CN102463100B - Adsorptive desulfurization adsorbent and preparation method thereof - Google Patents
Adsorptive desulfurization adsorbent and preparation method thereof Download PDFInfo
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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 cobalt; the cobalt 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 cobalt 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 hydrocarbon ils adsorption desulfurize and preparation and application.
Background technology
Compare with hydrogasoline with direct steaming gasoline, 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.Along with improving constantly and the reinforcement 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.
Conventional desulfurization of hydrocarbon oil method comprises hydrodesulfurization and adsorption desulfurize.Hydrodesulfurization meeting makes the olefin saturated in gasoline, and the octane number (organon and motor octane number) of gasoline is significantly declined, and thiophenes in gasoline is because sterically hindered effect is difficult to remove under conventional hydroconversion condition.For example S-Zorb technology of adsorption desulfurize [Zhao Xunzhi, Cheng Zhilin. the progress of low-sulfur clean fuel oil production technology. Industrial Catalysis .2007,15 (6): 1-5], remove the sulphur in gasoline by the effect of adsorbent, there is good desulfurized effect.
CN 1130253C discloses the granular adsorbent composition of the mixture that comprises zinc oxide, silica, aluminium oxide and substantially reduce valence state nickel, for make by the following method cracking gasoline or the desulfurization of diesel fuel feed stream in desulfurization zone, described method comprises: contact with described feed stream in desulfurization zone, 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 discloses the granular adsorbent composition of the mixture that comprises zinc oxide, silica, aluminium oxide and substantially reduce valence state cobalt, for make by the following method cracking gasoline or the desulfurization of diesel fuel feed stream in desulfurization zone, described method comprises: contact with described feed stream in desulfurization zone, 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 disclosed nickeliferous adsorbent of CN 1130253C 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 1327988A discloses a kind of S-Zorb adsorbent, it is to pass through promoter, as the precursor of nickel, nickel oxide or nickel oxide floods the adsorbing agent carrier that comprises zinc oxide, expanded perlite and aluminium oxide, 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 the sulfur content that can make after S-Zorb technology in cracking gasoline lower than 1ppm, and average octane number Δ (RON+MON)/2 declines and is less than 2.0.
Although existing adsorption-desulfurization sorbent can significantly reduce the sulfur content in cracking gasoline, can not improve the octane number of gasoline, also may cause the loss of octane number.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hydrocarbon ils adsorption-desulfurization sorbent composition, said composition is for hydrocarbon ils adsorption desulfurize, the condensation point that can improve cracking gasoline octane number and reduction diesel oil, the other technical problem that the present invention will solve is to provide preparation and the application process thereof of described adsorption-desulfurization sorbent composition.
The invention provides a kind of hydrocarbon ils adsorption-desulfurization sorbent composition, described adsorbent composition comprises:
(1) zinc oxide,
(2) silica,
(3) aluminium oxide,
(4) AEL structure aluminophosphate molecular sieve, and
(5) cobalt;
Described cobalt exists with reduction-state substantially;
Take the weight of adsorbent composition as benchmark, in described adsorbent composition, AEL structure aluminophosphate molecular sieve content is 1～40 % by weight, take the content of element cobalt as 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.
The present invention also provides a kind of preparation method of adsorbent composition provided by the present invention, comprises the following steps:
(a) mixed oxidization zinc source, silica source, alumina source and AEL structure aluminophosphate molecular sieve;
(b) (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 cobalt compound impregnation steps (c) gained;
(e) after step (d) gained impregnated granules is dry, carry out roasting;
(f) composition reduction step (e) being 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 being contacted with desulfuration adsorbent provided by the invention.
Adsorbent composition provided by the invention, for hydrocarbon ils adsorption desulfurize, has good desulfurized effect; For gasoline absorbing desulfurization, in reduction hydrocarbon ils, in sulfur content, can also improve the octane number of gasoline; For diesel oil adsorption desulfurizing, there is good adsorption desulfurize performance, 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 molecular screen can be purchased or prepare according to existing method, existing AEL structure molecular screen preparation method, for example [Xu Benjing, Yan Zifeng, Han Xuelian, Huo Quan, Yu Chunmei. the synthetic and sign of different magnesium source MAPO-11 molecular sieve. Journal of Molecular Catalysis .2004,18 (6): 409-415; Xu Benjing, Yan Zifeng, Zhang Chaoxia, Wang Huaiping, Han Xuelian, Huo Quan, Yu Chunmei, the synthetic and sign of Zhang Zhi China .CoAPO-11 molecular sieve. Industrial Catalysis .2004,12 (10): 38-43; Yan Zifeng, Xu Benjing, Qian Ling, Liu Xinmei, Song Chunmin, Song Linhua. a kind of synthetic method .CN101269822.2008-09-24 with heteroatom substituted AEL cage construction aluminophosphates molecular sieve].
