CN104741124A - Aluminum-base intermetallic compound catalyst for naphthalene selective hydrogenation and preparation method of compound catalyst - Google Patents
Aluminum-base intermetallic compound catalyst for naphthalene selective hydrogenation and preparation method of compound catalyst Download PDFInfo
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Abstract
The invention belongs to the technical fields of a novel catalytic material and petrochemical industry, and relates to a novel aluminum-base intermetallic compound catalyst for a tetrahydronaphthalene preparing reaction by virtue of efficient naphthalene selective hydrogenation. By virtue of a chemical synthesis method, the stable aluminum-base intermetallic compound catalyst is formed by carrying out a reflux reaction in an organic solvent by taking an aluminum-metal-containing organic precursor as a reducing agent and transition metal salt as a metal source, and then baking in an inert atmosphere. Under typical industrial application conditions, the prepared aluminum-base intermetallic compound catalyst is quite high in activity as well as simple selectivity and stability in preparing tetrahydronaphthalene by virtue of naphthalene selective hydrogenation, and the compound catalyst has a good industrial application prospect. Meanwhile, the novel catalytic material can be applied to a fuel cell cathodic oxygen reduction reaction, an alkyne selective hydrogenation alkyne-producing reaction, nitro compound selective hydrogenation to prepare an amino compound and the like.
Description
Technical field
The invention belongs to new catalytic material and technical field of petrochemical industry, relate to a kind of for naphthalene high efficiency selected Hydrogenation for a kind of novel aluminum based metal compound catalyst that uses in naphthane reaction.Concretely, adopt chemical synthesis with aluminiferous metals organic precursor be reducing agent, transition metal salt is for source metal back flow reaction in organic solvent, roasting under an inert atmosphere subsequently, namely forms the efficient naphthalene selec-tive hydrogenation catalytic applications of stable aluminum based metal compound catalyst and prepared material.
Background technology
Naphthalene, as a kind of typical product in coal tar, is widely used in the industrial circle such as synthetic dyestuffs, resin.In addition, naphthalene investigates the application of catalyst in condensed-nuclei aromatics hydrogenation and cracking reaction through being often used as model substrates.Naphthalene hydrogenation reaction can obtain multi-products, wherein the most mainly intermediate product naphthane and end product decahydronaphthalene.Naphthalene partial hydrogenation product naphthane, it is a kind of desirable high boiling solvent, can be widely used in the industrial circles such as coating, paint, the solvent of ink, the forming agent of carbide alloy, also can be used as the primary raw material producing tetralone, naphthane also can mix as automotive fuel with ethanol and benzene simultaneously.And full saturated products decahydronaphthalene is important organic solvent, is mainly used as solvent and paint remover, the lubricant of grease, resin, rubber etc., also for industrial circles such as dyestuff, agricultural chemicals, pharmacy, and turpentine oil can be replaced in the manufacture process of shoe polish, floor wax.At present, supply falls short of demand for the naphthane of China, mainly still relies on import.So for the research of naphthalene selec-tive hydrogenation technology, there is important economic worth and realistic meaning.The external method producing naphthane with naphthalene hydrogenation, is broadly divided into two classes: (1) low-temp low-pressure hydrogenation, adopts the high activated catalyst such as platinum, nickel usually at present, very high to the quality requirement of raw naphthalene material; (2) high-temperature and high-pressure hydrogenation, usually adopt oil Hydrobon catalyst, raw material can use thick naphthalene.In naphthalene hydrogenation process, the noble metal catalysts such as Pt or Pd have very high hydrogenation activity, but expensive, easy-sintering, and are easily poisoned by hetero atoms such as S and N, therefore can hinder the industrialization of noble metal catalyst to a certain extent.Therefore, the direction of person's unremitting effort that the selec-tive hydrogenation new catalytic material that development can substitute noble metal catalyst is catalyst operation always.
