TWI237630B - Process for preparing 2,6-dialkylnaphthalene - Google Patents

Abstract

A process for producing 2,6-dialkylnaphthalene from a hydrocarbon feedstock that contains at least one component selected from the group consisting of dialkylnaphthalene isomers, monoalkylnaphthalene isomers, polyalkylnaphthalenes, and naphthalene, is provided that includes the following steps: (I) separating the hydrocarbon feedstock and/or a dealkylation product fed from step (III) into a naphthalene fraction, a monoalkylnaphthalene fraction, a dialkylnaphthalene fraction and a remaining products fraction; (II) separating and purifying 2,6-dialkylnaphthalene from the dialkylnaphthalene fraction of step (I); (III) dealkylating the hydrocarbon feedstock and/or the remaining products fraction of step (I) and feeding the dealkylation product to step (I); and (IV) alkylating the naphthalene and monoalkylnaphthalene fractions of step (I); wherein the hydrocarbon feedstock is fed to step (I) or step (III).

Description

A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1237630 V. Description of the invention (1) Background of the invention The present invention relates to a method for preparing 2,6-dialkylnaphthalene (DAN), especially a self-contained alkylnaphthalene or A mixture of naphthalenes was used to prepare 2,6-dimethylnaphthalene (2,6-DMN). Discussion Background When manufacturing high-performance polyester resins such as polyethylene terephthalate polymer (PEN) or polybutylene phthalate polymer (PBN), 2,6-DMN is used as the 2,6-naphthalenedicarboxylic acid. Precursor of acid. This is because compared with other precursors (such as 2,6-diisopropylnaphthalene or 2-methyl-6-isobutylnaphthalene), 2,6-DMN is easily oxidized to 2,6-naphthalenedicarboxylic acid. . P EN has many applications, such as films and bottles, such as long-term recording film, advanced photo systems, hot-filled containers, refillable bottles, and t ir e c o de e. P E N has good physical properties in terms of strength, heat resistance and gas barrier properties. Typical p B N applications include electronics, insulators and automotive parts. However, because industrially available methods of manufacturing 2,6-DMN are limited, so far p e N and P B N have been too expensive to effectively expand the market. There have been many proposals for the preparation of 2,6-DMN. U.S. Patent No. 4'79 5'847 (Weitkamp et al.) Describes a method for preparing 2,6-dialkylnaphthalene, which is based on the presence of a zeolite (especially ZS M-5) as a catalyst. An alkylating agent alkylates naphthalene or 2-alkylnaphthalene. This paper size applies to China National Standards (CNS) A4 (210 X 297 mm)

-4- 1237630 A7 B7 V. Description of the invention (2) US Patent No. '0025 (Angevine et al.) Describes a method for preparing DMN, which uses 2-methylnaphthalene (MMN) and naphthalene as the Raw materials, and a synthetic zeolite (McM-2 2) as a catalyst 'and it showed that MCM-2 2 was more effective than Z SM-5 when alkylated 2 μ μN and naphthalene. However, the above method only provides unit operation (such as batch) of 2-MMN alkylation, which is an expensive raw material and cannot be obtained in large quantities on the market. U.S. Patent Nos. 4,990,717 (Sikkenga) and 5'073.67 (Sikkenga et al.) Describe a multi-step process for the production of 2,6-DMN from ortho-xylene and butadiene, which consists of The following steps are composed: 1) In the presence of a catalyst such as an alkali metal catalyst, using butadiene alkyl, please read the note on the back page to prepare o-o-methyl 5-o- (o-tolyl) -pentene-2 0TP ), 2) Cyclization under the presence of catalysts such as platinum and copper catalysts on super stable zeolite catalysts ττ P to prepare 1,5 methylnaphthalene 5-printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

Τ 3Μ DD 1 5 catalyzes the initiation of the oxygen magamma and 銶, and 1 lead preparations such as Mf, in the presence of chlorine in T) M 5 naphthyl methyl 5 5 Ν, Μ τ-ID 6 structure, In the first case, the medium N touches the medium D, the medium 6 touches the boiling point, and it needs to be prepared and stored as rich as possible; in,)) Ν Ν 4 Μ MDD-NM DI mixed with the material NM D 5 -5- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1237630 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) If separated from the DMN mixture 2, The 6-DMN method and the above steps can be used to provide a satisfactory method for producing purified 2,6-DMN. Because multiple steps complicate processing equipment and increase costs, it is not clear whether conventional methods can provide a method suitable for the economical preparation of purified 2,6-DMN. In addition, it is extremely difficult to separate 2,6-D Μ Ν from other isomers by conventional separation methods (such as distillation and cooling crystallization), because: 1) the difference between the boiling points of D Μ isomers is very small, especially The difference in boiling point between 2,6-DMN and 2,7-DMN is only 0.3 ° C, and it is almost impossible to separate 2,6-DMN by distillation. 2) The cooling effect of 2,6-D MN purification of D M N isomer mixture solution will form very fine 2,6-D MN precipitates in suspension, so the separation of 2, 6-DMN is equivalent difficult. U.S. Patent No. 4,992,619, proposed by Kode et al., Proposes a method for separating a high-purity naphthalene methyl derivative from a mixture of materials by pressure crystallization.

U.S. Patent No. 4,784,766 to Mcmtoki et al. Proposes a pressure crystallization apparatus. Therefore, a novel and more effective industrial preparation method for dialkylnaphthalene was found. Summary of the Invention According to one of the purposes of the present invention, a paper size of 2,6-dialkylnaphthalene was proposed to meet the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -------- Order --------- (Please read the note on the back? Matters to write on this page) 1237630 A7 B7 " " " V. Invention Explanation (4) Preparation method. According to other objects of the present invention, a method for preparing 2,6-dimethylnaphthalene is proposed. A method for producing 2,6-dialkylnaphthalene from a self-contained hydrocarbon raw material is to achieve these and other purposes, and the hydrocarbon includes at least one selected from the group consisting of a dialkylnaphthalene isomer, a monoalkyl Naphthalene isomers, polyalkylnaphthalenes, and naphthalene components. The method includes the following steps: I. Separating the hydrocarbon feedstock and / or dehydrocarbonation product fed from step III into naphthalene fractions and monoalkylnaphthalene fractions 2. Dialkylnaphthalene fraction and the remaining product fractions; II. Separation and purification of 2,6-dialkylnaphthalene from the dialkylnaphthalene fraction of step I; III. Hydrocarbon feedstock and / or the rest of the dehydrocarbonation step I Product fraction, and feed the dehydrocarbonated product to step I; and IV. Alkylate the naphthalene and monoalkylnaphthalene fractions of step I; wherein the hydrocarbon feedstock is fed to step I or step III. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Charts, Charts, Charts, and Diagrams I Simplified Maps Allison Allison Allegiance Comparison Law Comparison Law Comparison Item Item Item Item 1 2 3 4 5 6 No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Display Table Table Table Table Table List List View List This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm ^ ~

