CN102463098B - Adsorbent for adsorptive desulfurization of fuel oil - Google Patents
Adsorbent for adsorptive desulfurization of fuel oil Download PDFInfo
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Abstract
The invention relates to adsorbent for adsorptive desulfurization of fuel oil. An adsorbent composition contains a metal promoting agent, zinc oxide, an AEL-type structured phosphoaluminate molecular sieve and an oxide carrier. At least a part of promoting agent metal exists in a reduction state. A method for preparing the adsorbent composition comprises the steps of forming, roasting and reducing a mixture containing a zinc compound, a promoting agent metal compound, an oxide carrier component and the AEL-type structured phosphoaluminate molecular sieve. The adsorbent composition is applied to 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 methods for making and using same thereof.
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 produce colloid, foul smelling, corrosion and colour difference, although its research octane number (RON) can reach 90 left and right, can not directly use as qualified motor petrol.Simultaneously, along with improving constantly of environmental requirement, people's environmental consciousness is also in continuous change, 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 are the general trends of petroleum refining industry's development.
The method that removes the sulphur in gasoline has hydrodesulfurization and adsorption desulfurize.Hydrodesulfurization, although can remove the sulfur-containing compound in gasoline, can make the most of olefin saturated in gasoline, and octane number (organon and motor octane number) significantly declines; And some thiophene compound in gasoline, due in sterically hindered effect, is difficult to adopt common method of hydrotreating to remove, required condition harshness, this may make part aromatic saturation, thereby octane number is further declined.Adsorption desulfurize, for example S-Zorb adsorption technology [Zhao Xunzhi, Cheng Zhilin. the progress of low-sulfur clean fuel oil production technology. Industrial Catalysis .2007,15 (6): 1-5] be a kind of adsorption desulfurize technology of facing hydrogen, there is good gasoline desulfur effect, and the decline of octane number (organon and motor octane number) is less, but need suitable adsorbent.
CN 1130253 C disclose two kinds of similar S-Zorb adsorbent and production methods thereof with CN 1258396C.Adsorbent comprises zinc oxide, silica, aluminium oxide and metal simple-substance nickel or cobalt.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, 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.This adsorbent is applied to S-Zorb technology, and after desulfurization, the average octane number Δ (RON+MON)/2 of cracking gasoline declines.
Although 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 do not relate to for diesel oil adsorption desulfurizing and reduce 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 hydrocarbon ils adsorption desulfurize adsorption-desulfurization sorbent composition, and this adsorbent composition has good adsorption desulfurize ability, and can improve the condensation point of octane number and reduction diesel oil; The other technical problem that the present invention will solve is to provide preparation method and application's method of described adsorbent composition.
The invention provides a kind of hydrocarbon ils adsorption-desulfurization sorbent composition, this adsorbent composition comprises:
(a) zinc oxide,
(b) AEL structure aluminophosphate molecular sieve,
(c) oxide carrier, and
(d) promoter metals;
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 promoter metals as 5～50 % by weight; The content of zinc oxide is 10～80 % by weight; The content of oxide carrier is 10～84 % by weight; At least part of described promoter metals exists with reduction-state.
The invention provides the preparation method that described adsorbent composition is also provided, comprising: form and comprise particle, the roasting of zinc compound, promoter metals compound, oxide carrier component and AEL structure aluminophosphate molecular sieve, the step of reduction.
The present invention further provides a kind of hydrocarbon ils desulfurizing method by adsorption, comprise the step that hydrocarbon ils is contacted with adsorbent, it is characterized in that, described adsorbent is adsorbent composition provided by the invention.
Adsorption-desulfurization sorbent composition provided by the invention, has higher adsorption desulfurize ability, for hydrocarbon ils adsorption desulfurize, has good desulfurized effect, and adsorption desulfurize rate is higher.Described adsorbent composition is for gasoline absorbing desulfurization, can improve the octane number of gasoline after desulfurization, for diesel oil adsorption desulfurizing, can reduce condensation point of diesel oil, improves the low temperature flowability of diesel oil, improves the Cetane number of diesel oil.
