CA2207526C - Process for preparing dialkylnaphthalene - Google Patents
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- CA2207526C CA2207526C CA002207526A CA2207526A CA2207526C CA 2207526 C CA2207526 C CA 2207526C CA 002207526 A CA002207526 A CA 002207526A CA 2207526 A CA2207526 A CA 2207526A CA 2207526 C CA2207526 C CA 2207526C
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- dialkylnaphthalene
- naphthalene
- dmn
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- dimethylnaphthalene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/20—Polycyclic condensed hydrocarbons
- C07C15/24—Polycyclic condensed hydrocarbons containing two rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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Abstract
A process for producing alkylnaphthalene from a feedstock comprising isomers of dialkylnaphthalene and naphthalene by contacting the feedstock with a catalyst composition, in which the process comprising transalkylation between isomers of dialkylnaphthalene and naphthalene to produce monoalkylnaphthalene, and isomerization of dialkylnaphthalene, wherein the catalyst composition comprising a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A of the specification.
Description
T~'TI~ ~lF :THE II!1~EPFf~~N ..
PROCESS FOR PREPARING DIALKYLNAPHTHALENE
<FI11 Q~ :'CIE vl~'I~1N
This invention relates to a process for preparing alkylnaphthalene, and particularly to a method for preparing 2,6-dimethylnaphthalene(DMN) from naphthalene with an alkylating agent by using catalysts in both transalkylation and isomerization of DMN, as well as in alkylation of monomethylnaphthalene(MMN). This process is hereinafter described specifically by the preparation of 2,6-DMN, however, this process can be extentable to any dialkYlnaphthalene.
~~t~ ~F T:~t~f~N
The compound 2,6-DMN is used as a precursor of 2,6-naphthalenedicarboxylic acid in the manufacture of polyethylenenaphthalate resins, because 2,6-D~1N is easily oxidized to 2,6-naphthalenedicarboxylic acid compared with other precursors such as 2,6-diisopropylnaphthalene or 2-methyl-6-isobutyrylnaphthalenes.
There are a lot of proposal concerning the process for preparing the 2,6-DMN.
U.S. Pat. No. 4,795,847 (~eitkamp et al.) describes a process for the preparation of 2,6-dialkylnaphthalene by alkylating naphthalene or 2-alkyl-naphthalene with an alkylating agent in the presence of a zeolite (specifically ZSbi-5) as a catalyst.
U. S. Pat. No. 5, 001, 295 (Angevine et al. ) describes a process for preparing DMN by using 2-MblN and naphthalene as a feedstock and a synthetic zeolite (MCM-22) as a catalyst, and it shows MCM-22 is more effective than ZS~1-5 in alkylation of 2-~lbiN and naphthalene.
However these conventional arts provide only unit operation for alkylation of 2-bIMN, which is an expensive feedstock and is not available in a large amount commercially. In addition, there is no description concerning how to use the DbiN mixture(2,6-poor-DMN) after separation of 2,6-DMN, and the productivity of 2,6-DbfN is not sufficient for mass production.
To increase the productivity of 2,6-DUN, it is preferrable to utilize and isomerize 2,6-poor-DMN to enrich 2,6-DMN in DMN isomers.
In order to utilize the 2,6-poor-DUN isomers effectively, Japanese Patent Laid-Open No.4-1142 shows a process to recycle the 2,6-poor-DMN isomers for isomerization, and combines transalkylation between the 2,6-poor-DUN isomers with naphthalene to produce UMN. Produced UMN is all~ylated with an alkylating agent to produce DMN.
This process consists of 5 steps (1) ~-(5) ;
(1) lst step (transalkylation and isomerization based on a modified ZSM-5 as a catalyst) - DUN + P(L, -~ yD~N
DMN filtrate -i 2,6-rich-DMN isomers (2) 2nd step (separation of the product of the 1st step into naphthalene, UMN
and Db~1 by distillation) (3) 3rd step (methylation of MUN using methylating agent to produce DMN) UUN + methyl unit -j DMN
PROCESS FOR PREPARING DIALKYLNAPHTHALENE
<FI11 Q~ :'CIE vl~'I~1N
This invention relates to a process for preparing alkylnaphthalene, and particularly to a method for preparing 2,6-dimethylnaphthalene(DMN) from naphthalene with an alkylating agent by using catalysts in both transalkylation and isomerization of DMN, as well as in alkylation of monomethylnaphthalene(MMN). This process is hereinafter described specifically by the preparation of 2,6-DMN, however, this process can be extentable to any dialkYlnaphthalene.
~~t~ ~F T:~t~f~N
The compound 2,6-DMN is used as a precursor of 2,6-naphthalenedicarboxylic acid in the manufacture of polyethylenenaphthalate resins, because 2,6-D~1N is easily oxidized to 2,6-naphthalenedicarboxylic acid compared with other precursors such as 2,6-diisopropylnaphthalene or 2-methyl-6-isobutyrylnaphthalenes.
There are a lot of proposal concerning the process for preparing the 2,6-DMN.
U.S. Pat. No. 4,795,847 (~eitkamp et al.) describes a process for the preparation of 2,6-dialkylnaphthalene by alkylating naphthalene or 2-alkyl-naphthalene with an alkylating agent in the presence of a zeolite (specifically ZSbi-5) as a catalyst.
U. S. Pat. No. 5, 001, 295 (Angevine et al. ) describes a process for preparing DMN by using 2-MblN and naphthalene as a feedstock and a synthetic zeolite (MCM-22) as a catalyst, and it shows MCM-22 is more effective than ZS~1-5 in alkylation of 2-~lbiN and naphthalene.
However these conventional arts provide only unit operation for alkylation of 2-bIMN, which is an expensive feedstock and is not available in a large amount commercially. In addition, there is no description concerning how to use the DbiN mixture(2,6-poor-DMN) after separation of 2,6-DMN, and the productivity of 2,6-DbfN is not sufficient for mass production.
To increase the productivity of 2,6-DUN, it is preferrable to utilize and isomerize 2,6-poor-DMN to enrich 2,6-DMN in DMN isomers.
In order to utilize the 2,6-poor-DUN isomers effectively, Japanese Patent Laid-Open No.4-1142 shows a process to recycle the 2,6-poor-DMN isomers for isomerization, and combines transalkylation between the 2,6-poor-DUN isomers with naphthalene to produce UMN. Produced UMN is all~ylated with an alkylating agent to produce DMN.
This process consists of 5 steps (1) ~-(5) ;
(1) lst step (transalkylation and isomerization based on a modified ZSM-5 as a catalyst) - DUN + P(L, -~ yD~N
DMN filtrate -i 2,6-rich-DMN isomers (2) 2nd step (separation of the product of the 1st step into naphthalene, UMN
and Db~1 by distillation) (3) 3rd step (methylation of MUN using methylating agent to produce DMN) UUN + methyl unit -j DMN
(4) 4th step (separation of the product of the 3rd step into MUN and DbiN by distillation (5) 5th step (separation of 2,6-DUN from the DUN mixture of the second step and the 4th step by cooling crystallization) According to the process, 2,6-poor-DMN isomers can be enriched to 2,6-DIN
at least to some extent. However yield of 2,6-DUN is still low.
