CN103372416A - Adsorbent composition for desulfuration of hydrocarbon oil and preparation method thereof - Google Patents
Adsorbent composition for desulfuration of hydrocarbon oil and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an adsorbent composition for desulfuration of hydrocarbon oil and a preparation method thereof. The adsorbent composition contains metal accelerants, zinc oxide and phosphoaluminate molecular sieve (shell)/MFI-structured aluminum silicon molecular sieve (core) core-shell composite molecular sieves and oxide. The preparation method for the adsorbent composition comprises the following steps of: forming a mixture including zinc oxide compounds, metal accelerant compounds, oxide vector components and phosphoaluminate molecular sieve (shell)/MFI-structured aluminum silicon molecular sieve (core) core-shell composite molecular sieves, and carrying out roasting and reduction. The adsorbent composition is used for carrying out adsorption desulfurization on the hydrocarbon oil and has a relatively good desulfuration effect and a relatively good effect for enhancing the octane value of gasoline.
Description
Technical field
The present invention relates to adsorbent composition for desulfurization of hydrocarbon oil and preparation method 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 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, 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 sulphur emissions fuel are the general trends of petroleum refining industry's development.
A kind of production method of low-sulphur oil is adsorption desulfurize, [Zhao Xunzhi, Cheng Zhilin. the progress of low-sulfur clean fuel oil production technology. Industrial Catalysis .2007,15 (6): 1-5] this is introduced.Wherein, S-Zorb is a kind of adsorption desulfurize technology of facing hydrogen, has preferably gasoline desulfur effect, and the decline of octane number (organon and motor octane number) is less, but needs suitable adsorbent.
CN 1130253C discloses 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 octane number decline 0.1-0.4 of gasoline.
CN 1327988A discloses a kind of S-Zorb adsorbent, it is to pass through promoter, the adsorbing agent carrier that comprises zinc oxide, expanded perlite and aluminium oxide such as 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.
Although 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.
CN102343249A discloses a kind of hydrocarbon oil desulphurization adsorbing agent and its preparation method and application.Adsorbent comprises SAPO molecular sieve, alumina binder, laminated clay column, zinc oxide and promoter metals, and it is active that this adsorbent has very high adsorption desulfurize, can obviously increase octane number, how further do not increase octane number but relate to.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of hydrocarbon ils adsorption-desulfurization sorbent with higher raising octane number ability, and the other technical problem that the present invention will solve provides preparation method and application's method of described adsorbent.
The invention provides a kind of hydrocarbon oil desulphurization adsorbing agent composition, this adsorbent composition is composed of the following components:
(a) zinc oxide,
(b) aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, wherein the mass ratio of aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve is 0.01～100: 1
(c) oxide carrier, and
(d) promoter metals;
Take the weight of adsorbent composition as benchmark, aluminophosphate molecular sieve in the described adsorbent composition (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, 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 is 10～84 % by weight.
The invention provides the preparation method that described adsorbent composition also is provided, comprising: the step that forms the particle comprise zinc compound, promoter metals compound, oxide carrier component and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, roasting, 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, in hydrocarbon oil desulphurization adsorbing agent, introduce described composite molecular screen, two kinds of molecular sieve synergies, and be equipped with other suitable component, make this adsorbent have the preferably raising octane number ability of adsorption desulfurize ability and Geng Gao, this adsorbent is used for the hydrocarbon ils adsorption desulfurize, has preferably desulfurized effect, and can improve better octane number.
The specific embodiment
According to adsorption-desulfurization sorbent composition provided by the invention, described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, wherein aluminophosphate molecular sieve preferably has the AEL structure, described aluminophosphate molecular sieve is preferably one or more of aluminophosphate molecular sieve that element replaces, 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 aluminophosphate molecular sieve that described element replaces; Be substituted by example with the Si element, described aluminophosphate molecular sieve is preferably a kind of among SAPO-11, SAPO-5, SAPO-41 and the SAPO-31.In described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, wherein MFI structure Si-Al molecular sieve is for example one or more in ZSM-5 molecular sieve, ZRP Series Molecules sieve and the ZSP Series Molecules sieve of rare earth and/or phosphorus modification of ZSM-5, HZSM-5, element modified ZSM-5 molecular sieve.The silica alumina ratio (mol ratio of silica and aluminium oxide) of MFI structure Si-Al molecular sieve wherein is 15～300; The mass ratio of aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve is 0.01～100: 1, be preferably 0.05～20: 1, the rate of charge the when ratio of the mass ratio of described aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve can be according to preparation described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen calculates.
Described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is core-shell molecular sieve, comprise MFI structure Si-Al molecular sieve and aluminophosphate molecular sieve, MFI structure Si-Al molecular sieve is nuclear, aluminophosphate molecular sieve is in shell, and this shell is in the outer surface of MFI structure Si-Al molecular sieve.Described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen can be purchased or according to the preparation of existing method, for example, and [.ZSM-5 (the nuclear)/AlPO such as Zhang Zhe
4Synthetic and the Catalytic Cracking Performance of-5 (shell) binary structure zeolite. catalysis journal, 2003,24 (11): 856-860; Li Chunyi etc. a kind of synthetic method of core-shell structure compound molecular sieve and application .CN101279288.2008-04-30].The preparation method of described molecular sieve is as follows: will be synthetic or through the MFI of modification structure Si-Al molecular sieve, put into by a certain percentage in the synthetic colloidal dispersion of aluminophosphate molecular sieve, then the synthesis condition by aluminophosphate molecular sieve carries out crystallization, makes the composite molecular screen of aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear).Wherein the mass ratio of aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve be preferably 0.05: 1～20: 1, the content of alkali metal oxide preferably is no more than 0.2 % by weight in described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen.Aluminophosphate molecular sieve in described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is SAPO-11 for example, SAPO-31, SAPO-41, SAPO-5, CuAPO-31, ZrAPO-11, VAPO-11, SAPO-31MgAPO-5, CoAPO-41, among the CoAPSO-11 one or more, described MFI molecular sieve is for example: ZSM-5, ZRP, in the ZSP molecular sieve one or more, described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is the SAPO-5/ZSM-5 composite molecular screen for example, the SAPO-11/ZSM-5 composite molecular screen, the SAPO-11/ZRP composite molecular screen, the ZrAPO-11/ZSP composite molecular screen, the SAPO-31/ZSM-5 composite molecular screen, the VAPO-11/ZSM-5 composite molecular screen, the SAPO-41/ZRP composite molecular screen, the CuAPO-31/ZSP composite molecular screen, the MgAPO-5/ZRP composite molecular screen, the CoAPSO-11/ZSM-5 composite molecular screen, the CoAPO-41/ZSM-5 composite molecular screen, in the SAPO-41/ZSM-5 composite molecular screen one or more.
Take the gross weight of adsorbent composition as benchmark, the content of aluminophosphate molecular sieve in the described adsorbent composition (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is preferably 3～30 % by weight in the gross weight of described aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve, more preferably 5～20 % by 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; 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 the 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 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.Described 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, take the weight of adsorbent composition as benchmark, aluminophosphate molecular sieve (shell) in the described adsorption-desulfurization sorbent composition/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen 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 10～80 % by weight.The content of described zinc oxide is preferably 15～85 % by weight, more preferably 25～70 % by weight; Described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen content is preferably 3～30 % by weight, more preferably 5～25 % by weight.
Adsorbent composition preparation method provided by the invention, the particle that can prepare by any method zinc compound, oxide carrier source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen and metal promoted immunomodulator compounds, then again roasting after roasting or the drying, then reduce, for example can prepare by the following method described adsorbent composition:
(1) zinc oxide source, oxide carrier source, promoter metals compound and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is mixed, add or do not add entry;
(2) moulding of step (1) gained mixture is formed particle, if prepared mixture is slurries, the slurries spray-drying can be formed particle;
(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; Described reduction is included in 35 to 850 ℃ the temperature range and carries out the long enough time in 0.1 to 10MPa the pressure limit to form required reduction valence state, and the preferred recovery time is 30 to 180 minutes.
A kind of preferred preparation method of adsorbent composition provided by the invention may further comprise the steps:
(a) zinc oxide source, oxide carrier source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is 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.Wherein:
Zinc oxide source described in the step (a) can be there is or can be converted into zinc oxide in the zinc oxide form under preparation condition described herein one or more zinc compound forms, 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 the 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 the 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 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 described silicon oxide colloid is Ludox, silicon gel for example; The described 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 diatomite.Described alumina source can be the aluminium organic alcohol compound such as the inorganic compounds such as aluminium oxide form or one or more aluminum contained compound form such as aluminum nitrate that can be converted into aluminium oxide, aluminium chloride, aluminum sulfate and aluminium isopropoxide, 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; Described alumina source is one or more in aluminium colloidal sol, boehmite, gama-alumina or the η-aluminium oxide for example.In described zirconia source such as zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate and the zirconium sulfate etc. one or more.In described titania source such as titanium dioxide powder, titanium tetrachloride, Titanium Nitrate and the tetra-n-butyl titanate etc. one or more.Described silica-alumina (amorphous aluminum silicide) source for example Alusil maybe can generate silicon source and aluminium source mixture such as 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, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen 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 continuous mixing machine, impact-extrusion type mixer.If the gained mixture is the wet mixture form, can makes described wet mixture multiviscosisty, then by granulating it granulated, then drying and roasting.Described zinc oxide source, oxide source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen mixes when forming dough or paste mixture; can make described mixture moulding make grain, extrudate, sheet, ball, pill or microsphere particle in the step (b); the cylindrical extrudate of any suitable length of preferred diameter 0.75 to 13mm is then with gained particle drying and roasting.When described mixture was the slurries form, by described slurries spray-drying is made it granulating, for example spray-drying formation granularity was the microballoon of 20 to 500 μ m, then makes described microballoon roasting or dry roasting in step (c) in the step (b).Preferably form the adsorbent composition particle by spray-drying.Can make and comprise zinc oxide source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, oxide source and form with methods known in the art and be suitable for spray-dired mix slurry, 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, if be organic acid, then be preferably carboxylic acid, if acid constituents is 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.In acid constituents the consumption of acid usually based on about 0.01 volume % of the cumulative volume of acid constituents to about 20 volume %.The solid content that zinc oxide source, oxide carrier source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen and water is mixed with slurries is preferably 20～50 % by weight.Dry described particle temperature is preferably 50～180 ℃ in the step (c), and the temperature of the described 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.Described dipping makes in the final resulting adsorbent composition, take the gross weight of adsorbent composition as benchmark, and take the promoter component content of metal as 5～50 % by weight, preferred 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, 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.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 the nickelous sulfate, the compound of cobalt can be one or more in cobalt nitrate, cobalt chloride and the cobaltous sulfate, cupreous compound can be selected from one or more in copper nitrate, the chlorination copper and copper sulfate, and the compound of iron can be selected from one or more in ferric sulfate, iron chloride, ferric nitrate and the ferrous salt, 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.
In the step (e) step (d) is flooded impregnated granules drying and the roasting that obtains after the promoter metal, dry described particle temperature is preferably 50 to 180 ℃, the described particle temperature scope of roasting is preferably 200 to 850 ℃, preferred 0.5 to 6 hour of roasting time.
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, organic sulfide removal compound therefrom when providing the also original cost promoter metals of such amount so that resulting composition under the adsorption desulfurize condition, for example to contact with cracking gasoline under the S-Zorb adsorption desulfurize condition.Described 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 ℃, pressure is to carry out enough Long contact time in 0.1 to the 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.Described reduction makes the metallic promoter agent after the reduction exist with reduction-state basically, and preferred 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 the hydrogen adsorption desulfurize, is particularly useful for the S-Zorb process for adsorption desulfuration.When being used for adsorption desulfurize, at least part of described promoter metals exists with reduction-state in the described adsorbent composition.If used adsorbent composition then before use should be through reduction not through reduction, described reduction can take aforementioned method of reducing to carry out.
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 250～480 ℃, 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 %, hydrogen and hydrocarbon oil feed mol ratio are generally 0.1～10: 1, be preferably 0.2～3.0: 1.
Gasolene desulfurizing method by adsorption provided by the invention is applicable to the hydrocarbon ils adsorption desulfurize.Described hydrocarbon ils can be the hydrocarbon fuel oil of any sulfur-bearing, for example be cracking gasoline or diesel fuel, wherein said cracking gasoline refers to that boiling range is 40 ℃ to 210 ℃ hydrocarbon or its any cut, usually 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.Can be with described cracking gasoline fractionation and/or hydrotreatment before desulfurization when in some cases, implementing to be used as raw material among the present invention.
Term used herein " sulphur " refers to any type of element sulphur or the sulfur-containing compound that usually exists in hydrocarbon-containifluids fluids such as cracking gasoline or diesel oil.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 methyldibenzothiophene, and the normal larger thiophenes of molecular weight that exists in the diesel fuel.
The present invention is further described for the following examples.
Embodiment 1
Get 3.79 kilograms Ludox (Qingdao Marine Chemical Co., Ltd., SiO
2Percentage by weight is 25.5 % by weight, Na
2O is 0.3 % by weight, and the pH value is 9.0), 0.137 kilo sulfuric acid aluminium (technical grade, wherein Al
2O
3Weight content be 24%), 11.60 kilograms of deionized waters, 0.287 kilogram of n-butylamine (technical grade, n-butylamine content 98 % by weight) and 0.0627 kg of hydrogen sodium oxide molybdena (technical grade, sodium hydrate content 98.5 % by weight) join in the colloid generating kettle, the mol ratio of material is Na
2O: SiO
2: Al
2O
3: n-butylamine: H
2O=3: 60: 1: 12: 2000, stir and add sulfuric acid (technical grade, H after 30 minutes
2SO
4Content 98 % by weight) regulation system pH value is at 9-11, then under stirring condition, be warming up to 160 ℃ after steady temperature crystallization 32 hours, do not carry out filtration treatment, directly ZSM-5 product and mother liquor in the reactor are stirred, form mixture HA; With 1.888 kilograms of boehmites (technical grade, Al
2O
3Content 65%), 1.24 kilograms of triethylamines (technical grade, triethylamine content 98 % by weight), 2.83 kilograms of phosphoric acid (technical grade, H
3PO
4Content 85 % by weight), 2.20 kilograms of Ludox (Qingdao Marine Chemical Co., Ltd., SiO
2Content is 25.5 % by weight, Na
2O content is 0.05 % by weight, and the pH value is 3.5) and suitable deionized water mix, molar ratio of material is TEA: SiO
2: Al
2O
3: P
2O
5: H
2O=5: 5: 5: 6: 60, obtain gel NB, it is added among the mixture HA, and strong agitation is made uniform gel, and changes in the stainless steel autoclave, 30 hours synthetic composite molecular screens of crystallization under 180 ℃ of stirrings, the ammonium sulfate washing that the product that obtains is 1.5 % by weight with 50 kilograms of concentration after filtering, washed twice is filtered after each washing, then 120 ℃ lower dry 6 hours the SAPO-5/ZSM-5 composite molecular screen, be designated as FA (Na wherein
2O content is 0.18 % by weight, the Si of SAPO-5: Al: P mol ratio=5: 10: 12, the SiO among the ZSM-5
2/ Al
2O
3Mol ratio is that the mass ratio of 50, SAPO-5 and ZSM-5 is 4: 1).