1237630 A7 B7 V. Description of the invention (5) Figure 7 shows a better list of the eighth method in the scope of application. Figure 8 shows a preferred list of the 9th method in the scope of application. (Please read the precautions on the back before filling out this page.) Figure 9 shows the results of Example 7. Figure 10 shows the results of Example 12. The results of Example 13 are shown in FIG. 11. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS When the present invention is better understood with reference to the following detailed description with reference to the accompanying drawings, it is easy to obtain a more complete understanding of the present invention and many of its accompanying advantages. Unless otherwise stated, these drawings are not restrictive. It can be applied to any hydrocarbon raw materials containing alkyl naphthalenes (such as naphthalenes, M M N (monomethyl naphthalene) and D M N isomers. The present invention proposes a method for manufacturing 2,6-dialkylnaphthalene using cheap raw materials (DAN)-especially the method of 2,6-dimethylnaphthalene (DMN)-a high-value-added hafnium product. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In particular, LC0 (light cycle oil) and / Or it is derived from a central distillate fraction of f CC (fluidized bed catalytic cracking) or HC (hydrocracking). Although this feedstock typically contains about 40 to 45% by weight of naphthyl naphthalene in the feed stream, It has the following problems and difficulties in further processing: 1237630 A7 B7 V. Description of the invention (6) Alkyl naphthalenes are separated for further processing (such as alkylation step). Therefore, if not treated, the azeotrope will Reduce reaction efficiency. In the worst case, azeotrope will accumulate in the recycle stream of this treatment. 2) Polyalkylnaphthalene (PAN) PANs (such as trimethylnaphthalene, isopropylnaphthalene and tetramethylnaphthalene It is usually contained in the raw material and accounts for about 10 to 20% by weight of the raw material. That is, it is almost one-third to one-half of the content of the alkyl naphthalene. Other processing steps (such as alkylation and isomerization) will also produce PAN as a by-product. In conventional technology, 尙 has not proposed the use of PAN-type manufacturing An effective method for 2,6-dialkylnaphthalene. 3) Sulfur and nitrogen compounds This raw material contains sulfur and nitrogen compounds, which may contaminate the catalysts for alkylation and isomerization, so these compounds must be excluded from the recycle stream. With products outside. The inventors have discovered that dehydrocarbonation (DA)-especially hydrogenated dehydrocarbonation (HDA)-(i) is not only conducive to cracking and / or reforming azeotrope to lighter fractions, which is easier to interact with naphthalene , Dialkylnaphthalenes are separated from dialkylnaphthalenes; it also (ii) surprisingly facilitates the use of DA to make 2,6-dialkylnaphthalenes (especially 2,6-DMN), especially polyalkylnaphthalenes ( P AN) HDA such as trimethylnaphthalene and heavier alkylnaphthalene, which are included in the raw materials and are also produced as by-products during the academyization step; and (1 ii) facilitate the manufacture Applicable as the paper size of this paper. Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -9-(Please read the precautions on the back before filling this page)

-ϋ in ϋ ϋ ϋ II 1_ϋ ϋ ^ 1 I Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1237630 A7 ------- B7 _V. Description of the invention (7) Naphthalene and monoalkylnaphthalene . Printed by the Intellectual Property Office of the Ministry of Economic Affairs. This finding leads to more efficient manufacturing of 2,6-DMN because the present invention proposes a PAN effective use, which is more effective not only in the alkylation step, but also in the overall method. Although a high raw material conversion rate (μM N conversion rate) of about 50 to 60% provides a higher yield of 2,6-DMN, the resulting PAN also increases' which is shown in the conventional method in Table 4, US Patent No. 5, 7 4 4, 6 70 (Motoyuki et al.), The entire contents of which are incorporated herein by reference. (After the alkylation, the DMN and PAN contents were 55% and 23%, respectively, at a conversion rate of 58.28% ΜΜΜ). If PAN is no longer used in the recycle stream, this phenomenon causes loss of the naphthalene ring and reduces the process yield. Therefore, in order to minimize this loss, the MN conversion rate is limited to about 30%, which will reduce the 2,6-0 ^ 1 > ^ yield. Because the present invention can provide an effective use of PAN derived from the raw material (preferably from the raw material and the alkylation step) (additionally, 2,6-dialkylnaphthalene produced from DA of PAN), the alkylation step can obtain more A high raw material conversion rate of about 50% or more can also achieve a higher production rate of 2,6-dialkylnaphthalene. In addition, the present inventors found that dehydrocarbonation by simultaneous production of naphthalene and monoalkylnaphthalene is the second product of 2,6-dialkylnaphthalene which is a residue of the purification of 2,6-dialkylnaphthalene and is changed to dibasic A balanced distribution of naphthalene isomers or 2,6-dialkylnaphthalenes. Although the reaction mechanism of 2,6-dialkylnaphthalene DA is generally considered to be completely different, the results and product composition of DA are similar to the transalkylation and isomerization effects. This means that D A can receive customary methods such as effectively reading the notes in the United States.

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This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10- 1237630 A7 B7 V. Description of the invention (8) Patent No. 5, 7 4 4 6 7 0 The invention proposes an effective manufacturing method for printing high-value-added dysprosium products by using cheap raw materials to produce 2,6-secondary naphthalene, Ministry of Economic Affairs, Intellectual Property Bureau, and employee consumer cooperatives. As the preferred raw material of the present invention, any alkyl naphthalene-containing hydrocarbon raw material may be used, and the naphthalene includes at least one selected from the group consisting of a dibasic substrate, a monoalkylnaphthalene isomer, a polyalkylnaphthalene, and a naphthalene such as derived from a catalyst. A component of petroleum light circulating oil (LC0). Alternatively, it is preferable to pretreat a hydrocarbon feed such as L C 0 as a raw material, and then use the product method thereof as a raw material. The pretreatment preferably includes distillation (such as partial reaction), concentration, reforming sulfur and nitrogen compounds (which are usually in the raw materials, and which may pollute the catalyst) hydrogenation (), desulfurization, denitrification Effect and dehydration. As a pretreatment for distillation and concentration, it is best to separate light (such as diaromatic compounds and non-aromatic light paraffin) and heavy-weight ones such as bicyclic aromatic tobacco and the naphthalene component Heavy compounds) Preferred HDT conditions include about 200 to 1, 0 0 ° C, preferably 200 to 500 ° C, 0 to 250 atmospheric pressure, preferably 5 to 50 atmospheric pressure, from about 500 to 3 Hydrogen cycle rate of 1,000 / bb 1. It is preferred to complete the reaction using a feed space velocity of about 0.1 to 10.0 h. The naphthalene isomerization cracking method is used as the center distillation.

