CN104549293A - Method for preparing olefin compound based on catalyst obtained by compounding carbon tubes and transition metals - Google Patents
Method for preparing olefin compound based on catalyst obtained by compounding carbon tubes and transition metals Download PDFInfo
- Publication number
- CN104549293A CN104549293A CN201510026459.3A CN201510026459A CN104549293A CN 104549293 A CN104549293 A CN 104549293A CN 201510026459 A CN201510026459 A CN 201510026459A CN 104549293 A CN104549293 A CN 104549293A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- transition metal
- carbon pipe
- ethylbenzene
- alkenes compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing an olefin compound based on a catalyst obtained by compounding carbon tubes and transition metals. The method comprises the following steps: preheating and vaporizing an alkane compound, mixing the compound with carrier gas, and carrying out a dehydrogenation reaction in a reactor under the action of a catalyst; and collecting the olefin compound after condensation, wherein the catalyst contains 5-30wt% of transition metals/transition metal oxides and 70-95wt% of carbon tubes. The method is used for preparing aliphatic olefin compounds and aromatic olefin compounds, the catalyst compounded based on the carbon tubes and transition metal elements/transition metal oxides is stable to water, air and heat, the catalytic activity is invariable after the continuous experiment of over 150 hours, continuous operation can be realized, activation is not needed, and the catalyst is economic and convenient. According to the method disclosed by the invention, when the catalyst is applied to ethylbenzene gaseous phase direct dehydrogenation so as to prepare styrene, the conversion rate of the alkane compound is not less than10 percent, and the selectivity of the olefin compound can be more than or equal to 97 percent.
Description
Technical field
The present invention relates to organic synthesis field, particularly relate to a kind of method of the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound.
Background technology
Alkenes compounds is important industrial chemicals, is divided into fats olefin(e) compound and aromatics olefin(e) compound.Propylene/isobutene mainly from coproduction or the by-product of steam cracking and refinery factory fluid catalytic cracking process, can be widely used in synthetic polymer, gasoline additive, rubber and various chemical intermediate.Along with low-carbon alkene demand is growing, traditional production process is difficult to meet the need of market.Develop and opened up new alkene by low-carbon alkanes preparing low-carbon olefins process originate significant for making full use of low-carbon alkanes.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit catches fire seriously, and the catalyst of exploitation high activity, high selectivity and high stability becomes the key of this technology.Application number is that the Chinese patent application of 200710025372.X discloses a kind of catalyst, and be the preparation method of platinum-impregnated tin component on carrier at alumina modified mesoporous molecular sieve, conversion of propane is only 17%, and Propylene Selectivity is 93%.This catalyst have employed the active component tin of alumina load catalyst, the easy coking deactivation of catalyst in applied at elevated temperature process, the poor stability of catalyst.
Aromatics olefin(e) compound is for styrene, and styrene is important Organic Chemicals, and main application is the monomer as synthetic rubber and plastics, is used for producing butadiene-styrene rubber, polystyrene, foamed polystyrene; Also can be used for the engineering plastics manufacturing multiple different purposes from other monomer copolymerizations.In addition, styrene is also one of raw material producing ion exchange resin and pharmaceuticals, also can be used for the industries such as pharmacy, dyestuff, agricultural chemicals and ore dressing.
Styrene industrial manufacture process mainly contains ethylbenzene catalytic dehydrogenation method and ethylbenzene conjugated oxidation two kinds in the world.Ethylbenzene dehydrogenation is that a reversible heat absorption increases molecular reaction, and heating decompression is conducive to reaction and carries out to generation styrene direction.The method of industrial employing is in charging, mix a large amount of high-temperature vapor, to reduce hydrocarbon partial pressure, and provides the partial heat needed for reaction.For ethylbenzene catalytic dehydrogenation method, the early stage zinc system catalyst having the magnesium series catalysts of California, USA standard oil company and German method our company adopted.After World War II, that extensively adopt the exploitation of the Shell Oil Company of the U.S. take iron oxide as the catalyst (Fe of main component
2o
3: K
2o:Cr
2o
3=87:10:3), styrene yield about 60%, selective about 87%.
1978, occurred again a kind of Fe-series catalyst being added with multiple co-catalyst, selectivity of styrene can reach 95%, and the co-catalyst added mostly is alkali metal or alkaline-earth metal, as potassium, vanadium, molybdenum, tungsten, cerium, chromium etc.For the Fe-K catalyst of commercialization, due to the loss of its potassium in catalytic process, Fe
3 +state is very unstable, and clogged with soot active sites easily occurs and makes its catalytic stability energy poor, only can maintain several hours, in addition, there is harmful element Cr in this catalyst system and catalyzing, for environment, health etc. are all totally unfavorable.In order to overcome these problems, the oxidative dehydrogenation that carbon-based material catalyst is used for ethylbenzene becomes effective substitute technology.
Being used for the oxidative dehydrogenation of ethylbenzene with active carbon and showing good catalytic activity of Figueiredo seminar report, and find that the carbonyl/quinonyl ratio of activated carbon surface improves the key (Appl.Catal.A:Gen., 184,153) of catalytic performance.But in oxidative airstream atmosphere, the stability extreme difference of active carbon.The people such as D.S.Su and R.Schlogl report the oxidative dehydrogenation (Catal.Today 2005 of nano-carbon material as ethylbenzene of many walls carbon pipe and onion shape, 102,110-114), due to the essence of material with carbon element and microstructure thereof make its catalytic stability comparatively active carbon increase, but its catalytic activity is only reported in 10 hours.In addition, carry out oxidation processes by early stage to many walls carbon pipe, the oxy radical density improving carbon tube-surface also effectively can improve catalytic performance, and its stability can be made to significantly improve (Carbon, 2004,42,2807-2813), but its catalytic cycle is only limitted to several hours.Except the above-mentioned use dioxygen oxidation dehydrogenation mentioned, also can prepare styrene (Catal.Today 2003,81,425) by toluene chain hydrocarbonylation on the downside of the effect of methyl alcohol.Although these means of catalysis comparatively commercial catalyst are significantly improved, its selective poor and use of flammable mixture makes operation more dangerous.
Carbon-supported catalysts is used for the gas phase direct dehydrogenation of ethylbenzene becomes study hotspot in recent years.Wherein the most typically Nano diamond, D.S.Su (Angew.Chem.Int.Ed.2010,49, the Nano diamond of nucleocapsid structure that 8640-8644) etc. prepared by the method for the employing strong oxidizing property pickling blast of people's report can for the direct dehydrogenation of ethylbenzene in argon atmosphere, and by repeatedly being activated in air 400 DEG C by catalyst, its catalytic performance can be extended by 120 hours.Subsequently, D.S.Su seminar reports again two step synthesis Nano diamond/CNT-SiC carbon-supported catalysts, select the macropore SiC foam of high-termal conductivity and mechanical stability as carrier, one deck carbon pipe is wrapped up on SiC foam surface by the method for chemical vapour deposition (CVD), then the method for ultrasonic assistant soakage is adopted by the Nano diamond load of commercialization in substrate, although obtained catalyst has higher conversion ratio, but the preparation process of its catalyst is complicated, and cost is higher, in addition the stability reported is only 20 hours (Chem.Commun., 2014, 50, 7810-7812).And for example Nano diamond/carbonitride hybrid material (the J.Mater.Chem.A.2014 of the preparation such as Z.K.Zhao, 2,13442-13451) be fired to different temperatures after being mixed with Nano diamond by melamine and obtain, although improve its catalytic performance by melamine introducing hetero-atoms N, but in the preparation process of Nano diamond, need acid with strong oxidizing property explosive treatment, be very unfriendly for environment, its catalytic stability is also only reported in 20 hours in addition.
In view of said method Problems existing, develop a kind of excellent catalytic effect, low energy consumption, raw material sources are extensive, and the catalytic stability time is long, can while be vital for the preparation of the new catalyst of fats alkene compound and aromatics olefin(e) compound.
