CN108465479B - Self-assembled mordenite catalyst with special morphology and preparation method thereof - Google Patents
Self-assembled mordenite catalyst with special morphology 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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
- B01J29/26—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- 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
Abstract
The invention relates to a self-assembled mordenite catalyst with special morphology and a preparation method thereof, which mainly solves the problem that the catalyst has low activity and selectivity in aromatic hydrocarbon transalkylation reaction while improving the high-efficiency mass transfer performance of a molecular sieve catalyst with chain morphology.
Description
Technical Field
The invention relates to a self-assembled mordenite catalyst with special morphology, a preparation method and application thereof.
Background
In the reaction of the macromolecules of aromatic hydrocarbon, the catalytic action of the two-dimensional pore channel system of mordenite generally only takes place in the main elliptic cylinder pore channel of twelve-membered ring, and the eight-membered ring pore channel communicated with the main pore channel generally has no molecules, so that the two-dimensional pore channel system of mordenite is a main research idea for reducing diffusion limitation of reaction and inhibiting the rapid growth of mordenite crystals in the c-axis direction. Mordenite has strong growth potential along the 12MR (twelve-membered ring channel, namely c-axis) direction, and generally, mordenite nanorod crystals with two-dimensional dimensions are easily obtained to form needle-shaped or fibrous crystals, and the aggregates are in a radial shape, a bundle shape, a fibrous shape and the like. Mordenite is generally difficult to effectively inhibit the preferential growth of a chain structure formed by five-membered rings along a c axis, and is easy to directionally grow into rhombic flaky mordenite along a two-dimensional channel parallel to the c axis and the b axis. In the research of the three-dimensional high-crystallinity nano mordenite crystals, the growth in the ab direction can be easily controlled, and the mass transfer performance of the catalyst is directly influenced. Twelve-membered ring channels of the sheet-shaped mordenite lack compatibility, so that the mass transfer rate in the catalytic reaction process is seriously reduced, and the better exertion of the catalytic activity is not facilitated. The method effectively regulates the self-assembly of the mordenite crystals into the ordered self-supporting material, explores and researches the aggregation form of the nano-mordenite crystals, and is the key to solve the bottleneck of adsorption and diffusion on the catalyst in the reaction process. CN103274458A synthesizes the one-dimensional necklace-shaped titanium dioxide nano-crystal through the oriented contact among the basic units, and the specific surface area, the order and other properties of the material are greatly improved. The chain shape can effectively improve the mass transfer diffusion performance of the mordenite, but the mordenite consisting of silicon and aluminum is limited by surface acid distribution, so that the problems of low activity and low selectivity exist in specific reactions such as aromatic hydrocarbon transalkylation and the like, and the regulation and control are usually carried out in an element modification mode. For example, the transition metal elements are located at special periodic table positions of the elements, the endowed excellent physicochemical properties and the generated special carrier effect enable the catalyst to have a better catalytic assisting effect on a plurality of reactions, and the introduction of the transition metal elements can further enhance the dispersion and stability of other metals through synergistic effect.
The invention relates to a chain-shaped mordenite catalyst for an aromatic hydrocarbon transalkylation reaction and a preparation method thereof, which can remarkably improve the reaction performance of the catalyst by selecting IVA, IVB and VIIB elements for modification, and better solves the problems. The catalyst has controllable technology and cost, excellent reaction performance in aromatic hydrocarbon conversion reaction, effective inhibition of side reaction of polymerization of aromatic hydrocarbon such as carbon deposit, low hydrogen consumption side reaction, less application loss, better stability, adaptability to reaction working condition with high airspeed, high low-temperature catalytic activity, large aromatic hydrocarbon processing capacity, good catalytic effect, high concentration of xylene product and the like, and can be used in industrial production of aromatic hydrocarbon conversion such as aromatic hydrocarbon transalkylation reaction and the like.
Disclosure of Invention
One of the technical problems to be solved by the invention is to overcome the problem of poor diffusion performance of molecular sieve catalysts in the prior art, and provide a novel mordenite with a chain-shaped morphology as a carrier of the catalyst, wherein the catalyst has high-efficiency management performance on aromatic side chain alkyl in aromatic hydrocarbon conversion such as disproportionation, transalkylation and isomerization, and can adapt to the reaction working condition with high space velocity and the mass transfer requirement. Can selectively generate corresponding dealkylation or transalkylation performance, and has the characteristics of high yield and high selectivity of the main products of the benzene and the dimethylbenzene.
The second technical problem to be solved by the present invention is to provide a preparation method for the catalyst material used to solve the first technical problem, and to solve the matching problem between the catalytic effect of the molecular sieve and each synthesis parameter in the catalyst preparation process.
The third technical problem to be solved by the invention is to apply the catalyst to the conversion application of the aromatic hydrocarbon in the alkyl transfer of the aromatic hydrocarbon.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a mordenite catalyst with chain morphology for an aromatic hydrocarbon transalkylation reaction adopts mordenite with chain morphology as a carrier, and active components comprise at least one selected from IVB elements, at least one selected from VIIB elements and at least one selected from IVA metal elements.
In the above technical solution, preferably, the active component includes at least one metal element of group IVB elements, group VIIB elements, and group IVA elements.
In the above technical solution, the IVB element is selected from at least one of titanium, zirconium, and hafnium. More preferably, the IVB element is at least one selected from the group consisting of titanium and zirconium.
In the above technical solution, the VIIB element is preferably at least one of manganese and rhenium. More preferably, VIIB is selected from rhenium, a metal element.
In the above technical solution, the IVA metal element is selected from at least one of germanium, tin, and lead. In a more preferred embodiment, the IVA element is preferably at least one of germanium and tin, which are metal elements.
In the above technical solution, as the most preferable technical solution, the active component simultaneously includes an IVB group element, a VIIB group element, and an IVA group element; for example, the active component comprises titanium, manganese, germanium, or comprises zirconium, rhenium, tin, or comprises titanium, zirconium, rhenium, germanium, tin.
In the technical scheme, the content of the IVB element in the catalyst is preferably 0.08-6 wt%, and more preferably 0.7-5.5 wt% based on the total amount of the catalyst; based on the total amount of the catalyst, the content of the VIIB element is preferably 0.02-6 wt%, and more preferably 0.05-5 wt%; the two have synergistic effect in improving the selectivity and yield of xylene in the product.
In the technical scheme, the catalyst contains IVA group metals in an amount of 0.03 to 28 wt% based on the total amount of the catalyst, and the content is more preferably 0.7 to 16 wt%.
The carrier of the catalyst is chain-shaped mordenite, and the specific surface area of the carrier is preferably 268-568 m2(ii) in terms of/g. The single crystal plates are in a chain shape formed by orderly self-assembling along the c-axis (plate thickness), the thickness of each single crystal plate is between 8 and 360nm, and the chain is formed by self-assembling 6 to 80 crystal plates.
To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst in one technical scheme of the technical problems comprises the following steps:
A) mixing required amount of precursor of IVB, VIIB and IVA group metal compound for modification with chain-shaped mordenite carrier according to the composition formula of the catalyst,
B) kneading, molding and drying to obtain a catalyst matrix,
C) and roasting the matrix at 285-650 ℃ for 0.6-36 hours in an air atmosphere, and cooling to obtain the required catalyst material.
In the above technical solution, the compound of the group IVB element in the step a is preferably at least one selected from titanate, zirconium nitrate, zirconium oxychloride and hafnium nitrate.
In the above technical solution, the compound of the group VIIB element in step a is preferably at least one of manganese nitrate and ammonium perrhenate.
In the above technical solution, the compound of the group IVA metal element in step a is preferably at least one selected from germanium oxide, germanium nitrate, tin tetrachloride and lead nitrate.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the transalkylation of aromatic hydrocarbon feedstock is carried out in the presence of a catalyst according to one of the above technical problems.
