CN103372416B - A kind of adsorbent composition for desulfurization of hydrocarbon oil and preparation method thereof - Google Patents
A kind of adsorbent composition for desulfurization of hydrocarbon oil and preparation method thereof Download PDFInfo
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Abstract
A kind of adsorbent composition for desulfurization of hydrocarbon oil and preparation method thereof, described adsorbent composition contains metallic promoter agent, zinc oxide, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) nucleocapsid composite molecular screen and oxide.Described adsorbent composition preparation method, comprises the step that formation comprises the mixture of zinc compound, promoter metals compound, oxide carrier component and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, roasting, reduction.Described adsorbent composition is used for hydrocarbon ils adsorption desulfurize, has good desulfurized effect, has and better improves octane number effect.
Description
Technical field
The present invention relates to the adsorbent composition and preparation method thereof for desulfurization of hydrocarbon oil.
Background technology
Compare with hydrogasoline with direct steaming gasoline, in FCC gasoline, the content of sulphur, alkene, aromatic hydrocarbons is higher, and stability is poor, easy generation 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, the environmental consciousness of people 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] to this has been introduction.Wherein, S-Zorb is a kind of adsorption desulfurize technology of facing hydrogen, has good gasoline desulfur effect, and the decline of octane number (organon and motor octane number) is less, but needs suitable adsorbent.
CN 1130253C and CN 1258396C disclose two kinds of similar S-Zorb adsorbents and production method thereof.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 passes through promoter, precursor dipping as nickel, nickel oxide or nickel oxide comprises the adsorbing agent carrier of zinc oxide, expanded perlite and aluminium oxide, then make the chemical valence of the promoter metals in the promoter metals sorbent support composition of gained reduce, prepare wear-resisting adsorbent composition.This adsorbent is applied to S-Zorb technology, and after desulfurization, the average octane number Δ (RON+MON)/2 of cracking gasoline declines.
Although above existing desulfuration adsorbent can reduce the sulfur content in cracking gasoline, the octane number of gasoline can not be improved, and the loss of octane number may be caused.
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, obviously can increase octane number, but not relate to how increasing octane number further.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of hydrocarbon ils adsorption-desulfurization sorbent with higher raising octane number ability, and the other technical problem that the present invention will solve is to provide 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 (core) 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;
With the weight of adsorbent composition for benchmark, aluminophosphate molecular sieve (shell) in described adsorbent composition/MFI structure Si-Al molecular sieve (core) composite molecular screen, content is 1 ~ 40 % by weight, is 5 ~ 50 % by weight in the content of element promoter metals; 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 is also provided, comprising: form the step comprising the particle of zinc compound, promoter metals compound, oxide carrier component and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, roasting, reduction.
The present invention further provides a kind of hydrocarbon ils desulfurizing method by adsorption, comprise the step making hydrocarbon ils and adsorbent contact, it is characterized in that, described adsorbent is adsorbent composition provided by the invention.
Adsorption-desulfurization sorbent composition provided by the invention, described composite molecular screen is introduced in hydrocarbon oil desulphurization adsorbing agent, two kinds of molecular sieve synergies, and be equipped with other suitable component, this adsorbent is made to have the raising octane number ability of good adsorption desulfurize ability and Geng Gao, this adsorbent is used for hydrocarbon ils adsorption desulfurize, has good desulfurized effect, and can improve octane number better.
Detailed description of the invention
According to adsorption-desulfurization sorbent composition provided by the invention, described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, wherein aluminophosphate molecular sieve preferably has AEL structure, described aluminophosphate molecular sieve is preferably one or more of aluminophosphate molecular sieve that element replaces, and in the aluminophosphate molecular sieve that described element replaces, substituted element is one or more in Li, Be, B, Si, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce; Be substituted by example with Si element, described aluminophosphate molecular sieve is preferably the one in SAPO-11, SAPO-5, SAPO-41 and SAPO-31.In described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, wherein MFI structure Si-Al molecular sieve be ZSM-5, HZSM-5, element modified ZSM-5 molecular sieve such as rare earth and/or P Modification ZSM-5 molecular sieve, ZRP Series Molecules sieve and ZSP Series Molecules sieve in one or more.The silica alumina ratio (mol ratio of silica and aluminium oxide) of MFI structure Si-Al molecular sieve is wherein 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 ratio of the mass ratio of described aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve can calculate according to rate of charge when preparing described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen.
Described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) 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 core, 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 (core) composite molecular screen can be purchased or prepare according to existing method, such as, and [.ZSM-5 (the core)/AlPO such as Zhang Zhe
4the synthesis of-5 (shell) binary structure zeolite and Catalytic Cracking Performance. 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: by synthetic or through the MFI structure Si-Al molecular sieve of modification, put in the synthesis colloidal dispersion of aluminophosphate molecular sieve by a certain percentage, then crystallization is carried out by the synthesis condition of aluminophosphate molecular sieve, the composite molecular screen of obtained aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core).Wherein the mass ratio of aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve is preferably 0.05: 1 ~ 20: 1, and in described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, the content of alkali metal oxide is preferably more than 0.2 % by weight.Aluminophosphate molecular sieve such as SAPO-11 in described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, SAPO-31, SAPO-41, SAPO-5, CuAPO-31, ZrAPO-11, VAPO-11, SAPO-31MgAPO-5, CoAPO-41, one or more in CoAPSO-11, described MFI molecular sieves is as ZSM-5, ZRP, one or more in ZSP molecular sieve, described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen such as SAPO-5/ZSM-5 composite molecular screen, SAPO-11/ZSM-5 composite molecular screen, SAPO-11/ZRP composite molecular screen, ZrAPO-11/ZSP composite molecular screen, SAPO-31/ZSM-5 composite molecular screen, VAPO-11/ZSM-5 composite molecular screen, SAPO-41/ZRP composite molecular screen, CuAPO-31/ZSP composite molecular screen, MgAPO-5/ZRP composite molecular screen, CoAPSO-11/ZSM-5 composite molecular screen, CoAPO-41/ZSM-5 composite molecular screen, one or more in SAPO-41/ZSM-5 composite molecular screen.
With the gross weight of adsorbent composition for benchmark, the content of aluminophosphate molecular sieve (shell) in described adsorbent composition/MFI structure Si-Al molecular sieve (core) composite molecular screen is preferably 3 ~ 30 % by weight with the total weight of described aluminophosphate molecular sieve and MFI structure Si-Al molecular sieve, is more preferably 5 ~ 20 % by weight.
According to adsorption-desulfurization sorbent composition provided by the invention, described promoter metals at least one is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium; Described promoter metals is preferably one or more of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium, is more preferably nickel and/or cobalt.Described promoter metals exists with reduction-state, and described reduction-state refers to that promoter metals major part is reduced to lower chemical valence, is preferably zeroth order.Be 5 ~ 50 % by weight in the content of element promoter metals, 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 the inorganic oxide carrier that adsorbent commonly uses, preferably, be selected from silica, aluminium oxide, zirconia, titanium oxide, amorphous aluminum silicide and natural porous material one or more, be more preferably in silica, zirconia, titanium oxide and natural porous material one or more.One or more mixture in described natural porous material such as expanded perlite, kaolin, imvite, sepiolite, diatomite and rectorite.When oxide is two or more mixture, the weight in the 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, with the weight of adsorbent composition for benchmark, aluminophosphate molecular sieve (shell) in described adsorption-desulfurization sorbent composition/MFI structure Si-Al molecular sieve (core) composite molecular screen content is 1 ~ 40 % by weight, is 5 ~ 50 % by weight in the content of element promoter metals; Be 10 ~ 80 % by weight in the content of zinc oxide zinc oxide; Be 10 ~ 80 % by weight with the content of oxide basis oxide carrier.The content of described zinc oxide is preferably 15 ~ 85 % by weight, is more preferably 25 ~ 70 % by weight; Described aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen content is preferably 3 ~ 30 % by weight, is more preferably 5 ~ 25 % by weight.
Adsorbent composition preparation method provided by the invention, the particle of zinc compound, oxide carrier source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen and metal promoted immunomodulator compounds can be prepared by any method, then roasting again after roasting or drying, then reduce, such as, can prepare described adsorbent composition by the following method:
(1) by zinc oxide source, oxide carrier source, promoter metals compound and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen mixing, add or do not add water;
(2) by shaping for step (1) gained mixture formation particle, if obtained mixture is slurries, slurries spraying dry can be formed particle;
(3) the particle roasting making step (2) obtain or dry roasting; Dry dry temperature is preferably 50 ~ 180 DEG C; The temperature of roasting is preferably 200 ~ 850 DEG C, and the time of roasting is preferably 0.5 ~ 6 hour;
(4) particle reduction after roasting step (3) obtained, obtains adsorbent composition; Carry out the long enough time in the temperature range that described reduction is included in 35 to 850 DEG C and in the pressure limit of 0.1 to 10MPa to form required reduction valence state, the preferred recovery time is 30 to 180 minutes.
The preferred preparation method of one of adsorbent composition provided by the invention, comprises the following steps:
A () is by zinc oxide source, oxide carrier source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen mixing;
B step (a) gained compound particles granulation is formed particle by ();
C particle roasting that step (b) obtains by () or dry roasting;
D () uses the particle after the roasting of promoter metals compound impregnation steps (c) gained;
E () carries out roasting after making the drying of step (d) gained impregnated granules; Then
F composition reduction that step (e) obtains by ().
This Preparation Method preferably made, the adsorbent composition obtained, not only has good desulfurized effect, and has better raising octane number effect.Wherein:
Zinc oxide source described in step (a) can be that zinc oxide form exists or can be converted into one or more zinc compound forms of zinc oxide under preparation condition described herein, 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.
The source of oxide carrier described in step (a) is oxide form and/or the oxide precursor that can generate oxide under condition of the present invention.Described oxide carrier source is preferably one or more in silica source, alumina source, zirconia source, titania source, silica-alumina source and natural porous material, preferably includes one or more that be commonly used in the inorganic oxide carrier of binding agent.Described silica source can be one or more that silica form exists or one or more can be converted in the silicon-containing compound form of silica; One or more in silica source such as diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica that described silica form exists, described silicon oxide colloid is Ludox, Silica hydrogel such as; One or more being converted in silicon-containing compound such as silicic acid, sodium metasilicate, ammonium silicate and the ethyl orthosilicate (or methyl esters) of silica described; Preferred silica source is diatomite.Described alumina source can be alumina form or one or more can be converted into the aluminium such as inorganic compound and the aluminium isopropoxide organic alcohol compound such as aluminum contained compound form such as aluminum nitrate, aluminium chloride, the aluminum sulfate of aluminium oxide, also can be any commercially available alumina material, it be including, but not limited to colloidal alumina solutions and the usual alumina cpd produced by dehydration of alumina hydrates; One or more in described alumina source such as Alumina gel, boehmite, gama-alumina or η-aluminium oxide.One or more in described zirconia source such as zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate and zirconium sulfate etc.One or more in described titania source such as titanium dioxide powder, titanium tetrachloride, Titanium Nitrate and tetra-n-butyl titanate etc.Described silica-alumina (amorphous aluminum silicide) source such as Alusil maybe can generate the silicon source of amorphous aluminum silicide and aluminium source mixture as waterglass and aluminum sulfate.When oxide is two or more mixture, can be arbitrary proportion between any two kinds of components in the mixture, the weight ratio between any two kinds of components be preferably 1: 100 to 100: 1, is more preferably 1: 20 to 20: 1.
Zinc oxide source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen and oxide source are mixed in step (a), the mixture formed can be that the form of wet mixed feed, dough, cream or slurries etc. exists.Any mixing arrangement can be used, each component is fully disperseed.The mixing arrangement be applicable to includes but not limited to mixing rotating cylinder, set casing or groove, batch (-type) or continuous mixing machine, impact-extrusion type mixer.If gained mixture is wet mixture form, can makes described wet mixture multiviscosisty, then it is made to granulate by granulating, then dry and roasting.When described zinc oxide source, oxide source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen is mixed to form dough or paste mixture; can make in step (b) that described mixture is shaping makes grain, extrudate, sheet, ball, pill or microsphere particle; the cylindrical extrudates of any applicable length of preferred diameter 0.75 to 13mm, then by gained particle drying and roasting.When described mixture is slurry form; by described slurries spraying dry is made it granulating in step (b); such as spraying dry forms granularity is the microballoon of 20 to 500 μm, in step (c), then make described microballoon roasting or dry roasting.Combination of adsorbents composition granule is formed preferably by spraying dry.Can make to comprise zinc oxide source, aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen, oxide source forms formation 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, acid constituents can be used, 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; The mixture of these acid can also be used.Usually, acid is used together with water, to form the aqueous acid of dilution.In acid constituents, the consumption of acid is usually based on the about 0.01 volume % to about 20 volume % of the cumulative volume of acid constituents.The solid content that zinc oxide source, oxide carrier source and aluminophosphate molecular sieve (shell)/MFI structure Si-Al molecular sieve (core) composite molecular screen and water are mixed with slurries is preferably 20 ~ 50 % by weight.In step (c), dry described particle temperature is preferably 50 ~ 180 DEG C, and described in roasting, the temperature of particle is preferably 200 ~ 850 DEG C, and roasting time is preferably 0.5 ~ 6 hour.
The particle promoter metals compound dipping in step (d), step (c) obtained.Described dipping makes in the adsorbent composition finally obtained, and with the gross weight of adsorbent composition for benchmark, is 5 ~ 50 % by weight in the promoter component content of metal, and preferably 6 to 25 % by weight, more preferably 10 ~ 20 % by weight.Described promoter metal is the promoter being 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 comprises bimetallic promoter component, the ratio that bimetallic promoter component should comprise the two kinds of metals forming this bimetallic promoter component is preferably 50: 1 to 1: 50, is preferably 20: 1 to 1: 20.Described promoter metals compound can for containing the compound of promoter metals and/or the form of metal oxide precursor, and promoter metals compound can partly or entirely be converted into corresponding metal or metal oxide under condition of the present invention.Described promoter metals compound can be metallo-organic complex, slaine, and described slaine can be nitrate, chloride, sulfate, acylate, metal acid-salt.Such as, the compound of nickel can be one or more in nickel nitrate, nickel chloride and nickelous sulfate, the compound of cobalt can be one or more in cobalt nitrate, cobalt chloride and cobaltous sulfate, the compound of copper can be selected from one or more in copper nitrate, chlorination copper and copper sulfate, the compound of iron can be selected from ferric sulfate, iron chloride, ferric nitrate and ferrous salt one or more, the compound of molybdenum can be one or more in ammonium phosphomolybdate, ammonium molybdate and sodium molybdate; The compound of tungsten can be one or more in ammonium phosphotungstate, ammonium tungstate and sodium tungstate; The compound of silver can be a kind of in silver nitrate and silver fluoride or both mixtures; The compound of antimony can be one or more in trichloride antimony, Antimony pentachloride, antimony acetate, antimony sulfate and sodium antimonate; The compound of vanadium can be one or more in vanadic anhydride, vanadic sulfate, sodium metavanadate and ammonium metavanadate.
The impregnated granules drying obtained after step (d) being flooded promoter metal in step (e) and roasting, dry described particle temperature is preferably 50 to 180 DEG C, described in roasting, particle temperature ranges preferably from 200 to 850 DEG C, roasting time preferably 0.5 to 6 hour.
The particle reduction reduced described in step (f) in reducing zone after making the roasting of step (e) gained with reducing agent under the valent applicable condition of reduction accelerator metal substantially, provide amount like this also original cost promoter metals so that resulting composition contact with cracking gasoline under such as S-Zorb adsorption desulfurize condition under adsorption desulfurize condition time can therefrom organic sulfide removal compound.Described reduction can be carried out according to existing method, such as reduce according to the method provided in CN1331591C, comprise the composition grain after roasting step (e) obtained to contact with reducing agent (preferred hydrogen), the temperature of contact is 35 ~ 850 DEG C, pressure is carry out enough Long contact time in 0.1 to 10MPa pressure limit to form required reduction valence state, preferred reduction temperature is 400 ~ 600 DEG C, and the recovery time is 0.5 hour ~ 3 hours.Metallic promoter agent after described reduction makes reduction exists with substantially reduced state, 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 hydrogen adsorption desulfurize, is particularly useful for S-Zorb process for adsorption desulfuration.During for adsorption desulfurize, in described adsorbent composition, at least part of described promoter metals exists with reduction-state.If adsorbent composition used is not through reduction, then before use should through reduction, described reduction can take aforementioned method of reducing to carry out.
In hydrocarbon ils desulfurizing method by adsorption provided by the invention, contacted by hydrocarbon ils under the condition of adsorption desulfurize with adsorbent, described adsorption desulfurize condition comprises: temperature is 250 ~ 480 DEG C, and pressure is 0.2 ~ 8.0Mpa, volume space velocity 0.5 ~ 20h
-1, adsorption desulfurize under hydro condition, hydrogen purity is 70 volume % ~ 99 volume %, and hydrogen and hydrocarbon oil feed mol ratio, generally 0.1 ~ 10: 1, are preferably 0.2 ~ 3.0: 1.
Gasolene desulfurizing method by adsorption provided by the invention, is applicable to hydrocarbon ils adsorption desulfurize.Described hydrocarbon ils can be the hydrocarbon fuel oil of any sulfur-bearing, be such as cracking gasoline or diesel fuel, wherein said cracking gasoline refers to that boiling range is hydrocarbon or its any cut of 40 DEG C to 210 DEG C, usually from making larger crack hydrocarbon molecules become more micromolecular heat and catalytic process product.Thermal cracking process includes but not limited to coking, thermal cracking, visbreaker gasoil or its combination.Catalytic cracking process includes but not limited to fluid catalytic cracking and RFCC and combination thereof.In some cases, implementing can by described cracking gasoline fractionation and/or hydrotreatment before desulfurization when being used as raw material in the present invention.
The sulfur-containing compound that term used herein " sulphur " refers to any type of element sulphur or usually exists in hydrocarbon-containifluids fluids is as cracking gasoline or diesel oil.The sulphur existed in hydrocarbon-containifluids fluids of the present invention includes but not limited to hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS
2), mercaptan or other thiophenes etc. and combination thereof, especially comprise thiophene, benzothiophene, alkyl benzothiophenes and methyldibenzothiophene, and the thiophenes that in diesel fuel, the normal molecular weight existed is larger.
The present invention is further described for the following examples.
Embodiment 1
Get Ludox (Qingdao Marine Chemical Co., Ltd., the SiO of 3.79 kilograms
2percentage by weight is 25.5 % by weight, Na
2o is 0.3 % by weight, and 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 kilogram sodium hydroxide (technical grade, sodium hydrate content 98.5 % by weight) join in 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, and after being then warming up to 160 DEG C under agitation, steady temperature crystallization 32 hours, does not carry out filtration treatment, directly the ZSM-5 product in reactor and mother liquor is stirred, and forms mixture HA; By 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 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, added in mixture HA, strong agitation makes uniform gel, and proceeds in stainless steel autoclave, 180 DEG C are stirred lower crystallization 30 hours synthesis composite molecular screens, the product obtained is the ammonium sulfate washing of 1.5 % by weight after filtering by 50 kilograms of concentration, washes twice, filters after each washing, then within dry 6 hours at 120 DEG C, obtain SAPO-5/ZSM-5 composite molecular screen, be designated as FA (wherein Na
2o content is Si: Al: P mol ratio=5 of 0.18 % by weight, SAPO-5: the SiO in 10: 12, ZSM-5
2/ Al
2o
3mol ratio is the mass ratio of 50, SAPO-5 and ZSM-5 is 4: 1).
By 7.5 kilograms of kaolin (SiO
2content 45.6 % by weight, Al
2o
3content 38.5 % by weight, Suzhou China Kaolin Co., Ltd product), 20.2 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product), 3.5 kilograms of aluminum sulfate octadecahydrate (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 and form mixture in 15 minutes, this mixture is mixed with deionized water and pulls an oar, obtain the slurries that solid content is 30 % by weight, add the acetic acid 15.58 kilograms that concentration is 3 % by weight, stir 1.5 hours, spray drying forming, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, be designated as carrier A.By 15.3 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in obtained cobalt nitrate solution in 4.6 kilograms of heat (95 DEG C) deionized water; then by this cobalt nitrate solution and 27.7 kilograms of above-mentioned carrier A hybrid infusions; produce the granulate mixture after dipping; by the granulate mixture after described dipping 150 DEG C of dryings 2 hours; roasting 2 hours at 600 DEG C again, obtains sample A.Sample A is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition A1.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state substantially.Gained adsorbent composition the ratio of each component is: SiO
2: Al
2o
3: ZnO: SAPO-5/ZSM-5: Co=1: 1: 6: 1: 1 (weight ratio, lower same).
Wherein, in A1, 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
By 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 the mixing of 29.80 kilograms of deionized waters, molar ratio of material CoO: Al
2o
3: P
2o
5: amine: water=1: the ratio of 9: 10: 10: 1000, obtained aluminium phosphate molecular sieve synthesis liquid after stirring.Be ZRP molecular sieve finished product (catalyst asphalt in Shenli Refinery of China Petrochemical Industry product, the SiO of 1.2 % by weight by 4 kilograms of phosphorus contents
2/ Al
2o
3mol ratio is 28, Na
2o content is 0.15 % by weight, solid content is 92 % by weight) be added in obtained aluminium phosphate molecular sieve synthesis liquid, 180 DEG C of crystallization 24 hours under the condition of airtight stirring, filter, filter cake 10 times of deionized waters to filter cake weight are washed, filter and dry SAPO-11/ZRP composite molecular screen (Co: Al: P mol ratio=1 wherein in CoAPO-11: the SiO in 9: 10, ZRP
2/ Al
2o
3mole be the mass ratio of 28, CoAPO-11 and ZRP be 1: 1).
By 30.1 kilograms of zinc oxide (ZnO content 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 5.5 kilograms of CoAPO-11/ZRP composite molecular screens put into grinding machine for grinding and form mixture, by this mixture and 86.3 kilograms of acidic silicasol (SiO in 15 minutes
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd. product, pH value 2.1) and deionized water mixing pull an oar, stir 2 hours, obtain the slurries that solid content is 30 % by weight, then spray drying forming, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as carrier B.By 68.0 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) to be dissolved in 4.6 kilograms of temperature be obtain maceration extract in the hot deionized water of 85 DEG C; by this impregnation fluid of the carrier B of 23 kilograms of gained, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample B.The sample B obtained above is obtained adsorbent composition B1 in 1 hour with hydrogen reducing under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, and the nickel component of wherein said adsorbent composition is reduced to zero-valent state substantially.Finally make and consist of: SiO
2: the adsorbent composition of ZnO: CoAPO-11/ZRP: Ni=22: 30: 5: 13 (weight ratios).
