CN104971773A - Hydrogenation catalyst and application thereof - Google Patents
Hydrogenation catalyst and application thereof Download PDFInfo
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- CN104971773A CN104971773A CN201410140809.4A CN201410140809A CN104971773A CN 104971773 A CN104971773 A CN 104971773A CN 201410140809 A CN201410140809 A CN 201410140809A CN 104971773 A CN104971773 A CN 104971773A
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Abstract
A hydrogenation catalyst and an application thereof, wherein the hydrogenation catalyst includes a carrier, at least one metal component selected from the group VIII and at least one metal component selected from the group VIB. The hydrogenation catalyst is characterized in that the hydrogenation catalyst is an aluminum moulded material containing a nonionic surfactant. On the basis of the carrier, the mass percentage of the nonionic surfactant is 0.1-10%. Compared with a catalyst in the prior art, the hydrogenation catalyst is improved in performances.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and application thereof.
Background technology
The environmental consciousness day by day strengthened and more and more stricter environmental regulation force oil refining circle more to focus on Clean Fuel Production technological development, and the production super-low sulfur oil product of how economical rationality has become one of problem needing emphasis to solve in oil refining circle's current and expected future regular period.Exploitation have more high activity and optionally novel hydrogenation catalyst be then one of most economical method of production clear gusoline.
Summary of the invention
The technical problem to be solved in the present invention is to provide the improved hydrogenation catalyst of a kind of performance and application thereof.
The present invention relates to following content:
1. a hydrogenation catalyst, is selected from the VIIIth race containing carrier and at least one and at least one is selected from
The metal component of VI B race, is characterized in that, described carrier is a kind of aluminium oxide article shaped, and containing nonionic surface active agent in described aluminium oxide article shaped, with described carrier for benchmark, the mass fraction of described nonionic surface active agent is 0.1%-10%.
2. the catalyst according to 1, is characterized in that, with described carrier for benchmark, the mass fraction of described nonionic surface active agent is 0.3%-5%.
3. the catalyst according to 1, it is characterized in that, described nonionic surface active agent is selected from one or more in APES, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, the ethylene oxide adduct of polypropylene glycol, sorbitan ester, sucrose ester, ethoxylated dodecyl alcohol, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, Triton X-100, polyoxyethylene one polyoxypropylene one polyoxyethylene triblock copolymer, polyalcohol.
4. the catalyst according to 3, is characterized in that, described polyalcohol is selected from polysorbas20, polysorbate40, polysorbate60, Tween 80, Arlacel-20, Arlacel-80, triton x-100.
5. the catalyst according to 1, it is characterized in that, containing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide in described article shaped, with described carrier for benchmark, the mass fraction of described adjuvant component is less than 10%.
6. the article shaped according to 5, is characterized in that, with described carrier for benchmark, the mass fraction of described adjuvant component is 0.3%-5%.
7. the catalyst according to 1 or 5, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described carrier for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
8. the catalyst according to 7, is characterized in that, with described carrier for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
9. the catalyst according to 1, is characterized in that, with described catalyst for benchmark, described catalyst contains the carrier of 50-90 % by weight, the metal component of group VIII of 1-10 % by weight, the metal component of group VIB of 5-40 % by weight.
10. the catalyst according to 9, is characterized in that, with described catalyst for benchmark, described catalyst contains the carrier of 60-85 % by weight, the metal component of group VIII of 1.5-6 % by weight, the metal component of group VIB of 10-35 % by weight.
11. 1 kinds of hydrogenation method for hydrocarbon oils, under being included in hydrogenation conditions, reacting hydrocarbon ils and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in claim 1-10 any one.
In the present invention, described aluminium oxide can be selected from one or more in γ, η, θ, δ and χ, is preferably gama-alumina.Described aluminium oxide has specific surface and the pore volume of conventional alumina, and the specific surface of preferential oxidation aluminium is 150-350 rice
2/ gram, more preferably 180-320 rice
2/ gram, the pore volume of preferential oxidation aluminium is 0.4-1.1 ml/g, more preferably 0.5-0.9 ml/g.They can be that commercially available commodity also can be prepared by any one method in prior art.Such as, can be through shaping and obtained after roasting by the mixture of one or more be selected from hibbsite, monohydrate alumina and amorphous hydroted alumina.
The shaping employing customary way of described aluminium oxide carries out, as methods such as compressing tablet, spin, extrusions.When adopting customary way shaping, for guaranteeing shaping to carry out to aforesaid material to be formed (such as smoothly, the mixture of one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina) in introduce auxiliary agent be allow, such as when extrusion, appropriate extrusion aid and water can be introduced, extrusion molding afterwards in aforesaid material to be formed.The kind of described extrusion aid and consumption can be all this area routines, and such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH.
In one preferred embodiment, the described aluminium oxide article shaped gama-alumina that to be a kind of boehmite of modification and/or false boehmite obtain after shaping, roasting.
The method of described modification boehmite and/or false boehmite comprises: (1), by the roasting of at least one hydrated alumina, described roasting condition comprises: temperature is 300 DEG C-950 DEG C, and the time is 0.5 hour-24 hours; (2) product of roasting step (1) obtained and at least one boehmite and/or false boehmite and water mix, and obtain a kind of mixture; (3) mixture that step (2) obtains is carried out hydrothermal treatment consists in closed reactor, hydrothermal conditions comprises: temperature is 60 DEG C-250 DEG C, and the time is 0.5 hour-48 hours; (4) product step (3) obtained is dry, obtains the boehmite of modification and/or false boehmite.
