CN108465479A - Self assembly special appearance mordenite catalyst and preparation method thereof - Google Patents
Self assembly special appearance mordenite catalyst and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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Abstract
The present invention relates to a kind of self assembly special appearance mordenite catalysts and preparation method thereof, while chain pattern promotes molecular sieve catalyst efficient mass transfer performance, mainly solve the problems, such as that catalyst is active low with selectivity in transalkylation, the catalyst uses chain pattern modenite for carrier, active component includes, it is at least one selected from IVB elements, selected from VIIB elements are at least one and technical solution selected from least one of IVA metallic elements, preferably solves the technical problem, it can be used in the industrial production of the aromatic hydrocarbons such as transalkylation conversion.
Description
Technical field
The present invention relates to a kind of self assembly special appearance mordenite catalyst, preparation methods, and its application.
Background technology
The two-dimensional channel system of modenite, in the reaction of the macromoleculars such as aromatic hydrocarbons, catalytic action generally only occurs in
The oval straight tube main aperture road of twelve-ring, and the octatomic ring duct mutually linked up with main aperture road, general molecule are therefore right into not going
Diffusion limitation is reduced in reaction, it is main Research Thinking to inhibit fast-growth of the modenite crystal on c-axis direction.Mercerising
Zeolite has stronger growth potential energy along 12MR (twelve-ring duct, i.e. c-axis) direction, is usually readily available two-dimentional scale
Modenite nanoclub-like crystal, forms needle-shaped or fibrous, and aggregate is radial, pencil, threadiness etc..Modenite is logical
It is difficult often the preferred growth for effectively inhibiting crystal to be made of chain structure five-membered ring along c-axis, is also easy to edge and is parallel to c-axis and b axis
Two-dimensional channel oriented growth at rhombic sheet modenite.In three dimension scale high-crystallinity nano mordenite crystal
Research in, the growth in the directions ab can be relatively easy to be controlled, and directly affect the mass-transfer performance of catalyst.Piece shape mercerising
Lack interlinking between the twelve-ring duct of zeolite, the serious mass transfer rate reduced in catalytic reaction process is unfavorable for
Catalytic activity preferably plays.Effective Regulation modenite crystal is self-assembled into orderly self-supporting material, explores, research nanometer
The aggregated forms of modenite crystal are the key that solve to adsorb on catalyst in reaction process, spread bottleneck.
CN103274458A contacts synthesizing one-dimensional item chain titanium dioxide nano-crystal, the ratio of material by the orientation between basic unit
The performances such as surface area and order are significantly enhanced.Chain pattern can be effectively improved the mass transfer diffusivity of modenite
Can, but the modenite of sial composition is limited by surface acidity distribution, is existed in the specific reaction such as accordance transfer and is lived
Property with the low problem of selectivity, it usually needs regulated and controled by element modified mode.It is special as residing for transition metal element
Periodic table of elements position, the excellent physical chemical property of imparting generates special carrier effect and makes catalyst to many anti-
There should be preferable co-catalysis effect, introduce dispersion and the stabilization that can also further enhance other metals by synergistic effect
Property.
The present invention relates to a kind of for the chain pattern mordenite catalyst of transalkylation and its preparation side
Method can be obviously improved the reactivity worth of catalyst, preferably solve by selecting IVA, IVB and VIIB race element to be modified
The above problem.The technology and cost of the catalyst are controllable, have excellent reactivity worth in aromatic hydrocarbons conversion reaction, effectively press down
The generation of the aromatic hydrocarbons polymerization side reactions such as carbon deposit is made, consumption hydrogen side reaction is low, few using loss, has better stability, can fit
The reaction operating mode of high-speed is answered, and high with low-temperature catalytic activity, aromatic hydrocarbons treating capacity is big, excellent catalytic effect, and product dimethylbenzene is dense
The advantages that high is spent, can be used in the industrial production of the aromatic hydrocarbons such as transalkylation conversion.