The key to the invention is the choice of catalyst, and the skilled person knows how to determine the appropriate feed ratio, reaction temperature, reaction pressure and reaction space velocity according to the actual needs. In the technical scheme, the aromatic hydrocarbon transalkylation reaction takes toluene and trimethylbenzene which are formed in a molar ratio of 37:63 as model raw materials, the preferable reaction temperature is 280-650 ℃, the preferable reaction pressure is 1.5-3.5 MPa, and the preferable reaction space velocity is 0.05-5 h-1。
The reaction products in the technical scheme are analyzed by a gas chromatography-MASS spectrometer (GC-MASS), and the conversion rate of the aromatic hydrocarbon raw materials (toluene and trimethylbenzene) and the selectivity of the main products (benzene and xylene) are calculated according to the following formulas:
conversion (%). The moles reacted off/moles fed x 100%
Benzene selectivity (%). The mol of benzene produced by the reaction/mol of C6 hydrocarbon produced by the reaction. times.100%
Xylene selectivity (%) as the moles of xylene produced by the reaction/moles of C8 hydrocarbons produced by the reaction × 100%
Compared with the prior art, the technical innovation point of the invention is that the micro self-supporting nano material can obviously improve the reaction performance of the catalyst by adopting the novel chain-shaped mordenite as the active main body of the catalyst, the catalyst diffusion pore channel is more unobstructed, the microporous and mesoporous composite pore channel structure is more orderly and regular, the micro self-supporting nano material has excellent reaction performance in aromatic hydrocarbon conversion reaction, and compared with the conventional mordenite catalyst, the micro self-supporting nano material can adapt to the reaction condition with high space velocity, has large aromatic hydrocarbon treatment capacity, has the advantages of good catalytic effect, high xylene concentration of the product and the like, and can be used in the industrial production of aromatic hydrocarbon conversion. Meanwhile, the active component of the catalyst comprises a certain amount of at least one metal element selected from IVB group elements, VIIB group elements and IVA group elements, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield and selectivity of the main products of benzene and xylene in the aromatics transalkylation reaction. The catalyst is simple to prepare, has obvious effect, and greatly saves the production cost while remarkably improving the performance through composition blending.
Experimental results show that the catalyst prepared by the invention achieves better technical effects, particularly when the active component in the catalyst simultaneously comprises at least one metal element selected from IVB group elements, VIIB group elements and IVA group elements, the catalyst achieves more outstanding technical effects, and can be used in aromatic hydrocarbon conversion reactions such as aromatic hydrocarbon transalkylation and the like.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weighing 62 g of chain-shaped mordenite (marked as LM with a silicon-aluminum ratio of 27), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in the air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst is used for evaluating the catalyst on a fixed bed continuous micro reaction device in the presence of hydrogen, and the specification of the reactor is
The loading is 19.0 g, the aromatic hydrocarbon transalkylation reaction takes toluene and trimethylbenzene which are composed of the mol ratio of 37:63 as model raw materials, and the mol ratio of hydrogen and hydrocarbon is H23.1/HC. Firstly, discharging the air of a reaction system by using hydrogen, pressurizing to 1.9MPa, and controlling the feeding reaction airspeed of the raw materials to be 2.2h-1Respectively contacting the raw materials with a bed layer containing the catalyst, heating to the reaction temperature, controlling the reaction temperature to be 386 ℃ (the following examples and comparative examples are evaluated according to the conditions), continuously and stably reacting for 20 hours, cooling, decompressing and separating the reaction materials at the outlet of the catalyst bed layer, sampling and analyzing the obtained liquid mixture, and adopting gas chromatography-mass spectrometry to be used as the liquid phase materialsCombined instrument (GC-MASS) analysis.
[ COMPARATIVE EXAMPLE 1 ]
And simultaneously weighing 62 g of a conventional spindle-shaped micron-sized mordenite (marked as NM, the silicon-aluminum ratio is consistent with that of LM and is 27) sample in a laboratory, adding deionized water, kneading uniformly, extruding, forming and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in the air atmosphere for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
It can be seen from the comparison between example 1 and comparative example 1 that, compared with the conventional shuttle-shaped micron-sized mordenite, the chain nano-sheet mordenite adopted in the present invention has better comprehensive performance and higher conversion activity to toluene and trimethylbenzene which are reaction raw materials.
[ example 2 ]
Weighing 62 g of LM dry powder, adding titanate (according to the metal content of 2.1 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in the air atmosphere for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 3 ]
Weighing 62 g of LM dry powder, adding zirconium nitrate (according to the metal content of 2.1 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in the air atmosphere for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 4 ]
Weighing 62 g of LM dry powder, adding hafnium nitrate (according to the metal content of 2.1 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in the air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
By comparing examples 2-4 with example 1, it can be seen that the chain nanosheet mordenite catalyst disclosed by the invention has better comprehensive performance after loading IVB group metal.
[ example 5 ]
Weighing 62 g of LM dry powder, adding zirconium oxychloride and manganese nitrate (the metal content is respectively 2.1 wt% and 3 wt%), adding deionized water, kneading uniformly, extruding into strips, drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 6 ]
Weighing 62 g of LM dry powder, adding zirconium oxychloride and ammonium perrhenate (the metal content is respectively 2.1 wt% and 3 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
By comparing examples 5 and 6 with example 3, it can be seen that the chain nanosheet mordenite catalyst of the present invention is loaded with a group VIIB metal on the basis of loading a group IVB metal zirconium, such that the catalyst has a better comprehensive performance and exhibits a certain intermetallic synergistic effect.
[ example 7 ]
Weighing 62 g of LM dry powder, adding titanate and ammonium perrhenate (the metal content is respectively 2.1 wt% and 3 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 8 ]
Weighing 62 g of LM dry powder, adding titanate, ammonium perrhenate and germanium nitrate (the metal content is respectively 2.1 wt%, 3 wt% and 5 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 9 ]
Weighing 62 g of LM dry powder, adding titanate, ammonium perrhenate and stannic chloride (the metal content is respectively 2.1 wt%, 3 wt% and 5 wt%), adding deionized water, kneading uniformly, extruding into strips, forming and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 10 ]
Weighing 62 g of LM dry powder, adding titanate, ammonium perrhenate and lead nitrate (the metal content is respectively 2.1 wt%, 3 wt% and 5 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
By comparing examples 8-10 with example 7, it can be seen that the chain nanosheet mordenite catalyst provided by the invention is loaded with group IVA metal elements on the basis of loading group IVB metal titanium and group VIIB metal rhenium, so that the comprehensive performance is better, and a further synergistic effect is shown between metals.
[ example 11 ]
Weighing 62 g of LM dry powder, adding zirconium nitrate, titanate, ammonium perrhenate and germanium oxide (the metal content is respectively 1.2 wt%, 0.9 wt%, 3 wt% and 5 wt%), adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in air for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
[ example 12 ]
Weighing 62 g of LM dry powder, adding zirconium nitrate, titanate, ammonium perrhenate, germanium oxide and tin tetrachloride (the metal content is respectively 1.2 wt%, 0.9 wt%, 3 wt%, 2.5 wt% and 2.5 wt%), adding deionized water, kneading uniformly, extruding, forming and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in an air atmosphere for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
Through the examples 11 and 12, it can be seen that the chain nanosheet mordenite catalysts listed in the present invention, on the basis of the preferred loading of the group IVB metal, the group VIIB metal and the group IVA metal element in the foregoing examples, the intermetallic synergistic effect can show a further improvement in performance.
[ COMPARATIVE EXAMPLE 2 ]
And (2) adding zirconium nitrate, titanate, ammonium perrhenate, germanium oxide and tin tetrachloride (the metal content is respectively 1.2 wt%, 0.9 wt%, 3 wt%, 2.5 wt% and 2.5 wt%) into 62 g of NM sample in a laboratory, adding deionized water, kneading uniformly, extruding, molding and drying to obtain a catalyst matrix, roasting the matrix at 565 ℃ in an air atmosphere for 5 hours, and pelletizing to obtain the catalyst.
The catalyst prepared in the above example was evaluated, sampled and analyzed under the same conditions as in example 1.
The above examples and comparative examples, in which yield and selectivity data of the main product were obtained through calculation, are shown in tables 1 and 2 for the preparation of the catalyst and the evaluation data thereof in the conversion reaction of aromatic hydrocarbons, respectively, for the convenience of illustration and comparison.