In adsorbent composition provided by the invention, take the gross weight of adsorbent composition as benchmark, the content of described AEL structure aluminophosphate molecular sieve is preferably 5～30 % by weight, more preferably 10～25 % 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 85 % by weight, preferably 10～60 % by weight; The content of described aluminium oxide is 5～30 % by weight, is preferably 5～15 % by weight; Take the content of the described cobalt of element as 5～50 % by weight, be preferably 10～40 % by weight.Cobalt in wherein said composition exists with reduction-state substantially, and described cobalt substantially exists and refers to that most of cobalt component is reduced to chemical valence lower than 3 valencys, is preferably 0 valency with reduction-state.
In adsorbent composition preparation method provided by the invention, described step (a) can mix zinc oxide source, silica source, alumina source and AEL structure aluminophosphate molecular sieve by any applicable method in the proper ratio, for example can adopt existing applicable device to mix described absorbent component so that described material fully disperses, described device for example rotary drum, stationary housings or groove, grinder (intermittence or continous way), impact mixer.In the mixing of zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve component, preferably use grinder.The mixture that described absorbent component is mixed to form can be wet mixture, dough, lotion or slurries form.If gained mixture is wet mixture form, can make described wet mixture multiviscosisty, then by granulating, it is granulated, then dry and roasting.When described zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve are mixed to form dough or paste mixture; in step (b), can make described mixture moulding make grain, extrudate, sheet, ball, pill or microsphere particle; the preferably cylindrical extrudate of any applicable length of diameter 0.75 to 13mm, then by gained particle drying and roasting.When described mixture is slurries form, in step (b), make it granulating by the microballoon that is approximately 20 to 500 μ m by the dry formation of described slurries spraying granularity, then in step (c), make described microballoon be dried and roasting.In step (c), dry described particle temperature is preferably 50 to 180 ℃, and particle temperature scope is preferably 200 to 850 ℃ described in roasting, and roasting time is preferably 0.5 to 6 hour.After described granular mixture drying and roasting, the particle of available cobalt compound or cobalt oxide precursor dipping gained.
In the preparation process (a) of adsorbent composition provided by the invention, zinc oxide source used can be one or more zinc compounds that zinc oxide form existed or can be converted under this paper preparation condition zinc oxide.The example of this zinc compound includes but not limited to one or more in zinc sulphide, zinc sulfate, zinc hydroxide, zinc chloride, zinc carbonate, zinc acetate and zinc nitrate.Institute's dressing zinc oxide is preferably powdery zinc oxide.
In adsorbent composition preparation process provided by the invention (a), silica source used can be the silicon-containing compound form that silica form or one or more can be converted into silica.The silica of any application type all can be used for adsorbent composition of the present invention, one or more in the silica of described application type for example diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica, preferably diatomite.Can be converted into one or more in silicon-containing compound for example silicic acid, sodium metasilicate, ammonium silicate and the ethyl orthosilicate (or methyl esters) of silica.Preferred silica is diatomite form.
In adsorbent composition preparation method provided by the invention, described alumina source can be the aluminum contained compound form that aluminium oxide form or one or more can be converted into aluminium oxide, can be inorganic compound and/or aluminium organic alcohol compound, for example, be selected from one or more in aluminum nitrate, aluminium chloride, aluminum sulfate and aluminium isopropoxide; It can also be any commercially available alumina material, it is including, but not limited to colloidal alumina and the common alumina cpd that is dewatered to produce by hydrated alumina, for example, described alumina source can be one or more in aluminium colloidal sol, boehmite, gama-alumina and η-aluminium oxide.
Adsorbent composition preparation process provided by the invention (d) is flooded described particulate composition with applicable cobalt compound, the solution (aqueous solution or organic solution) that can contain element state cobalt, cobalt oxide or cobalt compound by use floods described mixture, and element state cobalt, cobalt oxide or cobalt compound are added in described granular mixture.Generally flood with described cobalt the granular composition that forms zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve and described cobalt metal, cobalt oxide or cobalt oxide precursor, described dipping solution can be any aqueous solution that is applicable to flood described zinc oxide, silica, aluminium oxide and AEL structure aluminophosphate molecular sieve mixture, and the cobalt tenor that reduces in the composition that the amount of this solution makes finally to obtain is enough to make said composition to remove sulphur from cracking gasoline fluid stream.