Application number be 201410338644.1 and 201410389748.5 Chinese patent application disclose a kind of novel Large Diameter Pipeline, overlength CNT Catalysts and its preparation method, described catalyst is made up of metallic 5wt% ~ 30wt% and carbon pipe carrier 70wt% ~ 95wt%, the catalyst of carbon pipe and transition metal compound can be prepared by one kettle way, by carbohydrate, template and the rear calcining of transition metal salt mixing are made, and dinectly bruning obtains the catalyst of carbon tube transitions metal composite.The catalyst preparing of this carbon pipe and transition metal compound is simple, to water, air and thermally-stabilised.
Summary of the invention
The invention provides a kind of method of the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound.The present invention adopts, highly selective catalysis alkane derivative one step dehydrogenation efficient based on the catalyst of carbon pipe and transition metal simple substance/transition metal oxide compound to synthesize alkenes compounds, and the method can be used for preparing fats alkene compound and aromatics olefin(e) compound.
Based on a method for the catalyst preparing alkenes compounds of carbon pipe and transition metal compound, the alkane derivative after preheating being vaporized and carrier gas mixing pass in reactor carries out dehydrogenation reaction under catalyst action, collects alkenes compounds after condensation;
Described catalyst contains the transition metal simple substance/transition metal oxide of 5wt% ~ 30wt% (percentage by weight) and the carbon pipe of 70wt% ~ 95wt%, and the average grain diameter of transition metal/transition metal oxide is 1-100nm;
Described alkane derivative structural formula is such as formula shown in (I):
R-CH
2CH
3(I)；
Described alkenes compounds structural formula is such as formula shown in (II):
R-CH＝CH
2(II)；
Formula (I) and the middle substituent R of formula (II) are hydrogen atom, C
1-C
4alkyl, substituted or unsubstituted aryl; If when substituent R is the aryl replaced, the substituting group on described aryl is selected from halogen, C
1-C
4alkyl or C
1-C
4alkoxyl.
The principle of the present invention's reaction is: the active sites of catalytic reaction is mainly-C=O and the defective bit (tube wall of carbon pipe) of catalyst surface, and alkane derivative is adsorbed on active sites and the fracture of-C-H occurs, thus dehydrogenation reaction occurs.Caliber large in catalyst is conducive to mass transport process, promotes the carrying out of reaction.And the transition metal/transition metal oxide in catalyst improves the stability of catalyst greatly.
Described aryl refers to not comprise heteroatomic aromatic rings, such as phenyl or naphthyl etc.; As preferably, described aryl is phenyl, now the selection rate of obtained alkenes compounds and conversion ratio all the highest.
As preferably, the substituting group of described aryl is selected from chlorine, fluorine, methyl or methoxy; Described substituting group can be one or more, can be identical or different separately.
As further preferred, described alkane derivative is selected from the one in following compound:
Ethylbenzene, 2-methyl-ethyl benzene, 4-methoxyl group ethylbenzene, adjacent chloroethene benzene, 2,3-dimethyl ethylbenzene, normal butane, n-propane or iso-butane.
Be filled into after catalyst mixes with quartz sand in reactor, the mass ratio 1:10-100 of catalyst and quartz sand, catalyst and quartz sand mixing are in order to dilute catalyst, improve the time of staying of reaction raw materials at beds, improve reaction efficiency, and catalyst is played a supporting role.
Described carrier gas is at least one in air, oxygen, nitrogen, argon gas and helium.Carrier gas is air or oxygen, and alkane derivative, under catalyst action, oxidative dehydrogenation occurs, obtained alkenes compounds; Carrier gas is nitrogen, argon gas or helium, alkane derivative under catalyst action self Oxidative Dehydrogenation for alkenes compounds.
As preferably, described carrier gas is air or argon gas, and under preferred carrier gas condition, the inventive method adopts oxidative dehydrogenation or self Oxidative Dehydrogenation for alkenes compounds, and conversion rate is very fast, and yield is higher.
Described alkane derivative pre-thermal evaporation after and carrier gas be mixed to form mist, carry out continuous dehydrogenation reaction in the reactor, the volume fraction of alkane derivative in carrier gas is 1.0%-40.0%, when the volume fraction of alkane derivative in carrier gas is less, prepare the selective lower of alkenes compounds, but productive rate is higher; When the volume fraction of alkane derivative in carrier gas is larger, the productive rate preparing alkenes compounds is lower, but selective higher.
The volume fraction of described alkane derivative in carrier gas represents the volume ratio of alkane derivative and carrier gas.
As preferably, the volume fraction of described alkane derivative in carrier gas is 1.0 ~ 25.0%, and within the scope of this, the conversion ratio of obtained alkenes compounds is higher.
The flow velocity of alkane derivative and carrier gas is 10-40mL/min, and the mass space velocity (WHSV) of described alkane compound is 0.2-20h
-1.
Mass space velocity is the gas flow by unit mass catalyst layer in the unit time;
Mass space velocity=material quality flow (kg.h
-1)/catalyst quality (kg).
Described dehydrogenation reaction temperature is 300 DEG C-600 DEG C, and this temperature can make reactant gasify, and heating up within the specific limits can the activity of augmenting response substrate, adds the carrying out of fast response.
As preferably, reaction temperature is 400 DEG C-600 DEG C, and in this temperature range, reaction substrate activity is higher, and reaction is very fast.
What described reaction was reacted by gas-chromatography on-line checkingi carries out degree, and the stable reaction time is 0.5h-1h, and substrate is different, stable reaction time slightly difference.
In described catalyst, carbon pipe is the CNT of N doping, and nitrogen content is 0.01wt%-20.0wt%.The CNT of N doping and the catalyst of transition metal compound, catalytic effect is better.
Described transition metal simple substance/transition metal oxide represents the mixture of transition metal simple substance and transition metal oxide.
In described catalyst, transition metal simple substance is Ni, Fe or Co; Described transition metal oxide is the oxide of Ni, Fe or Co.
Catalyst of the present invention can adopt application number preparation method disclosed in the patent application of 201410338644.1 and 201410389748.5 to obtain:
(1) carbohydrate, template and transition metal salt physical mixed, obtain solid precursor;
(2) solid precursor is in an inert atmosphere through two-part calcination procedure, prepares the catalyst of carbon pipe and transition metal simple substance/transition metal oxide compound;
Described transition metal salt is Fe salt, Ni salt or Co salt.
Preferably, described transition metal salt is Ni salt, and the catalyst activity adopting Ni salt obtained is higher.
More preferably, for direct dehydrogenation, reaction condition is: described alkane derivative is ethylbenzene, and described carrier gas is argon gas, and the volume fraction of ethylbenzene in carrier gas is 1% ~ 5%, and the mass space velocity of ethylbenzene is 0.2-1.8h
-1, reaction temperature is 450 DEG C ~ 600 DEG C.The conversion ratio of ethylbenzene is 15 ~ 25% under this condition, and selection rate is 95 ~ 100%.For oxidative dehydrogenation, reaction condition is: described alkane derivative is ethylbenzene, and described carrier gas is air, and the volume fraction of ethylbenzene in carrier gas is 10% ~ 25%, and the mass space velocity of ethylbenzene is 7-18h
-1, reaction temperature is 450 DEG C ~ 600 DEG C.The conversion ratio of ethylbenzene is 40 ~ 65% under this condition, and selection rate is 50 ~ 80%.
The inventive method in initial reaction stage by ethylbenzene through standard injection transport pump, then after preheating section, gasification section is entered in the lump with argon gas, finally enter superheater with the state of mist, reactor is entered after reaching reaction temperature, successive reaction on the catalyst that inside is filled, reacted olefin product is collected after condenser condenses.
The alkane derivative that the inventive method adopts is the product that market is sold, for ensureing the purity of alkene, the purity grade of alkane derivative is at least 99wt%, the purity of carrier gas is at least 99.99wt%, alkane derivative is by standard injection transport pump, and the flow velocity of carrier gas has mass-flow gas meter to control.