Wherein, adsorbent composition B1 consists of 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
According to the method adjustment pulp furnish of embodiment 2, preparation ZrAPO-11/ZSP composite molecular screen (Zr: Al: P mol ratio=1 wherein in ZrAPO-11: the SiO in 20: 20, ZSP
2/ Al
2o
3mol ratio is 45, and phosphorus content is 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, sea, Zibo is along Xin Ye Co., Ltd product) and 0.88 kilogram of ZrAPO-11/ZSP composite molecular screen are put into grinder and carries out grinding formation first mixture; By 15.3 kilograms of tetra-n-butyl titanates (content 98.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group) and 10.8 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd.) to stir after 1 hour to obtain the second mixture, first mixture, the second mixture are mixed with deionized water carry out pulling an oar solid content be 30 % by weight slurries, stir after 1 hour, spray drying forming, 150 DEG C of dryings are after 4 hours, then roasting 2 hours at 650 DEG C, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as support C.By the support C of 15.2 kilograms of gained with maceration extract [by 2.7 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) and 12.5 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) to be dissolved in 6.2 kilograms of heat (90 DEG C) deionized water obtained)] dipping, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample C.Sample C is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition C1.Cobalt and the nickel component of wherein said adsorbent composition are reduced to zero-valent state substantially.The weight ratio of each component of the adsorbent composition obtained is TiO
2: SiO
2: ZnO: ZrAPO-11/ZSP: Ni: Co=4: 3: 8: 1: 2: 1.
Wherein, in C1, 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
Preparation SAPO-31/ZSM-5 composite molecular screen (Si: Al: P mol ratio=1 wherein in SAPO-31: the SiO in 10: 10, ZSM-5
2/ Al
2o
3be 50, La
2o
3content is the mass ratio of 1.5%, SAPO-31 and ZSM-5 is 6: 1).
By 4.5 kilograms of aluminium isopropoxides (Al>=24.7 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 4.4 kilograms of zirconium oxychloride (ZrOCl
28H
2o>=99.0 % by weight, Chemical Reagent Co., Ltd., Sinopharm Group), 3.9 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 0.57 kilogram of SAPO-31/ZSM-5 composite molecular screen put into grinding machine for grinding and form mixture in 15 minutes, then this mixture being joined 42 kilograms of concentration is pull an oar in the salpeter solution of 0.3 % by weight, and add deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1 hour, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, be designated as carrier D.By 15 kilograms of above-mentioned carrier D nickel nitrate solutions [by 10.1 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 3.1 kilograms of heat (90 DEG C) deionized water obtain] dipping, produce dipping after granulate mixture.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample D.The sample D obtained above is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition D1 provided by the invention.The adsorbent composition obtained consist of ZrO
2: Al
2o
3: ZnO: SAPO-31/ZSM-5: Ni=3: 2: 7: 1: 2 (weight ratios).
Wherein, 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
Method with reference to embodiment 1 adjusts raw material and proportioning prepares VAPO-11/ZSM-5 composite molecular screen (V: Al: P mol ratio=1 wherein in VAPO-11: the SiO in 10: 10, ZSM-5
2/ Al
2o
3the mass ratio of mol ratio is 60, La content to be 1.2%, P content be 1.0%, VAPO-11 and ZSM-5 is 8: 1).
By 9.2 kilograms of rectorite (SiO
2content 45.0 % by weight, Al
2o
3content 35.7 % by weight, From Zhongxiang Hubei), 9.9 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye 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 mixing, stir 1.5 hours, obtain the slurries that solid content is 30 % by weight, spray drying forming, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as carrier E.By 15.2 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in obtained maceration extract in 4.6 kilograms of heat (90 DEG C) deionized water; by this maceration extract and 18 kilograms of above-mentioned carrier E hybrid infusions, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample E.The sample E prepared above is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition E1.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state substantially.The proportioning of gained adsorbent composition is: SiO
2: Al
2o
3: ZnO: VAPO-11/ZSM-5: Co=3: 2: 5: 2: 2 (weight ratios).
Wherein, in gained adsorbent E1, 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
Preparation SAPO-41/ZRP composite molecular screen (Si: Al: P mol ratio=3 wherein in SAPO-41: the SiO in 20: 20, ZRP
2/ Al
2o
3be 29, Re
2o
3the mass ratio of content to be 1.2%, P content be 1.2%, SAPO-41 and ZRP-5 is 1: 10).Can prepare according to the method for embodiment 2, corresponding adjustment raw material, proportioning.
By 8.8 kg of hydrogen zirconia (ZrO
2content 37.5 amount %, Chemical Reagent Co., Ltd., Sinopharm Group), 9.9 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 3.3 kilograms of SAPO-41/ZRP composite molecular screens put into grinder and carry out grinding and form mixture, by this mixture and 26.0 kilograms of acidic silicasol (SiO in 20 minutes
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) mixing making beating, and then mix with deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1.5 hours, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as carrier granular F.By 7.6 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) and 15.4 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (90 DEG C) deionized water and obtain maceration extract; by this impregnation fluid of carrier granular F of 21 kilograms of gained, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample F.Sample F is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition F1.Cobalt and the nickel component of wherein said adsorbent composition are reduced to zero-valent state substantially.ZrO in gained adsorbent composition
2: SiO
2: ZnO: SAPO-41/ZRP: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratios).
Wherein, 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, adjustment raw material and proportioning, preparation CuAPO-31/ZSP composite molecular screen (Cu: Al: P mol ratio=1 wherein in CuAPO-31: the SiO in 20: 20, ZSP
2/ Al
2o
3the mass ratio of mol ratio is 48, P content to be 1.4%, Fe content be 1.5%, CuAPO-31 and ZSP is 20: 1).
By 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 contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 2.2 kilograms of CuAPO-31/ZSP composite molecular screens put into after grinder is pulverized and form mixture, by this mixture and 13.0 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value 2.1) and 10.4 kg aluminium colloidal sols (alumina content is 21.2 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) mixing making beating, and then mix with deionized water, obtain the slurries that solid content is 30 % by weight, stir after 1 hour, spray drying forming, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as carrier G.By the carrier G of the 20.6 kilograms of gained 15.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight be dissolved in 4.6 kilograms of heat (90 DEG C) deionized water; Chemical Reagent Co., Ltd., Sinopharm Group) and 10.4 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) dipping, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample G.Sample G obtained is above used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition G1.Cobalt and the nickel component of wherein said adsorbent composition are reduced to zero-valent state substantially.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 ratios).
