CN102746102B - Preparation method of 2,6-DiMethylnaphthalene (DMN) by using SAPO-11 molecular sieve - Google Patents
Preparation method of 2,6-DiMethylnaphthalene (DMN) by using SAPO-11 molecular sieve Download PDFInfo
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Abstract
The invention relates to a preparation method of the 2,6-DMN, in particular to a preparation method of the 2,6-DMN by using a SAPO-11 molecular sieve. The preparation method mainly solves the problems that catalysts cannot be provided with high activity and 2,6-DMN selectivity simultaneously, and the catalysts are easy to inactivate. The method includes activating the SAPO-11 molecular sieve synthesized by microwave radiation and heating, mixing naphthalene and alkylation reagents with a solvent according to a molar ratio of 1:(2-4):(6-12), and performing alkylation reaction to obtain the 2,6-DMN at a temperature of 350 DEG C to 450 DEG C, at a pressure of 2 MPa to 5 MPa, at a quality airspeed of 0.5-2h-1 and at a carrier gas flow rate of 20-60 mL/min. According to the preparation method, the synthesized SAPO-11 molecular sieve can shorten the crystallization time greatly, and has high catalytic activity to the alkylation reaction of the naphthalene and high selectivity and good anti-carbon deposition competence to the 2,6-DMN.
Description
Technical field
The present invention relates to the method that one prepares 2,6-dimethylnaphthalene.
Background technology
1973, first Japanese Di Ren company developed a kind of novel polyester material PEN, was called for short PEN.Due to it, there is thermotolerance, erosion resistance and good stability of the dimension and the advantage such as mechanical property is strong, be widely used in the numerous areas such as aerospace, nuclear power material and electronic component.2,6-dimethylnaphthalene is the important monomer raw material of preparation PEN, but because the generating process of 2,6-DMN is complicated, manufacturing cost is high, seriously constrains PEN and come into the market on a large scale.And at present China 2,6-DMN depends on import substantially, thus develop the production method of technique simple 2,6-DMN, to reduce its production cost significant to the development promoting China PEN polyester material.
At present, the synthesis of 2,6-DMN is mainly passed through with dimethylbenzene is that raw material synthesizes through multistep processes.The method of one-step synthesis 2,6-DMN has abundant raw material source and the advantage such as operational path is short, has become the focus that recent domestic scholar endeavours to study.But ten of one-step synthesis method DMN kinds of isomer boiling points are close, be separated and difficulty, especially 2,6-DMN and 2, the boiling point of 7-DMN only differs 0.3 DEG C, thus how to improve the selectivity and 2 of in DMN product 2,6-DMN, 6-/2,7-DMN ratio is the key realizing One-step production 2,6-DMN.
Homogeneous catalyst and heterogeneous catalyst is divided into the catalyzer that naphthalene or methylnaphthalene are raw material one-step synthesis method 2,6-DMN.Although the homogeneous catalyst reactive behavior taking aluminum chloride as representative is high, the selectivity of 2,6-DMN is low, and catalyzer and product not easily separated, last handling process can produce a large amount of acid waste water, causes environmental pollution.Zeolite molecular sieve comprises ZSM-5, ZSM-11, ZSM-12, β, HM, Y, MCM-22 etc., it is as the environmentally friendly solid acid catalyst of a new generation, replacing the homogeneous catalyst such as liquid acid and aluminum trichloride (anhydrous), obtaining a wide range of applications at absorption, separation and catalytic field because having the characteristic such as stronger acidity, good thermostability and hydrothermal stability, evenly abundant pore structure.Wherein, take HM as catalyzer, during synthesis 2,6-DMN, the selectivity of 2,6-DMN and 1,6-DMN can reach more than 99%, and the purity of 2,6-DMN can be increased to more than 50% from 8.35%.Beta-molecular sieve is adopted to be catalyzer synthesis 2,6-DMN, because of catalyst surface coking after reaction 20h, the transformation efficiency of naphthalene reduces, and after reaction 35h, the transformation efficiency of naphthalene maintains 19.87%, 2,6-DMN selectivity remains at about 6.66% in whole process, and this molecular sieve is not only low to the selectivity of 2,6-DMN, and reaction process carbon distribution is serious, catalytic activity suppression ratio is very fast.When adopting HZSM-12 molecular sieve catalytic synthesis 2, the 6-DMN of sour Dealumination, found that HZSM-12 before modified has high initial reaction activity, the initial conversion of naphthalene is 64.6%, but along with the carrying out reacted, transformation efficiency significantly declines, the selectivity of 2,6-DMN is 23.6%.When after reaction 6h, transformation efficiency is down to 28.3%, have dropped 36.3%; And although the HZSM-12 molecular sieve deactivation rate after sour Dealumination declines, catalytic activity declines.Adopt NH
4the methylation reaction of the ZSM-5 catalysis 2-MN of F and Pt modification, the selectivity of 2,6-DMN reaches 63.4%, but the transformation efficiency of 2-MN only has 6.1%.Visible, the alkylated reaction of the zeolite molecular sieve reported to naphthalene is difficult to have good reactive behavior and the highly selective of 2,6-DMN concurrently, thus develops and has good catalytic activity and high by 2 concurrently, 6-DMN optionally molecular sieve catalyst is the key that exploitation single stage method prepares 2,6-DMN.