In adsorbent composition preparation process provided by the invention (e), by dry the impregnated granules obtaining after step (d) dipping cobalt and roasting, dry described particle temperature is preferably 50 to 180 ℃, described in roasting, particle temperature scope 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 in step (f), step (e) being obtained; Co is existed with reduction-state substantially; described reduction can substantially reduced in reducing zone and under the valent applicable condition of cobalt, made the particle reduction after the roasting of step (e) gained with reducing agent, organic sulfide removal compound therefrom 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 adsorption desulfurize condition.The preferred hydrogen of described reducing agent, makes the composition reduction after gained roasting, and the method for reduction can be carried out according to existing method, for example, reduce according to the method described in CN 1130253C.The reduction of described cobalt 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 cobalt component, and the recovery time is preferably 30～180 minutes.
Hydrocarbon ils of the present invention comprises cracking gasoline and diesel fuel, wherein " cracking gasoline " to mean boiling range be hydrocarbon or its any cut of 40 ℃ to 210 ℃, conventionally 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, can be by described cracking gasoline fractionation and/or hydrotreatment before desulfurization while being used as raw material in enforcement the present invention.Described " diesel fuel " means boiling range is the hydrocarbon mixture of 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 conventionally existing in as cracking gasoline or diesel oil in hydrocarbon-containifluids fluids.The sulphur existing in hydrocarbon-containifluids fluids of the present invention includes but not limited to hydrogen sulfide, carbonyl sulfide (COS) carbon disulfide (CS
2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkylbenzene bithiophene and methyldibenzothiophene, and the normal larger thiophenes of molecular weight existing 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, 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 %, in the time that 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; In the time that raw material is diesel oil, hydrogen and hydrocarbon oil feed volume ratio are generally 100～2000: 1 (Nm
3/ m
3), be preferably 400～1000: 1.
Adsorbent of the present invention is applicable to hydrocarbon ils adsorption desulfurize, for example, for S-Zorb process for adsorption desulfuration.The invention provides the vehicle fuel oil that hydrocarbon ils desulfurizing method by adsorption can be used for producing low sulfur content.
The present invention is further described for embodiment below.
In embodiment, AEL structure molecular screen used is that inventor makes by oneself according to existing method.For example, described SAPO-11 (Si: Al: P mol ratio=1: 9: 10) 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; Adding mass ratio is the di-n-propylamine of 1: 1 and the mixture of diisopropylamine, then stirs after 2 hours, and pH value is transferred to 5.5～6.5; Then reactant mixture is transferred in autoclave, at 180 ℃, thermostatic crystallization takes out cooling after 36 hours, then use deionized water filtering and washing constant to pH, at 100 ℃, be dried 24 hours, obtain molecular screen primary powder, finally at 500-600 ℃, roasting is removed template in 2 hours and is obtained molecular sieve.With other substituted element replacement silicon, 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 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 3.1 kilograms of SAPO-11 (Si: Al: P=1: 9: 10, mol ratio, down together) 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, obtaining solid content is the slurries of 30 % by weight, and then (alumina content is 21.2 % by weight to add 14.6 kg aluminium colloidal sols, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), with the salt acid for adjusting pH value that concentration is 31 % by weight be 3, then at 75 ℃, stir 2.5 hours, be cooled to 60 ℃, spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier granular A.By 15.3 kilograms of cobalt nitrate hexahydrates (purity 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (90 ℃) deionized water and make cobalt nitrate maceration extract; by this cobalt nitrate maceration extract dipping for the carrier granular A of 24.8 kilograms of gained, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 ℃ dry 2 hours, then roasting 2 hours at 600 ℃, obtains sample B.By obtained sample B under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state substantially.Gained adsorbent composition the ratio of each component is SiO
2: Al
2o
3: ZnO: SAPO-11: Co=1: 1: 6: 1: 1 (weight ratio, lower same).
The preparation process of following examples 2～9 is similar to embodiment 1, and Main change is raw material and proportioning difference thereof used.In institute's following examples, only list the proportioning of raw material wherein used and the each component of gained adsorbent composition.
Embodiment 2
Take diatomite, aluminium colloidal sol, zinc hydroxide, CoAPO-11 (Co: Al: P=1: 5: 5) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: CoAPO-11: Co=10: 2: 8: 5: 3.(weight ratio, lower same)
Embodiment 3
Take silica gel, boehmite, zinc carbonate, ZrAPO-11 (Zr: Al: P=3: 20: 20) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: ZrAPO-11: Co=4: 3: 8: 4: 5.