With 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 kilogram zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along zinc industry Co., Ltd product), 3.5 kilogram 18 water aluminum sulfate (content 99.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group) and the SAPO-5/ZSM-5 composite molecular screen (FA) of 3.4 kilograms of aforementioned preparations put into grinding machine for grinding 15 minutes and form mixture, this mixture is mixed making beating with deionized water, getting solid content is the slurries of 30 % by weight, add concentration and be 15.58 kilograms of the acetic acid of 3 % by weight, stirred 1.5 hours, spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier A.With 15.3 kilograms of cobalt nitrate hexahydrates (content 99.0 % by 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 after flooding; with the granulate mixture behind the described dipping 150 ℃ of dryings 2 hours; in 600 ℃ of lower roastings 2 hours, obtain sample A again.With sample A under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition A1.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-5/ZSM-5: Co=1: 1: 6: 1: 1 (weight ratio, lower same).
Wherein, among the A1, the SAPO-5/ZSM-5 composite molecular screen accounts for 10 % by weight, and zinc oxide accounts for 60 % by weight, and oxide carrier accounts for 20 % by weight, and metallic promoter agent accounts for 10 % by weight.
Embodiment 2
With 0.482 kilogram of cobalt nitrate hexahydrate (content 99.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 2.342 kilograms of boehmites (technical grade, Al
2O
3Content 65%), 3.817 kilograms of phosphoric acid (technical grade, purity 85%), 1.692 kilograms of di-n-propylamines (DPA, content 99 % by weight) and 29.80 kilograms of deionized waters are mixed molar ratio of material CoO: Al
2O
3: P
2O
5: amine: water=1: 9: 10: 10: 1000 ratio makes the synthetic liquid of aluminium phosphate molecular sieve after stirring.With 4 kilograms of phosphorus contents be 1.2 % by weight ZRP molecular sieve finished product (China Petrochemical Industry's catalyst asphalt in Shenli Refinery product, SiO
2/ Al
2O
3Mol ratio is 28, Na
2O content is 0.15 % by weight, solid content is 92 % by weight) be added in the synthetic liquid of the aluminium phosphate molecular sieve that makes, under the condition of airtight stirring 180 ℃ of crystallization 24 hours, filter, filter cake is with 10 times of deionized water washings to filter cake weight, filtration and dry the SAPO-11/ZRP composite molecular screen (Co among the CoAPO-11: Al wherein: P mol ratio=1: 9: 10, the SiO among the ZRP
2/ Al
2O
3Mole is that the mass ratio of 28, CoAPO-11 and ZRP is 1: 1).
With 30.1 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 5.5 kilograms of CoAPO-11/ZRP composite molecular screens put into grinding machine for grinding and formed mixture in 15 minutes, with this mixture and 86.3 kilograms of acidic silicasol (SiO
2Content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd. product, pH value 2.1) and deionized water mix and to pull an oar, stirred 2 hours, and got the slurries that solid content is 30 % by weight, then spray drying forming, 150 ℃ of dryings are after 4 hours, 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier B.With 68.0 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) being dissolved in 4.6 kilograms of temperature is to obtain maceration extract in 85 ℃ the hot deionized water; the carrier B of 23 kilograms of gained is flooded with this maceration extract, produce the granulate mixture after flooding.Granulate mixture behind the described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample B again.The above sample B that obtains was obtained adsorbent composition B1 in 1 hour with hydrogen reducing under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa, the nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.Finally make and consist of: SiO
2: ZnO: CoAPO-11/ZRP: Ni=22: the adsorbent composition of 30: 5: 13 (weight ratio).
Wherein, adsorbent composition B1 consists of the CoAPO-11/ZRP molecular sieve and accounts for 7.14 % by weight, and zinc oxide accounts for 42.86 % by weight, and oxide carrier accounts for 31.43 % by weight, and metallic promoter agent accounts for 18.57 % by weight.
Embodiment 3
Adjust the raw material proportioning according to the method for embodiment 2, the preparation ZrAPO-11/ZSP composite molecular screen (Zr among the ZrAPO-11: Al wherein: P mol ratio=1: 20: 20, the SiO among the ZSP
2/ Al
2O
3Mol ratio is 45, and phosphorus content is that the mass ratio of 1.5%, ZrAPO-11 and ZSP is 5: 1).
7.1 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 0.88 kilogram of ZrAPO-11/ZSP composite molecular screen are put into grinder to be ground and forms the first mixture; With 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.) stirring gets the second mixture after 1 hour, the first mixture, the second mixture mixed with deionized water 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 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as support C.Use maceration extract [by 2.7 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight the support C of 15.2 kilograms of gained; 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 the granulate mixture behind the dipping.Granulate mixture behind the described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample C again.With sample C under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition C1.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/ZSP: Ni: Co=4: 3: 8: 1: 2: 1.
Wherein, among the C1, the ZrAPO-11/ZSP molecular sieve accounts for 5.26 % by weight, and zinc oxide accounts for 42.11 % by weight, and oxide carrier accounts for 36.84 % by weight, and metallic promoter agent accounts for 15.79 % by weight.
Embodiment 4
The preparation SAPO-31/ZSM-5 composite molecular screen (Si among the SAPO-31: Al wherein: P mol ratio=1: 10: 10, the SiO among the ZSM-5
2/ Al
2O
3Be 50, La
2O
3Content is that the mass ratio of 1.5%, SAPO-31 and ZSM-5 is 6: 1).
With 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 kilogram zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 0.57 kilogram of SAPO-31/ZSM-5 composite molecular screen put into grinding machine for grinding and formed mixture in 15 minutes, then pull an oar in the salpeter solution that this mixture to be joined 42 kilograms of concentration be 0.3 % by weight, and adding deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1 hour, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier D.Use nickel nitrate solution [with 10.1 kilogram of six water nickel nitrate (content 98.0 % by weight 15 kilograms of above-mentioned carrier D; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 3.1 kilograms of heat (90 ℃) deionized water obtain] dipping, produce the granulate mixture behind the dipping.Granulate mixture behind the described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample D again.With the above sample D that obtains under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition D1 provided by the invention.Resulting adsorbent composition consist of ZrO
2: Al
2O
3: ZnO: SAPO-31/ZSM-5: Ni=3: 2: 7: 1: 2 (weight ratios).
Wherein, the SAPO-31/ZSM-5 molecular sieve accounts for 6.67 % by weight, and zinc oxide accounts for 46.67 % by weight, and oxide carrier accounts for 33.33 % by weight, and metallic promoter agent accounts for 13.33 % by weight.
Embodiment 5
Adjust raw material and proportioning with reference to the method for embodiment 1 and prepare the VAPO-11/ZSM-5 composite molecular screen (V among the VAPO-11: Al wherein: P mol ratio=1: 10: 10, the SiO among the ZSM-5
2/ Al
2O
3Mol ratio is that 60, La content is that 1.2%, P content is that the mass ratio of 1.0%, VAPO-11 and ZSM-5 is 8: 1).
With 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 zinc industry Co., Ltd product) and 8.2 kilograms of VAPO-11/ZSM-5 composite molecular screens put into grinder and mix 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 mix, stirred 1.5 hours, and got the slurries that solid content is 30 % by weight, spray drying forming, 150 ℃ of dryings are after 4 hours, 650 ℃ of lower 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 % by 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 described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample E again.With the sample E of above preparation under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition E1.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/ZSM-5: Co=3: 2: 5: 2: 2 (weight ratios).
Wherein, among the gained adsorbent E1, the VAPO-11/ZSM-5 molecular sieve accounts for 14.29 % by weight, and zinc oxide accounts for 35.71 % by weight, and oxide carrier accounts for 35.71 % by weight, and metallic promoter agent accounts for 14.29 % by weight.
Embodiment 6
The preparation SAPO-41/ZRP composite molecular screen (Si among the SAPO-41: Al wherein: P mol ratio=3: 20: 20, the SiO among the ZRP
2/ Al
2O
3Be 29, Re
2O
3Content is that 1.2%, P content is that the mass ratio of 1.2%, SAPO-41 and ZRP-5 is 1: 10).Can be according to the method preparation of embodiment 2, corresponding adjustment raw material, proportioning.
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 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 3.3 kilograms of SAPO-41/ZRP composite molecular screens put into grinder and grind and formed mixture in 20 minutes, with 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) mixes making beating, and then mix with deionized water, get the slurries that solid content is 30 % by weight, stir spray drying forming after 1.5 hours, 150 ℃ of dryings are after 4 hours, 650 ℃ of lower 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 % 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) 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 described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample F again.With sample F under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition F1.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: SAPO-41/ZRP: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratio).
Wherein, the SAPO-41/ZRP molecular sieve accounts for 11.76 % by weight, and zinc oxide accounts for 35.29 % by weight, and oxide carrier accounts for 35.29 % by weight, and metallic promoter agent accounts for 17.65 % by weight.
Embodiment 7
According to the method for embodiment 2, adjust raw material and proportioning, the preparation CuAPO-31/ZSP composite molecular screen (Cu among the CuAPO-31: Al wherein: P mol ratio=1: 20: 20, the SiO among the ZSP
2/ Al
2O
3Mol ratio is that 48, P content is that 1.4%, Fe content is that the mass ratio of 1.5%, CuAPO-31 and ZSP is 20: 1).
With 5.5 kilograms of titanium oxide (TiO
2Content 99.5 % by weight, Beijing Hairong Huazheng Technology Co., Ltd.), 8.3 kilograms of zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 2.2 kilograms of CuAPO-31/ZSP composite molecular screens put into the grinder rear formation mixture of pulverizing, with 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, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) mixing making beating, and then mix with deionized water, getting solid content is the slurries of 30 % by weight, stirs after 1 hour spray drying forming, 150 ℃ of dryings are after 4 hours, 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m again, be designated as carrier G.Carrier G 15.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight that are dissolved in 4.6 kilograms of heat (90 ℃) deionized water with 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 produces the granulate mixture after flooding.Granulate mixture behind the described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample G again.With the above sample G that makes under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition G1.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-31/ZSP: Ni: Co=5: 3: 2: 12: 2: 2: 3 (weight ratio).