One of SC's preferred catalysts for HDT is an activated alumina catalyst loaded with Group VIII metal oxides and Group VI-A metal oxides, preferably nickel and molybdenum, respectively. . The oxide is preferably treated at 600-120 ° F in the presence of sulfur compounds. Please read the "Notes" on the back first

Page I The size of the paper is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -11-1237630 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) The raw material can be fed Separation to step I and / or dehydrocarbonation of step III. In the case where the raw material is fed to the step, the effect of separating the light component and the heavy compound from the alkylnaphthalene component can be performed in step I. On the other hand, in the case where the raw material is fed to step I I I, the PAN component in the raw material can be reduced and changed to DMN or MMN before the separation effect in step I. In other examples, as seen in FIG. 1, the residual product of step I is fed to step I I I and the product of step I I I is fed to step I to obtain an effective manufacturing effect. Conventional techniques such as distillation can be used as the separation in Step I. In the case where the raw material stream contains a non-aromatic compound component having a boiling point very similar to that of alkylnaphthalene and / or MN, in addition to the distillation in step I above, conventional solvent extraction techniques can also be used. Isolation and purification of step II Purify 2,6- DA Ν, and separate 2,6--lean DAN from the DAN fraction of step I, as shown in Figure 1. Please read the notes on the back page. Often, in the words of the additive, the material is in the desired state. I know that this technology separates and can make a liquid mixture containing a specific substance in this method. The substance is placed at 2,6-the coexistence system is discharged, but crystallizes. Perform liquid-liquid mixed fruit self-harm operation, in a sealed pressure vessel-forming a solid and a liquid while making the solid-can be used. effect. By mixing the mixture out. For two or more, the coexistence of solidified parts is known to the artist. Purification uses two or more substances under high pressure, and is carried out by methods involving separation, such as cold crystallization. The pressure of the material is closely related to the purification technique Dialkylnaphthalene liquid, II-2 and / or adsorbed and pure compounds, retained liquid content will contain -12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237630 A7 B7 V. Description of the invention (10) The pressure of the liquid coexistence system is maintained at a level higher than the equilibrium pressure of the target substance ', and then the solid remaining in the container is pressurized to discharge the residual liquid between the solid particles and collect the solid particles. This technique is generally described in U.S. Patent No. 5,220,098, the entire contents of which are incorporated herein by reference. This method involves injecting a slurry or liquid at a temperature of 70 to 120 ° C (preferably 80 to 100 ° C) into a high-pressure container for crystallization under high pressure, and adiabaticly pressurizing the container to 300 to 4, 000 kgf / cm2, preferably 500 to 2, 000 kgf / cm2 to increase the amount, that is, 2,6-dialkylnaphthalene crystals, so please read the back of a solid solution © Notice

m Page I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the ratio of the rows; the ratio of this row; for this is in the high-pressure block. Borrowing—the first courtyard is good. The mixture was pre-concentrated under pressure to absorb benzene and cyclohexyl; the liquid phase group was discharged from the high-pressure vessel to improve the solid phase of the container so as to partially dissolve and purify the product. The action is to pressurize the solid phase in the high pressure vessel to reduce the pressure of the residual liquid phase under pressure to discharge the residual liquid phase. 2,6 naphthalene with a purity of 98% by weight (for example, 2,6-dimethylnaphthalene). In the separation and purification process with 99% by weight, it can be used before cooling and / or crystallization. The fixed bed adsorption system concentrates 2,6-dialkylnaphthalene from dialkylnaphthalene. As for the use of 2,6-DMN, adsorption is preferred, and it includes a boiling agent containing an alkali metal and an organic solvent desorbent mainly composed of at least one component selected from the group consisting of hexane, octane, and alkylalkane. Ordered by 釆, 二二二 II-13- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1237630 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Benzene and n-xylene are preferred as the alkylbenzene. During the cooling and crystallization in the separation and purification steps, since 2,7-DMN forms a fusible catalyst with a weight% ratio of 0.7 (= 2, 6 — DMN / 2, 7-D MN), only a low yield is obtained. Rate 2,6 -DMN. The theoretical yield of 2,6-DMN is obtained from the following formula: Yield (%) = (1-0.7 / k) x 100, where k 2 of the 2,6-D MN in the crystallizer feed / 2,7 — D M N. Therefore, in order to obtain higher 2,6-DMN yield, it is best to increase 2,6-DMN / 2,7-DMN. This fixed bed adsorption can increase the ratio of feed to 1.0 to output of more than 2.0, which results in higher separation yields and reduces the number of internal cycles of the overall process. For more efficient production, the separation and purification of step I I can be divided into a separation part, step I I 1 and a purification part, step I I 2 as shown in FIG. 5. In step II-1, the DAN level of step I is divided into 2,6—enriched with a DAN and 2,6—poor—DAN, and in step II—2 from step II—1-2, 6—enriched with one DAN separation 2, 6-DAN. For example, the separation effect of step I I-1 is performed by distillation, and step I I is performed, and the purification effect of crystallization by cooling and / or crystallization under high pressure is preferred. With this system, you can

Step I I A depletion D A N separation contains a small amount of 2,7 — DAN of 2,6 —lean Step I I 2 separates a large amount of 2,7 — DAN of 2,7 — D A N as a residual product of purification. The HDA conditions of step III include about 2000 to 10,000. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -14-Please read the precautions on the back © page 1237630 A7 B7 V. Description of the invention (12) ° C temperature, preferably from 300 to 700 X :, and pressure from 0 to 250 atmospheric pressure, preferably from 5 to 150 atmospheric pressure, the hydrogen cycle rate is from about 50 ° to 3, 000 scf / bbl. The reaction is suitably completed using a feed space rate of about 0.1 to 10 · 0 h r 1. One example of a suitable catalyst for HDA is an activated alumina catalyst, which contains an oxide of a Group VIII metal, and chromium is preferred. Another example of a suitable catalyst for HDA is an activated catalyst Alumina catalysts, which contain oxides of Group VIII metals and Group VI metals, preferably cobalt and molybdenum. The oxide is preferably pretreated at a temperature of 600 to 100 ° F in the presence of organic sulfides. Other preferred catalysts for HDA include a catalyst comprising a metal selected from precious metals, nickel, and combinations thereof, and a synthetic zeolite whose X-ray diffraction pattern features include the following interstellar d-space and relative intensity I / I. x 10 0: Please read the note on the back page printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

