TW315366B - - Google Patents

Description

315366 Λ 6 η 6 The Ministry of Economic Affairs has been approved by the central purse and the employee has been printed as a cooperative ^ V. Description of the invention (') The present invention is pseudo-related to an L-type zeolite, a catalyst for the production of aromatic hydrocarbons and a method of using the same Catalyst to produce aromatic hydrocarbons; more particularly, it relates to an L-type zeolite containing platinum and halogen components carried on it, a catalyst containing L-type zeolite suitable for aromatic reaction, and a method of using the same A method for producing aromatic hydrocarbons from non-aromatic hydrocarbons (such as panaxene) using a catalyst. Traditionally, when aromatizing non-aromatic hydrocarbons (such as aliphatic hydrocarbons) to produce aromatic hydrocarbons, platinum and aluminum strip catalysts are often used; The method of catalyst, and pointed out that it has better conversion efficiency (please refer to Japanese Patent Publication No. 57408/1983 and Japanese Patent Application Publication Nos. 223614/1983 and 80333/1984). However, all of these methods The platinum-carrying L-type zeolite catalysts used in are not ideal because they have low selectivity for aromatic hydrocarbons and the catalysts do not have long life. At this time, someone proposed a method of incorporating alkaline earth gold luteum (europium, strontium, calcium) into a platinum-supported L-type zeolite catalyst to improve the above disadvantages (please refer to Japanese Patent Application Publication No. 133835/1983) However, the follow-up study by the present inventors found that this catalyst is not practical because it does not sufficiently improve the selectivity of aromatic hydrocarbons and catalyst life, and the catalytic stability is not high. Later, some people even proposed; (1) A catalyst that has improved both in catalytic activity and catalyst life. It pseudo-oxidizes the L-type zeolite bearing the Group VIII metal of the periodic table with chlorine oxidation (please see Read Japanese Patent Application-3-(please read the back-end note-Ir code to write this page; the size of this paper is used in the Zhongyi a Jiayuban (CNS) 4 regulation IM210X29 / male dragon) 81. 7. 20.000 ^ (11) Λ fi Π 6 315366 V. Description of the invention (,) "; · Γ /] ^ 'Bulletin No. 168 5 39/1985 >; (2)-species with uniform dispersion and bearing lead The catalyst is treated with a solution containing platinum and a non-meal metal salt (see Japanese Patent Application Publication No. 138539/1986); (3) A catalyst carrying platinum on an L-type zeolite, Treated with halogen-containing compounds (please refer to Japanese Patent Application Publication No. 57653/1987); (4) A catalyst containing platinum-supported L-type zeolite, which is pseudo-treated with halogen-containing compounds. (Please See Japanese Patent Application Publication No. 91334/1988), etc. However, the catalyst mentioned in (1) is economically beneficial Very poor, because in order to carry out its production process at high temperature by gas oxidation, it requires expensive production equipment; and the catalyst (2) does not have sufficient catalytic activity. About the catalysts (3) and (4), Although their catalytic activity is improved, their catalyst life is still not long, and special equipment is required to handle halogen components. In addition, from the environmental protection point of view, if the halogen-containing compound used in the catalyst process For F! 〇n gas (gas alkane, gas chloride), you do not want to use this kind of catalyst, because Flon gas often causes many controversies because of its negative impact on the environment. As mentioned above, traditional contact The problems of the media are mostly its production method, catalyst activity, catalyst life, etc., so far there has not been found a satisfactory catalyst. Therefore, in order to improve the shortcomings of the traditional catalyst, and develop a better activity and more Long-term use of Saiming's catalysts for the production of aromatic hydrocarbons (only simple production methods and no special equipment are required to produce aromatic hydrocarbons), (CNS) 1Μ gauge (210X297 male dragon) (please read ^ contrary to legal matters Sun Chang wrote this page) 装-线 'Economic Ministry 屮 央 # 准 局 β 工 消 " printed by cooperatives 81.7 . 20,000 伥 ⑻ Λ 6 Π 6 V. Description of the Invention (Draft) The inventor has made many in-depth studies. It was found that the above purpose is due to the contact of an L-type zeolite with platinum and halogen components on it. The discovery of the media was achieved. The present invention was completed based on this discovery. One of the objectives of the present invention is to provide a new type of zeolite suitable for the production of catalysts for aromatic hydrocarbons. Another object of the present invention is to provide a method for producing aromatic hydrocarbons. The present invention provides an L-type zeolite with a sodium-containing compound and a halogen-containing compound supported on it. The special feature is that this zeolite can satisfy the following two conditions at the same time. One is: X-ray near-absorption structure (XANES ) When measured by analytical method, the zeolite with platinum-containing compound supported on it has an intensity peak of 0.4 (or slightly lower); the other is: the amount of aluminum removal in the zeolite is the total amount of aluminum in it 3% of the weight. The present invention also provides a catalyst for producing aromatic hydrocarbons, which contains the L-type zeolite. Printed by the Employees ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In addition, the present invention also provides a method for producing aromatic hydrocarbons. The Ye contacted this catalyst with at least one of the hydrocarbons listed below, such as paraffin strip hydrocarbons, Alkene hydrocarbons, acetylene strip hydrocarbons, cyclic stone flat hydrocarbons and cycloolefin strip hydrocarbons. In preparing the novel L-type zeolite of the present invention, the conventional L-type zeolite is used as a starting material. The L-type zeolite used in it has a chemical formula: 0.9-1.3 Μ2 / π 〇 · Α12〇3 · 5.0-7.0 Si02 · 0-9 H2 0, where Μ stands for alkali gold or alkaline earth metal, n Representative Μ 81. 7. 20,000¾ (H) (Please read the notes beforehand " Fill in this ry. The paper size is used in the Chinese Sleeping Standard (CNS) specifications (210X297 male dragon) Λ 6 Ιί 6 315366 Fifth, the invention description (+) (please read back-to-back notes-the price of the hard-and-forget matter, especially in Japanese Patent Application Publication No. 1 3 3 8 3 5/1 9 8 3 , Page 9-10 and No. 80333/1934, the L-type zeolite proposed on page 5. _1 pseudo indicates that the yield of the obtained aromatic hydrocarbon changes with time, the reaction is example 1, comparative example 1 and the reaction carried out in Comparative Example 2. Figure 2 is the XANES spectrum of the platinum-containing compound in the L-type zeolite of the present invention. The platinum-containing compound used in the present invention is not particularly limited and can be any Source of platinum material. It can be a general platinum salt, especially chlorinated tetraaminoplatinum, chlorinated lead acid, gas platinum salt, tetrahydroplatinum hydroxide Dinitrodiaminoplatinum, etc. In addition, halogen-containing compounds can also be various compounds. Especially gas-containing compounds, such as hydrogenated ammonium and ammonium chloride; fluorine-containing compounds, such as hydrogen fluoride and gaseous ammonium; containing iodine Compounds, such as hydrogen iodide and ammonium iodide; compounds containing bromine, such as argon bromide and ammonium bromide. Either a single compound mentioned above or a mixture of two or more compounds can be used It is used as a halogen compound. When printed by the Ministry of Labor Standards and Employee Price Cooperative, when preparing the L-type zeolite of the present invention, the platinum-containing compound and the halogen-containing compound are supported on the initial L-type zeolite. There are no restrictions on the procedure, but any procedure that traditionally supports platinum and halogen components on zeolites can be used, including general pressure impregnation, vacuum impregnation, impregnation, and ion exchange. The compounds containing dentin are all carried on L-type zeolite-6-81. 7. 20,000 sheets (H) This paper scale is used in China National Standard (CNS) 1M specifications (210X297 male dragon) V. Description of the invention (Death), the former can be carried on the zeolite at the same time as the latter, before, or after the latter. During the loading process, the most of the supported compounds are not subject to any restrictions, but the loaded compounds The amount is preferably 0.1 to 5.0% of the total weight of the catalyst (which is pseudo-calculated by the weight of platinum), and 0.3 to 1.5% is the most suitable range. In addition, the load The amount of the halogen-containing compound is preferably 0.1 to 5% of the total weight of the catalyst (the pseudo-calculated by the weight of _ element). The amount of dealumination of the L-type zeolite in the present invention can be minimized, usually the aluminum in the zeolite used as the starting material weighs 0 to 3.0% (or less), preferably 0 to 2.0% (or less ), With 0 to 1.0% (or lower) as the best. The amount of dealumination in L-type zeolite is measured by BSi-NMR analysis to determine the proportion of coordinated aluminum atoms around silicon atoms, and therefore the amount of aluminum in the framework can be calculated. The L-type zeolite of the present invention has a peak intensity of 0,4 (or less) when measured by X A N E S analysis. The Ministry of Economic Affairs, Ministry of Economic Affairs, KX Industrial Consumers, "Cooperative Du Printed X AN ES is an abbreviation of" X-ray absorption near-green structure ", which can reflect the electronic state of the element to be measured. The measurement of the L 3 absorption close structure made by the platinum-containing compound in the invention's L-type zeolite. Since the obtained X-ray absorption spectrum includes the background absorption due to the co-existing atoms, Figure 2 assumes The XANES spectrum obtained after the background absorption is subtracted (usually this part of the absorption is lower than the energy of the near structure, and its absorption can be roughly estimated by the V ict 〇ree η formula). -7-81. 7. 20.000¾ (II) (Please read the precautions in the first place, and then fill in this book, the paper is used in the middle of the paper as a family (CNS) < f4 regulations (2 丨 0X297 public: ":) 315366 Λ β Η 6 5. Description of the invention (b) The XAHES spectrum is considered to be related to the number of holes in the d-band of the compound, and it represents the electron density of lead. The following parameters are determined by the obtained XANES spectrum: h: initial maximum intensity-initial Minimum intensity Η: 12 · 7keV The parameter pseudo is obtained by dividing h by Η, that is, h / H, which represents the intensity peak determined by XANES analysis. For the L-type zeolite in the present invention, its h / Η value is equal to or less than 0.4, preferably 0.3, and 0.25 is better. The processing conditions of the load are not subject to any restrictions, depending on various environments. Usually, L-type zeolite is contacted with platinum-containing compounds and halogen-containing compounds at room temperature to 90 0 1 From 10 minutes to 10 hours to carry out the supporting treatment. Therefore, the prepared L-type zeolite can be used as the catalyst of the present invention, or it can be mixed with other additional ingredients as the catalyst of the present invention. Natural or synthetic inorganic oxides, such as alumina, silicon dioxide, aluminum silicate, etc., can be added to the catalyst of the present invention as a binder. The amount of these binders added is preferably the catalyst Between 5 and 90% of the total weight. (Please read the precautions beforehand. Sun fills in this page and installs it-order_line. The Ministry of Economic Affairs of the Ministry of Economic Affairs of the People ’s Republic of China will print 9i, which can produce that, high The method of producing media from France comes into effect or becomes available to prepare species that are very aromatic In particular, each party must do whatever it needs to do, and it should not be used to send out the media, and the article should be used by the lighting medium in accordance with the original and the same, and it can not be obtained; describe the hydrocarbon species. Before each aromatic hydrocarbon, use the Chinese standard (CNS) Τ 4 gauge (210 X 297 male dragon) at the production rate of aromatic paper produced by aromatics such as aromatics 81. 7. 20.000jk (ll) Λ 6 Π 6 Printed by the Zhengong Xiaoyi Cooperative of the Central Bureau of Economics, Ministry of Economic Affairs V. Description of the invention (7) When producing aromatic hydrocarbons by the method of the present invention, it is assumed that at least one of the hydrocarbons listed below, including panaxane Bonded alkenes, acetylenes, cyclic paraffins, and cycloparaffins are contacted with the catalyst of the present invention to produce aromatic hydrocarbons. As for the paraffin hydrocarbons used, paraffin hydrocarbons having 6 to 10 large atoms are preferred, especially n-hexane, methylpentane, n-heptane, methylhexane, dimethylpentane , N-octane, etc. The bond olefins used include those with 6 to 10 sulfon atoms, such as hexene, methylpentene, heptene, methylhexene, dimethylpentene, octene and so on. The alkyne strips used include those with 6 to 10 sulfon atoms, especially hexyne, heptyne, octyne, etc. The cyclic paraffin hydrocarbons used include those having 6 to 10 sulfonic atoms, especially methylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane and the like. In addition, cycloolefins include those having 6 to 10 sulfonic atoms, which are methylcyclopentene, cyclohexene, methylcyclohexene, dimethylcyclohexene, etc. The method of the present invention can be carried out by contacting the hydrocarbon feedstock with the catalyst, and the reaction conditions are not subject to any restrictions. However, it is preferred that the liquid space velocity (LHSV) be at a temperature of 350 to 60010 (preferably 400 to 50〇υ), a pressure of 0 to 40 kg / cm 2 (preferably 0 to 10 kg / cm 2). ) Is 0.1 to 20 hours (preferably 1 to 10 hours), and the hydrogen / hydrocarbon feedstock feed ratio is carried out in the range of 0 to 50 moles / mole, which can make this The method of the invention is even more -9-(please read the back and forth precautions first # fill in this page, this paper is used in the standard side a Β 家 楳 萍 (CNS) ΤΊ specification (210x297 public; ":) 81. 7. 20.000iMll) Ministry of Economic Affairs # 揮 央 # quasi-bureau Π3; industrial and consumer cooperation Du Yin ¾ 6_ [ί_6 V. Invention description (S) succeeded. · As mentioned above, the catalyst of the present invention is a very useful catalyst for the production of aromatic hydrocarbons, because it can be produced by a very simple method without using special equipment; and it can be stable for a long time In the case of operation, aromatic hydrocarbons are produced from various hydrocarbons, and have a high yield and high activity. In addition, the aromatic hydrocarbon production method of the present invention can be used to produce aromatic hydrocarbons with high yields, and the catalyst therein can maintain its activity after a long time. Therefore, according to the present invention, the aromatizing operation can be carried out for a long period of time, while maintaining a high aromatic hydrocarbon yield. At the same time, with regard to the catalyst of the present invention, the life of the catalyst has also been significantly improved; however, there is also a thorough impact on the activation of the catalyst and the production of the final product at a lower cost and higher yield Depressed. Therefore, the catalyst of the present invention is very useful in industry; while in the production of aromatic hydrocarbons in the petrochemical industry and in obtaining high-octane fuels in the petroleum refining industry, the catalyst of the present invention has a very wide range of applications. The present invention will be described in more detail below through several examples. (Please read the back and the precautions first # 塥 写 本 歹> ί is a commercial name for the co-branded sticky product silicon commercialization, the oxygen product is prepared by the second trader (-made of the stone's re-production of boiling medium, and the type is 20 L 1 } The example of the company (1 metric weight is called so and ο T, from the "I" in the middle) to add the name and mix the product and t, mix the product with the properties of the business, and the company will publish the paper. Zhang scale side use Chinese National Standard (CNS) 1Μ specification (210X297 male dragon) 81. 7. 20,000ifc (ll) 5. Description of the invention (9)

The temperature of the V-bonded silicic gas is 50 lb. It ££ It ’s the result of mixing the seeds together to make the mold. The young master will burn it afterwards. Biyang-< * Quasi-A Bureau of Industry and Commerce Co-operation Du Yin Formulation-Molded L-type zeolite. Next, 1.39 g of a 3.6% by weight gasified hydrogen solution, 0.097 g of sulfonated λ 0.17 g of triammonium tetrachloride, and 3.6 g of ion-exchanged water were added Mix to make an impregnation solution. The obtained impregnating solution was slowly dropped into 10 g of the silica-type adhesive-molded L-type zeolite, and was mixed with glycerin so that the loading treatment of platinum and dentin was carried out simultaneously. After allowing it to dry overnight at room temperature, this zeolite was treated in 300T: air for 30 minutes, and thus a catalyst was prepared. (2) Preparation of aromatic hydrocarbon 0.5 g of the catalyst prepared in Example 1 was placed in a quartz reactor and treated with a hydrogen gas flow at a temperature of 54010 for 24 hours. After that, light naphtha (weight composition: hexane / isohexane / methylcyclopentane = 49/43/8) and hydrogen were used as feeds, and the weight space velocity was 2 hours 4, hydrogen / light The naphtha mole ratio is 5 moles / 1 mole, the pressure is 5 kg / cm2, and the temperature is 500 t: the aromatization is performed. Figure 1 shows how the yield of benzene obtained changes with time as the reaction proceeds. Comparative Example 1 (1) Preparation of catalyst The two gasified silicon binders prepared in Example 1-molded L-type zeolite 20 -1 1-(please read the precautions and hardship page first) Pack < Order-This paper scale is used in the middle of the trapped house (MCNS) Ή specification (210x297 male dragon) 81. 7. 20,000 ^ (11) 315366 V. Description of the invention (β) It is placed in a quartz reactor , And nitrogen was introduced, and maintained at a temperature of 200C for 30 minutes; then the nitrogen was replaced by one gas and three gas methane, and the temperature was raised to 50010. After the temperature was raised to 500¾, the zeolite was treated for two hours, the gas was replaced with nitrogen, and the temperature was lowered to prepare a halogen-treated L-type zeolite. An impregnation solution containing 0.171 g of chlorinated tetraammine platinum and 4.0 g of ion-exchanged water was slowly dropped into 10 g of this halogen-treated L-type zeolite, and stirred for carrying treatment. After bearing treatment, the zeolite was placed in a dryer and dried at 80C for three hours, and then a catalyst was obtained. (2) Preparation of aromatic hydrocarbons In the same manner as described in Example 1 (2) except that the catalyst used in Example 1 (2) was replaced with the catalyst prepared in Comparative Example 1 (1) To carry out the aromatization reaction. Figure 1 shows how the yield of aromatic hydrocarbons obtained varies with time. Comparative Example 2 (1) Preparation of catalyst C3, Bureau of Standards, Ministry of Economic Affairs: Gongxiao & Co., Ltd. Seal 51 The impregnation solution containing 0.171 g of tetraammine platinum chloride and 4.8 g of ion-exchanged water was slowly dropped into 10 g The silicon dioxide binder-molded L-type zeolite obtained in Example 1 (1) and stirred; the zeolite was dried at room temperature for two hours and then treated in air at 80 υ for three hours , And then got a catalyst. Place the damaged catalyst in a quartz reactor, and nitrogen in 2001C-12-81. 7. 20.000 伥 (II) (please read the notes before you fill in this paper and use it in China Sleepy home you complete (CNS) Ή specification (210x297 male dragon) Fifth, the invention description (" hold the air in the air

Λ fi η 6 at ο V ο 8 4 to high temperature will be reconnected at the time = group 9 volume 99 body \ (1 body 0. gas Ια gas 1 0 οη \ F1 alkane to B, gas under two conditions 2- Love 1, of $: Qi 0 ^ 四 8 -4 2 is 2 degrees 1. Temperature 1, and then the medium of C 0 when touched into a small system of ten mediums, that is, the low temperature drop after touch is used to warm up and 、 Combined gas, Nitrogen to Nitrogen, replacement of the source gas, the prepared hydrocarbon incense will be compared to the use of the mediator, so that the time of the middle of the trip will be free The same production head · + Τ 白 的 擊 體 樹 中 芳 得 '2) Obtained by / V 1 exemplified to show, which is the graphic media of Outer 1. The reaction to C's inversion results in the formation of the system. Example 2 Mediator 0550 Prepare G to the mediator's heat to touch the additive formula. The other method will be the same as that obtained after the acquisition. Prepared 3 systems) rt ί got 1 made of lis of (liswu medium 1 香 ㊉ · case collection anti-independent β 芳 I P) ai))> mobilized (1 (2 pulses 1 into the set it will be combined)

And when the time is small, I, V, and the temperature should be adjusted to 0 at the time of 1 to reach the V of the mid-stream gas and hydrogen. 5 The gas at the time of the current is to be merged with V 0 7 4 to / Liters (please read 1? Contrary to this, please follow the instructions on this page) to install-book-line. The Ministry of Economic Affairs, the Ministry of Economic Affairs, Bureau of Examination and Consumer Affairs Cooperative Cooperative 5i got it. Fang traveled with a neutralizer. It responded to benzene, and the pulse rate was 7 to 55, and the actual rate was improved to 3%. The prepared medium contains BB 8 4 and platinum M. Nitrogen tetrachloride paper is used in the standard side a «Family Standards (CNS) (210χ2ΰ7 male dragon) 81. 7. 20,000i (c (11) Α β B 6 Printed by the Ministry of Economic Affairs Standard Staff Cooperative Cooperative Preparation V. Description of the invention (β) The infusion solution was slowly dropped into 10 g of the gasified silicon binder-molded L-type zeolite obtained in Example 1 (1 丨) and stirred; at room temperature The zeolite was dried overnight, and then treated at a temperature of 300 minutes for 30 minutes to prepare a catalyst. (2) Preparation of aromatic hydrocarbons except for the contact used in Example 2 (2) The media was replaced with the catalyst prepared in Comparative Example 3 (1), and the aromatization reaction was carried out in the same manner as described in Example 2 (2). As a result, a yield of 32.1% was obtained. Benzene. Example 3 (1) Preparation of catalyst 20 parts by weight of silicon dioxide binder (a commercial product produced by Nissan Kagaku, trade name " Snowtex ") was added to 100 parts by weight of L-type zeolite ( A product produced by Toso Corporation under the trade name "TSZ-500K0A", and this mixture is stirred, kneaded, and molded. The obtained molding mixture is then subjected to air at a temperature of 500 ° C. After calcining for two hours, a silicon dioxide binder-molded L-type zeolite was prepared. Next, 0.097 grams of ammonium fluoride, 0.171 grams of vaporized tetramine platinum, and 4.8 grams of ion-exchanged water were added Mix to prepare an impregnating solution. Slowly drop the obtained impregnating solution into 10 grams of the two-gasified silicon binder-molded L-type zeolite and stir to support lead and halogen The treatment is carried out at the same time. After allowing it to dry overnight at room temperature, the zeolite is dried at 300 t: It was processed in the air for three hours, so a kind of -14- was prepared (please read the back-end notes-notes ^ fill out this page; this paper uses the Chinese "Home Standard (〇Ν5) Ή regulations ^ (210X297 public; ¢) 81. 7. 20,000 ^ (11) Pinggong Xiaoyi Cooperative Society of the Ministry of Economic Affairs, Beigong Xiaoyi Cooperative Independence · 9 ·-:. Recognition, ..., A 6 _ί_ '欠 .i B 6 _ V. Description of invention ( A) j catalyst. (2) Preparation of aromatic hydrocarbon 0.5 g of the catalyst prepared in Example 3Π> was placed in a quartz reactor, and treated with a hydrogen gas flow at a temperature of 540 for 24 hours. After that, light naphtha (weight composition: hexane / isohexane / methylcyclopentane = 49/43/8) and hydrogen were used as feeds, and the weight space velocity was 16 hours 4, hydrogen / Mole number of light naphtha. The ratio is 5 mol / 1 mol, the pressure is 5 kg / cm2, and the temperature is 517C, and the aromatization reaction is carried out under the condition of maintaining for 20 hours. The yield of benzene obtained was 52.9%. Example 4 Π) Preparation of catalyst An impregnating cuvette containing 0.097 g of ammonium fluoride, 0.075 g of gasified ammonium, 0.171 g of tetraammine platinum chloride and 4.8 g of ion-exchanged water was slowly dropped into 10 g of Example 3 (1 ) The silicon dioxide binder-molded L-type zeolite obtained in) and stirred; the zeolite was dried overnight at room temperature, and then treated in air at 300TC for three hours to prepare a catalyst. (2) The preparation of aromatic hydrocarbons was carried out in the same manner as described in Example 3 (2) except that the catalyst used in Example 3 (2) was replaced with the catalyst prepared in Example 4 (1) Carry out aromatization reaction. As a result, benzene with a yield of 63.8% was prepared. Example 5 (1) Preparation of catalyst -1 5-(please read first-pay attention to this item, please fill in this page) Binding-Order _ Line paper size standard "National« Flat (CNS) 1Η specifications ( 210x297 public address) 81. 7. 20,000 ^ (11) 663513 * 4 / | \ 明明 发 > 5

Mold Drying-Drying Agent Stone Boiling Viscous Seed Silicone

Three m: Deal with the V of the air and the air. Prepare a hydrocarbon aroma with a catalyst of 0 when the catalyst is used. The example will be replaced by the use of the catalyst for the replacement of the catalyst. , The outside of the body should mediate the reaction of the aromatic compound. The percentage of benzene in the formula is the same as that of the benzene. ο Example #Is there a medium containing 5 touches? Compared with the fcbn agent and the mixed-boiling viscous silicon, the two-temperature room under oxygen will be obtained; the m 1 in the companion will be 3 (additional example. Gram in) 10 stone into boiling drop type slow L slow liquid mold immersion | made with the time small three RE treatment of the gas medium S touch f P] ο on 12 it lies in the back of the bearing, there are two kinds of dry and dry when sold The prepared hydrocarbon fragrances have been used in addition to the local conversion media (please read ¾ and follow the instructions before writing this page). Cooperative Du Yinhong's traveling formula is 0. The description of the aromatic hydrocarbons is fragrant.% 2 of 35 2) is 3%. To obtain, fruit of the outer junction media system. The anti-synthetic structure of the reaction e. The SS S media of the second-generation adhesive and the silicic gas prepared by the system 20} will be in π a υ ka This paper scale is used in the middle of the trapped 8 Jiaju standard (CNS) Ή Specifications (210X297 public: ":) 81. 7. 20,000 伥 (Π) Beigongxiao," Quan Standards Bureau, Ministry of Economic Affairs "" printed by cooperatives Λ 6 __Π_6_ V. Description of the invention (<) Product produced by the company, product name "S η owte χ") to 100 parts by weight of L-type zeolite (a product produced by Τ ο s ο company, the trade name is "TS Z-5 0 0 Κ 0 Α"), and This mixture was mixed, kneaded and molded. Then, the obtained molding mixture was calcined with air at 500 ° C for two hours, thereby preparing a silica-type binder-molded L-type zeolite. Next, 0.167 g of ammonium fluoride, 0.171 g of chlorinated tetraammine platinum, 0.075 g of ammonium chloride, and 4.5 g of ion-exchanged water were mixed to prepare an impregnation solution. The obtained impregnation solution was slowly dropped into 10 g of the silica-type adhesive-molded L-type zeolite, and stirred, so that the platinum and halogen loading treatment was performed simultaneously. After allowing it to dry overnight at room temperature, this zeolite was treated in air at 30Q 1C for three hours, and thus a catalyst was prepared. (2) Evaluation of catalyst physical properties 29 S i-NMR analysis was performed on the catalyst obtained in (1) above to measure the amount of dealumination; the results of the analysis were subjected to waveform separation to calculate the aluminum content in the framework Amount and compared with the aluminum content in the L-type zeolite of the starting material. XANES analysis put the top-up (catalyst in U in a hydrogen gas flow with a flow rate of 6.5 liters / hour, and perform a reduction reaction with hydrogen at a temperature of 540 υ for 24 hours, and grind and reduce the sample obtained by the reduction Model; place it in place -1 7-This paper is used in the national standard iMCNS) Τ 彳 regulations «5 (210X297 public; ¢) 81. 7. 20.000¾ (II) (please read ^ back first Things to Remember Sun Nan wrote this page, outfit-line ·

The Ministry of Economic Affairs, Central Bureau of Accreditation C3: Gongyongzhong cooperated with Du Yin ^ in the measurement equipment, and the reduction reaction with argon was carried out again for one hour at a hydrogen flow rate of 10 ml / min and a temperature of 5 4 0 t. Then the container is evacuated at a temperature of 5401C (that is, at the same temperature as the previous one). It is cooled to room temperature, and filled with nitrogen to seal it with the sample obtained by the reduction. The resulting product will be used for X A N E S analysis. The results obtained will be calculated according to the definitions described above. The calculated results are shown in Table 1. (3) Preparation of aromatic hydrocarbons 0.25 g of the catalyst prepared in Example 6 (1) was placed in a quartz reactor and treated with a hydrogen gas flow rate of 6.5 liters / hour at a temperature of 540 for 24 hours. After that, light naphtha (weight composition: hexane / isohexane / methylcyclopentane = 49/43/8) and hydrogen were used as feeds, and the weight space velocity was 32 hours 4, hydrogen / light The naphtha mole ratio is 5 moles / 1 mole, the pressure is 5 kg / cm2, and the aromatization reaction is carried out at a temperature of 517 ° C. Table 1 shows the benzene yield after 5 hours from the start of the reaction. Comparative Example 5 Π) Preparation of catalyst 20g of the second gasified silicon binder-molded L-type zeolite prepared in Example 6 (1) was placed in a quartz reactor, and nitrogen gas was introduced at 200 ° C. Maintain the temperature of C for 30 minutes; then replace nitrogen with one gas and three gas methane, and raise the temperature to 500 t :. After the temperature is increased to 500f, please write 1 8-(please read-back to the precautions #code to write this page) This paper is used in the standard a s family "ilMCNS> f Ί specification (210X2CI7 public) 81 . 7. 20.000 伥 (II) Λ 6 Π 6 315366 V. Description of invention (Q) (Please read the precautions before writing this page; this zeolite is treated for two hours, then the gas is replaced by nitrogen, and The temperature was lowered to prepare a L-type zeolite treated with zeolite, in which the halogen content was almost the same as in Example 6. An impregnation solution containing 0.171 g of sodium tetraammonium nitride and 4.5 g of ion-exchanged water was slowly dropped 10 grams of the halogen-treated L-type zeolite, and stirred for carrying treatment. After carrying treatment, the zeolite was placed in a dryer and dried at a temperature of 120t for three hours. Then a catalyst was prepared. (2) The physical properties of the catalyst were evaluated in Example 6 (2) except that the catalyst prepared in Comparative Example 5 U) was used to replace the catalyst used in Example 6. Steps. The results obtained are shown in Table 1. (3) Preparation of aromatic hydrocarbons except that the catalyst used in Example 6 (3) was replaced with the catalyst prepared in Comparative Example 5 (1) in the same manner as described in Example 6 (3) To carry out the aromatization reaction. Table 1 shows the yield of aromatic hydrocarbons obtained. Comparative Example 6 (1) Preparation of catalyst Printed by the Employee Explosive Cooperative of the Bureau of Standards, Ministry of Economic Affairs, the impregnating solution containing 0.17 g of ammoniated tetramine platinum and 4.5 g of ion-exchanged water was slowly dropped 10 g of the silica-adhesive-L zeolite obtained in Example 6 (1) was added and mixed; the zeolite was dried at a temperature of 120 ° for three hours, and then a contact was prepared Media. (2) Evaluation of the physical properties of the catalyst -19- 81. 7. 20.000 sheets (II) The standard size of this paper is used in a 戳 家 楳 准 (CN5) ΤΊ specification (2 丨 0x297 public address) Ministry of Economic Affairs Bureau of Standards Printed by β Gongxiao Cooperative Society Λ 6 η 6_ V. Description of the invention (,?) In addition to the catalyst prepared in Comparative Example 6 (1) to replace the catalyst used in Example 6, repeat Example 6 (2) Steps in. The results obtained are shown in Table 1. (3) Preparation of aromatic hydrocarbons In the same manner as described in Example 6 (3) except that the catalyst used in Example 6 (3) was replaced with the catalyst prepared in Comparative Example 6 (1) To carry out the aromatization reaction. Table 1 shows the changes in the yield of aromatic hydrocarbons. Comparative Example 7 (1) Preparation of catalyst Mix 0.107 g of vaporized potassium, 0.735 g of vaporized potassium, 0.120 g of vaporized tetramine platinum and 3.5 g of ion-exchanged water to prepare a Impregnation liquid. The prepared impregnation solution was slowly dropped into 7 g of the second vaporized silicon binder-type L zeolite obtained in Example 6 (II), and stirred. It was then allowed to dry at room temperature overnight, and the zeolite was then treated at 300 ° C for 30 minutes to prepare a catalyst. (2) Evaluation of catalyst physical properties The procedure in Example 6 (2) was repeated except that the catalyst prepared in Comparative Example 7 (1) was used instead of the catalyst used in Example 6. The results obtained are shown in Table 1. (3) Preparation of aromatic hydrocarbons In addition to replacing the catalyst used in Example 6 (3) with the catalyst prepared in Comparative Example 7 (1), Example 6 ( 3) proceed in the same way as described in -20-

(Please read the precautions first, and then write the FJ clothing on the paper side of the standard Η «家 楳 毕 (CNS) 悀 4 regulations (210 father 297 mm) 81. 7. 20.000jk (ll) Λ 6 Β 6 5. Description of the invention (》 <?) Aromatization reaction. Table 1 shows the variation of the yield of aromatic hydrocarbons obtained. Table 1 Examples of the yield of aromatic hydrocarbons measured by the amount of dealumination XANES (%) Peak intensity (H / H) (% by weight) (Please read the back and forth precautions ## cooker's copybooks, tools, and aluminum preparation offices. The system can be touched by the off-the-shelf type and the active medium. It should be based on the high touch point, and the emergence of the existing bright objects should be combined with the localization and halogenation; the mechanism of non-touching can be seen from the organic medium. Takara Group will use platinum as the basis for the use of high-tech media. The Ministry of Economic Affairs of the Ministry of Economic Affairs of the Central Bureau of Economics and Trade Beta Printing Industry Cooperative Cooperative 51 Case 6 0.8 0.22 56.5 hb Comparative Example 5 3.8 0.26 51.5 Comparative Example 6 Standard 0.59 22.9 Comparative Example 7 0.4 0.45 24.4 The ft scale of the paper is used in China National Standard (CNS) 1? 4 specifications (210X29 / male; ¢) 81. 7. 20.000¾ (II) 315366 Α7 Β7 Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives V. Description of the invention () 1! Example 7 1 I (1) Preparation of catalyst 1 I Prepare the catalyst in the same way as in Example 6 (1). 0r-V 1 I Please 1 I (2) Preparation of aromatic hydrocarbons. 1 I. Collect 0.5 g of the catalyst obtained in Example 1 (1) and place it in a pulsation reactor on the back side 1 1. Then, place it in a hydrogen gas stream. Heat to 540 1 1 for one hour, and hold at 540 TC for hours. Adjust the temperature of the reaction to 1 item 1 to 4 7 0 ¾. And pass n-octane into the hydrogen gas flow (1.2 l / h ) In the three-liter pulsation reactor in 1 to carry out the aromatization reaction. Result%% on this page%-I The yield of aromatic compounds is 42.8% ° The yield of aromatic compounds including benzene --- '1 I is 4.1%, toluene yield is 10. Q96 > ethylbenzene yield is 17.3% V 1 1 xylene yield 10.8% 〇1 | fch Comparative Example 8 Order 1 (1) Preparation of catalyst 1 1 Catalyst was prepared in the same manner as in Comparative Example 4 (1) 〇1 I (2) Preparation of aromatic hydrocarbon 1 1 Collection The catalyst obtained in Comparative Example 4 (1) was 0.05 g t and was placed in a pulsation reactor in line 1. After demonization, it was heated to 1 I 5 4 0 1C in a stream of hydrogen gas for 1 hour. , And maintained at 5 4 0 t for one hour. The temperature of the reaction was adjusted to 4 70 ¾ at 1 1 degree, and n-octane was passed into 3 liters in a stream of hydrogen gas (1.2 liters / 1 I hour) In the pulsating reactor, the aromatization reaction was carried out 1 1 〇 As a result, the yield of aromatic compounds was 36.6%. The aromatic compounds included 1 1: the yield of benzene was 2.4% and the yield of toluene was δ .1% The yield of ethylbenzene is 1 I 14.8 ¾, and the yield of xylene is 10.7% c 1 21 '-1 1 1 1 1 This paper scale applies the Chinese National Standard (CNS) A4 specification (210X 29 * 7 Centigrade)

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a situation where the yield of the obtained aromatic hydrocarbon changes with time, and the reactions therein are the reactions carried out in Example 1, Comparative Example 1, and Comparative Example 2. Fig. 2 is the XANES spectrum of the platinum-containing compound in the L-type zeolite of the present invention. (Please read the precautions on the back before filling in this page) Order Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

口 々 08 ..... M Patent Application for the Patent Cooperative No. 81106166 of the Ministry of Economic Affairs of the Central Bureau of Economic Cooperation and Consumer Cooperatives "Paper Case of" L-type zeolite and method for producing aromatic hydrocarbons using it as a catalyst " · (Amended on December 16, 1984) λ Application for patent scope: 1. An L-type zeolite, like an L-type zeolite with vaporized tetraammonium complex platinum and a halogen-containing compound carried on it, of which the L-type zeolite 0.9 ~ 1.3M2 / η Ο · A 12 〇3 · 5.0 ~ 7.0 S i 〇2 ♦ 0 ~ 9H2 0 (where M is alkali gold or alkaline earth metal, n is the atomic valence of M), which contains The halogen compound is selected from one or both of ammonium halide and hydrogen halide, and is characterized in that the zeolite is obtained by carrying out the bearing treatment of the tetraammonium chloride complex lead and the halogen-containing compound at the same time, which can simultaneously satisfy the following two The first condition is: when measured by X-ray near-absorption structure (XAHES) analysis, the zeolite with vaporized tetraammonium complex platinum supported on it has an intensity peak of 0.4 or slightly lower; the other is: The amount of aluminum removed in the zeolite is 3% by weight or less based on the total content of aluminum. 2. If the L-type zeolite of the first patent application is used, it is pseudo-used as a catalyst for the production of aromatic hydrocarbons. 3. A method for the preparation of aromatic hydrocarbons with 10 or less atoms, whose catalyst will be selected from the range of patent application item 2 and at least one selected from paraffins and Ce_i. Hydrocarbon feedstocks of naphthenes at a temperature of 350 to 600 °, a pressure of 0 to 40 kg / cm 2, a liquid space velocity of 0.1 to 20 hours-1, and a molar feed of hydrogen relative to this type of hydrocarbon Contact under the condition that the ratio is 0 to 50. This paper uses the Chinese National Standard (CNS) Λ4 specification (210X297mm) --------- ^ -------, order ------. Ii (please read the back first (Notes to fill out this page)