Embodiment 4
Take ethyl orthosilicate, boehmite, zinc acetate, TAPO-11 (Ti: Al: P=1: 10: 10) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: TAPO-11: Co=3: 2: 7: 3: 2.
Embodiment 5
Take silica sol, aluminium colloidal sol, zinc nitrate, VAPO-11 (V: Al: P=1: 10: 10) and cobalt nitrate as former, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: VAPO-11: Co=3: 2: 5: 2: 2.
Embodiment 6
Take ammonium silicate, aluminium colloidal sol, zinc sulfate, ZnAPO-11 (Zn: Al: P=1: 10: 10) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: ZnAPO-11: Co=2: 4: 6: 2: 3.
Embodiment 7
Take sodium metasilicate, aluminium colloidal sol, zinc sulphide, CuAPO-11 (Cu: Al: P=1: 10: 10) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: CuAPO-11: Co=6: 2: 8: 4: 3.
Embodiment 8
Take precipitated silica, aluminium colloidal sol, zinc oxide, MgAPO-11 (Mg: Al: P=1: 10: 10) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: MgAPO-11: Co=2: 3: 9: 3: 4.
Embodiment 9
Take methyl silicate, aluminium colloidal sol, zinc oxide, CoAPSO-11 (Co: Si: Al: P=1:: 1: 10: 10) and cobalt nitrate as raw material, the adsorbent composition obtaining the ratio of each component is SiO
2: Al
2o
3: ZnO: CoAPSO-11: Co=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 Xin Ye Co., Ltd product) put into after grinder is pulverized and form mixture, this mixture is pulled an oar to such an extent that solid content is the slurries of 30 % by weight with mixing in deionized water, and then (alumina content is 21.2 % by weight to add 14.6 kg aluminium colloidal sols, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) and the concentration hydrochloric acid that is 31% to adjust pH be 2～4, then 75 ℃ are stirred 2.5 hours, be cooled to 60 ℃, spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, make the carrier granular that particle diameter is 40～200 μ m, be designated as particle D.By 21.7 kilograms of described carrier granulars (particle D) be dissolved in 4.6 kilograms of heat (90 ℃) deionized water in 15.3 kilograms of cobalt nitrate hexahydrates (purity 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) dipping, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 ℃ dry 2 hours, then roasting 2 hours at 600 ℃, obtains particulate composition, is designated as particle E.By the particle E of preparation above under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain sample F.Nickel component in wherein said sample F is reduced to zero-valent state substantially.This sample F and 3.1 kilograms of SAPO-11 (Si: Al: P=1: 9: the 10 mol ratios) molecular sieve that is 40～200 μ m through the particle diameter (diameter) of moulding are mixed to get to adsorbent composition.The ratio of the each component of gained adsorbent composition is: SiO
2: Al
2o
3: ZnO: SAPO-11: Co=1: 1: 6: 1: 1 (weight ratio).
Comparative example 1
According to existing method (CN1258396C), prepare material ratio as SiO take diatomite, aluminium colloidal sol, zinc oxide and cobalt nitrate as raw material
2: Al
2o
3: ZnO: Co=2: the adsorbent of 1: 5: 1.
Comparative example 2
Prepare material ratio as SiO according to existing method preparation take diatomite, aluminium colloidal sol and SAPO-11 (Si: Al: P mol ratio=1: 9: 10) molecular sieve as raw material
2: Al
2o
3: SAPO-11=5: the adsorbent of 4: 1.
The absorbent particles (100～350 order) that the adsorbent composition that 10g is made as above embodiment 1～10 and comparative example 1～2 make is placed in respectively the stainless steel tube that diameter (interior warp) is 13mm, the length of described stainless steel tube is 30.5cm, and bottom more than 1/3 is placed with quartz sand (100～350 order), to be the adsorbent bed inert carrier that provides, adsorbent bed in quartz ampoule, be positioned at quartz sand above.Evaluating the hydrocarbon oil crude material adopting is the sulphur (weight content of the sulfur-containing compound based on described cracking gasoline weight) that catalytically cracked gasoline (40～210 ℃ of boiling ranges) contains 1400 μ g/g, weight based on sulfur-containing compound has 95 % by weight thiophenes (thiophene, benzothiophene, alkylthrophene and alkylbenzene bithiophene), octane number RON is that 92.9, MON is 80.6.Appreciation condition is: temperature is 410 ℃, gross pressure 1.4MPa, and under hydro condition, hydrogen partial pressure is 0.6MPa (hydrogen used is plant hydrogen, certified products, H2 content 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, (MON+RON)/2 of the gasoline after octane number variation=desulfurization deduct (MON+RON)/2 of gasoline stocks ,+represent that octane number increases ,-represent that octane number reduces; Except sulfur content × 100% in percentage=(sulfur content in the gasoline after the sulfur content-desulfurization in raw material)/raw material of desulfuration.