Invention content
The first technical problem to be solved by the present invention is that molecular sieve catalyst diffusion exists in the prior art in order to overcome
The problem of poor performance, a kind of carrier of the novel modenite with chain pattern as catalyst is provided, which exists
In the conversion of the aromatic hydrocarbons such as disproportionation, transalkylation and isomerization, there is efficient management of performance to aromatic ring pendant alkyl group, be suitable for high-altitude
The reaction operating mode and mass transfer demand of speed.It can occur to take off alkyl or transalkylation performance accordingly with high selectivity, there are benzene and two
The characteristics of toluene principal product high income and high selectivity.
The second technical problem to be solved by the present invention is to provide a kind of one of solution above-mentioned technical problem used catalyst
The corresponding preparation method of material solves the matching of every synthetic parameters in the catalytic effect and catalyst preparation process of molecular sieve
Problem.
The third technical problem to be solved by the present invention is to use above-mentioned catalyst, is applied to the virtue of accordance transfer
In hydrocarbon Transformation Application.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is shifted for accordance
The chain pattern mordenite catalyst of reaction, the catalyst use chain pattern modenite for carrier, active component packet
It includes, selected from IVB elements at least one, selected from VIIB elements at least one and selected from least one of IVA metallic elements.
In above-mentioned technical proposal, the preferred active component includes Group IVB element, VIIB races element and IVA races simultaneously
At least one of element metallic element.
In above-mentioned technical proposal, the IVB elements are selected from least one of titanium, zirconium, hafnium.Technical side more preferably
Case, the IVB elements are selected from least one of metal element of titanium, zirconium.
In above-mentioned technical proposal, VIIB races element preferably is selected from least one of manganese, rhenium.Technology more preferably
Scheme, the VIIB elements are selected from metallic element rhenium.
In above-mentioned technical proposal, the IVA metallic elements are selected from least one of germanium, tin, lead.Skill more preferably
Art scheme, the IVA elements are preferably at least one of metallic element germanium, tin.
In above-mentioned technical proposal, as most preferred technical solution, the active component simultaneously including Group IVB element,
VIIB races element and IVA races element；For example, the active component includes titanium, manganese, germanium, either including zirconium, rhenium, tin or including
Titanium, zirconium, rhenium, germanium, or including titanium, zirconium, rhenium, germanium, tin.
In above-mentioned technical proposal, the modifying element in the catalyst, in terms of catalyst total amount, the content of IVB elements is excellent
It is selected as 0.08~6%wt, more preferably 0.7~5.5%wt；In terms of catalyst total amount, the content of VIIB elements is preferably 0.02
~6%wt, more preferably 0.05~5%wt；The two has collaboration in improving product in terms of the selectivity of dimethylbenzene and yield
Effect.
In above-mentioned technical proposal, in catalyst containing IVA races metal in terms of catalyst total amount, content is 0.03~28%
Wt, content are more preferably 0.7~16%wt.
The carrier of the catalyst uses the modenite of chain pattern, and specific surface area is preferably 268~568m2/g。
For single piece shape crystal chain pattern, thickness of single piece shape crystal made of c-axis (piece shape thickness) orderly self assembly in direction
Between 8~360nm, chain is self-assembly of size by 6~80 piece shape crystal.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：One of above-mentioned technical problem technology
The preparation method of catalyst described in scheme, includes the following steps：
A) according to the compositing formula of catalyst, by the desired amount of chemical combination for modified IVB, VIIB and IVA race metal
Object presoma is mixed with chain pattern modenite carrier,
B it) mediates, be molded, obtain catalyst Precursors after drying,
C) parent in air atmosphere, roasts 0.6~36 hour at 285~650 DEG C, and cooling obtains required catalyst material
Material.
In above-mentioned technical proposal, the compound of Group IVB element described in step A preferably is selected from titanate esters, zirconium nitrate, oxychlorination
At least one of zirconium and hafnium nitrate.
In above-mentioned technical proposal, the compound of VIIB races element, preferably is selected from manganese nitrate and ammonium perrhenate described in step A
It is at least one.
In above-mentioned technical proposal, the compound of IVA races metallic element described in step A preferably is selected from germanium oxide, nitric acid germanium, four
At least one of stannic chloride and plumbi nitras.
To solve above-mentioned technical problem three, the technical solution adopted by the present invention is as follows：The transalkylation of aroamtic hydrocarbon raw material is anti-
It answers, using being reacted in the presence of catalyst in one of any above-mentioned technical problem technical solution.
The key of the present invention is the selection of catalyst, suitable skilled person will know how determining according to actual needs
Material proportion, reaction temperature, reaction pressure and reaction velocity.In above-mentioned technical proposal, transalkylation with mole
Than 37:The toluene and trimethylbenzene of 63 compositions are model charge, and preferable reaction temperature is 280~650 DEG C, and preferably reaction pressure is
1.5~3.5MPa, preferably reaction velocity are 0.05~5h-1。
Reaction product in above-mentioned technical proposal is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), by following public affairs
Formula calculates the selectivity of the conversion ratio and principal product (benzene, dimethylbenzene) of aroamtic hydrocarbon raw material (toluene, trimethylbenzene)：
Molal quantity/charging molal quantity × 100% for conversion ratio (%)=react away
Molal quantity/reaction that benzene selective (%)=reaction generates benzene generates C6 hydro carbons molal quantity × 100%
Molal quantity/reaction that dimethylbenzene selective (%)=reaction generates dimethylbenzene generates C8 hydro carbons molal quantity × 100%
Compared with prior art, innovation point of the invention is, by using a kind of novel chain pattern
Active main body of the modenite as catalyst, the microcosmic self-supporting nano material can be obviously improved the reactivity worth of catalyst,
Catalyst diffusion duct is more unobstructed, and microporous mesoporous compound pore passage structure is more orderly regular, has in aromatic hydrocarbons conversion reaction
Excellent reactivity worth is suitable for the reaction operating mode of high-speed compared to conventional mordenite catalyst, and aromatic hydrocarbons treating capacity is big, and
Has many advantages, such as excellent catalytic effect, product xylene concentration is high, can be used in the industrial production of aromatic hydrocarbons conversion.Meanwhile catalyst
Active component include it is a certain amount of selected from Group IVB element, selected from VIIB races element and in IVA races element at least one
Kind metallic element is conducive to the activity and stability that improve catalyst, to improve principal product in transalkylation
The yield and selectivity of benzene and dimethylbenzene.The catalyst preparation, it is easy to operate, it is with obvious effects, it is allocated by forming, is significantly being carried
While rising performance, production cost is greatly saved.
The experimental results showed that the catalyst prepared by the present invention achieves in preferable technique effect, especially catalyst
Active component is simultaneously including being selected from Group IVB element, selected from VIIB races element and selected from least one of IVA races element metal member
When plain, technique effect more outstanding is achieved, can be used in the aromatic hydrocarbons conversion reactions such as accordance transfer.
Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【Embodiment 1】
By chain pattern modenite (being denoted as LM, silica alumina ratio 27), weigh 62 grams, addition deionized water mediate uniformly,
Catalyst Precursors are obtained after extruded moulding, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
With above-mentioned catalyst, evaluating catalyst, reactor rule are carried out on the continuous micro-reaction equipment of fixed bed for facing hydrogen
Lattice are19.0 grams of loadings, transalkylation is with molar ratio 37:The toluene and trimethylbenzene of 63 compositions
For model charge, hydrogen hydrocarbon molar ratio H2/ HC=3.1.The air of reaction system first is discharged with hydrogen and is pressurized to 1.9MPa, controls
The charging reaction velocity of above-mentioned raw materials is 2.2h-1, raw material by being contacted with the bed containing above-mentioned catalyst, is heated to respectively
Reaction temperature, controlling reaction temperature are 386 DEG C (following embodiments and comparative examples, evaluated according to the above situation), are continued
After stablizing reaction 20 hours, the reaction mass of catalyst bed outlet is through cooling, decompression, separation, the liquid obtained by sampling analysis
Mixture, liquid phase material are analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
【Comparative example 1】
Laboratory simultaneously with conventional fusiformis micron order modenite (be denoted as NM, silica alumina ratio is consistent with LM, is all 27) sample,
62 grams are weighed, addition deionized water obtains catalyst Precursors after mediating uniform, extruded moulding, drying, and parent is in air atmosphere 565
DEG C roasting 5 hours, pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
By comparative example 1 and comparative example 1 as can be seen that chain nanometer sheet modenite of the present invention, phase
Than conventional fusiformis micron order modenite, the former comprehensive performance is more excellent, lives to the conversion of reaction raw materials toluene and trimethylbenzene
Property all highers.
【Embodiment 2】
62 grams of LM dry powder are weighed, titanate esters (amount of metal for pressing 2.1%wt) are added, addition deionized water is mediated uniform, crowded
Catalyst Precursors are obtained after item molding, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 3】
62 grams of LM dry powder are weighed, zirconium nitrate (amount of metal for pressing 2.1%wt) is added, addition deionized water is mediated uniform, crowded
Catalyst Precursors are obtained after item molding, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 4】
62 grams of LM dry powder are weighed, hafnium nitrate (amount of metal for pressing 2.1%wt) is added, addition deionized water is mediated uniform, crowded
Catalyst Precursors are obtained after item molding, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
By comparative example 2~4 and embodiment 1 as can be seen that chain nanometer sheet mordenite catalyst listed by the present invention
Agent, the comprehensive performance after loading Group IVB metal are more excellent.
【Embodiment 5】
62 grams of LM dry powder are weighed, zirconium oxychloride and manganese nitrate (amount of metal for pressing 2.1%wt and 3%wt respectively) is added, adds
Catalyst Precursors are obtained after adding deionized water to mediate uniform, extruded moulding, drying, parent is small in 565 DEG C of roastings 5 of air atmosphere
When, pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 6】
62 grams of LM dry powder are weighed, zirconium oxychloride and ammonium perrhenate (amount of metal for pressing 2.1%wt and 3%wt respectively) is added,
Addition deionized water obtains catalyst Precursors after mediating uniform, extruded moulding, drying, and parent is small in 565 DEG C of roastings 5 of air atmosphere
When, pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
By comparative example 5,6 and embodiment 3 as can be seen that chain nanometer sheet mordenite catalyst listed by the present invention
Agent, on the basis of loading Group IVB metal zirconium, then supported V Group IIB metal, comprehensive performance is more excellent, shows certain gold
Synergistic effect between category.
【Embodiment 7】
62 grams of LM dry powder are weighed, titanate esters, ammonium perrhenate (amount of metal for pressing 2.1%wt, 3%wt respectively), addition is added
Deionized water obtains catalyst Precursors after mediating uniform, extruded moulding, drying, and parent roasts 5 hours for 565 DEG C in air atmosphere,
Pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 8】
62 grams of LM dry powder are weighed, titanate esters, ammonium perrhenate and nitric acid germanium is added and (presses 2.1%wt, 3%wt and 5%wt respectively
Amount of metal), addition deionized water mediate uniformly, extruded moulding, it is dry after obtain catalyst Precursors, parent is in air atmosphere
565 DEG C roast 5 hours, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 9】
62 grams of LM dry powder are weighed, titanate esters, ammonium perrhenate and butter of tin is added and (presses 2.1%wt, 3%wt and 5% respectively
The amount of metal of wt), addition deionized water obtains catalyst Precursors after mediating uniform, extruded moulding, drying, and parent is in air atmosphere
565 DEG C roast 5 hours, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 10】
62 grams of LM dry powder are weighed, titanate esters, ammonium perrhenate and plumbi nitras is added and (presses 2.1%wt, 3%wt and 5%wt respectively
Amount of metal), addition deionized water mediate uniformly, extruded moulding, it is dry after obtain catalyst Precursors, parent is in air atmosphere
565 DEG C roast 5 hours, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
By comparative example 8~10 and embodiment 7 as can be seen that chain nanometer sheet mordenite catalyst listed by the present invention
Agent on the basis of loading Group IVB Titanium and VIIB races rhenium metal, then loads IVA races metallic element, and comprehensive performance will be more
It is excellent, further synergistic effect is shown between metal.
