The content of aluminium oxide is 5～30 % by weight;
One or more in the AEL structure aluminophosphate molecular sieve that described AEL structure aluminophosphate molecular sieve is the element replacement; In the AEL structure aluminophosphate molecular sieve that described element replaces, substituted element is one or more in Li, Be, B, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce.
2. according to adsorbent composition claimed in claim 1, it is characterized in that, in the AEL structure aluminophosphate molecular sieve that described element replaces, substituted element is one or more in Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce.
3. according to adsorbent composition claimed in claim 1, it is characterized in that, described AEL structure aluminophosphate molecular sieve is one or more in MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and CoAPO-11.
4. according to the described adsorbent composition of claim 1～3 any one, it is characterized in that, in described adsorbent composition, the content of AEL structure aluminophosphate molecular sieve is 5～30 % by weight; Described zinc oxide content is 15～60 % by weight; The content of silica is 10～60 % by weight; The content of described aluminium oxide is 5～15 % by weight; The content of element nickel of take is 10～40 % by weight.
5. according to adsorbent composition claimed in claim 4, it is characterized in that, described zinc oxide content is 45～60 % by weight, and the content of AEL structure aluminophosphate molecular sieve is 8～25 % by weight.
6. the preparation method of the described adsorbent composition of claim 1～5 any one comprises:
(a) zinc oxide source, silica source, alumina source and AEL structure aluminophosphate molecular sieve are mixed;
(b) step (a) gained compound particles granulation is formed to particle;
(c) particle drying step (b) obtained, then roasting;
(d) with the particle after the roasting of nickel compound containing impregnation steps (c) gained;
(e) will after step (d) gained impregnated granules drying, carry out roasting; Then
(f) composition reduction step (e) obtained.
7. in accordance with the method for claim 6, it is characterized in that, step (c) and (e) described in dry baking temperature be 50～180 ℃; Step (c) and (e) in the described particle temperature of roasting be 200～850 ℃.
8. according to the method for claim 6, it is characterized in that, described reduction is included in the temperature range of 35 to 850 ℃ and in 0.1 to 10MPa pressure limit carries out the long enough time to form required reduction valence state nickel component.
9. a desulfurizing method by adsorption, be included in the step under the condition of adsorption desulfurize, hydrocarbon ils contacted with adsorbent, it is characterized in that, described adsorbent is the described adsorbent of claim 1～5 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110074500 CN102463099B (en) | 2010-10-28 | 2011-03-24 | Adsorptive desulfurization adsorbent and preparation method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010522587.4 | 2010-10-28 | ||
| CN201010522587 | 2010-10-28 | ||
| CN 201110074500 CN102463099B (en) | 2010-10-28 | 2011-03-24 | Adsorptive desulfurization adsorbent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102463099A CN102463099A (en) | 2012-05-23 |
| CN102463099B true CN102463099B (en) | 2013-12-25 |
Family
ID=46067394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110074500 Active CN102463099B (en) | 2010-10-28 | 2011-03-24 | Adsorptive desulfurization adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102463099B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104511306B (en) * | 2013-09-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| CN104511309B (en) * | 2013-09-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| CN104511308B (en) * | 2013-09-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| CN104511300B (en) * | 2013-09-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of desulphurization catalyst and preparation method thereof and the method for desulfurization of hydrocarbon oil |
| CN104549486B (en) * | 2013-10-29 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and its preparation and desulfurization of hydrocarbon oil |
| CN105583002B (en) * | 2014-10-20 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
| CN107474870B (en) * | 2016-06-07 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of vulcanization process of adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382071A (en) * | 1999-08-25 | 2002-11-27 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
| CN102294222A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
-
2011
- 2011-03-24 CN CN 201110074500 patent/CN102463099B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382071A (en) * | 1999-08-25 | 2002-11-27 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN101481627A (en) * | 2008-01-09 | 2009-07-15 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbing agent and use method thereof |
| CN102294222A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102463099A (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102463098B (en) | Adsorbent for adsorptive desulfurization of fuel oil | |
| CN102463099B (en) | Adsorptive desulfurization adsorbent and preparation method thereof | |
| CN1382199B (en) | Desulfurization process and bimetallic sorbent systems for same | |
| AU2002357051B2 (en) | Desulfurization and sorbents for same | |
| JP4729232B2 (en) | Desulfurization and sorbent for desulfurization | |
| CA2533485C (en) | Desulfurization and novel process for same | |
| CN101618314B (en) | Desulfurizing adsorbent, preparation method and application thereof | |
| US6930074B2 (en) | Desulfurization and sorbent for the same | |
| CN103372416B (en) | A kind of adsorbent composition for desulfurization of hydrocarbon oil and preparation method thereof | |
| CN102294222A (en) | Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof | |
| US8268745B2 (en) | Silicate-resistant desulfurization sorbent | |
| CN102114407B (en) | Tin-containing desulfurization adsorbent and preparation method and application thereof | |
| CN101618313B (en) | Desulfurization adsorbent, preparation method and application thereof | |
| CN101766985A (en) | Desulfurizing sorbent and preparation method and application thereof | |
| WO2004052531A1 (en) | Desulfurization and novel compositions for same | |
| CN102114406B (en) | Zirconic desulphurization adsorbent, preparation method and application thereof | |
| MXPA04008466A (en) | Desulfurization and novel compositions for same. | |
| EP1670579B1 (en) | Desulfurization and novel methods for same | |
| CN102114404B (en) | Desulfurization adsorbent and preparation method and application thereof | |
| CN102463100B (en) | Adsorptive desulfurization adsorbent and preparation method thereof | |
| CN102114405B (en) | Desulfurizing and adsorption agent containing titanium, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |