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CN104971698A - Aluminum moulded material containing R1R2R3R4N<+>X<->, preparation and application thereof - Google Patents

Aluminum moulded material containing R1R2R3R4N<+>X<->, preparation and application thereof Download PDF

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Publication number
CN104971698A
CN104971698A CN201410140767.4A CN201410140767A CN104971698A CN 104971698 A CN104971698 A CN 104971698A CN 201410140767 A CN201410140767 A CN 201410140767A CN 104971698 A CN104971698 A CN 104971698A
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article shaped
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grams
mass fraction
benchmark
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CN104971698B (en
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李会峰
李明丰
褚阳
刘锋
夏国富
王奎
习远兵
聂红
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

An aluminum moulded material containing R1R2R3R4N<+>X<->, preparation and an application thereof. The aluminum moulded material contains the R1R2R3R4N<+>X<->, wherein the mass percentage of the R1R2R3R4N<+>X<-> is 0.1-10%. The R1R2R3R4N<+>X<-> is selected from one or more of a primary amine salt, a secondary amine salt, a tertiary amine salt or a quaternary amine salt and the R1, the R2, the R3 and the R4 are selected from hydrogen, a hydrocarbon substituted group and derivatives thereof. The moulded material can be used in adsorbents and catalyst carriers.

Description

A kind of containing R 1r 2r 3r 4n +x -aluminium oxide article shaped and Synthesis and applications
Technical field
The present invention relates to aluminium oxide and Synthesis and applications thereof, contain R more specifically to one 1r 2r 3r 4n +x -aluminium oxide article shaped and Synthesis and applications.
Background technology
There is the aluminium oxide (comprising the aluminium oxide of the porous character containing addO-on therapy) of porous character, because it has higher specific area and pore volume, be often used as adsorbent and matrix uses as catalyst carrier.Such as, in PETROLEUM PROCESSING field, the carrier that aluminium oxide is often used as hydrogenation class catalyst uses.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of containing R 1r 2r 3r 4n +x -aluminium oxide article shaped, the preparation method of this article shaped and application thereof.
The present invention relates to following content:
1. one kind contains R 1r 2r 3r 4n +x -aluminium oxide article shaped, containing R 1r 2r 3r 4n +x -, with described article shaped for benchmark, described R 1r 2r 3r 4n +x -mass fraction be 0.1%-10%, described R 1r 2r 3r 4n +x -be selected from one or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein said R 1, R 2, R 3, R 4be selected from hydrocarbon substituent, the derivative of hydrocarbon substituent or hydrogen.
2. the article shaped according to 1, is characterized in that, with described article shaped for benchmark, and described R 1r 2r 3r 4n +x -mass fraction be 0.3%-5%.
3. the article shaped according to 1, is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, or is selected from the cycloalkyl of C3-C20, or is selected from the aryl of C6-C20; The derivative of described hydrocarbon substituent is selected from the alkyl with hydroxyl and/or heterocyclic substituent.
4. the article shaped according to 3, is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C18; Or be selected from the cycloalkyl of C6-C18; Or be selected from the aryl of C6-C18.
5. the article shaped according to 1,2 or 3 any one, is characterized in that, described X is selected from chlorine, bromine or iodine.
6. the article shaped according to 5, is characterized in that, described X is selected from chlorine or bromine.
7. the article shaped according to 1,2 or 3 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from softex kw, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, one or more of DTAB and DTAC.
8. the article shaped according to 1,2 or 3 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from ethanolamine salt, dococylpyridinium hydrochloride.
9. the article shaped 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 article shaped for benchmark, the mass fraction of described adjuvant component is less than 10%.
10. the article shaped according to 9, is characterized in that, with described article shaped for benchmark, the mass fraction of described adjuvant component is 0.3%-5%.
11. article shaped according to 1 or 9, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
12. article shaped according to 11, it is characterized in that, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
13. 1 kinds containing R 1r 2r 3r 4n +x -the preparation method of aluminium oxide article shaped, be included in described aluminium oxide article shaped and introduce R 1r 2r 3r 4n +x -, with described article shaped for benchmark, described R 1r 2r 3r 4n +x -introduction volume make in described article shaped R 1r 2r 3r 4n +x -mass fraction is 0.1%-10%, described R 1r 2r 3r 4n +x -be selected from one or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein said R 1, R 2, R 3, R 4be selected from hydrocarbon substituent, the derivative of hydrocarbon substituent or hydrogen.
14. methods according to 13, is characterized in that, with described article shaped for benchmark, and described R 1r 2r 3r 4n +x -introduction volume make in described article shaped R 1r 2r 3r 4n +x -mass fraction be 0.3%-5%.
15. methods according to 13, it is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, or is selected from the cycloalkyl of C3-C20, or is selected from the aryl of C6-C20; The substituting group of the derivative of described hydrocarbon substituent is selected from the alkyl with hydroxyl and/or heterocyclic substituent.
16. methods according to 15, it is characterized in that, the substituting group of described hydrocarbon is selected from the straight or branched alkyl of C1-C18; Or be selected from the cycloalkyl of C6-C18; Or be selected from the aryl of C6-C18.
17. methods according to 13,14 or 15 any one, it is characterized in that, described X is selected from chlorine, bromine or iodine.
18. methods according to 13,14 or 15 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from softex kw, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, one or more of DTAB and DTAC.
19. methods according to 13,14 or 15 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from ethanolamine salt, dococylpyridinium hydrochloride.
20. methods according to 13, it is characterized in that, be included in described article shaped the step introducing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide in the process, with described article shaped for benchmark, the introduction volume of described adjuvant component makes the mass fraction of adjuvant component in described article shaped be less than 10%.
21. methods according to 20, it is characterized in that, with described article shaped for benchmark, the mass fraction of described adjuvant component is 0.3%-5%.
22. methods according to 13 or 20, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
23. methods according to 22, it is characterized in that, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
24. methods according to 13, is characterized in that, describedly in described aluminium oxide article shaped, introduce R 1r 2r 3r 4n +x -method, comprising: (1) is with containing R 1r 2r 3r 4n +x -solution impregnation described in aluminium oxide article shaped, the volume of described maceration extract is 0.5-20 with the ratio of the pore volume of described article shaped; (2) heat-treat flooding the mixture obtained in closed reactor, heat treatment temperature is room temperature to 250 DEG C, and the time is 0.5 hour-48 hours; (3) product of drying steps (2), described drying condition comprises: temperature is 40 DEG C-250 DEG C, and the time is 1 hour-24 hours.
25. methods according to 24, it is characterized in that, described in step (1), the volume of maceration extract is 1-15 with the ratio of the pore volume of described article shaped; Heat treatment temperature described in step (2) is 60 DEG C to 220 DEG C, and the time is 1 hour-36 hours, and the drying condition of step (3) comprising: temperature is 100 DEG C-180 DEG C, and the time is 2 hours-18 hours.
26. according to any one of 1-12 article shaped as the application of adsorbent.
27. according to any one of 1-12 article shaped as the application of catalyst carrier.
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 obtained after shaping, roasting by one or more being 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, preferred through 350 DEG C of-650 DEG C of roastings (heat treatment) hydrated aluminas of 2-10 hour and water mixing further, obtain a kind of mixture, 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, containing R in described aluminium oxide article shaped 1r 2r 3r 4n +x -, wherein, described R 1r 2r 3r 4n +x -mass fraction be 0.1%-10%, be preferably 0.3%-5%.R wherein 1r 2r 3r 4n +x -be selected from one or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt.Such as, be selected from softex kw, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, one or more of DTAB and DTAC, or be selected from ethanolamine salt and dococylpyridinium hydrochloride and their mixture etc.
Wherein, as described R 1r 2r 3r 4n +x -during for primary amine salt, described R 1, R 2, R 3or R 4in a kind of substituting group being selected from hydrocarbon substituent or hydrocarbon derivative, other are hydrogen; As described R 1r 2r 3r 4n +x -during for secondary amine salt, described R 1, R 2, R 3or R 4in two kinds of substituting groups being selected from hydrocarbon substituent and/or hydrocarbon derivative, other are hydrogen; As described R 1r 2r 3r 4n +x -during for tertiary ammonium salt, described R 1, R 2, R 3or R 4in three kinds of substituting groups being selected from hydrocarbon substituent and/or hydrocarbon derivative, another is hydrogen; As described R 1r 2r 3r 4n +x -during for quaternary amine, described R 1, R 2, R 3or R 4in four kinds of substituting groups being selected from hydrocarbon substituent and/or hydrocarbon derivative.Wherein, when there being the two or more derivative 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, softex kw, hexadecyltrimethylammonium chloride, TTAB, tetradecyl trimethyl ammonium chloride, DTAB, DTAC, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, or be selected from the cycloalkyl of C3-C20, be preferably the cycloalkyl of C6-C18, such as, cycloalkyl imidazoline quaternary ammonium salt, or be selected from the aryl of C6-C20, be preferably the aryl of C6-C18, such as, dodecyl benzyl dimethyl ammonium chloride, lauryl isoquinolinium bromide salt, the substituting group of the derivative of described hydrocarbon is selected from the alkyl with hydroxyl and/or heterocyclic substituent, as the substituent example of the derivative of hydrocarbon, as dococylpyridinium hydrochloride, glycidyl dodecyl dimethyl ammonium chloride, benzethonium chloride.
Described X is selected from iodine, is preferably chlorine or bromine.
Be enough to make, containing 0.1%-10% in described article shaped, to be preferably the R of 0.3%-5% 1r 2r 3r 4n +x -prerequisite under, the present invention does not limit the method that it is introduced.
In a concrete embodiment, in described article shaped, introduce R 1r 2r 3r 4n +x -method, comprising: (1) is with containing R 1r 2r 3r 4n +x -solution impregnation described in article shaped, the volume of described maceration extract is 0.5-20 with the ratio of the pore volume of described article shaped, be 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-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.
In the present invention, room temperature can be the indoor temperature in each season interior throughout the year, is generally 5-40 DEG C.
In the present invention, the solvent of described maceration extract is selected from water and/or alcohol (such as ethanol).
Be enough to make R in final described article shaped 1r 2r 3r 4n +x -the prerequisite that meets the demands of content under, the present invention is to the R in maceration extract 1r 2r 3r 4n +x -content and dipping number of times be not particularly limited.In concrete enforcement, the R in maceration extract described in preferred rate-determining steps (1) 1r 2r 3r 4n +x -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, in described aluminium oxide article shaped, introduce R 1r 2r 3r 4n +x -method in, the dry object of step (3) is the solvent removed in impregnation product, and be enough under the prerequisite realizing this object, the method for the present invention to described drying does not limit, such as, can be 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, and wherein, the mass fraction of described adjuvant component is less than 10%, are preferably as 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, wherein, 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.
Usually, provided by the invention containing R 1r 2r 3r 4n +x -aluminium oxide article shaped can be used as adsorbent or catalyst carrier and use.Further research shows, provided by the invention containing R 1r 2r 3r 4n +x -aluminium oxide article shaped be especially suitable as carrier for the preparation of loaded catalyst, such as hydrogenation catalyst etc.
Such as, R is contained with provided by the invention respectively 1r 2r 3r 4n +x -aluminium oxide article shaped and the carrier prepared of conventional method prepare tenor 2.4%NiO and 12%MoO 3catalyst 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.
Adopt Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometer in following examples, analysis is carried out to the content of element each in catalyst and measures.
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.
Embodiment 1-10 illustrates the modification boehmite that the present invention uses and/or false boehmite, its preparation method and the aluminium oxide prepared thus.
The hydrated alumina used in experiment is:
CL-A powder (false boehmite powder), 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 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 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 aluminium oxide prepared by the method for modifying of the conventional modification boehmite that the present invention uses and/or false boehmite and modifier therefrom.
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 provided by the invention containing R 1r 2r 3r 4n +x -aluminium oxide article shaped and preparation method thereof.
Embodiment 14
Take carrier S 1200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.36 grams of softex kws, in 90 DEG C of constant temperature 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S1.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 15
Take carrier S 2200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.85 grams of softex kws, after airtight, put 48 hours in ambient temperatare.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S2.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 16
Take carrier S 3200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 3.81 grams of softex kws, in 60 DEG C of constant temperature 18 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S3.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 17
Take carrier S 4200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.10 grams of softex kws, in 120 DEG C of constant temperature 6 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S4.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 18
Take carrier S 5200 grams and be placed in autoclave, add the aqueous solution 200 milliliters containing 0.89 gram of softex kw, in 160 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S5.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 19
Take carrier S 6200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 4.86 grams of softex kws, in 180 DEG C of constant temperature 2 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S6.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 20
Take carrier S 7200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 5.18 grams of softex kws, in 110 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S7.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 21
Take carrier S 8200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 4.56 grams of softex kws, in 120 DEG C of constant temperature 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S8.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 22
Take carrier S 9200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 4.69 grams of softex kws, in 130 DEG C of process 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S9.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 23
Take carrier S 10200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.02 grams of softex kws, in 80 DEG C of process 10 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S10.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 24
Take carrier S 11200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.36 grams of softex kws, in 90 DEG C of process 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S11.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 25
Take carrier S 12200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.36 grams of softex kws, in 90 DEG C of process 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S12.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 26
Take carrier S 13200 grams and be placed in autoclave, add the ethanol solution 200 milliliters containing 1.36 grams of softex kws, in 90 DEG C of process 4 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S13.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 27
Take support C L-A-Al 2o 3200 grams are placed in autoclave, add the ethanol solution 200 milliliters containing 1.36 grams of softex kws, in 90 DEG C of process 24 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S14.R in article shaped 1r 2r 3r 4n +x -mass fraction list 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, add the ethanol solution 200 milliliters containing 3.56 grams of softex kws and 3.89 grams of DTACs, in 100 DEG C of process 2 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S15.R in article shaped 1r 2r 3r 4n +x -mass fraction list 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, add the ethanol solution 200 milliliters containing 1.73 grams of softex kws, 1.12 grams of hexadecyltrimethylammonium chlorides, 3.08 grams of DTABs and 3.16 grams of DTACs, in 100 DEG C of process 3 hours after airtight.After cooling by sample in 120 DEG C of dryings 4 hours, obtain containing R 1r 2r 3r 4n +x -aluminium oxide article shaped R-S16.R in article shaped 1r 2r 3r 4n +x -mass fraction list in table 3.
Embodiment 30-45 illustrates the hydrogenation catalyst prepared with carrier provided by the invention.
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 (27)

1. one kind contains R 1r 2r 3r 4n +x -aluminium oxide article shaped, containing R 1r 2r 3r 4n +x -, with described article shaped for benchmark, described R 1r 2r 3r 4n +x -mass fraction be 0.1%-10%, described R 1r 2r 3r 4n +x -be selected from one or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein said R 1, R 2, R 3, R 4be selected from hydrogen, hydrocarbon substituent and derivative thereof.
2. the article shaped according to 1, is characterized in that, with described article shaped for benchmark, and described R 1r 2r 3r 4n +x -mass fraction be 0.3%-5%.
3. the article shaped according to 1, is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, or is selected from the cycloalkyl of C3-C20, or is selected from the aryl of C6-C20; The derivative of described hydrocarbon substituent is selected from the alkyl with hydroxyl and/or heterocyclic substituent.
4. the article shaped according to 3, is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C18; Or be selected from the cycloalkyl of C6-C18; Or be selected from the aryl of C6-C18.
5. the article shaped according to 1,2 or 3 any one, is characterized in that, described X is selected from chlorine, bromine or iodine.
6. the article shaped according to 5, is characterized in that, described X is selected from chlorine or bromine.
7. the article shaped according to 1,2 or 3 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from softex kw, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, one or more of DTAB and DTAC.
8. the article shaped according to 1,2 or 3 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from ethanolamine salt, dococylpyridinium hydrochloride.
9. the article shaped 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 article shaped for benchmark, the mass fraction of described adjuvant component is less than 10%.
10. the article shaped according to 9, is characterized in that, with described article shaped for benchmark, the mass fraction of described adjuvant component is 0.3%-5%.
11. article shaped according to 1 or 9, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
12. article shaped according to 11, it is characterized in that, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
13. 1 kinds containing R 1r 2r 3r 4n +x -the preparation method of aluminium oxide article shaped, be included in described aluminium oxide article shaped and introduce R 1r 2r 3r 4n +x -, with described article shaped for benchmark, described R 1r 2r 3r 4n +x -introduction volume make in described article shaped R 1r 2r 3r 4n +x -mass fraction is 0.1%-10%, described R 1r 2r 3r 4n +x -be selected from one or more in primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt, wherein said R 1, R 2, R 3, R 4be selected from hydrocarbon substituent, the derivative of hydrocarbon substituent or hydrogen.
14. methods according to 13, is characterized in that, with described article shaped for benchmark, and described R 1r 2r 3r 4n +x -introduction volume make in described article shaped R 1r 2r 3r 4n +x -mass fraction be 0.3%-5%.
15. methods according to 13, it is characterized in that, described hydrocarbon substituent is selected from the straight or branched alkyl of C1-C20, or is selected from the cycloalkyl of C3-C20, or is selected from the aryl of C6-C20; The derivative of described hydrocarbon substituent is selected from the alkyl with hydroxyl and/or heterocyclic substituent.
16. methods according to 15, it is characterized in that, the substituting group of described hydrocarbon is selected from the straight or branched alkyl of C1-C18; Or be selected from the cycloalkyl of C6-C18; Or be selected from the aryl of C6-C18.
17. methods according to 13,14 or 15 any one, it is characterized in that, described X is selected from chlorine, bromine or iodine.
18. methods according to 13,14 or 15 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from softex kw, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, TTAB, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, OTAC, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, two dodecyl dimethyl ammonium chloride, two dodecyldimethylamine base ammonium bromide, two dodecyldimethylamine ammonium chloride, DDA, dioctadecyl dimethyl ammonium chloride, one or more of DTAB and DTAC.
19. methods according to 13,14 or 15 any one, is characterized in that, described R 1r 2r 3r 4n +x -be selected from ethanolamine salt, dococylpyridinium hydrochloride.
20. methods according to 13, it is characterized in that, be included in described article shaped the step introducing one or more adjuvant components be selected from silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide in the process, with described article shaped for benchmark, the introduction volume of described adjuvant component makes the mass fraction of adjuvant component in described article shaped be less than 10%.
21. methods according to 20, it is characterized in that, with described article shaped for benchmark, the mass fraction of described adjuvant component is below 0.3%-5%.
22. methods according to 13 or 20, is characterized in that, containing clay and/or molecular sieve in described article shaped, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is less than 35%.
23. methods according to 22, it is characterized in that, with described article shaped for benchmark, the mass fraction of described clay and/or molecular sieve is 1%-20%.