Summary of the invention
Object of the present invention solves existing catalyzer can not have high reactivity and high 2,6-DMN selectivity simultaneously, and the problem of catalyzer easy in inactivation, and provides a kind of method of SAPO-11 molecular sieve 2,6-dimethylnaphthalene.
The method of a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene of the present invention is carried out according to following steps: the beds one, SAPO-11 molecular sieve being put into fixed-bed reactor, activates 2h at 500 DEG C ~ 600 DEG C; Two, by even to naphthalene, alkylating reagent and solvent, obtain stock liquid, and with volume pump by the beds of the fixed-bed reactor of continuous for stock liquid implantation step one, and be 350 DEG C ~ 450 DEG C in temperature, pressure is 2 ~ 5MPa, and mass space velocity is 0.5 ~ 2h-1, flow rate of carrier gas is under the condition of 20 ~ 60mL/min, carry out alkylated reaction 1 ~ 24h, obtain 2,6-dimethylnaphthalene; Wherein, the mol ratio of naphthalene and alkylating reagent is 1:2 ~ 4, and the mol ratio of naphthalene and solvent is 1:6 ~ 12.
The present invention comprises following beneficial effect:
1, adopt raw material to be mixed by reactant naphthalene, alkylating reagent methyl alcohol, solvent 1,2,4-trimethylbenzene in the present invention, react for heterogeneous successive reaction, reaction product and catalyzer easily separated; Simple to operate, be convenient to scale operation.
2, compared with conventional hydrothermal method, not only crystallization time is significantly reduced with a series of SAPO-11 molecular sieves of microwave heating method hydrothermal system synthesis, decrease energy consumption, reduce the synthesis cost of molecular sieve, and Si can be made more uniformly to enter the skeleton of molecular sieve, form that intensity is suitable for, acid amount can the acid site of modulation.
3, with the SAPO-11 molecular sieve that traditional electrical type of heating synthesizes in alcohol-water system, make prepared by gel evenly, Si is more effective enters skeleton, make acid amount and strength of acid moderate, thus while there is the catalytic stability that higher catalytic performance becomes reconciled, there is the selectivity of higher 2,6-DMN.
4, the present invention first by microwave heating method hydrothermal system and and prepare 2,6-DMN with the alkylated reaction that the SAPO-11 molecular sieve that traditional electrical heating means are synthesized in alcohol-water system is used for catalysis naphthalene, not only overcome anhydrous AlCl
3the drawbacks such as the serious and environmental pollution with product separation difficulty, equipment corrosion existed Deng homogeneous catalyst, and than the alkylated reaction of the zeolite [molecular sieves such as ZSM-5 to naphthalene and methyl alcohol, there is higher catalytic activity, 2, the selectivity, 2 of 6-DMN, 6-/2,7-DMN ratio and higher carbon accumulation resisting ability.
5, the SAPO-11 molecular sieve that the present invention adopts belongs to the molecular sieve of AEL topological framework, there is the straight pore passage structure of one dimension ten-ring, port size is 0.39 × 0.63nm, because SAPO-11 molecular sieve has suitable opening diameter, be conducive to the alkylated reaction thing of naphthalene and the diffusion of product, therefore be expected to have good reactive behavior and the highly selective to 2,6-DMN concurrently.Compared with traditional electrically heated hydrothermal synthesis method, the crystallization time of molecular sieve not only significantly can be shortened with carry out microwave radiation heating method synthesis SAPO-11, reduce energy consumption, and the SAPO-11 molecular sieve synthesized in alcohol-water system can promote that silicon enters the skeleton of molecular sieve and makes it be evenly distributed effectively, therefore the quantity in the acid site of SAPO-11 molecular sieve can be improved and its strength of acid of modulation, be expected to improve its catalytic activity and the selectivity to 2,6-DMN simultaneously.On the other hand, adopting the SAPO-11 of microwave heating method synthesis because having gentle acidity, will there is stronger carbon accumulation resisting ability and catalytic stability.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the SAPO-11 molecular sieve-4 A of preparation in experiment 1;
Fig. 2 is the SEM photo of the SAPO-11 molecular sieve-4 A of preparation in experiment 1;
Fig. 3 is the XRD spectra of the SAPO-11 molecular sieve B of preparation in experiment 2;
Fig. 4 is the SEM photo of the SAPO-11 molecular sieve B of preparation in experiment 2;
Fig. 5 is the XRD spectra of the SAPO-11 molecular sieve C of preparation in experiment 3;
Fig. 6 is the SEM photo of the SAPO-11 molecular sieve C of preparation in experiment 3;
Fig. 7 is the XRD spectra of the SAPO-11 molecular sieve D of preparation in experiment 4;
Fig. 8 is the SEM photo of the SAPO-11 molecular sieve D of preparation in experiment 4.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of SAPO-11 molecular sieve 2 of present embodiment, the method of 6-dimethylnaphthalene is carried out according to following steps: the beds one, SAPO-11 molecular sieve being put into fixed-bed reactor, at 500 DEG C ~ 600 DEG C, activate 2h; Two, naphthalene, alkylating reagent and solvent is even, obtain stock liquid, and with volume pump by the beds of the fixed-bed reactor of continuous for stock liquid implantation step one, and be 350 DEG C ~ 450 DEG C in temperature, pressure is 2 ~ 5MPa, and mass space velocity is 0.5 ~ 2h
-1, flow rate of carrier gas is under the condition of 20 ~ 60mL/min, carries out alkylated reaction 1 ~ 24h, obtains 2,6-dimethylnaphthalene; Wherein, the mol ratio of naphthalene and alkylating reagent is 1:2 ~ 4, and the mol ratio of naphthalene and solvent is 1:6 ~ 12.
Present embodiment comprises following beneficial effect:
1, adopt raw material to be mixed by reactant naphthalene, alkylating reagent methyl alcohol, solvent 1,2,4-trimethylbenzene in present embodiment, react for heterogeneous successive reaction, reaction product and catalyzer easily separated; Simple to operate, be convenient to scale operation.
2, compared with conventional hydrothermal method, not only crystallization time is significantly reduced with a series of SAPO-11 molecular sieves that microwave heating method synthesizes respectively in hydrothermal system and alcohol-water system, decrease energy consumption, reduce the synthesis cost of molecular sieve, and Si can be made more uniformly to enter the skeleton of molecular sieve, form that intensity is suitable for, acid amount can the acid site of modulation.
3, with the SAPO-11 molecular sieve that traditional electrical type of heating synthesizes in alcohol-water system, make prepared by gel evenly, Si is more effective enters skeleton, make acid amount and strength of acid moderate, thus while there is the catalytic stability that higher catalytic performance becomes reconciled, there is the selectivity of higher 2,6-DMN.
