TW565469B - Method for preparing selective hydrogenation catalyst with high stability - Google Patents

Abstract

A method for preparing a selective hydrogenation catalyst with a high stability is characterized in a change in the activation process. A catalyst obtained by the activation process, when used in a selective hydrogenation catalyst reaction with DMT (dimethyl terephthalate) to form DMCHD (dimethyl 1,4-cyclohexanedicarboxylate), has a high stability and an activity that can last for a long period of time without losing its activity. Meanwhile, the catalyst provides a suitable reaction condition and environment for the DMCHD synthesis reaction so that the DMCHD yield can be kept over 90% for a long period of time.

Description

565469 Collection dated 90120833 Amended _ V. Description of the invention (1) The present invention relates to a method for preparing a selective hydrogenation catalyst with high stability. When the catalyst is reacted with DMT to synthesize DMHCD, It can last more than 50 hours without loss of activity and can maintain training for a long time (;: The yield of 90% is more than 90%. The research and development of this catalyst can greatly reduce the production cost and improve the economic efficiency of the related industries that synthesize DMCHD. According to the contents of US Patent Nos. 5397942 and 53 1 9 1 29, cyclohexanedimethanol (CHDM) is a monomer widely used in the manufacture of polymers and special polyacetates, especially for The key raw material for the production of high performance and high added value PCT polyester [Poly (1,4-cyclohexylenedimethylene) terephthalate] and PETG copolymerized vinegar (Glycol modi f ied PET). However, in the manufacture of cyclohexane dimethanol (CHDM) At the time, 1,4-dicyclohexyl diferrate (Dimethyl 1,4- eye lohexanedi carboxylate, DMCHD) is one of the necessary intermediates for the reaction, so to make CHDM must be DMCHD is synthesized, so DMCHD has a very high economic value, and it is the industry's research and development direction. Where it is used to make it more relevant, it is currently used to synthesize 1,4-cyclohexanedicarboxylic acid dimethyl ester (DMCHD). Catalysts can be divided into two catalyst systems: Pd / Al2O3 and Ru / Al2O3. When using Pd / Al2O3 catalysts, a higher pressure (10-200 bar) and its Temperature (1 40-400. 0 and easy to be poisoned by the reaction by-product c0; although the new Ru / AlgO3 catalyst can react at a lower pressure (10-175 bar temperature range (1 50-230. 0) and There is no problem of poisoning by by-product ⑶, but the catalyst is easy to inactivate, leading to too short aging and lack of yield. The main reason is that the catalyst activation conditions are not used properly, and the product is on page 4 565469 ----- --tjfc 9012nS3. ^ _ 车 月 日 _i ± ^ _ 5. Description of the invention (2) Caused by the problem of large catalyst particles and uneven distribution. The activity and reaction life of the conventional Ru / A 12〇3 catalyst As shown in Table 7, the reaction conditions of this test are: pressure 700-750 psig, temperature 120 ° C, DMT space flow rate (LHSV) 24 h-1 (Hour-) Test on the conventional Ru / A 12 03 catalyst 5 Reaction starts to the 5th and 30th hours (Reaction term 2) '' DMT conversion rate, DMCHD selection rate, and DMCHD yield There were no significant changes. 'Efficient performance was maintained above 95%, but after 5 · 30 hours, the conversion rate of DMT, the selectivity of DMCHD, and the yield of DMC0 decreased sharply' to 240 · 1 hour. The conversion rate of DMT is reduced to 21.1%, and the yield of DMCHD is reduced to 16.47%. This efficiency is no longer in line with industrial utilization and economic benefits. Therefore, the conventional Ru / A 12 03 catalyst has the disadvantage of being easily inactivated in use. The problem that the DMCHD producers want to improve. Therefore, how to propose a novel solution to the above-mentioned problem that the ru / Ai2O3 catalyst used in the synthesis of dimethyl 1,4-cyclohexanedicarboxylic acid dimethyl succinate (DMCHD) is too short and easy to deactivate. The method can not only solve the problem that the catalyst is easily inactivated and the time limit for use is too short, but also greatly increase the output of DMCHD. For a long time, the relevant industry has been eagerly awaiting the difficulties of the inventors and the inventors want to solve the problem. Based on many years of research and development in related technologies, the inventor thought about and improved, and poor his personal professional knowledge. After many tests and discussions, and after countless experiments and improvements, he finally developed a method for preparing high The method of stable selective hydrogenation catalyst can not only be used for a long time without inactivation in the reaction for synthesizing DMCHD, but also can obtain very high yield of DMCHI at low temperature and low pressure) to solve the above problems. The main purpose is to provide a catalyst with high stability.

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Long-term activity, and improved the method, the catalyst obtained by this method can maintain the yield of DMCHD. By providing a catalyst with high stability for the reaction under temperature and pressure for DMHCD synthesis, after a long period of time, the catalyst can not only reduce costs, but also kill two birds with one stone. The DMCHD yield above the present invention is provided at an appropriate temperature, pressure, and liquid concentration to provide DMHCD synthesis. During the reaction of μHui, and the catalyst has excellent anti-maintenance to increase the output, a better hydrogen flow rate catalyst should be used for the secondary purpose of the present invention. In the chemical method, the activation method can make the synthesis process lower than before. Yingge's life is not easy to inactivate, that is, the stability and activity of the reaction, so that producers, for this industry and related industries, can achieve another object of the present invention, the reaction environment conditions, the reaction space, the DMT raw material space flow rate and DMT Solvent selective hydrogenation reaction can obtain 99%, in order to make your review members have a better understanding of the characteristics of the method of the present invention and the effect achieved by the invention, I would like to refer to the ML private diagram of the method of the present invention and comparison The diagram of the best practice example and the detailed description are as follows: First, please refer to the first figure, as shown in the figure is a preferred embodiment of the conventional catalyst and the catalyst manufacturing process of the present invention. First, step 丨 〇1 Put 丨 丨 〇g A 12〇3 in a 500 ml three-necked flask to evacuate; in step 丨 02, continue to heat it to 110 ° C. After 6 hours, stop heating and stop cooling after cooling to room temperature. Vacuum; step 1 In 03, add RuCi3 (4.60675 g) solution to the three-necked flask. In step 104, 'reheat to 600 ° C and vacuum dry the solvent; in step 105, The catalyst at the bottom of the bottle was taken out and dried in a 120 ° C oven for 16 hours. After that, the catalyst was divided into two equal parts, one of which was subjected to the catalyst activation step developed by the present invention, and the other half was used for the conventional catalyst. Media activation step ^

Page 6 565469-~ ^^ i〇i2〇m_ Year, month, and amendment V. Description of the invention (4) ----------- Jiang Yu! In the catalyst activation step developed by the present invention, in step 106, The dried catalyst precursor is placed in a stainless steel reactor; in step 107, it is heated to 45 (rc, 2,], and then the heating is stopped / step 10 8 I # 寺 ί to room temperature and a small amount of air is added Passivate the surface of the catalyst (it becomes pure forgiveness), and finally get the ND2 catalyst (2 ° / gRu / A12〇3). In the activation step of the conventional coal contact, air is used as the oxidant, step 1 09. , The dried catalyst is placed in a high-temperature furnace for calcination, heated to 500 ° C (10t / min), and calcined for 12 hours, and then stopped; in step 11, then the catalyst is placed in a stainless steel reactor In the middle, pass the hydrogen gas and heat it to 45 ° C (^ it / mi ^ i) for 2 ^ hours and then stop heating; in step 丨 丨 i, after the temperature has dropped to room temperature, add less I air to passivate the catalyst surface (make it blunt) State), and finally get the ND1 catalyst (2% Ru / A12〇3). In order to understand the reaction conditions under which the catalyst of the present invention can obtain a better yield of DMCHD better The stability and activity are shown below: First, please refer to Table 1. The table shows the hydrogenation reaction between the catalyst and DMT of the present invention. The reaction is that the catalyst of the present invention is placed in a fixed-bed reactor to carry out a butane hydrogenation reaction, and the benzene ring of DMT is hydrogenated to cyclohexane to form a DMCHD product. It is mainly used DMT dissolved in ethyl acetate as raw material (3.5 wt%) for selective hydrogenation reaction. The temperature and hydrogen flow rate on DMCHD yield are investigated at a pressure of 700-800 pSig. The effect of the reaction is to analyze the composition of the product obtained by f-1 ine GC (equipped with FID), calculate the DMT conversion rate and the selectivity of DMCHD products. The GC column is from Restek Corporation.