The selective of catalytic reaction can carry out modulation by the structure electrical to catalyst, chemical composition and dynamics etc.Introducing nonmetallic ingredient such as silicon, phosphorus, aluminium etc. is one of important method to metal catalytic activity and selective modulation.In aluminum based metal compound (Al-M) containing electropositive aluminium element can and different metals between Cheng Jian, the Al-M formed between metal alloy and ionic compound, may also have special catalytic performance.As far back as nineteen twenty-six, use alloy that nickel/aluminium is 1:1 to manufacture Raney Ni catalyst in US1628190 patent, find that its catalytic activity is more than 5 times of metallic nickel.Subsequently, Raney Ni, at unsaturated compound, as alkene, alkynes, nitrile, alkadienes, aromatic hydrocarbon, is widely used because it has high catalytic activity containing in the hydrogenation of the material of carbonyl and desulphurization reaction.US20120029254 patent and Nature Mater., 2012,11 (8): 690-693 report respectively and utilize the isolated and chemical bonding of avtive spot to change electronic structure, have synthesized low cost Al by high-temperature fusion
13fe
4intermetallic compound, can effectively substitute Pd in acetylene selective hydrogenation reaction catalyst based, conversion ratio reaches 80.0%, and selective up to 84.0%, and shows high stability.But the application that aluminum based metal compound is prepared in naphthane reaction at naphthalene selec-tive hydrogenation as a kind of new catalyst is not reported so far.
Aluminum based metal compound new catalyst prepared by the present invention, not only preparation method is simple, mild condition, synthesis cost is low, environmental friendliness, and prepared material is to hydrogen-involved reaction, especially there is higher catalytic activity in naphthalene selec-tive hydrogenation catalytic reaction and have target product naphthane selective very well.
Summary of the invention
The object of the invention there is provided a kind of aluminum based metal compound for the composition of naphthalene selective hydrogenation catalyst and preparation method.Prepare aluminum based metal compound catalyst in a mild condition in naphthalene selective hydrogenation reaction, to show higher activity, to the high selectivity of naphthane and stability, be used in continuous seepage naphthane on fixed bed reactors.
Aluminum based metal compound catalyst of the present invention is Al-M, and in formula, M is group VIII element, comprises Ni, Fe, Co, Mo, W, Pd, Pt, Ru etc. and not identical.
Above-mentioned aluminum based metal compound method for preparing catalyst be adopt chemical synthesis under anhydrous and oxygen-free condition with aluminiferous metals organic precursor be reducing agent, transition metal salt is for source metal back flow reaction in organic solvent, roasting under an inert atmosphere subsequently, namely forms stable aluminum based metal compound catalyst.
Above-mentioned aluminiferous metals organic precursor is one or more mixing in lithium aluminium hydride reduction, triethyl aluminum, aluminium chloride, aluminium secondary butylate, aluminium isopropoxide, trimethyl aluminium etc.Transition metal salt is the one in nickel chloride, iron chloride, cobalt chloride, molybdenum chloride, tungsten chloride, potassium chloroplatinate, ruthenium trichloride, potassium chloropalladate etc.Organic solvent comprises the one in oxolane, 1,3,5-trimethylbenzene, absolute ether.
Under above-mentioned inert atmosphere, sintering temperature is 400-1000 DEG C, and the best is 600-800 DEG C.
The aluminum based metal compound catalyst of above-mentioned preparation has very high catalytic activity, to the high selectivity of naphthane and stability in naphthalene hydrogenation reaction.
Above-mentioned aluminum based metal compound catalyst, except being applied to naphthalene Hydrogenation for except naphthane reaction, can also being applied to fuel battery negative pole oxygen reduction reaction, selective acetylene hydrocarbon hydrogenation olefine reaction, nitro compound selec-tive hydrogenation prepare amino-compound etc.
The invention provides a kind of at normal pressure, prepare the chemical synthesis process of aluminum based metal compound catalyst under moderate temperature conditions, the formation, particle diameter, specific area, catalytic activity etc. on aluminum based metal compound such as atomic ratio, sintering temperature of the selection of the choosing of its aluminiferous metals organic precursor, organic solvent, metal and aluminium have very important impact.Of the present invention preparation is simple, mild condition, and synthesis cost is low, environmental friendliness.Prepared aluminum based metal compound catalyst is prepared in naphthane reaction at naphthalene selec-tive hydrogenation and is shown higher activity and selective, improve catalytic process efficiency, successfully avoid the contradiction of the corresponding high cost of high catalyst selectivity, be with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of Al-Ni intermetallic compound catalyst.
Fig. 2 is that Al-Ni intermetallic compound catalyst naphthalene selec-tive hydrogenation prepares naphthane stability data.
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with accompanying drawing and technical scheme.
