CN1262147A - Hydrogenation catalyst with TiO2 as carrier of non-crystal NiB alloy - Google Patents

Hydrogenation catalyst with TiO2 as carrier of non-crystal NiB alloy Download PDF

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CN1262147A
CN1262147A CN 00103351 CN00103351A CN1262147A CN 1262147 A CN1262147 A CN 1262147A CN 00103351 CN00103351 CN 00103351 CN 00103351 A CN00103351 A CN 00103351A CN 1262147 A CN1262147 A CN 1262147A
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tio
carrier
nib
catalyst
alloy
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CN1090999C (en
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李伟
陶克毅
程庆彦
关乃佳
沈炳龙
沈燕君
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Nankai University
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Nankai University
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Abstract

A hydrogenation catalyst contains carrier of TiO2 and active component of non-crystal NiB alloy (5.26 wt.%) and rare-earth elements (1 wt.%). Said catalyst has very high low-temp activity and near 100% of selectivity for hydrogenating arylhydrocarbon and the activity of hydrogenation desulfurization (HDS). It can be used for hydrorefining oil.

Description

TiO 2Hydrogenation catalyst for carrier of non-crystal NiB alloy
The invention belongs to TiO 2The Catalysts and its preparation method of carrier of non-crystal NiB metal alloy and the application in hydrogenation reaction.
Amorphous alloy is that a class has the atomic arrangement shortrange order and the material of long-range disordered structure characteristics.Since nineteen sixty, Duwez etc. have prepared amorphous alloy first by melting quench method.After this develop more economic, simple and direct chemical reduction method, can prepare ultrafine amorphous attitude alloy (UFAAP) in this way.From the eighties in 20th century, the amorphous metal alloy excellent catalytic performance obtains the attention of academia gradually.Since Smith proposing in the 7th the international catalysis meeting first piece use amorphous alloy as catalyst after, the research of this respect is very active.But when amorphous metal alloy is used as catalyst, need to solve two key issues, one is the surface area that how to increase amorphous alloy, and another is how to make amorphous state stable in catalytic process.UFAAP has increased the surface area of amorphous metal alloy greatly, and amorphous alloy loaded on the amorphous alloy catalyst of making on the porous carrier, not only provide big surface area for active component, reduced the cost of catalyst, and improved catalytic performance greatly, heat endurance is improved.
TiO 2Be a kind of SiO of continuing of late nineteen seventies exploitation 2And Al 2O 3Novel carriers afterwards, it can produce " metal-carrier strong interaction " (SMSI) with the active component that supports, thereby has promoted metal at TiO 2The carrier surface high degree of dispersion has been improved the surface texture of catalyst.In addition, because TiO 2Ti in the carrier 4+Has reducibility (Ti 4+-Ti 3+), its electronics forwarding function can improve activity of such catalysts and selectivity to many important catalytic reactions.
After amorphous metal alloy has experienced the development of recent two decades as the research of hydrogenation catalyst, made significant headway.The strip that catalyst makes from melting quench method, banded amorphous alloy are to the ultrafine amorphous attitude alloy of preparations such as chemical reduction method, until with SiO 2, A1 2O 3Deng the carried non-crystal metal alloy that is carrier, the surface area and the heat endurance of catalyst progressively are improved, that amorphous state has also kept in catalytic process gradually is stable (it is generally acknowledged, the many more catalyst samples of former amorphous state composition, catalytic activity is good more).Present amorphous alloy hydrogenation catalyst mainly is with SiO 2, Al 2O 3Be carrier, the amorphous alloy active component of load is NiB and NiP, the further development but these catalyst are still needed on active and mechanical strength.Current topmost problem is the high-performance hydrogenation catalyst of development low reaction temperatures, high activity, high selectivity, high stability.Some hydrogenation catalysts in the existing document are listed in table 1:
As can be seen, loaded catalyst is widely adopted from the given catalizer variety of table 1, and wherein the NiB amorphous metal alloy is used more as the key component of catalyst.
The object of the invention provides a kind of novel TiO 2Hydrogenation catalyst for loading NiB amorphous alloy, be characterized in that catalyst is simple and easy to do on the preparation method, be convenient to the commercial scale preparation, catalyst has the selectivity of very high low temperature active and nearly 100% to aromatic hydrogenation, and have hydrodesulfurization (HDS) activity, help in oil hydrogenation is refining, using.
The present invention has at first successfully prepared pure whole NiB amorphous alloy, and is confirmed with X-ray diffraction and ESEM and transmission electron microscope.On this basis, further at TiO 2Preparation NiB amorphous state is closed on the carrier, simultaneously, is confirmed with above characterizing method.
The present invention adopts TiO 2Be carrier, with dipping-reducing process loading NiB amorphous alloy, and the adding rare earth element is a structural promotor.
The TiO of the present invention's preparation 2In the carrier loaded amorphous alloy NiB catalyst, NiB account for catalyst weight 5.26%, Ni: B=2.97 wherein: 9.99.
TiO of the present invention 2The concrete preparation method's step of carrier loaded amorphous alloy NiB catalyst:
At first under 450 ℃ with anatase titanium dioxide TiO 2Roasting 3-5 hour (preliminary treatment) adds Ni (NO 3) 2In the solution, stirred 4 hours, filter, washing 0 ℃, noble gas protection (nitrogen), adds MKBH 4Solution, 15-20min adds, and vigorous stirring when waiting not have gas and producing, is filtered, and filter cake is washed to neutrality, and absolute ethanol washing is placed in the absolute ethyl alcohol and preserves, during use it dried in the shade, compressing tablet, fragmentation is sieved and is got the 40-60 order and get final product.
Catalyst of the present invention has the active and certain HDS activity of good low temperature hydrogenation.With NiB/TiO 2Be example, to benzene hydrogenation, in the time of 100 ℃, just have higher activity, conversion ratio reaches 25.9%; In the time of 140 ℃, reached 98.6%, and selectivity is 100%, is retained to 170 ℃ always.To thiophene HDS reaction, in the time of 220 ℃, n-butane conversion is 18%.
Catalyst of the present invention has good anti-sulphur.With LNSR (limiting number of sulfur resistance) expression, the quantity of the poisonous substance sulphur that Shi Suoneng holds even catalyst loses activity fully is with catalyst n iB/TiO 2Be example, the anti-sulfur content of the limit is 124 μ 1CS 2/ gNiB can solve the industry sulfur poisoning problem of hydrogenation reaction on a large scale.
The adding thulium can obviously improve the sulfur poisoning-resistant ability of amorphous alloy.As above-mentioned NiB/TiO 2The LNSR=124 μ lCS of catalyst 2/ gNiB, behind the adding La, anti-sulphur is greatly improved, LNSR=184 μ lCS 2/ gNiBLa.
Substantive distinguishing features that the present invention gives prominence to and remarkable result can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Embodiment 1
Under 450 ℃ to TiO 2Carrier preliminary treatment 4 hours takes by weighing 5gTiO 2, under agitation slowly add the 1.3MNi (NO of 11.1ml 3) 2In the solution, stir 4h, filter, filtrate adds in the distilled water of 11.1ml, under 0 ℃, nitrogen protection, vigorous stirring, drips 2MKBH 4Solution 18.55ml drips off in 15min; When waiting not have the gas generation, filter, filter cake is washed till neutrality with a large amount of distilled water, uses absolute ethanol washing again, places absolute ethyl alcohol to preserve at last, before the use, catalyst is dried in the shade, and compressing tablet, fragmentation is sieved.
The present invention reacts the employing pulse micro-inverse--the benzene hydrogenation and the thiophene HDS reaction unit of gas-chromatography coupling.
The catalyst 1ml of measuring above-mentioned drying is in reactor; Pulse benzene hydrogenation condition: carrier gas is a hydrogen, and flow velocity is 50ml/min, in 140 ℃ of reduction 1h, reduces to reaction temperature again under hydrogen stream.The gas chromatographic analysis product, the yield of ring hexane and selectivity the results are shown in Table 2.
With CS 2For poisonous substance carries out the test of sulfur resistance, CS 2With benzene dilution, with the volume ratio of benzene be 1: 10, under reaction temperature, each sample size is 2 μ l, is zero until catalyst activity, calculates the anti-sulfur content of the limit, the results are shown in Table 2.
Pulse thiophene HDS reaction condition: carrier gas and flow velocity be with 2 in the reaction condition, under hydrogen stream in 220 ℃ of reduction 1h.The gas chromatographic analysis product, the yield and the selectivity of calculating normal butane the results are shown in Table 3.
Embodiment 2
With catalyst and the Al that makes among the embodiment 1 2O 3Mechanical lapping mixes, and adds Al 2O 3Weight percentage be respectively 20%, 30%, 40% and 50%, all the other are all with embodiment 1.
Embodiment 3
TiO 2The same Comparative Examples of the dipping of powder and dry run adds 18mlH then 2O drips the KBH of 2M under 0 ℃, nitrogen protection, high degree of agitation 433.45ml, drip off in the 20min.Treatment conditions of remaining and reaction condition are with embodiment 1.The anti-sulfur content of the yield of cyclohexane and selectivity and the limit sees Table 2, and the yield and the selectivity of normal butane see Table 3.
Embodiment 4
With the Ni (NO among the embodiment 3 3) 2Solution change into same concentrations contain rare-earth elements La, Nd, Sm, Eu (in oxide, account for catalyst weight 1%) Ni (NO of (adding) with the nitrate aqueous solution form 3) 2Solution, all the other are all with embodiment 3.
Comparative Examples:
Use Detitanium-ore-type TiO 2Carrier loaded NiO does not add any co-catalyst.With TiO 2Carrier gives in 450 ℃, air atmosphere and handles 4h, to contain 8.65gNi (NO 3) 26H 212mlNi (the NO of O 3) 2Aqueous solution dipping 9g carrier 4h filters then, the air 1h that dries in the shade, and 125 ℃ of baking 2h, 450 ℃ of roasting 4h, experiment condition is with embodiment 1.Experimental result is: the benzene conversion ratio is 0 (100-200 ℃), and the thiophene conversion ratio is 6-12% (295-355 a ℃).The basic condition of the various amorphous alloy hydrogenation catalysts of table 1.
Catalyst Hydrogenating materials Reaction temperature (℃) Conversion ratio (%) Selectivity (%) The preparation method Simple declaration
????NiB Benzene ??150 ??74.3 ?------ Electronation ???0.1gNiB
????NiBSm Benzene ??150 ??89.7 ?------ Electronation ???0.1gNiBSm
????NiB/Al 2O 3 Benzene ??150 ??98.4 ?------ Dipping-reduction ???0.05gNiB
????NiPCe Benzene ??100 ??68 ?------ Electronation Autoclave
????NiB/SiO 2 Benzene ??100 ??9.2 ?------ Chemical deposition ???1.3MP
????NiP/SiO 2 Cyclopentadiene ??150 ??96 ??100 Dipping-reduction Air speed 4h -1
????NiP/SiO 2 Styrene ??180 ??100 ?------ Chemical deposition ???------
????NiB/SiO 2 Cyclopentadiene ??120 ??100 ??96.2 Dipping-reduction Air speed 10h -1
????NiP/SiO 2 Benzaldehyde ??110 ??4.4 ??∽100 Electronation Autoclave
The cyclohexane yield of table 2. different catalysts and selectivity and the anti-sulfur content of the limit (LNSR)
Reaction temperature (℃) Conversion ratio (%) Selectivity (%) ????LNSR ??(μlCS 2/gNiB ????(RE))
Embodiment 1 ??NiB/TiO 2 ??100-140 ???25.9-98.6 ??100 ????120
Embodiment 2 ??NiB/TiO 2-Al 2O 3??(20％) ??95-140 ???100 ??100 ????80
??NiB/TiO 2-Al 2O 3??(30％) ??95-140 ???100 ??100 ????133.3
??NiB/TiO 2-Al 2O 3??(40％) ??95-140 ???100 ??100 ????162.8
??NiB/TiO 2-Al 2O 3??(50％) ??100-140 ???54.6-89.5 ??100 ????228
Embodiment 3 ??NiB/TiO 2 ??100-140 ???75.3-100 ??100 ????124
Embodiment 4 ??NiBLa/TiO 2 ??100-140 ??100 ????184
Embodiment 4 ??NiBNd/TiO 2 ??100-140 ???24.9-65.5 ??100 ????148
??NiBSm/TiO 2 ??100-140 ???29.9-48.6 ??100 ????152
??NiBEu/TiO 2 ??100-140 ???48.2-76.4 ??100 ????212
The normal butane yield and the selectivity of table 3. different catalysts
Reaction temperature (℃) Conversion ratio (%) Selectivity (%)
Embodiment 1 ????NiB/TiO 2 ????220-270 ????18-23 ????100
Embodiment 2 ????NiB/TiO 2-Al 2O 3????(20％) ????240-350 ????6-10 ????100
????NiB/TiO 2-Al 2O 3????(30％) ????240-350 ????1-3 ????100
????NiB/TiO 2-Al 2O 3????(40％) ????240-350 ????1-3 ????100
????NiB/TiO 2-Al 2O 3????(50％) ????240-350 ????1-4 ????100
Embodiment 3 ????NiB/TiO 2 ????270-350 ????1-6 ????100
Embodiment 4 ????NiBLa/TiO 2 ????260-350 ????7-12 ????100
????NiBNd/TiO 2 ????260-350 ????3-10 ????100
????NiBSm/TiO 2 ????260-350 ????3-7 ????100
????NiBEu/TiO 2 ????260-350 ????2-10 ????100

Claims (3)

1. TiO 2Be the hydrogenation catalyst of carrier of non-crystal NiB alloy, it is characterized in that it is with TiO 2Be carrier, the NiB amorphous alloy of load effective dose and rare earth element active component constitute; Described TiO 2Carrier loaded effective active composition NiB accounts for 5.26% of catalyst weight, wherein Ni: B=2.97: 9.99; Described rare earth element accounts for 1% of catalyst weight.
2. according to the described TiO of claim 1 2Be the hydrogenation catalyst of carrier of non-crystal NiB alloy, it is characterized in that described rare earth element active component is to comprise La, Nd, Sm or Eu.
3. the described TiO of claim 1 2Be the hydrogenization catalyst preparation method of carrier of non-crystal NiB alloy, it is characterized in that it comprises the steps: under 450 ℃ TiO 2Preliminary treatment 4 hours adds Ni (NO 3) 2In the solution, stirred 4 hours, filter, washing 0 ℃, noble gas protection, adds MKBH 4Solution, 15-20min adds, and vigorous stirring when waiting not have the gas generation, is filtered, and filter cake is washed to neutrality, and absolute ethanol washing is placed in the absolute ethyl alcohol and preserves, during use it dried in the shade, compressing tablet, fragmentation, sieving gets final product.
CN00103351A 2000-03-02 2000-03-02 Hydrogenation catalyst with TiO2 as carrier of non-crystal Nib alloy Expired - Fee Related CN1090999C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100357286C (en) * 2005-12-13 2007-12-26 天津市瑞凯科技发展有限公司 Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol
CN101549284B (en) * 2009-05-12 2012-05-23 南开大学 Method for preparing high dispersion supported hydrogenation catalyst
CN104001528A (en) * 2014-05-04 2014-08-27 昆明理工大学 Preparation method and application of loaded-type Ni-P/TiO2 amorphous catalyst
CN105772031A (en) * 2016-04-12 2016-07-20 中山大学 Application of amorphous transition metal boride to preparation of photocatalytical water splitting hydrogen making catalyst
CN111804268A (en) * 2020-09-09 2020-10-23 苏州大学 Beaded Pd-Ni adsorbent for deep desulfurization of refined benzene

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4599469A (en) * 1984-05-29 1986-07-08 Phillips Petroleum Company Hydrogenation process
CN1022545C (en) * 1989-01-30 1993-10-27 天津大学 Resin-carried nickel boride catalyst and preparation thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100357286C (en) * 2005-12-13 2007-12-26 天津市瑞凯科技发展有限公司 Process for preparing tetrahydrofurfuryl alcohol by catalytic hydrogenation of furfuralcohol
CN101549284B (en) * 2009-05-12 2012-05-23 南开大学 Method for preparing high dispersion supported hydrogenation catalyst
CN104001528A (en) * 2014-05-04 2014-08-27 昆明理工大学 Preparation method and application of loaded-type Ni-P/TiO2 amorphous catalyst
CN105772031A (en) * 2016-04-12 2016-07-20 中山大学 Application of amorphous transition metal boride to preparation of photocatalytical water splitting hydrogen making catalyst
CN105772031B (en) * 2016-04-12 2019-01-04 中山大学 Purposes of the amorphous transition metal boride in preparation photolytic hydrogen production catalyst
CN111804268A (en) * 2020-09-09 2020-10-23 苏州大学 Beaded Pd-Ni adsorbent for deep desulfurization of refined benzene

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