The reasons of low yield of 2,6-DUN in the conventional process is considered to be based on the following two difficulties.
* difficulty of the effective isomerization Ten isomers of DUN can be categorized into the following four groups (i)~-(iv) .
(i) 1, 4-DbQY al, 3-DUN a2, 3-D1~1 (ii) 1, 5-DMN tal, 6-DMN tat, 6-DMN
(iii) 1, 8-DUN al, 7-DMN a2, 7-DMN
(iv) 1, 2-DUN
a s lea a a Isomerization within each groups is easily proceeded, however the isomerization beyond three groups is very difficult to be carried out.
Specifically, the polarity of the naphthalene molecule allows the methyl-transition between cz-position and (3 -position (e. g. 1,5-DUN H1,6-DMN), however transition between !3-position and !3-position (e.g. 2,6-DUN H
2,7-DUN) within the ring is not easily allowed. Therefore, isomerization of 2,6-poor-DUN isomers is not effective to enrich 2,6-DUN. In the above-mentioned Japanese Patent Laid-Open No. 4-1142, low catalyst performance in the transalkylation and the alkylation causes the low separation yield of 2,6-DUN from DMN isomers.
Therefore, it is very important to use a catalyst which has high selectivity of 2,6-DUN in isomerization.
*difficulty in separation of 2,6-DUN from DUN isomers Furthermore it is very difficult to separate 2,6-DMN from other isomers by conventional separation methods such as distillation or cooling crystallization owing to the presense of 2,7-DUN.
In distillation, 2,6-DUN and 2,7-DUN can not be separated from each other because the difference in boiling point between 2,6-DUN and 2,7-DMN is only 0. 3 °C .
As for the cooling crystallization, since 2,6-DUN and 2,7-DUN form an eutectic crystal at the weight ratio of 0.7(= 2,6- DUN / 2,7-DUN) only a Iow yield of 2,6-DUN is achieved. For example, according to the above-mentioned Japanese Patent Laid-Open No. 4-1142, the ratio of 2,6-DUN/2,7-DUN is 1Ø
Therefere, the yield of 2,6-DMN is not high.
Consequently it is very important to increase the ratio of 2,6-DMN/2,7-DMN
for a higher yeild of 2,6-DMN.
~J~tI~IAR~' 0~ 'I~~'LOP~;
The present invention has been made in view of the foregoing situation and it intends to provide a process for preparing useful alkylnahthalene such as 2,6-DMN at a high yield.
Provided herein is a process for producing alkylnaphthalene from a feedstock comprising isomers of dialkylnaphthalene and naphthalene by contacting said feedstock with a catalyst composition, said process consisting essentially of transalkylation between isomers of dialkylnaphthalene and naphthalene to produce monoalkylnaphthalene, and isomerization of dialkylnaphthalene, wherein said catalyst composition comprising a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A.
[Table A]
interplanar relative intensity d-spacing ( I/Io X 100 A
) 12.36 0.4 M-VS
11.03 0.2 M-S
8.83 0.14 M-VS
at least to some extent. However yield of 2,6-DUN is still low.
The reasons of low yield of 2,6-DUN in the conventional process is considered to be based on the following two difficulties.
* difficulty of the effective isomerization Ten isomers of DUN can be categorized into the following four groups (i)~-(iv) .
(i) 1, 4-DbQY al, 3-DUN a2, 3-D1~1 (ii) 1, 5-DMN tal, 6-DMN tat, 6-DMN
(iii) 1, 8-DUN al, 7-DMN a2, 7-DMN
(iv) 1, 2-DUN
a s lea a a Isomerization within each groups is easily proceeded, however the isomerization beyond three groups is very difficult to be carried out.
Specifically, the polarity of the naphthalene molecule allows the methyl-transition between cz-position and (3 -position (e. g. 1,5-DUN H1,6-DMN), however transition between !3-position and !3-position (e.g. 2,6-DUN H
2,7-DUN) within the ring is not easily allowed. Therefore, isomerization of 2,6-poor-DUN isomers is not effective to enrich 2,6-DUN. In the above-mentioned Japanese Patent Laid-Open No. 4-1142, low catalyst performance in the transalkylation and the alkylation causes the low separation yield of 2,6-DUN from DMN isomers.
Therefore, it is very important to use a catalyst which has high selectivity of 2,6-DUN in isomerization.
*difficulty in separation of 2,6-DUN from DUN isomers Furthermore it is very difficult to separate 2,6-DMN from other isomers by conventional separation methods such as distillation or cooling crystallization owing to the presense of 2,7-DUN.
In distillation, 2,6-DUN and 2,7-DUN can not be separated from each other because the difference in boiling point between 2,6-DUN and 2,7-DMN is only 0. 3 °C .
As for the cooling crystallization, since 2,6-DUN and 2,7-DUN form an eutectic crystal at the weight ratio of 0.7(= 2,6- DUN / 2,7-DUN) only a Iow yield of 2,6-DUN is achieved. For example, according to the above-mentioned Japanese Patent Laid-Open No. 4-1142, the ratio of 2,6-DUN/2,7-DUN is 1Ø
Therefere, the yield of 2,6-DMN is not high.
Consequently it is very important to increase the ratio of 2,6-DMN/2,7-DMN
for a higher yeild of 2,6-DMN.
~J~tI~IAR~' 0~ 'I~~'LOP~;
The present invention has been made in view of the foregoing situation and it intends to provide a process for preparing useful alkylnahthalene such as 2,6-DMN at a high yield.
Provided herein is a process for producing alkylnaphthalene from a feedstock comprising isomers of dialkylnaphthalene and naphthalene by contacting said feedstock with a catalyst composition, said process consisting essentially of transalkylation between isomers of dialkylnaphthalene and naphthalene to produce monoalkylnaphthalene, and isomerization of dialkylnaphthalene, wherein said catalyst composition comprising a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A.
[Table A]
interplanar relative intensity d-spacing ( I/Io X 100 A
) 12.36 0.4 M-VS
11.03 0.2 M-S
8.83 0.14 M-VS
6.18 0.12 M-VS
6.00 0.10 W-M
4. 06 0. W - S
3.91 0.07 M-VS
3. 42 0. V S
* The relative intensities are given in terms of the symbols;
W=weak, M=medium, S =strong, V S =very strong.
:.~:.::-.::..:..;.:.: -.-.;::..:. ::;..::.. ::::.
FIG.1 is a schematic diagram to show a preferable process of the present invention.
~ES~BI'If~Pf Q::'~~t~ ~~~I~ .
The present inventors have made earnest studies to increase the yield of 2, 6-DMN, and as a result, have accomplished the present invention based on the finding that the ratio of 2, 6-DMN/2, 7-DMN can be increased more than 1.2 by employing a particular catalyst in reaction such as alkylation, transalkylation and isomerization to enrich 2, 6-DMN in DMN isomers.
The particular catalyst is a zeolite which comprises a synthetic porous crystalline material characterized by an X-ray diffraction pattern including interplanar d-spacing can be set forth in the Table A.
The zeolite is known as MCM-22.
Conditions of transalkylation and isomerization in step I include a temperature of between about 0 to 500 °C, and preferable between 200 and 450 °C, and a pressure of between 0 to 250 atmospheres and preferably between 1 to 25 atmospheres. The mole ratio of naphthalene to DMN can be from about 10:1 to 1:10 and preferably can be from 5:1 to 1:5. The reaction is suitably accomplished utilizing a feed space velocity of between about 0.1 to 10.0 hr ~.
In the transalkylation and isomerization of the present invention, 2, 6-poor-DMN which contains less than 11 weight % of 2, 6-DMN in the isomers is preferred as isomers of DMN in the feedsock, more preferably content of 2, 6-DMN is less than 9 %.
As mentioned above, a high ratio of 2, 6-DMN / 2, 7- DMN is required to obtain high yield of 2, 6-DMN. According to the present invention, the ratio of '?, 6-DMN/ 2, 7-DMN can be more than 1.2 in step I and can be more than 1.1 in step III.
Further, the performance of catalyst in isomerization can be evaluated by a molar ratio of 2, 6-DMN content in total DMN after isomerization against 2, 6-DMN
content in total DMN before isomerization. According to the present invention, this ratio can be more than 1.5.
By the way, the ratio between 2-MMN and 1-MMN is desired to be as high as possible because higher 2-M MN l 1-MMN ration gives higher 2, 6-DMN yield at alkylation. Theoretically the ratio is said to be around 2.2, however, it is - SA -difficult to achieve such a high ratio in the conventional process. According to the present invention, the ratio can be more than 2.0 in the transalkylation and isomerization by using MGM-22.
The present invention also provides a process for producing DMN from a feedstock comprising MMN and an alkylating agent with the catalyst MCM-22, and MMN of the feedstock is the separated MMN of the product by the transalkylation and isomerization. In this alkylation, the molar ratio of 2,6-dialkylnaphthalene / 2,7-dialkylnaphthalene of the alkylated product can be more than 1.1.
Furthermore, the present invention provides a process for producing 2,6-DMN from a feedstock comprising isomers of DMN and naphthalene by contacting the feedstock with the catalyst MCM-22, comprising step I [step for transalkylation between isomers of DMN and naphthalene to produce MI~1, and isomerization of DbQV] , step II [step for separation of the product in said step I into naphthalene, bIb0~1 , DMN and other components] , step III [step for alkylation of MMN fraction from step II using alkylating agent to produce DMN], step IV [step for separation of the product in said step III into MMN and DMN] , step V [step for separation of 2,6-DMN from mixture of DbIN fraction in said step II and said step IV].
In this process, as illustrated in Fig. 1, naphthalene fraction in step II is recycled to step I, blMN fraction in step IU is recycled to step III, DMN fraction after 2,6-DMN is separated therefrom in step V is recycled to step I.
As a method for separation of step II or step IV, distillation can be employed. To make this system simpler, step II and step IU can be combined as a single step by recycling the product of step III to step II.
As for separation of step U, any method for separation of isomers such as cooling crystallization or adsorption can be used. However, to obtain high yield of 2,6-DMN, High Pressure Crystallization is preferable.
Preferred alkylating agents include alcohols, olefins, aldelZydes, halides, and ethers, such as methanol, dimethylether, polyalkylbenzene. Especially preferred is methanol.
The alkylation can be carried out in any of the known reactors usually employed for alkYlation. For example, a tubular reactor with a downflow of reactants over a fixed bed of catalyst can be employed.
The present invention will now be explained refering to examles.
Example 1 (transalkylation and isomerization) 30 grams of blCbl-22 (1/4"D x 3/8"L, cylindrical pellet) are charged in a tubular reactor (volume: 122cc). The reactor was heated from room temperature to 400°C at the rate of 100 °C /hr over introducing nitrogen gas into the reactor at atmospheric pressure.
As a feedstock for transalkylation and isomerization, isomers of DMN and naphthalene were used for mixing DMN and naphthalene by l:l at molar ratio. ~feight % of isomers of DMN is shown in Table 1.
[ T a b 1 a 1 ] (feedstock) component weight %
dimethylnaphthalene9 9 . 7 0 2, 6-DMN 6.21 2, 7-DMN 8.63 other isomers 84.86 monomett~ylnaphthalene0 . 3 0 2-MMN 0.17 1 -MMN 0.13 The feedstock was introduced into the reactor at the rate of 30g/hr for 8 hours, and obtained product was analyzed by gas chromatography. The result of the product is shown in Table 2 with the component of the reactant.
[ T a b 1 a 2 ] (transalkvlation and isomerization) component before after (wt reaction reaction %) * dimethylnaphthalene 5 1 9 3 4 1 3. 9.
2, 6-DMN 3.30 6.65 2, 7-DMN 4.59 4.59 other isomers 45.30 28.17 * monomethylnaphthalene 0. 1 0 1 5 9 7.
2 - MM N 0. 12.16 1 - M M N 0. 5.
* naphthalene 4 7 1 3 1 5 6 8.
.
* other component 0 4. 8 5 evaluation beforereaction afterreaction 2, 6 2 ---DI 1 9 ---~2 6-Db~N . 6 / .
total DMN
(%) 2, 0 7 2 1 4 5 6-DbIN . .
/
Z, 7-DbIN
content - 2 7 3 of .
2, (after/before) :
_@
conversion 8.
(%) conversion 5.
(%) produced - 0 7 0 bIMN .
/
(converted DMN
x 2) :
_@
2-MMI~1 - 2 2 3 / .
I-b4a~1 (note) @ 1 in the table means a ratio of 02 / 10 in 2,6-DMN / total DMN.
2 is calculated on molar basis.
As can be seen from Table 2, the ratio of 2,6-DMN / 2,7-DMN is over 1.2 and the ratio of 2-b~~N/_ 1-b4~ is over 2. 0.
Example 2 (transalkylation and isomerization) The same experiment with Example 1 except the molar ratio between DMN and naphthalene is 5:1 was carried out. The result of the product is shown in Table 3 with the component of the reactant.
6.00 0.10 W-M
4. 06 0. W - S
3.91 0.07 M-VS
3. 42 0. V S
* The relative intensities are given in terms of the symbols;
W=weak, M=medium, S =strong, V S =very strong.
:.~:.::-.::..:..;.:.: -.-.;::..:. ::;..::.. ::::.
FIG.1 is a schematic diagram to show a preferable process of the present invention.
~ES~BI'If~Pf Q::'~~t~ ~~~I~ .
The present inventors have made earnest studies to increase the yield of 2, 6-DMN, and as a result, have accomplished the present invention based on the finding that the ratio of 2, 6-DMN/2, 7-DMN can be increased more than 1.2 by employing a particular catalyst in reaction such as alkylation, transalkylation and isomerization to enrich 2, 6-DMN in DMN isomers.
The particular catalyst is a zeolite which comprises a synthetic porous crystalline material characterized by an X-ray diffraction pattern including interplanar d-spacing can be set forth in the Table A.
The zeolite is known as MCM-22.
Conditions of transalkylation and isomerization in step I include a temperature of between about 0 to 500 °C, and preferable between 200 and 450 °C, and a pressure of between 0 to 250 atmospheres and preferably between 1 to 25 atmospheres. The mole ratio of naphthalene to DMN can be from about 10:1 to 1:10 and preferably can be from 5:1 to 1:5. The reaction is suitably accomplished utilizing a feed space velocity of between about 0.1 to 10.0 hr ~.
In the transalkylation and isomerization of the present invention, 2, 6-poor-DMN which contains less than 11 weight % of 2, 6-DMN in the isomers is preferred as isomers of DMN in the feedsock, more preferably content of 2, 6-DMN is less than 9 %.
As mentioned above, a high ratio of 2, 6-DMN / 2, 7- DMN is required to obtain high yield of 2, 6-DMN. According to the present invention, the ratio of '?, 6-DMN/ 2, 7-DMN can be more than 1.2 in step I and can be more than 1.1 in step III.
Further, the performance of catalyst in isomerization can be evaluated by a molar ratio of 2, 6-DMN content in total DMN after isomerization against 2, 6-DMN
content in total DMN before isomerization. According to the present invention, this ratio can be more than 1.5.
By the way, the ratio between 2-MMN and 1-MMN is desired to be as high as possible because higher 2-M MN l 1-MMN ration gives higher 2, 6-DMN yield at alkylation. Theoretically the ratio is said to be around 2.2, however, it is - SA -difficult to achieve such a high ratio in the conventional process. According to the present invention, the ratio can be more than 2.0 in the transalkylation and isomerization by using MGM-22.
The present invention also provides a process for producing DMN from a feedstock comprising MMN and an alkylating agent with the catalyst MCM-22, and MMN of the feedstock is the separated MMN of the product by the transalkylation and isomerization. In this alkylation, the molar ratio of 2,6-dialkylnaphthalene / 2,7-dialkylnaphthalene of the alkylated product can be more than 1.1.
Furthermore, the present invention provides a process for producing 2,6-DMN from a feedstock comprising isomers of DMN and naphthalene by contacting the feedstock with the catalyst MCM-22, comprising step I [step for transalkylation between isomers of DMN and naphthalene to produce MI~1, and isomerization of DbQV] , step II [step for separation of the product in said step I into naphthalene, bIb0~1 , DMN and other components] , step III [step for alkylation of MMN fraction from step II using alkylating agent to produce DMN], step IV [step for separation of the product in said step III into MMN and DMN] , step V [step for separation of 2,6-DMN from mixture of DbIN fraction in said step II and said step IV].
In this process, as illustrated in Fig. 1, naphthalene fraction in step II is recycled to step I, blMN fraction in step IU is recycled to step III, DMN fraction after 2,6-DMN is separated therefrom in step V is recycled to step I.
As a method for separation of step II or step IV, distillation can be employed. To make this system simpler, step II and step IU can be combined as a single step by recycling the product of step III to step II.
As for separation of step U, any method for separation of isomers such as cooling crystallization or adsorption can be used. However, to obtain high yield of 2,6-DMN, High Pressure Crystallization is preferable.
Preferred alkylating agents include alcohols, olefins, aldelZydes, halides, and ethers, such as methanol, dimethylether, polyalkylbenzene. Especially preferred is methanol.
The alkylation can be carried out in any of the known reactors usually employed for alkYlation. For example, a tubular reactor with a downflow of reactants over a fixed bed of catalyst can be employed.
The present invention will now be explained refering to examles.
Example 1 (transalkylation and isomerization) 30 grams of blCbl-22 (1/4"D x 3/8"L, cylindrical pellet) are charged in a tubular reactor (volume: 122cc). The reactor was heated from room temperature to 400°C at the rate of 100 °C /hr over introducing nitrogen gas into the reactor at atmospheric pressure.
As a feedstock for transalkylation and isomerization, isomers of DMN and naphthalene were used for mixing DMN and naphthalene by l:l at molar ratio. ~feight % of isomers of DMN is shown in Table 1.
[ T a b 1 a 1 ] (feedstock) component weight %
dimethylnaphthalene9 9 . 7 0 2, 6-DMN 6.21 2, 7-DMN 8.63 other isomers 84.86 monomett~ylnaphthalene0 . 3 0 2-MMN 0.17 1 -MMN 0.13 The feedstock was introduced into the reactor at the rate of 30g/hr for 8 hours, and obtained product was analyzed by gas chromatography. The result of the product is shown in Table 2 with the component of the reactant.
[ T a b 1 a 2 ] (transalkvlation and isomerization) component before after (wt reaction reaction %) * dimethylnaphthalene 5 1 9 3 4 1 3. 9.
2, 6-DMN 3.30 6.65 2, 7-DMN 4.59 4.59 other isomers 45.30 28.17 * monomethylnaphthalene 0. 1 0 1 5 9 7.
2 - MM N 0. 12.16 1 - M M N 0. 5.
* naphthalene 4 7 1 3 1 5 6 8.
.
* other component 0 4. 8 5 evaluation beforereaction afterreaction 2, 6 2 ---DI 1 9 ---~2 6-Db~N . 6 / .
total DMN
(%) 2, 0 7 2 1 4 5 6-DbIN . .
/
Z, 7-DbIN
content - 2 7 3 of .
2, (after/before) :
_@
conversion 8.
(%) conversion 5.
(%) produced - 0 7 0 bIMN .
/
(converted DMN
x 2) :
_@
2-MMI~1 - 2 2 3 / .
I-b4a~1 (note) @ 1 in the table means a ratio of 02 / 10 in 2,6-DMN / total DMN.
2 is calculated on molar basis.
As can be seen from Table 2, the ratio of 2,6-DMN / 2,7-DMN is over 1.2 and the ratio of 2-b~~N/_ 1-b4~ is over 2. 0.
Example 2 (transalkylation and isomerization) The same experiment with Example 1 except the molar ratio between DMN and naphthalene is 5:1 was carried out. The result of the product is shown in Table 3 with the component of the reactant.
[ T a b 1 a 3 ] (transalkylation and isomerization) component before after (wt reaction reaction %) * dimethylnaphthalene 8 3 6 91 4. 7 5.
2, 6-DMN 5.22 11.39 2, 7-DMN 7.28 7.42 other isomers 71.87 47.10 * monomethylnaphthalene 0. 1 1 81 7 3.
2 -MMN 0.02 9.54 1 -MMN 0.15 4.27 * naphthalene 1 4 1 65 5. 6 2.
* other component 0 7. 63 evaluation beforereaction afterreaction 2, 6 2 1 3 -6-DMN . ---~l 7 / .
total DMN
(%) 2, 0 7 1 53 6-DMN . 2 .
/
2, content - 2 7g of .
2, 6-DIllY
(after/before) :
@
conversion 8.
(%) DbtN - 2 9 conversion 1 (%) .
produced - 0 41 bD~1 .
/
(converted DMN
x 2) :
_~
2-bfl~N/ - 2 23 1-bI~IN .
(note) C~ 1 in the table means a ratio of 2~/ 1~ in 2, 6-D~(N / total DMN.
2 is calculated on molar basis.
As can be seen from Table 3, the ratio of 2,6-D~1N / 2,7-DMN is over 1.2 and the ratio of 2-M1IN/ 1-MbIN is over 2Ø
Example 3 (allLylation) 153 grams of biCbl-22 were charged in the tubular reactor(volume:370cc).
As a feedstock for all~ylation, 1-blblN (purity 95.5%) and 2-~I (purity 96.6%) were used, and mixed at the molar ratio of 2.2 of 2-~MN/1-MblN. Feedstock was supplied in the reactor (350°C) at the rate of 76.7g/hr for 4 hours.
Thereafter, methanol was started to be supplied in the reactor at the rate of 17.3g/hr and the reaction was proceeded for 20 hours. The obtained product was analyzed by gas chromatography, and the result is summarized in Table 4.
g [ T a b 1 a 4 ] (alI~,vlation) component before after (wt reaction reaction ~) * dimethylnaphthalene 0 3 45 5.
2, 6-DMN 0 5.12 2, 7-DMN 0 4.44 other isomers 0 25.89 * monomethylnaphthalene 9 6 6 4 16 8 1.
.
2 - M M N 67. 61 28.
1 -MvIN 31.05 12.32 * naphthalene 0 0. 19 * other component 1 5 3 2 20 . 3.
evaluation beforereaction afterreaction 2-1~(/ 2 2 1-MbQV .
conversion 8 (~) .
2, - 1 45 6-D1~1 4 / .
total DbllV
(~) 2, - 1 16 6-Db4Y .
/
2, As can be seen from Table 4, the ratio of 2,6-DMN / 2,7-DbIN is over 1.1 and the ratio of 2-MN1V/ 1-~f is over 2Ø
Example 4 (alkylation) 153 grams of MCbt-22 were charged in the tubular reactor(volume:370cc).
The same feedstock as in Example 3 was used. Feedstock was supplied in the reactor(400 °C) at the. rate of 153.4 g/hr for 4 hours. Thereafter, methanol was started to be supplied in the reactor at the rate of 17.3g/hr and the reaction proceeded for 20 hours. The obtained product was analyzed by gas chromatography, and the result is summarized in Table 5.
[ T a b 1 a 5 ] (alkylation) component before after (wt reaction reaction %) * dimethylnaphthalene 0 5. 0 2, 6-DMN 0 0.52 2, 7-DMN 0 0.37 other isomers 0 4.16 * monomethylnaphthalene 9 6 6 8 9. 0 .
2 - M M N 67. 61 59.
1 -MMN 31.05 29.17 * naphthalene 0 0 * other component 1 5 3 g, g . 3 evaluation beforereaction after reaction 2-b~b(N/ 2 2 2 . 1 1-btMN .
MN - g , 7 conversion 8 (~) 2, - 1 0 3 6-Db~V . 7 /
total Db~V
(%) 2, - 1 . 4 /
2, As can be seen from Table 5, the ratio of 2,6-DbIN / 2,7-DbIN is over 1.1 and the ratio of 2-MMN/ I-b~MN is over 2Ø
Example 5 (separation) (1) high pressure crystallization 2,636 grams of D11N isomers were supplied into the high pressure crystallizer (KOBELCO 3L type), and separated 396 grams of 2,6-DMN crystals (purity 92%) at the condition of 2000 kgf/cm2 and 45°C.
(2) cooling crystallization Using vessel for crystallization (3 litter), 1,980g of DMN isomers was cooled quickly from 50°C to 40°C over stirring slowly. Then, 0.5 grams of seed crystal was charged and kept the temperature at 40°C for an hour.
Thereupon, the feedstock was cooled to 10 °C at 2 °C /min.
29.7 grams of 2,6-DMN crystals (purity 80%) was separated by filtration under pressure.
The results of separation by both of high pressure crystallization and cooling crystallization were summarized in Table 6.
[ T a b 1 a 6 ] (separation) HIGH
PRESSURE
CRYSTALLIZATION
component before (grams) crystallization crystal filtrate 2 , 6 - D M 528 364 164 N
2, 7 - D M 405 32 373 N
other D M N 1, 703 0 1, 703 T 0 T A L 2,636 396 2,240 2, 1 . 3 0. 4 /
2, 2,6-DMN 2 0. 0 7. 3 /
total DuN
purity - 9 2 i6 -of crystal recovery - 6 9 i6 -of 2,6-DMN
yield - 13. 8i6 -of 2, COOLING
CRYSTALLIZATION
component before reaction (grams) crystallization crystal filtrate 2 , 6 - D M 396 237.6 158.4 N
2 , 7 - D M 305 59. 4 245. 6 N
other D M N 1,286 1,286 T 0 T A L 1,987 297 1,690 2, 1 . 3 0 . 6 6-DbIN
/
2, 7-DbIN
2, 1 9 . 9 9 . 4 /
total Db~1 purity - 8 0 rb -of crystal recovery - 6 0 36 -of 2,6-DMN
yield - 11. 9% -of 2, ~
(note) - "recovery of 2,6-DMN" means the rate of 2,6-DMN content in crystal against of 2, 6-DbIN content in feedstock.
"yield of 2,6-DMN" means the rate of 2,6-DMN content in crystal against of total weight of feedstock.
As shown in Table 6, yield of 2,6-DMN by high pressure crystallization is much higher than by cooling crystallizaiton. Further, 2,6-DMN / total-DMN of the filtrate by high pressure crystallization is less than 8~. Therefore, the filtrate is more effective as a feedstock for trasalkylation and isomerization of 2,6-poor-DMN. Furthermore, when the purity of crystal was tried to increase in cooling crystallization, the yield of 2,6-DMN was lowered drastically.
As described above, according to the present invention, the yield of 2,6-DMN can be increased compared with conventional processes. An obtained 2,6-DMN can be used in a process of preparing a polyethylenenaphthalate polymer by steps of oxidizing 2,6-DbIN to form 2,6-naphthalene-dicarboxylic acid, or oxidising and esterifying 2,6-DMN to form ester of 2,6-naphthalene-dicarboxylic acid, and condensing said 2,6-naphthalene-dicarboxylic acid or ester thereof with ethyleneglycol to form the polyethylenenaphthalate polymer.
2, 6-DMN 5.22 11.39 2, 7-DMN 7.28 7.42 other isomers 71.87 47.10 * monomethylnaphthalene 0. 1 1 81 7 3.
2 -MMN 0.02 9.54 1 -MMN 0.15 4.27 * naphthalene 1 4 1 65 5. 6 2.
* other component 0 7. 63 evaluation beforereaction afterreaction 2, 6 2 1 3 -6-DMN . ---~l 7 / .
total DMN
(%) 2, 0 7 1 53 6-DMN . 2 .
/
2, content - 2 7g of .
2, 6-DIllY
(after/before) :
@
conversion 8.
(%) DbtN - 2 9 conversion 1 (%) .
produced - 0 41 bD~1 .
/
(converted DMN
x 2) :
_~
2-bfl~N/ - 2 23 1-bI~IN .
(note) C~ 1 in the table means a ratio of 2~/ 1~ in 2, 6-D~(N / total DMN.
2 is calculated on molar basis.
As can be seen from Table 3, the ratio of 2,6-D~1N / 2,7-DMN is over 1.2 and the ratio of 2-M1IN/ 1-MbIN is over 2Ø
Example 3 (allLylation) 153 grams of biCbl-22 were charged in the tubular reactor(volume:370cc).
As a feedstock for all~ylation, 1-blblN (purity 95.5%) and 2-~I (purity 96.6%) were used, and mixed at the molar ratio of 2.2 of 2-~MN/1-MblN. Feedstock was supplied in the reactor (350°C) at the rate of 76.7g/hr for 4 hours.
Thereafter, methanol was started to be supplied in the reactor at the rate of 17.3g/hr and the reaction was proceeded for 20 hours. The obtained product was analyzed by gas chromatography, and the result is summarized in Table 4.
g [ T a b 1 a 4 ] (alI~,vlation) component before after (wt reaction reaction ~) * dimethylnaphthalene 0 3 45 5.
2, 6-DMN 0 5.12 2, 7-DMN 0 4.44 other isomers 0 25.89 * monomethylnaphthalene 9 6 6 4 16 8 1.
.
2 - M M N 67. 61 28.
1 -MvIN 31.05 12.32 * naphthalene 0 0. 19 * other component 1 5 3 2 20 . 3.
evaluation beforereaction afterreaction 2-1~(/ 2 2 1-MbQV .
conversion 8 (~) .
2, - 1 45 6-D1~1 4 / .
total DbllV
(~) 2, - 1 16 6-Db4Y .
/
2, As can be seen from Table 4, the ratio of 2,6-DMN / 2,7-DbIN is over 1.1 and the ratio of 2-MN1V/ 1-~f is over 2Ø
Example 4 (alkylation) 153 grams of MCbt-22 were charged in the tubular reactor(volume:370cc).
The same feedstock as in Example 3 was used. Feedstock was supplied in the reactor(400 °C) at the. rate of 153.4 g/hr for 4 hours. Thereafter, methanol was started to be supplied in the reactor at the rate of 17.3g/hr and the reaction proceeded for 20 hours. The obtained product was analyzed by gas chromatography, and the result is summarized in Table 5.
[ T a b 1 a 5 ] (alkylation) component before after (wt reaction reaction %) * dimethylnaphthalene 0 5. 0 2, 6-DMN 0 0.52 2, 7-DMN 0 0.37 other isomers 0 4.16 * monomethylnaphthalene 9 6 6 8 9. 0 .
2 - M M N 67. 61 59.
1 -MMN 31.05 29.17 * naphthalene 0 0 * other component 1 5 3 g, g . 3 evaluation beforereaction after reaction 2-b~b(N/ 2 2 2 . 1 1-btMN .
MN - g , 7 conversion 8 (~) 2, - 1 0 3 6-Db~V . 7 /
total Db~V
(%) 2, - 1 . 4 /
2, As can be seen from Table 5, the ratio of 2,6-DbIN / 2,7-DbIN is over 1.1 and the ratio of 2-MMN/ I-b~MN is over 2Ø
Example 5 (separation) (1) high pressure crystallization 2,636 grams of D11N isomers were supplied into the high pressure crystallizer (KOBELCO 3L type), and separated 396 grams of 2,6-DMN crystals (purity 92%) at the condition of 2000 kgf/cm2 and 45°C.
(2) cooling crystallization Using vessel for crystallization (3 litter), 1,980g of DMN isomers was cooled quickly from 50°C to 40°C over stirring slowly. Then, 0.5 grams of seed crystal was charged and kept the temperature at 40°C for an hour.
Thereupon, the feedstock was cooled to 10 °C at 2 °C /min.
29.7 grams of 2,6-DMN crystals (purity 80%) was separated by filtration under pressure.
The results of separation by both of high pressure crystallization and cooling crystallization were summarized in Table 6.
[ T a b 1 a 6 ] (separation) HIGH
PRESSURE
CRYSTALLIZATION
component before (grams) crystallization crystal filtrate 2 , 6 - D M 528 364 164 N
2, 7 - D M 405 32 373 N
other D M N 1, 703 0 1, 703 T 0 T A L 2,636 396 2,240 2, 1 . 3 0. 4 /
2, 2,6-DMN 2 0. 0 7. 3 /
total DuN
purity - 9 2 i6 -of crystal recovery - 6 9 i6 -of 2,6-DMN
yield - 13. 8i6 -of 2, COOLING
CRYSTALLIZATION
component before reaction (grams) crystallization crystal filtrate 2 , 6 - D M 396 237.6 158.4 N
2 , 7 - D M 305 59. 4 245. 6 N
other D M N 1,286 1,286 T 0 T A L 1,987 297 1,690 2, 1 . 3 0 . 6 6-DbIN
/
2, 7-DbIN
2, 1 9 . 9 9 . 4 /
total Db~1 purity - 8 0 rb -of crystal recovery - 6 0 36 -of 2,6-DMN
yield - 11. 9% -of 2, ~
(note) - "recovery of 2,6-DMN" means the rate of 2,6-DMN content in crystal against of 2, 6-DbIN content in feedstock.
"yield of 2,6-DMN" means the rate of 2,6-DMN content in crystal against of total weight of feedstock.
As shown in Table 6, yield of 2,6-DMN by high pressure crystallization is much higher than by cooling crystallizaiton. Further, 2,6-DMN / total-DMN of the filtrate by high pressure crystallization is less than 8~. Therefore, the filtrate is more effective as a feedstock for trasalkylation and isomerization of 2,6-poor-DMN. Furthermore, when the purity of crystal was tried to increase in cooling crystallization, the yield of 2,6-DMN was lowered drastically.
As described above, according to the present invention, the yield of 2,6-DMN can be increased compared with conventional processes. An obtained 2,6-DMN can be used in a process of preparing a polyethylenenaphthalate polymer by steps of oxidizing 2,6-DbIN to form 2,6-naphthalene-dicarboxylic acid, or oxidising and esterifying 2,6-DMN to form ester of 2,6-naphthalene-dicarboxylic acid, and condensing said 2,6-naphthalene-dicarboxylic acid or ester thereof with ethyleneglycol to form the polyethylenenaphthalate polymer.
Claims (12)
1. A process for producing alkylnaphthalene from a feedstock comprising isomers of dialkylnaphthalene and naphthalene by contacting the feedstock with a catalyst composition, the process comprising:
I. transalkylating between the isomers of the dialkylnaphthalene and the naphthalene to produce monoalkylnaphthalene, and isomerizing the isomers of the dialkynaphthalene, wherein the catalyst composition comprises a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A
Table A
Interplanar d-spacing(.ANG.) relative intensity I/I0 X100 12.36~0.4 M-VS
11.03~0.2 M-S
8.83~0.14 M-VS
6.18~0.12 M-VS
6.00~0.10 W-M
4.061~0.07 W-S
3.91~0.0 7 M-V S
3.42~0.06 VS
wherein the relative intensities are given in terms of the symbols;
W = weak, M = medium, S = strong, VS = very strong.
I. transalkylating between the isomers of the dialkylnaphthalene and the naphthalene to produce monoalkylnaphthalene, and isomerizing the isomers of the dialkynaphthalene, wherein the catalyst composition comprises a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A
Table A
Interplanar d-spacing(.ANG.) relative intensity I/I0 X100 12.36~0.4 M-VS
11.03~0.2 M-S
8.83~0.14 M-VS
6.18~0.12 M-VS
6.00~0.10 W-M
4.061~0.07 W-S
3.91~0.0 7 M-V S
3.42~0.06 VS
wherein the relative intensities are given in terms of the symbols;
W = weak, M = medium, S = strong, VS = very strong.
2. The process of claim 1 wherein the isomers of the dialkylnaphthalene contain less than 11 weight % of 2,6-dialkylnaphthalene.
3. The process of claim 1 or 2 wherein the monoalkylnaphthalene is produced at a molar ratio of 2-monoalkylnaphthalene /
monoalkylnaphthalene of more than 2Ø
monoalkylnaphthalene of more than 2Ø
4. The process of claim 1 or 2 wherein resulting product includes 2,6-dialkylnapthalene and 2,7-dialkylanphthalene at a molar ratio of 2,6-dialkylnaphthalene /
2,7-dialkylnaphthalene of more than 1.2.
2,7-dialkylnaphthalene of more than 1.2.
5. The process of claim l or 2 wherein the isomers of dialkylnaphthalene include 2,6-dialkylnaphthalene and wherein a molar ratio of 2,6-dialkylnaphthalene after isomerization / the 2,6-dialkylnaphthalene before isomerization is more than 1.5.
6. The process of claim 1 or 2 further comprising the steps of;
II. separating the product of the step t into fractions of naphthalene, monoalkylnaphthalene and dialkylnaphthalene; and III. contacting the fraction of the monoalkylnaphthalene with an alkylating agent and the catalyst composition to produce an alkylate containing 2,6-dialkylnaphthalene.
II. separating the product of the step t into fractions of naphthalene, monoalkylnaphthalene and dialkylnaphthalene; and III. contacting the fraction of the monoalkylnaphthalene with an alkylating agent and the catalyst composition to produce an alkylate containing 2,6-dialkylnaphthalene.
7. The process of claim 6 wherein the alkylate further contains 2,7-dialkylnaphthalene and has a molar ratio of the 2,6-dialkylnaphthalene / the 2,7-dialkylnaphthalene of more than 1.1.
8. The process of claim I for producing 2,6-dialkylnaphthalene from the feedstock comprising the isomers of the dialkylnaphthalene and the naphthalene, further comprising the steps of II. separating the product of the step I into fractions of naphthalene, mono alkylnaphthalene and dialkylnaphthalene, III. alkylating the fraction of monoalkylnaphthalene of the step II with an alkylating agent to produce dialkylnaphthalene, IV. separating the product of the step III into fractions of monoalkylnaphthalene and dialkylnaphthalene, and V. separating the 2,6-dialkylnaphthalene from the fractions of the dialkylnaphthalene of the steps II and IV, wherein the step III is conducted in the presence of the catalyst composition.
9.. The process of claim 8 wherein the fraction of the naphthalene of the step II is recycled to the step I; the fraction of the monoalkylnaphthalene of the step IV is recycled to the step III; and a fraction of dialkylnaphthalene produced after separating the 2,6-dialkylnaphthalene of the step V is recycled to the step I.
10. The process of claim 8 or 9 wherein the 2,6-dialkylnaphthalene is separated from the tiactions of the dialkylnaphthalene by high pressure crystallization.
11. The process of claim 8 or 9 wherein the dialkylnaphthalene is dimethylnaphthalene, and the monoalkylnaphthalene is monomethylnaphthalene.
12. A process for preparing a polyethylenenaphthalate polymer comprising:
(A) oxidizing 2,6-dimethylnaphthalene to form 2,6-naphthalene-dicarboxylic acid, or oxidizing and esterifying 2,6-dimethylnaphthalene to form ester of 2,6-naphthalene-dicarboxylic acid; and (B) condensing the 2,6-naphthalene-dicarboxylic acid or ester thereof with ethyleneglycol to form the polyethylenenaphthalate polymer wherein the 2,6-dimethylnaphthalene is prepared from a feedstock comprising isomers of dimethylnaphthalene and naphthalene comprising:
I) transalkylating the isomers of the dimethylnaphthalene and the naphthalene to produce monomethylnaphthalene; and isomerizing the isomers of the dimethylnaphthalene;
II) separating the product of the step I into fractions of naphthalene, monomethylnaphthalene and dimethylnaphthalene;
III) alkylating the fraction of monomethylnaphthalene of the step II with an alkylating agent to produce dimethylnaphthalene;
IV) separating the product of the step III into fractions of monomethylnaphthalene and dimethylnaphthalene; and V) separating 2,6-dimethylnaphthalene from the fractions of the dimethylnaphthalene of the steps II and IV, wherein the steps I and III are each conducted in the presence of a catalyst composition comprising a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A
Table A
Interplanar d-spacing(A) relative intensity I/I0 X100 12.3 60.4 M-V S
11.0310.2 M-S
8.830.14 M-V S
6.1810.12 M-V S
6.000.10 W-M
4.060.07 W-S
3 .91 X0.07 M-V S
3.420.06 VS
wherein the relative intensities are given in terms of the symbols;
W = weak, M = medium, S = strong, VS = very strong.
(A) oxidizing 2,6-dimethylnaphthalene to form 2,6-naphthalene-dicarboxylic acid, or oxidizing and esterifying 2,6-dimethylnaphthalene to form ester of 2,6-naphthalene-dicarboxylic acid; and (B) condensing the 2,6-naphthalene-dicarboxylic acid or ester thereof with ethyleneglycol to form the polyethylenenaphthalate polymer wherein the 2,6-dimethylnaphthalene is prepared from a feedstock comprising isomers of dimethylnaphthalene and naphthalene comprising:
I) transalkylating the isomers of the dimethylnaphthalene and the naphthalene to produce monomethylnaphthalene; and isomerizing the isomers of the dimethylnaphthalene;
II) separating the product of the step I into fractions of naphthalene, monomethylnaphthalene and dimethylnaphthalene;
III) alkylating the fraction of monomethylnaphthalene of the step II with an alkylating agent to produce dimethylnaphthalene;
IV) separating the product of the step III into fractions of monomethylnaphthalene and dimethylnaphthalene; and V) separating 2,6-dimethylnaphthalene from the fractions of the dimethylnaphthalene of the steps II and IV, wherein the steps I and III are each conducted in the presence of a catalyst composition comprising a synthetic zeolite characterized by an X-ray diffraction pattern including interplanar d-spacing as set forth in Table A
Table A
Interplanar d-spacing(A) relative intensity I/I0 X100 12.3 60.4 M-V S
11.0310.2 M-S
8.830.14 M-V S
6.1810.12 M-V S
6.000.10 W-M
4.060.07 W-S
3 .91 X0.07 M-V S
3.420.06 VS
wherein the relative intensities are given in terms of the symbols;
W = weak, M = medium, S = strong, VS = very strong.
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| US08/661,114 | 1996-06-10 | ||
| US08/661,114 US5744670A (en) | 1996-06-10 | 1996-06-10 | Process for preparing dialkylnaphthalene |
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| US6011190A (en) * | 1997-07-02 | 2000-01-04 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing dialkylnaphthalene |
| US6018086A (en) * | 1997-10-10 | 2000-01-25 | Kabushiki Kaisha Kobe Seiko Sho | Process for preparing 2,6-dialkylnaphthalene |
| US6018087A (en) * | 1997-10-10 | 2000-01-25 | Kabushiki Kaisha Kobe Seiko Sho. | Isomerization of dimethylnaphthalene to produce 2,6-dimethylnaphthalene |
| US6057487A (en) * | 1997-12-30 | 2000-05-02 | Chevron Chemical Company | Method for producing 2,6-DMN from mixed dimethylnaphthalenes by crystallization, adsorption and isomerization |
| IT1300061B1 (en) * | 1998-04-17 | 2000-04-19 | Eniricerche S P A Ora Enitecno | PROCESS FOR PREPARING 2,6-DIMETHYLNAPHTHALENE |
| JP2002541231A (en) * | 1999-04-08 | 2002-12-03 | 株式会社神戸製鋼所 | Method for producing 2,6-dialkylnaphthalene |
| US6523063B1 (en) | 1999-08-30 | 2003-02-18 | Zaplet, Inc. | Method system and program product for accessing a file using values from a redirect message string for each change of the link identifier |
| US6463461B1 (en) | 1999-08-30 | 2002-10-08 | Zaplet, Inc. | System for communicating information among a group of participants |
| US6505233B1 (en) | 1999-08-30 | 2003-01-07 | Zaplet, Inc. | Method for communicating information among a group of participants |
| US6496849B1 (en) | 1999-08-30 | 2002-12-17 | Zaplet, Inc. | Electronic media for communicating information among a group of participants |
| US6507865B1 (en) | 1999-08-30 | 2003-01-14 | Zaplet, Inc. | Method and system for group content collaboration |
| US6691153B1 (en) | 1999-08-30 | 2004-02-10 | Zaplet, Inc. | Method and system for process interaction among a group |
| AU6864100A (en) | 1999-08-31 | 2001-03-26 | Kabushiki Kaisha Kobe Seiko Sho | Method for producing 2,6-dimethylnaphthalene |
| US6453337B2 (en) * | 1999-10-25 | 2002-09-17 | Zaplet, Inc. | Methods and systems to manage and track the states of electronic media |
| AU2001296866A1 (en) | 2000-09-05 | 2002-03-22 | Zaplet, Inc. | Methods and apparatus providing electronic messages that are linked and aggregated |
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| US7447802B2 (en) * | 2001-03-30 | 2008-11-04 | Oracle International Corporation | Method and system for maintaining a configuration state |
| ITMI20011205A1 (en) * | 2001-06-07 | 2002-12-07 | Enichem Spa | INTEGRATED 2.6 DIMETHYLPHAPHALENE PRODUCTION PROCESS |
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| JP2003026614A (en) * | 2001-07-13 | 2003-01-29 | Kobe Steel Ltd | Method for concentrating 2,6-dimethylnaphthalene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS535293B2 (en) * | 1973-05-10 | 1978-02-25 | ||
| JPS58204817A (en) * | 1982-05-19 | 1983-11-29 | Teijin Yuka Kk | Production of crystalline aluminosilicate zeolite |
| JPS6045536A (en) * | 1983-08-22 | 1985-03-12 | Teijin Yuka Kk | Trans-methylation of methyl-substituted naphthalene |
| DE3703291A1 (en) * | 1987-02-04 | 1988-08-18 | Ruetgerswerke Ag | METHOD FOR PRODUCING 2,6-DIALKYLNAPHTHALINE |
| US5001295A (en) * | 1988-10-06 | 1991-03-19 | Mobil Oil Corp. | Process for preparing dialkylnaphthalene |
| JPH041142A (en) * | 1990-04-17 | 1992-01-06 | Teijin Ltd | Production of 2,6-dimethylnaphthalene |
| KR920702336A (en) * | 1990-07-27 | 1992-09-03 | 모리구찌 엔지 | Method for preparing 2-alkyl-6-ethylnaphthalene |
-
1996
- 1996-06-10 US US08/661,114 patent/US5744670A/en not_active Expired - Lifetime
-
1997
- 1997-06-10 JP JP9152662A patent/JPH10101592A/en active Pending
- 1997-06-10 SG SG9804343A patent/SG87779A1/en unknown
- 1997-06-10 KR KR1019970023731A patent/KR100265483B1/en not_active IP Right Cessation
- 1997-06-10 DE DE69711120T patent/DE69711120T2/en not_active Expired - Fee Related
- 1997-06-10 SG SG1997002014A patent/SG50023A1/en unknown
- 1997-06-10 CA CA002207526A patent/CA2207526C/en not_active Expired - Fee Related
- 1997-06-10 TW TW086108229A patent/TW486455B/en not_active IP Right Cessation
- 1997-06-10 EP EP97304001A patent/EP0812813B1/en not_active Expired - Lifetime
- 1997-11-19 US US08/974,231 patent/US5844064A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2207526A1 (en) | 1997-12-10 |
| US5844064A (en) | 1998-12-01 |
| JPH10101592A (en) | 1998-04-21 |
| EP0812813A3 (en) | 1998-01-07 |
| KR980001989A (en) | 1998-03-30 |
| DE69711120T2 (en) | 2002-11-14 |
| TW486455B (en) | 2002-05-11 |
| US5744670A (en) | 1998-04-28 |
| DE69711120D1 (en) | 2002-04-25 |
| KR100265483B1 (en) | 2000-09-15 |
| SG50023A1 (en) | 1998-06-15 |
| SG87779A1 (en) | 2002-04-16 |
| EP0812813B1 (en) | 2002-03-20 |
| EP0812813A2 (en) | 1997-12-17 |
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