CN102463098A - 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 and methods for making and using same thereof that is used for the hydrocarbon ils adsorption desulfurize.
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; Be prone to produce colloid, foul smelling, corrosion and colour difference; Though its research octane number (RON) can reach about 90, 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; How to reduce the environmental pollution that fuel consume brought that increases day by day, become the major issue that petroleum refining industry and auto industry sustainable development are faced, production super-low sulfur, zero-emission fuel are the general trends of petroleum refining industry's development.
The method that removes the sulphur in the gasoline has hydrodesulfurization and adsorption desulfurize.Hydrodesulfurization though can remove the sulfur-containing compound in the gasoline, can make the most of alkene in the gasoline saturated, and octane number (organon and motor octane number) descends significantly; And some thiophene compound in the gasoline is owing in sterically hindered effect, be difficult to adopt common method of hydrotreating to remove, and required condition is harsh, and this possibly make part aromatic hydrocarbons saturated, thereby octane number is further descended.Adsorption desulfurize; S-Zorb adsorption technology [Zhao Xunzhi for example; Cheng Zhilin. low-sulfur clean fuel oil Study on Production Technology progress. Industrial Catalysis .2007,15 (6): 1-5] be a kind of adsorption desulfurize technology of facing hydrogen, have gasoline desulfur effect preferably; And the decline of octane number (organon and motor octane number) is less, but needs 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 through promoter; The adsorbing agent carrier that comprises zinc oxide, expanded perlite and aluminium oxide like the precursor dipping of nickel, nickel oxide or nickel oxide; The chemical valence of the promoter metals in the promoter metals adsorbing agent carrier composition of gained is reduced, prepare wear-resisting adsorbent composition.This adsorbent is applied to the S-Zorb technology, and the average octane number Δ (RON+MON)/2 of cracking gasoline descends after the desulfurization.
Though above existing desulfuration adsorbent can reduce the sulfur content in the cracking gasoline, can not improve the octane number of gasoline, and may cause the loss of octane number; And do not relate to and be used for diesel oil adsorption desulfurizing reduction condensation point of diesel oil.
Summary of the invention
The technical problem that the present invention will solve provides a kind of hydrocarbon ils adsorption desulfurize adsorption-desulfurization sorbent composition, and this adsorbent composition has adsorption desulfurize ability preferably, and can improve octane number and the condensation point that reduces diesel oil; The other technical problem that the present invention will solve provides preparation method's and methods for using them of said adsorbent composition.
The present invention provides a kind of hydrocarbon ils adsorption-desulfurization sorbent composition, and this adsorbent composition comprises:
(a) zinc oxide,
(b) AEL structure aluminophosphate molecular sieve,
(c) oxide carrier and
(d) promoter metals;
Weight with adsorbent composition is benchmark, and AEL structure aluminophosphate molecular sieve content is 1～40 weight % in the said adsorbent composition, is 5～50 weight % in the content of element promoter metals; The content of zinc oxide is 10～80 weight %; The content of oxide carrier is 10～84 weight %; At least the said promoter metals of part exists to go back ortho states.
The present invention provides the preparation method that said adsorbent composition also is provided, and comprising: form the particle, roasting, the step of reducing that comprise zinc compound, promoter metals compound, oxide carrier component and AEL structure aluminophosphate molecular sieve.
The present invention further provides a kind of hydrocarbon ils desulfurizing method by adsorption, comprises the step that hydrocarbon ils is contacted with adsorbent, it is characterized in that, described adsorbent is an adsorbent composition provided by the invention.
Adsorption-desulfurization sorbent composition provided by the invention has higher adsorption desulfurize ability, is used for the hydrocarbon ils adsorption desulfurize, has desulfurized effect preferably, and the adsorption desulfurize rate is higher.Said adsorbent composition is used for gasoline absorbing desulfurization, can improve the octane number of gasoline after the desulfurization, is used 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 the substituted AEL structure of element aluminophosphate molecular sieve, and substituted element is one or more among 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 the substituted AEL structure of the said element aluminophosphate molecular sieve.Described AEL structure phosphate molecule sieve is preferably one or more among SAPO-11, CoAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and the CoAPSO-11.Said AEL structure molecular screen can be purchased or prepare according to existing method, for example, [originally wait quietly perhaps. 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].Gross weight with adsorbent composition is a benchmark, and the content of AEL structure aluminophosphate molecular sieve is preferably 5～40 weight % in the said adsorbent composition, more preferably 5～30 weight %.
