CN102616808A - Mordenite containing mesoporous structures, hydrogen mordenite catalyst prepared from mordenite containing mesoporous structures and application of catalyst. - Google Patents
Mordenite containing mesoporous structures, hydrogen mordenite catalyst prepared from mordenite containing mesoporous structures and application of catalyst. Download PDFInfo
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- CN102616808A CN102616808A CN2012100981643A CN201210098164A CN102616808A CN 102616808 A CN102616808 A CN 102616808A CN 2012100981643 A CN2012100981643 A CN 2012100981643A CN 201210098164 A CN201210098164 A CN 201210098164A CN 102616808 A CN102616808 A CN 102616808A
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Abstract
The invention discloses mordenite containing mesoporous structures, a hydrogen mordenite catalyst prepared from the mordenite containing the mesoporous structures and application of the catalyst. According to the mordenite containing the mesoporous structures, water glass, silica sol or white carbon black is used as a silicon source, sodium aluminate and/or aluminum sulfate are/is used as an aluminum source, a fastness improver DM-2588 is used as a soft template agent; and the mordenite is prepared through the conventional hydrothermal synthesis method. The invention also discloses the hydrogen mordenite catalyst prepared from the mordenite containing the mesoporous structures and application of the catalyst to alkylation reaction of pyrene. An MOR-M zeolite material synthesized by the invention has a large number of mesoporous structures while having the conventional molecular sieve cellular structure, and has broad application prospect; the synthesis method is simple; the requirements on equipment are not high; and the enterprises for producing molecular sieve can produce the mordenite by utilizing the conventional equipment. According to the hydrogen mordenite catalyst, the conversion rate for the alkylation reaction of the pyrene can be greatly increased.
Description
(1) technical field
The present invention relates to a kind of mordenite (MOR-M) that contains meso-hole structure, and the h-mordenite catalyzer that makes by this mordenite that contains meso-hole structure, and the h-mordenite Application of Catalyst.
(2) background technology
The micro-pore zeolite molecular sieve is widely used in the compound probability of refining of petroleum, fine chemicals as the carrier of solid acid catalyst or catalyzer.
Traditional micropore mordenite molecular sieve (MOR) is widely used in the alkylated reaction as catalyzer, has extraordinary product selectivity, for example, and at the isopropylation preparation 2 of naphthalene, 6-diisopropylnaphthalene.But; As a kind of acidic zeolite catalytic material; (0.65 * 0.70nm) becomes the major defect that it does the catalyzer widespread use to its less duct size, and especially this defective is then more serious when the size of reactant molecule has surpassed the orifice diameter of micro-pore zeolite molecular sieve.
Therefore,, help macromolecular catalyzed conversion undoubtedly, can also keep the strong acid character of traditional molecular sieve simultaneously if can in traditional micropore MOR zeolite molecular sieve, introduce mesoporously.
Recent years, people attempt utilizing different mould plate technique preparations to have the zeolite crystal of meso-hole structure.As adopt nano active carbon be the gas gel of hard template, carbon be template, carbon nanotube be template synthesized have BEA, the isostructural mesoporous zeolite of MFI.But the mordenite that up to the present, contains meso-hole structure still is not synthesized out.
(3) summary of the invention
First technical problem that the present invention will solve is to provide a kind of mordenite (MOR-M) that contains meso-hole structure; When described MOR-M zeolite has traditional microporous molecular sieve structure; Also has a large amount of meso-hole structures; And compound method is simple, not high to equipment requirements, and the enterprise that produces molecular sieve utilizes existing equipment to put into production.
Second technical problem that the present invention will solve provides a kind of h-mordenite catalyzer (HMOR-M) that is made by the described mordenite that contains meso-hole structure; Because the existence of a large amount of meso-hole structures; Help macromolecular diffusion, make catalyzer be difficult for the carbon distribution inactivation.
The 3rd technical problem that the present invention will solve provides the application of a kind of said HMOR-M zeolite catalyst in the alkylated reaction of pyrene, and said HMOR-M zeolite catalyst can make the transformation efficiency of pyrene significantly improve.
Following mask body is set forth technical scheme of the present invention.The invention provides a kind of mordenite that contains meso-hole structure; The described mordenite that contains meso-hole structure is to be the silicon source with water glass or silicon sol or WHITE CARBON BLACK; With sodium aluminate and/or Tai-Ace S 150 is the aluminium source; With fastness elevator DM-2588 is soft template, prepares through the traditional water thermal synthesis method.
Concrete, when being the silicon source with water glass, the present invention recommends the described preparation that contains the mordenite of meso-hole structure to comprise the steps:
(1-1) prepare aluminum sulfate aqueous solution 1., wherein the concentration of Tai-Ace S 150 is 4-10.5wt.%, adds a certain amount of water glass, SiO in the described water glass
2Concentration is 4-5.0mol/L, Na
2O concentration is 1-2.0mol/L, stirs 0.5-3 hour; Add sodium aluminate aqueous solution then 2., the sodium aluminate aqueous solution 2. concentration of middle sodium aluminate is 1.5-4.5wt.%, stirs to add fastness elevator DM-2588 after 0.5-3 hour, continues to stir 0.5-3 hour again; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (450-800), and Al wherein
2O
3The source be Tai-Ace S 150 and sodium aluminate, Na
2The source of O is water glass and sodium aluminate, SiO
2The source be water glass; The volume ratio that feeds intake of said fastness elevator DM-2588 and water glass is 0.2-0.6: 1;
(2-1) step (1) gained mixed solution is placed the autoclave crystallization, obtain containing the mordenite of meso-hole structure.
Further, the feed ratio of raw material described in the preferred steps of the present invention (1-1) is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (6-11): (20-38): (500-650).
Further, the volume ratio that feeds intake of fastness elevator DM-2588 and water glass described in the preferred steps of the present invention (1-1) is 0.2-0.4: 1.
The described crystallization condition of step of the present invention (2-1) is: crystallization temperature is 150-190 ℃, crystallization time 24-96 hour.
Further, the described crystallization condition of preferred steps (2-1) is: crystallization temperature is 160-180 ℃, crystallization time 48-72 hour.
Concrete, when being the silicon source with the silicon sol, the present invention recommends the described preparation that contains the mordenite of meso-hole structure to comprise the steps:
(1-2) get a certain amount of silicon sol, SiO in the described silicon sol
2Concentration is 7-11.5mol/L, Na
2O concentration is 0.05-0.2mol/L; Add sodium hydroxide solution then 3., wherein concentration sodium hydroxide is 6-13wt.%, and system stirred 0.5-3 hour; Add aluminum sulfate aqueous solution then 4., the aluminum sulfate aqueous solution 4. concentration of middle Tai-Ace S 150 is 4-12.5wt.%, and system stirred 0.5-3 hour; Add fastness elevator DM-2588 at last, stirred 0.5-3 hour; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (400-800), and Al wherein
2O
3The source be Tai-Ace S 150, Na
2The source of O is silicon sol and sodium hydroxide, SiO
2The source be silicon sol; The volume ratio that feeds intake of said fastness elevator DM-2588 and silicon sol is 0.2-0.7: 1;
(2-2) step (1-2) gained mixed solution is placed the autoclave crystallization, obtain containing the mordenite of meso-hole structure.
Further, the feed ratio of raw material described in the preferred steps of the present invention (2-1) is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (6-11): (20-38): (500-650).
Further, the volume ratio that feeds intake of preferred steps of the present invention (2-1) said fastness elevator DM-2588 and silicon sol is 0.4-0.6: 1.
The described crystallization condition of step of the present invention (2-2) is: crystallization temperature is 150-190 ℃, crystallization time 24-96 hour.
Further, the described crystallization condition of preferred steps (2-2) is: crystallization temperature is 160-180 ℃, crystallization time 48-72 hour.
Concrete, when being the silicon source with the WHITE CARBON BLACK, the present invention recommends the described preparation that contains the mordenite of meso-hole structure to comprise the steps:
(1-3) configuration sodium aluminate alkaline solution 5., wherein the concentration of sodium aluminate is 0.5-1.0wt.%, concentration sodium hydroxide is 15-24wt.%; Add a certain amount of WHITE CARBON BLACK, 6. system adds aluminum sulfate aqueous solution after stirring 0.5-3 hour; The aluminum sulfate aqueous solution 6. concentration of middle Tai-Ace S 150 is 4-10.5wt.%; After system stirs 0.5-3 hour, add fastness elevator DM-2588, stirred 0.5-3 hour; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (500-800), and Al wherein
2O
3The source be sodium aluminate and Tai-Ace S 150, Na
2The source of O is sodium hydroxide and sodium aluminate, SiO
2The source be WHITE CARBON BLACK; The adding volume of said fastness elevator DM-2588 is counted 0.5～1.6mL/g with the quality of WHITE CARBON BLACK;
(2-3) step (1-3) gained mixed solution is placed the autoclave crystallization, obtain containing the mordenite of meso-hole structure.
Further, the feed ratio of raw material described in the preferred steps of the present invention (1-3) is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (6-11): (20-38): (500-650).
Further, the adding volume of fastness elevator DM-2588 is counted 0.8～1.5mL/g with the quality of WHITE CARBON BLACK described in the preferred steps of the present invention (1-3).
The described crystallization condition of step of the present invention (2-3) is: crystallization temperature is 150-190 ℃, crystallization time 24-96 hour.
Further, the described crystallization condition of preferred steps (2-3) is: crystallization temperature is 160-180 ℃, crystallization time 48-72 hour.
Silicon of the present invention source (water glass, silicon solution, WHITE CARBON BLACK), aluminium source (Tai-Ace S 150, sodium aluminate), sodium hydroxide, fastness elevator DM-2588 etc. all use the commercial goods.
The mordenite specific surface area that contains meso-hole structure that the present invention obtains is at 420～500m
2/ g, mesoporous pore volume is at 0.10～0.53m
3/ g.
The present invention also provides a kind of h-mordenite catalyzer that is made by the described mordenite that contains meso-hole structure; Described h-mordenite catalyzer makes through following method: the mordenite that will contain meso-hole structure is warming up to 500～600 ℃ of calcinings 3～5 hours, mordenite that contains meso-hole structure and the NH after the calcining then
4NO
3Solution exchanges 3～5 hours down at 70～90 ℃, and the mordenite that contains meso-hole structure after will exchanging again is warming up to 450～550 ℃ of calcinings 3～5 hours, and cooling obtains the h-mordenite catalyzer, is labeled as HMOR-M.
Preferably, the mordenite that will contain meso-hole structure is warming up to 100 ℃ from room temperature with the speed of 4～10 ℃/min, rises to 500～600 ℃ of calcinings 3～5 hours with 2～5 ℃/min again.
Preferably, the mordenite that contains meso-hole structure after the exchange is warming up to 100 ℃ from room temperature with the speed of 4～10 ℃/min, rises to 450～550 ℃ of calcinings 3～5 hours with 2～5 ℃/min again.
Preferred, described h-mordenite catalyzer prepares according to following method: the mordenite that will contain meso-hole structure begins to rise to 100 ℃ with 5 ℃/min from room temperature, rises to 550 ℃ with 3 ℃/min again, keeps 4 hours at 550 ℃; Mordenite of having calcined and the NH of 1M
4NO
3Solution exchanges 4 hours down at 80 ℃; The mordenite that contains meso-hole structure after will exchanging after exchange finishes begins to rise to 100 ℃ with 5 ℃/min from room temperature; Rise to 550 ℃ with 3 ℃/min again; Kept 4 hours at 550 ℃, the mordenite of having calcined just becomes h-mordenite catalyzer (HMOR-M).
The present invention further provides the application of the mesoporous mordenite catalyst of described Hydrogen in the alkylated reaction of pyrene.Alkylating reagent can be Virahol, methyl alcohol, ethanol etc., and the present invention program does alkylating reagent with Virahol.
Described being applied as of the concrete recommendation of the present invention: in inert atmosphere; Pyrene and Virahol in reaction solvent under the mesoporous mordenite catalyst effect of Hydrogen; In temperature is that 200～280 ℃, pressure are to react under the condition of 0.2～0.8MPa, obtains 1-sec.-propyl pyrene.
In the described concrete application, reaction solvent can be sym-trimethylbenzene, perhydronaphthalene, hexanaphthene, dodecyl, tridecane etc., preferred sym-trimethylbenzene.
The molar ratio of described pyrene, Virahol and reaction solvent is 1: 2～6: 20～50, is preferably 1: 4: 25; The quality consumption of said catalyzer be pyrene quality 1.0～3.5%, be preferably 2.0%.
Described alkylated reaction temperature is preferably 250 ℃, and reaction pressure is 0.45MPa.
The alkylated reaction of pyrene of the present invention can carry out in fixed-bed reactor.Reaction product can be through detecting with fid detector on the Agilent 7890A GC.
Compared with prior art, beneficial effect of the present invention is:
A) the present invention utilizes Industrial products fastness elevator DM-2588 to be soft template, has synthesized MOR (MOR-M) zeolite that contains meso-hole structure through traditional hydrothermal method.When synthetic MOR-M zeolitic material has traditional microporous molecular sieve structure, also has a large amount of meso-hole structures.Therefore, this product has broad application prospects as catalyzer and carrier thereof on the compound probability of heavy oil refining industry, macromole fine chemicals.
B) compound method of the MOR zeolite that contains meso-hole structure of the present invention is simple, not high to equipment requirements, and the enterprise that produces molecular sieve utilizes existing equipment to put into production.
C) the present invention has made the HMOR-M zeolite catalyst by the MOR zeolite that contains meso-hole structure, and the existence owing to a large amount of meso-hole structures in the MOR zeolite that contains meso-hole structure helps macromolecular diffusion, makes catalyzer be difficult for the carbon distribution inactivation.
D) HMOR-M zeolite catalyst of the present invention has high catalytic activity in the alkylated reaction of pyrene, makes the transformation efficiency of pyrene improve greatly.
(4) description of drawings
Fig. 1 contains the stereoscan photograph of the MOR zeolite of meso-hole structure for embodiment 3 synthetic.
Fig. 2 contains the pore distribution curve of mesoporous MOR zeolite for embodiment 3 synthetic.
Fig. 3 is the stereoscan photograph that embodiment 5 synthetic contain the MOR zeolite of meso-hole structure.
Fig. 4 contains the pore distribution curve of mesoporous MOR zeolite for embodiment 5 synthetic.
Fig. 5 is the stereoscan photograph that embodiment 9 synthetic contain the MOR zeolite of meso-hole structure.
Fig. 6 contains the pore distribution curve of mesoporous MOR zeolite for embodiment 9 synthetic.
Fig. 7 is the MOR zeolite that contains meso-hole structure among the embodiment 3 and the traditional MOR zeolite active comparison diagram to the alkylated reaction of pyrene.
(5) embodiment
Through specific embodiment the present invention is described further below, but protection scope of the present invention is not limited to this.
Raw material and solution that the embodiment of the invention is used are following:
With water glass is the silicon source, the synthetic method:
Water glass is formed: SiO
2: 4.2471mol/L, Na
2O:1.1706mol/L, H
2O:51.8109mol/L;
Solution is 1.: the 5.0g Patent alum is dissolved into 40g H
2Among the O;
Solution is 2.: with 0.4g NaAlO
2Be dissolved into 10g H
2Among the O;
With the silicon sol is the silicon source, the synthetic method:
Silicon sol is formed: SiO
2: 8.4332mol/L, Na
2O:0.0702mol/L, H
2O:42.8139mol/L;
Solution is 3.: the H that 1.85g NaOH is dissolved in 20ml
2Among the O;
Solution is 4.: the 8.0g Patent alum is dissolved into 40g H
2Among the O;
With WHITE CARBON BLACK (Shenyang Chemical Co., Ltd.'s production) is the silicon source, the synthetic method:
Solution is 5.: with 0.2g NaAlO
2Be dissolved in the H of 25ml
2Among the O, add 5.0g NaOH again;
Solution is 6.: the 6.0g Patent alum is dissolved into 40g H
2Among the O;
Experimental example 1
With water glass is the silicon source
Get 10mL solution 1.; After stirring 30min; Add 18mL water glass, stirs after 1 hour and add 5.0mL solution 2., solution continued stirring after 1 hour; Add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) at last, stir and adorn still after 1 hour 170 ℃ of reactions 48 hours.