4, the alkylated reaction that the SAPO-11 molecular sieve that microwave heating method synthesizes in hydrothermal system and alcohol-water system is used for catalysis naphthalene is prepared 2,6-DMN by present embodiment first, not only overcomes anhydrous AlCl
3the drawbacks such as the serious and environmental pollution with product separation difficulty, equipment corrosion existed Deng homogeneous catalyst, and than the alkylated reaction of the zeolite [molecular sieves such as ZSM-5 to naphthalene and methyl alcohol, there is higher catalytic activity, 2, the selectivity, 2 of 6-DMN, 6-/2,7-DMN ratio and higher carbon accumulation resisting ability.
5, the SAPO-11 molecular sieve that present embodiment adopts belongs to the molecular sieve of AEL topological framework, there is the straight pore passage structure of one dimension ten-ring, port size is 0.39 × 0.63nm, because SAPO-11 molecular sieve has suitable opening diameter, be conducive to the alkylated reaction thing of naphthalene and the diffusion of product, therefore be expected to have good reactive behavior and the highly selective to 2,6-DMN concurrently.Compared with traditional electrically heated hydrothermal synthesis method, the crystallization time of molecular sieve not only significantly can be shortened with carry out microwave radiation heating method synthesis SAPO-11, reduce energy consumption, and the SAPO-11 molecular sieve synthesized in alcohol-water system can promote that silicon enters the skeleton of molecular sieve and makes it be evenly distributed effectively, therefore the quantity in the acid site of SAPO-11 molecular sieve can be improved and its strength of acid of modulation, be expected to improve its catalytic activity and the selectivity to 2,6-DMN simultaneously.On the other hand, adopting the SAPO-11 of microwave heating method synthesis because having gentle acidity, will there is stronger carbon accumulation resisting ability and catalytic stability.
Embodiment two: present embodiment and embodiment one unlike: the standby SAPO-11 molecular sieve described in step one synthesizes in aqueous systems by the mode of microwave heating, and concrete steps are as follows: by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o mol ratio is that the ratio of 1:0.2 ~ 1.2:1:1:40 stirs, and obtains gel, the polytetrafluoroethyllining lining that gel is housed is put in ceramic outer lining, then putting into microwave oven, is 600W at power, and temperature is under the condition of 160 DEG C ~ 180 DEG C, crystallization 0.5 ~ 4h, the solidliquid mixture obtained; Then, after being washed by the solid formation obtained after filtration, putting into temperature is dry 12h at 110 DEG C of temperature, then at 650 DEG C of roasting temperature 7h, obtains SAPO-11 molecular sieve.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the SAPO-11 molecular sieve described in step one adopts traditional electrical heating method to synthesize in alcohol-water system, and concrete steps are as follows: by Al
2o
3: SiO
2: P
2o
5: DPA:C
2h
5oH:H
2o mol ratio is 1:0.2 ~ 1.2::1:1:10:(10 ~ 100) ratio stir, obtain gel, the polytetrafluoroethyllining lining that gel is housed put into stainless steel outer lining, then baking oven is put into, be that under the condition of 160 DEG C ~ 180 DEG C, crystallization 12-48h, obtains solidliquid mixture in temperature; Then, after being washed by the solid formation obtained after filtration, putting into temperature is dry 12h at 110 DEG C of temperature, then at 650 DEG C of roasting temperature 7h, obtains SAPO-11 molecular sieve.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike described C
2h
5oH:H
2the mol ratio of O is 1:3.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are unlike described SiO
2with Al
2o
3mol ratio is 0.2:1,0.6:1,0.8:1,1.0:1 or 1.2:1.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the alkylating reagent described in step 2 is methyl alcohol.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the solvent described in step 2 is 1,2,4-trimethylbenzene.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the temperature of reaction described in step 2 is 420 DEG C, and reaction pressure is 4MPa, and mass space velocity is 1h
-1.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the gas of the carrier gas described in step 2 is nitrogen.Other is identical with one of embodiment one to eight.