【Embodiment 11】
62 grams of LM dry powder are weighed, zirconium nitrate, titanate esters, ammonium perrhenate and germanium oxide is added and (presses 1.2%wt, 0.9% respectively
The amount of metal of wt, 3%wt and 5%wt), addition deionized water obtains catalyst Precursors after mediating uniform, extruded moulding, drying,
Parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
【Embodiment 12】
62 grams of LM dry powder are weighed, zirconium nitrate, titanate esters, ammonium perrhenate, germanium oxide and butter of tin is added and (presses respectively
The amount of metal of 1.2%wt, 0.9%wt, 3%wt, 2.5%wt and 2.5%wt), addition deionized water mediate uniformly, extrusion at
Catalyst Precursors are obtained after type, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
By embodiment 11 and 12 as can be seen that chain nanometer sheet mordenite catalyst listed by the present invention, is loading IVB
Race's metal, VIIB races metal and IVA races metallic element, on the basis of previous embodiment is preferred, synergistic effect can express between metal
Go out the promotion in further performance.
【Comparative example 2】
Laboratory with 62 grams of NM samples, is added zirconium nitrate, titanate esters, ammonium perrhenate, germanium oxide and butter of tin and (divides simultaneously
Not An 1.2%wt, 0.9%wt, 3%wt, 2.5%wt and 2.5%wt amount of metal), addition deionized water mediate uniformly, extrusion
Catalyst Precursors are obtained after molding, drying, parent roasts 5 hours for 565 DEG C in air atmosphere, and pelletizing obtains catalyst.
The catalyst made from above-described embodiment, evaluation, sampling analysis under the working condition consistent with embodiment 1.
The yield and selective data of principal product is obtained by calculation, for the ease of saying in the above embodiments and comparative example
It is bright and compare, the preparation of catalyst and its evaluation data in aromatic hydrocarbons conversion reaction are listed in Tables 1 and 2 respectively.
The preparation of 1 catalyst of table
Transalkylation result on 2 catalyst of table
According to raw material composition and product composition, the reactivity worth of catalyst, the specific evaluation result of catalyst such as 2 institute of table are calculated
Show：Appraisal result shows, the chain pattern mordenite catalyst prepared using the present invention, have in aromatic hydrocarbons conversion reaction compared with
High transalkylation reaction activity can effectively facilitate the transalkylation reaction of aromatic hydrocarbons and have higher methyl conservation rate, product
Dimethylbenzene yield is obviously high；Chain pattern mordenite catalyst has preferable reaction stability simultaneously, and comparative example is catalyzed
There is different degrees of decline after 100 hours in every indicator reaction in agent, by temperature raising can not long-time stable performance,
Chain pattern is conducive to be promoted the transalkylation performance of catalyst, this is diffused with much relations with the mass transfer reacted.Contrast sample
Evaluation data result under similar reaction working condition is it is found that the active component of catalyst includes a certain amount of being selected from Group IVB
Element is selected from VIIB races element and selected from least one of IVA races element metallic element, is conducive to the activity for improving catalyst
And stability, to improve the yield and selectivity of principal product benzene and dimethylbenzene in transalkylation.The catalysis
Modifying element in agent, IVB elements and VIIB elements have collaboration in improving product in terms of the selectivity of dimethylbenzene and yield
Effect.Active component includes simultaneously selected from Group IVB element, selected from VIIB races element and in IVA races element in catalyst
When at least one metallic element, technique effect more outstanding is achieved, it is anti-to can be used for the aromatic hydrocarbons conversion such as accordance transfer
Ying Zhong.
