CN106140308A - A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils - Google Patents
A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils Download PDFInfo
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Abstract
A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils, described catalyst contain carrier and at least one selected from group VIII and at least one is selected from the metal component of vib, it is characterised in that described carrier is containing R1R2R3R4N+X-Aluminium oxide article shaped, on the basis of described carrier, described R1R2R3R4N+X-Mass fraction be 0.1%-10%, described catalyst is possibly together with except R1R2R3R4N+X-The second outer Organic substance, on the basis of catalyst, described second organic mass fraction is 0.1-30%.Compared with prior art, the present invention provides the performance of catalyst to be improved.
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 the strictest environmental regulation force oil refining circle more to focus on Clean Fuel Production technological development, and how the productions super-low sulfur oil product of economical rationality has become and refines oil one of problem of needing emphasis to solve in boundary's current and expected future regular period.Exploitation has more high activity and selective novel hydrogenation catalyst is then to produce one of most economical method of clear gusoline.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of improved hydrogenation catalyst of performance and application thereof.
The present invention relates to herein below:
1. a hydrogenation catalyst, containing carrier and at least one selected from group VIII and at least one is selected from the metal component of vib, it is characterised in that described carrier is containing R1R2R3R4N+X-Aluminium oxide article shaped, on the basis of described carrier, described R1R2R3R4N+X-Mass fraction be 0.1%-10%, described R1R2R3R4N+X-One or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein said R1、R2、R3、R4Selected from hydrogen, hydrocarbon substituent and derivant thereof；Described catalyst is possibly together with except R1R2R3R4N+X-The second outer Organic substance, on the basis of catalyst, described second organic mass fraction is 0.1-30%.
2. according to the catalyst described in 1, it is characterised in that on the basis of described carrier, described R1R2R3R4N+X-Mass fraction be 0.3%-5%, on the basis of catalyst, described second organic mass fraction is 1-22%.
3. according to the catalyst described in 1, it is characterised in that described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, or the cycloalkyl selected from C3-C20, or the aryl selected from C6-C20；The derivant of described hydrocarbon substituent is selected from hydroxyl and/or the alkyl of heterocyclic substituent.
4. according to the catalyst described in 3, it is characterised in that described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C18；Or the cycloalkyl selected from C6-C18；Or the aryl selected from C6-C18.
5. according to the catalyst described in 1,2 or 3 any one, it is characterised in that described X is selected from chlorine, bromine or iodine.
6. according to the catalyst described in 5, it is characterised in that described X is selected from chlorine or bromine.
7. according to the catalyst described in 1,2 or 3 any one, it is characterised in that described R1R2R3R4N+X-Selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromide, double dodecyldimethylamine ammonium chlorides, DDA, dioctadecyl dimethyl ammonium chloride, one or more of Dodecyl trimethyl ammonium chloride and Dodecyl trimethyl ammonium chloride.
8. according to the catalyst described in 1,2 or 3 any one, it is characterised in that described R1R2R3R4N+X-Selected from ethanolamine salt, dococylpyridinium hydrochlorate.
9. according to the catalyst described in 1, it is characterised in that one or more in organic carboxyl acid and ammonium salt thereof of described second Organic substance.
10. according to the catalyst described in 9, it is characterized in that, one or more in trans CDTA, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid of described organic carboxyl acid.
11. according to the catalyst described in 1, it is characterized in that, described group VIII metal is selected from nickel and/or cobalt, described vib metals is selected from molybdenum and/or tungsten, on the basis of described catalyst, the mass fraction of described group VIII metal component is 1-10%, and the mass fraction of vib metals component is 5-40%.
12. according to the catalyst described in 11, it is characterised in that on the basis of described catalyst, and the mass fraction of described group VIII metal component is 1.5-6%, and the mass fraction of vib metals component is 10-35%.
13. according to the catalyst described in 1, it is characterized in that, containing one or more adjuvant components in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide in described aluminium oxide article shaped, on the basis of described carrier, the mass fraction of described adjuvant component is less than 10%.
14. according to the article shaped described in 13, it is characterised in that on the basis of described carrier, and the mass fraction of described adjuvant component is 0.3%-5%.
15. according to the catalyst described in 1 or 13, it is characterised in that containing clay and/or molecular sieve in described aluminium oxide article shaped, on the basis of described carrier, the mass fraction of described clay and/or molecular sieve is less than 35%.
16. according to the catalyst described in 15, it is characterised in that on the basis of described carrier, and the mass fraction of described clay and/or molecular sieve is 1%-20%.
17. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, by hydrocarbon ils and catalyst haptoreaction, it is characterised in that described catalyst is the catalyst described in aforesaid 1-16 any one.
In the present invention, described aluminium oxide can be one or more in γ, η, θ, δ and χ, preferably gama-alumina.Described aluminium oxide has specific surface and the pore volume of conventional alumina, and the specific surface of preferential oxidation aluminum is 150-350 rice2/ gram, more preferably 180-320 rice2/ gram, the pore volume of preferential oxidation aluminum 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.For example, it may be prepared after molding, roasting by one or more in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina.
The molding of described aluminium oxide uses customary way to carry out, such as methods such as tabletting, spin, extrusions.When using customary way molding, it is smoothed out to aforesaid material to be formed (such as guarantee molding, the mixture of one or more in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina) in introduce auxiliary agent be allow, such as when extrusion, appropriate peptizer, extrusion aid and water, extrusion molding afterwards can be introduced in aforesaid material to be formed.Described peptizer, the kind of extrusion aid and consumption may each be this area routine, the most common peptizer can be selected from one or more in nitric acid, acetic acid, citric acid, formic acid, trichloroacetic acid, hydrochloric acid, malonic acid, and described extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH.
In one preferred embodiment, the gama-alumina that described aluminium oxide article shaped is the boehmite of a kind of modification and/or false boehmite obtains after molding, roasting.
The method of described modified boehmite and/or false boehmite includes: at least one hydrated alumina roasting, described roasting condition are included by (1): 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 mixs, obtain one mixture；(3) mixture that step (2) obtains being carried out in closed reactor hydrothermal treatment consists, hydrothermal conditions includes: temperature is 60 DEG C-250 DEG C, and the time is 0.5 hour-48 hours；(4) product that step (3) obtains is dried, obtains the boehmite of modification and/or false boehmite.
Wherein, the roasting condition of preferred described step (1) including: temperature is 300-750 DEG C, and the time is 1-24 hour.The roasting condition of further preferred described step (1) including: temperature is 350-650 DEG C, and the time is 2-10 hour.
In the mixture that the product of roasting that step (1) is obtained by the most described step (2) and at least one boehmite or false boehmite and water are mixed to get, solid content in mass is 1%-80%, wherein, described product of roasting and the mass ratio of the boehmite counted with butt or false boehmite are as 0.1-20.In the mixture that the product of roasting that step (1) is obtained by further preferred described step (2) and at least one boehmite or false boehmite and water are mixed to get, solid content in mass is 5%-70%, wherein, described product of roasting and the mass ratio of the boehmite counted with butt or false boehmite are as 0.2-12.
When the water content in described mixture be enough to make described mixture be serosity (such as, solid content in mass is less than 35%) time, described step (4) be dried before preferably include filter step.
The hydrothermal conditions of preferred described step (3) including: temperature be 60 DEG C to less than 140 DEG C, the time is 0.5-48 hour.The hydrothermal conditions of further preferred described step (3) including: temperature is 80-120 DEG C, and the time is 4-24 hour.Or, the hydrothermal conditions of preferred described step (3) including: temperature is that the time is 0.5-48 hour more than or equal to 140 DEG C to less than or equal to 250 DEG C；The hydrothermal conditions of further preferred described step (3) including: temperature is 150-220 DEG C, and the time is 4-24 hour.
The baking temperature of the most 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, one or more in Alumina hydrate, false boehmite, boehmite of described hydrated alumina.
Wherein, described Alumina hydrate includes gibbsite (α-Al2O3·3H2O), surge aluminum stone (β1-Al2O3·3H2And promise diaspore (β O)2-Al2O3·3H2O)。
Described false boehmite is also called boehmite, characterizes with X-ray diffraction, occurs the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse for one at 14.5 ° ± 0.5 ° (2 θ).
Described boehmite is also called boehmite, characterize with X-ray diffraction, the hydrated alumina (boehmite the diffraction maximum not available for the false boehmite corresponding to (131), (220) and (151) crystal face occurs respectively 45.8 °, 51.6 ° and 55.2 °) of the strongest, narrow and sharp-pointed (020) crystallographic plane diffraction peak occurs at 14.5 ° ± 0.5 ° (2 θ) for one.
Inventors of the present invention have surprisingly found that, by boehmite and/or false boehmite with one or more 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, further preferably mix through 350 DEG C of-650 DEG C of roastings (heat treatment) hydrated aluminas of 2-10 hour and water, obtain a kind of mixture, and by this mixture in hermetic container in 60 DEG C of-250 DEG C of hydrothermal treatment consists 0.5-48 hour, it is preferable over 80-220 DEG C of hydrothermal treatment consists 4-24 hour, thus the relative crystallinity of the modified boehmite obtained and/or false boehmite improves, and the most fired aluminium oxide obtained maintains higher specific surface area and pore volume.
In the present invention, when controlling hydrothermal treatment consists temperature and being more than 140 DEG C, gained modified product is boehmite；When controlling hydrothermal treatment consists temperature less than 140 DEG C, the crystalline phase of products therefrom keeps consistent with initiation material.
In a detailed description of the invention, preferably make the hydrothermal conditions of the described step (3) that the crystalline phase of described modified product is consistent with initiation material include: temperature be 60 DEG C to less than 140 DEG C, the time is 0.5-48 hour；The hydrothermal conditions of further preferred described step (3) including: temperature is 80-120 DEG C, and the time is 1-24 hour.
In another embodiment, the hydrothermal conditions of the described step (3) preferably making described modified product be boehmite including: temperature is that the time is 0.5-48 hour more than or equal to 140 DEG C to less than or equal to 250 DEG C；The hydrothermal conditions of further preferred described step (3) including: 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, it is also possible to be to use arbitrary prior art to prepare, this is not particularly limited.
Be enough to described hydrated alumina 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, further preferably through 350 DEG C of-650 DEG C of roastings (heat treatment) under conditions of 2-10 hour, the method for roasting described in step (1) is not particularly limited by the present invention.For example, it may be described hydrated alumina to be carried out in usual baking oven or roaster under air atmosphere roasting, it is also possible to be in the baking oven or roaster of vacuum-pumping under vacuum or be passed through under inert gas conditions and carry out.When described roasting is passed through noble gas, described noble gas can be the not oxygen-containing gas that be enough to arbitrarily gasify under described roasting condition, such as, can be one or more in nitrogen, argon, helium, carbon dioxide and water vapour.
Butt in the present invention refers to: be raised to 600 DEG C with the heating rate of 4 DEG C/min in a certain amount of described hydrated alumina Muffle furnace in air atmosphere, then 600 DEG C of constant temperature 4 hours, the percent of the weight ratio of described hydrated alumina, weight × 100% of described hydrated alumina before the weight ÷ roasting of butt=roasting afterproduct before the weight of roasting afterproduct and roasting.
In the present invention, described airtight reactor can be the reactor that can realize described hydro-thermal reaction arbitrarily, such as, autoclave etc., and described reaction can be to carry out under static conditions, also carries out under stirring, preferably carries out hydrothermal treatment consists under stirring.
In the present invention, containing the first organic compound R in described aluminium oxide article shaped1R2R3R4N+X-, on the basis of described carrier, described R1R2R3R4N+X-Mass fraction be 0.1%-10%, preferably 0.3%-5%.R therein1R2R3R4N+X-One or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt.Such as, selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromide, double dodecyldimethylamine ammonium chlorides, DDA, dioctadecyl dimethyl ammonium chloride, one or more of Dodecyl trimethyl ammonium chloride and Dodecyl trimethyl ammonium chloride, or it is selected from ethanolamine salt and dococylpyridinium hydrochlorate and their mixture etc..
Wherein, as described R1R2R3R4N+X-During for primary amine salt, described R1、R2、R3Or R4In a kind of selected from hydrocarbon substituent or the substituent group of hydrocarbon derivative, other are hydrogen；As described R1R2R3R4N+X-During for secondary amine salt, described R1、R2、R3Or R4In two kinds selected from hydrocarbon substituent and/or the substituent group of hydrocarbon derivative, other are hydrogen；As described R1R2R3R4N+X-During for tertiary ammonium salt, described R1、R2、R3Or R4In three kinds selected from hydrocarbon substituent and/or the substituent group of hydrocarbon derivative, another is hydrogen；As described R1R2R3R4N+X-During for quaternary amine, described R1、R2、R3Or R4In four kinds selected from hydrocarbon substituent and/or the substituent group of hydrocarbon derivative.Wherein, when there being the two or more derivant for hydrocarbon substituent and/or hydrocarbon substituent in R1, R2, R3 and R4, they can be the same or different.
Described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, be preferably C1-C18 straight or branched alkyl, such as, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromide, double dodecyldimethylamine ammonium chlorides, DDA, dioctadecyl dimethyl ammonium chloride；Or the cycloalkyl selected from C3-C20, the cycloalkyl of preferably C6-C18, such as, cycloalkyl imidazoline quaternary ammonium salt；Or the aryl selected from C6-C20, the aryl of preferably C6-C18, such as, dodecyl dimethyl benzyl ammonium chloride, lauryl isoquinolinium bromide salt；The substituent group of the derivant of described hydrocarbon is selected from hydroxyl and/or the alkyl of heterocyclic substituent, as the example of substituent group of the derivant of hydrocarbon, such as dococylpyridinium hydrochlorate, glycidyl dodecyl dimethyl ammonium chloride, benzethonium chloride.
Described X is selected from iodine, preferably chlorine or bromine.
Be enough to make in described article shaped the R containing 0.1%-10%, preferably 0.3%-5%1R2R3R4N+X-On the premise of, its method introduced is not limited by the present invention.
In a specific embodiment, described article shaped introduces R1R2R3R4N+X-Method, including: (1) is with containing R1R2R3R4N+X-Solution impregnation described in article shaped, the volume of described impregnation liquid is 0.5-20, preferably 1-15 with the ratio of the pore volume of described article shaped；(2) mixture obtained by dipping carries out heat treatment in closed reactor, heat treatment temperature be room temperature to 250 DEG C, preferably 60 DEG C-220 DEG C, the time is 0.5 hour-48 hours, preferably 1 hour-36 hours；(3) product of drying steps (2), described drying condition includes: temperature is 40 DEG C-250 DEG C, preferably 100 DEG C-180 DEG C, and the time is 1 hour-24 hours, preferably 2 hours-18 hours.
In the present invention, room temperature can be the indoor temperature in each season interior throughout the year, generally 5-40 DEG C.
In the present invention, the solvent of described impregnation liquid is selected from water and/or alcohol (such as ethanol).
Make R in final described article shaped being enough to1R2R3R4N+X-Content meet require on the premise of, the present invention is to the R in impregnation liquid1R2R3R4N+X-Content and dipping number of times be not particularly limited.
In the case of being enough to ensure that and carrying out under described heat treatment is at air tight condition, described closed reactor is not particularly limited by the present invention, common such as autoclave high-pressure reactor etc..
In the present invention, described aluminium oxide article shaped introduces R1R2R3R4N+X-Method in, the purpose that step (3) is dried is to remove the solvent in impregnation product, and on the premise of being enough to realize this purpose, described dry method is not limited by the present invention, can be such as the method for heat drying, it is also possible to be vacuum drying method.
In the present invention, described aluminium oxide can be containing one or more adjuvant components in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, on the basis of described carrier, the mass fraction of described adjuvant component is less than 10%, is preferably as 0.3%-5%.
When described article shaped contains one or more adjuvant components in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, preparation process in described article shaped includes the step introducing one or more adjuvant components in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide, and the method for described introducing adjuvant component is conventional method.For example, it may be will prepare after molding roasting containing the mixture of one or more in the Alumina hydrate of one or more adjuvant components, monohydrate alumina and the amorphous hydroted alumina in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide.Can also be that aluminium oxide and/or its precursor are mixed with the compound containing adjuvant component, after obtain through molding, drying and roasting.
In the present invention, can contain clay and/or molecular sieve in described article shaped, on the basis of described carrier, the mass fraction of described clay and/or molecular sieve is less than 35%, preferably 1%-20%.
When in described article shaped containing clay and/or molecular sieve, the preparation process in described article shaped includes introducing clay and/or the step of molecular sieve, the method thing conventional method of described introducing clay and/or molecular sieve.Such as, the mixture of described clay and/or molecular sieve and one or more in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina described is prepared after molding roasting.
In the present invention, described clay can be selected from one or more in Kaolin, halloysite, montmorillonite, kieselguhr, galapectite, saponite, rectorite, meerschaum, attapulgite, brucite and bentonite.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, it would however also be possible to employ prepared by conventional method.For example, it is possible to the ammonium ion exchange process that sodium form molecular sieve is conventional is carried out ion exchange and is dried, form ammonium type molecular sieve, more fired formation hydrogen type molecular sieve.
Described second organic compound organic carboxyl acid and one or more in trans CDTA, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid and ammonium salt thereof of ammonium salt thereof.
In the present invention, described hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or hydrocracking catalyst.The metal component selected from group VIII with selected from vib in described catalyst is conventional selection, and such as, described group VIII metal component is selected from cobalt and/or nickel, and vib metals component is selected from molybdenum and/or tungsten.
In the present invention, counting and on the basis of described catalyst by oxide, described catalyst preferably comprises the carrier of 50-90 weight %, the group VIII metal component of 1-10 weight %, the vib metals component of 5-40 weight %；Further preferably catalyst contains the carrier of 60-85 weight %, the group VIII metal component of 1.5-6 weight %, the vib metals component of 10-35 weight %.
In the present invention, the method introducing at least one group VIII and at least one vib metals component in described carrier is method customary in the art, for example, it may be by containing at least one group VIII and at least one method impregnating described carrier after vib metals compound is configured to mixed solution；Can be by containing at least one group VIII and at least one method impregnating carrier after vib metals compound individually prepares solution.Wherein, by the concentration of the solution to metallic components, consumption or the regulation of carrier consumption and control, can prepare the described catalyst specifying content, this is that those skilled in the art are readily appreciated by.
According to the present invention, after described impregnation steps completes, optionally can be dried, the step such as roasting or not roasting, the most only be dried, not roasting.The described condition being dried with roasting is all conventional, and such as, baking temperature is 100-300 DEG C, preferably 100-280 DEG C, and drying time is 1-12 hour, preferably 2-8 hour；Sintering temperature is 350-550 DEG C, preferably 400-500 DEG C, and roasting time is 1-10 hour, preferably 2-8 hour.
One or more in the soluble compound of these metals of described group VIII metallic compound, for example, it may be one or more in the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.
One or more in the soluble compound of these metals of described vib metals compound, for example, it may be one or more in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
The catalyst provided according to the present invention, the most in presence of hydrogen, presulfurization is carried out with sulfur, hydrogen sulfide or sulfur-bearing raw material at a 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 it loaded is converted into metal sulfide component.
In the present invention, to described hydrotreating reaction condition, there is no particular limitation, preferably reaction condition includes: 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 any be enough to make described raw oil in hydrogenation conditions under catalytic with described catalyst reaction dress device in carry out, such as, described reaction is carried out in fixed bed reactors, moving-burden bed reactor or fluidized bed reactor.
Compared with prior art, the present invention provides the hydrogenation activity of catalyst to be improved, particularly by containing R1R2R3R4N+X-The catalyst prepared of the carrier prepared of the hydrated alumina using the method provided through the present invention modified, this modification is particularly evident.
Such as, respectively with the present invention provide containing R1R2R3R4N+X-Aluminium oxide article shaped and the carrier prepared of conventional method prepare tenor 2.4%NiO and 12%MoO3Hydrobon catalyst C and DC (reference agent).With containing 4, the mixed solution of the n-decane of 6-dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 weight % is raw material, is evaluated the hydrodesulfurization activity of two kinds of catalyst.With the activity of catalyst DC for 100, the hydrodesulfurization activity of catalyst C is 114.Result shows, compared with the catalyst that prior art provides carrier to prepare, the present invention hydrodesulfurization activity providing carrier to prepare catalyst significantly improves.
The catalyst using the present invention to provide 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, such as 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.
Detailed description of the invention
Example below will be further illustrated the present invention, but not thereby limiting the invention.
In following example, (RIPP132-90, sees: Petrochemical Engineering Analysis method (RIPP test method) to use x-ray fluorescence method that the content of element each in catalyst is analyzed mensuration, Yang Cui surely waits and compiles, Science Press, 1990,371-375).First by catalyst sample 450 DEG C of roastings 6 hours in air atmosphere before XRF test.
The mensuration of sample crystalline phase, relative crystallinity and mean grain size is with reference to " solid catalyst Practical Research method " (Liu Weiqiao, the big 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) the X-ray diffraction method in is carried out.
Modified boehmite that embodiment 1-10 declaratives carrier is used and/or false boehmite, its preparation method and the alumina support thus prepared.
The hydrated alumina used in experiment is:
CL-A powder (false boehmite powder), relative crystallinity is 100%, grain size 2.9nm, butt 70 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.
CL-B powder (boehmite), relative crystallinity is 100%, grain size 5.2nm, butt 78 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company).
CL-C powder (gibbsite (α-Al2O3·3H2O)), relative crystallinity is 100%, grain size 156nm, butt 65 weight %, purchased from middle petrochemical industry Chang Ling catalyst branch company.
Wherein, weigh 10000 grams of CL-A powder, be extruded into, with 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support CL-A-Al in air atmosphere2O3.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Weigh 10000 grams of CL-B powder, be extruded into, with 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support CL-B-Al in air atmosphere2O3.Characterizing its crystalline phase, degree of crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
The product of roasting obtained according to the step (1) in the method for modified boehmite of the present invention and/or false boehmite is:
CL-A-600: weigh in 10000 grams of CL-A powder Muffle furnaces in air atmosphere and be raised to 600 DEG C with the heating rate of 4 DEG C/min, and obtain CL-A-600 in 4 hours at 600 DEG C of constant temperature.
CL-A-450: weigh in 10000 grams of CL-A powder Muffle furnaces in air atmosphere and be raised to 450 DEG C with the heating rate of 3 DEG C/min, and obtain CL-A-450 in 4 hours at 450 DEG C of constant temperature.
CL-A-400: weigh in 10000 grams of CL-A powder Muffle furnaces in a nitrogen atmosphere and be raised to 400 DEG C with the heating rate of 5 DEG C/min, and obtain CL-A-400 in 4 hours at 400 DEG C of constant temperature.
CL-A-350: weigh in 10000 grams of CL-A powder baking ovens in a nitrogen atmosphere and be raised to 350 DEG C with the heating rate of 3 DEG C/min, and obtain CL-A-350 in 4 hours at 350 DEG C of constant temperature.
CL-B-600: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere and be raised to 600 DEG C with the heating rate of 4 DEG C/min, and obtain CL-B-600 in 4 hours at 600 DEG C of constant temperature.
CL-B-450: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere and be raised to 450 DEG C with the heating rate of 4 DEG C/min, and obtain CL-B-450 in 4 hours at 450 DEG C of constant temperature.
CL-B-400: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere and be raised to 400 DEG C with the heating rate of 4 DEG C/min, and obtain CL-B-400 in 4 hours at 400 DEG C of constant temperature.
CL-B-350: weigh in 10000 grams of CL-B powder Muffle furnaces in air atmosphere and be raised to 350 DEG C with the heating rate of 4 DEG C/min, and obtain CL-B-350 in 4 hours at 350 DEG C of constant temperature.
CL-C-600: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere and be raised to 600 DEG C with the heating rate of 4 DEG C/min, and obtain CL-C-600 in 4 hours at 600 DEG C of constant temperature.
CL-C-450: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere and be raised to 450 DEG C with the heating rate of 4 DEG C/min, and obtain CL-C-450 in 6 hours at 450 DEG C of constant temperature.
CL-C-400: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere and be raised to 400 DEG C with the heating rate of 4 DEG C/min, and obtain CL-C-400 in 6 hours at 400 DEG C of constant temperature.
CL-C-350: weigh in 10000 grams of gibbsite-powder Muffle furnaces in air atmosphere and be raised to 350 DEG C with the heating rate of 4 DEG C/min, and obtain CL-C-350 in 6 hours at 350 DEG C of constant temperature.
Embodiment 1
Weigh 350 grams of CL-A powder in terms of butt, 120 grams of CL-A-600 powder (CL-A-600 powder is 0.34 with the mass ratio of the powder of CL-A in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C, and under agitation constant temperature 4 hours；Afterwards, it is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S1 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S1 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 2
Weigh 224 grams of CL-A powder in terms of butt, 300 grams of CL-A-600 powder (CL-A-600 powder is 1.34 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S2 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 3
Weigh 109 grams of CL-A powder in terms of butt, 464 grams of CL-A-600 powder (CL-A-600 powder is 4.25 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S3 being modified.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.
The formed alumina of present invention offer 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 4
Weigh 84 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, 150 grams of CL-A-400 powder, 250 grams of CL-A-450 powder, 180 grams of CL-A-600 powder (total amount of CL-A-350～600 powder is 8.10 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S4 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 5
Weigh 140 grams of CL-A powder in terms of butt, 100 grams of CL-A-350 powder, 200 grams of CL-A-400 powder, 300 grams of CL-A-450 powder, 10 grams of CL-A-600 powder (total amount of CL-A-350～600 powder is 4.36 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3100 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 60 DEG C constant temperature 48 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S5 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 6
Weigh 70 grams of CL-A powder in terms of butt, 200 grams of CL-A-350 powder, 100 grams of CL-A-400 powder, 400 grams of CL-A-450 powder, 20 grams of CL-A-600 powder (total amount of CL-A-350～600 powder is 10.29 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3200 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 100 DEG C constant temperature 24 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S6 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 7
Weigh 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, 60 grams of CL-A-350 powder, 20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder (total amount of CL-350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S7 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S7 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 8
Weigh 70 grams of CL-A powder in terms of butt, 14 grams of CL-B powder, 60 grams of CL-A-350 powder, 20 grams of CL-B-350 powder, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, 220 grams of CL-A-450 powder, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder (total amount of CL-350～600 powder is 8.09 with the mass ratio of the CL powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours.After being down to room temperature, high pressure kettle cover is opened, add 11.75 grams of ammonium dihydrogen phosphates, continue stirring 24 hours in room temperature, after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina Q-S8 containing auxiliary agent phosphorus being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S8 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.Using X-fluorescence method to measure the content of adjuvant component, the mass fraction of the described phosphate builder in terms of element is 0.41%.
Embodiment 9
Weigh 224 grams of CL-A powder in terms of butt, 300 grams of CL-A-600 powder (CL-A-600 powder is 1.34 with the mass ratio of the CL-A powder in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours.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.Filter cake is dried 8 hours through 120 DEG C, obtains the hydrated alumina Q-S9 containing auxiliary agent titanium being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.Using X-fluorescence method to measure the content of adjuvant component, the mass fraction of the described titanium auxiliary agent in terms of element is 3.12%.
Embodiment 10
Weigh 230 grams of CL-B powder in terms of butt, 320 grams of CL-A-450 powder (CL-A-600 powder is 1.39 with the mass ratio of the powder of CL-B in terms of butt) respectively, they and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 200 DEG C, and under agitation constant temperature 4 hours；Afterwards, it is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the product Q-S10 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S10 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
What the embodiment 11-13 explanation present invention used is prepared boehmite and/or the modifier of false boehmite and the alumina support prepared by this modifier by conventional method of modifying.
Embodiment 11
Weigh 470 grams of CL-A powder in terms of butt, itself and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina QBF-1 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S11 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 12
Weigh 470 grams of CL-A-600 powder, itself and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 160 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina QBF-2 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S12 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface area and pore volume, and the results are shown in Table 2.
Embodiment 13
Weigh 470 grams of CL-B powder in terms of butt, itself and 3600 grams of deionized waters are mixed into serosity；In the autoclave of the stainless steel band polytetrafluoro liner that volume is 5 liters that this serosity is transferred to band stirring, airtight post-heating to 200 DEG C constant temperature 4 hours；It is down to room temperature after filtering, filter cake is dried 8 hours in 120 DEG C, obtains the hydrated alumina QBF-3 being modified.Characterizing 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 dried after 4 hours through 120 DEG C, and 600 DEG C of constant temperature 4 hours in Muffle furnace, obtain alumina support S13 in air atmosphere.Characterizing its crystalline phase, relative crystallinity and grain size by X-ray diffraction method, the results are shown in Table 1.Pass through N2Absorption/desorption measures its specific surface 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 as standard specimen；Measure a water admire the degree of crystallinity of aluminum stone time, with CL-B powder as standard specimen；When measuring gama-alumina degree of crystallinity, with CL-B-Al2O3For standard specimen.
Table 2
| Embodiment | Aluminium oxide | Specific surface area, m2/g | Pore volume, cm3/g |
| CL-A-Al2O3 | 283 | 0.71 | |
| CL-B-Al2O3 | 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 |
The carrier that the embodiment 14-29 explanation present invention provides, i.e. contains R1R2R3R4N+X-Aluminium oxide article shaped and preparation method thereof.
Embodiment 14
Weigh carrier S 1 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.36 grams of cetyl trimethylammonium bromide, airtight after in 90 DEG C of constant temperature 24 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S1.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 15
Weigh carrier S 2 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.85 grams of cetyl trimethylammonium bromide, airtight after place 48 hours at room temperature.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S2.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 16
Weigh carrier S 3 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 3.81 grams of cetyl trimethylammonium bromide, airtight after in 60 DEG C of constant temperature 18 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S3.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 17
Weigh carrier S 4 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.10 grams of cetyl trimethylammonium bromide, airtight after in 120 DEG C of constant temperature 6 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S4.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 18
Weigh carrier S 5 200 grams to be placed in autoclave, add containing the aqueous solution 200 milliliters of 0.89 gram of cetyl trimethylammonium bromide, airtight after in 160 DEG C of constant temperature 4 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S5.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 19
Weigh carrier S 6 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 4.86 grams of cetyl trimethylammonium bromide, airtight after in 180 DEG C of constant temperature 2 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S6.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 20
Weigh carrier S 7 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 5.18 grams of cetyl trimethylammonium bromide, airtight after in 110 DEG C of constant temperature 4 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S7.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 21
Weigh carrier S 8 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 4.56 grams of cetyl trimethylammonium bromide, airtight after in 120 DEG C of constant temperature 4 hours.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S8.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 22
Weigh carrier S 9 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 4.69 grams of cetyl trimethylammonium bromide, airtight after process 4 hours in 130 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S9.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 23
Weigh carrier S 10 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.02 grams of cetyl trimethylammonium bromide, airtight after process 10 hours in 80 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S10.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 24
Weigh carrier S 11 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.36 grams of cetyl trimethylammonium bromide, airtight after process 24 hours in 90 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S11.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 25
Weigh carrier S 12 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.36 grams of cetyl trimethylammonium bromide, airtight after process 24 hours in 90 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S12.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 26
Weigh carrier S 13 200 grams to be placed in autoclave, add containing the ethanol solution 200 milliliters of 1.36 grams of cetyl trimethylammonium bromide, airtight after process 4 hours in 90 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S13.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 27
Weigh support C L-A-Al2O3200 grams are placed in autoclave, add containing the ethanol solution 200 milliliters of 1.36 grams of cetyl trimethylammonium bromide, airtight after process 24 hours in 90 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S14.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 28
Preparation and the hydrated alumina Q-S2 powder of embodiment 2 equivalent, then with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory after mixing with 25 grams of silicon dioxide powders (purchased from middle petrochemical industry Chang Ling catalyst branch company), model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, it is dried 4 hours through 120 DEG C, last Muffle furnace in air atmosphere is raised to 600 DEG C with the heating rate of 4 DEG C/min, then 600 DEG C of constant temperature 4 hours, alumina support S14 is obtained.
Weigh carrier S 14 200 grams to be placed in autoclave, add containing 3.56 grams of cetyl trimethylammonium bromide and the ethanol solution 200 milliliters of 3.89 grams of Dodecyl trimethyl ammonium chloride, airtight after process 2 hours in 100 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S15.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
Embodiment 29
Preparation and the hydrated alumina Q-S2 powder of embodiment 2 equivalent, then with 36 grams of Hydrogen Y molecular sieve (Na2O content 0.2%, cell parameter 2.464, relative crystallinity 88%, purchased from middle petrochemical industry Chang Ling catalyst branch company) after mixing with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) it is extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, it is dried 4 hours through 120 DEG C, last Muffle furnace in air atmosphere is raised to 600 DEG C with the heating rate of 4 DEG C/min, then 600 DEG C of constant temperature 4 hours, alumina support S15 is obtained.
Weigh carrier S 15 200 grams to be placed in autoclave, add containing 1.73 grams of cetyl trimethylammonium bromide, 1.12 grams of hexadecyltrimethylammonium chlorides, 3.08 grams of Dodecyl trimethyl ammonium chloride and the ethanol solution 200 milliliters of 3.16 grams of Dodecyl trimethyl ammonium chloride, airtight after process 3 hours in 100 DEG C.After cooling, sample is dried 4 hours in 120 DEG C, obtains containing R1R2R3R4N+X-Aluminium oxide article shaped R-S16.R in carrier1R2R3R4N+X-Mass fraction be listed in table 3.
The catalyst of embodiment 30-48 explanation present invention offer and preparation thereof.
Embodiment 30-45
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 embodiment 14～29 prepares is impregnated respectively with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of ethylenediaminetetraacetic acid, dip time 2 hours, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and C16.
Embodiment 46
With containing 34.96 grams of ammonium heptamolybdates, 1.28 grams trans 1, the R-S1 that the ammonia spirit 199 milliliters dipping embodiment 14 of 2-1,2-diaminocyclohexane tetraacetic acid, 3.56 grams of ethylenediaminetetraacetic acid, 2.58 grams of malic acids, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates prepares, impregnation product is dried 4 hours in 120 DEG C afterwards；Impregnating above-mentioned carrier, dip time 2 hours with the ammonia spirit 199 milliliters containing 22.62 grams of Nickelous nitrate hexahydrates, 12.27 grams of ethylenediaminetetraacetic acid and 3.26 grams of ammonium oxalate the most again, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C17.
Embodiment 47
Impregnating, with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates, 0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acid, 1.56 grams of formic acid, 6.98 grams of ammonium citrates and 36.23 grams of citric acids, the R-S1 that embodiment 14 prepares, impregnation product is dried 4 hours in 120 DEG C afterwards；Impregnating above-mentioned carrier, dip time 2 hours with the ammonia spirit 199 milliliters containing 22.62 grams of Nickelous nitrate hexahydrates, 21.27 grams of ethylenediaminetetraacetic acid and 1.86 grams of aminotriacetic acids the most again, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C18.
Embodiment 48
Impregnating, with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates and 22.51 grams of citric acids, the R-S1 that embodiment 14 prepares, impregnation product is dried 4 hours in 120 DEG C afterwards；Impregnating above-mentioned carrier, dip time 2 hours with the ammonia spirit 199 milliliters containing 22.62 grams of Nickelous nitrate hexahydrates and 23.27 grams of ethylenediaminetetraacetic acid the most again, impregnation product is dried 4 hours in 120 DEG C afterwards, obtains catalyst C19.
Comparative example 1-5 explanation comparative catalyst and preparation thereof.
Comparative example 1
Weigh carrier S 11 200 grams, impregnate 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 and 8.15 grams of ethylenediaminetetraacetic acid, be then dried 4 hours at 120 DEG C, obtain catalyst D1.
Comparative example 2
Weigh carrier S 12 200 grams, impregnate 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 and 8.15 grams of ethylenediaminetetraacetic acid, be then dried 4 hours at 120 DEG C, obtain catalyst D2.
Comparative example 3
Weigh carrier S 13 200 grams, impregnate 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 and 8.15 grams of ethylenediaminetetraacetic acid, be then dried 4 hours at 120 DEG C, obtain catalyst D3.
Comparative example 4
Weigh support C L-A-Al2O3200 grams, impregnate 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 and 8.15 grams of ethylenediaminetetraacetic acid, be then dried 4 hours at 120 DEG C, obtain catalyst D4.
Comparative example 5
Impregnate the R-S1 for preparing of embodiment 14 2 hours with the ammonia spirit 199 milliliters containing 34.96 grams of ammonium heptamolybdates and 22.62 grams of Nickelous nitrate hexahydrates, be then dried 4 hours at 120 DEG C, obtain catalyst D5.
Catalyst performance evaluation:
Evaluating the hydrodesulfurization performance of the comparative catalyst that embodiment 30-48 provides catalyst and comparative example 1-5 to provide, result is listed in table 3.
Evaluating catalyst is with containing 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) mixed solution of the n-decane of 0.59 weight % is raw material, in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation company, model: DADI) the upper hydrodesulfurization activity evaluating catalyst, catalyst breakage becomes the granule of a diameter of 40-60 mesh, and the loadings of catalyst is 0.15 gram.Before formal charging, first respectively catalyst being carried out presulfurization with the hexamethylene containing 6 weight % Carbon bisulfide for sulfurized oil, the condition of presulfurization includes: pressure is 4.14MPa, and temperature is 362 DEG C, and the 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, cuts raw material.Reaction condition includes: raw material feed rate is 0.2 ml/min, and pressure is 4.14MPa, and hydrogen to oil volume ratio is 900.Sample in high-pressure separator exit after reacting 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 4, the desulfurization degree of 6-DMDBT (circular of X see " catalysis journal) ", 2002,23 (3): 271-275).
Taking the 4 of comparative catalyst D1, the hydrodesulfurization activity of 6-DMDBT is 100, then relative the 4 of other catalyst, and the hydrodesulfurization activity of 6-DMDBT can be represented by the formula:
Relative activity=(AQT/AD1) × 100%, A in formulaQTFor the activity of other catalyst, AD1Activity for reference catalyst.
Table 3
Shown by the result of table 3, all show higher hydrodesulfurization activity according to the hydrogenation catalyst of the present invention.
Claims (17)
1. a hydrogenation catalyst, containing carrier with at least one selected from group VIII and at least one choosing
From the metal component of vib, it is characterised in that described carrier is containing R1R2R3R4N+X-Oxidation
Aluminum article shaped, on the basis of described carrier, described R1R2R3R4N+X-Mass fraction be 0.1%-10%,
Described R1R2R3R4N+X-One or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt,
Wherein said R1、R2、R3、R4Selected from hydrogen, hydrocarbon substituent and derivant thereof；Described catalyst possibly together with
Except R1R2R3R4N+X-The second outer Organic substance, on the basis of catalyst, described second organic quality
Mark is 0.1-30%.
Catalyst the most according to claim 1, it is characterised in that on the basis of described carrier, described
R1R2R3R4N+X-Mass fraction be 0.3%-5%, on the basis of catalyst, described second organic
Mass fraction is 1-22%.
Catalyst the most according to claim 1, it is characterised in that described hydrocarbon substituent is selected from C1-
The straight or branched alkyl of C20, or the cycloalkyl selected from C3-C20, or selected from C6-C20
Aryl；The derivant of described hydrocarbon substituent is selected from hydroxyl and/or the alkyl of heterocyclic substituent.
Catalyst the most according to claim 3, it is characterised in that described hydrocarbon substituent is selected from C1-
The straight or branched alkyl of C18；Or the cycloalkyl selected from C6-C18；Or selected from C6-C18
Aryl.
5. according to the catalyst described in any one of claim 1,2 or 3, it is characterised in that described X selects
From chlorine, bromine or iodine.
Catalyst the most according to claim 5, it is characterised in that described X is selected from chlorine or bromine.
7. according to the catalyst described in any one of claim 1,2 or 3, it is characterised in that described
R1R2R3R4N+X-Selected from cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecane
Base amine hydrochlorate, octadecyl amine hydrochloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyltrimethylammonium
Ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl ammonium chloride, didecyl Dimethy
Ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyl two
Ammonio methacrylate, double dodecyldimethylamine base ammonium bromide, double dodecyldimethylamine ammonium chloride, double 18
Alkyl dimethyl ammonium bromide, dioctadecyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride and ten
One or more of dialkyl group trimethyl ammonium chloride.
8. according to the catalyst described in any one of claim 1,2 or 3, it is characterised in that described
R1R2R3R4N+X-Selected from ethanolamine salt, dococylpyridinium hydrochlorate.
Catalyst the most according to claim 1, it is characterised in that described second Organic substance is selected from having
One or more in machine carboxylic acid and ammonium salt thereof.
Catalyst the most according to claim 9, it is characterised in that described organic carboxyl acid is selected from trans
CDTA, ethylenediaminetetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid,
One or more in formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid.
11. catalyst according to claim 1, it is characterised in that described group VIII metal is selected from
Nickel and/or cobalt, described vib metals is selected from molybdenum and/or tungsten, on the basis of described catalyst, described the
The mass fraction of group VIII metal component is 1-10%, and the mass fraction of vib metals component is 5-40
%.
12. catalyst according to claim 11, it is characterised in that with described catalyst as base
Standard, the mass fraction of described group VIII metal component is 1.5-6%, and the quality of vib metals component is divided
Number is 10-35%.
13. catalyst according to claim 1, it is characterised in that contain in described aluminium oxide article shaped
There are one or more in silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide, beryllium oxide
Adjuvant component, on the basis of described carrier, the mass fraction of described adjuvant component is less than 10%.
14. article shaped according to claim 13, it is characterised in that on the basis of described carrier,
The mass fraction of described adjuvant component is 0.3%-5%.
15. according to the catalyst described in claim 1 or 13, it is characterised in that described aluminium oxide molding
Containing clay and/or molecular sieve in thing, on the basis of described carrier, described clay and/or the quality of molecular sieve
Mark is less than 35%.
16. catalyst according to claim 15, it is characterised in that on the basis of described carrier,
The mass fraction of described clay and/or molecular sieve is 1%-20%.
17. 1 kinds of hydrogenation method for hydrocarbon oils, are included under hydrogenation conditions, are contacted instead with catalyst by hydrocarbon ils
Should, it is characterised in that described catalyst is the catalyst described in claim 1-16 any one.
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