According to adsorption-desulfurization sorbent composition provided by the invention, at least a nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and the vanadium of being selected from of described promoter metals; Said 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.Said promoter metals exists to go back ortho states, and the said ortho states of going back is meant that the promoter metals major part is reduced to lower chemical valence, is preferably zeroth order.Content in the element promoter metals is 5～50 weight %, is preferably 6～25 weight %, further is preferably 10～20 weight %.
According to adsorption-desulfurization sorbent composition provided by the invention; Said oxide carrier is selected from one or more of adsorbent inorganic oxide carrier commonly used; Preferably; Be selected from silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and the natural porous material one or more, more preferably one or more in silica, zirconia, titanium oxide and the natural porous material.Said natural porous material is the mixture of one or more in expanded perlite, kaolin, imvite, sepiolite, diatomite and the rectorite for example.When oxide was 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; Weight with adsorbent composition is benchmark; AEL structure aluminophosphate molecular sieve content is 1～40 weight % in the said adsorption-desulfurization sorbent composition, is 5～50 weight % in the content of element promoter metals; Content in zinc oxide zinc oxide is 10～80 weight %; Content in the oxide oxide carrier is
weight %.The content of said zinc oxide is preferably
weight %, more preferably 25～70 weight %; Said AEL structure aluminophosphate molecular sieve content is preferably 5～30 weight %, 5～25 weight % more preferably, further preferred 8～25 weight %; The content of said oxide carrier is preferably 10～70 weight %.
Adsorbent composition preparation method provided by the invention; The particle that can prepare zinc compound, oxide carrier source, AEL structure molecular screen and metal promoted immunomodulator compounds through any method; Roasting again after roasting or the drying then; Reduce then, for example can prepare described adsorbent composition through following method:
(1) zinc oxide source, oxide carrier source, promoter metals compound and AEL structure aluminophosphate molecular sieve are mixed, add or do not add entry;
(2) moulding of step (1) gained mixture is formed particle,, can the slurries spray-drying be formed particle if prepared mixture is slurries;
(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 the roasting that step (3) is obtained obtains adsorbent composition; Said reduction is included in 35～850 ℃ the temperature range in the pressure limit with 0.1～10MPa carries out the long enough time to form required reduction valence state, and the preferred recovery time is 0.5～3 hour.
A kind of preferred for preparation method of adsorbent composition provided by the invention may further comprise the 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 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 drying; Then
(f) the composition reduction that step (e) is obtained.
The Preparation Method that should preferably make, resulting adsorbent composition not only has good desulfurized effect, and has better raising octane number effect and reduce the condensation point of diesel oil effect.Wherein:
Zinc oxide source described in the step (a) can be one or more zinc compound forms that there is or under preparation condition described herein, can be converted into 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.Said zinc oxide source is preferably powdery zinc oxide.
Oxide carrier source described in the step (a) is oxide form and/or the oxide precursor that under condition of the present invention, can generate oxide.Described oxide carrier source is preferably one or more in silica source, alumina source, zirconia source, titania source, silica-alumina source and the natural porous material, preferably includes in the inorganic oxide carrier of making binding agent commonly used one or more.Described silica source can be that the silica form exists or one or more can be converted in the silicon-containing compound form of silica one or more; The silica source that described silica form exists is one or more in diatomite, silicon oxide colloid, silica gel, silicalite and the precipitated silica for example, and said silicon oxide colloid is Ludox, silicon gel for example; The said silicon-containing compound that is converted into silica is one or more in silicic acid, sodium metasilicate, ammonium silicate and the ethyl orthosilicate (or methyl esters) for example; Preferred silica source is a diatomite.Said alumina source can be the aluminum contained compound form aluminium organic alcohol compound such as inorganic compound such as aluminum nitrate, aluminium chloride, aluminum sulfate and aluminium isopropoxide for example that aluminium oxide form or one or more can be converted into aluminium oxide; Also can be any commercially available alumina material, it be including, but not limited to colloidal alumina solution and the alumina cpd that is dewatered and produced by hydrated alumina usually; Said alumina source is one or more in aluminium colloidal sol, boehmite, gama-alumina or the η-aluminium oxide for example.Described zirconia source is one or more in zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate and the zirconium sulfate etc. for example.Described titania source is one or more in titanium dioxide powder, titanium tetrachloride, Titanium Nitrate and the tetra-n-butyl titanate etc. for example.Described silica-alumina (amorphous aluminum silicide) source for example Alusil maybe can generate silicon source and aluminium source mixture such as the waterglass and the aluminum sulfate of amorphous aluminum silicide.When oxide is two or more mixture, in mixture, can be arbitrary proportion between any two kinds of components, the weight ratio between any two kinds of components is preferably 1: 100 to 100: 1, more preferably 1: 20 to 20: 1.