By following experimental verification effect of the present invention:
Experiment 1
A kind of SAPO-11 molecular sieve 2 of this experiment, the method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 object SAPO-11 molecular sieves (sample A), getting 1.06g, load the flat-temperature zone of the stainless steel reaction pipe of fixed-bed micro-reactor, inert stone sand is equipped with at two ends, 2h is activated under 550 DEG C of conditions, remove water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after activation step one obtained, at N
2flow rate of carrier gas be 10mL/min, temperature is 420 DEG C, and pressure is 4MPa, and mass space velocity is 1h
-1condition under, naphthalene, methyl alcohol and 1,2,4-trimethylbenzene are mixed and made into stock liquid with mol ratio 1:2:8, are injected the beds of fixed-bed reactor by Micro-metering Pumps continuously, carry out alkylated reaction, obtain 2,6-dimethylnaphthalene (2,6-DMN); Three, the time of outflow first product is counted t=0, and gather the product once flowed out every 1h, carry out quantitative analysis by gas-chromatography, calculate the transformation efficiency of naphthalene, the selectivity of 2,6-dimethylnaphthalenes and the selectivity of other products with area normalization method.
This experiment is as shown in table 1 in the result of alkylated reaction 4h and 6h, the selectivity of high reactivity and high 2,6-DMN is not only had as shown in Table 1 concurrently with the SAPO-11 molecular sieve that microwave heating method synthesizes in aqueous systems, and 2,6-/2, the ratio of 7-DMN significantly improves.Meanwhile, we can also see, along with the carrying out in reaction times, the activity of sample remains unchanged, and the sample of this explanation this method synthesis has very high catalytic stability.
SAPO-11 molecular sieve (sample A) preparation method described in this experiment is as follows: by pseudo-boehmite (Al
2o
3mass percentage is 60.6%), silicon sol (SiO
2mass percentage is 26.8%), mass percentage is that 85% phosphoric acid, di-n-propylamine (DPA) and deionized water are by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o mol ratio is after the ratio of 1:0.4:1:1:40 stirs and makes gel, crystallization 3h at 180 DEG C of temperature, after filtration, washs, collects filtrate dry 12h at 110 DEG C of temperature, then, after 650 DEG C of roasting temperature 7h, SAPO-11 molecular sieve (sample A) is obtained.
Experiment 2
A kind of SAPO-11 molecular sieve 2 of this experiment, the method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 object SAPO-11 molecular sieves (sample B), getting 1.06g, load the flat-temperature zone of the stainless steel reaction pipe of fixed-bed micro-reactor, inert stone sand is equipped with at two ends, 2h is activated under 550 DEG C of conditions, remove water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after activation step one obtained, at N
2flow rate of carrier gas be 10mL/min, temperature is 420 DEG C, and pressure is 4MPa, and mass space velocity is 1h
-1condition under, naphthalene, methyl alcohol and 1,2,4-trimethylbenzene are mixed and made into stock liquid with mol ratio 1:2:8, are injected the beds of fixed-bed reactor by Micro-metering Pumps continuously, carry out alkylated reaction, obtain 2,6-dimethylnaphthalene (2,6-DMN); Three, the time of outflow first product is counted t=0, and gather the product once flowed out every 1h, carry out quantitative analysis by gas-chromatography, calculate the transformation efficiency of naphthalene, the selectivity of 2,6-dimethylnaphthalenes and the selectivity of other products with area normalization method.
SAPO-11 molecular sieve (sample B) preparation method described in this experiment is as follows: by pseudo-boehmite (Al
2o
3mass percentage is 60.6%), silicon sol (SiO
2mass percentage is 26.8%), mass percentage is that 85% phosphoric acid, di-n-propylamine (DPA) and deionized water are by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o mol ratio is after the ratio of 1:0.6:1:1:40 stirs and makes gel, crystallization 3h at 180 DEG C of temperature, after filtration, washing, collects filtrate dry 12h at 110 DEG C of temperature, then after 650 DEG C of roasting temperature 7h, obtains SAPO-11 molecular sieve B.
