TW583169B - Methods and apparatus for removing catalyst from oxidation reactor effluent - Google Patents

Abstract

Methods and apparatus for removing a catalyst from a reaction mixture formed by reacting a hydrocarbon and an oxidant in the presence of the catalyst in a reactor, in which the reaction mixture contains one or more dibasic acids. The catalyst is removed by adding water and/or cooling the reaction mixture to cause phase separation, recycling the polar phase to the reactor, and transferring the non-polar phase to an ion exchange unit to remove catalyst contained therein.

Description

583169 A7 B7 V. Description of the Invention (1) This application requests the benefit of US Provisional Application No. 60 / 208,666, dated June 1, 2000. BACKGROUND OF THE INVENTION There are two different types of procedures for making adipic acid. The conventional procedure for the oxidation of cyclohexane (CH) to adipic acid includes two steps: the first step uses oxygen to oxidize CH at 150 ° C in the presence of a cobalt or manganese catalyst to produce cyclohexanone (CHO) and cyclohexanol ( CHOL); The second step is to react a mixture of nitric acid with CHO and CHOL in the presence of vanadium / copper catalyst at 50-80 ° C to obtain adipic acid. Recently, the industry is committed to developing a so-called π-step process π to directly oxidize cyclohexane to adipic acid in the presence of solvents, catalysts and accelerators. One of the one-step processes is published in U.S. Patent No. 5,547,905 (Kulsrestha et al.) And contains catalyst preparation and activation to oxidize cyclohexane with air or oxygen to make adipic acid. The catalyst has 70-99 wt% of a divalent cobalt salt and 1-30 wt% of a ferrous salt, and is prepared in the presence of an initiator. The reaction takes place in the pressure range of 1-70 kg / em2 and the temperature in the range of 70 ° -150 ° C at a space velocity of 1-200 h · 1 for 1-8 hours. The reactor effluent typically contains unreacted cyclohexane, acetic acid (solvent), water (reaction product), adipic acid, succinic acid (glutaric acid), and catalyst. Several developments have recently been made in removing catalysts and recycling (mainly) from the product stream of these one-step processes. The following references are considered representative: International publications WO 99/14178 (Rostami et al.), Wo 99/14179 (Dassel et al.), WO 99/37599 (DeCoster et al.), And WO 99/42430 (Dassel et al.). In addition, these applications are related to the following U.S. patents, including many of the same inventors: 5,908,589 (DeCoster, etc.); 6,039,902 (Rostami, etc.); 6,103,933 (DeCoster, etc.); 6,129,875 (Dassel, etc.); and 6,218,573 -4 -This paper size applies to China National Standard (CNS) A4 (210 X 297 male)