In the step (a) zinc oxide source, AEL structure aluminophosphate molecular sieve and oxide source are mixed, formed mixture 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.The mixing arrangement that is fit to includes but not limited to mix rotating cylinder, set casing or groove, batch (-type) or continous way mixer, impact extrusion formula mixer.If the gained mixture is the wet mixture form, can makes said wet mixture multiviscosisty, through granulating it granulated then, then drying and roasting.Said zinc oxide source, oxide source and AEL structure aluminophosphate molecular sieve mix when forming dough or paste mixture; Can make said mixture moulding process grain, extrudate, sheet, ball, pill or microsphere particle in the step (b); The cylindrical extrudate of any suitable length of preferred diameter 0.75～13mm is then with gained particle drying and roasting.When said mixture was the slurries form, through said slurries spray-drying is made it granulating, for example spray-drying formation granularity was the microballoon of 20～500 μ m, in step (c), makes said microballoon roasting or dry roasting then in the step (b).Preferably form the adsorbent composition particle through spray-drying.Can make and comprise zinc oxide source, AEL structure aluminophosphate molecular sieve, oxide source and form with methods known in the art and be suitable for spray-dired mix slurry; Be used for the process of spray-dired adsorbent composition slurries in preparation, can use acid constituents, said acid can be organic acid or inorganic acid; If be organic acid; Then be preferably carboxylic acid, if acid constituents is an inorganic acid, then preferred hydrochloric acid, nitric acid or phosphoric acid; Can also use these sour mixtures.Usually, acid is used with water, to form the aqueous acid of dilution, the concentration of acid is generally in the scope of 0.01 weight %～20 weight % in the common acid solution.The solid content that zinc oxide source, oxide carrier source and AEL structure aluminophosphate molecular sieve and water is mixed with slurries is preferably 20～50 weight %.Dry said particle temperature is preferably 50～180 ℃ in the step (c), and the temperature of the said particle of roasting is preferably 200～850 ℃, and roasting time is preferably 0.5～6 hour.
The particle that in the step (d) step (c) is obtained floods with the promoter metals compound.Said dipping makes in the final resulting adsorbent composition, is benchmark with the gross weight of adsorbent composition, is 5～50 weight % in the promoter component content of metal, preferred 6 to 25 weight %, more preferably 10～20 weight %.Said 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, the mixture of preferred nickel, cobalt or cobalt and nickel.When promoter component comprised the bimetallic promoter component, the 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 the compound that contains promoter metals and/or the form of metal oxide precursor, and the promoter metals compound can partly or entirely be converted into corresponding metal or metal oxide under condition of the present invention.Said 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 the nickelous sulfate; The compound of cobalt can be one or more in cobalt nitrate, cobalt chloride and the cobaltous sulfate; The compound of copper can be selected from one or more in copper nitrate, copper chloride and the copper sulphate, the compound of iron can be selected from ferric sulfate, iron chloride, ferric nitrate and the ferrous salt one or more, the compound of molybdenum can be in ammonium phosphomolybdate, ammonium molybdate and the sodium molybdate one or more; The compound of tungsten can be one or more in ammonium phosphotungstate, ammonium tungstate and the sodium tungstate; The compound of silver can be a kind of in silver nitrate and the silver fluoride or both mixtures; The compound of antimony can be one or more in trichloride antimony, Antimony pentachloride, antimony acetate, antimony sulfate and the sodium antimonate; The compound of vanadium can be in vanadic anhydride, vanadic sulfate, sodium metavanadate and the ammonium metavanadate one or more.
With the impregnated granules drying and the roasting that obtain after step (d) the dipping promoter metal, dry said particle temperature is preferably 50～180 ℃ in the step (e), and the said particle temperature scope of roasting is preferably 200～850 ℃, preferred 0.5～6 hour of roasting time.
Organic sulfide removal compound therefrom when the particle reduction of reduction described in the step (f) after making the roasting of step (e) gained with reducing agent under the valent suitable condition of reducing zone at reduction accelerator metal basically, also original cost promoter metals so that the resulting composition that such amount is provided for example contact with cracking gasoline under the S-Zorb adsorption desulfurize condition under the adsorption desulfurize condition.Said reduction can be carried out according to existing method; For example reduce according to the method that provides among the CN1331591C; Comprise that the composition grain after the roasting that step (e) is obtained contacts with reducing agent (preferred hydrogen), the temperature of contact is 35～850 ℃, and pressure is to carry out enough Long contact time in 0.1～10MPa pressure limit to form required reduction valence state; Preferred reduction temperature is 400～600 ℃, and the recovery time is 0.5 hour～3 hours.Said reduction makes the metallic promoter agent after the reduction exist to go back ortho states basically, and preferably the said promoter metals of part exists with 0 valence state at least.