Experimental example 2
With water glass is the silicon source
Get 10mL solution 1.; After stirring 30min; Add 18mL water glass, stirs after 1 hour and add 5.0mL solution 2., solution continued stirring after 1 hour; Add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) at last, stir and adorn still after 1 hour 170 ℃ of reactions 72 hours.
Experimental example 3
With water glass is the silicon source
Get 10mL solution 1.; After stirring 30min; Add 18mL water glass, stirs after 1 hour and add 5.0mL solution 2., solution continued stirring after 1 hour; Add 6.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) at last, stir and adorn still after 1 hour 170 ℃ of reactions 48 hours.
Experimental example 4
With water glass is the silicon source
Get 10mL solution 1.; After stirring 30min; To wherein adding 18mL water glass, stir after 1 hour and to add 5.0mL solution 2., solution continues to stir after 1 hour; Add 6.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) at last, stir and adorn still after 1 hour 170 ℃ of reactions 72 hours.
Experimental example 5
With the silicon sol is the silicon source
Get the 10mL silicon sol; To the solution that wherein adds 15.0mL 3., stirred 30 minutes, add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) afterwards; Stirred 1 hour; Add 10mL solution more 4., stirred 30 minutes, mixture is moved on to be sealed in 170 ℃ of reactions 48 hours in the reaction kettle afterwards.The high resolution scanning electromicroscopic photograph of obtained sample is seen Fig. 1.Visible by Fig. 1, prepared mordenite is bar-shaped array structure.
Experimental example 6
With the silicon sol is the silicon source
Get the 10mL silicon sol; To the solution that wherein adds 15.0mL 3., stirred 30 minutes, add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) afterwards; Stirred 1 hour; Add 10mL solution more 4., stirred 30 minutes, mixture is moved on to be sealed in 170 ℃ of reactions 72 hours in the reaction kettle afterwards.
Experimental example 7
With the silicon sol is the silicon source
Get the 10mL silicon sol; To the solution that wherein adds 15.0mL 3., stirred 30 minutes, add 6.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) afterwards; Stirred 1 hour; Add 10mL solution more 4., stirred 30 minutes, mixture is moved on to be sealed in 170 ℃ of reactions 48 hours in the reaction kettle afterwards.
Experimental example 8
With the silicon sol is the silicon source
Get the 10mL silicon sol; To the solution that wherein adds 15.0mL 3., stirred 30 minutes, add 6.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) afterwards; Stirred 1 hour; Add 10mL solution more 4., stirred 30 minutes, mixture is moved on to be sealed in 170 ℃ of reactions 72 hours in the reaction kettle afterwards.
Experimental example 9
With the WHITE CARBON BLACK is the silicon source
5. the solution of getting 12mL stirred 30 minutes, to wherein adding 5mL H
2O; Stir after 1 hour, add the 4.5g WHITE CARBON BLACK, stir after 1 hour; Add 10mL solution more 6.; Stirred 30 minutes, and added 4.0mL fastness elevator DM-2588 (buy from Guangdong dolantin Fine Chemical Co., Ltd) at last, stirs after 1 hour mixture moved on to and be sealed in 170 ℃ in the reaction kettle and reacted 48 hours.
Experimental example 10
With the WHITE CARBON BLACK is the silicon source
5. the solution of getting 12mL stirred 30 minutes, to wherein adding 5mL H
2O; Stir after 1 hour, add the 4.5g WHITE CARBON BLACK, stir after 1 hour; Add 10mL solution more 6.; Stirred 30 minutes, and added 4.0mL fastness elevator DM-2588 (buy from Guangdong dolantin Fine Chemical Co., Ltd) at last, stirs after 1 hour mixture moved on to and be sealed in 170 ℃ in the reaction kettle and reacted 72 hours.
Experimental example 11
With the WHITE CARBON BLACK is the silicon source
5. the solution of getting 12mL stirred 30 minutes, to wherein adding 5mL H
2O; Stir after 1 hour, add the 4.5g WHITE CARBON BLACK, stir after 1 hour; Add 10mL solution more 6.; Stirred 30 minutes, and added 6.0mL fastness elevator DM-2588 (buy from Guangdong dolantin Fine Chemical Co., Ltd) at last, stirs after 1 hour mixture moved on to and be sealed in 170 ℃ in the reaction kettle and reacted 48 hours.
Experimental example 12
With the WHITE CARBON BLACK is the silicon source
5. the solution of getting 12mL stirred 30 minutes, to wherein adding 5mL H
2O; Stir after 1 hour, add the 4.5g WHITE CARBON BLACK, stir after 1 hour; Add 10mL solution more 6.; Stirred 30 minutes, and added 6.0mL fastness elevator DM-2588 (buy from Guangdong dolantin Fine Chemical Co., Ltd) at last, stirs after 1 hour mixture moved on to and be sealed in 170 ℃ in the reaction kettle and reacted 72 hours.
Experimental example 13
With water glass is the silicon source
Get 8.0mL solution 1.; After stirring 30min; Add 18mL water glass, stirs after 1 hour and add 5.0mL solution 2., solution continued stirring after 1 hour; Add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) at last, stir and adorn still after 1 hour 170 ℃ of reactions 72 hours.
Experimental example 14
With the silicon sol is the silicon source
Get the 8mL silicon sol; To the solution that wherein adds 15.0mL 3., stirred 30 minutes, add 4.0mL fastness elevator DM-2588 (buying from Guangdong dolantin Fine Chemical Co., Ltd) afterwards; Stirred 1 hour; Add 8.0mL solution more 4., stirred 30 minutes, mixture is moved on to be sealed in 170 ℃ of reactions 72 hours in the reaction kettle afterwards.
Experimental example 15
With the WHITE CARBON BLACK is the silicon source
5. the solution of getting 12mL stirred 30 minutes, to wherein adding 5mL H
2O; Stir after 1 hour, add the 4.0g WHITE CARBON BLACK, stir after 1 hour; Add 10mL solution more 6.; Stirred 30 minutes, and added 6.0mL fastness elevator DM-2588 (buy from Guangdong dolantin Fine Chemical Co., Ltd) at last, stirs after 1 hour mixture moved on to and be sealed in 170 ℃ in the reaction kettle and reacted 48 hours.
The character of the product that the foregoing description makes is seen table 1:
Table 1 different instances obtains the character of sample
Comparative example: traditional MOR prepare zeolite
The synthesis step of the MOR zeolite that contains meso-hole structure among the synthesis step of tradition MOR zeolite and the embodiment 3 is compared, and except not adding the template, other are all identical.
The textural property of prepared traditional MOR zeolite is seen table 2:
Synthetic contains the texture character of MOR zeolite and traditional MOR zeolite of meso-hole structure under table 2 similarity condition
Table 2 contains the mordenite (MOR-M) of meso-hole structure and the BET surface-area of traditional mordenite, mesoporous pore volume, micropore pore volume for synthetic.Significantly, the mesoporous pore volume of traditional mordenite is merely 0.02cm
3/ g, and contain meso-hole structure mordenite (MOR-M) for 0.37cm
3/ g.
Embodiment 16: method for preparing catalyst
The mordenite (MOR-M) that contains meso-hole structure is synthesizing the back 550 ℃ of calcinings, and the incinerating program is: begin to rise to 100 ℃ with 5 ℃/min from room temperature, rise to 550 ℃ with 3 ℃/min again, kept 4 hours at 550 ℃.Mordenite of having calcined and the NH of 1M
4NO
3Solution exchanges 4 hours down at 80 ℃; Burnt 4 hours at 500 ℃ again; The incinerating program is: begin to rise to 100 ℃ with 5 ℃/min from room temperature, rise to 550 ℃ with 3 ℃/min again, kept 4 hours at 550 ℃; The mordenite of having calcined just becomes h-mordenite (HMOR-M), obtains catalyst A.