The specific embodiment
According to adsorption-desulfurization sorbent 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, CoAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and CoAPSO-11.Described AEL structure molecular screen can be purchased or prepare according to existing method, for example, [perhaps originally wait quietly. the synthetic and sign of different magnesium source MAPO-11 molecular sieve. 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; Yan Zifeng etc. a kind of synthetic method .CN101269822A.2008-09-24 with heteroatom substituted AEL cage construction aluminophosphates molecular sieve].Take the gross weight of adsorbent composition as benchmark, in described adsorbent composition, the content of AEL structure aluminophosphate molecular sieve is preferably 5～40 % by weight, more preferably 5～30 % by weight.
According to adsorption-desulfurization sorbent composition provided by the invention, at least one is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium described promoter metals; Described promoter metals is preferably one or more of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium, more preferably nickel and/or cobalt.Described promoter metals exists with reduction-state, and described reduction-state refers to that promoter metals major part is reduced to lower chemical valence, is preferably zeroth order.Take the content of element promoter metals as 5～50 % by weight, be preferably 6～25 % by weight, more preferably 10～20 % by weight.
According to adsorption-desulfurization sorbent composition provided by the invention, described oxide carrier is selected from one or more of inorganic oxide carrier that adsorbent is conventional, preferably, be selected from one or more in silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and natural porous material, more preferably one or more in silica, zirconia, titanium oxide and natural porous material.The mixture of one or more in described natural porous material for example expanded perlite, kaolin, imvite, sepiolite, diatomite and rectorite.In the time that oxide is two or more mixture, the weight in mixture between any two kinds of components can be 1: 100～100: 1, is preferably 1: 20～20: 1.
According to adsorption-desulfurization sorbent composition provided by the invention, take the weight of adsorbent composition as benchmark, in described adsorption-desulfurization sorbent composition, AEL structure aluminophosphate molecular sieve content is 1～40 % by weight, take the content of element promoter metals as 5～50 % by weight; Take the content of zinc oxide zinc oxide as 10～80 % by weight; Take the content of oxide oxide carrier as
% by weight.The content of described zinc oxide is preferably
% by weight, more preferably 25～70 % by weight; Described AEL structure aluminophosphate molecular sieve content is preferably 5～30 % by weight, more preferably 5～25 % by weight, further preferred 8～25 % by weight; The content of described oxide carrier is preferably 10～70 % by weight.
Adsorbent composition preparation method provided by the invention, can prepare by any method the particle of zinc compound, oxide carrier source, AEL structure molecular screen and metal promoted immunomodulator compounds, then roasting or dry after roasting again, then reduce, for example, can prepare by the following method described adsorbent composition:
(1) zinc oxide source, oxide carrier source, promoter metals compound and AEL structure aluminophosphate molecular sieve are mixed, add or do not add water;
(2) moulding of step (1) gained mixture is formed to particle, if prepared mixture is slurries, can be by the dry slurries spraying particle that forms;
(3) the particle roasting or the dry roasting that step (2) are obtained; Dry dry temperature is preferably 50～180 ℃; The temperature of roasting is preferably 200～850 ℃, and the time of roasting is preferably 0.5～6 hour;
(4) the particle reduction after roasting step (3) being obtained, obtains adsorbent composition; Described reduction is included in the temperature range of 35～850 ℃ and in the pressure limit of 0.1～10MPa carries out the long enough time to form required reduction valence state, and preferably the recovery time is 0.5～3 hour.
The preferred preparation method of one of adsorbent composition provided by the invention, comprises the following steps:
(a) zinc oxide source, oxide carrier source and AEL structure aluminophosphate molecular sieve are mixed;
(b) step (a) gained compound particles granulation is formed to particle;
(c) the particle roasting or the dry roasting that step (b) are obtained;
(d) with the particle after the roasting of promoter metals compound impregnation steps (c) gained;
(e) carry out roasting after making step (d) gained impregnated granules dry; Then
(f) composition reduction step (e) being obtained.