Experiment 3
A kind of SAPO-11 molecular sieve 2 of this experiment, the method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 object SAPO-11 molecular sieves (sample C), getting 1.06g load the flat-temperature zone of the stainless steel reaction pipe of fixed-bed micro-reactor, inert stone sand is equipped with at two ends, 2h is activated under 550 DEG C of conditions, remove water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after activation step one obtained, at N
2flow rate of carrier gas be 10mL/min, temperature is 420 DEG C, and pressure is 4MPa, and mass space velocity is 1h
-1condition under, naphthalene, methyl alcohol and 1,2,4-trimethylbenzene are mixed and made into stock liquid with mol ratio 1:2:8, are injected the beds of fixed-bed reactor by Micro-metering Pumps continuously, carry out alkylated reaction, obtain 2,6-dimethylnaphthalene (2,6-DMN); Three, the time of outflow first product is counted t=0, and gather the product once flowed out every 1h, carry out quantitative analysis by gas-chromatography, calculate the transformation efficiency of naphthalene, the selectivity of 2,6-dimethylnaphthalenes and the selectivity of other products with area normalization method.
This experiment is as shown in table 2 in the result of alkylated reaction 4h and 6h, and the SAPO-11 molecular sieve synthesized in alcohol-water system as shown in Table 2 not only has the selectivity of high reactivity and high 2,6-DMN concurrently, and 2,6-/2, and the ratio of 7-DMN significantly improves.Meanwhile, we can also see, along with the carrying out in reaction times, the activity of sample remains unchanged, and the sample of this explanation this method synthesis has very high catalytic stability.Compared with the sample synthesized in aqueous systems, the sample synthesized in alcohol-water system, when identical silica alumina ratio, the content of multi-methylnaphthalene obviously reduces, and the selectivity of 2,6-DMN significantly improves.
SAPO-11 molecular sieve (sample C) preparation method described in this experiment is as follows: by pseudo-boehmite (Al
2o
3mass percentage is 60.6%), silicon sol (SiO
2mass percentage content is 26.8%), mass percentage is that 85% phosphoric acid, di-n-propylamine (DPA), deionized water and dehydrated alcohol are by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o:C
2h
5oH mass ratio is after the ratio of 1:0.4:1:1:30:10 stirs and makes gel, crystallization 48h at 180 DEG C of temperature, after filtration, washing, collects filtrate dry 12h at 110 DEG C of temperature, then after 650 DEG C of roasting temperature 7h, obtains SAPO-11 molecular sieve C.
Experiment 4
A kind of SAPO-11 molecular sieve 2 of this experiment, the novel method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 object SAPO-11 molecular sieve C one, getting 1.06g load the flat-temperature zone of the stainless steel reaction pipe of fixed-bed micro-reactor, inert stone sand is equipped with at two ends, 2h is activated under 550 DEG C of conditions, remove water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after activation step one obtained, at N
2flow rate of carrier gas be 10mL/min, temperature is 420 DEG C, and pressure is 4MPa, and mass space velocity is 1h
-1condition under, naphthalene, methyl alcohol and 1,2,4-trimethylbenzene are mixed and made into stock liquid with mol ratio 1:2:8, are injected the beds of fixed-bed reactor by Micro-metering Pumps continuously, carry out alkylated reaction, obtain 2,6-dimethylnaphthalene (2,6-DMN); Three, the time of outflow first product is counted t=0, and gather the product once flowed out every 1h, carry out quantitative analysis by gas-chromatography, calculate the transformation efficiency of naphthalene, the selectivity of 2,6-dimethylnaphthalenes and the selectivity of other products with area normalization method.
SAPO-11 molecular sieve (sample D) preparation method described in this experiment is as follows: by pseudo-boehmite (Al
2o
3mass percentage is 60.6%), silicon sol (SiO
2mass percentage is 26.8%), mass percentage is that 85% phosphoric acid, di-n-propylamine (DPA), deionized water and dehydrated alcohol are by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o:C
2h
5oH mass ratio is after the ratio of 1:0.6:1:1:30:10 stirs and makes gel, crystallization 48h at 180 DEG C of temperature, after filtration, washs, collects filtrate dry 12h at 110 DEG C of temperature, then, after 650 DEG C of roasting temperature 7h, SAPO-11 molecular sieve (sample D) is obtained.