Wherein, the roasting condition of preferred described step (1) comprising: temperature is 300-750 DEG C, and the time is 1-24 hour.The roasting condition of further preferred described step (1) comprising: temperature is 350-650 DEG C, and the time is 2-10 hour.
In the mixture that the product of roasting that step (1) obtains by preferred described step (2) and at least one boehmite or false boehmite and water are mixed to get, solid content is in mass 1%-80%, wherein, described product of roasting with in the mass ratio of the boehmite of butt or false boehmite for 0.1-20.In the mixture that the product of roasting that step (1) obtains by further preferred described step (2) and at least one boehmite or false boehmite and water are mixed to get, solid content is in mass 5%-70%, wherein, described product of roasting with in the mass ratio of the boehmite of butt or false boehmite for 0.2-12.
When water content in described mixture is enough to make described mixture be slurries (such as, solid content is in mass less than 35%), before the drying of described step (4), preferably include the step of filtration.
The hydrothermal conditions of preferred described step (3) comprising: temperature be 60 DEG C to being less than 140 DEG C, the time is 0.5-48 hour.The hydrothermal conditions of further preferred described step (3) comprising: temperature is 80-120 DEG C, and the time is 4-24 hour.Or the hydrothermal conditions of preferred described step (3) comprising: temperature is for being more than or equal to 140 DEG C to being less than or equal to 250 DEG C, and the time is 0.5-48 hour; The hydrothermal conditions of further preferred described step (3) comprising: temperature is 150-220 DEG C, and the time is 4-24 hour.
The baking temperature of preferred described step (4) is 60 DEG C-180 DEG C, and drying time is 0.5 hour-24 hours.The baking temperature of further preferred described step (4) is 80 DEG C-150 DEG C, and drying time is 1 hour-12 hours.
In the present invention, described hydrated alumina is selected from one or more in hibbsite, false boehmite, boehmite.
Wherein, described hibbsite comprises gibbsite (α-Al
2o
33H
2o), surge aluminium stone (β
1-Al
2o
33H
2and promise diaspore (β O)
2-Al
2o
33H
2o).
Described false boehmite is also called boehmite, characterizes with X-ray diffraction, for one occurs wide and hydrated alumina that is (020) crystallographic plane diffraction peak of disperse at 14.5 ° ± 0.5 ° (2 θ).
Described boehmite is also called boehmite, characterize with X-ray diffraction, for the hydrated alumina (diffraction maximum corresponded to not available for the false boehmite of (131), (220) and (151) crystal face appears in boehmite respectively 45.8 °, 51.6 ° and 55.2 °) of the strongest, narrow and sharp-pointed (020) crystallographic plane diffraction peak to appear in one at 14.5 ° ± 0.5 ° (2 θ).
The present inventor is surprised to find, by boehmite and/or false boehmite and one or more are through 300 DEG C of-950 DEG C of roastings (heat treatment) 0.5-24 hour, preferably through 300 DEG C of-750 DEG C of roastings (heat treatment) 1-24 hour, preferably further be mixed to get a kind of mixture through 350 DEG C of-650 DEG C of roastings (heat treatment) hydrated aluminas of 2-10 hour and water, and by this mixture in closed container in 60 DEG C of-250 DEG C of hydrothermal treatment consists 0.5-48 hour, be preferable over 80-220 DEG C of hydrothermal treatment consists 4-24 hour, the relative crystallinity of the boehmite that obtains of modification and/or false boehmite improves thus, and the aluminium oxide obtained through roasting thus maintains higher specific area and pore volume.
In the present invention, when control hydrothermal treatment consists temperature is more than 140 DEG C, gained modified product is boehmite; When control hydrothermal treatment consists temperature is less than 140 DEG C, crystalline phase and the initiation material of products therefrom are consistent.
In a detailed description of the invention, the hydrothermal conditions of the described step (3) preferably making the crystalline phase of described modified product consistent with initiation material comprising: temperature be 60 DEG C to being less than 140 DEG C, the time is 0.5-48 hour; The hydrothermal conditions of further preferred described step (3) comprising: temperature is 80-120 DEG C, and the time is 1-24 hour.
In another embodiment, described modified product is preferably made to be that the hydrothermal conditions of the described step (3) of boehmite comprises: temperature is for being more than or equal to 140 DEG C to being less than or equal to 250 DEG C, and the time is 0.5-48 hour; The hydrothermal conditions of further preferred described step (3) comprising: temperature is 150-220 DEG C, and the time is 4-24 hour.
In the present invention, described boehmite, false boehmite and gibbsite can be commercially available commodity, also can be to adopt the preparation of arbitrary prior art, are not particularly limited this.
Be enough to described hydrated alumina at 300 DEG C of-950 DEG C of roastings (heat treatment) 1-24 hour, preferably through 300 DEG C of-750 DEG C of roastings (heat treatment) 1-24 hour, preferred under 350 DEG C of-650 DEG C of roastings (heat treatment) condition of 2-10 hour further, the present invention is not particularly limited the method for roasting described in step (1).Such as, can be that described hydrated alumina is carried out roasting in usual baking oven or roaster under air atmosphere, also can be carry out under vacuum or under passing into inert gas conditions in the baking oven or roaster of vacuum-pumping.When described roasting passes into inert gas, described inert gas can be the oxygen-free gas being enough to arbitrarily gasify under described roasting condition, such as, can be selected from one or more in nitrogen, argon gas, helium, carbon dioxide and water vapour.