Adsorbent composition provided by the invention is applicable to that hydrocarbon ils faces the hydrogen adsorption desulfurize, is particularly useful for the S-Zorb process for adsorption desulfuration.
In the 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 the hydro condition, hydrogen purity is 70 volume %～99 volume %, when raw material was cracking gasoline, hydrogen and hydrocarbon oil feed mol ratio were generally 0.1～10: 1, be preferably 0.2～3.0: 1; When raw material was diesel oil, hydrogen and hydrocarbon oil feed volume ratio (hydrogen-oil ratio) were 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 the hydrocarbon ils adsorption desulfurize.Said hydrocarbon ils can be any sulfur containing hydrocarbon fuels oil; For example be cracking gasoline or diesel fuel; Wherein said cracking gasoline is meant that boiling range is 40 ℃ to 210 ℃ hydrocarbon or its any cut, usually from making bigger hydrocarbon molecule be cracked into the heat and the catalytic process product of less molecule.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.Can be when in some cases, being used as raw material in the embodiment of the present invention with said cracking gasoline fractionation and/or hydrotreatment before desulfurization.Said " diesel fuel " means boiling range is 150 ℃ to 450 ℃ the hydrocarbon mixture 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 that in hydrocarbon-containifluids fluids such as cracking gasoline or diesel oil, exists usually.The sulphur that exists in the 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 alkyl diphenyl bithiophene, and the normal bigger thiophenes of molecular weight that exists in the diesel fuel.
Following embodiment further specifies the present invention, and used AEL structure molecular screen is that the inventor makes by oneself according to existing method among the embodiment.For example, (Si: Al: P mol ratio=1: 9: 10) the molecular sieve synthesis step is following: earlier 18.6 kilograms aluminium isopropoxide, water and phosphoric acid solution mixing were stirred 2 hours, add 0.78 kilogram Ludox then, stirred 1 hour for described SAPO-11; Adding mass ratio is 1: 1 the di-n-propylamine and the mixture of diisopropylamine, stir 2 hours again after, the pH value is transferred to 5.5～6.5; Then reactant mixture is transferred in the autoclave; 180 ℃ of following thermostatic crystallizations take out cooling after 36 hours; Use the deionized water filtering and washing constant then to pH; Drying is 24 hours under 100 ℃, obtains molecular screen primary powder, obtains molecular sieve in 500-600 ℃ of following roasting 2 hours (to remove template) at last.Replace silicon with other substituted element, and corresponding adjustment proportioning, can obtain the substituted AEL structure molecular screen of other element, can be with reference to CN101269822A.
Embodiment 1
With 7.5 kilograms of kaolin (SiO
2Content 45.6 weight %, Al
2O
3Content 38.5 weight %, Suzhou China Kaolin Co., Ltd product), 20.2 kilograms of zinc oxide (ZnO content 99.8 weight %, sea, Zibo is along zinc industry Co., Ltd product), 3.5 kilograms of 18 water aluminum sulfate (content 99.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) and 3.4 kilograms of SAPO-11 (Si: Al: P mol ratio=1: 9: 10) molecular sieve is put into grinding machine for grinding and was formed mixture in 15 minutes; This mixture is mixed making beating with deionized water, solid content be the slurries of 30 weight %, add concentration and be 15.58 kilograms of the acetate of 3 weight %; Stirred 1.5 hours; Spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of following roastings 2 hours; Make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier A.With 15.3 kilograms of cobalt nitrate hexahydrates (content 99.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in 4.6 kilograms of heat (95 ℃) deionized water and makes cobalt nitrate solution; Then with this cobalt nitrate solution and 27.7 kilograms of above-mentioned carrier A hybrid infusions, produce the granulate mixture behind the dipping, with the granulate mixture behind the said dipping 150 ℃ of dryings 2 hours; In 600 ℃ of following roastings 2 hours, obtain sample A again.With sample A in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state basically.The 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, down together).
Embodiment 2
With 8.8 kilograms of zinc oxide (ZnO content 99.8 weight %; Zibo sea is along zinc industry Co., Ltd product) and 5.5 kilograms of CoAPO-11 (Co: Al: P mol ratio=1: 9: 10) molecular sieve is put into grinding machine for grinding and was formed mixture in 15 minutes, with this mixture and 42.9 kilograms of acidic silicasol (SiO
2Content 25.5% weight %, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and deionized water mix and pull an oar; Getting solid content is the slurries of 35 weight %, to wherein adding deionized water, stirs 2 hours then; Solid content be the slurries of 30 weight %, spray drying forming then, 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier B.15.7 kilogram of six water nickel nitrate (content 98.0 weight %, Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (85 ℃) deionized water obtain maceration extract, the carrier B of 23 kilograms of gained with this maceration extract dipping, is produced the granulate mixture behind the dipping.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample B again.The above sample B that obtains 1 hour is obtained adsorbent composition with Hydrogen Vapor Pressure 1.4MPa is following with hydrogen reducing in 530 ℃, and the nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.Finally process and consist of: SiO
2: ZnO: CoAPO-11: Ni=10: the adsorbent composition of 8: 5: 3 (weight ratio).
Embodiment 3
7.1 kilograms of zinc oxide (ZnO content 99.8 weight %, Zibo sea is along zinc industry Co., Ltd product) and 3.5 kilograms of ZrAPO-11 (Zr: Al: P=1: 10: 10, mol ratio) molecular sieve is put into grinder to be ground and forms first mixture; With 15.3 kilograms of tetra-n-butyl titanates (content 98.0 weight %, Chemical Reagent Co., Ltd., Sinopharm Group) and 10.8 kilograms of acidic silicasol (SiO
2Content 25.5% weight %, Qingdao micro-nano silica gel Science and Technology Ltd.) mix, stir and get second mixture after 1 hour; First mixture, second mixture mixed with deionized water pull an oar to such an extent that solid content is the slurries of 30 weight %, stir after 1 hour spray drying forming; 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as support C.With the support C of 15.2 kilograms of gained with maceration extract [by 8.0 kilograms of cobalt nitrate hexahydrates (content 99.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) and 12.5 kilogram of six water nickel nitrate (content 98.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 6.2 kilograms of heat (90 ℃) deionized water make)] dipping, produce the granulate mixture behind the dipping.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample C again.With sample C in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state basically.The weight ratio of each component of adsorbent composition that obtains is TiO
2: SiO
2: ZnO: ZrAPO-11: Ni: Co=4: 3: 8: 4: 2: 3.
Embodiment 4
With 4.5 kilograms of aluminium isopropoxides (Al>=24.7 weight %, Chemical Reagent Co., Ltd., Sinopharm Group), 4.4 kilograms of zirconium oxychloride (ZrOCl
28H
2O>=99.0 weight %, Chemical Reagent Co., Ltd., Sinopharm Group), (Ti: Al: P mol ratio=1: 10: 10) molecular sieve is put into grinder and is ground and formed mixture in 15 minutes for 3.9 kilograms of zinc oxide (ZnO content 99.8 weight %, sea, Zibo is along zinc industry Co., Ltd product) and 1.7 kilograms of TAPO-11; Then with pulling an oar in this mixture salpeter solution that to join 42 kilograms of concentration be 0.3 weight %; And the adding deionized water, obtain the slurries that solid content is 30 weight %, stir spray drying forming after 1 hour; 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier D.15 kilograms of above-mentioned carrier D with nickel nitrate solution [be dissolved in 3.1 kilogram heat (90 ℃) deionized water obtain 10.1 kilogram of six water nickel nitrate (content 98.0 weight %, Chemical Reagent Co., Ltd., Sinopharm Group)] dipping, are produced the granulate mixture behind the dipping.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample D again.With the above sample D that obtains 530 ℃ with Hydrogen Vapor Pressure 1.4MPa under with hydrogen reducing 1 hour, obtain adsorbent composition provided by the invention.Resulting adsorbent composition consist of ZrO
2: Al
2O
3: ZnO: TAPO-11: Ni=3: 2: 7: 3: 2 (weight ratios).