The Preparation Method that this is preferably made, the adsorbent composition obtaining, not only has good desulfurized effect, and has better raising octane number effect and reduce condensation point of diesel oil effect.Wherein:
Zinc oxide source described in step (a) can be one or more zinc compound forms that zinc oxide form existed or can be converted under preparation condition described herein zinc oxide, 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.Described zinc oxide source is preferably powdery zinc oxide.
Oxide carrier source described in step (a) is oxide form and/or the oxide precursor that can generate oxide under condition of the present invention.Described oxide carrier source is preferably one or more in silica source, alumina source, zirconia source, titania source, silica-alumina source and natural porous material, preferably includes one or more in the inorganic oxide carrier that is commonly used for binding agent.Described silica source can be that silica form exists or one or more can be converted into one or more in the silicon-containing compound form of silica; One or more in silica source for example diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica that described silica form exists, described silicon oxide colloid is Ludox, silicon gel for example; One or more in described silicon-containing compound for example silicic acid, sodium metasilicate, ammonium silicate and the ethyl orthosilicate (or methyl esters) that is converted into silica; Preferred silica source is diatomite.Described alumina source can be that aluminium oxide form or one or more can be converted into the aluminium such as inorganic compound and the aluminium isopropoxide organic alcohol compound such as aluminum contained compound form such as aluminum nitrate, aluminium chloride, the aluminum sulfate of aluminium oxide, also can be any commercially available alumina material, it be including, but not limited to colloidal alumina solution and the common alumina cpd that is dewatered to produce by hydrated alumina; One or more in described alumina source for example aluminium colloidal sol, boehmite, gama-alumina or η-aluminium oxide.One or more in described zirconia source such as zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate and zirconium sulfate etc.One or more in described titania source such as titanium dioxide powder, titanium tetrachloride, Titanium Nitrate and tetra-n-butyl titanate etc.He Lv source, the silicon source mixture that described for example Alusil of silica-alumina (amorphous aluminum silicide) source maybe can generate amorphous aluminum silicide is as waterglass and aluminum sulfate.In the time that oxide is two or more mixture, in mixture, between any two kinds of components, can be arbitrary proportion, the weight ratio between any two kinds of components is preferably 1: 100 to 100: 1, more preferably 1: 20 to 20: 1.
In step (a), zinc oxide source, AEL structure aluminophosphate molecular sieve and oxide source are mixed, the mixture forming can be that the form of wet mixed feed, dough, cream or slurries etc. exists.Can use any mixing arrangement, each component is fully disperseed.Applicable mixing arrangement includes but not limited to mix rotating cylinder, set casing or groove, batch (-type) or continuous mixing machine, impact-extrusion type mixer.If gained mixture is wet mixture form, can makes described wet mixture multiviscosisty, then by granulating, it is granulated, then dry and roasting.When described zinc oxide source, oxide source 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 0.75～13mm, then by gained particle drying and roasting.When described mixture is slurries form; in step (b), by being sprayed to be dried, described slurries make it granulating; for example the dry formation of spraying granularity is the microballoon of 20～500 μ m, then in step (c), makes described microballoon roasting or dry roasting.Preferably be dried and form adsorbent composition particle by spraying.Can make to comprise zinc oxide source, AEL structure aluminophosphate molecular sieve, oxide source forms and is suitable for spray-dired mix slurry with methods known in the art, in the process for the preparation of spray-dired adsorbent composition slurries, can use acid constituents, described acid can be organic acid or inorganic acid, organic acid if, be preferably carboxylic acid, if acid constituents is inorganic acid, preferred hydrochloric acid, nitric acid or phosphoric acid; Can also use these sour mixtures.Conventionally, acid is used together with water, to form the aqueous acid of dilution, in common acid solution, the concentration of acid is generally in the scope of 0.01 % by weight～20 % by weight.The solid content that zinc oxide source, oxide carrier source and AEL structure aluminophosphate molecular sieve and water is mixed with to slurries is preferably 20～50 % by weight.In step (c), dry described particle temperature is preferably 50～180 ℃, and the temperature of particle is preferably 200～850 ℃ described in roasting, and roasting time is preferably 0.5～6 hour.