Butt in the present invention refers to: a certain amount of described hydrated alumina is raised to 600 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, then 600 DEG C of constant temperature 4 hours, the percentage of the ratio of the weight of described hydrated alumina before the weight of roasting afterproduct and roasting, weight × 100% of described hydrated alumina before the weight ÷ roasting of butt=roasting afterproduct.
In the present invention, described airtight reactor can be the reactor that can realize described hydro-thermal reaction arbitrarily, such as, autoclave etc., described reaction can be carry out under static conditions, also carries out under stirring, carries out hydrothermal treatment consists under preferred stirring.
In the present invention, described non-ionic surface active agent refers to the surfactant not producing ion in aqueous, can be divided into polyoxyethylene-type and polyol type two class by hydrophilic radical; In addition, also have other non-ionic surface active agents, such as, alkylolamides type, non-ion fluorin carbon surface active agent etc.Wherein, polyoxyethylene-type comprises: the ethylene oxide adduct of APES, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, polypropylene glycol; Polyol type comprises: sorbitan ester, sucrose ester.Preferably, TWEEN Series non-ionic surface active agent (comprising polysorbas20, polysorbate40, polysorbate60, Tween 80), Arlacel-20 (SP-20 laurate); Arlacel-80 (SP-80 monoleate), triton x-100 (polyoxyethylene-8-octyl phenyl ether), ethoxylated dodecyl alcohol, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, Triton X-100, polyoxyethylene one polyoxypropylene one polyoxyethylene triblock copolymer (pluronic123).
Be enough to make containing 0.1%-10% in described article shaped, under being preferably the prerequisite of the non-ionic surface active agent of 0.3%-5%, the present invention does not limit the method introducing nonionic surface active agent in described aluminium oxide article shaped.
In one preferred embodiment, the method of nonionic surface active agent is introduced in described aluminium oxide article shaped, comprise: (1) uses aluminium oxide article shaped described in the solution impregnation containing nonionic surface active agent, the volume of described maceration extract is 0.5-20 with the ratio of the pore volume of described article shaped, is preferably 1-15; (2) heat-treat flooding the mixture obtained in closed reactor, heat treatment temperature is room temperature to 250 DEG C, and be preferably 60 DEG C to 220 DEG C, the time is 0.5 hour-48 hours, is preferably 1 hour-36 hours; (3) product of drying steps (2), described drying condition comprises: temperature is 40 DEG C-250 DEG C, and be preferably 100 DEG C-180 DEG C, the time is 1 hour-24 hours, is preferably 2 hours-18 hours.
Wherein, described room temperature can be the indoor temperature in each season interior throughout the year, is generally 5-40 DEG C.The solvent of described maceration extract for dissolving the various solvents of described non-ionic surface active agent, can be preferably water and/or ethanol.
Be enough under the prerequisite that the content of non-ionic surface active agent in final described article shaped is met the demands, the present invention is not particularly limited the content of the non-ionic surface active agent in maceration extract and dipping number of times.In concrete enforcement, the non-ionic surface active agent in maceration extract described in preferred rate-determining steps (1) be 0.01-10:100, more preferably 0.1-8:100 with the ratio of the weight of aluminium oxide article shaped, be more preferably 0.3-5:100.
When being enough to ensure that described heat treatment is carried out under air tight condition, the present invention is not particularly limited described closed reactor, common as autoclave high-pressure reactor etc.
In the present invention, introduce in the method for non-ionic surface active agent in described aluminium oxide article shaped, the object of step (3) drying is the solvent removed in impregnation product, be enough under the prerequisite realizing this object, the method of the present invention to described drying does not limit, can be such as the method for heat drying, also can be vacuum drying method.
In the present invention, described aluminium oxide can containing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide, with described carrier for benchmark, the mass fraction of described adjuvant component is less than 10%, is preferably 0.3%-5%.
When in described article shaped containing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide time, comprise the step introducing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide in the preparation process of described article shaped, the method for described introducing adjuvant component is conventional method.Such as, can be by containing the mixture of one or more in the hibbsite of one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide, monohydrate alumina and amorphous hydroted alumina through shaping and obtained after roasting.Also can be that just aluminium oxide and/or its precursor mix with the compound containing adjuvant component, after obtain through shaping, drying and roasting.
In the present invention, can contain clay and/or molecular sieve in described article shaped, with described carrier for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%, is preferably 1%-20%.
When containing clay and/or molecular sieve in described article shaped, comprise the step introducing clay and/or molecular sieve in the preparation process of described article shaped, the method thing conventional method of described introducing clay and/or molecular sieve.Such as, by described clay and/or molecular sieve and be describedly selected from the mixture of one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina through shaping and obtained after roasting.
In the present invention, described clay can be selected from kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite one or more.Described molecular sieve can be zeolite molecular sieve and/or non-zeolite molecular sieve.Described zeolite molecular sieve can be one or more in erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta zeolite and omega zeolite.Described non-zeolite molecular sieve can be one or more in phosphate aluminium molecular sieve, HTS and SAPO (that is, SAPO) molecular sieve.According to the present invention, described molecular sieve is preferably hydrogen type molecular sieve.Described hydrogen type molecular sieve can be commercially available, also can adopt conventional method preparation.Such as, the ammonium ion exchange method that sodium form molecular sieve is conventional can be carried out ion-exchange and drying, form ammonium type molecular sieve, then form hydrogen type molecular sieve through roasting.
In the present invention, described hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or hydrocracking catalyst.Being selected from group VIII and being selected from the metal component of group vib for conventional selection in described catalyst, such as, described metal component of group VIII is selected from cobalt and/or nickel, and metal component of group VIB is selected from molybdenum and/or tungsten.
In a specific embodiment, with oxide basis and with described catalyst for benchmark, the carrier of catalyst of the present invention preferably containing 50-90 % by weight, the metal component of group VIII of 1-10 % by weight, the metal component of group VIB of 5-40 % by weight; Further preferred catalyst contains the carrier of 60-85 % by weight, the metal component of group VIII of 1.5-6 % by weight, the metal component of group VIB of 10-35 % by weight.
In the present invention, the method introducing at least one group VIII and at least one group vib metal component in described carrier is this area conventional process, such as, can be will be selected from the method for flooding described carrier after group vib metallic compound is mixed with mixed solution containing at least one group VIII and at least one; It can be the method by being selected from impregnated carrier after the independent obtain solution of group vib metallic compound containing at least one group VIII and at least one.Wherein, by the regulation and control of the concentration of the solution to metallic components, consumption or carrier consumption, can prepare the described catalyst of specifying content, this is those skilled in the art institute easy understand.
According to the present invention, after described impregnation steps completes, optionally the steps such as drying, roasting or not roasting can be carried out.The condition of described drying and roasting is all conventional, and such as, baking temperature is 100-300 DEG C, and be preferably 100-280 DEG C, drying time is 1-12 hour, is preferably 2-8 hour; Sintering temperature is 350-550 DEG C, and be preferably 400-500 DEG C, roasting time is 1-10 hour, is preferably 2-8 hour.
Described group VIII metallic compound is selected from one or more in the soluble compound of these metals, such as, can be one or more in the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
Said group vib metallic compound is selected from one or more in the soluble compound of these metals, such as, can be one or more in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
According to catalyst provided by the invention, before the use preferably in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
In the present invention, to described hydrotreatment reaction condition, there is no particular limitation, preferred reaction condition comprises: reaction temperature 200-420 DEG C, more preferably 220-400 DEG C, pressure 2-18 MPa, more preferably 2-15 MPa, liquid hourly space velocity (LHSV) 0.3-10 hour
-1, more preferably 0.3-5 hour
- 1, hydrogen to oil volume ratio 50-5000, more preferably 50-4000.
The device of described hydrogenation reaction can fill in device in any reaction being enough to make described feedstock oil react with described catalyst exposure under hydrogenation conditions and carry out, such as, described reaction at fixed bed reactors,
Carry out in moving-burden bed reactor or fluidized bed reactor.
Adopt catalyst provided by the invention can process all kinds of hydrocarbon oil crude material.Such as, described hydrocarbon oil crude material can be various heavy mineral oil or artificial oil or their mixed fraction oil, is such as selected from one or more in crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.
Compared with prior art, the hydrogenation activity that the invention provides catalyst improves, and the catalyst particularly prepared through carrier prepared by the hydrated alumina of method modification provided by the invention by the employing containing non-ionic surface active agent, this modification is particularly evident.
Such as, tenor 2.4%NiO and 12%MoO is prepared with carrier prepared by the aluminium oxide article shaped containing non-ionic surface active agent provided by the invention and conventional method respectively
3hydrobon catalyst C and the agent of DC(reference).With the mixed solution of the n-decane containing 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 % by weight for raw material, the hydrodesulfurization activity of two kinds of catalyst is evaluated.With the activity of catalyst DC for 100, the hydrodesulfurization activity of catalyst C is 112.Result shows, compared with the catalyst providing carrier to prepare, is significantly improved by the hydrodesulfurization activity that the invention provides carrier Kaolinite Preparation of Catalyst with prior art.
Detailed description of the invention
Example below will further illustrate the present invention, but not thereby limiting the invention.
In following examples, the content of x-ray fluorescence method to element each in catalyst is adopted to carry out analysiss mensuration (RIPP132-90, see: Petrochemical Engineering Analysis method (RIPP test method), the volumes such as Yang Cuiding, Science Press, 1990,371-375).
The mensuration of sample crystalline phase, relative crystallinity and mean grain size is with reference to " solid catalyst Practical Research method " (Liu Weiqiao, the large volume of Sun Gui, Sinopec publishing house, 2000,57-89) and " Petrochemical Engineering Analysis method (RIPP test method) " (Yang Cuiding, Gu Kanying, Wu Wenhui compiles, Science Press, 1990,394-405) in X-ray diffraction method carry out.
The modification boehmite that embodiment 1-10 declaratives carrier uses and/or false boehmite, its preparation method and the alumina support prepared thus.
The hydrated alumina used in experiment is:
CL-A powder (false boehmite powder), relative relative crystallinity is 100%, grain size 2.9nm, butt 70 % by weight, purchased from Chang Ling catalyst branch company of China Petrochemical Industry.
CL-B powder (boehmite), relative relative crystallinity is 100%, grain size 5.2nm, butt 78 % by weight, purchased from Chang Ling catalyst branch company of China Petrochemical Industry).
CL-C powder (gibbsite (α-Al
2o
33H
2o)), relative relative crystallinity is 100%, grain size 156nm, butt 65 % by weight, purchased from Chang Ling catalyst branch company of China Petrochemical Industry.
Wherein, take 10000 grams of CL-A powder, be extruded into banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support CL-A-Al in air atmosphere
2o
3.Characterize its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Take 10000 grams of CL-B powder, be extruded into banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support CL-B-Al in air atmosphere
2o
3.Characterize its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
The product of roasting obtained according to the step that the invention provides in method (1) is:
CL-A-600: take 10000 grams of CL-A powder and be raised to 600 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-A-600 in 4 hours at 600 DEG C of constant temperature.
CL-A-450: take 10000 grams of CL-A powder and be raised to 450 DEG C with the heating rate of 3 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-A-450 in 4 hours at 450 DEG C of constant temperature.
CL-A-400: take 10000 grams of CL-A powder and be raised to 400 DEG C with the heating rate of 5 DEG C/min in Muffle furnace in a nitrogen atmosphere, and obtain CL-A-400 in 4 hours at 400 DEG C of constant temperature.
CL-A-350: take 10000 grams of CL-A powder and be raised to 350 DEG C with the heating rate of 3 DEG C/min in baking oven in a nitrogen atmosphere, and obtain CL-A-350 in 4 hours at 350 DEG C of constant temperature.
CL-B-600: take 10000 grams of CL-B powder and be raised to 600 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-B-600 in 4 hours at 600 DEG C of constant temperature.
CL-B-450: take 10000 grams of CL-B powder and be raised to 450 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-B-450 in 4 hours at 450 DEG C of constant temperature.
CL-B-400: take 10000 grams of CL-B powder and be raised to 400 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-B-400 in 4 hours at 400 DEG C of constant temperature.
CL-B-350: take 10000 grams of CL-B powder and be raised to 350 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-B-350 in 4 hours at 350 DEG C of constant temperature.
CL-C-600: take 10000 grams of gibbsite-powder and be raised to 600 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-C-600 in 4 hours at 600 DEG C of constant temperature.
CL-C-450: take 10000 grams of gibbsite-powder and be raised to 450 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-C-450 in 6 hours at 450 DEG C of constant temperature.
CL-C-400: take 10000 grams of gibbsite-powder and be raised to 400 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-C-400 in 6 hours at 400 DEG C of constant temperature.
CL-C-350: take 10000 grams of gibbsite-powder and be raised to 350 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, and obtain CL-C-350 in 6 hours at 350 DEG C of constant temperature.
Embodiment 1
Take respectively in 350 grams, the CL-A powder of butt, 120 grams, CL-A-600 powder (CL-A-600 powder with in the mass ratio of butt CL-A powder for 0.34), they and 3600 grams of deionized waters are mixed into slurries; These slurries being transferred to the volume that band stirs is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C after airtight, and under agitation constant temperature 4 hours; Afterwards, be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the product Q-S1 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S1 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 2
Take respectively in 224 grams, the CL-A powder of butt, 300 grams, CL-A-600 powder (CL-A-600 powder with in the mass ratio of the CL-A powder of butt for 1.34), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S2 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S2 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 3
Take respectively in 109 grams, the CL-A powder of butt, 464 grams, CL-A-600 powder (CL-A-600 powder with in the mass ratio of the CL-A powder of butt for 4.25), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S3 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Formed alumina provided by the invention and preparation thereof:
Q-S3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S3 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 4
Take respectively in 84 grams, the CL-A powder of butt, 100 grams, CL-A-350 powder, 150 grams, CL-A-400 powder, 250 grams, CL-A-450 powder, 180 grams, CL-A-600 powder (total amount of CL-A-350 ~ 600 powder with in the mass ratio of the CL-A powder of butt for 8.10), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S4 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S4 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S4 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 5
Take respectively in 140 grams, the CL-A powder of butt, 100 grams, CL-A-350 powder, 200 grams, CL-A-400 powder, 300 grams, CL-A-450 powder, 10 grams, CL-A-600 powder (total amount of CL-A-350 ~ 600 powder with in the mass ratio of the CL-A powder of butt for 4.36), they and 3100 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 60 DEG C of constant temperature 48 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S5 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S5 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S5 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 6
Take respectively in 70 grams, the CL-A powder of butt, 200 grams, CL-A-350 powder, 100 grams, CL-A-400 powder, 400 grams, CL-A-450 powder, 20 grams, CL-A-600 powder (total amount of CL-A-350 ~ 600 powder with in the mass ratio of the CL-A powder of butt for 10.29), they and 3200 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 100 DEG C of constant temperature 24 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S6 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S6 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S6 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 7
Take respectively in 70 grams, the CL-A powder of butt, 14 grams, CL-B powder, 60 grams, CL-A-350 powder, 20 grams, CL-B-350 powder, 20 grams, CL-C-350 powder, 100 grams, CL-A-400 powder, 30 grams, CL-B-400 powder, 20 grams, CL-C-400 powder, 220 grams, CL-A-450 powder, 20 grams, CL-B-450 powder, 10 grams, CL-C-450 powder, 150 grams, CL-A-600 powder, 22 grams, CL-B-600 powder, 8 grams, CL-C-600 powder (total amount of CL-350 ~ 600 powder with in the mass ratio of the CL powder of butt for 8.09), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S7 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S7 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 8
Take respectively in 70 grams, the CL-A powder of butt, 14 grams, CL-B powder, 60 grams, CL-A-350 powder, 20 grams, CL-B-350 powder, 20 grams, CL-C-350 powder, 100 grams, CL-A-400 powder, 30 grams, CL-B-400 powder, 20 grams, CL-C-400 powder, 220 grams, CL-A-450 powder, 20 grams, CL-B-450 powder, 10 grams, CL-C-450 powder, 150 grams, CL-A-600 powder, 22 grams, CL-B-600 powder, 8 grams, CL-C-600 powder (total amount of CL-350 ~ 600 powder with in the mass ratio of the CL powder of butt for 8.09), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight.After being down to room temperature, high pressure kettle cover is opened, add 11.75 grams of ammonium dihydrogen phosphate (ADP)s, continue stirring 24 hours in room temperature, after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S8 containing auxiliary agent phosphorus through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S8 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.X-fluorescence method is adopted to measure the content of adjuvant component, in the mass fraction of the described phosphate builder of element for 0.41%.
Embodiment 9
Take respectively in 224 grams, the CL-A powder of butt, 300 grams, CL-A-600 powder (CL-A-600 powder with in the mass ratio of the CL-A powder of butt for 1.34), they and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight.After being down to room temperature, high pressure kettle cover is opened, add 84.51 grams of titanium sulfates, continue stirring 24 hours, then filter.By filter cake through 120 DEG C of dryings 8 hours, obtain the hydrated alumina Q-S9 containing auxiliary agent titanium through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S9 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S9 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.X-fluorescence method is adopted to measure the content of adjuvant component, in the mass fraction of the described titanium auxiliary agent of element for 3.12%.
Embodiment 10
Take respectively in 230 grams, the CL-B powder of butt, 320 grams, CL-A-450 powder (CL-A-600 powder with in the mass ratio of butt CL-B powder for 1.39), they and 3600 grams of deionized waters are mixed into slurries; These slurries being transferred to the volume that band stirs is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 200 DEG C after airtight, and under agitation constant temperature 4 hours; Afterwards, be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the product Q-S10 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S10 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 11-13 illustrates the modifier preparing boehmite and/or false boehmite by conventional method of modifying that the present invention uses and the alumina support prepared by this modifier.
Embodiment 11
Take 470 grams, the CL-A powder in butt, itself and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina QBF-1 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
QBF-1 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S11 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 12
Take 470 grams of CL-A-600 powder, itself and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 160 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina QBF-2 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
QBF-2 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S12 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Embodiment 13
Take 470 grams, the CL-B powder in butt, itself and 3600 grams of deionized waters are mixed into slurries; The volume these slurries being transferred to band stirring is in the autoclave of stainless steel band polytetrafluoro liner of 5 liters, is heated to 200 DEG C of constant temperature 4 hours after airtight; Be down to room temperature and after filtering, by filter cake in 120 DEG C of dryings 8 hours, obtain the hydrated alumina QBF-3 through modification.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
QBF-3 banded extruder (with embodiment 1) is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.Wet bar is through 120 DEG C of dryings after 4 hours, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtains alumina support S13 in air atmosphere.Characterize its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N
2absorption/desorption measures its specific area and pore volume, and the results are shown in Table 2.
Table 1
Wherein, when measuring the degree of crystallinity of false boehmite, with CL-A powder for standard specimen; When measuring the degree of crystallinity of boehmite, with CL-B powder for standard specimen; When measuring gama-alumina degree of crystallinity, with CL-B-Al
2o
3thing standard specimen.
Table 2
| Embodiment | Aluminium oxide | Specific area, m 2/g | Pore volume, cm 3/g |
| CL-A-Al 2O 3 | 283 | 0.71 | |
| CL-B-Al 2O 3 | 201 | 0.51 | |
| 1 | S1 | 255 | 0.66 |
| 2 | S2 | 238 | 0.62 |
| 3 | S3 | 213 | 0.61 |
| 4 | S4 | 236 | 0.62 |
| 5 | S5 | 265 | 0.68 |
| 6 | S6 | 258 | 0.66 |
| 7 | S7 | 216 | 0.60 |
| 8 | S8 | 222 | 0.61 |
| 9 | S9 | 243 | 0.63 |
| 10 | S10 | 185 | 0.60 |
| 11 | S11 | 233 | 0.52 |
| 12 | S12 | 173 | 0.60 |
| 13 | S13 | 131 | 0.45 |
Embodiment 14-29 illustrates the carrier that the invention provides, aluminium oxide article shaped namely containing nonionic surface active agent and preparation method thereof.
Embodiment 14
Take carrier S 1200 grams and be placed in autoclave; 1.31 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 90 DEG C of constant temperature 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S1 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 15
Take carrier S 2200 grams and be placed in autoclave; 1.76 grams of Tween-60s are dissolved in ethanol water 200 milliliters (by 180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, after airtight, put 48 hours in ambient temperatare.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S2 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 16
Take carrier S 3200 grams and be placed in autoclave; 3.65 grams of Tween-80s are dissolved in ethanol water 200 milliliters (by 180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 60 DEG C of constant temperature 18 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S3 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 17
Take carrier S 4200 grams and be placed in autoclave; Containing 1.07 grams of Triton X-100 aqueous solution 200 milliliters, then will join in autoclave, in 120 DEG C of constant temperature 6 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S4 containing non-ionic surface active agent.In carrier, the mass fraction value of non-ionic surface active agent lists in table 3.
Embodiment 18
Take carrier S 5200 grams and be placed in autoclave; 0.85 gram of polyoxyethylene one polyoxypropylene one polyoxyethylene triblock copolymer is dissolved in absolute ethyl alcohol 200 milliliters, then joins in autoclave, in 160 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S5 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 19
Take carrier S 6200 grams and be placed in autoclave; 4.51 grams of Triton X-100s are dissolved in ethanol water 200 milliliters (by 170 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 180 DEG C of constant temperature 2 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S6 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 20
Take carrier S 7200 grams and be placed in autoclave; 5.05 grams of Tween-20s are dissolved in ethanol water 200 milliliters (by 160 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 110 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S7 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 21
Take carrier S 8200 grams and be placed in autoclave; 4.46 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 120 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S8 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 22
Take carrier S 9200 grams and be placed in autoclave; 4.58 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 130 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S9 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 23
Take carrier S 10200 grams and be placed in autoclave; 1.03 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 80 DEG C of constant temperature 10 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S10 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 24
Take carrier S 11200 grams and be placed in autoclave; 1.31 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 90 DEG C of constant temperature 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S11 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 25
Take carrier S 12200 grams and be placed in autoclave; 1.31 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 90 DEG C of constant temperature 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S12 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 26
Take carrier S 13200 grams and be placed in autoclave; 1.31 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 90 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S13 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 27
Take support C L-A-Al
2o
3200 grams are placed in autoclave; 1.31 grams of Tween-20s are dissolved in ethanol water 200 milliliters (180 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 90 DEG C of constant temperature 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S14 containing non-ionic surface active agent.In non-carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 28
The hydrated alumina Q-S2 powder of preparation and embodiment 2 equivalent, then rear banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory is mixed with 25 grams of silicon dioxide powders (purchased from Chang Ling catalyst branch company of China Petrochemical Industry), model: F-26 (III)) be extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, through 120 DEG C of dryings 4 hours, 600 DEG C are raised to the heating rate of 4 DEG C/min in last Muffle furnace in air atmosphere, then 600 DEG C of constant temperature 4 hours, alumina support S14 is obtained.
Take carrier S 14200 grams and be placed in autoclave; 5.38 grams of Tween-20s and 0.96 gram of Triton X-100 are dissolved in ethanol water 200 milliliters (by 190 milliliters of absolute ethyl alcohols, surplus is water, mixes), then join in autoclave, in 100 DEG C of constant temperature 2 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S15 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 29
The hydrated alumina Q-S2 powder of preparation and embodiment 2 equivalent, then with 36 grams of Hydrogen Y molecular sieve (Na
2o content 0.2%, cell parameter 2.464, relative crystallinity 88%, purchased from Chang Ling catalyst branch company of China Petrochemical Industry) the rear banded extruder of mixing (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) be extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, through 120 DEG C of dryings 4 hours, be finally raised to 600 DEG C with the heating rate of 4 DEG C/min in Muffle furnace in air atmosphere, then 600 DEG C of constant temperature 4 hours, alumina support S15 is obtained.
Take carrier S 15200 grams and be placed in autoclave; 6.56 grams of Tween-20s, 1.23 grams of Triton X-100s and 0.86 gram of polyoxyethylene one polyoxypropylene one polyoxyethylene triblock copolymer are dissolved in ethanol water 200 milliliters (by 185 milliliters of absolute ethyl alcohols, surplus is water, mix), then join in autoclave, in 100 DEG C of constant temperature 3 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain the aluminium oxide article shaped R-S16 containing non-ionic surface active agent.In carrier, the mass fraction of non-ionic surface active agent lists in table 3.
Embodiment 30-45 illustrates catalyst provided by the invention and preparation thereof.
Respectively with R-S1, R-S2, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8, R-S9, R-S10, R-S11, R-S12, R-S13, R-S14, R-S15 and R-S16 that the ammonia spirit 199 milliliters dipping embodiment 14 ~ 29 containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates prepares, dip time 2 hours, impregnation product was in 120 DEG C of dryings 4 hours afterwards, obtained catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and C16.
Comparative example 1-4 illustrates comparative catalyst and preparation thereof.
Comparative example 1
Take carrier S 11200 grams, the ammonia spirit 199 milliliter of this carrier S 11 containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates is flooded above-mentioned carrier 2 hours, then 120 DEG C of dryings 4 hours, obtains catalyst D1.
Comparative example 2
Take carrier S 12200 grams, the ammonia spirit 199 milliliter of this carrier S 12 containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates is flooded above-mentioned carrier 2 hours, then 120 DEG C of dryings 4 hours, obtains catalyst D2.
Comparative example 3
Take carrier S 13200 grams, the ammonia spirit 199 milliliter of this carrier S 13 containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates is flooded above-mentioned carrier 2 hours, then 120 DEG C of dryings 4 hours, obtains catalyst D3.
Comparative example 4
Take support C L-A-Al
2o
3200 grams, by this support C L-A-Al
2o
3flood above-mentioned carrier 2 hours with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates, then 120 DEG C of dryings 4 hours, obtain catalyst D4.
Catalyst performance evaluation:
The hydrodesulfurization performance of the comparative catalyst that Evaluation operation example 30-45 provides catalyst and comparative example 1-4 to provide, the results are shown in table 3.
Evaluating catalyst is to contain 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) mixed solution of n-decane of 0.59 % by weight is raw material, in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation company, model: DADI) hydrodesulfurization activity of upper evaluate catalysts, become by catalyst breakage diameter to be 40-60 object particle, the loadings of catalyst is 0.15 gram.Before formal charging, first carry out presulfurization to catalyst with the cyclohexane containing 6 % by weight carbon disulfide respectively for sulfurized oil, the condition of presulfurization comprises: pressure is 4.14MPa, and temperature is 362 DEG C, time is 3.5 hours, and sulfurized oil feed rate is 0.2 ml/min.After sulfuration terminates, being cooled to reaction temperature is 280 DEG C, incision raw material.Reaction condition comprises: raw material feed rate is 0.2 ml/min, and pressure is 4.14MPa, and hydrogen to oil volume ratio is 900.React and sample in high-pressure separator exit after 3 hours.Gained sample Agilent6890N gas chromatograph is analyzed.Wherein, the hydrodesulfurization activity A of 4,6-DMDBT is calculated as follows:
A＝ln[100/(100-X)]，
In formula, X is the desulfurization degree (circular of X see " catalysis journal ", 2002,23(3) of 4,6-DMDBT: 271-275).
The hydrodesulfurization activity getting 4,6-DMDBT of comparative catalyst D1 is 100, then other catalyst relative 4,6-DMDBT hydrodesulfurization activity can be represented by the formula:
Relative activity=(A
qT/ A
d1) × 100%, A in formula
qTfor the activity of other catalyst, A
d1for the activity of reference catalyst.
Table 3
Shown by the result of table 3, all show higher hydrodesulfurization activity according to hydrogenation catalyst of the present invention.
Claims (11)
1. a hydrogenation catalyst, the metal component that the VIIIth race and at least one are selected from group VIB is selected from containing carrier and at least one, it is characterized in that, described carrier is a kind of aluminium oxide article shaped, containing nonionic surface active agent in described aluminium oxide article shaped, with described carrier for benchmark, the mass fraction of described nonionic surface active agent is 0.1%-10%.
2. the catalyst according to 1, is characterized in that, with described carrier for benchmark, the mass fraction of described nonionic surface active agent is 0.3%-5%.
3. the catalyst according to 1, it is characterized in that, described nonionic surface active agent is selected from one or more in APES, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, polyoxyethylene amine, polyoxyethylate amide, the ethylene oxide adduct of polypropylene glycol, sorbitan ester, sucrose ester, ethoxylated dodecyl alcohol, polyoxyethylene oleic acid ester, polyoxyethylene stearic acid ester, Triton X-100, polyoxyethylene one polyoxypropylene one polyoxyethylene triblock copolymer, polyalcohol.
4. the catalyst according to 3, is characterized in that, described polyalcohol is selected from polysorbas20, polysorbate40, polysorbate60, Tween 80, Arlacel-20, Arlacel-80, triton x-100.
5. the catalyst according to 1, it is characterized in that, containing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide in described article shaped, with described carrier for benchmark, the mass fraction of described adjuvant component is less than 10%.
6. the article shaped according to 5, is characterized in that, with described carrier for benchmark, the mass fraction of described adjuvant component is 0.3%-5%.
7. the catalyst according to 1 or 5, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described carrier for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
8. the catalyst according to 7, is characterized in that, with described carrier for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
9. the catalyst according to 1, is characterized in that, with described catalyst for benchmark, described catalyst contains the carrier of 50-90 % by weight, the metal component of group VIII of 1-10 % by weight, the metal component of group VIB of 5-40 % by weight.
10. the catalyst according to 9, is characterized in that, with described catalyst for benchmark, described catalyst contains the carrier of 60-85 % by weight, the metal component of group VIII of 1.5-6 % by weight, the metal component of group VIB of 10-35 % by weight.
11. 1 kinds of hydrogenation method for hydrocarbon oils, under being included in hydrogenation conditions, reacting hydrocarbon ils and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in claim 1-10 any one.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724163A (en) * | 2005-07-13 | 2006-01-25 | 北京化工大学 | Preparation for high dispersing, amorphous, high efficient novel desulfate catalyst |
| CN101374598A (en) * | 2006-01-17 | 2009-02-25 | 埃克森美孚研究工程公司 | Selective catalysts having high temperature alumina supports for naphtha hydrodesulfurization |
| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101462080A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with non-uniform distribution of active metal component |
| CN102039138A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Heavy oil or residual oil hydrogenation catalyst and preparation method thereof |
| CN103052445A (en) * | 2010-08-13 | 2013-04-17 | 国际壳牌研究有限公司 | A chelant and polar additive containing composition useful in the hydroprocessing of hydrocarbon feedstocks and method of making and use thereof |
-
2014
- 2014-04-09 CN CN201410140809.4A patent/CN104971773B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724163A (en) * | 2005-07-13 | 2006-01-25 | 北京化工大学 | Preparation for high dispersing, amorphous, high efficient novel desulfate catalyst |
| CN101374598A (en) * | 2006-01-17 | 2009-02-25 | 埃克森美孚研究工程公司 | Selective catalysts having high temperature alumina supports for naphtha hydrodesulfurization |
| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101462080A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Method for preparing catalyst with non-uniform distribution of active metal component |
| CN102039138A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Heavy oil or residual oil hydrogenation catalyst and preparation method thereof |
| CN103052445A (en) * | 2010-08-13 | 2013-04-17 | 国际壳牌研究有限公司 | A chelant and polar additive containing composition useful in the hydroprocessing of hydrocarbon feedstocks and method of making and use thereof |
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