Embodiment 5
With 9.2 kilograms of rectorite (SiO
2Content 45.0 weight %, Al
2O
3Content 35.7 weight %; Zhongxiang City, Hubei), 9.9 kilograms of zinc oxide (ZnO content 99.8 weight %; Zibo sea is along zinc industry Co., Ltd product) and 8.2 kilograms of VAPO-11 (V: Al: P mol ratio=1: 10: 10) molecular sieve is put into grinder and is ground and formed mixture, gained mixture and 3.1 kilograms of acidic silicasol (SiO in 15 minutes
2Content 25.5% weight %, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and the deionized water mixing; Stirred 1.5 hours, getting solid content is the slurries of 30 weight %, spray drying forming; 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier E.With 15.2 kilograms of cobalt nitrate hexahydrates (content 99.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in 4.6 kilograms of heat (90 ℃) deionized water and makes maceration extract; With this maceration extract and 18 kilograms of above-mentioned carrier E hybrid infusions, produce the granulate mixture after flooding.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample E again.With the sample E of above preparation in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state basically.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
With 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 weight %; Sea, Zibo is along zinc industry Co., Ltd product) and 3.3 kilograms of ZnAPO-11 (Zn: Al: P=1: 10: 10; Mol ratio) molecular sieve is put into grinding machine for grinding and was formed mixture in 20 minutes, with this mixture and 26.0 kilograms of acidic silicasol (SiO
2Content 25.5% 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, solid content be the slurries of 30 weight %, stir spray drying forming after 1.5 hours; 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier granular F.With 7.6 kilograms of cobalt nitrate hexahydrates (content 99.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) and 15.4 kilogram of six water nickel nitrate (content 98.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in 4.6 kilograms of heat (90 ℃) deionized water and obtains maceration extract; The carrier granular F of 21 kilograms of gained is flooded with this maceration extract, produce the granulate mixture after flooding.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample F again.With sample F in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state basically.ZrO in the gained adsorbent composition
2: SiO
2: ZnO: ZnAPO-11: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratio).
Embodiment 7
With 3.3 kilograms of titanium oxide (TiO
2Content 99.5 weight %; Beijing Hairong Huazheng Technology Co., Ltd.), 5.5 kilograms of zinc oxide (ZnO content 99.8 weight %; Sea, Zibo is along zinc industry Co., Ltd product) and 4.4 kilograms of CuAPO-11 ((Cu: Al: P=1: 10: 10; Mol ratio) molecular sieve is put into the grinder back of pulverizing and is formed mixture, with this mixture and 13.0 kilograms of acidic silicasol (SiO
2Content 25.5% 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 weight %; Catalyst Shandong branch company of China Petrochemical Industry product) mix making beating, and then mix with deionized water, getting solid content is the slurries of 30 weight %; Stir after 1 hour, spray drying forming, 150 ℃ of dryings are after 4 hours; 650 ℃ of following roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier G.The carrier G usefulness of 20.6 kilograms of gained is dissolved in 5.0 kilograms of cobalt nitrate hexahydrates (the content 99.0 weight % in 4.6 kilograms of heat (90 ℃) deionized water; Chemical Reagent Co., Ltd., Sinopharm Group) and 10.4 kilogram of six water nickel nitrate (content 98.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) dipping produces the granulate mixture after flooding.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample G again.With the above sample G that makes in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state basically.The 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
With 6.2 kilograms of expanded perlite (SiO
2Content 70.8 weight %, Al
2O
3Content 12.6 weight %, Pingqiao District sky, Xinyang, Henan Li Pengruntuchang), 19.8 kilograms of zinc oxide (ZnO content 99.8 weight %, sea, Zibo is along zinc industry Co., Ltd product) and 6.6 kilograms of MgAPO-11 (Mg: Al: P=1: 10: 10; Mol ratio) molecular sieve is put into grinder and is ground the formation mixture; With this mixture and 27.4 kg aluminium colloidal sols (alumina content is 21.2 weight %, catalyst Shandong branch company of China Petrochemical Industry product) and deionized water mixing making beating, getting solid content is the slurries of 30 weight %; Stirred 1 hour; Spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of following roastings 2 hours; Make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier granular H.The carrier granular H of 17 kilograms of gained is flooded with the 20.0 kilograms of cobalt nitrate hexahydrates (content 99.0 weight %, Chemical Reagent Co., Ltd., Sinopharm Group) that are dissolved in 6.0 kilograms of heat (95 ℃) deionized water, produce the granulate mixture after flooding.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample H again.With the sample H of above preparation in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state basically.The composition SiO of gained adsorbent composition
2: Al
2O
3: ZnO: MgAPO-11: Co=2: 3: 9: 3: 4 (weight ratios).