12.36 ± 0.4 M-VS 11.03 ± 0.2 MS 8.83 ± 0.14 M-VS 6.18 soil 0.12 M-VS 6.00 ± 0.10 WM 4.06 ± 0.07 WS 3.91 ± 0.07 M-VS 3.42 soil 0.06 VS This paper size applies to the Chinese National Standard (CNS) A4 size (210 X 297 mm) 1237630 A7 B7 V. Description of the invention (13) The preferred noble metal is selected from the group consisting of aluminum, palladium and combinations thereof. The alkylation conditions of step IV preferably include a temperature of about 0 to 500 ° C ', preferably 240 to 450 ° C, and a pressure between 0 and 250 atmospheric pressure', preferably 1 to 50 atmospheric pressure. The molar ratio of the alkylating agent to the dialkylnaphthalene or naphthalene feed may be from about 20 ·· 1 to 1: 2 0, preferably from 10 ·· 1 to 1:10. The reaction is appropriately completed using a feed space of about 0.1 to 10.0 hr-1. Preferred alkylating agents include alcohols, olefinic hydrocarbons, aldehydes, halides and ethers. For example, methanol, dimethyl ether and polyalkylbenzene are preferred. Particularly preferred are methanol and dimethyl ether. A suitable catalyst for alkylation is a synthetic zeolite whose X-ray diffraction pattern features include the following interstellar d-space and relative intensity I / I. X 10 0 ·

1 2 · 3 6 ± 〇 · 4 M-VS 1 1.03 ± 0.2 MS 8.83 ± 0.14 M-VS 6.18 ± 0.12 M-VS 6.00 ± 0.10 WM 4.06 ± 0.07 WS 3.91 ± 0.07 M-VS 3.42 ± 0.06 VS Applicable catalyst It is described in U.S. Patent Nos. 5,001,295 and MCM-22, the entire contents of which are incorporated herein by reference. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Please read the precautionary page of © © Printed by the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative. 16-1237630 A7 _B7 V. Description of Invention (14) The alkylation can be carried out in any conventional reactor commonly used for alkylation. For example, a tubular reactor can be used which allows the reactants to flow down through a fixed bed of catalyst. In order to maintain a high feed conversion rate, methanol can be injected into the reactor, preferably in multiple stages, and more preferably in two steps. For example, it is preferred to use one reactor with a top and intermediate methanol feed, or two reactors with a top and intermediate methanol feed in succession. In a preferred specific example, heterogeneous conditions can be applied to step II 1-2, 6-lean-DAN fractions to provide one with more 2, 6-two fires 7 Π Cai Cai heavier weight * hospital base table fractions such as Shown in Figure 6. This isomerized product can be fed to step I and / or step I I-2 for more efficient recovery. The preferred heterogeneous conditions are broadly disclosed in the co-pending applications in the United States | Serial No. 08/6 1 1 '1 1 4 (the entire contents of which are incorporated herein by reference)' and are suitable for simultaneous two Alkylation of alkylnaphthalene with naphthalene, and the isomerization of dialkylnaphthalene. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

A preferred heterogeneous catalyst is a synthetic zeolite. Its x-ray diffraction pattern features include the following interstellar d-space and relative intensity. / Χ i 〇 〇: 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 ± 0.07 W-S • 17- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) Yuan Jicai: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

I I I 123763〇 A7 V. Description of the invention (15)

3.91 ± 0.07 M-VS

3.42 ± 0.06 VS applicable catalyst is disclosed in US Patent No. 5,001, 295 'is MCM-2, the entire content of which is incorporated herein by reference. The isomerization is carried out at a weight hourly space velocity (WHSV) of dialkylnaphthalene from 0.1 to 10 h-1, preferably from 0.5 to 5 h-1, and more preferably from 0.775 to 1.511-1 good. Isomerization is carried out at a temperature of 100 to 500 ° C, preferably 150 to 350 ° C, more preferably 200 to 300 ° C. The isomerization is carried out at a pressure from atmospheric pressure to 1000 kg f / cm2, and preferably from atmospheric pressure to 30 kg f / cm2. During the isomerization, it is also possible to selectively co-feed hydrogen, the amount of which is from 0.1 to 10 mole-H2 / mol-hydrocarbon. According to a preferred specific example of FIG. 2 or 3, 2,6 I can be prepared from a hydrocarbon feedstock as follows: Isolate a feedstock and / or the product obtained from step III into a naphthalene-containing fraction, a monoalkylnaphthalene-containing fraction, Fractions containing dialkylnaphthalene and fractions containing the remaining product; II. Separation and purification of 2,6-dialkylamine from the dialkylnaphthalene fraction of step I; separation of 2,6-dialkyl from step II Dialkyl naphthalene fraction is dehydrocarbonated after naphthalene, and the dehydrocarbonated product is recycled to the step. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm). -18- Please read the first page Precautions

Page II of 1237630 A7 B7 V. Description of the invention (16) III b · The hydrocarbon feedstock of dehydrocarbonation step I and / or step I contains the remaining product fractions, and feed the dehydrocarbonation product to step I; and V. The alkylation step I comprises naphthalene and monoalkylnaphthalene fractions. In this method, 2,6-depleted-DAN remaining in the separation / purification effect of step I I is dehydrocarbonated and fed to the separation effect of step I. Therefore, the 2,6-DAN isomer in 2,6-lean-DAN can be changed to MMN or NL, and can be basicized in step IV. As for the preferred specific example in Fig. 4, the alkylation product of Step IV is fed to the separation effect of Step I. Therefore, the PAN produced in Step IV can be separated in Step I and fed to the dehydrocarbonation of Step I I I. Therefore, it is possible to effectively utilize P A N as described above and to make the raw material conversion rate of the alkylation step higher. The schematic diagram of the method of FIG. 8 is a preferred embodiment of the present invention. Examples Although the present invention has been described, a further understanding can be obtained by referring to specific examples. Unless otherwise specified, they are presented here for illustrative purposes only and not for limiting the present invention. Example 1 Alkylation of M M N with naphthalene A 153 g quantity of MCM-2 2 catalyst was charged into a tubular reactor (volume: 370 cubic centimeters). Use 1-ΜΜΝ, 2-ΜΜΝ and naphthalene as raw materials for alkylation, and use 2-ΜΜΝ / 1-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Please read the notes on the back first Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-T9-1237630 A7 B7 _ ----- ^ ----- V. Description of the invention (17) The MMN molar ratio is 2 · 2 and MMN weight ratio ~ ( 1 ~ μμΝ + 2-ΜΜΝ) / naphthalene-mixed at a ratio of 3.0. Therefore, the raw material was supplied to the reactor (254C, 5 kg / cm2) at a rate of 153 · 4 g / hour, and fed at a rate of 1 · 8f t3 / hr at a WHSV of 1 · Ohr-1. Feed hydrogen. After four hours, methanol as an alkylating agent was introduced into the reactor at 35 · 5 g / hour, and alkylation was performed for 20 hours. The product was analyzed by gas chromatography. The results are summarized in Table 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -2σ- This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 1237630 A7 B7 V. Description of the invention (18) Table 1 (monomethylnaphthalene and Alkylation of naphthalene) Component (% by weight) Dimethylnaphthalene before reaction 0 17.19 2,6-DMN 0 1.72 2,7-DMN 0 1.20 Other isomers 0 14.27 Monomethylnaphthalene 73.63 60.10 2 -MMN 50.55 40.32 1-MMN 23.08 19.78 Naphthalene 25.28 18.67 Other components 1.00 3.91 Evaluate NL conversion rate after reaction before reaction (%) — 26.15 2-MMN / 1-MMN 2.2 2.04 MMN conversion rate (%) 18.37 2,6- DMN / Total DMN (%) 10.02 2,6-DMN / 2,7-DMN-1.44 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, as can be seen in Table 1, 2, 6 — DMN / 2, 7 — DMN The ratio is higher than 1 · 1 and the ratio of 2-MMN / 1-MMN is higher than 2 · 〇 ° -21-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237630 A7 _____JB7___ 5 2. Description of the invention (彳 9) (Alkylation) Fill the tube reactor with a quantity of 153 g of MCM-2 2 (volume: 370 Square centimeter). 1-MMN (purity 95.5%) and 2-M MN (purity 96.6%) were used as the raw materials for alkylation, and the molar ratio of 2-M Μ Ν / 1-Μ Μ Ν was 2. The ratio of 2 is mixed. The raw material was supplied to the reactor (350 ° C) for 4 hours at a rate of 76 · 7 g / hour and a WHSV of 0.5 · 5hr-1. Thereafter, methanol was supplied to the reactor at 17 · 3 g / hour, and the reaction was performed for 20 hours. The product was obtained by gas chromatography analysis. The results are summarized in the table. Please read the notes on the back page. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. ) 1237630 A7 B7 V. Description of the invention (20) Table 2 (Alkylation) Components (% by weight) After the reaction * Dimethylnaphthalene 0 35.45 2,6-DMN 0 5.12 2,7-DMN 0 4.44 Other isomers 0 25.89 * monomethyl naphthalene 98.66 41.16 2-MMN 67.61 28.84 1-MMN 31.05 12.32 * naphthalene 0 0.19 * other components (mainly PAN) 1.53 23.20 after evaluation 2-MMN / 1-MMN 2.2 2.3 MMN Conversion Rate (%)-58.28 2,6-DMN / Total DMN (%)-14.45 2,6-DMN / 2,7-DMN-1.16 (Please read the notes on the back before filling in this page)

-------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs It can be seen from Table 2 that the ratio of 2, 6—DMN / 2, 7—DMN is higher than 1 · 1 and the ratio of 2-MMN / 1-MMN is higher than 2 · 0. Example 3 (Alkylation and Distillation) The alkylation of MN and naphthalene was carried out in the same manner as described in Example 1. The paper size was adapted to Chinese National Standard (CNS) A4 (210 X 297 mm). -23- 1237630 A7 B7 V. Description of the invention (21) It takes several months and collects about 400 kg of product. A batch type distillation column having a packed column was used for the distillation of the product. The number of expected theoretical disks is at least 50. The operating pressure at the top of the column was controlled between 15 and 36, and distillation was performed at a reflux ratio of 50 to 75. The product was separated into 17 fractions with differences in boiling points, as shown in Table 3. Table 3 (Alkylation and Distillation) Amount (kg) DMN concentration (%) 2,6-DMN concentration (%) Fraction 1 -1 0 270.8 0.0 Unanalyzed fraction -11 30.9 0.5 Unanalyzed fraction- 1 2 8.8 38.9 Unanalyzed Fraction-1 3 11.0 64.8 11.2 Fraction-1 4 6.3 92.3 25.4 Fraction-1 5 15.7 99.6 4.3 Fraction-1 6 4.8 98.7 0.0 Fraction-1 7 5.3 41.6 0.0 Residue 21.2 0.0 0.0 Example K such as hydrogen degassing)

'Mix the fractions of Table 3-17 parts with the raw materials (blend-A) used for residue preparation such as hydrogen dehydrocarbonation. A 50 g quantity of the catalyst C I * 2 03 / A 1 2 03 made by Sud-Chemie AG was charged into a tubular reactor. At the same time as the hydrogen was supplied, the reactor was gradually heated from room temperature to 6 6 2 ° F --------- (Please read the notes on the back before filling out this page) Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Development 97 2 X 10 2 / IV G4 A4 5) N (C quasi-standard country Guojia week K food paper winter 24 1237630 A7 B7 / hr when supplying hydrogen ^ 1 WHSV will be mixed with 0hg V. Description of the invention (22) The catalyst was dried. Therefore, the reactor was fed at a rate of 50 g / h and 1-A-A at a rate of 1. Dehydrogenation at 8 8 7 ° F and 8 5 4 ρ. The product was analyzed by GC, and the results of the hydrogen dehydrocarbonation are summarized in the following Table 4. As shown in Table 4, the C r 2 03 / A 1 2 03 type catalyst is beneficial to make 2,6-DMN lean feed Enriched with 2,6—DMN. Please read the note of the back page first. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm). 1237630 A7 B7 5 2. Description of the invention (23) Table 4 (such as hydrogen dehydrocarbonation) Printed feed of consumer cooperatives of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs (blend-A) HDA products naphthalene 0.0 3.11 2-MN 0.0 15.68 1-MN 0.0 3.71 2 -EN 0.0 0.57 1-EN 0.0 0.26 2,6-DMN 0.0 4.86 2,7-DMN 0.0 4.58 1,3- + 1,7-DMN 0.0 7.58 1,6-DMN 0.0 2.92 2,3- + 1,4 -DMN 0.14 4.84 1,5-DMN 0.0 0.39 1,2-DMN 20.18 9.42 1,8-DMN 0.0 0.12 Unknown component before the first DMN 0.0 2.50 Unknown component between DMN 1.34 0.39 Including polymethylnaphthalenes Heavy group 78.34 39.08 copies Total DMN (%) 20.20 34.71 2,6-DMN / Total DMN (%) 0.0 13.20 -------- Order --------- (Please read the back page first Note: Please fill in this page again.) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -26-1237630 A7 B7 V. Description of the invention (24) Example 5 Heterogeneous effect will be 25 grams The MCM-2 2 catalyst was charged into the tubular reactor (volume: 200 cubic centimeters). While supplying nitrogen, the reactor was gradually heated from room temperature to 400 ° C to dry the catalyst, and the nitrogen flow was stopped when the temperature was set at 400 ° C. Therefore, at a rate of 25 g / h and a WHSV of 1.0 hr -1, 2,6-lean-DMN was fed and the D M N isomerization was performed for four hours. The content of the product was analyzed by gas chromatography. The results are summarized in Table 5. (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 (Isomerization 1 component (% by weight) Dimethylnaphthalene before reaction 98.09 80.10 2,6-DMN 6.21 13.96 2,7-DMN 8.48 8.66 Other isomers 83.40 57.48 Monomethylnaphthalene 0.20 9.77 2-MMN 0.03 6.71 1-MMN 0.17 3.06 Naphthalene 0 0.78 Other components 1.71 9.35 After evaluating the reaction 2,6-DMN / total DMN (%) 6.3 17.4 2,6-DMN / 2,7-DMN 0.73 1.61 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -27 ^ Order --------- Support 1237630 Employees' Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs Print A7 V. Description of the invention (25) [J 6 Isolation and purification as 1: (1) Crystallization under high pressure crystallization The amount of DM N isomers of 1,505 grams was supplied to the high pressure crystallizer (KOBELCO 1.5L type), and separated 236 g of 2,6 D MN crystals (purity 87.7%) under conditions of 2,000 and 45 t: (2) cooling crystallization using a container for crystallization (3 Liters), and rapidly cooled 2,01 g of the DM Ν isomer from 50 to 40 ° C while stirring. Then, 0.5 g of seed crystals were put into the container, It was held at 40 ° C for one hour. Therefore, the raw material was cooled to 10 ° C at 2 ° C / minute. The filtration was performed under pressure to separate 3,60 grams of 2,6-DMN crystals (purity 6). The results of the crystallization of 8% under high pressure and cooling crystallization are summarized in Table 6. This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

1237630 A7 B7 V. Description of the invention (26) Table 6 (Separation and purification effect) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs under high pressure Crystallization components (g) Crystallization filtrate before crystallization 2,6-DMN 301 205 96 2 7-DMN 232 22 210 Other DMNs 972 9 963 Total 1505 236 1269 2,6-DMN / 2,7-DMN 1.3 0.5 2,6_DMN / Total DMN 20.0% 7.6% Crystal purity-87% 2,6-DMN Recovery rate-68% 2,6-DMN yield-13.6%-cooling crystallization component (g) crystallization filtrate before crystallization 2,6-DMN 400 244 156 2,7-DMN 308 67 241 other DMN 1293 49 1244 Total 200 1 360 1641 2,6-DMN / 2,7-DMN 1.3 0.65 2,6-DMN / Total DMN 20.0% 9.5% Crystal purity-68%-2,6-DMN recovery rate-61 %-2,6-DMN Yield-12.2%-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ 29- (Please read the precautions on the back before filling this page )

Order ---------. 1237630 Α7 Β7 V. Description of the invention (27) "2,6-D Μ N recovery" means the content of 2,6-D Μ N in the crystal relative to 2 in the raw material , 6 — DMN content. "2,6-D MN yield" means that the content of 2,6-D MN in the crystal is relative to the total weight of the raw material. As shown in Table 6, the yield of 2,6-D MN that crystallizes under high pressure is far Higher yield than cooling crystallization. Also, the filtrate crystallized under high pressure has a ratio of 2,6 -ϋ Μ Ν / total D Μ Ν less than 8%. Therefore, this filtrate is more conducive to 2 '6 -depleted DMN alkyl Transfer and isomerization of raw materials. In addition, when trying to increase the crystalline purity of cooled crystals, 2,6-D ΜΝ decreased sharply. Example 7 (Purification, attempted to cool DM mixtures by cooling crystallization (Table 7) Pre-condensate 2 '6-D ΜΝ, and separate 2' 6-Μ Ν filter cake rich by experimental-scale pressure filtration unit, using them as raw materials for crystallization under high pressure. Use Kobelco's Η PC test machine, high pressure The following crystallization method was used to perform a series of experiments on the purification effect of 2,6-D MN from the filter cake rich in 2,6-D MN, and the results are summarized in Figure 9. It can be seen from Figure 9 that: 2,6 — DMN purity in a single stage of crystallization is higher than that of two-stage cooling crystallization under high pressure It can achieve more effective purification performance. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) Please read the note on the back page printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives -30-1237630 A7 B7 V. Description of the invention (28) Table 7 (2 sets of DMN mixture stand ------ ^ DMN mixture sulfur (ppm) 430 nitrogen (ppm) 140 2,6-DMN---- 13.8 2,7 -DMN 14.1 1,6-DMN 7.1 1,3- & 1,7-DMN 20.5 1,4-DMN-1,2- & 1,5-DMN 0.4 2,3-DMN 0.5 Other components 43.6 Implementation Example 8 (Distillation) Alkyl naphthalene was separated from LC 0 using two batch distillation towers. Steaming (fractionator-A) had a 167-liter distillation pot, and p-PAK (Scientific Development Company) 〇f Please read the phonetic on the back? Matters before filling out this page} Then fill out this order --------- R ο w. Ft. Tower printed by an employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The other distillation column (fractionator B) has a 27-liter steamed shabu-shabu, which has a 11-foot long column with PRO-PAK. 164 male 5 L C0 is charged into fractionator A, 50 to reflux rate 60 Torr pressure distillation. Collect 8 0.5 liters at a take-out rate of 0.7 liters per hour. Then, take out the 25 kg fractionator after the first distillation—a steamed paper. The size of the paper applies the Chinese National Standard (CNS) A4 (210 X 297 cm) (Centi) -31-1237630 A7 B7 V. Description of the invention (29) Residue in the still. Additional batch distillation was performed at 50 reflux rate and 50 Torr pressure. 14 litres were collected at a removal rate of 125 ml per hour. The components of the product (blend one B) obtained by the above two-step distillation are shown in Table 8 ° Example 9 (such as hydrogen dehydrocarbonation) A quantity of 70 g of C r 2 prepared by Sud-Chemie AG The 〇3〆A 1 203 catalyst was charged into a tubular reactor. While supplying hydrogen, the reactor was gradually heated from room temperature to 9 3 2 ° F to dry the catalyst. Therefore, when hydrogen was supplied at 0.98 scf / hr, the distillation product (blend-B) prepared in Example 8 was supplied to the reaction at a rate of 70 g / hr and a WHSV of 1.0-hr-1. Device. Perform a dehydrocarbon reaction such as hydrogen at 9 3 3 ° F with 1 1 3 8 p s i g. The product was analyzed by G C and the results of the hydrogen dehydrocarbonation are summarized in Table 8 below. Example 10 (such as hydrogen dehydrocarbonation) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a quantity of 70 g of C 〇〇 / Mo 〇3 / A 1 203 catalyst produced by Akzo Chemicals Inc. Load a tube reactor. The reactor was gradually heated from room temperature to 300 ° F, and the nitrogen flow rate was 5 s c f / h r. Then, the flowing gas was changed to hydrogen of 2 s c f / h r and the pressure was increased to 500 p s i g. At the same time that the hydrogen was supplied, the catalyst was vulcanized with an organic sulfide (Kerosene, with 1.0% methyl sulfide), and then the temperature was raised to 650 ° F. Therefore, when supplying oxygen at 0.98 scf / hr, at a rate of 70 grams per hour and 1.0 hr—1, this paper size applies to China National Standard (CNS) A4 (210 x 297 mm)-1237630 A7 B7 5. WHSV of the invention description (3G) The distillation product (blend-B) obtained in Example 8 was fed to the reactor. Hydrogen dehydrogenation was performed at 932 ° F with I425 ps lg. The product was analyzed by G C, and the results of the hydrogen dehydrocarbonation are summarized in Table 8 below. As shown in Table 8, 〇〇〇〇〇〇〇〇〇 03 / 〇 〇 00 /

Both the Mo 〇3 / A 1 203 catalysts are beneficial for making the DMN lean feed rich in D M N isomers. Please read back & note items first

Page I No. 4 Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed to the Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1237630 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (31) Table 8 (such as hydrogen dehydrocarbonation) Example 7 Example 8 Example 9 Distilled product (blend-B) HDA product HDA product catalyst C r 2 0 3 / A12 〇3 Co〇 / Mo〇 3 / A1 2〇3 naphthalene_ 0.0 1.33 4.75 2-MN 0.0 4.31 9.48 1-MN 0.0 1.05 2.44 2-EN 0.0 1.56 2.13 1-EN 0.0 0.36 0.44 2,6-DMN 0.0 2.46 3.53 2,7-DMN 0.0 2.56 3.76 1,3- + 1,7-DMN 0.0 2.55 3.82 1,6-DMN 0.0 1.43 2.17 2,3- + 1,4-DMN 0.0 1.18 1.44 1,5-DMN 0.0 0.24 0.34 1,2-DMN 0.04 0.40 0.32 1,8-DMN 0.04 0.25 0.47 Unknown component before the first DMN 0.0 8.67 17.68 Unknown component between DMN 0.0 0.54 0.68 Heavy component including polymethylnaphthalene 99.92 71.11 46.56 Total DMN (%) 0.08 11.07 15.85 2,6-DMN-Total DMN 0.0 22.22 22.27 丨 丨 丨 丨 | ------ ΛΎ (Please read the note on the back? Matters before filling this page) Order --------- ^- 34- Paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 1237630 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (32) ι_ι __ (__ Distillation and hydrogenation treatment) 4 kg of LC0 was charged into fractionator A and steamed and retained at a reflux rate of 50 and a pressure of 60 Torr. 120 litres were collected at a rate of 0.7 litres per hour, and a blend of 10 was prepared as a raw material for hydrogenation treatment. The Ni 〇 / Μ〇〇 3 / A 1 2 03 catalyst prepared by Akzo Chemicals Inc. was used as a hydrogenation catalyst and charged into a tubular reactor. After drying and vulcanizing the catalyst, Blend-c was fed to the reactor at a WH SV rate of 0.43 hr-1, and was gasified at 400 psig and 7 26 ° F. 349 5 scf / bb 1 Supply hydrogen. The results of the hydrogenation treatment are shown in Table 9 below. As shown in Table 9, the Ni / Mo 03 / A 1 2 03 catalyst helps reduce nitrogen and / or sulfur compounds in L C0 and minimizes the loss of dM N isomers. Table 9 (Distillation and Hydrogenation)

Nickel ρρ m Sulfur PP m API 400F + Conversion rate (%) 400F + Conversion rate (%) 500F + Conversion rate (%) Total DM N Weight% Blend-C 230 388 18.7---26.56 HDT product 7 5 20.6 0.6 7 21 21.24 This paper size applies Chinese National Standard (CNS) A4 specification (210 χ 297 mm) · 35 _ 1237630 Α7 Β7 V. Description of the invention (33) ϋ! Example 1 2 (Adsorption) Mixing 2, 6 — D M N and 2,7 — D M N were dissolved in isooctane at a concentration of 2.0% by weight, respectively. Then, the DMN isooctane solution was fed to an adsorption column (4.6 mm 10 and 5000111) containing K-fluorenite zeolite at a rate of 0.5 ml / min, while the column temperature was controlled at 15 8 ° F. G C analysis was used to collect DM N concentration time history data and obtain the penetration curve of the adsorption step. After the adsorption step, the liquid feed was converted to pure isooctane, and the effluent was also analyzed to collect time course data of the D M N concentration in the effluent. The results of the penetration curve and desorption curve are summarized in FIG. 10. As shown in the figure, comparing the 2,7-D MN and 2,6-D MN that are adsorbed on the zeolite, the contact of the D MN isomer with the K monofluorite zeolite can obviously be improved by 2, 6-/ 2, 7-DMN. Example 13 Another adsorption test was performed in the same manner as described in Example 12 except that it was used as a solvent. The results of the penetration curve and the adsorption curve are summarized in the figure. Please read the note of Φ first.

Λ Page I I I I Order 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs It is clear that many improvements and changes to the present invention may be made in accordance with the above teachings. Therefore, it must be understood that within the scope of the appended patent application, the present invention can be carried out except as specifically described herein. This application is based on US Application Serial No. 08 / 948,299, filed on October 10, 1997, and its entire contents are incorporated herein by reference. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -36-

Claims (1)

12376 Mine A8 B8 C8 D8 VI. T ¥ Patent Range No. 88 1 056 1 Patent Application No. 1 Chinese Application Patent Range Amendment October 24, 1992 Amendment 1 · Preparation of 2,6-dialkyl from a hydrocarbon feedstock A method for naphthalene. The hydrocarbon feedstock comprises at least one component selected from the group consisting of a dialkylnaphthalene isomer, a monoalkylnaphthalene isomer, a polyalkylnaphthalene and a naphthalene. The method includes the following steps: The dealkylated product and selectivity of the hydrocarbon raw material are separated into a naphthalene-containing fraction, a monoalkylnaphthalene-containing fraction, a dialkylnaphthalene-containing fraction, and a fraction containing the remaining products; II. Isolate and purify the 2,6-dialkylnaphthalene fraction of the naphthalene fraction; III. Dealkylate the hydrocarbon feedstock with the remaining product fractions of step I and send the dealkylated product to step I; 1 V. step The naphthalene fraction of I is alkylated with an alkylnaphthalene fraction, wherein the hydrocarbon feedstock is sent to step m and optionally step I. 2. The method according to item 1 of the scope of patent application, which further comprises dealkylating the dialkylnaphthalene fraction after separating the 2,6-dialkylnaphthalene in step II, and dealkylating the product obtained. Loop to step I. 3. The method according to item 1 of the scope of patent application, wherein after separating the 2,6-dynylnaphthalene in step II, dealkylating the dialkylnaphthalene fraction in step III and separating the hydrocarbon feedstock and / Or the remaining product fractions of step I are dealkylated. This paper size applies Chinese National Standard (CNS) specifications (2IOX297 mm) (Please read the precautions on the back before filling this page), TΓ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1237630 Α8 Β8 C8 D8 VI. Patent Application Scope 4 · For the method in the first scope of patent application, the product of step 丨 v is sent to step I. (Please read the precautions on the reverse side before filling out this page) 5. If the method of the scope of patent application is the first step, the steps include the following sub-steps: II — 1 · Separate the dialkylnaphthalene fraction from step I Into 2,6-dialkylnaphthalene-rich fractions and 2,6-depleted di-dialkylnaphthalene fractions; II—2 · from step π-1 of 2, 6-dialkylnaphthalene-rich fractions 2,6-Dialkylnaphthalene was separated and purified. 6. The method of claim 5 in the scope of patent application, further comprising isomerizing at least a portion of the 2 ′ 6-depleted-dialkylnaphthalene fraction obtained from step II-1 1-2, wherein at least a portion isomerized The product is sent to step process and / or step II-2. 7 · The method according to item 6 of the scope of patent application, wherein the isomerization is performed in the presence of a catalyst composition 'This catalyst composition contains an X-ray having a d-spacing (A) between Synthetic zeolite with the diffraction pattern printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2.3 6 ± 0.4 11.03 Soil 0.2 8 · 83 ± 0 · 14 6 · 18 ± 0.12 6.00 ± 〇1〇4.06 ± 0.07 3.91 ± 0.07 3.42 Soil 0.06 This paper size is applicable to Chinese National Standard (CNS) A4 pit (2) 0 × 297 mm 1237630 A8 B8 C8 D8 VI. Application for patent scope 8 · If the method of the patent scope item 6 is applied, at least a part of it Step II-2 The residual product after purification of 2,6-dialkylnaphthalene is sent to Step III. 9. The method according to item 6 of the patent application, wherein at least a part of the product of step IV is sent to step I, and at least a part of the residual product after purification of 2,6-dialkylnaphthalene from step II-2 is sent to step III. 〇1 0. The method according to item 1 of the scope of patent application, wherein the demethylation in step I is a hydrodehydrogenation. 1 1 · The method of claim 10, wherein the hydrodealkylation includes contacting a hydrocarbon feedstock with a catalyst composition comprising a group VI-A metal oxide Activated alumina catalyst support. 1 2 · The method according to item 11 of the scope of patent application, wherein the group VI-A metal is chromium. 13. The method of claim 10 in the scope of patent application, wherein the hydrodealkylation includes contacting a hydrocarbon feedstock with a catalyst composition including a group VI metal and a group VI metal. -Activated alumina catalyst support for Group A metal oxides. 14 · The method according to item 13 of the scope of patent application, wherein the group V I I I metal is cobalt. 15 · The method according to item 13 of the scope of patent application, wherein the group VI-A metal is molybdenum. 1 6 · If the method of item 13 of the scope of patent application is in existence, the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1237630 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 VI. Application for Patent Scope Organic oxides are pretreated at 6 0-1 0 0 0 ° F物 07. The method of claim 10, wherein the hydrodealkylation is performed in the presence of a catalyst composition including at least one selected from the group consisting of precious metals, nickel, The metal of the composition and a synthetic zeolite characterized by an X-ray diffraction pattern characterized by the following d-spacing (A) 12.36 soil 0.4 1 1.03 soil 0.2 8.83 soil 0.14 6.18 soil 0.12 6.00 soil 0.10 4.06 soil 0.07 3.91 Soil 0.07. 3.42 Soil 0.06 1 8 · As in the method of claim 1 in the scope of patent application, the alkylation is performed in the presence of a catalyst composition, the catalyst composition includes a (A) Synthetic zeolite characterized by X-ray diffraction pattern 12.36 soil 0.4 11.03 soil 0.2 8.83 soil 0.14 6.18 soil 0.12 6.00 soil 0.10 This paper size applies to China National Standards (CN s) μ size (210 X 297 mm) -4-(Please read the precautions on the back before filling this page) 1237630 A8 B8 C8 D8 VI. Patent application range 4 · 0 6 ± 0 · 0 7 3.91 ± 0.07 3.42 ± 0.06 1 9. The method of item 1 in the patent application range, in which the alkylating agent is used for alkylation Department of methanol or dimethyl ether. (Please read the notes on the back before filling out this page), τ Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with Chinese National Standards (0 ^) six 4 rules ¥ (2) (^ 297 mm) -5-