Wherein, 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
Preparation MgAPO-5/ZRP composite molecular screen (Mg: Al: P mol ratio=1 wherein in MgAPO-5: the SiO in 20: 25, ZRP
2/ Al
2o
3the mass ratio of mol ratio to be 28, P content be 1.4%, MgAPO-5 and ZRP is 1: 20).Prepare according to the method for embodiment 2, corresponding adjustment raw material, proportioning.
By 6.2 kilograms of expanded perlite (SiO
2content 70.8 % by weight, Al
2o
3content 12.6 % by weight, Pingqiao District, District, Xinyang Area, Henan Province city Tian Li bentonite factory), 19.8 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 6.6 kilograms of MgAPO-5/ZRP composite molecular screens put into grinder and carry out grinding formation mixture, by this mixture and 27.4 kg aluminium colloidal sols, (alumina content is 21.2 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) and deionized water mixing making beating, obtain the slurries that solid content is 30 % by weight, stir 1 hour, spray drying forming, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, be designated as carrier granular H.By the carrier granular H of the 17 kilograms of gained 20.0 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight be dissolved in 6.0 kilograms of heat (95 DEG C) deionized water; Chemical Reagent Co., Ltd., Sinopharm Group) dipping, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample H.The sample H prepared above is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition H1.The cobalt component of wherein said adsorbent composition is reduced to zero-valent state substantially.The composition SiO of gained adsorbent composition
2: Al
2o
3: ZnO: MgAPO-5/ZRP: Co=2: 3: 9: 3: 4 (weight ratios).
Wherein, 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, adjustment pulp furnish, preparation CoAPSO-11/ZSM-5 composite molecular screen (Co: Si: Al: P mol ratio=1 wherein in CoAPSO-11: the SiO in 1: 20: 20, ZSM-5
2/ Al
2o
3the mass ratio of mol ratio to be 30, P content be 1.4%, CoSAPO-11 and ZSM-5 is 2: 1).
By 5.9 kilograms of sepiolite (SiO
2content 56.5 % by weight, content of MgO 22.6 % by weight, Neixiang County, Henan Province east wind sepiolite Co., Ltd), 9.1 kilograms of Zinc oxide powder (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 0.55 kilogram of CoAPSO-11/ZSM-5 composite molecular screen put into after grinder is pulverized and form mixture, by this mixture and 29.88 kilograms of acidic silicasol (SiO
2content 25.5% % by weight, Qingdao micro-nano silica gel Science and Technology Ltd., pH value is 2.1) mixing, stir spray drying forming after 1 hour, 150 DEG C of dryings are after 4 hours, then roasting 2 hours at 650 DEG C, obtained particle diameter is the carrier granular of 40 ~ 200 μm, is designated as carrier K; By 11.7 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.0 kilograms of heat (90 DEG C) deionized water and obtain maceration extract; by the carrier K hybrid infusion described in this maceration extract and 15 kilograms, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample K.The sample K prepared above is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition K1.The nickel component of wherein said adsorbent composition is reduced to zero-valent state substantially.The proportioning of the adsorbent composition finally made is SiO
2: MgO:: ZnO: CoAPSO-11/ZSM-5: Ni=14: 2: 33: 2: 9 (weight ratios).
Wherein, 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
Preparation CoAPO-41/ZSM-5 composite molecular screen (Co: Al: P mol ratio=1 wherein in CoAPO-41: the SiO in 8: 8, ZSM-5
2/ Al
2o
3mole be 80, Re
2o
3the mass ratio of content to be 1.2%, P content be 1.2%, SAPO-41 and ZSM-5 is 10: 1).Can prepare according to the method for embodiment 2, corresponding adjustment raw material, proportioning.
By 8.8 kg of hydrogen zirconia (ZrO
2content 37.5 amount %, Chemical Reagent Co., Ltd., Sinopharm Group), 9.9 kilograms of zinc oxide (ZnO contents 99.8 % by weight, sea, Zibo is along Xin Ye Co., Ltd product) and 3.3 kilograms of SAPO-41/ZSM-5 composite molecular screens put into grinder and carry out grinding and form mixture in 20 minutes, by this mixture and 31.3 kg aluminium colloidal sols, (alumina content is 21.2 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product) mixing making beating, and then mix with deionized water, obtain the slurries that solid content is 30 % by weight, stir spray drying forming after 1.5 hours, 150 DEG C of dryings are after 4 hours, roasting 2 hours at 650 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, be designated as carrier granular F.By 7.6 kilograms of cobalt nitrate hexahydrates (content 99.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) and 15.4 kilogram of six water nickel nitrate (content 98.0 % by weight; Chemical Reagent Co., Ltd., Sinopharm Group) be dissolved in 4.6 kilograms of heat (90 DEG C) deionized water and obtain maceration extract; by this impregnation fluid of carrier granular F of 21 kilograms of gained, produce the granulate mixture after dipping.By the granulate mixture after described dipping 150 DEG C of dryings 2 hours, then roasting 2 hours at 600 DEG C, obtain sample L.Sample L is used hydrogen reducing 1 hour under 530 DEG C and Hydrogen Vapor Pressure 1.4MPa, obtains adsorbent composition M1.Cobalt and the nickel component of wherein said adsorbent composition are reduced to zero-valent state substantially.ZrO in gained adsorbent composition
2: Al
2o
3: ZnO: CoAPO-41/ZRP: Ni: Co=2: 4: 6: 2: 1: 2 (weight ratios).
Wherein, 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 example 1
Prepare adsorbent according to the method for CN102343249A, by 4.43 kilograms of Zinc oxide powders, 1.00 kilograms of SAPO-31 and 4.57 kilogram of deionized water mixing, stir the mixed serum obtaining zinc oxide and SAPO-31 after 30 minutes.