Wherein, the CuAPO-31/ZSP molecular sieve accounts for 6.90 % by weight, and zinc oxide accounts for 41.38 % by weight, and oxide carrier accounts for 34.48 % by weight, and metallic promoter agent accounts for 17.24 % by weight.
Embodiment 8
The preparation MgAPO-5/ZRP composite molecular screen (Mg among the MgAPO-5: Al wherein: P mol ratio=1: 20: 25, the SiO among the ZRP
2/ Al
2O
3Mol ratio is that 28, P content is that the mass ratio of 1.4%, MgAPO-5 and ZRP is 1: 20).According to the method preparation of embodiment 2, corresponding adjustment raw material, proportioning.
With 6.2 kilograms of expanded perlite (SiO
2Content 70.8 % by weight, Al
2O
3Content 12.6 % by weight, Pingqiao District sky, District, Xinyang Area, Henan Province city Li Pengruntuchang), 19.8 kilogram zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 6.6 kilograms of MgAPO-5/ZRP composite molecular screens put into grinder and grind the formation mixture, (alumina content is 21.2 % by weight with this mixture and 27.4 kg aluminium colloidal sols, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) and deionized water mix making beating, getting solid content is the slurries of 30 % by weight, stirred 1 hour, spray drying forming, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as 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 % by 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 described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample H again.With the sample H of above preparation under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition H1.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-5/ZRP: Co=2: 3: 9: 3: 4 (weight ratios).
Wherein, the MgAPO-5/ZRP molecular sieve accounts for 14.29 % by weight, and zinc oxide accounts for 42.86 % by weight, and oxide carrier accounts for 23.81 % by weight, and metallic promoter agent accounts for 19.05 % by weight.
Embodiment 9
With reference to the method for embodiment 1, adjust the raw material proportioning, the preparation CoAPSO-11/ZSM-5 composite molecular screen (Co among the CoAPSO-11: Si: Al wherein: P mol ratio=1: 1: 20: the SiO among 20, the ZSM-5
2/ Al
2O
3Mol ratio is that 30, P content is that the mass ratio of 1.4%, CoSAPO-11 and ZSM-5 is 2: 1).
With 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), 9.1 kilograms of Zinc oxide powder (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 0.55 kilogram of CoAPSO-11/ZSM-5 composite molecular screen put into the grinder rear formation mixture of pulverizing, with this mixture and 29.88 kilograms of acidic silicasol (SiO
2Content 25.5% % by 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 lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier K; With 11.7 kilogram of six water nickel nitrate (content 98.0 % by 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 described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample K again.With the sample K of above preparation under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition K1.The nickel component of wherein said adsorbent composition is reduced to zero-valent state basically.The proportioning of the adsorbent composition of finally making is SiO
2: MgO:: ZnO: CoAPSO-11/ZSM-5: Ni=14: 2: 33: 2: 9 (weight ratios).
Wherein, the CoAPSO-11/ZSM-5 molecular sieve accounts for 3.33 % by weight, and zinc oxide accounts for 55 % by weight, and oxide carrier accounts for 26.67 % by weight, and metallic promoter agent accounts for 15 % by weight.
Embodiment 10
The preparation CoAPO-41/ZSM-5 composite molecular screen (Co among the CoAPO-41: Al wherein: P mol ratio=1: 8: 8, the SiO among the ZSM-5
2/ Al
2O
3Mole is 80, Re
2O
3Content is that 1.2%, P content is that the mass ratio of 1.2%, SAPO-41 and ZSM-5 is 10: 1).Can be according to the method preparation of embodiment 2, corresponding adjustment raw material, proportioning.
With 8.8 kg of hydrogen zirconia (ZrO
2Content 37.5 amount %, Chemical Reagent Co., Ltd., Sinopharm Group), 9.9 kilogram zinc oxide (ZnO content 99.8 % by weight, Zibo sea is along zinc industry Co., Ltd product) and 3.3 kilograms of SAPO-41/ZSM-5 composite molecular screens put into grinder and grind and formed mixture in 20 minutes, (alumina content is 21.2 % by weight with this mixture and 31.3 kg aluminium colloidal sols, China Petrochemical Industry's catalyst asphalt in Shenli Refinery product) mixes making beating, and then mix with deionized water, getting solid content is the slurries of 30 % by weight, stir spray drying forming after 1.5 hours, 150 ℃ of dryings are after 4 hours, again 650 ℃ of lower roastings 2 hours, make the carrier granular that particle diameter is 40～200 μ m, be designated as carrier granular F.With 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) 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 described dipping 150 ℃ of dryings 2 hours, in 600 ℃ of lower roastings 2 hours, is obtained sample L again.With sample L under 530 ℃ and Hydrogen Vapor Pressure 1.4MPa with hydrogen reducing 1 hour, obtain adsorbent composition M1.The cobalt of wherein said adsorbent composition and nickel component are reduced to zero-valent state basically.ZrO in the gained adsorbent composition
2: Al
2O
3: ZnO: CoAPO-41/ZRP: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratio).