Page 7 565469 Case No. 90120833 V. Description of Invention (5). According to the experimental data, in terms of temperature variation, when the reaction temperature is 100 C, a DMT conversion of 99.71%, a DMCHD product selectivity of 9 9.36%, and a yield of 0 ^ 1 (: 0 It is 99.07% (the hydrogen flow rate at this time is 40111 / min); when the temperature is increased to 12 (TC, the conversion rate of DMT is 99.51%, the selectivity of DMCHD products is 98.63%, and the yield of DMCHD is 9815 %, So in this experiment, a higher conversion rate of DMt and a higher selectivity and yield of DMCHD products can be obtained at a reaction temperature of 100 ° C, which shows that the catalyst developed in this research can be extremely mild At the reaction temperature (100 t;) and low H2 / DMT Molar ratio x (27.6), a very good yield can be obtained 'can save energy and hydrogen use at the same time' 'has greatly helped reduce production costs. In & amp In terms of the flow rate, when the reaction temperature is 〇〇t :, the hydrogen flow rate is reduced to 10 ml / mi η and 20 ml / min, respectively, and the conversion rates of DMT are ^ to 88.58% and 93.46%, respectively. The rate also decreased to 87.63% and 92.60%, respectively, and the conversion rate of DMT at a specific hydrogen flow rate of 40ml / min

The yield of 99.71% and DMHCD was 99.07%; however, it was 120 at the reaction temperature. . At the same time, when the hydrogen flow rate was reduced to 10 ml / min and 20 ml / min, respectively, the conversion rate of DMT was also reduced to 94.68% and 94.68%, respectively, and the DMCHD yield was also reduced to 92.66% and 94.38%, which is lower than the DMT conversion rate of 99.51% and the DMCHD yield of 98.15% when the hydrogen flow rate is 40 mi / min, so it can be seen that the hydrogen flow rate is 100 ° c or 120 ° c. At 40 m 1 / mi η, the DMT conversion rate and DMCHD yield are higher than those of the gas flow rate at 10 ml / min or 20 ml / min. Continuation 'Please refer to Table 2. As shown in the table, the effect of the DMT space flow rate on the DMCHD yield under the hydrogenation reaction between the catalyst of the present invention and DMT is shown. According to the experimental data, when the reaction temperature is 120 ° C, the control DM ^ ^