Promoter metals compound dipping for the particle in step (d), step (c) being obtained.In the adsorbent composition that described dipping makes finally to obtain, take the gross weight of adsorbent composition as benchmark, take the promoter component content of metal as 5～50 % by weight, preferably 6 to 25 % by weight, more preferably 10～20 % by weight.Described promoter metal is the promoter that is selected from one or more metals, metal oxide or metal oxide precursor, wherein said metal is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium, preferably the mixture of nickel, cobalt or cobalt and nickel.In the time that promoter component comprises bimetallic promoter component, bimetallic promoter component should comprise that the ratio of two kinds of metals that form this bimetallic promoter component is preferably 50: 1 to 1: 50, is preferably 20: 1 to 1: 20.Described promoter metals compound can be for containing the compound of promoter metals and/or the form of metal oxide precursor, and promoter metals compound can partly or entirely be converted into corresponding metal or metal oxide under condition of the present invention.Described promoter metals compound can be metallo-organic complex, slaine, and described slaine can be nitrate, chloride, sulfate, acylate, metal acid-salt.For example, the compound of nickel can be one or more in nickel nitrate, nickel chloride and nickelous sulfate, the compound of cobalt can be one or more in cobalt nitrate, cobalt chloride and cobaltous sulfate, the compound of copper can be selected from one or more in copper nitrate, chlorination copper and copper sulfate, the compound of iron can be selected from one or more in ferric sulfate, iron chloride, ferric nitrate and ferrous salt, the compound of molybdenum can be one or more in ammonium phosphomolybdate, ammonium molybdate and sodium molybdate; The compound of tungsten can be one or more in ammonium phosphotungstate, ammonium tungstate and sodium tungstate; The compound of silver can be a kind of in silver nitrate and silver fluoride or both mixtures; The compound of antimony can be one or more in trichloride antimony, Antimony pentachloride, antimony acetate, antimony sulfate and sodium antimonate; The compound of vanadium can be one or more in vanadic anhydride, vanadic sulfate, sodium metavanadate and ammonium metavanadate.
In step (e), the impregnated granules obtaining after step (d) dipping promoter metal is dried and roasting, dry described particle temperature is preferably 50～180 ℃, described in roasting, particle temperature scope is preferably 200～850 ℃, roasting time preferably 0.5～6 hour.
Reduction described in step (f) makes the particle reduction after the roasting of step (e) gained with reducing agent under the valent applicable condition at reduction accelerator metal substantially in reducing zone, organic sulfide removal compound therefrom while providing the also original cost promoter metals of such amount so that resulting composition for example to contact with cracking gasoline under S-Zorb adsorption desulfurize condition under adsorption desulfurize condition.Described reduction can be carried out according to existing method, for example reduce according to the method providing in CN1331591C, comprise that the composition grain after the roasting that step (e) is obtained contacts with reducing agent (preferably hydrogen), the temperature of contact is 35～850 ℃, pressure is in 0.1～10MPa pressure limit, to carry out enough Long contact time to form required reduction valence state, preferably reduction temperature is 400～600 ℃, and the recovery time is 0.5 hour～3 hours.Described reduction makes the metallic promoter agent after reduction exist with reduction-state substantially, and preferably at least part of described promoter metals exists with 0 valence state.
Adsorbent composition provided by the invention is applicable to hydrocarbon ils and faces hydrogen adsorption desulfurize, is particularly useful for S-Zorb process for adsorption desulfuration.
In hydrocarbon ils desulfurizing method by adsorption provided by the invention, under the condition of adsorption desulfurize, hydrocarbon ils is contacted with adsorbent, described 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 (hydrogen-oil ratio) are generally 100～2000: 1 (Nm
3/ m
3), be preferably 400～1000: 1 Nm
3/ m
3.
Hydrocarbon ils desulfurizing method by adsorption provided by the invention, is applicable to hydrocarbon ils adsorption desulfurize.Described hydrocarbon ils can be the hydrocarbon fuel oil of any sulfur-bearing, be for example cracking gasoline or diesel fuel, wherein said cracking gasoline refers to that boiling range is hydrocarbon or its any cut of 40 ℃ to 210 ℃, conventionally from making larger hydrocarbon molecule be cracked into more micromolecular heat and catalytic process product.Thermal cracking process includes but not limited to coking, thermal cracking, visbreaking gasoline or its combination.Catalytic cracking process 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 hydrocarbonaceous liquid 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.
The present invention is further described for the following examples, and 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 2 hours (to remove template) obtains molecular sieve.With other substituted element replacement silicon, and corresponding adjustment proportioning, can obtain the AEL structure molecular screen that other element replaces, can be with reference to CN101269822A.
Embodiment 1
By 7.5 kilograms of kaolin (SiO
2content 45.6 % by weight, Al
2o
3content 38.5 % by weight, Suzhou China Kaolin Co., Ltd product), 20.2 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product), 3.5 kilograms of 18 water aluminum sulfate (content 99.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group) and 3.4 kilograms of SAPO-11 (Si: Al: P mol ratio=1: 9: 10) molecular sieve put into grinding machine for grinding 15 minutes and form mixture, this mixture is mixed to making beating with deionized water, obtaining solid content is the slurries of 30 % by weight, adding concentration is 15.58 kilograms of the acetic acid of 3 % by weight, stir 1.5 hours, 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 A.By 15.3 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (95 ℃) deionized water and make cobalt nitrate solution; then by this cobalt nitrate solution and 27.7 kilograms of above-mentioned carrier A hybrid infusions; produce the granulate mixture after dipping; granulate mixture after described dipping is dried to 2 hours at 150 ℃; roasting 2 hours at 600 ℃ again, obtains sample A.By sample A 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).
Embodiment 2
By 8.8 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along Xin Ye Co., Ltd product) and 5.5 kilograms of CoAPO-11 (Co: Al: P mol ratio=1: 9: 10) molecular sieve put into grinding machine for grinding and form mixture in 15 minutes, by this mixture and 42.9 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and deionized water mix and pull an oar, obtain the slurries that solid content is 35 % by weight, then add wherein deionized water, stir 2 hours, obtain the slurries that solid content is 30 % by weight, then spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, makes the carrier granular that particle diameter is 40～200 μ m, is designated as carrier B.By 15.7 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (85 ℃) deionized water and obtain maceration extract; by this maceration extract dipping for the carrier B of 23 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.The sample B obtaining is above obtained to adsorbent composition for 1 hour with hydrogen reducing under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa, and the nickel component of wherein said adsorbent composition is reduced to zero-valent state substantially.Finally make and consist of: SiO
2: ZnO: CoAPO-11: Ni=10: the adsorbent composition of 8: 5: 3 (weight ratio).
Embodiment 3
By 7.1 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along Xin Ye Co., Ltd product) and 3.5 kilograms of ZrAPO-11 (Zr: Al: P=1: 10: 10, mol ratio) molecular sieve put into grinder and grind formation the first mixture; By 15.3 kilograms of tetra-n-butyl titanates (content 98.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group) and 10.8 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd.) mix, stir after 1 hour to obtain the second mixture, the first mixture, the second mixture are mixed with deionized water and pull an oar to such an extent that solid content is the slurries of 30 % by weight, stir after 1 hour spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, makes the carrier granular that particle diameter is 40～200 μ m, is designated as support C.By the maceration extract for support C of 15.2 kilograms of gained [by 8.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) and 12.5 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 6.2 kilograms of heat (90 ℃) deionized water make)] dipping, produce dipping after granulate mixture.By the granulate mixture after described dipping 150 ℃ dry 2 hours, then roasting 2 hours at 600 ℃, obtains sample C.By sample C under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state substantially.The weight ratio of the each component of adsorbent composition obtaining is TiO
2: SiO
2: ZnO: ZrAPO-11: Ni: Co=4: 3: 8: 4: 2: 3.
Embodiment 4
By 4.5 kilograms of aluminium isopropoxides (Al>=24.7 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 4.4 kilograms of zirconium oxychloride (ZrOCl
28H
2o>=99.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 3.9 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along Xin Ye Co., Ltd product) and 1.7 kilograms of TAPO-11 (Ti: Al: P mol ratio=1: 10: 10) molecular sieve put into grinder and grind and within 15 minutes, form mixture, then this mixture is joined in the salpeter solution that 42 kilograms of concentration are 0.3 % by weight and pulled an oar, and add deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1 hour, 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 D.By 15 kilograms of above-mentioned carriers for D nickel nitrate solution [by 10.1 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 3.1 kilograms of heat (90 ℃) deionized water obtain] dipping, produce dipping after granulate mixture.By the granulate mixture after described dipping 150 ℃ dry 2 hours, then roasting 2 hours at 600 ℃, obtains sample D.By the sample D obtaining above under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition provided by the invention.The adsorbent composition obtaining consist of ZrO
2: Al
2o
3: ZnO: TAPO-11: Ni=3: 2: 7: 3: 2 (weight ratios).
Embodiment 5
By 9.2 kilograms of rectorite (SiO
2content 45.0 % by weight, Al
2o
3content 35.7 % by weight, From Zhongxiang Hubei), 9.9 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along Xin Ye Co., Ltd product) and 8.2 kilograms of VAPO-11 (V: Al: P mol ratio=1: 10: 10) molecular sieve put into grinder and grind and within 15 minutes, form mixture, gained mixture and 3.1 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and deionized water mixing, stir 1.5 hours, obtain the slurries that solid content is 30 % by weight, spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, makes the carrier granular that particle diameter is 40～200 μ m, is designated as carrier E.By 15.2 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (90 ℃) deionized water and make maceration extract; by this maceration extract and 18 kilograms of above-mentioned carrier E hybrid infusions, 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 E.By the sample E of preparation above 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.The proportioning of gained adsorbent composition is: SiO
2: Al
2o
3: ZnO: VAPO-11: Co=3: 2: 5: 2: 2 (weight ratios).
Embodiment 6
By 8.8 kg of hydrogen zirconia (ZrO
2content 37.5 amount %, Chemical Reagent Co., Ltd., Sinopharm Group), 9.9 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 3.3 kilograms of ZnAPO-11 (Zn: Al: P=1: 10: 10, mol ratio) molecular sieve puts into grinding machine for grinding 20 minutes and forms mixture, by this mixture and 26.0 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) mix and pull an oar, and then mix with deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1.5 hours, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, makes the carrier granular that particle diameter is 40～200 μ m, is designated as carrier granular F.By 7.6 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) and 15.4 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (90 ℃) deionized water and obtain maceration extract; by this maceration extract dipping for the carrier granular F of 21 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 F.By sample F under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state substantially.ZrO in gained adsorbent composition
2: SiO
2: ZnO: ZnAPO-11: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratio).
Embodiment 7
By 3.3 kilograms of titanium oxide (TiO
2content 99.5 % by weight, Beijing Hairong Huazheng Technology Co., Ltd.), 5.5 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 4.4 kilograms of CuAPO-11 ((Cu: Al: P=1: 10: 10, mol ratio) molecular sieve puts into after grinder is pulverized and forms mixture, by this mixture and 13.0 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and 10.4 kg aluminium colloidal sols (alumina content is 21.2 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) mixing making beating, and then mix with deionized water, obtaining solid content is the slurries of 30 % by weight, stirs after 1 hour spray drying forming, 150 ℃ dry after 4 hours, roasting 2 hours at 650 ℃ again, makes the carrier granular that particle diameter is 40～200 μ m, is designated as carrier G.By 5.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight that are dissolved in 4.6 kilograms of heat (90 ℃) deionized water for the carrier G of 20.6 kilograms of gained; Chemical Reagent Co., Ltd., Sinopharm Group) and 10.4 kilogram of six water nickel nitrate (content 98.0 % 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 sample G.By the sample G making above under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state substantially.Gained adsorbent composition consist of TiO
2: SiO
2: Al
2o
3: ZnO: CuAPO-11: Ni: Co=3: 3: 2: 8: 4: 2: 1 (weight ratio).
Embodiment 8
By 6.2 kilograms of expanded perlite (SiO
2content 70.8 % by weight, Al
2o
3content 12.6 % by weight, Pingqiao District, District, Xinyang Area, Henan Province city Tian Li bentonite factory), 19.8 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 6.6 kilograms of MgAPO-11 (Mg: Al: P=1: 10: 10, mol ratio) molecular sieve put into grinder grind form mixture, by this mixture and 27.4 kg aluminium colloidal sols, (alumina content is 21.2 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) and deionized water mixing making beating, obtaining solid content is the slurries of 30 % by weight, stir 1 hour, 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 H.By 20.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight that are dissolved in 6.0 kilograms of heat (95 ℃) deionized water for the carrier granular H of 17 kilograms of gained; 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 sample H.By the sample H of preparation above 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.The composition SiO of gained adsorbent composition
2: Al
2o
3: ZnO: MgAPO-11: Co=2: 3: 9: 3: 4 (weight ratios).
Embodiment 9
By 5.9 kilograms of sepiolite (SiO
2content 56.5 % by weight, MgO content 22.6 % by weight, Neixiang County, Henan Province east wind sepiolite Co., Ltd), 7.7 kilograms of Zinc oxide powder (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 3.3 kilograms of CoAPSO-11 (Co: Si: Al: P=1: 1: 20: 20, mol ratio) molecular sieve puts into after grinder is pulverized and forms mixture, by this mixture and 3.3 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value is 2.1) mix, stir spray drying forming after 1 hour, 150 ℃ dry after 4 hours, then roasting 2 hours at 650 ℃, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier K; By 13.0 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.0 kilograms of heat (90 ℃) deionized water and obtain maceration extract; by the carrier K hybrid infusion described in this maceration extract and 15 kilograms, 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 K.By the sample K of preparation above 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 substantially.The proportioning of the adsorbent composition of finally making is SiO
2: MgO: Al
2o
3: ZnO: CoAPSO-11: Ni=15: 5: 28: 12: 10 (weight ratios).
Comparative example 1
Prepare material ratio as SiO according to existing method preparation take diatomite, aluminium colloidal sol, zinc oxide and nickel nitrate as raw material
2: Al
2o
3: ZnO: Ni=3: the adsorbent of 2: 5: 2.
Comparative example 2
Prepare material ratio as SiO according to existing method preparation take diatomite, aluminium colloidal sol and CoAPO-11 (Co: Al: P mol ratio=1: 10: 10) molecular sieve as raw material
2: Al
2o
3: CoAPO-11=14: the adsorbent of 7: 5.
Embodiment 10
10.5 grams of sample of sorbent (SiO that make by the method for comparative example 1
2: Al
2o
3: ZnO: Ni=8: 2: 8: 3) even with 2.5 grams of CoAPO-11 (Co: Al: P mol ratio=1: 10: 10) molecular sieve mechanical mixture, finally make material ratio and be: SiO
2: Al
2o
3: ZnO: CoAPO-11: Ni=8: 2: 8: 5: 3 adsorbent composition.
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 about 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 cracking gasoline weight) that the gasoline stocks (40～210 ℃ of boiling ranges) that evaluation adopts contains 1400 μ g/g, weight based on the sulfur-containing compound 95% thiophenes (thiophene of having an appointment, benzothiophene, alkylthrophene and alkylbenzene bithiophene), olefin(e) centent 46.8% (volume fraction), octane number RON is that 92.9, MON is 80.6.Appreciation condition is: 410 ℃ of temperature, and pressure 1.4MPa, hydrogen partial pressure is that (hydrogen used is plant hydrogen to 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, (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, adsorption-desulfurization sorbent composition provided by the invention, can improve the octane number of gasoline, and has good desulfurized effect, and its desulfurization degree is higher, can reach more than 95%, even can exceed 98.5%.