The rectorite getting boehmite 1.37 kilograms and 2.75 kilograms under agitation mixes, and then adds after deionized water 4.6 kilograms mixes, the hydrochloric acid adding 360 milliliters of 30wt.% stir acidifying be warming up to after 1 hour 80 DEG C aging 2 hours.Stir after adding the mixing of zinc oxide slurries and obtain carrier pulp in 1 hour, carrier pulp is carried out spray drying forming, 180 DEG C of dryings are after 1 hour, roasting 1 hour at 635 DEG C again, obtained particle diameter is the carrier granular of 40 ~ 200 μm, by the adsorbing agent carrier of 3.2 kilograms 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 obtained is through 180 DEG C of dryings after 4 hours, and at air atmosphere 635 DEG C, roasting can obtain adsorbent precursors in 1 hour.Adsorbent precursors reductase 12 hour in the hydrogen atmosphere of 425 DEG C can be obtained adsorbent composition, be designated as L1.The chemical composition of the adsorbent composition finally made is: zinc oxide content 44.3wt.%, and rectorite content is 20.6wt.%, SAPO-31 content is 7.0wt.%, and alumina binder is 10.0wt.%, and metallic nickel content is 18.1wt.%,
Comparative example 2
Adsorbent composition L2 is prepared with boehmite, kaolin, zinc oxide, CoAPO-11 and six water nickel nitrates according to the method for CN102343249A, the final chemistry of the adsorbent composition made consists of: 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 example 3
Prepare with acidic silicasol, zinc oxide and nickel nitrate for raw material prepares material ratio for SiO according to existing method
2: the adsorbent of ZnO: Ni=22: 30: 13.Upper sample of sorbent and CoAPO-11/ZRP composite molecular screen (with embodiment 2) molecular sieve mechanical mixture is even, and making final material ratio is: SiO
2: the adsorbent composition L3 of ZnO: CoAPO-11: Ni=22: 30: 5: 13 (weight ratios).
Wherein, 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 example 4
Prepare with acidic silicasol, zinc oxide and nickel nitrate for raw material prepares material ratio for SiO according to existing method
2: the adsorbent of ZnO: Ni=22: 30: 13.Upper sample of sorbent and ZRP molecular sieve (with embodiment 2) mechanical mixture is even, and making final material ratio is: SiO
2: the adsorbent composition L4 of ZnO: ZRP: Ni=22: 30: 5: 13 (weight ratios).
Wherein, 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 example 5
According to existing method, with acidic silicasol, CoAPO-11 molecular sieve (Co: Al: P mol ratio=1: 9: 10), ZRP molecular sieve (with embodiment 2), zinc oxide and nickel nitrate be that raw material is prepared adsorbent final material ratio and is: SiO
2: the adsorbent composition L5 of ZnO: CoAPO-11: ZRP: Ni=44: 60: 5: 5: 26 (weight ratios).
Wherein, CoAPO-11 and ZRP molecular sieve accounts 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 obtained to embodiment 1 ~ 10 and comparative example 1 ~ 5 obtain carries out reaction evaluating.
Evaluate gasoline stocks (boiling range 40 ~ 210 DEG C) sulphur containing 1100 μ g/g (weight content based on the sulfur-containing compound of described gaseous cracked-gasoline weight) adopted, weight based on sulfur-containing compound is had an appointment 95% thiophenes (thiophene, benzothiophene, alkylthrophene and alkyl benzothiophenes), olefin(e) centent 34.8% (volume fraction), octane number RON is 91.3, MON is 79.9.The absorbent particles (100 ~ 350 order) that adsorbent composition as obtained in above embodiment 1 ~ 9 for 10g and comparative example 1 ~ 5 obtain is placed in stainless steel tube (diameter (interior warp) is 13mm) respectively and carries out adsorption reaction evaluation, appreciation condition is: temperature 410 DEG C, pressure 1.4MPa, hydrogen partial pressure is that (hydrogen used is plant hydrogen to 0.6MPa, certified products, H
2content is 99 volume %), gasoline-volume air speed 4h
-1, adsorption time is 4 hours, for accurately symbolizing the performance of adsorbent in industrial actual motion, has reacted rear adsorbent at 550 DEG C, carries out regeneration process in air atmosphere.After adsorbent carries out reaction regeneration 6 circulation, its reactivity worth is basicly stable, then judges with the adsorbent that reactivity worth is stable, and evaluation result is in table 1.
Table 1
In table 1, (MON+RON)/2 of the gasoline after octane number change=desulfurization deduct (MON+RON)/2 of gasoline stocks ,+represent that octane number increases ,-represent that octane number reduces;
Sulfur content × 100% in desulfurization degree (percentage except desulfuration)=(sulfur content in the gasoline after the sulfur content-desulfurization in raw material)/raw material.
From table 1, adsorption-desulfurization sorbent composition provided by the invention, can improve the octane number of gasoline, and have higher raising octane number effect, have good desulfurized effect, desulfurization degree is higher, can reach more than 95%, even can more than 98%.
Claims (16)
1. a hydrocarbon oil desulphurization adsorbing agent composition, described adsorbent composition consists of:
(a) zinc oxide,
(b) aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen, wherein, aluminophosphate molecular sieve is shell, and MFI structure Si-Al molecular sieve is core, and the weight ratio of aluminophosphate molecular sieve and MFI structure molecular sieve is 0.01 ~ 100,
(c) oxide carrier, and
(d) promoter metals;
With the weight of adsorbent composition for benchmark, the content of aluminophosphate molecular sieve described in described adsorbent composition/MFI structure Si-Al molecular sieve composite molecular screen is 1 ~ 40 % by weight, is 5 ~ 50 % by weight in the content of element promoter metals; The content of zinc oxide is 10 ~ 80 % by weight; Be 10 ~ 80 % by weight with the content of oxide basis oxide carrier;
The preparation method of described adsorbent composition, comprising: form the step comprising the particle of zinc compound, promoter metals compound, oxide carrier component and described aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen, roasting, reduction.
2. adsorbent composition according to claim 1, it is characterized in that, the content of aluminophosphate molecular sieve described in described adsorption-desulfurization sorbent composition/MFI structure Si-Al molecular sieve composite molecular screen is 2 ~ 25 % by weight, and the content of described zinc oxide is 25 ~ 75 % by weight.