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V. Description of the invention (6) The interval flow rate (LHSV) ranges from 12 hr1, 24 h · 1, 36 Ir1 '48 ΡΓ1. When changing the D MT space flow rate, adjust the hydrogen flow rate to maintain the% / J) μ τ The mole ratios are 27.6, and the DMT conversions obtained are 99.41%, 99.51%, 99.56%, and 98.50%, respectively, and the yield of DMHCD can be maintained above Q7 25%. . Refer to Table 3. As shown in the table, the catalyst of the present invention and the effect of the concentration of DMT solution on the yield of DMCHD under the gasification reaction are discussed. The raw material is 10% (wt) DMT dissolved in ethyl acetate. The solution, the spatial flow velocity π and the reaction temperature were 117. 〇⑷. C 'results show that excellent DMCHD yields of more than 98% can be obtained within the range of =. When the reaction temperature is 117 C, the DMT conversion rate and DMCHD selectivity are 98.93% and 99.15%, respectively, as shown in Table 1. The results were similar when using 3.5% (wt) DMT raw materials and the reaction temperature was 120 ° C, the yields were all above 98%, but a lower Η? / DMT molar ratio (1 5 · 5) can be used. It can be known that the catalyst developed in this research is suitable for 10% (wt) concentration of DMT solution. Secondly, the reaction between the catalyst obtained from the conventional activation process and the hydrogenation of DMT is discussed. The effects of temperature and hydrogen flow rate on the yield of DMHCD are discussed below. The results of the experiments are as follows: Please refer to Table 4. As shown in the table, the effect of the hydrogen flow rate D ^ CHD yield under the hydrogenation reaction of the conventional activation catalyst Ru / A1203 and DMT is discussed. According to the data of the experimental results, the reaction C and the knife Do not test the lice gas flow rate of 10 gua 1 / mi ^, 200 mM 1 / m, the results of the DMT conversion rate and DMCHD production ^ ', and the yield under the same conditions are compared with Table 1 using the present invention ^ _ ^ 4+ The best result is that the hydrogen flow is 4Πηι1 / πη · n B #,

565469

The conversion rate of DMT and the selectivity of DMCHD products are eight and the yield is only 95.43%, which is lower than the table: ί; =. W and 97. For example, the rate of 98.15% at the time of the case is obviously lower. Product selectivity and yield efficiency "Mingzhi catalyst can improve the continuity, please refer to Table 5. As shown in the table, the catalyst obtained by the conventional activation process is hydrogenated with DMT. Shadow plastic, the reaction temperature is 12 (TC-20 (TC, the results show that the DMT conversion rate increases with increasing temperature ^, from 97.89% at 12 (TC to 99 58% at rc, but DMCHD selection The rate decreased from 97.49% at 120 ° C to 2000. 93.66% at 0. The reaction showed that the temperature should not be too high. When the temperature was at 14o: the highest DMCHD yield was 95 ·. 79%, but still lower than the DMCHD yields obtained by using the catalyst of the present invention in Table 1, 9 9.07% (100%) and DMCHD yields of 98.15% (120.00), so it is clear that using the catalyst of the present invention is not only possible It is also possible to obtain a higher DMCHD yield by carrying out the reaction at a lower temperature than the conventional one, so using the catalyst of the present invention to produce DMCHD can not only save energy, but also greatly reduce Production cost 0 In order to understand that the catalyst of the present invention has the advantages of higher stability, higher activity, and inactivation than conventional catalysts, the relevant characteristic data of the catalyst of the present invention is as follows: Please refer to Table 6 As shown in the table, the catalyst life test is discussed under the hydrogenation reaction of the coal contact with the DMT of the present invention. As shown in the experimental test in Table 1, the reaction is to place the coal contact of the present invention in a fixed-bed reactor for DMT. Hydrogenation reaction. DMT (3.5 wt%) dissolved in ethyl acetate was subjected to benzene ring hydrogenation reaction to produce DMCHD products. The reaction pressure and temperature were 700-800 psig and 120 ° C, respectively. The DMT space flow rate was controlled to 12 Ir1 and 241Γ1, the hydrogen flow rate is

565469 _Case No. 90120833_ Modification of Year and Month_ V. Description of the invention (8) 10ml / min (H2 / DMT Molar ratios are 55 · 2 and 27.6, respectively), and the reaction products are analyzed by GC (equipped with F ID) Composition, calculate DMT conversion rate and product selectivity. The data shows that the reaction terms 1 to 5: At a space flow rate of 12 h-1, the DMT conversion rate remains above 99% after 70 hours of reaction, and the selectivity of 01! (: 110 product is not significant. The change remained around 99%, showing no catalyst inactivation. However, when the spatial flow rate was increased to 24 h_1, the DMT conversion rate and the selectivity of DMCHD products decreased to 92. 10% and 97.78%, respectively. The main reason is that the contact time between the raw materials and the catalyst is shortened and the & / DMT molar ratio is reduced (from 55 · 2 to 27.6). When the reaction continues to 5 7 2 · 5 hours, the data show that the catalyst The original activity and selectivity are still maintained, and no obvious inactivation occurs. It can be seen that the catalyst developed in this research has excellent stability and is suitable for industrial mass production. Continued, refer to Table 7, as shown in the table, it will be customary The catalyst obtained during the activation process is also tested for stability, and the DMT space flow rate is controlled to 24} rl. When the reaction is performed for 5.30 hours, the DMT conversion rate (between 97.89% -99.74%) and the selectivity of DMCHD products are selected. (Between 96 · 94% _97 · 81%), there is no obvious change. There was no obvious inactivation in 5.3 hours. However, after the reaction proceeded to 76 hours, the DMT conversion rate decreased to 73.52% and the selectivity of other (: 111) products also decreased to 94.73%, showing The catalyst has been inactivated, and the reaction performance has increased to 2401. After 1 hour, the DMT conversion rate and DMCHD selection rate have dropped to 21.0% and 78.06%, respectively, indicating that the catalyst has been severely inactivated. At this time, the production capacity is not in line with economic benefits. The results of Table 6 and Table 7 show that the catalyst of the present invention has better stability than the conventional catalyst, and is suitable for industrialization. Jinlian 0565469 90,120 along the month of the fifth, the description of the invention (9) to modify the comprehensive selectivity is to extract or acetic acid, so that the anti-DMCHD industry uses Ming patents but is only used to limit the description, all of which should be described above 'The present invention is a hydrogenation catalyst preparation 1,4_ For a better activation strip, the purpose and gaseous hydrogen storage should be at a relatively low temperature. Therefore, the present invention is really a function, it should meet the special application. The experimental conditions and characteristics that determine the scope of the present invention are included in the application of the present invention. In addition, we have applied for new and innovative applications under the pressure of advancement, and we have granted patents for the invention. Therefore, we would like to ask for patents (fixing the catalyst line with dicarboxylic acid), and the advantages and advantages are not beneficial. Wherever dimethyl is placed in the solution bed according to the scope of God, there can be doubts about progress. I pray for the equal and stable method of the present invention, the high yield of the dioxane hydrogenation reaction of the main agent, and Available for production according to law, not for patent application. Changes and modifications Table 1: Hydrogen $ speed on reaction Yingli (using ND2 catalyst) Item temperature CC) H2 flow rate (ml / min) DMT LHSVCh'1) m Conversion Rate «) DMCHD selection rate (%) DMCHD yield (» 1 100 10 24 88.58 98.92 87.63 2 100 20 24 93.46 99.09 92.60 3 100 40 24 99.71 99.36 99.07 4 120 10 24 94.68 97.86 92.66 5 120 20 24 96.30 98.00 94.38 6 120 40 24 99.51 98.63 98.15 E 3.5% Li / ethyl acetate solution as raw material Table 2: Influence of DMT space flow rate on reaction (using ND2 catalyst) Item temperature (° C) H2 flow rate (ml / min) m LHSV (h_l ) DMT conversion rate (%) DMCHD selection Yield 00 DMCHD (X) 1 120 20 12 99.41 98.79 98.20 2 120 40 24 99.51 98.63 98.15 3 120 60 36 99.56 98.77 98.34 4 120 80 48 98.50 98.73 97.25

