CN102746102A - 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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- CN102746102A CN102746102A CN2012102616837A CN201210261683A CN102746102A CN 102746102 A CN102746102 A CN 102746102A CN 2012102616837 A CN2012102616837 A CN 2012102616837A CN 201210261683 A CN201210261683 A CN 201210261683A CN 102746102 A CN102746102 A CN 102746102A
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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 a kind of preparation 2, the method for 6-dimethylnaphthalene.
Background technology
1973, Japanese Supreme Being people company at first developed a kind of novel polyester material PEN, was called for short PEN.Because it has advantages such as the good and mechanical property of thermotolerance, erosion resistance and dimensional stability is strong, is widely used in numerous areas such as aerospace, nuclear power material and electronic component.2, the 6-dimethylnaphthalene is the important monomer raw material of preparation PEN, but because 2, the generation complex process of 6-DMN, manufacturing cost height have seriously restricted PEN and have come into the market on a large scale.And present China 2,6-DMN depends on import basically, thereby it is simple 2 to develop technology, and the working method of 6-DMN, to reduce its production cost significant to the development that promotes China PEN polyester material.
At present, 2,6-DMN synthetic mainly is through being that raw material is through the multistep processes synthetic with YLENE.One-step synthesis 2, the method for 6-DMN have raw material sources abundant with advantages such as operational path is short, become the focus that Chinese scholars is in recent years endeavoured to study.But ten kinds of isomer boiling points of the synthetic DMN of single stage method are approaching, separate and difficulty, and especially 2,6-DMN and 2; The boiling point of 7-DMN only differs 0.3 ℃, thereby how to improve in the DMN product 2, the selectivity of 6-DMN and 2; 6-/2,7-DMN ratio are to realize single stage method production 2, the key of 6-DMN.
With naphthalene or methylnaphthalene is raw material single stage method Synthetic 2, and the catalyzer of 6-DMN is divided into homogeneous catalyst and heterogeneous catalyst.Though the homogeneous catalyst reactive behavior that with the aluminum chloride is representative is high, 2, the selectivity of 6-DMN is low, and catalyzer and product are not easily separated, and 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, because of have stronger acidity, good thermostability and hydrothermal stability, evenly abundant characteristics such as pore structure replaces homogeneous catalysts such as liquid acid and aluminum trichloride (anhydrous), obtained to use widely at absorption, separation and catalytic field.Wherein, be catalyzer with HM, Synthetic 2, during 6-DMN, 2,6-DMN and 1, the selectivity of 6-DMN can reach more than 99%, and 2, the purity of 6-DMN can be increased to more than 50% from 8.35%.Adopting beta-molecular sieve is the catalyzer Synthetic 2,6-DMN, behind the reaction 20h because of the catalyst surface coking; The transformation efficiency of naphthalene reduces, and the transformation efficiency of naphthalene maintains 19.87%, 2 behind the reaction 35h; The 6-DMN selectivity remains at about 6.66% in whole process, and this molecular sieve is not only to 2, and the selectivity of 6-DMN is low; And the reaction process carbon distribution is serious, and the catalytic activity suppression ratio is very fast.When the HZSM-12 molecular sieve catalytic Synthetic 2 that adopts sour dealuminzation modification, 6-DMN, the result finds that the HZSM-12 before the modification has high initial reaction activity; The initial conversion of naphthalene is 64.6%, but along with the carrying out that reacts, transformation efficiency descends significantly; 2, the selectivity of 6-DMN is 23.6%.Behind reaction 6h, transformation efficiency reduces to 28.3%, has descended 36.3%; Though and the HZSM-12 molecular sieve deactivation rate after the sour dealuminzation modification descends, catalytic activity descends.Adopt NH
4The methylation reaction of the ZSM-5 catalysis 2-MN of F and Pt modification, 2, the selectivity of 6-DMN reaches 63.4%, but the transformation efficiency of 2-MN has only 6.1%.It is thus clear that; The zeolite molecular sieve of having reported is difficult to have concurrently good reaction activity and 2 to the alkylated reaction of naphthalene, the highly selective of 6-DMN, thereby develop and have good catalytic activity and high by 2 concurrently; 6-DMN optionally sieve catalyst is exploitation single stage method preparation 2, the key of 6-DMN.