Wherein, the CoAPO-41/ZSM-5 molecular sieve accounts for 11.76 % by weight, and zinc oxide accounts for 35.29 % by weight, and oxide carrier accounts for 35.29 % by weight, and metallic promoter agent accounts for 17.65 % by weight.
Comparative Examples 1
Method according to CN102343249A prepares adsorbent, and with 4.43 kilograms of Zinc oxide powders, 1.00 kilograms of SAPO-31 and 4.57 kilograms of deionized waters are mixed, and stir the mixed serum that obtains zinc oxide and SAPO-31 after 30 minutes.
The rectorite of getting 1.37 kilograms of boehmites and 2.75 kilograms under agitation mixes, and then adds after 4.6 kilograms of deionized waters mix, the hydrochloric acid that adds 360 milliliters of 30wt.% stir acidifying be warming up to after 1 hour 80 ℃ aging 2 hours.After adding the mixing of zinc oxide slurries, stir and obtained carrier pulp in 1 hour, carrier pulp is carried out spray drying forming, 180 ℃ of dryings are after 1 hour, again 635 ℃ of lower roastings 1 hour, make the carrier granular that particle diameter is 40～200 μ m, with 3.2 kilograms adsorbing agent carriers with 3.53 kilogram of six water nickel nitrate (content 98.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 0.6 kilogram of deionized water solution dipping, the mixture that obtains after 4 hours, 1 hour can make adsorbent precursor in 635 ℃ of lower roastings of air atmosphere through 180 ℃ of dryings.Adsorbent precursor reductase 12 in 425 ℃ hydrogen atmosphere hour can be made adsorbent composition, be designated as L1.The chemical composition of the adsorbent composition of finally making is: zinc oxide content 44.3wt.%, rectorite content are 20.6wt.%, and SAPO-31 content is 7.0wt.%, and alumina binder is 10.0wt.%, and metallic nickel content is 18.1wt.%,
Comparative Examples 2
Method according to CN102343249A prepares adsorbent composition L2 with boehmite, kaolin, zinc oxide, CoAPO-11 and six water nickel nitrates, the final chemical composition of the adsorbent composition of making is: zinc oxide content 44.3wt.%, rectorite content is 20.6wt.%, CoAPO-11 content is 7.0wt.%, alumina binder is 10.0wt.%, metallic nickel content is 18.1wt.%
Comparative Examples 3
Prepare material ratio according to existing method preparation take acidic silicasol, zinc oxide and nickel nitrate as raw material and be SiO
2: ZnO: Ni=22: 30: 13 adsorbent.Upper sample of sorbent and CoAPO-11/ZRP composite molecular screen (with embodiment 2) molecular sieve mechanical mixture is even, make the final material ratio and be: SiO
2: ZnO: CoAPO-11: Ni=22: the adsorbent composition L3 of 30: 5: 13 (weight ratio).
Wherein, the CoAPO-11/ZRP molecular sieve accounts for 7.14 % by weight, and zinc oxide accounts for 42.86 % by weight, and oxide carrier accounts for 31.43 % by weight, and metallic promoter agent accounts for 18.57 % by weight.
Comparative Examples 4
Prepare material ratio according to existing method preparation take acidic silicasol, zinc oxide and nickel nitrate as raw material and be SiO
2: ZnO: Ni=22: 30: 13 adsorbent.Upper sample of sorbent and ZRP molecular sieve (with embodiment 2) mechanical mixture is even, make the final material ratio and be: SiO
2: ZnO: ZRP: Ni=22: the adsorbent composition L4 of 30: 5: 13 (weight ratio).
Wherein, the ZRP molecular sieve accounts for 7.14 % by weight, and zinc oxide accounts for 42.86 % by weight, and oxide carrier accounts for 31.43 % by weight, and metallic promoter agent accounts for 18.57 % by weight.
Comparative Examples 5
P mol ratio=1: 9: 10), ZRP molecular sieve (with embodiment 2), zinc oxide and nickel nitrate prepare adsorbent final material ratio as SiO as raw material according to existing method, take acidic silicasol, CoAPO-11 molecular sieve (Co: Al:
2: ZnO: CoAPO-11: ZRP: Ni=44: 60: 5: 5: the adsorbent composition L5 of 26 (weight ratios).
Wherein, CoAPO-11 and ZRP molecular sieve account for 7.14 % by weight (both content are respectively 3.57 % by weight) altogether, and zinc oxide accounts for 42.86 % by weight, and oxide carrier accounts for 31.43 % by weight, and metallic promoter agent accounts for 18.57 % by weight.
The adsorbent composition that the adsorbent composition that embodiment 1～10 is made and Comparative Examples 1～5 make carries out reaction evaluating.