Binding

Line 583169 A7 V. Description of the invention (2) (Vassiliou, etc.) 〇 (Please read the notes on the back before filling out this page) These closely related documents are issued as one .m ^ * Lean table step% hexane oxidation It is a recycling method of catalyst used in adipic acid. Before and after the catalyst precipitated in the reactor mud, the hemp eight _ and the other _ I _ products are preferably recovered by filtration after a sudden pressure). Υ + stomach Na The catalyst in the filtrate is partially precipitated by reducing the amount of water in the mixture and / or cooling the mixture to the catalyst sink. After the catalyst started to sink, the remaining mother liquor was added. 2. At least most of the solvent in the acetic acid reactor was removed during the treatment. The remaining dissolved meta-acids precipitated and removed the additional catalyst. Heat treatment and catalyst removal can be completed in two stages to improve catalyst recovery. However, because the reaction product is recovered and then the catalyst is removed, these methods allow the catalyst and the product to sink or crystallize together, which makes the downstream product purification process more complicated and less effective. • Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Other patents have studied various methods to remove catalysts from oxidation reaction mixtures. For example, in the method described in U.S. Patent No. 5,880,3 13 (Zaima et al.), The aromatic carboxylic acid product is crystallized from the reaction solution before the catalyst is precipitated. U.S. Patent No. 5,756,83 No. 7 ((: (^ & 11, 11 丨, etc.) describes the procedure of catalyst circulation in the reaction for the direct oxidation of cyclohexane to adipic acid. The raw glutamic acid and Succinic acid circulates the catalyst. U.S. Patent No. 4,254,283 (Mock) describes a method for producing adipic acid from cyclohexanol and cyclohexanone by nitric acid oxidation. Recovery of glutamic acid and succinic acid as by-products. Removal of nitric acid catalyst This method crystallizes the product from the reaction solution. Finally, U.S. Patent No. 4,162,991 (Jones) describes a method for recovering cobalt and bromide catalysts by using a strongly basic anion exchange resin, followed by self-exchange using a low-fat monobasic acid. Resin ions are recovered in the resin. US Patent No. 3,959,449 (Shigayasu et al.) Describes when the monobenzene is in contact with -5- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 583169 A7 B7 V. Description of the invention (3 (Please read the precautions on the reverse side before filling out this page) Method for removing catalyst components containing cobalt and Wei from the reaction mixture generated during low-fat monocarboxylic acid oxidation in a solvent. Mix the reaction mixture with water under oxygen The catalyst is separated from the catalyst by stirring in the presence of a sulfur compound and a water extract as a catalyst. The extract is then sent through a strong acidic cationic resin to recover the catalyst. US Patent 5,840,643 (Park et al.) Describes the oxidation of pseudobenzene to benzene The catalyst removal from the reaction mixture produced by meta-dicarboxylic acid includes a method of acetic acid tetrahydrate and manganese acetate tetrahydrate. The reaction mixture is removed first and then the crystallization and distillation procedures are performed. The method includes adding the amount of the reaction mixture to the reaction mixture. To 11 times the amount of water. The dilute reaction mixture is subsequently heated to make the dilute reaction mixture a liquid phase. The mixture is then passed through a cation exchange resin to recover the catalyst.-• Line · US Patent 5,955,394 (Kelly) describes the production of alkane oxidation Method for separating catalyst containing manganese and manganese from reaction mixture produced by aromatic carboxylic acid. The reaction product is recovered after removing catalyst from reaction mixture. The method includes heating the mixture to maintain aromatic acid in a dissolved state through a strong acid cation exchange resin Circulate the recovered catalyst to the reactor, and the solvent can be recovered and recycled. Consumption by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs None of the documents published by the cooperatives above suggested that the subject of the present invention is a new method and device for removing catalysts from the reaction mixture. Therefore, it is necessary to develop more effective methods and methods for recovering catalysts from the oxidation reaction mixture than are currently known. Device Summary of the Invention The present invention provides a novel method and device for effectively removing the catalyst, and then recovers and purifies the reaction product, which greatly simplifies the purification part of the recovery process. Therefore, it can be oxidized to produce adipic acid from the presence of cyclohexane catalyst A high-purity reaction product is obtained in the obtained reaction mixture. In addition, the reaction efficiency is improved due to the ability of the catalyst to cycle. 6- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing 583169 A7 B7 V. Description of the invention (4) Rate. The scope of patent application from the detailed description and appendix of the present invention will reveal other purposes and advantages. According to the first feature of the present invention, a method for removing catalyst from a reaction mixture formed by the reaction of a hydrocarbon and an oxidant in the presence of a catalyst includes the steps of cooling and / or adding water to the reaction mixture, and separating the reaction mixture into polar and non-polar phases. 'Cyclic polar phase' and removal of catalyst from non-polar phase with ion exchange units. According to another aspect of the present invention, a method for removing a catalyst from a reaction mixture produced by the reaction of a hydrocarbon and an oxidant in the presence of a catalyst includes the steps of cooling the reaction mixture, and removing the catalyst from the reaction mixture with an ion exchange unit. Another feature of the present invention relates to a device for removing a catalyst from a reaction mixture formed by a reaction between a hydrocarbon and an oxidizing agent in an oxidation reactor in the presence of a catalyst. The device includes a phase separator to separate the reaction mixture into a polar phase and a non-polar phase. The steaming tower removes excess water in the polar phase, circulates the polar phase back to the reactor, and an ion exchange unit removes the non-polar phase contact. Media. Yet another feature of the present invention relates to a device for removing a catalyst from a reaction mixture formed by the reaction of a hydrocarbon and an oxidant in an oxidation reactor in the presence of a catalyst. The device includes a cooling unit for the reaction mixture and an ion exchange unit for separating the catalyst in the reaction mixture. These and other features of the invention will become apparent from the following description and drawings. Brief description of the drawings Fig. 1 illustrates an ion exchange unit according to the present invention. Fig. 2 is a schematic diagram showing a method and an apparatus for separating a catalyst from a reaction effluent according to the present invention. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ----------- installation --------- 1 order ---------- -Line ^^ (Please read the notes on the back before filling out this page) 583169 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (5) Detailed description of the preferred specific examples of oxidation of hydrocarbons at ambient temperature In the one-step process, the reactor effluent contains two liquid phases and a solid phase mainly comprising adipic acid. Throughout this description, the terms reactor effluent and reaction mixture are used interchangeably. International publication WO 97/49485 and US Patent No. 6,039,902 report that at this temperature the polar phase (mainly water) is much less than the non-polar phase, which accounts for approximately 97% of the effluent capacity. However, adding a small amount of water of about 0.4 to 1 wt% can generate a considerable amount of polar phase. Since both acetic acid and ferrous acetate are soluble in water, phase-related adjustments can be made so that substantially all of the metal acetate remains in this polar phase. After phase separation, the polar phase can be processed to recover and recycle the catalyst to the reactor. At the same time, the non-polar phase can be arbitrarily sent to the ion exchange unit or other facilities to remove the last trace of catalyst and then send the reaction product to the product purification section of the process. . We have also found that even without extraction with water to reduce the concentration in the liquid stream in advance-an ion exchange resin bed is extremely effective at removing the effluent from the reactor. It was found that this resin bed effectively removed about 8,000 ppm of cobalt from the reactor effluent. As discussed above, if the amount of effluent in the reactor exceeds the resin's ability to remove cobalt • It can be reduced in advance with water extraction and then the effluent is subjected to ion exchange treatment. Figure 1 shows a laboratory setup for continuous ion exchange of reactor effluent. The apparatus includes a feed vessel 101 to hold the extraction reactor effluent. The feed vessel is led to a pump 102, and the reactor effluent is drawn from the feed vessel 101 and sent to the ion exchange column 103. The ion-exchange column 103 is prepared so that the ion-exchange resin 104 is filled on the surface of the quartz layer 105 above the glass frit 106. The effluent column 103 is returned to the feed container 101. This system allows the effluent to be subjected to a continuous ion exchange process that is optimal for catalyst removal. Although Figure 1 shows the continuous use of a laboratory -8-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- · install i ——: —— 丨Order 1 -------- Line · (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives 583169 A7 ________ B7 5. Invention Description (6) System 'Industry Technology It is understood that it is necessary to improve the device for the system to continuously extract the catalyst contained in the one-step oxidation reactor and continuously remove the catalyst. Removal of the catalyst from the effluent may recover higher purity reaction products and simplify the purification process. It is also possible to wash out the catalyst trapped in the ion exchange resin and use it in the oxidation process after recovery. Figure 2 is a schematic diagram illustrating a preferred method and apparatus for oxidizing hydrocarbons to form dibasic acids. This method allows the catalyst to be recovered from the reactor effluent and recycled to the oxidation duster. This method also allows the purification of the dibasic acid end product and returns the hydrocarbon and solvent to the oxidation reactor. The hydrocarbons may be cyclohexane, cyclohexanone, cyclohexanol, cyclohexyl hydroperoxide or a mixture of two or more of these. A particularly preferred hydrocarbon is cyclohexane. The di-7G acid end product preferably contains adipic acid, but additional end products may include succinic acid and glutaric acid. The solvent is preferably acetic acid. The catalyst may contain a cobalt salt, an iron salt, a manganese salt, or a mixture of two or more of these salts. This preferred method and apparatus will be described in detail later. The method according to the preferred embodiment includes several steps: an oxidation step; a phase separation step; an ion exchange step; an initial product and solvent recovery step; and a final product recovery and purification step. These steps will be discussed in more detail individually. The oxidation step converts cyclohexane to adipic acid. The reaction is carried out in an acetic acid solvent in the presence of a catalyst and oxygen as an oxidant. Catalysts include iron salts, and catalyst activators such as cyclohexanone can be used. The reaction effluent is cooled to a temperature preferably from about 3 ° C to about 100 ° C, preferably from about 30 ° C to about 50 ° C. The final product contained in the oxidation step effluent and the unreacted starting material accept phase Separation step. In this step, the effluent can be arbitrarily filled with water to separate its polarity and non-polarity. Install ------- Γ-Order --------- line · (Please read the precautions on the back first Refill this page) -9-