The absorbent particles (100～350 order) that the adsorbent composition that 10g embodiment 1～10 is made and comparative example 1～2 make is placed in respectively the stainless steel tube that diameter is 13mm, the length of described stainless steel tube is about 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 the sulfur-containing compound 95% thiophenes (thiophene of having an appointment, 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: 1 (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, has good desulfurized effect, and its desulfurization degree is higher, can reach more than 98%, even can exceed 99.5%.And can reduce the condensation point of diesel oil and improve its Cetane number, thering is unexpected effect.
Claims (15)
1. a hydrocarbon ils adsorption-desulfurization sorbent composition, described adsorbent composition comprises:
(a) zinc oxide,
(b) AEL structure aluminophosphate molecular sieve,
(c) oxide carrier, and
(d) promoter metals;
Wherein at least part of described promoter metals exists with reduction-state;
Take the weight of adsorbent composition as benchmark, in described adsorbent composition, AEL structure aluminophosphate molecular sieve content is 5～30 % by weight, take the content of element promoter metals as 5～50 % by weight; The content of zinc oxide is 10～80 % by weight; Take the content of oxide oxide carrier as 10～70 % by weight, in described adsorbent composition, the content sum of each component is 100 % by weight.
2. adsorbent composition according to claim 1, is characterized in that, in described adsorption-desulfurization sorbent composition, AEL structure aluminophosphate molecular sieve content is 5～25 % by weight, and the content of described zinc oxide is 25～75 % by weight.
3. adsorption-desulfurization sorbent composition according to claim 1 and 2, is characterized in that, the content of described metallic promoter agent is 6～25 % by weight.
4. adsorption-desulfurization sorbent composition according to claim 1 and 2, it is characterized in that, described AEL structure aluminophosphate molecular sieve is 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.
5. adsorption-desulfurization sorbent composition according to claim 4, it is characterized in that, described AEL structure aluminophosphate molecular sieve is one or more in SAPO-11, CoAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and CoAPSO-11.
6. according to the adsorption-desulfurization sorbent composition described in claim 1 any one, it is characterized in that, at least one is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium described promoter metals.
7. according to the adsorption-desulfurization sorbent composition described in claim 1 any one, wherein said promoter metals is nickel and/or cobalt.
8. adsorption-desulfurization sorbent composition according to claim 1, is characterized in that, described oxide carrier is selected from one or more the mixture in silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and natural porous material.
9. the preparation method of adsorption-desulfurization sorbent composition described in claim 1～8 any one, comprising:
(a) zinc oxide source, oxide carrier 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) being obtained, then roasting;
(d) with the particle after the roasting of promoter metals 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.
10. method according to claim 9, is characterized in that, in step (a), zinc oxide source, oxide carrier source, AEL structure aluminophosphate molecular sieve and water is mixed to form to slurries, stirs 0.5～2 hour.
11. methods according to claim 9, 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 is 200～850 ℃.
12. according to the method described in claim 9～11 any one, it is characterized in that, described zinc oxide source is one or more in Zinc oxide powder, zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc chloride and zinc nitrate; Described oxide source is one or more in diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica, silicic acid, sodium metasilicate, ammonium silicate, ethyl orthosilicate, methyl silicate, aluminium colloidal sol, boehmite, gama-alumina, η-aluminium oxide, aluminum sulfate, zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate, titanium dioxide powder, titanium tetrachloride, Titanium Nitrate, Alusil, swollen perlite, kaolin, imvite, sepiolite and rectorite.
The preparation method of adsorption-desulfurization sorbent composition described in 13. claim 1～8 any one, comprising:
(1) zinc oxide source, oxide carrier source, promoter metals compound and AEL structure aluminophosphate molecular sieve are formed to mixture;
(2) by step (1) gained mixture forming particle;
(3) by the particle drying of step (2), then roasting;
(4) composition reduction step (3) being obtained.
14. 1 kinds of hydrocarbon ils desulfurizing method by adsorption, comprise the step that hydrocarbon ils is contacted with adsorbent, it is characterized in that, described adsorbent is the adsorbent described in claim 1～8 any one.
15. in accordance with the method for claim 14, it is characterized in that, described hydrocarbon ils is gasoline or diesel oil.
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