TABLE 1 preparation of the catalysts
TABLE 2 results of aromatic transalkylation reaction over catalyst
The reaction performance of the catalyst was calculated according to the composition of the raw materials and the composition of the product, and the specific evaluation results of the catalyst are shown in table 2: evaluation results show that the mordenite catalyst with chain morphology prepared by the method has higher transalkylation reaction activity in aromatic hydrocarbon conversion reaction, can effectively promote the transalkylation reaction of aromatic hydrocarbon and has higher methyl retention rate, and the product xylene yield is obviously high; meanwhile, the chain-shaped mordenite catalyst has better reaction stability, various reaction indexes on the catalyst of the comparative example are reduced in different degrees after 100 hours, the performance cannot be stabilized for a long time by raising the temperature, the chain-shaped mordenite catalyst is beneficial to improving the transalkylation performance of the catalyst, and the chain-shaped mordenite catalyst has a great relationship with the mass transfer diffusion of the reaction. The evaluation data result of the comparative sample under the similar reaction condition shows that the active component of the catalyst comprises a certain amount of at least one metal element selected from IVB group elements, VIIB group elements and IVA group elements, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield and selectivity of the main products, namely benzene and xylene in the aromatic hydrocarbon transalkylation reaction. The modification elements, IVB element and VIIB element in the catalyst have synergistic effect in improving the selectivity and yield of xylene in the product. When the active component in the catalyst simultaneously comprises at least one metal element selected from IVB group elements, VIIB group elements and IVA group elements, more outstanding technical effects are achieved, and the catalyst can be used in aromatic hydrocarbon conversion reactions such as aromatic hydrocarbon transalkylation and the like.
Claims (9)
1. A self-assembled mordenite catalyst with special morphology is used for an aromatic hydrocarbon transalkylation reaction, and is characterized in that the catalyst adopts chain-shaped mordenite as a carrier, and active components comprise at least one selected from IVB elements, at least one selected from VIIB elements and at least one selected from IVA elements;
the mercerized boiling water with the chain-shaped appearanceStone with a specific surface area of 268-568 m2(ii)/g; the single crystal plates are in a chain shape formed by orderly self-assembling along the c axis, namely the thickness direction of the plate shape, the thickness dimension of the single crystal plates is between 8 nm and 360nm, and the chain shape is formed by self-assembling 6 to 80 crystal plates.
2. The catalyst according to claim 1, wherein the IVB element is selected from at least one of titanium, zirconium and hafnium.
3. The catalyst of claim 1, wherein said VIIB element is selected from at least one of manganese and rhenium.
4. The catalyst according to claim 1, wherein the IVA element is at least one selected from the group consisting of germanium, tin and lead.
5. The catalyst according to claim 1, wherein the content of IVB element in the catalyst is 0.08-6 wt% and the content of VIIB element in the catalyst is 0.02-6 wt% based on the total weight of the catalyst.
6. The catalyst according to claim 1, wherein the amount of IVA in the catalyst is 0.03 to 28 wt% based on the total amount of the catalyst.
7. The process for preparing a self-assembled special morphology mordenite catalyst, as claimed in claim 1, comprising the steps of:
A) according to the composition formula of the catalyst, compound precursors of IVB, VIIB and IVA elements for modification are mixed with a chain-shaped mordenite carrier,
B) kneading, molding and drying to obtain a catalyst matrix,
C) and roasting the matrix at 285-650 ℃ for 0.6-36 hours in an air atmosphere, and cooling to obtain the required catalyst material.
8. A method for transalkylation of an aromatic hydrocarbon feedstock, comprising reacting the feedstock with the catalyst of any one of claims 1 to 6 or the catalyst prepared by the method of claim 7.
9. The method of claim 8, wherein the method comprises the steps of using toluene and trimethylbenzene as model raw materials, the reaction temperature is 280-650 ℃, the reaction pressure is 1.5-3.5 MPa, and the reaction space velocity is 0.05-5 h-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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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