Traditional mordenite (MOR) in synthetic back 100 ℃ of dryings after 24 hours, with the NH of 1M
4NO
3Solution exchanges 4 hours down at 80 ℃, burns 4 hours at 500 ℃ again.The incinerating program is: begin to rise to 100 ℃ with 5 ℃/min from room temperature, rise to 550 ℃ with 3 ℃/min again, kept 4 hours at 550 ℃, the mordenite of having calcined just becomes h-mordenite (HMOR), obtains catalyst B.
The alkylated reaction of embodiment 17 pyrenes
Be reflected on the stainless steel fixed-bed reactor and carry out, the internal diameter of reactor drum is 6.5nm, and length is 50cm.The catalyzer loading amount is 0.3g, and pyrene, Virahol are dissolved in the sym-trimethylbenzene solution, pyrene: Virahol: sym-trimethylbenzene=1: 4: 25 (mol ratio), with volume pump reaction mixture is transported to reactor drum, and flow is 3.5mL/h.Temperature of reaction is 250 ℃, and nitrogen pressure is 0.45MPa, through the fid detector detection reaction product on the Agilent 7890A GC.Catalyst A that makes with embodiment 16 or catalyst B are that the transformation efficiency of the pyrene that obtains of catalyzer and the graph of a relation in reaction times are seen Fig. 3, and each product selectivity is seen table 3.Can be known by Fig. 3: when making catalyzer with HMOR-M, the transformation efficiency of pyrene explains that apparently higher than the mordenite of traditional H type the synthetic MOR-M of institute helps macromolecular diffusion, makes catalyzer be difficult for the carbon distribution inactivation.
The transformation efficiency of pyrene and the relation of selectivity of product when table 3 is 6h in the reaction times
Claims (10)
1. mordenite that contains meso-hole structure; It is characterized in that: the described mordenite that contains meso-hole structure is to be the silicon source with water glass or silicon sol or WHITE CARBON BLACK; With sodium aluminate and/or Tai-Ace S 150 is the aluminium source; With fastness elevator DM-2588 is soft template, prepares through the traditional water thermal synthesis method.
2. the mordenite that contains meso-hole structure as claimed in claim 1 is characterized in that: when being the silicon source with water glass, the described preparation that contains the mordenite of meso-hole structure comprises the steps:
(1-1) prepare aluminum sulfate aqueous solution 1., wherein the concentration of Tai-Ace S 150 is 4-10.5wt.%, adds a certain amount of water glass, SiO in the described water glass
2Concentration is 4-5.0mol/L, Na
2O concentration is 1-2.0mol/L, stirs 0.5-3 hour; Add sodium aluminate aqueous solution then 2., the sodium aluminate aqueous solution 2. concentration of middle sodium aluminate is 1.5-4.5wt.%, stirs after 0.5-3 hour to add fastness elevator DM-2588, stirs 0.5-3 individual hour; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (450-800); The volume ratio that feeds intake of said fastness elevator DM-2588 and water glass is 0.2-0.6: 1;
(2-1) step (1) gained mixed solution is placed the autoclave crystallization, obtain containing the mordenite of meso-hole structure.
3. the mordenite that contains meso-hole structure as claimed in claim 1 is characterized in that: when being the silicon source with the silicon sol, the described preparation that contains the mordenite of meso-hole structure comprises the steps:
(1-2) get a certain amount of silicon sol, SiO in the described silicon sol
2Concentration is 7-11.5mol/L, Na
2O concentration is 0.05-0.2mol/L; Add sodium hydroxide solution then 3., wherein concentration sodium hydroxide is 6-13wt.%, and system stirred 0.5-3 hour; Add aluminum sulfate aqueous solution then 4., the aluminum sulfate aqueous solution 4. concentration of middle Tai-Ace S 150 is 4-12.5wt.%, and system stirred 0.5-3 hour; Add fastness elevator DM-2588 at last, stirred 0.5-3 hour; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (400-800); The volume ratio that feeds intake of said fastness elevator DM-2588 and silicon sol is 0.2-0.7: 1;
(2-2) step (1) gained mixed solution is placed the autoclave crystallization, obtain containing the mordenite of mesoporous structure.