Claims (10)
1. a kind of self assembly special appearance mordenite catalyst, for the aromatic hydrocarbons conversion reactions such as accordance transfer, feature
It is, the catalyst uses chain pattern modenite for carrier, and active component includes, choosing at least one selected from IVB elements
From VIIB elements at least one and selected from least one of IVA metallic elements.
2. catalyst according to claim 1, it is characterised in that carrier uses the modenite of chain pattern, specific surface area
For 268~568m2/g；For single piece shape crystal chain pattern made of c-axis, that is, orderly self assembly of piece shape thickness direction, individually
Between 8~360nm, chain is self-assembly of the thickness of piece shape crystal by 6~80 piece shape crystal.
3. catalyst according to claim 1, which is characterized in that the IVB elements are selected from least one of titanium, zirconium, hafnium.
4. catalyst according to claim 1, which is characterized in that the VIIB elements are selected from least one of manganese, rhenium.
5. catalyst according to claim 1, which is characterized in that the IVA metallic elements in germanium, tin, lead at least
It is a kind of.
6. catalyst according to claim 1, which is characterized in that in catalyst, in terms of catalyst total amount, IVB elements contain
Amount is 0.08~6%wt, and the content of VIIB elements is 0.02~6%wt.
7. catalyst according to claim 1, which is characterized in that IVA races metal in the catalyst, with catalyst total amount
Meter, content are 0.03~28%wt.
8. the preparation method of chain pattern mordenite catalyst according to claim 1, includes the following steps：
A) according to the compositing formula of catalyst, by the compounds precursors and chain for modified IVB, VIIB and IVA race metal
Shape pattern modenite carrier mixes,
B it) mediates, be molded, obtain catalyst Precursors after drying,
C) parent in air atmosphere, roasts 0.6~36 hour at 285~650 DEG C, and cooling obtains required catalyst material.
9. a kind of method of the transalkylation reaction of aroamtic hydrocarbon raw material, in the presence of any catalyst in claim 1~8
It is reacted.
10. the transalkylation reaction of aroamtic hydrocarbon raw material according to claim 9, it is characterized in that using toluene, trimethylbenzene as model original
Material, reaction temperature are 280~650 DEG C, and reaction pressure is 1.5~3.5MPa, and reaction velocity is 0.05~5h-1。
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| CA903696A (en) * | 1972-06-27 | Texaco Development Corporation | Catalytic dewaxing | |
| CN1174184A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Methylbenzene disproportionating and alkyl group transfering process |
| CN102578388A (en) * | 2012-02-12 | 2012-07-18 | 南京农业大学 | Feed used lactate modified zeolite and preparing method and application thereof |
| CN103274458A (en) * | 2013-06-05 | 2013-09-04 | 浙江大学 | One-dimensional necklace-shaped titanium dioxide nanocrystal and preparation method thereof |
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| CA903696A (en) * | 1972-06-27 | Texaco Development Corporation | Catalytic dewaxing | |
| CN1174184A (en) * | 1996-08-20 | 1998-02-25 | 中国石油化工总公司 | Methylbenzene disproportionating and alkyl group transfering process |
| CN102578388A (en) * | 2012-02-12 | 2012-07-18 | 南京农业大学 | Feed used lactate modified zeolite and preparing method and application thereof |
| CN103274458A (en) * | 2013-06-05 | 2013-09-04 | 浙江大学 | One-dimensional necklace-shaped titanium dioxide nanocrystal and preparation method thereof |
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