The preparation of embodiment 1:Al-Ni intermetallic compound catalyst
Get Dehydrated nickel chloride 1.0g, measure 1,3, the 5-trimethylbenzene of 30mL, join together in there-necked flask, pass into argon gas, put into rotor, start stirring at room temperature.Add 0.6g lithium aluminium hydride reduction again after 15 minutes, continue stirred at ambient temperature.Open recirculated water backflow after 20 minutes, start heating oil bath to 160 DEG C, and react 12 hours at such a temperature, obtain Al-Ni intermetallic compound presoma through centrifugal and vacuum drying.By this precursor 700 DEG C of roasting 2h under an argon atmosphere, namely obtain Al-Ni intermetallic compound catalyst.The X-ray diffractogram of Al-Ni intermetallic compound catalyst as shown in Figure 1.The mol ratio of modulation nickel chloride and lithium aluminium hydride reduction, can obtain the Al-Ni intermetallic compound catalyst (Al of different phase
3ni, AlNi, Al
3ni
2).
The preparation of embodiment 2:Al-Co intermetallic compound catalyst
Get waterless cobaltous chloride 1.50g, measure the absolute ether of 30mL, join in there-necked flask together, pass into argon gas, put into rotor, start stirring at room temperature.Add 1.0g lithium aluminium hydride reduction again after 15 minutes, continue stirred at ambient temperature.Open recirculated water back flow reaction after 20 minutes 12 hours, obtain Al-Co intermetallic compound presoma through centrifugal and vacuum drying.By this precursor 600 DEG C of roasting 2h under an argon atmosphere, namely obtain Al-Co intermetallic compound catalyst.The mol ratio of modulation cobalt chloride and lithium aluminium hydride reduction, can obtain the Al-Co intermetallic compound catalyst (Al of different phase
3co, Al
13co
4, Al
5co
2).
The preparation of embodiment 3:Al-Fe intermetallic compound catalyst
Get the ferrous 2.0g of anhydrous chlorides of rase, measure 1,3, the 5-trimethylbenzene of 60mL, join together in there-necked flask, pass into argon gas, put into rotor, start stirring at room temperature.Add 1.5g triethyl aluminum again after 15 minutes, continue stirred at ambient temperature.Open recirculated water backflow after 20 minutes, start heating oil bath to 160 DEG C, and react 12 hours at such a temperature, obtain Al-Fe intermetallic compound presoma through centrifugal and vacuum drying.By this precursor 1000 DEG C of roasting 2h under an argon atmosphere, namely obtain Al-Fe intermetallic compound catalyst.The mol ratio of modulation frerrous chloride and triethyl aluminum, can obtain the Al-Fe intermetallic compound catalyst (Al of different phase
2fe, Al
13fe
4, AlFe, AlFe
3, Al
5fe
2).
The preparation of embodiment 4:Al-Pd intermetallic compound catalyst
Get potassium chloropalladate 0.20g, measure the oxolane of 15mL, join in there-necked flask together, pass into argon gas, put into rotor, start stirring at room temperature.Add 0.30g lithium aluminium hydride reduction again after 15 minutes, continue stirred at ambient temperature.Open recirculated water backflow after 20 minutes, start to be heated to 70 DEG C, and react 12 hours at such a temperature, obtain Al-Pd intermetallic compound presoma through centrifugal and vacuum drying.By this precursor 400 DEG C of roasting 2h under an argon atmosphere, namely obtain Al-Pd intermetallic compound catalyst.The mol ratio of modulation potassium chloropalladate and lithium aluminium hydride reduction, can obtain the Al-Pd intermetallic compound catalyst (Al of different phase
3pd, AlPd, Al
3pd
2, Al
6pd, Al
21pd
8).
The preparation of embodiment 5:Al-Pt intermetallic compound catalyst
Get potassium chloroplatinate 0.3g, measure the absolute ether of 20mL, join in there-necked flask together, pass into argon gas, put into rotor, start stirring at room temperature.Add 0.4g lithium aluminium hydride reduction again after 15 minutes, continue stirred at ambient temperature.Open recirculated water back flow reaction after 20 minutes 12 hours, obtain Al-Pt intermetallic compound presoma through centrifugal and vacuum drying.By this precursor 350 DEG C of roasting 2h under an argon atmosphere, namely obtain Al-Pt intermetallic compound catalyst.The mol ratio of modulation potassium chloroplatinate and lithium aluminium hydride reduction, can obtain the Al-Pt intermetallic compound catalyst (Al of different phase
2pt, AlPt
3, Al
6pt, AlPt
2).