Compared with prior art, the present invention has following beneficial effect:
(1) comparatively business carbon pipe catalyst is high by more than 50% for the conversion ratio of the catalyst direct catalytic dehydrogenating reaction in argon atmosphere based on carbon pipe and transition metal simple substance/transition metal oxide compound that adopts of the present invention.
(2) be directly prepared by one kettle way based on the catalyst of carbon pipe and transition metal simple substance/transition metal oxide compound in the present invention, the metallic nanoparticle that original position is formed and carbon duct ligation close firmly, limit migration and the reunion of nano particle, thus effectively raise the stability of catalyst.
(3) the inventive method adopt high activity and high selectivity based on the catalyst of carbon pipe with transition metal simple substance/transition metal oxide compound, raw material is cheap and easy to get, energy-conserving and environment-protective, reaction condition gentleness, handling safety.
(4) catalyst based on carbon pipe and transition metal simple substance/transition metal oxide compound that adopts of the inventive method is to water, air and thermally-stabilised, continuous experiment more than 150 hours, catalytic activity is constant, can realize continued operation, without the need to activation, economical convenient.In the present invention, catalyst can be used for preparation fats alkene compound and aromatics olefin(e) compound, be applied to ethylbenzene gas phase direct dehydrogenation when preparing styrene, the conversion ratio of alkane derivative can reach more than 10%, and the selection rate obtaining alkenes compounds can reach more than 97%.
(5) catalyst based on carbon pipe and transition metal simple substance/transition metal oxide compound that the inventive method adopts can be used for direct dehydrogenation and oxidative dehydrogenation, and has superpower stability in air and argon atmosphere.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound.
Fig. 2 is the continuity catalytic effect figure of the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound.
Detailed description of the invention
Embodiment 1
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, obtain the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound.Transmission electron microscope picture as shown in Figure 1.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.08g catalyst obtained is in the quartz tube reactor of 5mm, and the volume fraction of ethylbenzene in argon gas is 5%, and the mass space velocity of ethylbenzene is 1.0h
-1, flow velocity is 10mL/min, and reaction temperature is 450 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the conversion ratio of ethylbenzene is 5%, cinnamic selective be 97-98%, impurity content is less than 0.5%, and through the operation of 150h, catalyst activity does not reduce.
Embodiment 2
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800 ~ 1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.08g catalyst obtained is in the quartz tube reactor of 5mm, and the volume fraction of ethylbenzene in argon gas is 1.0%, and the mass space velocity of ethylbenzene is 1.2h
-1, flow velocity is 10mL/min, and reaction temperature is 500 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the conversion ratio of ethylbenzene is 10%, cinnamic selective be 97-98%, impurity content is less than 0.5%, and through the operation of 150h, catalyst activity does not reduce.
Embodiment 3
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 1000 DEG C of calcining 1h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 25wt% nickel/nickel oxide and 75wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.08g catalyst obtained is in the quartz tube reactor of 5mm, and the volume fraction of ethylbenzene in argon gas is 1.0%-5.0%, and flow velocity is 10mL/min, and the mass space velocity of ethylbenzene is 1.8h
-1, reaction temperature is 550 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the conversion ratio of ethylbenzene is 10-20%, cinnamic selective be 97-98%, impurity content is less than 0.5%, and through the operation of 150h, catalyst activity does not reduce, as shown in Figure 2.
Embodiment 4
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.16g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 10.0%, and the mass space velocity of ethylbenzene is 12h
-1, flow velocity is 20mL/min, and reaction temperature is 300 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 5%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 5
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 80-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.16g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 15%, and the mass space velocity of ethylbenzene is 10h
-1, speed is 20mL/min, and reaction temperature is 350 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 8%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 6
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.16g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 25.0%, and the mass space velocity of ethylbenzene is 18h
-1, flow velocity is 20mL/min, and reaction temperature is 400 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 18%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 7
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.16g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 15.0%, and the mass space velocity of ethylbenzene is 10-18h
-1, flow velocity is 20mL/min, and reaction temperature is 450 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 20-45%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 7
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 10.0%, and the mass space velocity of ethylbenzene is 7-10h
-1, flow velocity is 20mL/min, and reaction temperature is 500 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 30-45%, cinnamic selective be 75-85%, through the operation of 50h, catalyst activity does not reduce.