24. methods according to 13, is characterized in that, describedly in described aluminium oxide article shaped, introduce R 1r 2r 3r 4n +x -method, comprising: (1) is with containing R 1r 2r 3r 4n +x -solution impregnation described in aluminium oxide article shaped, the volume of described maceration extract is 0.5-20 with the ratio of the pore volume of described article shaped; (2) place flooding the mixture obtained in room temperature or heat-treat in closed reactor, preferably heat-treat in closed reactor, heat treatment temperature is room temperature to 250 DEG C, and the time is 0.5 hour-48 hours; (3) product of drying steps (2), described drying condition comprises: temperature is 40 DEG C-250 DEG C, and the time is 1 hour-24 hours.
25. methods according to 24, it is characterized in that, described in step (1), the volume of maceration extract is 1-15 with the ratio of the pore volume of described article shaped; Heat treatment temperature described in step (2) is 60 DEG C to 220 DEG C, and the time is 1 hour-36 hours, and the drying condition of step (3) comprising: temperature is 100 DEG C-180 DEG C, and the time is 2 hours-18 hours.
26. according to any one of 1-12 article shaped as the application of adsorbent.
27. according to any one of 1-12 article shaped as the application of catalyst carrier.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106669729A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Slurry reactor Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
DE112016006477T5 (en) 2016-05-23 2018-11-22 Petrochina Company Limited Palladium-based supported hydrogenation catalyst and method of preparation and use thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462079A (en) * 2007-12-20 2009-06-24 中国石油化工股份有限公司 Method for preparing catalyst with lamella distribution
CN101575110A (en) * 2008-05-09 2009-11-11 大连路明纳米材料有限公司 Preparation method of alumina powder
CN102861601A (en) * 2011-07-07 2013-01-09 中国石油化工股份有限公司 Hydrogenation catalyst containing fluorine and preparation method thereof
CN103480426A (en) * 2012-06-08 2014-01-01 中国石油化工股份有限公司 Magnesium-containing hydrate alumina forming product, applications thereof, eggshell type catalyst, preparation method thereof, and preparation method of carboxylic acid vinyl ester
CN103480429A (en) * 2012-06-12 2014-01-01 中国石油化工股份有限公司 Hydrated alumina molded matter and application thereof, eggshell-type catalyst, and preparation method and application of eggshell-type catalyst, and method for preparing carboxylic acid vinyl ester

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101462079A (en) * 2007-12-20 2009-06-24 中国石油化工股份有限公司 Method for preparing catalyst with lamella distribution
CN101575110A (en) * 2008-05-09 2009-11-11 大连路明纳米材料有限公司 Preparation method of alumina powder
CN102861601A (en) * 2011-07-07 2013-01-09 中国石油化工股份有限公司 Hydrogenation catalyst containing fluorine and preparation method thereof
CN103480426A (en) * 2012-06-08 2014-01-01 中国石油化工股份有限公司 Magnesium-containing hydrate alumina forming product, applications thereof, eggshell type catalyst, preparation method thereof, and preparation method of carboxylic acid vinyl ester
CN103480429A (en) * 2012-06-12 2014-01-01 中国石油化工股份有限公司 Hydrated alumina molded matter and application thereof, eggshell-type catalyst, and preparation method and application of eggshell-type catalyst, and method for preparing carboxylic acid vinyl ester

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106669729A (en) * 2015-11-09 2017-05-17 中国石油化工股份有限公司 Slurry reactor Fischer-Tropsch synthesis catalyst, and preparation method and application thereof
CN106669729B (en) * 2015-11-09 2019-03-19 中国石油化工股份有限公司 A kind of syrup state bed Fischer Tropsch synthetic catalyst and its preparation method and application
DE112016006477T5 (en) 2016-05-23 2018-11-22 Petrochina Company Limited Palladium-based supported hydrogenation catalyst and method of preparation and use thereof
US10800717B2 (en) 2016-05-23 2020-10-13 Petrochina Company Limited Palladium-based supported hydrogenation catalyst, and preparation method and application thereof

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