Embodiment 9
With 5.9 kilograms of sepiolite (SiO
2Content 56.5 weight %; MgO content 22.6 weight %; Neixiang County, Henan Province east wind sepiolite Co., Ltd), 7.7 kilograms of Zinc oxide powder (ZnO content 99.8 weight %; Zibo sea is along zinc industry Co., Ltd product) and 3.3 kilograms of CoAPSO-11 (Co: Si: Al: P=1: 1: 20: 20, mol ratio) molecular sieve put into the grinder back of pulverizing and form mixture, with this mixture and 3.3 kilograms of acidic silicasol (SiO
2Content 25.5% weight %, Qingdao micro-nano silica gel Science and Technology Ltd., the pH value is 2.1) mix; Stir spray drying forming after 1 hour, 150 ℃ of dryings are after 4 hours, again 650 ℃ of following roastings 2 hours; Make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier K; With 13.0 kilogram of six water nickel nitrate (content 98.0 weight %; Chemical Reagent Co., Ltd., Sinopharm Group) is dissolved in 4.0 kilograms of heat (90 ℃) deionized water and obtains maceration extract; With this maceration extract and 15 kilograms of described carrier K hybrid infusions, produce the granulate mixture after flooding.Granulate mixture behind the said dipping 150 ℃ of dryings 2 hours, in 600 ℃ of following roastings 2 hours, is obtained sample K again.With the sample K of above preparation in 530 ℃ with Hydrogen Vapor Pressure 1.4MPa down with hydrogen reducing 1 hour, obtain adsorbent composition.The nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.The proportioning of the adsorbent composition of finally processing is SiO
2: MgO: Al
2O
3: ZnO: CoAPSO-11: Ni=15: 5: 28: 12: 10 (weight ratios).
Comparative Examples 1
Is that the feedstock production material ratio is SiO according to existing method preparation with diatomite, aluminium colloidal sol, zinc oxide and nickel nitrate
2: Al
2O
3: ZnO: Ni=3: 2: 5: 2 adsorbent.
Comparative Examples 2
(Co: Al: P mol ratio=1: 10: 10) molecular sieve is that the feedstock production material ratio is SiO with diatomite, aluminium colloidal sol and CoAPO-11 according to existing method preparation
2: Al
2O
3: CoAPO-11=14: 7: 5 adsorbent.
Embodiment 10
The 10.5 gram sample of sorbent (SiO that make by the method for Comparative Examples 1
2: Al
2O
3: ZnO: Ni=8: 2: 8: 3) (Co: Al: P mol ratio=1: 10: 10) the molecular sieve mechanical mixture is even, finally processes material ratio to be: SiO with 2.5 gram CoAPO-11
2: Al
2O
3: ZnO: CoAPO-11: Ni=8: 2: 8: 5: 3 adsorbent composition.
The absorbent particles (100～350 order) that adsorbent composition that 10g such as above embodiment 1～10 are made and Comparative Examples 1～2 make places diameter (interior warp) to be the stainless steel tube of 13mm respectively; The length of said stainless steel tube is about 30.5cm; And the bottom is placed with quartz sand (100～350 order) more than 1/3; So that for the adsorbent bed inert carrier that provides, and adsorbent bed in quartz ampoule, be positioned at quartz sand above.Estimate the sulphur that the gasoline stocks (40～210 ℃ of boiling ranges) adopted contains 1400 μ g/g (based on the weight content of the sulfur-containing compound of said gaseous state cracking gasoline weight); Based on the weight of 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 92.9, and MON is 80.6.Appreciation condition is: 410 ℃ of temperature, pressure 1.4MPa, hydrogen partial pressure are that (used hydrogen 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 seen table 1.
Table 1
In the table 1, (MON+RON)/2 of the gasoline after the octane number variation=desulfurization deduct (MON+RON)/2 of gasoline stocks, and+expression octane number increases, and-expression octane number reduces;
Remove sulfur content * 100% in percentage=(sulfur content in the gasoline after the sulfur content-desulfurization in the raw material)/raw material of desulfuration.
Visible by table 1, adsorption-desulfurization sorbent composition provided by the invention can improve the octane number of gasoline, and has desulfurized effect preferably, and its desulfurization degree is higher, can reach more than 95%, even can surpass 98.5%.
It is the stainless steel tube of 13mm that the absorbent particles (100～350 order) that adsorbent composition that 10g embodiment 1～10 is made and Comparative Examples 1～2 make places diameter respectively; The length of said stainless steel tube is about 30.5cm; And the bottom is placed with quartz sand (100～350 order) more than 1/3; So that for the adsorbent bed inert carrier that provides, and adsorbent bed in quartz ampoule, be positioned at quartz sand above.Estimate the sulphur that the straight-run diesel oil raw material (230～350 ℃ of boiling ranges) adopted contains 1400 μ g/g (based on the weight content of the sulfur-containing compound of said gaseous state straight-run diesel oil weight); Based on the weight of the sulfur-containing compound 95% thiophenes (thiophene of having an appointment; Benzothiophene; Alkylthrophene and alkylbenzene bithiophene), 9.6 ℃ of condensation points, Cetane number are 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 seen table 2.
Table 2
In the table 2, remove sulfur content * 100% in percentage=(sulfur content in the diesel oil after the sulfur content-desulfurization in the raw material)/raw material of desulfuration.