565469 Case No. 90120833_Year_Month_Revision V. Description of the invention (10) Table III. DMT space flow rate and reaction temperature versus reaction shadow engine (using ND2 catalyst) Item temperature (° C) H2 flow rate (ml / min) DMT LHSVCh · 1) Conversion rate (%) DMCHD selectivity (¾) DMCHD yield (¾) 1 140 50 6 99.53 99.29 98.82 2 141 50 12 99.64 98.88 98.52 3 117 50 12 98.93 99.15 98.09 * Use 10% DMT / acetic acid Ethyl acetate solution as raw material Table IV. Effect of hydrogen flow rate on reaction (using ND1 catalyst) Item (° C) H2 ship (ml / min) m LHSVCh1) m Conversion rate (%) DMCHD selection rate (%) DfCHD production ( %) Rate 1 120 10 24 79.42 95.31 75.70 2 120 20 24 89.71 97.06 85.07 3 120 40 24 97.89 97.49 95.43 Table 5. Reaction temperature vs. reaction (using ND1 catalyst) Item temperature (° C) H2 flow rate (ml / min) DMT LHSVCh-1) DMT conversion rate 00 DMCHD selection rate (W DMCHD yield 00 rate 1 120 40 24 97.89 97.49 95.43 2 140 40 24 98.03 97.72 95.79 3 160 40 24 99.54 96.18 95.73 4 180 40 24 99.58 93.66 93.27 5 200 40 24 99.58 93.66 93.27 Table 6. Catalyst stability test items of the present invention DMT space flow rate Of1) reaction time (hours) DMT conversion ⑻ DMCHD selectivity (¾) DMCHD yield (¾) 1 12 1 99.5 99.5 99.00 2 12 10 99.41 98.79 98.20 3 12 20 99.85 93. 34 99.20 4 12 30 99.04 99. 26 98.31 5 12 70 99.08 99.60 98.69 6 24 80 92.10 97.78 90.05 7 24 100 92.90 97.95 91.00 8 24 120 94.21 97.64 91.96 9 24 140 94.34 97.50 91.98 10 24 171 93.19 98.55 91.84 11 24 200 93.77 97.89 91.79 12 24 210 92.42 99.60 92.05 13 24 240 93.71 98.22 92 · 05 14 24 360.0 93.60 98.05 91.78 15 24 384.5 93.00 97.62 90.79 16 24 408.3 94.39 98.19 92. 68 17 24 480.0 92.69 97.74 90.59 18 24 527.5 92.15 97.79 90.35 * 700-800psig; 120 ° C ; H2 flow rate 10ml / min III 1 1 page 13 565469 _ case number 90120833_ year month day _ amendment five, description of the invention (11)

Table 7. Reaction time of conventional catalyst life test items (hours) m Conversion rate (%) DICHD selection rate 00 DMCHD yield 00 1 0.4 99.74 96.94 96.69 2 3.15 98.76 97.52 96.31 3 5.30 97.89 97.49 95.43 4 76.00 73.52 94.73 69.64 5 148.60 72.95 94.72 69.10 6 169.75 68.58 93.76 64.30 7 240.1 21.10 78.06 16.47 * 700-750psig; 120 ° C; DMT space flow rate 24h_1 Page 14 565469 _ Case No. 90120833 _ year month day __ Schematic illustration first diagram: conventional Catalyst ND1 and catalyst ND2 of the present invention are prepared and activated in a preferred embodiment. Table 1: Effect of hydrogen flow rate on the reaction of DMCHD using the catalyst ND2 of the present invention Table 2: DMT spatial flow rate on the synthesis of the catalyst ND2 of the present invention Effect of DMCHD reaction Table 3: The effect of DMT space flow rate and reaction temperature on the reaction of DMHCD synthesis using the catalyst ND2 of the present invention Table 4. The effect of radon flow rate on the reaction of DMCHD synthesis using conventional catalyst ND1 Effect of conventional catalyst ND1 on DMHCD synthesis Table 6: Catalyst stability test of the present invention Table 7 · Common catalyst brother test

Claims (1)

565469 ^ S_90120833__ VI. Scope of patent application " ^ _ 日 Chromium _ 5 · If applying for patent 笳 ifj 篦 τ ~ 40 Ul / mirO. 2. The method, wherein the flow rate of the hydrogen gas is 6 = 1: the method described in item 1 of Liganwei, wherein the catalyst can be maintained under the reaction conditions for 500 to 60 hours without losing activity. 7. The method according to item 1 of the scope of patent application, wherein the method is extended. The yield of DMCHD can be maintained above 90% for a long time. Use this catalyst Page 17