The alkylated reaction result of the SAPO-11 molecular sieve catalytic naphthalene that table 1 synthesizes in aqueous systems with microwave heating method
The alkylated reaction result of the SAPO-11 molecular sieve catalytic naphthalene that table 2 synthesizes in alcohol-water system by traditional electrical heating means
Claims (6)
1. a SAPO-11 molecular sieve 2, the method of 6-dimethylnaphthalene, it is characterized in that SAPO-11 molecular sieve 2, the method of 6-dimethylnaphthalene is carried out according to following steps: the beds one, SAPO-11 molecular sieve being put into fixed-bed reactor, at 500 DEG C ~ 600 DEG C, activate 2h; Two, by even to naphthalene, alkylating reagent and solvent, obtain stock liquid, and with volume pump by the beds of the fixed-bed reactor of continuous for stock liquid implantation step one, and be 350 DEG C ~ 450 DEG C in temperature, pressure is 2 ~ 5MPa, and mass space velocity is 0.5 ~ 2h
-1, flow rate of carrier gas is under the condition of 20 ~ 60mL/min, carries out alkylated reaction 1 ~ 24h, obtains 2,6-dimethylnaphthalene; Wherein, the mol ratio of naphthalene and alkylating reagent is 1:2 ~ 4, and the mol ratio of naphthalene and solvent is 1:6 ~ 12;
Wherein, the SAPO-11 molecular sieve described in step one synthesizes in aqueous systems by the mode of microwave heating, and concrete steps are as follows: by Al
2o
3: SiO
2: P
2o
5: DPA:H
2o mol ratio is that the ratio of 1:0.2 ~ 1.4:1:1:40 stirs, and obtains gel, the polytetrafluoroethyllining lining that gel is housed is put in ceramic outer lining, then putting into microwave oven, is 600W at power, and temperature is under the condition of 160 DEG C ~ 180 DEG C, crystallization 0.5 ~ 4h, the solidliquid mixture obtained; Then, after being washed by the solid formation obtained after filtration, putting into temperature is dry 12h at 110 DEG C of temperature, then at 650 DEG C of roasting temperature 7h, obtains SAPO-11 molecular sieve.
2. the method for a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene according to claim 1, is characterized in that described SiO
2with Al
2o
3mol ratio is 0.2:1,0.6:1,0.8:1,1.0:1 or 1.2:1.
3. the method for a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene according to claim 1, is characterized in that the alkylating reagent described in step 2 is methyl alcohol.
4. the method for a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene according to claim 1, is characterized in that the solvent described in step 2 is 1,2,4-trimethylbenzene.
5. the method for a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene according to claim 1, it is characterized in that the temperature of reaction described in step 2 is 420 DEG C, reaction pressure is 4MPa, and mass space velocity is 1h
-1.
6. the method for a kind of SAPO-11 molecular sieve 2,6-dimethylnaphthalene according to claim 1, is characterized in that the gas of the carrier gas described in step 2 is nitrogen.
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| CN105566052B (en) * | 2015-12-24 | 2017-11-14 | 太原科技大学 | A kind of method that 2,6 dimethylnaphthalenes are prepared using the molecular sieve catalytics of CuSAPO 11 |
| CN107262146B (en) * | 2016-12-04 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing 2, 6-dimethylnaphthalene and preparation and application thereof |
| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
| CN112657538B (en) * | 2020-12-31 | 2023-03-17 | 西北大学 | Preparation method and application of catalyst for preparing 2-methylnaphthalene/2, 6-dimethylnaphthalene by synthesis gas and naphthalene one-step method |
| CN114054082B (en) * | 2021-11-10 | 2022-11-08 | 南昌大学 | Nano hierarchical pore SAPO-11 molecular sieve and preparation method and application thereof |
| CN114805000B (en) * | 2022-05-23 | 2023-09-26 | 煤炭科学技术研究院有限公司 | Method for preparing 2-methylnaphthalene by decalin |
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| CN1362392A (en) * | 2001-12-31 | 2002-08-07 | 黑龙江省石油化学研究院 | Prepn of 2,6-dimethylnaphthalene |
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| CN1362392A (en) * | 2001-12-31 | 2002-08-07 | 黑龙江省石油化学研究院 | Prepn of 2,6-dimethylnaphthalene |
| CN102001907A (en) * | 2010-10-08 | 2011-04-06 | 同济大学 | Method for synthetizing 2,6-dimethylnaphthalene with methanol, C10 arene and 2-methylnaphthalene through alkylation |
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