JPH05504332A - Selective jetylation of naphthalene to 2,6-diethylnaphthalene - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] l suck 25 and Selective diethylation of naphthalene to 2,6-dinithylnaphthalene This is US Patent Application No. 07/4, filed on October 17, 1989. 22.784, the entire original application is incorporated herein by reference. It's included.

＆Sudan Standing The present invention provides 2,6-dinithylnaphthalene by alkylation of naphthalene compounds. related to the manufacture of We use certain acidic zeolite catalysts (e.g. ZSM-12, 5APO-11, and EU-1) were used to maximize the yield of the cono isomer. I discovered something that can be used.

This isomer is useful as a precursor for 2,6-dicarboxynaphthalene, 2.6-Dicarboxynaphthalene can be used to produce polyester films. It is an important monomer.

Good beans Wataru Blue 1 2.6-dicarboxynaphthalene compounds are precursors for polyester films It is an important monomer used as a body.

Therefore, the search for inexpensive sources of 2,6-dicarboxynaphthalene has been the subject of intense research. It was a target.

Aromatic alkyl compounds can be converted to analogous aromatic carboxylic acids. This is Koba Fluid in acetic acid solvent using various catalyst mixtures of manganese, manganese and bromide salts. This is done by oxidizing radicals. This technology converts p-xylene into terephthalate. It is used commercially in converting it to acid. If the alkyl group is ethyl or isopropyl Alkylaromatics that are either lopyls may be used with the same or similar catalyst system. can be oxidized to the corresponding carboxylic acid using

The selective synthesis of specific isomers of dialkylnaphthalenes has been the focus of many research groups. was the subject of research. U.S. patent application filed by the applicant on October 5, 1988 Application No. 254.284 discloses 2,6- The preparation of diitubropylnaphthalene is described.

European Patent Application No. 317.907 and corresponding U.S. Patent No. 4. 891.448, the Dow Chemical Company (DotChemical Con+pany> is acidic mordenite zeolite for the production of rose isomers. (acidic ll1ordenite zeolite) using a catalyst is taught. This rose isomer is useful for the preparation of thermotropic liquid crystal polymers. It is for use. German patent application No. DE 370, 3291A is based on methanol and or 2-methylnaphthalene to 2,6-dimethylnaphthalene. Discloses and claims the use of ZSM-5 as a suitable catalyst for converting are doing.

Japanese Patent Application No. 63-211243 states that 2-methylnaphthalene is can be alkylated with propylene using a selective solid acid catalyst to form 2-methyl 6 in high yield. - It is taught to produce ituprovir naphthalene.

U.S. Pat. No. 4,813,385 discloses that 2,6 by a transalkylation process - shows selective production of dinitylnaphthalene. This reaction is similar to naphthalene or is used as an ethylating agent in one reaction with at least one of 2-ethylnaphthalene. 1 mole to about 10 moles of 1,4-diethylbenzene per mole; 2. At least one of 4-triethylbenzene, tetraethylbenzene, or This includes liquid phase contact with at least one type of pentaethylbenzene. that time , this reaction involves aluminum chloride, aluminum bromide, tantalum chloride, and ammonium fluoride. Lewis selected from the group consisting of timone, or red oil. It is carried out in the presence of an acid catalyst. The catalyst is about 0.01 per mole in one reaction. (For red oil, this is about 1 mole of aluminum chloride in red oil.) um content) and then at a temperature range of about 10°C to about 100°C. The reaction takes place.

A certain Japanese patent, namely Japanese Patent No. 51-6953, was filed with Mitsubishi Kasei Corporation. The diethylization of naphthalene using a non-shape-selective catalyst, AlCl3, has been It is stated that The ethylation reaction was carried out for 9 hours at 135°C in contact with a catalyst. It will be done. The desired yield of 2.6-dinithylnaphthalene is between 17% and 20% in the composition. 2.6/2.7 diethylnaphthalene isomer It was confirmed that the ratio was approximately 1. This result is in line with other achievements in this field. Match.

More specifically, the prior art for H-forming diisopropylnaphthalene is Selective catalysts (when operated at equilibrium) give a ratio of 2,6/2.7 of approximately 1 and the amount of the 2.6 isomer does not exceed 39% of the total amount of alkyl compounds present. to show something 2,6-diethylnaphthalene with a total sialylate mixture of approximately 20% The finding that it contains isomers seems reasonable.

This is because ethyl substitution is more diabetic than isopropyl substitution. This is because a larger amount of the rukyl isomer can be obtained. For the isopropyl group, Adjacent carbon atoms of the phthalene ring cannot be alkylated. This replaces ethyl substitution with If you do, there is no problem. As a result, diisopropylnaphthalene The triaddition isomer of ethylnaphthalene is easier to obtain.

The purpose of the present invention is to eliminate the necessity of operating in harsh reaction conditions while - To improve the selectivity of the production of diethylnaphthalene.

A further object of the present invention is to obtain a desired 2 ．． Highly substituted species while maximizing the yield of 6-diethylnaphthalene isomer To provide a shape-selective catalyst with pores of a size and shape that minimize the formation of It is.

We have stated that non-shape-selective catalysts, or those with unsuitable pore sizes, . In conclusion, we found that either the zeolite-catalyzed olide catalyst was approximately 5.6 between 5.6 angstroms and 7.0 angstroms, preferably 5.6 angstroms shape-selective catalysts with a maximum pore size of 6.4 angstroms, e.g. Olite ZSM-12, 5APO-11, and EU-1 were mixed with acidic crystalline Molecule. 2,6-diethylna It was discovered that the selectivity for phthalene was enhanced.

My friend [1] The present invention converts naphthalene or 2-ethylnaphthalene into ethylene or ethylnaphthalene. This is the process of reacting with the metal.

This process converts naphthalene, or 2-ethylnaphthalene to 2,6-diethyl An acidic zeolite catalyst, preferably ZS, under conditions sufficient for conversion to lunaphthalene. M-12, EU-1, or 5APO-11 (and most preferably ZSM-1 2) is carried out in the presence of.

Detailed description of the invention The ethylation of naphthalene is very similar to the isopropylation of naphthalene. It seems likely that it will proceed in a similar step-by-step manner. The ethylation reaction is slower than the propylation reaction. It is. This is because the first step in the ethylation reaction is acid-catalyzed carbonation. This is due to the formation of umium ions. Regarding the isopropylation of some naphthalenes. There is a literature that states that ethylation of naphthalene is very difficult to occur. (5parse) r, chem, soc, 98.1839 (1976 ). Fundamentals of improvements to shape selective synthesis using 2.67 medium in equilibrium In order to be able to establish the equilibrium of product distribution in the naphthalene ethylation reaction, I thought it was most important to decide. The equilibrium of the alkylation reaction is that the alkylation isomerization between the given species and the most thermodynamically stable product distribution is faster than alkylation. It happens when it happens. Generally, the equilibrium mixture is alkylated (not isomerized) is obtained at slow olefin feed rates such that is the rate-limiting step.

For non-shape selective catalysts, the yield of the 2,6-isomer is maximum at equilibrium. Na Therefore, the 2,6- and 2,7-isomers are β, β isomers, and the equilibrium This is because it is a preferable form in the current state. 2.6/2.7 - The ratio of isomers is approximately 1 is expected.

As mentioned earlier, between the ethylene groups of diethylnaphthalene, diisopropylnaphthalene Since there is less steric hindrance than between the isopropyl groups of phthalene, possible The total number of ethylnaphthalene isomers is compared to the number of diisopropylnaphthalene isomers. There are many. The total number of diisopropyl isomers observed was 7, and diethylnaphthalene The number of isomers is 10. The presence of this large number of isomers complicates the system Not only that, but the absolute amounts of the 2, 6, and 2.7 isomers produced at equilibrium are also small. Eliminate.

For example, due to steric inhibition, isopropylation reaction in equilibrium with AlCl. The β isomer in all monoalkylates is 98.5%, but in the ethylation reaction, 98.5% is the β isomer. Only 0.5%. J, Ame2.7 ratio of G, A, 01ah et al. is not 1.0. Always close, the DEN content will be from 17% to 22%.

As previously mentioned, the present invention uses a suitable shape-selective catalyst to produce 2,6-diethyl This is a process for producing naphthalene.

Suitable shape-selective catalysts are approximately 56 angstroms and 7.0 angstroms thick. between 5.6 angstroms and 6.4 angstroms, preferably between 5.6 angstroms and 6.4 angstroms. It has a pore size.

Examples of molecular sieves with maximum pore sizes within the desired range are shown in the table below. this Among them, ZSM-12, 5APO-11, and EU-1 are synthetic zeolites. ZSM-12MTW 5.5x 5.7x 6.2 MeirerEU-I EUO4, I X 5.4 X 5.7 M eirer SAPO-11・AEL 3.9X6.3 MeirerMAPSO -46AFS　6.4　x　6.2　MeirerCancrinite　CA N 5.9 Meirer Partheite PAR3,5X6.9 Mei rerStilbite STI 4.9X 6. I Meirer Cancri Cancrinite, parteite, and 5tilbite is a naturally occurring zeolite; Their purity, stability, and availability vary. Offrate tight (offr) etite) and MAPSO-45 can be selective catalysts, but they are It is also difficult to obtain. The preferred zeolite is ZS! +1-12, EU-1, and There is 5APO-11r. The most preferred zeolite catalyst is ZSM-12. Z The pore structure of SM-12 is linear, with non-interpenetrating grooves consisting of 12-membered rings. (non-interpenetrating channels), pore size The law is 5.5 angstroms, 57 angstroms, 6.2 angstroms. It is. Jacobs, P.A., et al. Kate synthesis J 5 studies in 5 surface 5 science a nd Catalysis, No. 33, Elsevier, 1 987, 7 pages 301. Meier, W, M, "Illustration of Zeolite Structure Types" 2nd edition, 5structure Comm1ssi on of the International Zeolite As5o See also cation, 1987.

The term ``dimension'' refers to ``diameter''. It is preferable to the term J. Because 1, the latter term requires a circular opening. This is because it is not necessarily appropriate to describe crystalline molecular sieves.

When we quote the term "pore size or width" we mean (non-circular zeolite means the longest length of the pore (relative to the open pore). For example, ZSM-1 2 is a pore diameter of 55 angstroms x 57 angstroms x 62 angstroms. It is an amorphous zeolite of the same size. Similarly, 5APO-11 is 39 angstroms A pore size of 6.3 angstroms x 6.3 angstroms is prepared. Therefore, the pores of ZSM-12 The diameter is 62 angstroms, 5APO-11 is 63 angstroms, The diameter of EU-1 is 57 angstroms.

A substrate molecule of a defined size and shape enters an active site located in free space within the crystal. product molecules of a given size and shape diffuse from free space within the crystal. When the zeolite framework and pore structure are as shown in the figure, shape-selective reactions occur. Koru. Therefore, the pore structure present in the framework of various crystalline sieves It is important to accurately characterize the structure.

Crystal sheet structures are often defined by the number of tetrahedral units (T, atoms).

For example, in sodalite, silicon and alumina tetrahedra are A cubic decahedron joined together and chamfered perpendicular to all 04 axes of the dome. (cubooctahedron) is formed. The sodalite unit is 4, and Consists of a 6-membered oxygen ring. A more complete characterization of zeolites can be found in E, G, De Rouane, “Diffusion and shape-selective catalysis in zeolites”, Interca. Lascicon chemistry (Intercalation Chemistry), Edited by J1M, Stanley Witchingum (M, Stanleyylhittin) gham) rA (Academic Press) 1 982). 5APO-11 is 7-lical aluminophosphate molecular First published in 1984 in U.S. Patent No. 4.440.1171. It was reported to The pore structure of 5APO-11 is linear with a phase limited to 10-membered rings. Non-interconnected grooves, 3.9 angstroms and 63 angstroms It has a loamy pore size.

See 0. Meyer, W. M., and Olson. on), D, H, “Illustration of Zeolite Structure Types”, 2nd edition, Struct ureCommission of the International Z eolite As5ocation, Butterworth rths), 1987, see also.

It should be noted that ZSM-12 and EU-1 are also available in cationic form. It is. Zeolite does not contain an organic template. In addition, calcination may also be necessary. To convert these to hydrogen form, one ammonium Only ion exchange with mucation followed by calcination under appropriate conditions is required. Ru. These catalysts can produce the desired diethylnaphthalate without significantly changing its pore size. It can be optimized to selectively produce more len. Such a pleasant touch One modification to the medium is a dealumination reaction. Acidic crystalline molequinyl sieve A quality dealumination reaction is performed using HF2. up to ON (preferably up to 1.5N) and This occurs when a solid catalyst is exposed to an acid mixture, such as an acid (up to 16N). obtain. The dealumination method for ponds is steam treatment followed by mild acid treatment and calcination. Ru.

Preferred steaming parameters are as follows.

Harameter ■ Favorite stem-U”→”ton 1■ Even temperature (”C) 3 00-1000 400-850 450-750 Total pressure (ATV) 0.001 -15 0.001-5 0.2-2 Reaction time 0-24 hours 10 minutes-4 hours 20 minutes - 2 hours Zeolite with low aluminum (alufflinum-d For further instructions on preparing ef1cientzeolites), No. 5 Cherzer's "Preparation and characteristics of zeolite with low aluminum content" "Catalytic materials: Structure and reaction relationship" by Thaddeus E., Whyte et al. "Relationship", p. 156'160 ACS Symposium 5eries 248 (American Chemical 5ociety 1984) Shine on. A wide range of dealuminated zeolite materials are initially available for isopropylation reactions. We have found that only substances that are suitable can retain their suitability for long periods of time. I started it. For example, dealumination techniques using strong acid leach Initially, highly active but short-lived catalysts are typically produced. In some situations, Although such an activity profile is desirable, long-lived catalysts are typically preferred. .

The method of dealumination reaction that has been discovered to produce such a desirable material One is steam treatment (in one or more steps) followed by weak acid extraction.

Dealuminated crystalline molecular 7-builds can be treated at temperatures between 400°C and 1000°C. The calcination may be performed at temperatures between 400″C and 700′C. , dealumination followed by dehydration or 5i-OH bonding (or nest structure). We provide restoration work (construction). Repairing these unstruck structures is a way to create more single, crystalline structures. pore structure in the material. It provides structural stability and thus selectivity. leading to improved selectivity and longevity.

Catalyst calcination conditions can strictly affect catalyst activity. selected calcining gas (e.g. , oxygen or nitrogen) may affect the catalyst species differently. Generally, crystalline leakage The calcination temperature of the cyclic sieve catalyst can be varied from 300″C to 1ooo″C . For zeolites like ZSM-12, the optimum temperature range has been experimentally determined to be 400"C. and 1000°C. If there are organic residues on the catalyst surface. Both the calcination temperature and the gas are important.

If there are organic residues, when the catalyst is calcined to temperature A, the amount of residual moisture is minimal. Atmosphere (preferably nitrogen) is used so that the

After a sufficient time for the organic residue to be carbonized, the carbonization residue is removed with minimal water formation. At temperatures sufficient for the distillates to burn to CO2, the atmosphere is converted to oxygen.

Preferred enzymes) ZSM-12, 5APO-11, and EU-1 When combined, ethylene and naphthalene or 2-ethylnaphthalene are combined in an equilibrium state. It was a surprising discovery that 2,6-ethylnaphthalene was formed in high yield by Met. The synthetic procedure for creating ZSM-12 is described in Yafub et al., supra, p. 303. I was being lied to.

Typically, the Si/AI ratio of these catalysts ranges from 5 to 2000, which is preferred. Preferably from 10 to 1000, more preferably from 2 to 500. and most preferred The range is 2o to 100. Furthermore, the ZSM-12 particle size is preferably 40μ We find that it is less than 0.018 m to 3.75 μm, and more preferably from 0.18 m to 3.75 μm. I started it.

ZS synthesized like this! 1! To convert -12 to the active acidic form, first the empty 05 to 05 at temperatures between 400'C and 1000'C in flowing air or oxygen. Bake for 8 hours. The calcination temperature is preferably between 400"C and 700°C. Next , any residual cations can be removed using NH4Cl (0°01N to 6N) at 20 Perform ion exchange for 1° to 300 minutes at a temperature between ’C and 100’C, or One is a strong acid, such as HCI, HNO, etc.

) 12304 etc. (0.01N to 6N), temperature between 20'C and 100'C It is removed by either treating it for 10 minutes to 300 minutes. ion exchange Afterwards, the catalyst is dried in air at a temperature between 5°C and 200°C for 1 to 20 hours. may be dried and then heated at 1°C between 400°C and 1000°C in an air or nitrogen atmosphere. It is activated by calcination for 8 hours from os at 100 ml. Preferably, this calcination temperature The temperature is between 400"Cb' and 700°C.

Catalyst treatment according to the invention involves removing or blocking acidic sites on the outer surface of the catalyst. . The reason for removing or blocking the outer acidic sites is to remove or block the outer surface of the zeolite catalyst. By making it inactive, the properties of the outer surface as a shape-selective catalyst are enhanced. This is for the purpose of If not, the outer surface acts as a non-shape selective catalyst. external surface A further reason to remove or block acidic sites is to remove or block acidic sites. Related to King.

Over time, acidic catalytic reactions such as the ethylation of naphthalene can cause the pore openings of the catalyst to Coke is formed. This accumulation makes the pore less accepting of substrate molecules. , ultimately causing the pores to close and these channels to become inactive.

Inactivation of external acidic sites is desirable to prevent non-shape selective reactions of the external surface. outside Inactivation of surface acidic sites can be achieved by either blocking the acidic sites or removing the acid. On the other hand, it can be obtained. The acidic sites on the outer surface of the catalyst are ■A, rVA, rVB, and and group VA halogen derivatives, hydride derivatives, and organic derivatives. It is obtained by contacting the catalyst with a deactivating agent selected from the group. death However, both techniques have one major limitation. It prevents internal diffusion. The deactivating agent should be selected so as to This limitation applies to deactivating agents. This can be easily handled by using either the liquid phase or the gas phase. inactivation The agent molecules are too large to fit into even the largest pores of known zeolites. This is because you cannot get into it. One such molecule is triphenylchloride. It's a run. Martens, J.A. et al., 2eolites , April 4, 1984, pp. 98-100. Furthermore, this surface Precaulking with one of the brecoking agents or other brecaulking agents.

In another embodiment of external acid site modification, the internal pores of the crystal are filled with hydrocarbons. By doing so, a catalyst whose inner surface is protected can be obtained. Then the crystal Either an aqueous acid solution or a complexing agent that is insoluble in the hydrocarbons contained in the internal pores. contact with the protected reagent. Once the outer surface is passivated, the crystal is then Hydrocarbons are removed from the internal pores.

