CN103265396A - Method for preparing 2,6-dimethyl naphthalene by alkylation reaction of MgAPO-11 molecular sieve catalytic naphthalene - Google Patents
Method for preparing 2,6-dimethyl naphthalene by alkylation reaction of MgAPO-11 molecular sieve catalytic naphthalene Download PDFInfo
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Abstract
The invention discloses a method for preparing 2,6-dimethyl naphthalene by alkylation reaction of MgAPO-11 molecular sieve catalytic naphthalene. The method comprises the following steps of: I, activating an MgAPO-11 molecular sieve; and II, mixing naphthalene with an alkylation reagent and a solvent to prepare a feed solution, and carrying out alkylation reaction on the feed solution and the activated MgAPO-11 molecular sieve catalytic naphthalene to obtain the 2,6-dimethyl naphthalene. According to the method for preparing 2,6-dimethyl naphthalene by alkylation reaction of MgAPO-11 molecular sieve catalytic naphthalene, the used MgAPO-11 molecular sieve is synthesized by adopting a conventional electric heating method or a microwave heating method; the alkylation reaction of the MgAPO-11 molecular sieve catalytic naphthalene can be used for overcoming the defects that the homogeneous catalysts including anhydrous AlCl3 and the like are difficult to separate from the product, severe in device corrosion and severe in environment pollution, so that the reaction activity and 2,6-DMN (Dimethylnitrosamine) selectivity are higher, the 2,6-/2,7-DMN ratio and anti-carbon deposition capacity are higher. Moreover, the reaction products and the catalysts are easy to separate. Besides, the method is simple to operate and convenient for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation 2, (be abbreviated as 2, method 6-DMN) is specifically related to utilize the alkylation of the synthetic MgAPO-11 molecular sieve catalytic naphthalene of traditional electrical heating means and microwave heating method to prepare the method for 2,6-dimethylnaphthalene to the 6-dimethylnaphthalene.
Background technology
Aluminum phosphate series molecular sieve is a class novel molecular sieve of early 1980s U.S. combinating carbide company exploitation, have good adsorption, thermostability and hydrothermal stability, but because its skeleton structure is electric neutrality, do not have the ion-exchange performance surface acidity extremely a little less than, its application is very limited.The Al that different metal Me (as Si, Fe, Co, Mn, Mg etc.) is replaced in the aluminium phosphate molecular sieve skeleton introduces skeleton, under the prerequisite that does not change skeleton structure, can improve its acidity and catalytic performance greatly, wherein the MgAPOs molecular sieve of Mg replacement has special acidity and redox property, synthesizes a research focus of aspect for molecular sieve always.The MgAPO-11 molecular sieve is a kind of AEL type molecular sieve that synthesizes first in 1986, and it is by Mg
2+Isomorphous substitution Al
3+Enter that the AlPO-11 framework of molecular sieve forms, Mg
2+Introducing make framework of molecular sieve electronegative, if the positively charged ion of compensation skeleton negative charge is H
+, on molecular sieve, just formed so and had more highly acid Bronsted acidic site MgP-OH.In addition, because the P-O key has the character of covalent linkage in the phosphoric acid salt molecular sieve, and the Al-O key has the character of ionic linkage, Mg
2+Ionic replacement Al
3+After, also can form with Mg
2+Lewis acidic site centered by the ion.Therefore, Mg
2+After ionic replacement entered the AlPO-11 skeleton, the quantity of the Lewis acidic site of molecular sieve and stronger Bronsted acidic site all was improved, and this has widened the application space of AlPO-11 molecular sieve in the multiphase solid acid catalyzed reaction.(catalysis journal such as Yang Xiaomei, 2006,27:1039) synthesize the MgAPO-11 molecular sieve of different Mg content, and be applied to the hygrogenating isomerization reaction of n-dodecane hydrocarbon, reaction result shows that the strong acidic site number of the catalytic activity of Pt/MgAPO-11 catalyzer and MgAPO-11 molecular sieve is closely related.Short crystallization time, the P/Al mol ratio of synthesized gel rubber are 1.0 and use Mg (NO
3)
2For the Mg source is conducive to improve the strong acidic site number of MgAPO-11, thereby improve the catalytic activity of Pt/MgAPO-11.(catalysis journal such as Feng Lili, 2009,30:340) studied the kinetics that MgAPO-11 molecular sieve catalytic n-hexane cracking reacts, the result shows: MgAPO-11 has medium catalytic activity at 450～550 ℃, the catalytic cracking reaction of normal hexane on the MgAPO-11 molecular sieve is based on unimolecular reaction, normal hexane concentration item reaction order in the rate process is 1, the available Arrhenius formulate of relation between apparent speed constant and the temperature of reaction, and the selectivity of propylene is still for the highest, temperature of reaction is higher, and the product kind the more.
Because the strength of acid of MgP-OH is than the strength of acid height of SiAl-OH, MgAPO-11 shows higher alkylation activity and 2,6-/2, the ratio of 7-DMN.So far, not about the report of MgAPO-11 molecular sieve for the preparation of 2,6-DMN, the MgAPO-11 molecular sieve that we will synthesize with traditional electrical heating means and microwave heating method first is for the preparation of 2,6-DMN, and is significant.
Summary of the invention
The alkylated reaction that the object of the invention provides a kind of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene.
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 350～450 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, the mol ratio 1 that naphthalene and alkylating reagent and solvent are pressed: (2～4): (6～12) are mixed and made into stock liquid, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 350～450 ℃, pressure are that 2～5MPa, mass space velocity are 0.5～2h
-1, nitrogen flow rate is 20～60ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene; Wherein the molecular sieve of MgAPO-11 described in the step 1 is to adopt traditional electrical heating method or microwave heating method to synthesize.
The invention has the advantages that:
1, raw material is that the 4-trimethylbenzene mixes by reactant naphthalene, alkylating reagent methyl alcohol, solvent 1,2 among the present invention, reacts to be heterogeneous successive reaction, and reaction product and catalyzer are easily separated; Simple to operate, be convenient to scale operation.
2, used MgAPO-11 molecular sieve is to adopt traditional electrical heating means or microwave heating method to synthesize among the present invention, when synthetic, introduce the magnesium atom of minute quantity, molecular sieve just has higher acid amount, thereby the alkylated reaction that makes the molecular sieve catalytic naphthalene has higher reactive behavior and the selectivity of 2,6-DMN, and has obviously improved 2,6-/2, the ratio of 7-DMN.
3, used MgAPO-11 molecular sieve adopts microwave heating method synthetic among the present invention, not only shorten crystallization time significantly, reduced energy consumption, reduced the synthetic cost of molecular sieve, and can make Mg enter the skeleton of molecular sieve more equably, intensity is suitable, the acid site of acid amount modulation but form.
4, the present invention will prepare 2,6-DMN with the alkylated reaction that traditional electrical heating means and microwave heating method synthetic MgAPO-11 molecular sieve in aqueous systems is used for the catalysis naphthalene first, 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 than zeolite [molecular sieves such as ZSM-5 the alkylated reaction of naphthalene and methyl alcohol had higher catalytic activity, 2, the selectivity of 6-DMN, 2,6-/2,7-DMN ratio and higher carbon accumulation resisting ability.Compare with the MgAPO-11 molecular sieve that the traditional water by the use of thermal means is synthetic, the present invention adopts the synthetic MgAPO-11 molecular sieve of microwave heating method as catalyzer, has obviously improved 2 in the alkylation reaction product of naphthalene, 6-/2,7-DMN ratio.
Description of drawings
Fig. 1 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 1;
Fig. 2 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 1;
Fig. 3 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 2;
Fig. 4 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 2;
Fig. 5 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 3;
Fig. 6 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 3;
Fig. 7 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 4;
Fig. 8 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 4;
Fig. 9 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 5;
Figure 10 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 5;
Figure 11 is the XRD spectra of the MgAPO-11 molecular sieve of preparation among the embodiment 6;
Figure 12 is the SEM figure of the MgAPO-11 molecular sieve of preparation among the embodiment 6.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the alkylated reaction of present embodiment MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 350～450 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, the mol ratio 1 that naphthalene and alkylating reagent and solvent are pressed: (2～4): (6～12) are mixed and made into stock liquid, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 350～450 ℃, pressure are that 2～5MPa, mass space velocity are 0.5～2h
-1, nitrogen flow rate is 20～60ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene; Wherein the molecular sieve of MgAPO-11 described in the step 1 is to adopt traditional electrical heating method or microwave heating method to synthesize.
Embodiment two: what present embodiment and embodiment one were different is that the magnesium source of the molecular sieve of MgAPO-11 described in the step 1 is Mg (NO
3)
26H
2O or Mg (CH
3COO)
24H
2O.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is MgO and Al in the molecular sieve of MgAPO-11 described in the step 1
2O
3Mol ratio be (0.01～0.40): 1.Other step and parameter are identical with embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is that alkylating reagent described in the step 2 is methyl alcohol.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what present embodiment was different with one of embodiment one to four is that solvent described in the step 2 is 1,2,4-trimethylbenzene.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what present embodiment was different with one of embodiment one to five is the mol ratio that naphthalene described in the step 2 and alkylating reagent and solvent are pressed 1: 3: 8.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to six is, temperature of reaction described in the step 2 is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min.Other step and parameter are identical with one of embodiment one to six.
Embodiment 1:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt traditional electrical heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (CH
3COO)
24H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.220: 7.817: 3.5: 23.053 ratio of weight and number stirs and makes behind the gel in 180 ℃ of following crystallization 48h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Fig. 1 and 2.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 1.
Table 1
Embodiment 2:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt traditional electrical heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (CH
3COO)
24H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.440: 7.817: 3.5: 23.090 ratio of weight and number stirs and makes behind the gel in 180 ℃ of following crystallization 48h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Fig. 3 and 4.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 2.
Table 2
Embodiment 3:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt traditional electrical heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (NO
3)
26H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.261: 7.817: 3.5: 25.199 ratio of weight and number stirs and makes behind the gel in 180 ℃ of following crystallization 48h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Fig. 5 and 6.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 3.
Table 3
Embodiment 4:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt microwave heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (CH
3COO)
24H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.220: 7.817: 3.5: 23.053 ratio of weight and number stirs and makes gel, places microwave dissolver then, at 180 ℃ of following crystallization 3h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Fig. 7 and 8.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 4.
Table 4
Embodiment 5:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt microwave heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (CH
3COO)
24H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.440: 7.817: 3.5: 23.090 parts by weight frequently stir and make gel, place microwave dissolver then, at 180 ℃ of following crystallization 3h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Fig. 9 and 10.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 5.
Table 5
Embodiment 6:
The alkylated reaction of MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 420 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, with naphthalene and methyl alcohol and 1,2, the mol ratio that the 4-trimethylbenzene is pressed is mixed and made into stock liquid at 1: 2: 8, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene.
MgAPO-11 molecular sieve described in the present embodiment step 1 is to adopt microwave heating method synthetic, and concrete synthetic method is as follows: pseudo-boehmite (is amounted to into Al
2O
3Content is 60.6%), Mg (NO
3)
26H
2O, mass concentration are that 85% phosphoric acid, DPA (di-n-propylamine), deionized water are pressed Al
2O
3: MgO: P
2O
5: DPA: H
2O=5.709: 0.261: 7.817: 3.5: 25.199 ratio of weight and number stirs and makes gel, places microwave dissolver then, at 180 ℃ of following crystallization 3h, after filtration, washing, make behind dry 12h, 650 ℃ of following roasting 7h down in 110 ℃; The XRD spectra of products therefrom and SEM figure are referring to Figure 11 and 12.
The time that to flow out first product in the present embodiment is counted t=0 constantly, and every product of 1h collection, carry out quantitative analysis with gas-chromatography, calculate the transformation efficiency, 2 of naphthalene with area normalization method, the selectivity of 6-dimethylnaphthalene and other product selectivity, the reaction times be 4h the results are shown in Table 6.
Table 6
Claims (7)
1. the alkylated reaction of a MgAPO-11 molecular sieve catalytic naphthalene prepares the method for 2,6-dimethylnaphthalene, it is characterized in that it realizes according to the following steps:
One, 20～40 purpose MgAPO-11 molecular sieves are packed into the flat-temperature zone of stainless steel reaction pipe of fixed-bed micro-reactor, be that 550 ℃, nitrogen flow rate are to activate 2h under the condition of 10ml/min in temperature, be cooled to 350～450 ℃ then, and the MgAPO-11 molecular sieve after will activating places the beds of fixed-bed micro-reactor;
Two, the mol ratio 1 that naphthalene and alkylating reagent and solvent are pressed: (2～4): (6～12) are mixed and made into stock liquid, MgAPO-11 molecular sieve after the beds that stock liquid is injected fixed-bed micro-reactor continuously with volume pump and the activation carries out alkylated reaction then, and temperature of reaction is that 350～450 ℃, pressure are that 2～5MPa, mass space velocity are 0.5～2h
-1, nitrogen flow rate is 20～60ml/min, the reaction times is 4h, the alkylated reaction of namely finishing MgAPO-11 molecular sieve catalytic naphthalene prepares 2,6-dimethylnaphthalene; Wherein the molecular sieve of MgAPO-11 described in the step 1 is to adopt traditional electrical heating method or microwave heating method to synthesize.
2. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 1 prepares the method for 2,6-dimethylnaphthalene, and the magnesium source that it is characterized in that the molecular sieve of MgAPO-11 described in the step 1 is Mg (NO
3)
26H
2O or Mg (CH
3COO)
24H
2O.
3. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 1 and 2 prepares the method for 2,6-dimethylnaphthalene, it is characterized in that MgO and Al in the molecular sieve of MgAPO-11 described in the step 1
2O
3Mol ratio be (0.01～0.40): 1.
4. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 3 prepares the method for 2,6-dimethylnaphthalene, it is characterized in that alkylating reagent described in the step 2 is methyl alcohol.
5. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 4 prepares the method for 2,6-dimethylnaphthalene, it is characterized in that solvent described in the step 2 is 1,2,4-trimethylbenzene.
6. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 5 prepares the method for 2,6-dimethylnaphthalene, it is characterized in that naphthalene described in the step 2 and alkylating reagent and solvent by mol ratio 1: 3: 8.
7. the alkylated reaction of a kind of MgAPO-11 molecular sieve catalytic naphthalene according to claim 6 prepares the method for 2,6-dimethylnaphthalene, it is characterized in that temperature of reaction described in the step 2 is that 420 ℃, pressure are that 4MPa, mass space velocity are 1h
-1, nitrogen flow rate is 40ml/min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105268471A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Naphthalene alkylation catalyst preparation method |
| CN105294377A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Method for nathphalene alkylation |
| CN106831547A (en) * | 2017-01-04 | 2017-06-13 | 安徽国星生物化学有限公司 | A kind of method with the molecular sieves of MgAPO 41 as catalyst preparation pyridine |
| 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 |
| 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 |
| CN114289062A (en) * | 2021-11-10 | 2022-04-08 | 浙江恒逸石化研究院有限公司 | Alkaline synthesized aluminium phosphate molecular sieve alkylation catalyst and application thereof |
| CN114289062B (en) * | 2021-11-10 | 2024-05-14 | 浙江恒逸石化研究院有限公司 | Alkaline synthesized aluminum phosphate molecular sieve alkylation catalyst and application thereof |
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| CN102746101A (en) * | 2012-07-26 | 2012-10-24 | 黑龙江大学 | Method for preparing 2,6-dimethylnaphthalene by catalyzing naphthalene alkylation reaction with CoAPO-11 molecular sieve |
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| EP0249913A1 (en) * | 1986-06-16 | 1987-12-23 | Union Carbide Corporation | Selective production of para-aromatics |
| CN102746101A (en) * | 2012-07-26 | 2012-10-24 | 黑龙江大学 | Method for preparing 2,6-dimethylnaphthalene by catalyzing naphthalene alkylation reaction with CoAPO-11 molecular sieve |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105268471A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Naphthalene alkylation catalyst preparation method |
| CN105294377A (en) * | 2014-07-03 | 2016-02-03 | 中国石油化工股份有限公司 | Method for nathphalene alkylation |
| CN105268471B (en) * | 2014-07-03 | 2017-11-21 | 中国石油化工股份有限公司 | The preparation method of decalin base catalyst |
| 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 |
| CN106831547A (en) * | 2017-01-04 | 2017-06-13 | 安徽国星生物化学有限公司 | A kind of method with the molecular sieves of MgAPO 41 as catalyst preparation pyridine |
| CN106831547B (en) * | 2017-01-04 | 2019-04-12 | 安徽国星生物化学有限公司 | A method of using MgAPO-41 molecular sieve as catalyst preparation pyridine |
| 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 |
| CN114289062A (en) * | 2021-11-10 | 2022-04-08 | 浙江恒逸石化研究院有限公司 | Alkaline synthesized aluminium phosphate molecular sieve alkylation catalyst and application thereof |
| CN114289062B (en) * | 2021-11-10 | 2024-05-14 | 浙江恒逸石化研究院有限公司 | Alkaline synthesized aluminum phosphate molecular sieve alkylation catalyst and application thereof |
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