Summary of the invention
The object of the invention solves existing catalyzer can not have high reactivity and high by 2 simultaneously, 6-DMN selectivity, and the problem of the easy inactivation of catalyzer, and a kind of SAPO-11 molecular sieve preparation 2 is provided, the method for 6-dimethylnaphthalene.
A kind of SAPO-11 molecular sieve preparation 2 of the present invention, the method for 6-dimethylnaphthalene is carried out according to following steps: one, the SAPO-11 molecular sieve is put into the beds of fixed-bed reactor, at 500 ℃ ~ 600 ℃ following activation 2h; Two, naphthalene, alkylating reagent and solvent is even, promptly get liquid stock, and with in the beds of volume pump with the fixed-bed reactor of the continuous implantation step one of liquid stock; And be 350 ℃ ~ 450 ℃ in temperature, pressure is 2 ~ 5MPa, 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, promptly get 2, the 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, adopting raw material among the present invention is that the 4-trimethylbenzene mixes by reactant naphthalene, alkylating reagent methyl alcohol, solvent 1,2, reacts to be the heterogenetic successive reaction, and reaction product and catalyzer are easily separated; Simple to operate, be convenient to scale operation.
2, compare with the traditional water by the use of thermal means; Not only shortened crystallization time significantly with a series of SAPO-11 molecular sieves of microwave heating method hydrothermal system synthetic; Reduced energy consumption; Reduced the synthetic cost of molecular sieve, and can make Si get into the skeleton of molecular sieve more equably, intensity is suitable, the acid site of acid amount modulation but form.
3, with traditional electrical type of heating synthetic SAPO-11 molecular sieve in alcohol-water system; Make the more even of preparing gel; The more effective entering skeleton of Si makes that acid amount and strength of acid are moderate, thereby when having the catalytic stability that higher catalytic performance becomes reconciled; Have higher by 2, the selectivity of 6-DMN.
4, the present invention first with microwave heating method hydrothermal system and and be used for the alkylated reaction preparation 2 of catalysis naphthalene with traditional electrical heating means synthetic SAPO-11 molecular sieve in alcohol-water system, 6-DMN has not only overcome anhydrous AlCl
3Exist Deng homogeneous catalyst with the product separation difficulty, equipment corrosion is serious and drawback such as environmental pollution; And the alkylated reaction of naphthalene and methyl alcohol had higher catalytic activity, 2 than zeolite [molecular sieves such as ZSM-5; The selectivity of 6-DMN, 2; 6-/2,7-DMN ratio and higher carbon accumulation resisting ability.
5, the SAPO-11 molecular sieve of the present invention's employing belongs to the molecular sieve of AEL topological framework; Has one dimension ten-ring straight hole road structure; Port size is 0.39 * 0.63nm, because the SAPO-11 molecular sieve has suitable opening diameter, helps the alkylated reaction thing of naphthalene and the diffusion of product; Therefore be expected to have concurrently good reaction activity and to 2, the highly selective of 6-DMN.Compare with traditional electrically heated hydrothermal synthesis method; Not only can significantly shorten the crystallization time of molecular sieve with the synthetic SAPO-11 of carry out microwave radiation heating method; Cut down the consumption of energy, and synthetic SAPO-11 molecular sieve can promote silicon to get into the skeleton of molecular sieve effectively and it is evenly distributed in alcohol-water system, therefore can improve quantity and its strength of acid of modulation in the acid site of SAPO-11 molecular sieve; Be expected to improve simultaneously its catalytic activity and to 2, the selectivity of 6-DMN.On the other hand, adopt microwave heating method synthetic SAPO-11, will have stronger carbon accumulation resisting ability and catalytic stability because of having gentle acidity.
Description of drawings
Fig. 1 is the XRD spectra of the SAPO-11 molecular sieve-4 A of preparation in the experiment 1;
Fig. 2 is the SEM photo of the SAPO-11 molecular sieve-4 A of preparation in the experiment 1;
Fig. 3 is the XRD spectra of the SAPO-11 molecular sieve B of preparation in the experiment 2;
Fig. 4 is the SEM photo of the SAPO-11 molecular sieve B of preparation in the experiment 2;
Fig. 5 is the XRD spectra of the SAPO-11 molecular sieve C of preparation in the experiment 3;
Fig. 6 is the SEM photo of the SAPO-11 molecular sieve C of preparation in the experiment 3;
Fig. 7 is the XRD spectra of the SAPO-11 molecular sieve D of preparation in the experiment 4;
Fig. 8 is the SEM photo of the SAPO-11 molecular sieve D of preparation in the experiment 4.
Embodiment
Technical scheme 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 preparation 2 of this embodiment; The method of 6-dimethylnaphthalene is carried out according to following steps: one, the SAPO-11 molecular sieve is put into the beds of fixed-bed reactor, at 500 ℃ ~ 600 ℃ following activation 2h; Two, naphthalene, alkylating reagent and solvent is even, promptly get liquid stock, and with in the beds of volume pump with the fixed-bed reactor of the continuous implantation step one of liquid stock, and be 350 ℃ ~ 450 ℃ in temperature, pressure is 2 ~ 5MPa, 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, promptly gets 2, the 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.
This embodiment comprises following beneficial effect:
1, adopting raw material in this embodiment is that the 4-trimethylbenzene mixes by reactant naphthalene, alkylating reagent methyl alcohol, solvent 1,2, reacts to be the heterogenetic successive reaction, and reaction product and catalyzer are easily separated; Simple to operate, be convenient to scale operation.
2, compare with the traditional water by the use of thermal means; With microwave heating method respectively in hydrothermal system and alcohol-water system a series of SAPO-11 molecular sieves of synthetic not only shortened crystallization time significantly; Reduced energy consumption; Reduced the synthetic cost of molecular sieve, and can make Si get into the skeleton of molecular sieve more equably, intensity is suitable, the acid site of acid amount modulation but form.
3, with traditional electrical type of heating synthetic SAPO-11 molecular sieve in alcohol-water system; Make the more even of preparing gel; The more effective entering skeleton of Si makes that acid amount and strength of acid are moderate, thereby when having the catalytic stability that higher catalytic performance becomes reconciled; Have higher by 2, the selectivity of 6-DMN.
4, this embodiment is used for microwave heating method synthetic SAPO-11 molecular sieve in hydrothermal system and alcohol-water system the alkylated reaction preparation 2 of catalysis naphthalene first, and 6-DMN has not only overcome anhydrous AlCl
3Exist Deng homogeneous catalyst with the product separation difficulty, equipment corrosion is serious and drawback such as environmental pollution; And the alkylated reaction of naphthalene and methyl alcohol had higher catalytic activity, 2 than zeolite [molecular sieves such as ZSM-5; The selectivity of 6-DMN, 2; 6-/2,7-DMN ratio and higher carbon accumulation resisting ability.
5, the SAPO-11 molecular sieve of this embodiment employing belongs to the molecular sieve of AEL topological framework; Has one dimension ten-ring straight hole road structure; Port size is 0.39 * 0.63nm, because the SAPO-11 molecular sieve has suitable opening diameter, helps the alkylated reaction thing of naphthalene and the diffusion of product; Therefore be expected to have concurrently good reaction activity and to 2, the highly selective of 6-DMN.Compare with traditional electrically heated hydrothermal synthesis method; Not only can significantly shorten the crystallization time of molecular sieve with the synthetic SAPO-11 of carry out microwave radiation heating method; Cut down the consumption of energy, and synthetic SAPO-11 molecular sieve can promote silicon to get into the skeleton of molecular sieve effectively and it is evenly distributed in alcohol-water system, therefore can improve quantity and its strength of acid of modulation in the acid site of SAPO-11 molecular sieve; Be expected to improve simultaneously its catalytic activity and to 2, the selectivity of 6-DMN.On the other hand, adopt microwave heating method synthetic SAPO-11, will have stronger carbon accumulation resisting ability and catalytic stability because of having gentle acidity.
Embodiment two: what this embodiment and embodiment one were different is: described in the step 1 to be equipped with the SAPO-11 molecular sieve be the mode synthetic in aqueous systems with microwave heating, concrete steps are following: press Al
2O
3: SiO
2: P
2O
5: DPA:H
2The O mol ratio is that the ratio of 1:0.2～1.2:1:1:40 stirs, and gets gel, and the polytetrafluoroethyllining lining that gel is housed is put in the ceramic outer lining; Putting into microwave oven then, is 600W at power, and temperature is under 160 ℃ ~ 180 ℃ the condition; Crystallization 0.5 ~ 4h, the solidliquid mixture that obtains; After will passing through the solid formation washing that filters then, putting into temperature is dry 12h under 110 ℃ of temperature, at 650 ℃ of roasting temperature 7h, promptly gets the SAPO-11 molecular sieve then.Other is identical with embodiment one.
Embodiment three: what this embodiment was different with embodiment one or two is: the SAPO-11 molecular sieve described in the step 1 adopts traditional electrical heating method synthetic in alcohol-water system, and concrete steps are following: press Al
2O
3: SiO
2: P
2O
5: DPA:C
2H
5OH:H
2The O mol ratio is 1:0.2 ~ 1.2::1:1:10: the ratio of (10 ~ 100) stirs, and gets gel, and the polytetrafluoroethyllining lining that gel is housed is put into the stainless steel outer lining; Put into baking oven then; Be that crystallization 12-48h obtains solidliquid mixture under 160 ℃ ~ 180 ℃ the condition in temperature; After will passing through the solid formation washing that filters then, putting into temperature is dry 12h under 110 ℃ of temperature, at 650 ℃ of roasting temperature 7h, promptly gets the SAPO-11 molecular sieve then.Other is identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: 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: what this embodiment was different with one of embodiment one to four is: 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: what this embodiment was different with one of embodiment one to five is: the alkylating reagent described in the step 2 is a methyl alcohol.Other is identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: the solvent described in the step 2 is 1,2, the 4-trimethylbenzene.Other is identical with one of embodiment one to six.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is: the temperature of reaction described in the step 2 is 420 ℃, and reaction pressure is 4MPa, and mass space velocity is 1h
-1Other is identical with one of embodiment one to seven.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the gas of the carrier gas described in the step 2 is nitrogen.Other is identical with one of embodiment one to eight.
Through following experimental verification effect of the present invention:
Experiment 1
A kind of SAPO-11 molecular sieve preparation 2 of this experiment; The method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 purpose SAPO-11 molecular sieves (sample A) of one, getting 1.06g; Pack into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, inertia silica sand is equipped with at two ends, activation 2h under 550 ℃ of conditions; Remove the water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after the activation that step 1 is obtained is at N
2Flow rate of carrier gas be 10mL/min, temperature is 420 ℃, pressure is 4MPa, mass space velocity is 1h
-1Condition under, with naphthalene, methyl alcohol and 1,2, the 4-trimethylbenzene is mixed and made into liquid stock with mol ratio 1:2:8, injects the beds of fixed-bed reactor continuously by the micro-measurement pump, carries out alkylated reaction, 2, the 6-dimethylnaphthalene (2,6-DMN); Three, the time that will flow out first product is counted t=0, and the once effusive product of every separated 1h collection, carries out quantitative analysis with gc, calculates transformation efficiency, 2, the selectivity of 6-dimethylnaphthalene and other product selectivity of naphthalene with area normalization method.
This experiment is as shown in table 1 in the result of alkylated reaction 4h and 6h; Can know with microwave heating method synthetic SAPO-11 molecular sieve in aqueous systems by table 1 not only to have high reactivity and high by 2 concurrently, the selectivity of 6-DMN, and 2; 6-/2, the ratio of 7-DMN obviously improves.Simultaneously, we can also see that along with the carrying out in reaction times, the activity of sample remains unchanged, and this explanation has very high catalytic stability with this method synthetic sample.
It is following that this tests described SAPO-11 molecular sieve (sample A) preparation method: with pseudo-boehmite (Al
2O
3The quality percentage composition is 60.6%), silicon sol (SiO
2The quality percentage composition is 26.8%), the quality percentage composition is that 85% phosphoric acid, di-n-propylamine (DPA) and deionized water are pressed Al
2O
3: SiO
2: P
2O
5: DPA:H
2The O mol ratio be the ratio of 1:0.4:1:1:40 stir process gel after; Crystallization 3h under 180 ℃ of temperature through filtering, washing, collects filtrating dry 12h under 110 ℃ of temperature; Behind 650 ℃ of roasting temperature 7h, promptly get SAPO-11 molecular sieve (sample A) then.
Experiment 2
A kind of SAPO-11 molecular sieve preparation 2 of this experiment; The method of 6-dimethylnaphthalene is carried out according to following steps: 20 ~ 40 purpose SAPO-11 molecular sieves (sample B) of one, getting 1.06g; Pack into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, inertia silica sand is equipped with at two ends, activation 2h under 550 ℃ of conditions; Remove the water and the impurity of surface adsorption, active sites is come out; Two, the SAPO-11 molecular sieve after the activation that step 1 is obtained is at N
2Flow rate of carrier gas be 10mL/min, temperature is 420 ℃, pressure is 4MPa, mass space velocity is 1h
-1Condition under, with naphthalene, methyl alcohol and 1,2, the 4-trimethylbenzene is mixed and made into liquid stock with mol ratio 1:2:8, injects the beds of fixed-bed reactor continuously by the micro-measurement pump, carries out alkylated reaction, 2, the 6-dimethylnaphthalene (2,6-DMN); Three, the time that will flow out first product is counted t=0, and the once effusive product of every separated 1h collection, carries out quantitative analysis with gc, calculates transformation efficiency, 2, the selectivity of 6-dimethylnaphthalene and other product selectivity of naphthalene with area normalization method.
It is following that this tests described SAPO-11 molecular sieve (sample B) preparation method: with pseudo-boehmite (Al
2O
3The quality percentage composition is 60.6%), silicon sol (SiO
2The quality percentage composition is 26.8%), the quality percentage composition is that 85% phosphoric acid, di-n-propylamine (DPA) and deionized water are pressed Al
2O
3: SiO
2: P
2O
5: DPA:H
2The O mol ratio be the ratio of 1:0.6:1:1:40 stir process gel after, crystallization 3h under 180 ℃ of temperature, through filter, washing, collect filtrating dry 12h under 110 ℃ of temperature, behind 650 ℃ of roasting temperature 7h, promptly get SAPO-11 molecular sieve B then.
Experiment 3
A kind of SAPO-11 molecular sieve preparation 2 of this experiment; The method of 6-dimethylnaphthalene is carried out according to following steps: the flat-temperature zone of stainless steel reaction pipe of one, getting 20 ~ 40 purpose SAPO-11 molecular sieve (sample C) fixed-bed micro-reactors of packing into of 1.06g; Inertia silica sand is equipped with at two ends; Activation 2h under 550 ℃ of conditions, the water and the impurity of removal surface adsorption come out active sites; Two, the SAPO-11 molecular sieve after the activation that step 1 is obtained is at N
2Flow rate of carrier gas be 10mL/min, temperature is 420 ℃, pressure is 4MPa, mass space velocity is 1h
-1Condition under, with naphthalene, methyl alcohol and 1,2, the 4-trimethylbenzene is mixed and made into liquid stock with mol ratio 1:2:8, injects the beds of fixed-bed reactor continuously by the micro-measurement pump, carries out alkylated reaction, 2, the 6-dimethylnaphthalene (2,6-DMN); Three, the time that will flow out first product is counted t=0, and the once effusive product of every separated 1h collection, carries out quantitative analysis with gc, calculates transformation efficiency, 2, the selectivity of 6-dimethylnaphthalene and other product selectivity of naphthalene with area normalization method.
This experiment is as shown in table 2 in the result of alkylated reaction 4h and 6h, can know that by table 2 in alcohol-water system synthetic SAPO-11 molecular sieve not only has high reactivity and high by 2 concurrently, the selectivity of 6-DMN, and 2,6-/2, the ratio of 7-DMN obviously improves.Simultaneously, we can also see that along with the carrying out in reaction times, the activity of sample remains unchanged, and this explanation has very high catalytic stability with this method synthetic sample.Compare with synthetic sample in aqueous systems, synthetic sample in the alcohol-water system, under the situation of identical silica alumina ratio, the content of multi-methylnaphthalene obviously reduces, and 2, the selectivity of 6-DMN obviously improves.
It is following that this tests described SAPO-11 molecular sieve (sample C) preparation method: with pseudo-boehmite (Al
2O
3The quality percentage composition is 60.6%), silicon sol (SiO
2Mass percentage content is 26.8%), the quality percentage composition is that 85% phosphoric acid, di-n-propylamine (DPA), deionized water and absolute ethyl alcohol are pressed Al
2O
3: SiO
2: P
2O
5: DPA:H
2O:C
2H
5The OH mass ratio be the ratio of 1:0.4:1:1:30:10 stir process gel after, crystallization 48h under 180 ℃ of temperature, through filter, washing, collect filtrating dry 12h under 110 ℃ of temperature, behind 650 ℃ of roasting temperature 7h, promptly get SAPO-11 molecular sieve C then.
Experiment 4
A kind of SAPO-11 molecular sieve preparation 2 of this experiment; The novel method of 6-dimethylnaphthalene is carried out according to following steps: pack into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor of 20 ~ 40 purpose SAPO-11 molecular sieve C that, get 1.06g; Inertia silica sand is equipped with at two ends; Activation 2h under 550 ℃ of conditions, the water and the impurity of removal surface adsorption come out active sites; Two, the SAPO-11 molecular sieve after the activation that step 1 is obtained is at N
2Flow rate of carrier gas be 10mL/min, temperature is 420 ℃, pressure is 4MPa, mass space velocity is 1h
-1Condition under, with naphthalene, methyl alcohol and 1,2, the 4-trimethylbenzene is mixed and made into liquid stock with mol ratio 1:2:8, injects the beds of fixed-bed reactor continuously by the micro-measurement pump, carries out alkylated reaction, 2, the 6-dimethylnaphthalene (2,6-DMN); Three, the time that will flow out first product is counted t=0, and the once effusive product of every separated 1h collection, carries out quantitative analysis with gc, calculates transformation efficiency, 2, the selectivity of 6-dimethylnaphthalene and other product selectivity of naphthalene with area normalization method.
It is following that this tests described SAPO-11 molecular sieve (sample D) preparation method: with pseudo-boehmite (Al
2O
3The quality percentage composition is 60.6%), silicon sol (SiO
2The quality percentage composition is 26.8%), the quality percentage composition is that 85% phosphoric acid, di-n-propylamine (DPA), deionized water and absolute ethyl alcohol are pressed Al
2O
3: SiO
2: P
2O
5: DPA:H
2O:C
2H
5The OH mass ratio be the ratio of 1:0.6:1:1:30:10 stir process gel after; Crystallization 48h under 180 ℃ of temperature through filtering, washing, collects filtrating dry 12h under 110 ℃ of temperature; Behind 650 ℃ of roasting temperature 7h, promptly get SAPO-11 molecular sieve (sample D) then.
Table 1 is with the alkylated reaction result of microwave heating method synthetic SAPO-11 molecular sieve catalytic naphthalene in aqueous systems
Table 2 is with the alkylated reaction result of traditional electrical heating means synthetic SAPO-11 molecular sieve catalytic naphthalene in alcohol-water system
Claims (9)
1. SAPO-11 molecular sieve preparation 2; The method of 6-dimethylnaphthalene; It is characterized in that SAPO-11 molecular sieve preparation 2; The method of 6-dimethylnaphthalene is carried out according to following steps: one, the SAPO-11 molecular sieve is put into the beds of fixed-bed reactor, at 500 ℃ ~ 600 ℃ following activation 2h; Two, naphthalene, alkylating reagent and solvent is even, promptly get liquid stock, and with in the beds of volume pump with the fixed-bed reactor of the continuous implantation step one of liquid stock, and be 350 ℃ ~ 450 ℃ in temperature, pressure is 2 ~ 5MPa, 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, promptly gets 2, the 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.
2. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene is characterized in that the SAPO-11 molecular sieve described in the step 1 is the mode synthetic in aqueous systems with microwave heating, concrete steps are following: press Al
2O
3: SiO
2: P
2O
5: DPA:H
2The O mol ratio is that the ratio of 1:0.2 ~ 1.4:1:1:40 stirs, and gets gel, and the polytetrafluoroethyllining lining that gel is housed is put in the ceramic outer lining; Putting into microwave oven then, is 600W at power, and temperature is under 160 ℃ ~ 180 ℃ the condition; Crystallization 0.5 ~ 4h, the solidliquid mixture that obtains; After will passing through the solid formation washing that filters then, putting into temperature is dry 12h under 110 ℃ of temperature, at 650 ℃ of roasting temperature 7h, promptly gets the SAPO-11 molecular sieve then.
3. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene is characterized in that the SAPO-11 molecular sieve described in the step 1 adopts traditional electrical heating method synthetic in alcohol-water system, concrete steps are following: press Al
2O
3: SiO
2: P
2O
5: DPA:C
2H
5OH:H
2The O mol ratio is that the ratio of 1:0.2 ~ 1.2:1:1:10:10 ~ 100 stirs, and gets gel, and the polytetrafluoroethyllining lining that gel is housed is put in the ceramic outer lining; Put into baking oven then; Be that crystallization 12 ~ 48h obtains solidliquid mixture under 160 ℃ ~ 180 ℃ the condition in temperature; After will passing through the solid formation washing that filters then, putting into temperature is dry 12h under 110 ℃ of temperature, at 650 ℃ of roasting temperature 7h, promptly gets the SAPO-11 molecular sieve then.
4. a kind of SAPO-11 molecular sieve preparation 2 according to claim 3, the method for 6-dimethylnaphthalene is characterized in that described C
2H
5OH:H
2The mol ratio of O is 1:3.
5. according to claim 2 or 3 described a kind of SAPO-11 molecular sieve preparations 2, the method for 6-dimethylnaphthalene 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.
6. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene is characterized in that the alkylating reagent described in the step 2 is a methyl alcohol.
7. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene is characterized in that the solvent described in the step 2 is 1,2, the 4-trimethylbenzene.
8. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene is characterized in that the temperature of reaction described in the step 2 is 420 ℃, and reaction pressure is 4MPa, and mass space velocity is 1h
-1
9. a kind of SAPO-11 molecular sieve preparation 2 according to claim 1, the method for 6-dimethylnaphthalene, the gas that it is characterized in that the carrier gas described in the step 2 is nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210261683.7A CN102746102B (en) | 2012-07-26 | 2012-07-26 | Preparation method of 2,6-DiMethylnaphthalene (DMN) by using SAPO-11 molecular sieve |
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| CN105566052A (en) * | 2015-12-24 | 2016-05-11 | 太原科技大学 | Method for using CuSAPO-11 molecular sieve for preparation of 2,6-dimethylnaphthalene |
| CN107262146A (en) * | 2016-12-04 | 2017-10-20 | 中国科学院大连化学物理研究所 | One kind prepares 2,6 dimethylnaphthalene catalyst and its preparation and application |
| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
| CN112657538A (en) * | 2020-12-31 | 2021-04-16 | 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 |
| CN114054082A (en) * | 2021-11-10 | 2022-02-18 | 南昌大学 | Nano hierarchical pore SAPO-11 molecular sieve and preparation method and application thereof |
| CN114805000A (en) * | 2022-05-23 | 2022-07-29 | 煤炭科学技术研究院有限公司 | Method for preparing 2-methylnaphthalene by naphthalene alkylation |
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| CN105566052A (en) * | 2015-12-24 | 2016-05-11 | 太原科技大学 | Method for using CuSAPO-11 molecular sieve for preparation of 2,6-dimethylnaphthalene |
| CN107262146A (en) * | 2016-12-04 | 2017-10-20 | 中国科学院大连化学物理研究所 | One kind prepares 2,6 dimethylnaphthalene catalyst and its preparation and application |
| CN109896531A (en) * | 2019-04-21 | 2019-06-18 | 王干 | A kind of preparation method of SAPO-11 molecular sieve |
| CN112657538A (en) * | 2020-12-31 | 2021-04-16 | 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 |
| 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 |
| CN114054082A (en) * | 2021-11-10 | 2022-02-18 | 南昌大学 | Nano hierarchical pore SAPO-11 molecular sieve and preparation method and application thereof |
| 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 |
| CN114805000A (en) * | 2022-05-23 | 2022-07-29 | 煤炭科学技术研究院有限公司 | Method for preparing 2-methylnaphthalene by naphthalene alkylation |
| 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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