4. the mordenite that contains meso-hole structure as claimed in claim 1 is characterized in that: when being the silicon source with the WHITE CARBON BLACK, the described preparation that contains the mordenite of meso-hole structure comprises the steps:
(1-3) configuration sodium aluminate alkaline solution 5., wherein the concentration of sodium aluminate is 0.5-1.0wt.%, concentration sodium hydroxide is 15-24wt.%; Add a certain amount of WHITE CARBON BLACK, 6. system adds aluminum sulfate aqueous solution after stirring 0.5-3 hour; The aluminum sulfate aqueous solution 6. concentration of middle Tai-Ace S 150 is 4-10.5wt.%; After system stirs 0.5-3 hour, add fastness elevator DM-2588, stirred 0.5-3 hour; The feed ratio of said raw material is with Al
2O
3: Na
2O: SiO
2: H
2The molar ratio computing of O is 1: (5-15): (15-50): (500-800); The adding volume of said fastness elevator DM-2588 is counted 0.5～1.6mL/g with the quality of WHITE CARBON BLACK;
(2-3) step (1) gained mixed solution is placed the autoclave crystallization, obtain the described mordenite that contains mesoporous structure.
5. like the described mordenite that contains meso-hole structure of one of claim 2～4, it is characterized in that: step (2-1) or step (2-2) or the described crystallization condition of step (2-3) are: crystallization temperature is 150-190 ℃, crystallization time 24-96 hour.
6. h-mordenite catalyzer that makes by the mordenite that contains meso-hole structure as claimed in claim 1; Described h-mordenite catalyzer makes through following method: the mordenite that will contain meso-hole structure is warming up to 500～600 ℃ of calcinings 3～5 hours, mordenite that contains meso-hole structure and the NH after the calcining then
4NO
3Solution exchanges 3～5 hours down at 70～90 ℃, and the mordenite that contains meso-hole structure after will exchanging again is warming up to 450～550 ℃ of calcinings 3～5 hours, and cooling obtains the h-mordenite catalyzer.
7. h-mordenite catalyzer as claimed in claim 6 is characterized in that: the mordenite that will contain meso-hole structure is warming up to 100 ℃ from room temperature with the speed of 4～10 ℃/min, rises to 500～600 ℃ of calcinings 3～5 hours with 2～5 ℃/min again.
8. h-mordenite catalyzer as claimed in claim 6; It is characterized in that: the mordenite that contains meso-hole structure after will exchanging is warming up to 100 ℃ from room temperature with the speed of 4～10 ℃/min, rises to 450～550 ℃ of calcinings 3～5 hours with 2～5 ℃/min again.
9. the application of h-mordenite catalyzer as claimed in claim 6 in the alkylated reaction of pyrene; Described application is specially: in inert atmosphere; Pyrene and Virahol in reaction solvent under the h-mordenite catalyst action; In temperature is that 200～280 ℃, pressure are to react under the condition of 0.3～0.8MPa, obtains 1-sec.-propyl pyrene.
10. application as claimed in claim 9 is characterized in that: described reaction solvent is sym-trimethylbenzene, perhydronaphthalene, hexanaphthene, dodecyl, tridecane; The molar ratio of described pyrene, Virahol and reaction solvent is 1: 2～6: 20～50, the quality consumption of described h-mordenite be pyrene quality 1.0～3.5%.
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| CN105037063A (en) * | 2015-08-10 | 2015-11-11 | 长春工业大学 | Method for synthesizing isopropyl pyrene by pyrene and isopropyl alcohol through liquid phase alkylation |
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| XIANFENG LI ETAL.: "Synthesis and characterization of mesoporous mordenite", 《JOURNAL OF CATALYSIS》 * |
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