Embodiment 6:Al-Ni intermetallic compound catalyst is to the catalytic performance of naphthalene hydrogenation reaction
Detecting catalyst naphthalene hydrogenation reaction in fixed bed reactors, wherein the mixture of naphthalene, normal octane and decane is by reaction bed, and wherein naphthalene is reactant, and concentration is 5wt%; Normal octane is as solvent; Decane is as internal standard compound, and concentration is the consumption that 1wt%, Al-Ni intermetallic fills compound catalyst is 0.2g, dilutes with quartz sand.Reaction procatalyst reduces 4h at hydrogen atmosphere 450 DEG C.Naphthalene selective hydrogenation reaction temperature is 340 DEG C, and reaction pressure is 4MPa, and hydrogen-oil ratio is 1000.The liquid product that in course of reaction, timed collection is obtained by condenser, the method adopting reference material to demarcate determines the conversion ratio and selective reacted, and find that naphthalene conversion ratio is 98%, the selective of naphthane is 100%.
Embodiment 7:Al-Ni intermetallic compound catalyst is to the catalytic performance of naphthalene hydrogenation reaction
Detecting catalyst naphthalene hydrogenation reaction in fixed bed reactors, wherein the mixture of naphthalene, normal octane and decane is by reaction bed, and wherein naphthalene is reactant, and concentration is 5wt%; Normal octane is as solvent; Decane is as internal standard compound, and concentration is the consumption that 1wt%, Al-Ni intermetallic fills compound catalyst is 0.2g, dilutes with quartz sand.Reaction procatalyst reduces 4h at hydrogen atmosphere 450 DEG C.Naphthalene selective hydrogenation reaction temperature is 340 DEG C, and reaction pressure is 4MPa, and hydrogen-oil ratio is 1000.The liquid product that in course of reaction, timed collection is obtained by condenser, the method adopting reference material to demarcate determines the conversion ratio and selective reacted, and find that naphthalene conversion ratio is 98%, the selective of naphthane is 100%.
Embodiment 8:Al-Co intermetallic compound catalyst is to the catalytic performance of naphthalene hydrogenation reaction
Detecting catalyst naphthalene hydrogenation reaction in fixed bed reactors, wherein the mixture of naphthalene, normal octane and decane is by reaction bed, and wherein naphthalene is reactant, and concentration is 5wt%; Normal octane is as solvent; Decane is as internal standard compound, and concentration is the consumption that 1wt%, Al-Co intermetallic fills compound catalyst is 0.2g, dilutes with quartz sand.Reaction procatalyst reduces 4h at hydrogen atmosphere 450 DEG C.Naphthalene selective hydrogenation reaction temperature is 360 DEG C, and reaction pressure is 4MPa, and hydrogen-oil ratio is 1000.The liquid product that in course of reaction, timed collection is obtained by condenser, the method adopting reference material to demarcate determines the conversion ratio and selective reacted, and find that naphthalene conversion ratio is 97%, the selective of naphthane is 100%.
Embodiment 9:Al-Fe intermetallic compound catalyst is to the catalytic performance of naphthalene hydrogenation reaction
Detecting catalyst naphthalene hydrogenation reaction in fixed bed reactors, wherein the mixture of naphthalene, normal octane and decane is by reaction bed, and wherein naphthalene is reactant, and concentration is 5wt%; Normal octane is as solvent; Decane is as internal standard compound, and concentration is the consumption that 1wt%, Al-Fe intermetallic fills compound catalyst is 0.2g, dilutes with quartz sand.Reaction procatalyst reduces 4h at hydrogen atmosphere 450 DEG C.Naphthalene selective hydrogenation reaction temperature is 360 DEG C, and reaction pressure is 4MPa, and hydrogen-oil ratio is 1000.The liquid product that in course of reaction, timed collection is obtained by condenser, the method adopting reference material to demarcate determines the conversion ratio and selective reacted, and find that naphthalene conversion ratio is 95%, the selective of naphthane is 100%.
Embodiment 10:Al-Ni intermetallic compound catalyst is to the stability test of naphthalene hydrogenation reaction
Detecting catalyst naphthalene hydrogenation reaction in fixed bed reactors, wherein the mixture of naphthalene, normal octane and decane is by reaction bed, and wherein naphthalene is reactant, and concentration is 5wt%; Normal octane is as solvent; Decane is as internal standard compound, and concentration is the consumption that 1wt%, Al-Ni intermetallic fills compound catalyst is 0.2g, dilutes with quartz sand.Reaction procatalyst reduces 4h at hydrogen atmosphere 450 DEG C.Naphthalene selective hydrogenation reaction temperature is 360 DEG C, and reaction pressure is 4MPa, and hydrogen-oil ratio is 1000.The liquid product that in course of reaction, timed collection is obtained by condenser, the method adopting reference material to demarcate determines the conversion ratio and selective reacted, after reaction 125h, find that naphthalene conversion ratio is stabilized in 98%, the selective of naphthane was 100% (as shown in Figure 2).To reaction before and after catalyst carry out XRD analysis, find that its structure and phase are stablized, show Al-Ni catalyst naphthalene selec-tive hydrogenation prepare naphthane reaction in there is lasting stability.
Claims (4)
1. aluminum based metal compound is used for a naphthalene selective hydrogenation catalyst, and it is characterized in that, aluminum based metal compound catalyst is Al-M, M is group VIII element, comprises Ni, Fe, Co, Mo, W, Pd, Pt or Ru.
2. aluminum based metal compound according to claim 1 is used for the preparation method of naphthalene selective hydrogenation catalyst, it is characterized in that, adopt chemical synthesis under anhydrous and oxygen-free condition, with aluminiferous metals organic precursor be reducing agent, transition metal salt is for source metal, back flow reaction in organic solvent, then roasting under an inert atmosphere, sintering temperature is 400-1000 DEG C, namely forms stable aluminum based metal compound catalyst;
Described aluminiferous metals organic precursor is one or more mixing in lithium aluminium hydride reduction, triethyl aluminum, aluminium chloride, aluminium secondary butylate, aluminium isopropoxide or trimethyl aluminium.
Described transition metal salt is nickel chloride, iron chloride, cobalt chloride, molybdenum chloride, tungsten chloride, potassium chloroplatinate, ruthenium trichloride or potassium chloropalladate.
Described organic solvent is oxolane, 1,3,5-trimethylbenzene or absolute ether.
3. preparation method according to claim 2, is characterized in that, described sintering temperature 600-800 DEG C.
4. aluminum based metal compound according to claim 1 is used for the application of naphthalene selective hydrogenation catalyst, it is characterized in that, this aluminum based metal compound is used for naphthalene selective hydrogenation catalyst and prepares amino-compound for naphthalene Hydrogenation for naphthane reaction, fuel battery negative pole oxygen reduction reaction, selective acetylene hydrocarbon hydrogenation olefine reaction and nitro compound selec-tive hydrogenation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927154A (en) * | 2018-06-11 | 2018-12-04 | 大连理工大学 | A kind of preparation method of intermetallic compound nanocatalyst |
| CN109289860A (en) * | 2018-09-29 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The catalyst and preparation method of Hydrorefining of Industrial Naphthalene production refined naphthalene by-product naphthane and application |
| CN113042055A (en) * | 2021-03-23 | 2021-06-29 | 天津理工大学 | Safety porous nickel catalyst |
| CN113422080A (en) * | 2021-06-09 | 2021-09-21 | 大连理工大学 | Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation |
| CN114471570A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst, and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927154A (en) * | 2018-06-11 | 2018-12-04 | 大连理工大学 | A kind of preparation method of intermetallic compound nanocatalyst |
| CN109289860A (en) * | 2018-09-29 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The catalyst and preparation method of Hydrorefining of Industrial Naphthalene production refined naphthalene by-product naphthane and application |
| CN109289860B (en) * | 2018-09-29 | 2021-08-20 | 中国科学院山西煤炭化学研究所 | Catalyst for producing refined naphthalene and byproduct tetrahydronaphthalene by hydrofining industrial naphthalene and preparation method and application thereof |
| CN114471570A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst, and preparation method and application thereof |
| CN114471570B (en) * | 2020-10-23 | 2024-01-30 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst and preparation method and application thereof |
| CN113042055A (en) * | 2021-03-23 | 2021-06-29 | 天津理工大学 | Safety porous nickel catalyst |
| CN113422080A (en) * | 2021-06-09 | 2021-09-21 | 大连理工大学 | Preparation method and application of carbon-supported non-platinum palladium-ruthenium-tungsten alloy nanoparticle electrocatalyst for alkaline hydrogen oxidation |
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