In EP 86543, non-polar *W base material is added to fill the pores of zeolite. has been added. A solution of deactivator in a polar solvent is then introduced to the catalyst. Al Potash metal salt solution (which contains acidic protons associated with aluminum) 　proton)　acts as a removal ion exchange molecule) acts as an inactivating agent. It is stated that See also US Pat. No. 4,415,544. this is, To seal pores before surface treatment with hydrogen fluoride to remove aluminum He teaches the use of Balafinowanox.

The naphthalene compound may be present in liquid form or in solution. Alkylation The agent can be present in a liquid or gaseous state and, depending on the reactor selected, can be The reaction cycle in a batch reactor is It is sometimes added at the beginning of a file. The catalyst can be present in either particulate or granular form. It is possible. and placed in either a fluidized bed, stirred bed, moving bed, or fixed bed. be able to. The catalyst can also be placed in suspension or in a pouted bed. can.

Reactive distillation columns can also be used.

The ratio of alkylating agent to naphthalene compound is between 0.01 and 100. Yes, preferably between 1.0 and 10.0.

This reaction is preferably carried out in the liquid state, at temperatures of 100'C and 400°C. C, preferably between 225°C and 350°C, and the pressure is between 1 atm and 1 atm. It should be 00 atm. The amount of catalyst is easily determined. It is generally An excess of 2.6- Drive reactions to produce products such as ethylnaphthalene products The amount should be sufficient for Typically, the weight ratio of aromatics to catalyst ranges from 11 to 200:l. Optimization within this range is clearly Beautiful.

Isolation of 2,6-DEN is performed by standard techniques such as distillation, crystallization, and adsorption. obtain.

When a silica-alumina catalyst is used for the alkylation of naphthalene, the product distribution is Regardless of how ethylene is delivered to the system, the It was revealed that the cloth was shown. During the reaction, which isomer of diethylnaphthalene -Scentage has essentially remained the same. At low conversions, diethyl There are very few naphthalene plates, and other gas chromatography (GLC) plates are The peak overlapped with the peak of the 2.6-isomer. This gives the 2.6-isomer shows unnaturally high selectivity. For high conversions, the 2.6-isomer Body mass was approximately 17%, or 19% to 22%.

Ethylating agents include ethylene, ethanol, ethyl ether, ethyl chloride or other It is a suitable ethylated substance. Preferably, the agent is ethylene, optionally with the addition of water. available.

- Conditions used to the extreme A stirred autoclave reactor was chosen for this work.

It is convenient to operate and suitable for screening improvements in selectivity. There is. The catalyst is a 300cc autoclave engineer (Autoclave) This reaction used ethylene gas. this The ethylene feed rate was controlled by a mass flow controller (mass flow controller). controller) or a pressure controller. Adjustment of ethylene feed rate Depending on the section, the system can be divided into ethylene-limited and ethylene-rich conditions. I was able to operate between. The former condition mimics the limited conditions of equilibrium. rear conditions mimic a kinetically controlled reaction.

Analytical results were obtained by gas chromatography.

To test the catalyst, 90g naphthalene and 0.5g to 50g The catalyst is loaded and the propylene gas is supplied at a constant flow rate from the mass flow controller or was supplied from a pressure control device.

In all cases not otherwise specified, samples should be collected periodically and analyzed by GLC. Therefore, I analyzed it. The temperature of the reactor can be varied between 40°C and 355°C; Both reactions were varied between 225°C and 350°C. The pressure of ethylene is 0. The pressure may be from 1 atmosphere to 100 atmospheres, preferably from 1 atmosphere to 10 atmospheres.

All data in the table are based on the mole percent selectivity (1epercent 5electivity). In this study, we compare the performance of catalysts The method used to calculate the parameters used in is as follows: It is.

Number of carbons in rXJ Conversion % = 100 - number of moles of mole percent of substrate in Sanoblu 2.6 In order to compare with the matter dealing only with selectivity, other than the selectivity of the 2.6DEN isomer, A more useful measure of the performance of 0 or mfl is needed. this Instead, a more convenient measure was devised for performance comparisons, i.e., 2.6/2.7 ratio, which means trying to produce more 2.6 than 2.7. ℃＼ Give credit to the initial objectives. 2.6-DEN/Nual scale-F, <-Se Tentene is a measure of the amount of the desired isomer produced in the total sialylate. Issei 1: Comparison) This example shows the value of the 2.672.7 ratio at equilibrium and the It shows the percentage value of 2.6. Ethylating naphthalene with silica/alumina However, when conducting the experiment using the method described above, these values are 10%, 17%, and 22%, respectively. % (Figure 1).

Based on these data, the 2.5/2.7 ratio and the 2.6/DEN percentage Shape selectivity effects are evident when either of the components exceeds 1, 0 and 22%, respectively. That's it. However, a more reliable parameter is the 2.6/2.7 ratio.