Estimate the sulphur that the gasoline stocks (40～210 ℃ of boiling ranges) adopt contains 1100 μ g/g (based on the weight content of the sulfur-containing compound of described 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 34.8% (volume fraction), octane number RON is that 91.3, MON is 79.9.The absorbent particles (100～350 order) that the adsorbent composition that 10g such as above embodiment 1～9 are made and Comparative Examples 1～5 make places respectively stainless steel tube (diameter (interior warp) is 13mm) to carry out the adsorption reaction evaluation, appreciation condition is: 410 ℃ of temperature, pressure 1.4MPa, hydrogen partial pressure is that (used hydrogen is plant hydrogen to 0.6MPa, certified products, H
2Content is 99 volume %), gasoline volume space velocity 4h
-1, adsorption time is 4 hours, for accurately characterizing out the performance of adsorbent in industrial actual motion, after reaction is finished adsorbent under 550 ℃, the processing of regenerating in the air atmosphere.Its reactivity worth was basicly stable after adsorbent carried out 6 circulations of reaction regeneration, judged with the stable adsorbent of reactivity worth again, and evaluation result sees 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;
Sulfur content in desulfurization degree (except the percentage of desulfuration)=(sulfur content in the gasoline after the sulfur content-desulfurization in the raw material)/raw material * 100%.
By as seen from Table 1, adsorption-desulfurization sorbent composition provided by the invention can improve the octane number of gasoline, has higher raising octane number effect, has preferably desulfurized effect, and desulfurization degree is higher, can reach more than 95%, even can surpass 98%.
Claims (16)
1. hydrocarbon oil desulphurization adsorbing agent composition, described adsorbent composition comprises:
(a) zinc oxide,
(b) aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, wherein the weight ratio of phosphate molecule sieve and MFI structure molecular screen is 0.01～100,
(c) oxide carrier, and
(d) promoter metals;
Take the weight of adsorbent composition as benchmark, the content of aluminophosphate molecular sieve in the described adsorbent composition (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen 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; Take the content of oxide oxide carrier as 10～80 % by weight.
2. composition according to claim 1, it is characterized in that, the content of aluminophosphate molecular sieve (shell) described in the described adsorption-desulfurization sorbent composition/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is 2～25 % by weight, and the content of described zinc oxide is 25～75 % by weight.
3. composition according to claim 1 and 2 is characterized in that, the content of described metallic promoter agent is 5～25 % by weight.
4. adsorbent composition according to claim 1, it is characterized in that, described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, aluminophosphate molecular sieve wherein is one or more of the aluminophosphate molecular sieve that replaces of element, 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 aluminophosphate molecular sieve that described element replaces; The silica alumina ratio of MFI structure Si-Al molecular sieve wherein is 15～300; The weight ratio of aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve is 0.05～20.
5. adsorbent composition according to claim 4, it is characterized in that, in described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen, described aluminophosphate molecular sieve is one or more among SAPO-11, SAPO-31, SAPO-41, SAPO-5, CuAPO-31, ZrAPO-11, VAPO-11, CoAPO-41, SAPO-31, MgAPO-5, the CoAPSO-11; Described MFI structure Si-Al molecular sieve is one or more in ZSM-5 molecular sieve, ZRP Series Molecules sieve and the ZSP Series Molecules sieve.
6. adsorbent composition according to claim 5 is characterized in that, described ZSM-5 molecular sieve is one or more of ZSM-5 molecular sieve of HZSM-5, rare earth and/or phosphorus modification.
7. each described adsorbent composition is characterized in that according to claim 1～6, at least a nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and the vanadium of being selected from of described promoter metals.
8. each described adsorbent composition according to claim 1～6, wherein said promoter metals is nickel and/or cobalt.
9. adsorbent 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 the natural porous material.
10. the preparation method of each described adsorbent composition of claim 1～9 comprises:
(a) zinc oxide source, oxide carrier source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is mixed;
(b) step (a) gained compound particles granulation is formed particle;
(c) particle drying that step (b) is obtained, then roasting;
(d) with the particle after the roasting of promoter metals compound impregnation steps (c) gained;
(e) will carry out roasting after step (d) the gained impregnated granules drying;
(f) the product reduction that step (e) is obtained.
11. method according to claim 10, it is characterized in that, in the step (a), zinc oxide source, oxide carrier source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen and water mixed-shaped are become slurries, stirred 0.5～2 hour.
12. method according to claim 10 is characterized in that, step (c) and (e) described in dry baking temperature be 50～180 ℃; Step (c) and (e) in the described particle temperature of roasting be 200～850 ℃.
13. each described method is characterized in that according to claim 10～12, 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; Described oxide source is in diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica, silicic acid, sodium metasilicate, ammonium silicate and the ethyl orthosilicate (or methyl esters), in 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 the rectorite one or more.
14. the preparation method of each described adsorbent composition of claim 1～9 comprises:
(1) zinc oxide source, oxide carrier source, promoter metals compound and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (nuclear) composite molecular screen is formed mixture;
(2) with step (1) gained mixture forming particle;
(3) with the particle drying of step (2), then roasting;
(4) the composition reduction that step (3) is obtained.
15. 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 1～9.
16. in accordance with the method for claim 15, it is characterized in that described hydrocarbon ils is gasoline or diesel oil.
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