Visible by 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 surpass 99.5%.And can reduce the condensation point and its Cetane number of raising of diesel oil, have unexpected effect.
Claims (15)
1. hydrocarbon ils adsorption-desulfurization sorbent composition, said adsorbent composition comprises:
(a) zinc oxide,
(b) AEL structure aluminophosphate molecular sieve,
(c) oxide carrier and
(d) promoter metals;
Wherein the said promoter metals of part exists to go back ortho states at least;
Weight with adsorbent composition is benchmark, and AEL structure aluminophosphate molecular sieve content is 1～40 weight % in the said adsorbent composition, is 5～50 weight % in the content of element promoter metals; The content of zinc oxide is 10～80 weight %; Content in the oxide oxide carrier is 10～84 weight %.
2. adsorbent composition according to claim 1 is characterized in that, AEL structure aluminophosphate molecular sieve content is 5～25 weight % in the said adsorption-desulfurization sorbent composition, and the content of said zinc oxide is 25～75 weight %.
3. adsorption-desulfurization sorbent composition according to claim 1 and 2 is characterized in that, the content of said metallic promoter agent is 6～25 weight %.
4. according to claim 1 or 2 or 3 described adsorption-desulfurization sorbent compositions; It is characterized in that; Said AEL structure aluminophosphate molecular sieve is one or more of the substituted AEL structure of element aluminophosphate molecular sieve, and substituted element is one or more among 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 the substituted AEL structure of the said element aluminophosphate molecular sieve.
5. adsorption-desulfurization sorbent composition according to claim 4; It is characterized in that said AEL structure aluminophosphate molecular sieve is one or more among SAPO-11, CoAPO-11, MnAPO-11, ZrAPO-11, VAPO-11, ZnAPO-11, CuAPO-11, MgAPO-11, TAPO-11 and the CoAPSO-11.
6. according to each described adsorption-desulfurization sorbent composition of claim 1～5, it is characterized in that at least a nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and the vanadium of being selected from of said promoter metals.
7. according to each described adsorption-desulfurization sorbent composition of claim 1～5, wherein said promoter metals is nickel and/or cobalt.
8. adsorption-desulfurization sorbent composition according to claim 1 is characterized in that, said oxide carrier is selected from one or more the mixture in silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and the natural porous material.
9. each said adsorption-desulfurization sorbent preparation of compositions method of claim 1～8 comprises:
(a) zinc oxide source, oxide carrier source and AEL structure aluminophosphate molecular sieve are mixed;
(b) step (a) gained compound particles granulation is formed particle;
(c) particle drying that step (b) is obtained, roasting then;
(d) with the particle after the roasting of promoter metals compound impregnation steps (c) gained;
(e) with carrying out roasting after step (d) the gained impregnated granules drying; Then
(f) the composition reduction that step (e) is obtained.
10. method according to claim 9 is characterized in that, in the step (a), zinc oxide source, oxide carrier source, AEL structure aluminophosphate molecular sieve and water is mixed the formation slurries, stirs 0.5～2 hour.
11. method according to claim 9 is characterized in that, step (c) and (e) described in dry baking temperature be 50～180 ℃; Step (c) and (e) in the said particle temperature of roasting be 200～850 ℃.
12., 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 the zinc nitrate according to each described method of claim 9～11; Said 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, expand perlite, kaolin, imvite, sepiolite and the rectorite.
13. each said adsorption-desulfurization sorbent preparation of compositions method of claim 1～8 comprises:
(1) zinc oxide source, oxide carrier source, promoter metals compound and AEL structure aluminophosphate molecular sieve are formed mixture;
(2) with step (1) gained mixture forming particle;
(3) with the particle drying of step (2), roasting then;
(4) the composition reduction that step (3) is obtained.
14. a hydrocarbon ils desulfurizing method by adsorption comprises the step that hydrocarbon ils is contacted with adsorbent, it is characterized in that, described adsorbent is each described adsorbent of claim 1～8.
15., it is characterized in that described hydrocarbon ils is gasoline or diesel oil according to the described method of claim 14.
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| CN111111767A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN111111768A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN111111768B (en) * | 2018-10-31 | 2023-07-11 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN112742370A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Catalyst composition, application thereof and selective mercaptan removal method |
| CN112742370B (en) * | 2019-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Catalyst composition, application thereof and method for selectively removing mercaptan |
| RU2750100C1 (en) * | 2020-04-03 | 2021-06-22 | Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук | Method for production of granular micro-meso-macroporous magnesium aluminophosphate molecular sieve maro-11 exhibiting high crystallinity |
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