In an attempt to confirm the shape selectivity effect of the catalyst in Table 1, several zeolites were used. selected. A sample of 5APO-11 was obtained from Union Carbide and Samples of EU-1 were prepared according to literature methods. Sun of ZSM-11 Pulls were also prepared according to literature methods. Other comparative catalysts are mordenite and It was zeolite β. Mordenite is commercially available, and it is It was used in its original acidic state. Zeolite β was prepared with reference to literature .

ZSM-11, ZSM-12, 5APO-11, EU-1, and mordenite samples were tested for alkylation activity in the diethylation of naphthalene. did. No attempt was made to optimize these catalysts prior to testing.

(Margin below) 7'oride ta; cedar 1'' and L1Σ 2,6 otl F 2.6-DEN 仝DE ! J (%) ZSM-1120,534 30, 629 EU-130,532 SAPO-1151, 123 ZSM-1271,734 631, 225 Momordenite 59 1.0 17 88 0.8 13 Figure 2 shows a comparison of the results of the diethylation reaction using all of these catalysts.

ZSM-12 has clear shape selectivity because the initial value of 2.6/2.7 is equal to 17. Show clearly.

Since ZSM-11 has a 2.6/2.7 ratio of less than 1.0, it does not exhibit shape selectivity.

Mordenite exhibits high activity, which means that internal active sites are easily accessible but still unformed. It shows that there is no selectivity (that is, the 2.672.7 ratio is about 1). 5AP O-11 did show shape selectivity. 2.6/2.7 ratio (approximately equal to 11) was almost constant in this trial. This is true at very low conversion rates. It is clear that even if 2.6-DEN has the highest selectivity. child The fact is that 5APO-11 is not the best catalyst, but it can be used to produce 2.6-DEN. supports the concept of being suitable for EU-1 result is 2.6/2.7 ratio was initially observed to be very low, but the maximum value of 2.672.7 reached 1.3. It rose and was interesting.

As the conversion progresses, the value of the 2.6/2.7 ratio decreases. 2.6/2.7 ratio , rises or falls as a function of conversion rate, which indicates that shape-selective catalysts are in batch mode. Typically seen when operated on a These data indicate shape selectivity Effective ZSM-12, 5APO-11, and EU-1i: Yes, ZSM-1 2 is preferred.

If you have a plan This example was synthesized with almost the same particle size but different silica/alumina ratio. 2 shows the effect on the performance of ZSM-12 catalyst when These catalysts are 30 psi of ethylene and 30 l of ethylene at 325°C in an autoclave. The naphthalene/catalyst ratio was tested. A sample was removed and analyzed. these minutes The results of the analysis are shown below.

dog m2 This example shows the effect of dealumination on the performance of the preferred ZSM-12 catalyst. . The catalyst was treated with 0.5N HF in 16N HNO3 at approximately 100°C for 2 hours. I understood. After drying and calcination, the catalyst was treated in the same manner as in Example 2.

(Margin below) Particle IS conversion rate 2,6-DENZSM-12220,1-0,561, 745351, 530 451, 429 681, 225 691,226 791, l 24 ZSM-12340,1-0,531,152281,736 331,735 441,633 491,532 561, 531 821, 228 Obviously, the higher the silica/alumina ratio of ZSM-12 catalyst, the better the performance. Indicated.

cold 1'' knee Higher level of dealumination due to larger particles on the performance of ZSM-12 catalyst The effects of this are shown below. The catalyst was heated in 16N FINO3 at about 100°C 1. ON of HF for 2 hours. After drying and calcination, the catalyst was tested as described above. .

Catalysts with larger particle sizes are also larger if the catalyst has a higher silica/alumina ratio. The higher the performance, the more advanced the performance was obtained.

K blood 5dan 2 This example demonstrates the synthesis of ZSM-12 with various particle sizes. Gel at 165℃ By changing the silica/alumina ratio in the initial gel while keeping the water content constant. Therefore, the particle size was varied. The sources of various reaction components are as follows: It is.

That is, /Rica is colloidal silicon dioxide and alumina is A+ (803) It is a hydrate of No. 3. For the synthesis, 160 g of water and 336 Na0t ( Combined and stirred. Add 296g of triethylmethylammonium bromide to this solution. 3.36g17+Al(NO3)3 was added and dissolved by stirring. this 42 g of 30% colloidal silicon dioxide was added to the solution. Apply this gel to Teflon The tube was placed in a lined autoclave and heated at 165°C for several days. crystallized ZSM-12 was isolated by filtration and washed with water. bulk ICP Analysis shows that the crystalline ZSM-12 is very close to the stoichiometry used for its synthesis. It was shown to have a silica/alumina ratio. In any case, the zeolite is 10 It was 0% crystalline and did not contain large amounts of contaminants. The table below also shows the water content and changes in silica/alumina ratio can both greatly affect particle size. show.

1 1:23:2400 21 0. LX 0.5mm2 1:35:240 0 29 1 X 1rnn3 1:50:2400 43 1 X 2mm4 1 near 5:2400 66 1 x 3.50+105 1:33:8700 30 lx 3゜5mm6 0:1400:9000 430 2X 15m The ZSM-12 obtained from the reaction mixture was prepared using a sodium template (thetempl ate-sodium). To activate this catalyst, add it to 6 It was calcined at 50°C for 8 hours. Subsequently, 2 hours at 100°C with 5N NH, CI An ammonium type compound was obtained by ion exchange.

It was then dried at 110°C for 2 hours and then calcined at 650"C for 12 hours. The acid type compound was obtained (both in air).

m gong 2 This example is a series of runs using Example 5 and the process described below. Naphthalene was dioxidized by ethylene using ZSM-12 catalyst synthesized by Indicates ethylation.

ZSM-12220,1-0,561,745 approximately 15 μm catalyst, And the DEN reaction was shown to rapidly deactivate the catalyst. This is clearly against This is because the response path is too long. Caulking was dominant. From this result, this ZS with large particle size due to reaction! It can be seen that +1-12 is undesirable.

Figure 1 Time (closed) 0.10.20.30°40.50. G C1, 70, 80, 91, 0 − international search report i-One-One-One-One-One-TmPCr10590105916

Claims (42)