Embodiment 8
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g cobalt nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt cobalt/cobalt oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 10.0%-20.0%, and the mass space velocity of ethylbenzene is 10-18h
-1, flow velocity is 20mL/min, and reaction temperature is 450 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 15-25%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 9
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g ferric nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% iron/iron oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of ethylbenzene is 10.0%-25.0%, and the mass space velocity of ethylbenzene is 15-18h
-1, flow velocity is 20mL/min, and reaction temperature is 450 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of ethylbenzene is 10-25%, cinnamic selective be 75-85%, through the operation of 25h, catalyst activity does not reduce.
Embodiment 10
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of normal butane is 5%, and the mass space velocity of normal butane is 1.5h
-1, flow velocity is 15mL/min, and reaction temperature is 400 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of n-butene is 20%, and the selective of n-butene is 55%, and through the operation of 50h, catalyst activity does not reduce.
Embodiment 11
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, in inert atmosphere, be cooled to room temperature, the catalyst of 20wt% ~ 25wt% nickel/nickel oxide and 75wt% ~ 80wt% carbon pipe compound can be obtained.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the aerial volume fraction of n-propane is 10%, and the mass space velocity of n-propane is 2h
-1, flow velocity is 20mL/min, and reaction temperature is 400 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of positive propylene is 10%, and the selective of positive propylene is 60%, and through the operation of 50h, catalyst activity does not reduce.
Embodiment 12
Being encased in internal diameter after being mixed with 6g quartz sand by the business carbon pipe that 0.10g buys is in the quartz tube reactor of 5mm, and the aerial volume fraction of n-propane is 5%-10%, and the mass space velocity of n-propane is 0.2-1.8h
-1, flow velocity is 20mL/min, and reaction temperature is 400 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the yield of positive propylene is 5%, and the selective of positive propylene is 20-40%, and through the operation of 50h, catalyst activity does not reduce.
Embodiment 13
By 1g aminoglucose hydrochloride, 20g melamine and 0.7g nickel nitrate physical mixed, mixed uniformly pressed powder is placed in crucible and calcines in inert atmosphere, calcination procedure is be incubated 0.5-1.5h at 550-650 DEG C, then at 800-1200 DEG C of calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, the catalyst of the higher nickel/nickel oxide of purity and nitrogenous carbon pipe compound can be obtained through dust technology process, wherein carbon pipe content is 93wt% ~ 95wt%, and nickel/nickel oxide content is 5wt% ~ 7wt%.
Being encased in internal diameter after being mixed with 6g quartz sand by the 0.10g catalyst obtained is in the quartz tube reactor of 5mm, and the volume fraction of ethylbenzene in argon gas is 1-5.0%, and the mass space velocity of ethylbenzene is 0.2-1.0h
-1, flow velocity is 10mL/min, and reaction temperature is 550 DEG C, and pressure is normal pressure, after question response is stable, through being furnished with the gas chromatographic detection of capillary chromatographic column and hydrogen flame detector.Under this reaction temperature, the conversion ratio of ethylbenzene is 15%, cinnamic selective be 97-98%, impurity content is less than 0.5%, and through the operation of 50h, catalyst activity does not reduce.
Claims (10)
1. the method based on the catalyst preparing alkenes compounds of carbon pipe and transition metal compound, it is characterized in that, alkane derivative after preheating being vaporized and carrier gas mixing pass in reactor carries out dehydrogenation reaction under catalyst action, collects alkenes compounds after condensation;
Described catalyst contains the transition metal simple substance/transition metal oxide of 5wt% ~ 30wt% and the carbon pipe of 70wt% ~ 95wt%;
Described alkane derivative structural formula is such as formula shown in (I):
R-CH
2CH
3(I)；
Described alkenes compounds structural formula is such as formula shown in (II):
R-CH＝CH
2(II)；
Formula (I) and the middle substituent R of formula (II) are hydrogen atom, C
1-C
4alkyl, substituted or unsubstituted aryl; If when substituent R is the aryl replaced, the substituting group on described aryl is selected from halogen, C
1-C
4alkyl or C
1-C
4alkoxyl.
2. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, the substituting group on described aryl is selected from fluorine, chlorine, methyl or methoxy.
3. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, described aryl is phenyl.
4. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, be filled into catalysis alkane derivative in reactor after catalyst mixes with quartz sand to react, the mass ratio 1:10-100 of catalyst and quartz sand.
5. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, described carrier gas is at least one in air, oxygen, nitrogen, argon gas and helium.
6. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, continuous dehydrogenation reaction is carried out in the reactor after alkane derivative mixes with carrier gas, the volume fraction of alkane derivative in carrier gas is 1.0%-40.0%, the flow velocity of alkane derivative and carrier gas is 10-40mL/min, and the mass space velocity of described alkane compound is 0.2-20h
-1.
7. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, in described catalyst, carbon pipe is the CNT of N doping, and nitrogen content is 0.01wt%-20.0wt%.
8. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 1, it is characterized in that, described transition metal simple substance is Ni, Fe or Co; Described transition metal oxide is the oxide of Ni, Fe or Co.
9., according to the method for the arbitrary described catalyst preparing alkenes compounds based on carbon pipe and transition metal compound of claim 1-8, it is characterized in that, the temperature of dehydrogenation reaction is 300 DEG C-600 DEG C.
10. the method for the catalyst preparing alkenes compounds based on carbon pipe and transition metal compound according to claim 9, it is characterized in that, described alkane derivative is ethylbenzene, described carrier gas is air or argon gas, the volume fraction 1% ~ 25% of ethylbenzene in carrier gas, the mass space velocity of ethylbenzene is 0.2-18h
-1, reaction temperature is 450 DEG C ~ 600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026459.3A CN104549293B (en) | 2015-01-20 | 2015-01-20 | A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510026459.3A CN104549293B (en) | 2015-01-20 | 2015-01-20 | A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549293A true CN104549293A (en) | 2015-04-29 |
| CN104549293B CN104549293B (en) | 2018-03-09 |
Family
ID=53066998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510026459.3A Active CN104549293B (en) | 2015-01-20 | 2015-01-20 | A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549293B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008244A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN109529907A (en) * | 2018-12-30 | 2019-03-29 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and preparation method thereof and the application in N- heterocyclic compound catalysis oxidation |
| CN114367295A (en) * | 2020-10-15 | 2022-04-19 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
| CN102225337A (en) * | 2011-04-24 | 2011-10-26 | 大连理工大学 | Preparation method of foamed nanometer carbon capsule assembly and its application in catalyzing oxidative dehydrogenation of ethylbenzene |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
-
2015
- 2015-01-20 CN CN201510026459.3A patent/CN104549293B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014412A (en) * | 2004-07-16 | 2007-08-08 | 那诺克有限公司 | Catalyst comprising nanocarbon structures for the production of unsaturated hydrocarbons |
| CN102225337A (en) * | 2011-04-24 | 2011-10-26 | 大连理工大学 | Preparation method of foamed nanometer carbon capsule assembly and its application in catalyzing oxidative dehydrogenation of ethylbenzene |
| CN104174421A (en) * | 2014-08-08 | 2014-12-03 | 浙江大学 | Heterogeneous catalyst for selective hydrogenation reaction of aryl nitro-compound and application of heterogeneous catalyst |
Non-Patent Citations (6)
| Title |
|---|
| B. NIGROUSKI ET AL.: ""Microwave-assisted catalytic oxidative dehydrogenation of ethylbenzene on iron oxide loaded carbon nanotubes"", 《CARBON》 * |
| NAN XIAO ET AL.: ""Carbon foams made of in situ produced carbon nanocapsules and the use as a catalyst for oxidative dehydrogenation of ethylbenzene"", 《CARBON》 * |