3. adsorbent 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/MFI structure Si-Al molecular sieve composite molecular screen, aluminophosphate molecular sieve is wherein one or more of aluminophosphate molecular sieve that element replaces, and in the aluminophosphate molecular sieve that described element replaces, substituted element is one or more in Li, Be, B, Si, Mg, Ca, Ge, As, Ga, Zn, Mn, Fe, Ni, Co, Cu, Zr, Cd, Ti, Pd, V, La and Ce; The silica alumina ratio of MFI structure Si-Al molecular sieve is wherein 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/MFI structure Si-Al molecular sieve composite molecular screen, described aluminophosphate molecular sieve is one or more in SAPO-11, SAPO-41, SAPO-5, CuAPO-31, ZrAPO-11, VAPO-11, CoAPO-41, SAPO-31, MgAPO-5, CoAPSO-11; Described MFI structure Si-Al molecular sieve is one or more in ZSM-5 molecular sieve, ZRP Series Molecules sieve and 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 the ZSM-5 molecular sieve of HZSM-5, rare earth and/or P Modification.
7. the adsorbent composition according to claim 1,2,4,5 or 6, is characterized in that, described promoter metals at least one is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony and vanadium.
8. the adsorbent composition according to claim 1,2,4,5 or 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 natural porous material.
10. the preparation method of adsorbent composition described in any one of claim 1 ~ 9, comprising:
A () is by zinc oxide source, oxide carrier source and aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen mixing, in wherein said aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen, aluminophosphate molecular sieve is shell, and MFI structure Si-Al molecular sieve is core;
B step (a) gained compound particles granulation is formed particle by ();
C particle drying that step (b) obtains by (), then roasting;
D () uses the particle after the roasting of promoter metals compound impregnation steps (c) gained;
E () carries out roasting by after the drying of step (d) gained impregnated granules;
F product reduction that step (e) obtains by ().
11. methods according to claim 10, it is characterized in that, in step (a), zinc oxide source, oxide carrier source, aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen and water are mixed to form slurries, stir 0.5 ~ 2 hour.
12. methods according to claim 10, is characterized in that, step (c) is 50 ~ 180 DEG C with baking temperature dry described in (e); Step (c) is 200 ~ 850 DEG C with particle temperature described in roasting in (e).
13. methods according to any one of claim 10 ~ 12, is characterized in that, described zinc oxide source is one or more in Zinc oxide powder, zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc chloride and zinc nitrate; Described oxide carrier source is one or more in diatomite, silicon oxide colloid, silica gel, silicalite and precipitated silica, silicic acid, sodium metasilicate, ammonium silicate and ethyl orthosilicate or methyl silicate, Alumina gel, boehmite, gama-alumina, η-aluminium oxide, aluminum sulfate, zirconium hydroxide, Zirconium oxide powder, zirconium oxychloride, zirconium nitrate, titanium dioxide powder, titanium tetrachloride, Titanium Nitrate, Alusil, swollen perlite, kaolin, imvite, sepiolite and rectorite.
The preparation method of adsorbent composition described in 14. any one of claim 1 ~ 9, comprising:
(1) zinc oxide source, oxide carrier source, promoter metals compound and aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen are formed mixture, in wherein said aluminophosphate molecular sieve/MFI structure Si-Al molecular sieve composite molecular screen, aluminophosphate molecular sieve is shell, and MFI structure Si-Al molecular sieve is core;
(2) by step (1) gained mixture forming particle;
(3) by the particle drying of step (2), then roasting;
(4) composition reduction step (3) obtained.
15. 1 kinds of hydrocarbon ils desulfurizing method by adsorption, comprise the step by hydrocarbon ils and adsorbent contact, it is characterized in that, described adsorbent is the adsorbent composition described in any one 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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| CN104707565A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulphurization and olefin reduction adsorbent, and preparation method and application thereof |
| CN105080475B (en) * | 2014-05-14 | 2018-02-13 | 中国石油化工股份有限公司 | For lifting the adsorbent of octane number |
| CN107970941B (en) | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN107267223B (en) * | 2017-06-30 | 2020-06-12 | 武汉科林化工集团有限公司 | Medium-temperature zinc oxide desulfurizer and preparation method thereof |
| CN110152595A (en) * | 2018-03-28 | 2019-08-23 | 山东联星能源集团有限公司 | A kind of gasoline desulphurization sorbent |
| 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 |
| CN110560171A (en) * | 2019-09-09 | 2019-12-13 | 沈阳师范大学 | Composite nanofiber with desulfurization performance and preparation method and application thereof |
| CN110681346A (en) * | 2019-09-10 | 2020-01-14 | 咏铨洁能科技有限公司 | Adsorbent with low boiling point VCOS, filter material set, filter material box and method for producing adsorbent |
| CN111408339A (en) * | 2020-05-09 | 2020-07-14 | 中国科学院生态环境研究中心 | Preparation method and application of sepiolite composite adsorbent loaded with nano zinc sulfide |
| CN112812864B (en) * | 2021-02-10 | 2022-10-21 | 于向真 | S-Zorb process octane number auxiliary agent and preparation method thereof |
| CN113083282B (en) * | 2021-04-09 | 2023-03-10 | 浙江工业大学 | Composite metal desulfurization catalyst with double functions of conversion and absorption and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382071A (en) * | 1999-08-25 | 2002-11-27 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN1524617A (en) * | 2003-02-28 | 2004-09-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5/AIPO4-5 double structure molecular sieve |
| CN102294223A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent and preparation method and application thereof |
| CN102343249A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, its preparation method and its application |
-
2012
- 2012-04-26 CN CN201210127207.6A patent/CN103372416B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382071A (en) * | 1999-08-25 | 2002-11-27 | 菲利浦石油公司 | Sorbent composition, process for producing same and use in desulfurization |
| CN1524617A (en) * | 2003-02-28 | 2004-09-01 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5/AIPO4-5 double structure molecular sieve |
| CN102294223A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent and preparation method and application thereof |
| CN102343249A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Hydrocarbon oil desulphurization adsorbent, its preparation method and its application |
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