[Claims] 1.Process for producing diethylnaphthalene, rich in 2,6-diethylnaphthalene A process comprising the following steps a and b: a. Large pore size from 5.6 angstroms to 7.0 angstroms Naphthalene or 2-ethyl alcohol is added to the alkylation reactor containing the acidic zeolite catalyst. providing tilnaphthalene and an ethylating agent; and b. of the naphthalene or 2-ethylnaphthalene in the presence of the catalyst. under conditions sufficient to convert a portion of the alkyl to 2,6-diethylnaphthalene. The naphthalene or 2-ethylnaphthalene is reacted with an ethylating agent in a reaction vessel. process. 2. The acidic zeolite may be ZSM-12, EU-1, or SAPO-11. 2. The process of claim 1, wherein the process is selected from: 3. The ethylating agent is ethylene, ethanol, ethyl ether, and ethyl chloride. The process according to claim 1, wherein the process is selected from chill. 4. 4. The process of claim 3, wherein the ethylating agent comprises ethylene. 5. The proportion of 2,6-diethylnaphthalene in the diethylated isomer is 20% or more. 3. The process of claim 2, wherein the process is larger. 6. The reaction produces 2,6-diethylnaphthalene and 2,7-diethylnaphthalene. Claim 5, wherein both rens are produced and the 2,6/2,7 isomer ratio is greater than 1. The process described in. 7. 3. The catalyst according to claim 2, wherein the Si/Al ratio of the catalyst is about 5 to 2000. Roces. 8. 8. The catalyst according to claim 7, wherein the Si/Al ratio of the catalyst is about 10 to 1000. process. 9. 9. The catalyst according to claim 8, wherein the Si/Al ratio of the catalyst is about 20 to 500. Roces. 10. Claim 9, wherein the catalyst is calcined at a temperature between 400°C and 1000°C. The process described in. 11. The acidic portion on the outer surface of the zeolite catalyst makes the catalyst IVB, and VA group halogen derivatives, hydride derivatives, and ester derivatives. The claimant is inactivated by contacting with an inactivating reagent selected from the group consisting of: The process described in claim 2. 12. The acidic portion on the outer surface of the catalyst includes the following steps a, b, and c. The process according to claim 2, wherein the process is inertized: a. The open pores inside the crystal of the catalyst are filled with hydrocarbons to protect the inside. obtaining a catalyst; b. The internally protected catalyst is placed in an acidic aqueous solution or within a crystal. treatment with a complexing agent that is insoluble in the hydrocarbons contained in the pores; and c. A step of removing the hydrocarbons and recovering the catalyst. 13. The acidic portion of the outer surface is inactivated by pre-coking. The process described in claim 2. 14. Oxidation of 2,6-diethylnaphthalene to produce 2,6-dicarboxynaphthalene 3. The process of claim 2, further comprising the step of producing a . 15.2,6-diethylnaphthalene-enriched diethylnaphthalene producing process A process comprising the following steps a and b: a. Naphthalene was added to the alkylation reactor containing acidic zeolite ZSM-12. , 2-ethylnaphthalene, and an ethylating agent; and b. at least a portion of the naphthalene or 2-ethylnaphthalene in the presence of a catalyst is converted to 2,6-diethylnaphthalene. Reacting naphthalene or 2-ethylnaphthalene with an ethylating agent in a reaction vessel Process. 16. The ethylating agent is ethylene, ethanol, ethyl ether, and chloride. 16. The process according to claim 15, selected from ethyl. 17. 17. The process of claim 16, wherein the ethylating agent comprises ethylene. 18. The proportion of 2,6-diethylnaphthalene in the diethylated isomer is 20% 16. The process of claim 15, wherein the process is higher. 19. The reaction produces 2,6-diethylnaphthalene and 2,7-diethylnaphthalene. Claim 1, wherein both rens are produced and the 2,6/2,7 isomer ratio is greater than 1. The process described in 8. 20. 1 . The silica/alumina ratio of the catalyst is about 10 to 1000. The process described in 5. 21. 20. The silica/alumina ratio of the catalyst is about 20 to 500. The process described in. 22. Claim 2, wherein the catalyst is calcined at a temperature between 400°C and 1000°C. The process described in 1. 23. The acidic portion on the outer surface of the zeolite catalyst makes the catalyst IVB, and VA group halogen derivatives, hydride derivatives, and organic derivatives. inactivated by contacting with an inactivating reagent selected from the group 16. The process of claim 15. 24. The acidic portion on the outer surface of the catalyst includes the following steps a, b, and c. The process according to claim 15, wherein the process is inertized: a. The open pores inside the crystal of the catalyst are filled with hydrocarbons to protect the inside. (b) The internally protected catalyst is dissolved in an acidic aqueous solution or inside a crystal. treatment with a complexing agent that is insoluble in the hydrocarbons contained in the pores; and c. A step of removing the hydrocarbons and recovering the catalyst. 25. the acidic part on the outer surface of the catalyst is inactivated by pre-coking; 16. Process according to claim 15. 26. 16. The catalyst of claim 15, wherein the catalyst has a particle size of less than about 4.0 μm. Roces. 27. 27. The particle size of claim 26, wherein the particle size is between 0.1 μm and 3.75 μm. process. 28. The 2,6-diethylnaphthalene is oxidized to produce 2,6-dicarboxynaphthalene. 16. The process of claim 15, further comprising the step of producing talen. 29.2,6-diethylnaphthalene-enriched diethylnaphthalene producing process A process comprising the following steps a and b: a. 5.1 angstroms and approximately 7.0 angstroms in diameter. Naphs are added to an alkylation reactor containing a catalyst containing a catalyst with a selected shape. providing talene or 2-ethylnaphthalene and an ethylating agent; and b ．． at least a portion of the naphthalene or 2-ethylnaphthalene in the presence of the catalyst; However, if the proportion of 2,6-diethylnaphthalene in the diethyl isomer is higher than 20%, in the alkylation reaction vessel under conditions sufficient to convert the naphthalene into Or a step of reacting 2-ethylnaphthalene with an ethylating agent. 30. The ethylating agent is ethylene, ethanol, ethyl ether, and chloride. 30. The process according to claim 29, selected from ethyl. 31. 31. The process of claim 30, wherein the ethylating agent comprises ethylene. 32. The reaction produces 2,6-diethylnaphthalene and 2,7-diethylnaphthalene. Claim 2, wherein both rens are produced and the 2,6/2,7 isomer ratio is greater than 1. 9. The process described in 9. 33. 30. The silica/alumina ratio of the catalyst is about 5 to 200. Process described. 34. 3. The silica/alumina ratio of the catalyst is about 10 to 1000. The process described in 3. 35. 34. The silica/alumina ratio of the catalyst is about 20 to 500. The process described in. 36. Claim 2, wherein the catalyst is calcined at a temperature between 400°C and 1000°C. 9. The process described in 9. 37. The acidic portion on the outer surface of the catalyst makes the catalyst and from the group consisting of halogen derivatives, hydride derivatives, and organic derivatives of group VA Claim 2 is inactivated by contacting with a selected inactivating reagent. 9. The process described in 9. 38. The acidic portion on the outer surface of the catalyst includes the following steps a, b, and c. 30. The process of claim 29, wherein the process is inert. a. The open pores inside the crystal of the catalyst are filled with hydrocarbons to protect the inside. obtaining a catalyst; b. The internally protected catalyst is placed in an acidic aqueous solution or within a crystal. treatment with a complexing agent that is insoluble in the hydrocarbons contained in the pores; and c. A step of removing the hydrocarbons and recovering the catalyst. 39. The acidic portion of the outer surface is inactivated by pre-coking. The process according to claim 29. 40. 30. The catalyst of claim 29, wherein the catalyst has a particle size of less than about 4.0 μm. Roces. 41. 41. The process of claim 40, wherein the particle size is between 0.1 μm and 3.75 μm. vinegar. 42. The 2,6-diethylnaphthalene is oxidized to produce 2,6-dicarboxynaphthalene. 30. The process of claim 29, further comprising the step of producing talen.