| ZHONGKUI ZHAO ET AL.: ""Highly-Ordered Mesoporous Carbon Nitride With Ultrahigh Surface Area and Pore Volume as a Superior Dehydrogenation Catalyst"", 《CHEM. MATER.》 * |
| 张云飞等: ""碳纳米管催化氧化脱氢反应研究进展"", 《化学通报》 * |
| 肖南: ""纳米碳材料/泡沫炭复合材料制备及应用研究"", 《中国博士学位论文全文数据库工程科技I辑》 * |
| 谌春林: ""氧化和掺氮碳纳米管的制备、表征及丙烷氧化脱氢催化性能研究"", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107008244A (en) * | 2016-01-27 | 2017-08-04 | 中国石油化工股份有限公司 | A kind of nano-carbon material containing hetero atom and its preparation method and application and a kind of hydrocarbon dehydrogenation reaction method |
| CN107008244B (en) * | 2016-01-27 | 2020-04-28 | 中国石油化工股份有限公司 | Heteroatom-containing nano carbon material, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method |
| CN109529907A (en) * | 2018-12-30 | 2019-03-29 | 中南民族大学 | A kind of nitrogen-doped carbon material load cobalt catalyst and preparation method thereof and the application in N- heterocyclic compound catalysis oxidation |
| CN109529907B (en) * | 2018-12-30 | 2021-10-15 | 中南民族大学 | Nitrogen-doped carbon material supported cobalt catalyst, preparation method thereof and application thereof in catalytic oxidation of N-heterocyclic compound |
| CN114367295A (en) * | 2020-10-15 | 2022-04-19 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
| CN114367295B (en) * | 2020-10-15 | 2023-04-18 | 中国科学院大连化学物理研究所 | Application of monodisperse carbon-supported non-noble metal material as ethylbenzene anaerobic dehydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549293B (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Masih et al. | Low-temperature methanol dehydration to dimethyl ether over various small-pore zeolites | |
| CN101773850B (en) | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and application thereof | |
| CN100392047C (en) | Method for preparing olefin by catalytic oxidation of petroleum hydrocarbon | |
| Li et al. | Highly efficient synchronized production of phenol and 2, 5-dimethylfuran through a bimetallic Ni–Cu catalyzed dehydrogenation–hydrogenation coupling process without any external hydrogen and oxygen supply | |
| CN102019178A (en) | Propane dehydrogenation to propylene catalyst and preparation and applications thereof | |
| TW201127785A (en) | Process for the oxidative coupling of hydrocarbons | |
| CN104107718B (en) | Catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| CN104107712B (en) | Mix C3/C4 alkane dehydrogenating catalysts and preparation method thereof | |
| CN103086821B (en) | A kind of production method of low-carbon alkene | |
| CN103464193A (en) | Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof | |
| CN104549293A (en) | Method for preparing olefin compound based on catalyst obtained by compounding carbon tubes and transition metals | |
| CN105080596A (en) | Isobutane oxidation dehydrogenation catalyst and preparation method and application method thereof | |
| CN111167460A (en) | Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof | |
| CN107008255B (en) | Nano diamond platinum catalyst and its preparation method and application for normal butane direct dehydrogenation butylene | |
| CN106552657B (en) | A kind of platinum based catalyst and preparation method thereof of SiC carrier confinement | |
| CN104549321A (en) | Catalyst for dehydrogenating light alkane and application of catalyst | |
| CN103086820B (en) | Light olefin production method | |
| CN107970954A (en) | Catalyst for Oxidative Dehydrogenation of Butene into Butadiene and preparation method thereof | |
| CN103553863A (en) | Method and system for preparing propylene by using methanol | |
| CN104043456B (en) | Oxidative dehydrogenation of propane catalyst, preparation method and its usage | |
| CN105664999A (en) | Preparation method of nickel-based catalyst and application of nickel-based catalyst to methanation of synthesized gas | |
| CN102962054A (en) | Cr2O3 catalyst for isobutene preparation by isobutane dehydrogenation and preparation method thereof | |
| CN111054410B (en) | Liquid phase dehydrogenation catalyst, preparation and use | |
| WO2018048629A1 (en) | Multi-stage adiabatic oxidative coupling of methane | |
| CN111111726A (en) | Preparation method and application of catalyst for preparing propylene by oxidative dehydrogenation of propane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |