TW416938B - Process for the production of cumene and its catalyst preparation - Google Patents

Abstract

The present invention relates to an improvement in a process for the production of isopropylbenzene (cumene) under suitable operation conditions by the catalytic alkylation of benzene with propylene over zeolite and cation-exchanged zeolite catalysts. The catalysts include mordenite, Y, ZSM-5 and Beta with various Si/Al ratio and cation contents. The present invention also relates to the operation conditions, the optimum components of the catalysts, and the preparation method of said specific catalysts.

Description

Printed by A7 B7, Shellfish Consumer Cooperatives, Central Bureau of Standards and Quarantine, Ministry of Economic Affairs 5. Description of the Invention (Engineering) Isopropylbenzene (IPB), also known as cumeme, is an important raw material for the petrochemical industry. It is used to produce phenol and acetone. In order to synthesize malonylphene U isphe η ο 1 A), the synthesis reaction was developed as early as 1974. 'Using sulfuric acid was used as the catalyst. In igS8, UoP company successfully developed a phosphoric acid catalyst (Solid phosphoric acid). , SPA) gas phase reaction process, 丨 982ns- 0 & Lummusy co-developed as a catalyst for the development of chemical compounds, applied to the synthesis of already benzyl and isopropylbenzyl, these sharp use The catalysts all have their disadvantages. * Among them, sulfuric acid and gasified aluminum have equipment corrosion and Guangjun processing problems, SPA catalysts have acidic loss, are not easy to regenerate, and waste catalyst treatment. Because of its high activity, polyfluorene (such as diisopropylbenzyl) can be used as high-octane gasoline. How to find a suitable solid catalyst to improve this disadvantage is the goal of industrial research. Catalyst is a feasible way Since the beginning of the 19th century, it has been launched with the use of Jishi as the contact system, such as UnocaWABB (Zeolite, cumene Λ

PrOdu-ction, 1988) rU0P / A1 kymax (HYF benzene redurt ^ 1 i ο nr 1990) FChemical R & L (LZY-82, cumene producti〇n 1991), H〇bi 1 / Badger / MBR (ZSM- 12 / ZSM-5, benzene eaucti 〇nr 1992) f〇〇 / 3'DDM (dealuminated mordenite rfcumene-P r 0 duct 1 ο n, 1 9 9 3) F Μ 0 bi 1 / B adger (z SM- 5, cumenepr 0 duc-tion, 1993) r CDTECH (Y, EB and cumene prdur +-^ ti ο n, 1993) t UOP / Lummus / Monsanto / Unocal / CRLiY pv pr〇duc " tion, 1 9 9 3), UCI / FINA (CDS zeolitetEB Pr0ducti0nt 1 9 9 5) o Regarding the application of fossil catalysts in the production of isopropylbenzyl, it is currently not universally applicable to this paper standard of China Garden Standard (CNS) A4 (2 丨OX297mm) 83.3.1〇 ， 〇〇0 (Please read the notes on the back before filling in this page) 'etc. 41BG38 Α7 Β7 Printed by the Bayer Consumer Cooperation Department of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2)- -Commercialization, the main reason is that traditional zeolite catalysts such as rey.zsm ZZSM-5, Beta and mordenite will add diisopropylazine, acupoint 1 丨 Rongben (diiSopr〇p 1 m > enzene, DlPB) and the by-products n-prUpyzeenief NPB and triisopropylbenzyl, and the activity decayed rapidly. The n-propylbenzene content must be less than 100 ppm. Once formed, it is not easy to separate it from isopropylbenzene by distillation. In order to improve the selection of isopropylbenzyl in the product, it is possible to increase the ratio of dibenzyl and propylene in the feed and increase the propylene injection point. The research report by Meii et al. Pointed out that dea 1 uminatedm 〇rde η 彳 te, to improve this In the process, uotl can achieve the complete conversion of propylene (SPA requires “〇 · ◦). When the temperature is increased, the selectivity of IPB is increased because of the conversion reaction of DIPB. In addition, ZSM-12 jWr-Al2〇3 The application of zeolites such as ^^^^ 口 ^ in the alkylation reaction has also been explored. The application of metafossil catalysts in the alkylation reaction of benzene and propylene is based on its special pore structure and nature. Among them, the nature is divided into Lewis acid and Bronsted acid, and other reactions such as diisopropylbenzyl and benzylic alkylation reactions are accompanied by the reaction of incineration. Heterogeneous reaction and isomerization reaction of propylbenzyl, etc. Different distribution and acidity of Liao and B acid will affect the selectivity of these side reactions, how to choose the type of zeolite, and adjust its nature, improve the conversion rate, and reduce The occurrence of side reactions, improving the selectivity of the main reaction and the catalyst Stability is the focus of process improvement. The present invention uses ion-exchange technology to improve the properties of zeolite, which is used in the process of the reaction of jasmine and propylene to produce isopropylbenzyl. The results of the examples show that The improved Beta zeolite can obtain better isopropyl bulk yield than m mordenite 嗤, Y, ZS M-S zeolite and non-zeolite catalyst, and at the same time --------- t ----------- '+ i (Please read the precautions on the back before filling out this page) This paper is applicable to 0 countries (CMS) A4 specifications (21〇297297). 3.! 0, 〇〇〇41 41 A7 B7 V. Description of the invention (3) It can inhibit the formation of by-products such as NPB during high temperature operation. The general steps of the preparation of the present invention are as follows: Step 1. Take 15 g of zeolite The sample (c PC-B 1) was placed in a flask, and 300 ml of an aqueous solution of metal levitation with cleanliness was added. Step 2. The suspension was stirred at 65 ° C for 24 hours. m 1 steamed with water and washed with water. Step 3. After drying, the solid is dried at i! 0 «c for 4 hours, and then fired at 500 ° C for 4 hours. Sieve into i0 ~ 20mesh particles to obtain zeolite catalysts with different metal contents.-.-. ---------- 'pack — (Please read the precautions on the back before filling this page) [^ -------- Institute of Industrial and Consumer Cooperatives, Central Standards Bureau of the Ministry of Economic Affairs 83. 3.10,000 This paper is standard and applicable to the National Standard (CNS) A4 (2) 〇297297 mm

41803S A7 B7 Central Standards of Ministry of Economic Affairs, "Industrial and Consumer Cooperation" Du Yin, V. Description of the Invention (4) Example 1: Effect of Reaction Temperature and Pressure on Isopropylbenzyl Synthesis Table 1 CP c-B 1 As a result of the chemical reaction, the reaction condition is 6 ′ 〇, WHSV = S 5 hr · ”, the results show that the conversion rate of benzyl increases with increasing temperature, and the selectivity of isopropylbenzyl varies with It increases with increasing temperature, and has the highest selectivity at 250 ° C. When the temperature is increased, the selectivity decreases. The reason is that n-propylbenzine is significantly increased at 25 ° C-300 ° C, and the temperature is lower than 15 At 〇 < 〇, heavy components were generated, and it was judged to be an oligomer of propylene, and the yield of isopropylbenzyl had a maximum value over time. For CPC-Bn ^ stone, a suitable reaction temperature is iso ~ 275C. Momentum is mainly to make the whole reaction can be carried out in the liquid phase, and the pressure of 5000 PS ig at 25 0 t! The above reaction is The reaction of coexistence of gas phase and liquid phase should be 500 ~ 100 psig. Example 2 The influence of the ratio of stupid / propene mole on the reaction in the feed. Table 2 shows the results of the alkylation reaction of CPC-B1. The reaction conditions are: 500 psigf 200 ° C »WHSV = 55hr-i, change the stupid / propene molar ratio, and the results in Table 2 show that as the stupid / propene molar ratio increases in the feed, the conversion of stupidity decreases, isopropyl The selectivity of the main product of phenylbenzyl is increased, and the yield is significantly decreased. The selectivity of diisopropylbenzyl is also reduced. When the molar ratio is too low, triisopropylbenzyl is formed. At the same time, isopropylbenzyl is also produced. It has a high selectivity to isopropylbenzyl, which is more suitable for a molar ratio of 3 to 10, and a large amount of isopropylbenzyl at a low molar ratio can be used to increase the reaction temperature and increase the alkylation activity. To reduce the amount of production. For example, if the molar ratio is 4 and the reaction temperature is 27.5 * C, the yield of isopropyl is 137.4mol / kg.cat'hi ", isopropylbenzene selectivity 91.0¾, under the same selectivity, the molar ratio is 6.0, the reaction temperature is 25 ° t: only the isopropyl group produced paper size is used, using Chinese national standards ( CNS) A4 specification (210 × 297 mm > 83.3.10,000. ^^ 1 ·. ^ —— I 1 ^ 1 f 11— 1 ^ 1 ^ (n US .- # (Please read the notes on the back before filling in this Page} 418033 A7 ___ B7____ V. Description of the invention (5) Rate 0 Example III. Effect of feed space flow rate on alkylation reaction (C p C _ B i) Table 3 shows the results of the alkylation reaction of CPC-B 1, The reaction conditions were stupid / propylene mole 6.0, pressure 700 psig, and the change in VJHSVO showed that as WHSV increased, the stupidity and propylene conversion rate decreased, the isopropylbenzyl selectivity was low, and the diisopropylbenzyl selectivity The yield of isopropylbenzyl is increased, and n-propylbenzyl is easily formed when the temperature is higher than 25 ° C. However, the amount of n-propylbenzyl is reduced as the "" increases. Based on the conversion of propylene and the production rate of n-propylbenzyl In consideration, the more suitable reaction conditions for the unified hills are the stupid / c-mole ratio of 3 to i Q, the reaction temperature of 150 to 250 ° C, and WHSV = 40 to li0hr l Example 4: Comparison of zeolite thixotropic reaction activity. Table 4 shows the comparison of alkylation reaction conditions of various zeolites. The reaction conditions are stupid / propylene mole ratio of 6.0, WHSV = 55hr-, and pressure of 700ps. , Where CPC-B 1 and B 3 are Beta zeolites, S 彳 / A] ratios are respectively! 2 5 and 3 7 5, CPC-M2 is mordenite (Si / A1 = l〇〇), cpcz2 & zsM_5 Central Government Bureau of the Ministry of Economic Affairs, shellfish consumer cooperation Du printed (Please read the precautions on the back before filling this page ) (Si / Al = 25,0), CPC_Y2 & Y-type zeolite (si / Ai = i5 〇), the results show that the isopropyl bulk yield is better than Beta-type zeolite, especially high-value Beta can be compared with Higher isopropyl bulk yields were obtained at high temperatures, while no NPB was formed. Example 5 Comparison of Reactivity of Ion-exchange Beta Metafossilization Table 5 is a comparison of the situation of various ion-exchange Beta fossilization reactions. This paper is suitable for China National Standards (CNS) Eighty-four Secrets (210x29? ^^----- '83 · 3-10,000 A7 B7 416333 V. Description of the invention (6 * The reaction conditions are stupid / propene mole ratio 6,0, WHS and S 5 hr _], and the degree of annihilation is 275C The force is 700 psig, and the results show that the β a fossil after ion exchange can obtain a higher yield of isopropyl bulk than the original Beta zeolite at 2 7 5 * C, and τ to inhibit The formation of n-propylbenzyl, especially * Mn, Fe ^ significantly reduces the amount of N 卩 B produced, which is helpful for the separation of isopropylbenzyl main products. The metal content is manganese 1.50 »/ 1;% , Iron 1.100%, starting 2.10 wt% 'nickel 1'39 wt%, steel 1.65 wt%, lanthanum 1.48 wt%, 钸 2.05 wt%. Example 6: Improved Beta stone and other catalyst systems Comparison Table 6 shows the comparison between the improved zeolite and other catalyst systems. The results show that the improved bet a zeolite catalyst of the present invention has better isopropyl bulk yield than other fossil catalysts and non-catalysts; Stone catalyst (AKB-02) 〇 Among them HM〇rd, H-ZSM-5, and Η-EU-1 literature data, results are carried out under normal pressure gas phase, the rest are liquid phase reaction 〇 (please first K1 (Please read the note on the reverse side and fill in this page again.) _ _ Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 83.3.10,000 逋 Use China National Rubbing Rate (CNS) A # grade grid (2 × 〇297mm) 416D38

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Claims (1)

416333 Patent application A: A method for producing isopropylbenzene from benzene and propylene through an alkylation reaction, which is characterized by using Beta-type zeolite containing different metal ions as a catalyst, in which the silicon / aluminum atom ratio of ta zeolite is]. ~ 40, the metal ion content is manganese (11) 12 ~ 1,6 wt. /. , Iron (II) 1.0-2.0 wt. /. , Cobalt (π) 1.0-1.5 wt%, 1.2-1.8 wt% ’Copper (Π) 1.2-1.8 wt%, Lanthanum (melon) 0.6-1.5 wt. /. And 钸 〇H) 0'8 ~ 2.0 wt%; the conditions of the alkylation reaction are: temperature Π 5 ~ 25 ° C, pressure 500 ~ 800 psig, space flow rate WHSV 50 ~ 100 hr-1, in the feed The dilute Morse ratio is 3 to 6. (Please read the precautions on the reverse side before filling in this poverty.) Jingtao India Central Standards Bureau staff boneless cooperatives seal S- This paper size is applicable to the national bacteria family rubbing rate (CNS) M said (210x297 public shame) Install ------ Order—1 * -----_____ 41bi5 jo Application date search, U " 2Ί case number y 丄 1. 〇 wdou Category 丨 C is called αΥΆ — (The above pastes are filled by this bureau) Bulletin 1 Patent Specification Chinese Isopropyl Mining Synthesis and Preparation Method Using Its Catalyst Invention New Name English Name (Name) National borrowing Process for the production of cumene Bnd its catalyst: preparation 2 3 negative length 3 case study W long specialized research institute s' institute ordered foreign research research research refining t elephant refining oil refining oil Oil in the middle, middle and middle rft, taxis, taxis, masters, blogs, bloggers, 1 workers, 1 industrialization, chemical ccc (C Cheng Zongcheng Song Song Rong Guozong Rong Zhijia Kunmin Lai Wu Lingu Cai Zhongwu No. 239, Minsheng South Road, Yimin Citizen III. Residence, Residence (Office) Representative Name China Petroleum Corporation, People's Republic of China. No. 83, Section 1, Zhonghua Road, Taipei, Taiwan. Rate (⑽) 8 4 specifications (2ΙΟΧ297 公 楚) line 416333 Patent application A: A method for producing isopropylbenzene from benzene and propylene through an alkylation reaction, which is characterized by using Beta-type zeolite containing different metal ions as a catalyst, in which the silicon / aluminum atom ratio of ta zeolite is]. ~ 40, the metal ion content is manganese (11) 12 ~ 1,6 wt. /. , Iron (II) 1.0-2.0 wt. /. , Cobalt (π) 1.0-1.5 wt%, 1.2-1.8 wt% ’Copper (Π) 1.2-1.8 wt%, Lanthanum (melon) 0.6-1.5 wt. /. And 钸 〇H) 0'8 ~ 2.0 wt%; the conditions of the alkylation reaction are: temperature Π 5 ~ 25 ° C, pressure 500 ~ 800 psig, space flow rate WHSV 50 ~ 100 hr-1, in the feed The dilute Morse ratio is 3 to 6. (Please read the precautions on the reverse side before filling in this poverty.) Jingtao India Central Standards Bureau staff boneless cooperatives seal S- This paper size is applicable to the national bacteria family rubbing rate (CNS) M said (210x297 public shame) Install ------ Order—1 * -----_____