CN117185889B - Industrial production process for preparing diisopropylnaphthalene - Google Patents
Industrial production process for preparing diisopropylnaphthalene Download PDFInfo
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- 238000009776 industrial production Methods 0.000 title claims abstract description 11
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 51
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 44
- GWLLTEXUIOFAFE-UHFFFAOYSA-N 2,6-diisopropylnaphthalene Chemical compound C1=C(C(C)C)C=CC2=CC(C(C)C)=CC=C21 GWLLTEXUIOFAFE-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006482 condensation reaction Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 230000007062 hydrolysis Effects 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000008213 purified water Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 239000012043 crude product Substances 0.000 description 13
- YGDMAJYAQCDTNG-UHFFFAOYSA-N 2,7-di(propan-2-yl)naphthalene Chemical compound C1=CC(C(C)C)=CC2=CC(C(C)C)=CC=C21 YGDMAJYAQCDTNG-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- HMAMGXMFMCAOPV-UHFFFAOYSA-N 1-propylnaphthalene Chemical compound C1=CC=C2C(CCC)=CC=CC2=C1 HMAMGXMFMCAOPV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- MNIGYIKCFSPQRJ-UHFFFAOYSA-N N,N-bis(2-hydroxypropyl)nitrosamine Chemical compound CC(O)CN(N=O)CC(C)O MNIGYIKCFSPQRJ-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 dicarboxylic acid ester Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for preparing diisopropyl naphthalene by industrialized production, which comprises the steps of heat treatment, condensation reaction, hydrolysis reaction, rectification and the like of a catalyst, wherein naphthalene and propylene are used as raw materials, aluminum trichloride is used as the catalyst, and the process adopts a specific heating process to carry out AlCl treatment on the catalyst 3 The catalyst selectivity is obviously improved by pretreatment, and the content of 2, 6-diisopropylnaphthalene after rectification reaches more than 93 percent; the preparation method is optimized, and particularly the addition speed, stirring speed, reaction temperature, reaction molar ratio and the like of the gaseous propylene are optimized, so that the prepared byproducts are obviously reduced, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a preparation process of diisopropylnaphthalene
Background
The 2, 6-diisopropyl naphthalene (2, 6-DIPN) has the advantages of no color, no smell, low toxicity, low condensation point, strong dissolving capacity and the like, is mainly used in the production of carbonless copy paper, and can be used as a solvent of a leuco dye, insulating oil of a power capacitor, jet printing ink, a wood preservative, an organic heat carrier and the like. Meanwhile, further, 2,6-DIPN is a main intermediate for synthesizing 2, 6-naphthalene dicarboxylic acid (2, 6-NDCA), and the polynaphthalene dicarboxylic acid ester synthesized by taking 2,6-NDCA as a monomer can be prepared into ultrathin high-strength color films and video tapes, clothing fibers, electronic elements, containers for foods and beverages, and the performance of the container is far better than that of the container of the polynaphthalate.
Naphthalene is generally used to synthesize 2,6-DIPN by alkylation with propylene or isopropanol over a catalyst. Because eight different positions on the naphthalene ring may be substituted, other isomers may be formed at the same time as 2,6-DIPN. In addition, while DIPN is being produced, monopropylnaphthalene (MIPN) and triisopropylnaphthalene (PIPN) are also produced, and propylene itself can be polymerized to produce byproducts by using propylene as an alkylating agent.
Therefore, research on the preparation process of 2, 6-diisopropylnaphthalene is still needed, and a preparation process which has few byproducts and high 2,6-DIPN content and is suitable for industrial production is developed.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation process of 2, 6-diisopropylnaphthalene, which has few side effects and high content and is suitable for industrial production.
The preparation process of 2, 6-diisopropyl naphthalene suitable for industrial production comprises the following preparation reactions:
the method comprises the following steps:
(1) Heat treatment of the catalyst: catalyst AlCl 3 Heating at 70-80deg.C for 2-4 hr, heating to 90-100deg.C for 4-6 hr; heating to 120-130 deg.C for 8-10h for use.
(2) Condensation reaction: adding naphthalene into a reaction kettle, controlling the temperature to be 80-120 ℃, and adding a heat-treated catalyst AlCl 3 Stirring for 10-15min, replacing nitrogen for 2-5 times, controlling the stirring speed to 8-10 r/min, introducing gas propylene into the reaction kettle at a speed of 0.07-0.12% of the total propylene amount per minute for 9-11h, adjusting the stirring speed to 10-12 r/min, and introducing residual gas propylene into the reaction kettle at a speed of 0.18-0.22% of the total propylene amount per minute. Nitrogen is replaced for 1 to 3 times;
(3) Hydrolysis reaction: adding purified water for hydrolysis, controlling the kettle temperature at 40-60 ℃, keeping the temperature and stirring for 20-30min, standing and separating liquid, and taking an organic phase; adding sodium hydroxide solution, controlling the kettle temperature at 30-50deg.C, maintaining the temperature and stirring for 20-30min, standing for separating liquid, taking organic phase, and sampling the content of each component in the organic phase.
(4) And (3) rectifying: rectifying under normal pressure, and collecting 260-300 deg.C fraction.
In the step (1), heating is preferably performed at 70-80 ℃ for 3 hours, heating is performed at 90-100 ℃ for 5 hours, and heating is performed at 120-130 ℃ for 9 hours; more preferably, the heating is performed at 75℃for 3 hours, at 95℃for 5 hours, and at 130℃for 9 hours.
In the step (2), the catalyst AlCl 3 The weight ratio of the added amount of (2) to the added amount of naphthalene is (0.2-2): 100, preferably 1:100;
in the step (2), the molar ratio of the total amount of propylene to the addition amount of naphthalene is (1.85-1.91): 1, preferably 1.89:1.
in the step (2), the stirring speed is preferably controlled to be 8-10 r/min, and the gas propylene is introduced into the reaction kettle for 10h at a speed of 0.1% of the total propylene per minute.
In the step (2), the stirring rate is preferably adjusted to be controlled to be 10-12 r/min, and the residual gas propylene is introduced into the reaction kettle at a rate of 0.2% of the total propylene per minute.
In the step (3), the weight ratio of the adding amount of the purified water to the adding amount of the naphthalene is (5-20): 100, preferably (10-12): 100.
in the step (3), the sodium hydroxide solution is 10% -20% sodium hydroxide solution, preferably 15% sodium hydroxide solution.
In the step (3), the weight ratio of the adding amount of the sodium hydroxide solution to the adding amount of the naphthalene is (5-20): 100, preferably (10-12): 100.
in the step (4), the fraction at 280-300 ℃ is preferably collected.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts a specific heating process to carry out the reaction on the catalyst AlCl 3 The pretreatment is carried out, the selectivity of the catalyst is obviously improved, the content of 2, 6-diisopropylnaphthalene is obviously increased, the content of crude products reaches more than 85%, and the content of 2, 6-diisopropylnaphthalene reaches more than 93% after rectification.
(2) The preparation method is optimized, and particularly the addition speed, stirring speed, reaction temperature, reaction molar ratio and the like of the gaseous propylene are optimized, so that the prepared byproducts are obviously reduced, and the method is suitable for industrial production.
Detailed Description
The invention discloses a preparation process of 2, 6-diisopropyl naphthalene suitable for industrial production, and a person skilled in the art can refer to the content of the invention and combine the related principles of organic chemistry and chemical engineering principles to properly improve the process parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the scope of the present invention. While the invention has been described with reference to preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, or in appropriate changes and combinations, without departing from the spirit and scope of the invention.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Preparation example 1: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 3h, heating to 95deg.C for 5h, and heating to 130deg.C for 9h.
Preparation example 2: heat treatment of catalyst
Catalyst AlCl 3 Heating at 77 deg.C for 3 hr, heating to 96 deg.C for 5 hr, and heating to 132 deg.C for 9 hr.
Preparation example 3: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 2.5h, heating to 95deg.C for 5.5h, and heating to 130deg.C for 9h.
Preparation example 4: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 3h for use.
Preparation example 5: heat treatment of catalyst
Catalyst AlCl 3 Heating at 95deg.C for 5 hr.
Preparation example 6: heat treatment of catalyst
Catalyst AlCl 3 Heating at 130deg.C for 9h for use.
Preparation example 7: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 17h for use.
Preparation example 8: heat treatment of catalyst
Catalyst AlCl 3 Heating at 95deg.C for 17 hr.
Preparation example 9: heat treatment of catalyst
Catalyst AlCl 3 Heating at 130deg.C for 17h for use.
Preparation example 10: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 3h, and heating to 95deg.C for 5 h.
Preparation example 11: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 3h, and heating to 130deg.C for 9h.
Preparation example 12: heat treatment of catalyst
Catalyst AlCl 3 Heating at 95deg.C for 5h, and heating to 130deg.C for 9h.
Preparation example 13: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 1 hr, heating to 95deg.C for 7 hr, and heating to 130deg.C for 9 hr.
Preparation example 14: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 4h, heating to 95deg.C for 3h, and heating to 130deg.C for 10h.
Preparation example 15: heat treatment of catalyst
Catalyst AlCl 3 Heating at 75deg.C for 4h, heating to 95deg.C for 7h, and heating to 130deg.C for 6 h.
Examples 1 to 16: preparation process of 2, 6-diisopropylnaphthalene
1. Preparation process
(1) Condensation reaction: adding 5Kg (39.01 mol) of naphthalene into a reaction kettle, controlling the temperature to be 95-105 ℃, adding a heat-treated catalyst AlCl 3 50g (see Table 1), stirring for 5min, nitrogen substitution for 3 times, controlling the stirring rate to be 8-10 revolutions per minute, introducing gaseous propylene into the reaction kettle at a rate of 0.1% of the total propylene amount per minute (i.e. 3.1g propylene is added per minute) for 10h, adjusting the stirring rate to be 10-12 revolutions per minute, introducing residual gaseous propylene into the reaction kettle at a rate of 0.2% of the total propylene amount per minute (i.e. 6.2g propylene is added per minute), adding 3.1Kg (73.67 mol) of propylene, and nitrogen substitution for 1-3 times;
(2) Hydrolysis reaction: adding 550g of purified water for hydrolysis, controlling the kettle temperature at 48-52 ℃, preserving heat and stirring for 20-30min, standing and separating liquid, and taking an organic phase; 550g of 15% sodium hydroxide solution is added, the kettle temperature is controlled at 30-50 ℃, the temperature is kept and stirred for 20-30min, the mixture is kept stand and separated, and an organic phase is taken to obtain a crude product of 2, 6-diisopropylnaphthalene; the crude product was sampled and the content of each component was examined.
(3) And (3) rectifying: rectifying under normal pressure, and collecting 260-300 deg.C fraction.
Table 1: catalyst sheets used in examples 1 to 16
| Examples | The catalyst AlCl used 3 |
| Example 1 | AlCl prepared in preparation example 1 3 |
| Example 2 | AlCl prepared in preparation example 2 3 |
| Example 3 | Preparation example 3 AlCl 3 |
| Example 4 | AlCl prepared in preparation example 4 3 |
| Example 5 | Preparation example 5 AlCl 3 |
| Example 6 | Preparation example 6 preparationAlCl of (C) 3 |
| Example 7 | Preparation example 7 AlCl 3 |
| Example 8 | Preparation example 8 AlCl 3 |
| Example 9 | Preparation example 9 AlCl 3 |
| Example 10 | AlCl prepared in preparation example 10 3 |
| Example 11 | AlCl prepared in preparation example 11 3 |
| Example 12 | Preparation example 12 AlCl 3 |
| Example 13 | AlCl prepared in preparation example 13 3 |
| Example 14 | Preparation example 14 AlCl 3 |
| Example 15 | AlCl prepared in preparation example 15 3 |
| Example 16 | AlCl without heat treatment 3 |
2. Examples 1 to 16 test results
(1) The detection results of the crude 2, 6-diisopropylnaphthalene product obtained after hydrolysis are shown in Table 2.
Table 2: examples 1 to 16 sample detection results after hydrolysis
(2) The weight and content of the product obtained by the rectification are shown in Table 3.
Table 3: examples 1 to 16 weight and content of the products obtained by rectification
As can be seen from table 1: examples 1 to 16 differ only in the catalyst AlCl 3 Is different from the heat treatment method of (a).
As can be seen from table 2: the crude 2, 6-diisopropylnaphthalene product obtained in examples 1-16 was significantly different in 2, 6-diisopropylnaphthalene content.
As can be seen from table 3: the weight of the products obtained by rectification in examples 1-16 and the content of 2, 6-diisopropylnaphthalene in the products are significantly different.
(1) Examples 1-3 employ "heating at 70-80deg.C for 2-4h, heating to 90-100deg.C for 4-6h; heating to 120-130 deg.C for 8-10 hr (three-stage heating method for short) to obtain the catalyst AlCl 3 The selectivity of the reaction is greatly improved, the content of 2, 6-diisopropyl naphthalene in the crude product obtained after hydrolysis is not less than 82%, and the content of isomer 2, 7-diisopropyl naphthalene is less than 6%; the weight of the product obtained by rectification is not less than 6.1Kg, and the content of 2, 6-diisopropyl naphthalene in the product obtained by rectification is not less than 93 percent.
(2) Compared with the example 1, the three-stage heating method is adopted in the examples 13-15, the difference is only that the time of the heating treatment is different, the content of 2, 6-diisopropylnaphthalene in the crude product obtained after the hydrolysis is 72.2-73.1%, the content of the isomer 2, 7-diisopropylnaphthalene is 7.5-8.6%, and the method is obviously inferior to the example 1; the weight of the product obtained by rectification is 5.38-5.45Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 90.6-91.8 percent, which is obviously inferior to that of the example 1.
(3) Compared with the example 1, the examples 10-12 adopt a two-stage heating method, the content of 2, 6-diisopropyl naphthalene in the crude product obtained after hydrolysis is 66.5-70.2%, and the content of isomer 2, 7-diisopropyl naphthalene is 7.3-8.8%, which is obviously inferior to the example 1; the weight of the product obtained by rectification is 4.96-5.23Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 90.8-91.7 percent, which is obviously inferior to that of the example 1.
(4) Compared with the example 1, the examples 4-9 adopt a one-stage heating method, the content of 2, 6-diisopropyl naphthalene in the crude product obtained after hydrolysis is 57.5-66.7%, and the content of isomer 2, 7-diisopropyl naphthalene is 9.3-10.9%, which is obviously inferior to the example 1; the weight of the product obtained by rectification is 4.29-4.97Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 88.2% -89.8%, which is obviously inferior to that of example 1.
Examples 17 to 21: preparation process of 2, 6-diisopropylnaphthalene
1. Preparation method
(1) Heat treatment of the catalyst: the same as in preparation example 1.
(2) Condensation reaction: table 4.
(3) Hydrolysis reaction: as in example 1;
(4) And (3) rectifying: as in example 1;
table 4: step (2) condensation reaction procedure Table of examples 17-20
2. Examples 17 to 21 test results
(1) The results of the sample detection after hydrolysis are shown in Table 5.
Table 5: sample detection results after hydrolysis of examples 17-21
(2) The weight and content of the product obtained by the rectification are shown in Table 6.
Table 6: examples 17 to 21 weight and content of the product obtained by rectification
As can be seen from table 4: examples 17 to 21 differ from example 1 only in the rate and amount of addition of propylene in step (2).
As can be seen from table 5: the crude 2, 6-diisopropylnaphthalene product obtained in examples 17 to 21 was significantly different from example 1 in the content of 2, 6-diisopropylnaphthalene.
As can be seen from table 6: the weight of the product obtained by rectification in examples 17-21 compared with example 1, and the content of 2, 6-diisopropylnaphthalene in the product were significantly different.
(1) In the embodiment 1, the specific propylene adding speed is adopted, namely, the stirring speed is controlled to be 8-10 revolutions per minute, the gas propylene is introduced into the reaction kettle at the speed of 0.1 percent of the total propylene per minute (namely, 3.1g of propylene is added per minute), the stirring speed is adjusted to be 10-12 revolutions per minute, the residual gas propylene is introduced into the reaction kettle at the speed of 0.2 percent of the total propylene per minute (namely, 6.2g of propylene is added per minute), the reaction selectivity is greatly improved, the content of 2, 6-diisopropylnaphthalene in the crude product obtained after hydrolysis is 84.8 percent, and the content of the isomer 2, 7-diisopropylnaphthalene is 5.3 percent; the weight of the product obtained by rectification is 6.32Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 93.7 percent.
(2) Compared with example 1, the difference between examples 17-18 and examples 21-21 is only that the propylene addition rate is different, the content of 2, 6-diisopropylnaphthalene in the crude product obtained after hydrolysis is 76.2% -78.4%, and the content of isomer 2, 7-diisopropylnaphthalene is 7.1% -7.9%, which is significantly inferior to example 1; the weight of the product obtained by rectification is 5.68-5.84Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 91.2-91.9 percent, which is obviously inferior to that of the example 1.
(3) Example 19 differs from example 1 in that the total amount of propylene added is different, the total amount of propylene added in example 1 is 73.67mol, the amount of naphthalene added is 39.01mol, and the molar ratio of total amount of propylene to amount of naphthalene added is 1.89:1; example 19 the total amount of propylene added was 78.02mol, the amount of naphthalene added was 39.01mol, the molar ratio of total propylene to naphthalene added was 2:1, the 2, 6-diisopropylnaphthalene content in the crude product obtained after hydrolysis was 79.6%, the isomer 2, 7-diisopropylnaphthalene content was 6.9%, which is significantly inferior to example 1; the product obtained by rectification has a weight of 5.93Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 92.4%, which is significantly inferior to example 1.
Example 22: preparation process of 2, 6-diisopropylnaphthalene suitable for industrial production
1. Preparation method
(1) Heat treatment of the catalyst: the same as in preparation example 1.
(2) Condensation reaction: 500Kg (3901 mol) of naphthalene is added into a reaction kettle, the temperature is controlled to be 95-105 ℃, and a heat-treated catalyst AlCl is added 3 5Kg (see Table 1), stirring for 5min, nitrogen substitution for 3 times, controlling the stirring rate to be 8-10 revolutions per minute, introducing gaseous propylene into the reaction kettle at a rate of 0.1% of the total propylene amount per minute (i.e. 310g propylene is added per minute) for 10h, adjusting the stirring rate to be 10-12 revolutions per minute, introducing residual gaseous propylene into the reaction kettle at a rate of 0.2% of the total propylene amount per minute (i.e. 620g propylene is added per minute), adding 310Kg (7367 mol) of propylene, and nitrogen substitution for 1-3 times;
(3) Hydrolysis reaction: adding 5500g of purified water for hydrolysis, controlling the kettle temperature at 48-52 ℃, keeping the temperature and stirring for 20-30min, standing and separating liquid, and taking an organic phase; adding 5500g of 15% sodium hydroxide solution, controlling the kettle temperature at 30-50 ℃, keeping the temperature, stirring for 20-30min, standing, separating liquid, and taking an organic phase; obtaining a crude product of 2, 6-diisopropyl naphthalene; the crude product was sampled and the content of each component was examined. .
(4) And (3) rectifying: rectifying under normal pressure, and collecting fraction at 280-300 deg.C.
2. Test results
(1) The results of the sample detection after hydrolysis are shown in Table 7.
Table 7: example 22 sample detection results after hydrolysis
(2) The weight and content of the product obtained by the rectification are shown in Table 8.
Table 8: EXAMPLE 22 weight and content of the product obtained by rectification
Example 1 differs from example 22 in the amount of naphthalene fed, in example 1, 5Kg, 500Kg, in example 22, 2, 6-diisopropylnaphthalene content in the crude product obtained after hydrolysis of example 22, 85.2% and isomer 2, 7-diisopropylnaphthalene content, 5.1%, slightly better than example 1; the product obtained by rectification has a weight of 635.39Kg, and the content of 2, 6-diisopropylnaphthalene in the product obtained by rectification is 94.2% which is slightly better than that of example 1.
The results of example 22 show that the preparation process of 2, 6-diisopropylnaphthalene provided by the invention is suitable for industrial production.
Claims (10)
1. The preparation process of 2, 6-diisopropyl naphthalene suitable for industrial production comprises the following preparation reactions:
the method comprises the following steps:
(1) Heat treatment of the catalyst: catalyst AlCl 3 Heating at 70-80deg.C for 2-4 hr, heating to 90-100deg.C for 4-6 hr; heating to 120-130 ℃ for 8-10h for standby;
(2) Condensation reaction: into the reaction kettleAdding naphthalene, controlling the temperature to 80-120 ℃, adding a heat-treated catalyst AlCl 3 Stirring for 10-15min, replacing nitrogen for 2-5 times, controlling the stirring speed to be 8-10 revolutions per minute, introducing gas propylene into the reaction kettle at a speed of 0.07-0.12% of the total propylene per minute for 9-11h, adjusting the stirring speed to be 10-12 revolutions per minute, and introducing residual gas propylene into the reaction kettle at a speed of 0.18-0.22% of the total propylene per minute; nitrogen is replaced for 1 to 3 times;
(3) Hydrolysis reaction: adding purified water for hydrolysis, controlling the kettle temperature at 40-60 ℃, keeping the temperature and stirring for 20-30min, standing and separating liquid, and taking an organic phase; adding sodium hydroxide solution, controlling the kettle temperature at 30-50deg.C, maintaining the temperature and stirring for 20-30min, standing for separating liquid, and collecting organic phase;
(4) And (3) rectifying: rectifying under normal pressure, and collecting 260-300 deg.C fraction;
in the step (2), the catalyst AlCl 3 The weight ratio of the adding amount of (2) to the adding amount of naphthalene is 0.2-2:100;
in the step (2), the mol ratio of the total amount of propylene to the addition amount of naphthalene is 1.85-1.91:1.
2. The process according to claim 1, wherein in the step (1), the heating is performed at 75 ℃ for 3 hours, at 95 ℃ for 5 hours, at 130 ℃ for 9 hours.
3. The process of claim 1, wherein said catalyst AlCl 3 The weight ratio of the added amount of (2) to the added amount of naphthalene is 1:100.
4. The process of claim 1, wherein in step (2), the molar ratio of the total amount of propylene to the amount of naphthalene added is 1.89:1.
5. The preparation process according to claim 1, wherein in the step (2), the stirring speed is 8-10 rpm, and the gas propylene is introduced into the reaction kettle at a speed of 0.1% of the total amount of propylene per minute for 10 hours; the stirring rate is adjusted to be 10-12 r/min, and the residual gas propylene is introduced into the reaction kettle at a rate of 0.2% of the total propylene per minute.
6. The process according to claim 1, wherein in the step (3), the weight ratio of the amount of the purified water to the amount of naphthalene added is 5-20:100.
7. The process according to claim 5, wherein the weight ratio of the purified water to naphthalene is 10-12:100.
8. The process according to claim 1, wherein in the step (3), the sodium hydroxide solution is 10% -20% sodium hydroxide solution.
9. The process according to claim 1, wherein in the step (3), the weight ratio of the addition amount of the sodium hydroxide solution to the addition amount of naphthalene is 10-12:100.
10. The process according to claim 1, wherein in step (4), the fraction at 280-300 ℃ is collected.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02204419A (en) * | 1989-02-03 | 1990-08-14 | Agency Of Ind Science & Technol | Recovery of 2,6-diisopropylnaphthalene |
| JPH02209818A (en) * | 1989-02-03 | 1990-08-21 | Agency Of Ind Science & Technol | Method for concentrating and separating 2,6-diisopropylnaphthalene |
| EP0565821A2 (en) * | 1992-02-13 | 1993-10-20 | Idemitsu Petrochemical Co. Ltd. | Method of preparing 2,6-diisopropylnaphthalene |
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
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- 2023-08-25 CN CN202311081396.2A patent/CN117185889B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02204419A (en) * | 1989-02-03 | 1990-08-14 | Agency Of Ind Science & Technol | Recovery of 2,6-diisopropylnaphthalene |
| JPH02209818A (en) * | 1989-02-03 | 1990-08-21 | Agency Of Ind Science & Technol | Method for concentrating and separating 2,6-diisopropylnaphthalene |
| EP0565821A2 (en) * | 1992-02-13 | 1993-10-20 | Idemitsu Petrochemical Co. Ltd. | Method of preparing 2,6-diisopropylnaphthalene |
| CN101130478A (en) * | 2006-08-25 | 2008-02-27 | 北京石油化工学院 | Method for preparing high purity2, 6-diisopropyl naphthalene |
Non-Patent Citations (1)
| Title |
|---|
| 王志钢 ; 王金普 ; 吴朝阳 ; .固体酸催化剂催化合成二异丙基萘的研究.精细与专用化学品.2018,(07),43-48页. * |
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