From table 1, adsorbent composition provided by the invention, for gasoline absorbing desulfurization, has good desulfurized effect, and can improve the octane number of gasoline.
The absorbent particles (100～350 order) that the adsorbent composition that 10g is made as above embodiment 1～10 and comparative example 1～2 make is placed in respectively the stainless steel tube that diameter (interior warp) is 13mm, the length of described stainless steel tube is 30.5cm, and bottom more than 1/3 is placed with quartz sand (100～350 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 the straight-run diesel oil raw material (230～350 ℃ of boiling ranges) that evaluation adopts contains 1400 μ g/g, weight based on sulfur-containing compound has 95 % by weight 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 sulfur content × 100% in percentage=(sulfur content in the diesel oil after the sulfur content-desulfurization in raw material)/raw material of desulfuration.
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, tool has an unexpected effect, and has good desulfurized effect, and its desulfurization degree is higher, can reach more than 98%, even can exceed 99.5%.
Claims (9)
1. a hydrocarbon ils adsorption-desulfurization sorbent composition, described adsorbent composition comprises:
(1) zinc oxide,
(2) silica,
(3) aluminium oxide,
(4) AEL structure aluminophosphate molecular sieve, and
(5) cobalt;
Described cobalt exists with reduction-state substantially;
Take the weight of adsorbent composition as benchmark, in described adsorbent composition, AEL structure aluminophosphate molecular sieve content is 1～30 % by weight, take the content of element cobalt as 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; Described AEL structure aluminophosphate molecular sieve is the one in the AEL structure aluminophosphate molecular sieve that replaces of element, and in the AEL structure aluminophosphate molecular sieve that described element replaces, substituted element is multiple in a kind of or Li, Be, B, Si, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and the Ce in Li, Be, B, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce; Or described AEL structure aluminophosphate molecular sieve is multiple in the AEL structure aluminophosphate molecular sieve that replaces of element, 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.
2. according to adsorbent composition claimed in claim 1, it is characterized in that, described AEL structure aluminophosphate molecular sieve is multiple in a kind of or SAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and the CoAPO-11 in MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and CoAPO-11.
3. according to the adsorbent composition described in claim 1～2 any one, it is characterized in that, in described adsorbent composition, the content of AEL structure aluminophosphate molecular sieve is 10～30 % 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; Take the content of element cobalt as 10～40 % by weight.
4. adsorbent composition according to claim 3, is characterized in that, described zinc oxide content is 45～60 % by weight, and the content of AEL structure molecular screen is 10～25 % by weight.
5. the preparation method of adsorbent composition described in claim 1～4 any one, 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 cobalt compound impregnation steps (c) gained;
(e) after step (d) gained impregnated granules is dry, carry out roasting; Then
(f) composition reduction step (e) being obtained.
6. in accordance with the method for claim 5, it is characterized in that, step (c) and (e) described in dry baking temperature be 50～180 ℃; Described in step (c) and (e) middle roasting, particle temperature scope is at 200 to 850 ℃.
7. in accordance with the method for claim 5, 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 cobalt component.
8. in accordance with the method for claim 5, it is characterized in that, described zinc oxide source is one or more in zinc oxide, zinc sulfate, zinc chloride, zinc carbonate, zinc sulphide, zinc hydroxide, zinc acetate and zinc nitrate; Described silica source is one or more in diatomite, silicon oxide colloid, silica gel, silicalite, precipitated silica, silicic acid, sodium metasilicate, ammonium silicate, ethyl orthosilicate and methyl silicate; Described alumina source is one or more in aluminium oxide, hydrated alumina and aluminium salt.
9. a desulfurizing method by adsorption, is included in the step under the condition of adsorption desulfurize, hydrocarbon ils being contacted with adsorbent, it is characterized in that, described adsorbent is the adsorbent composition described in claim 1～4 any one, and described hydrocarbon ils is gasoline or diesel oil; 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.
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| 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 |
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