583169 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of Invention (7) Relevant. The amount of water added is preferably from about 0 to about 10% by weight of the total reaction mixture, and more preferably from about 0.1 to about 5% by weight. The polar phase contains dissolved catalysts because the cobalt and iron compounds of the catalysts are soluble in water. This polar phase can be recycled back to the oxidation step to catalyze the oxidation reaction. Alternatively, the catalyst can be recycled to the oxidation step before the oxidation step can be incorporated to remove water from the polar phase. The non-polar phase may contain a small amount of catalyst in addition to the adipic acid reaction product, other unreacted starting materials of other reaction by-products, and the solvent. In order to obtain a high-purity end product without complicated purification treatment, it is required to substantially remove all catalysts contained in the polar phase or a large amount which is economical and practical. To this end, the non-polar phase is passed through an ion-exchange tower 231 to remove the catalyst. We found a highly acidic, cationic ion exchange resin such as a chelated isobutyric acid cation exchange resin or a sulfonated polystyrene cation exchange resin. In particular, it was found that Resin Teep cG8 (NJ, manufactured by Resin Teeh of Cherry Hill, Inc.) had an excellent effect in removing cobalt and iron catalyst components from the effluent. Non-polar phase effluent can be arbitrarily distilled and evaporated after passing through the ion exchange column. This step enables both the unreacted cyclohexane starting material and the acetic acid solvent to be removed in the non-polar phase and recycled to the oxidation step. Adding this step makes the method more efficient. The remaining components of the non-polar effluent are subjected to end product recovery and purification to obtain high-quality adipic acid end products. Recovery and purification are accomplished by crystallizing adipic acid from the effluent, recovering the liquid remaining after hydrolysis of adipic acid after crystallization, and then performing a second crystallization step to recover the remaining adipic acid. After the second step of crystallization, the remaining liquid has been completed, which mainly contains reaction by-products and is considered to be waste. Referring to Figure 2, according to a preferred embodiment, the device contains several units: the oxidation unit Chuan _ -10-this paper size · Chinese National Standard (CN & A4 specification (210 x 297)) ---------- --Lu Zhuang ------- 1 order -------- line · (Please read the notes on the back before filling this page) 583169 A7 ____ B7 V. Description of the invention (8); Phase separation Unit 220; ion exchange unit 230; arbitrary circulation unit 240; product recovery and purification unit 250. Each unit will be thoroughly studied individually. Oxidation unit 210 includes an oxidation reactor 211, in which cyclohexane is oxidized to adipic acid. The reactor can be A catalyst adding unit 212 and a cooling device 213 are optionally combined to reduce the temperature of the reactor effluent after leaving the reactor. The phase separation unit 220 includes a phase separator 221 and an arbitrary device 222 that adds water to the reactor effluent. A phase separator separates the effluent from the reactor into polar and non-polar phases. The polar phase is sent to a random distillation column 223 to remove excess water in the polar phase. A catalyst has also been found in the polar phase, because the catalyst can be dissolved in water. Therefore, the polar phase is directly circulated to the catalyst addition unit 212 or the oxidation reaction. 2 11 is used to continue the catalytic oxidation reaction. The non-polar phase formed by the phase knife ionizer is sent to the ion exchange unit 2 3 0, which can remove all remaining catalyst contained in the polar phase. The catalyst remains in the ion exchange tower 231 The non-polar components of the reactor effluent pass through the ion exchange unit 230, and are optionally sent to a starting product and reaction solvent circulation section 240 and then the end product of adipic acid is recovered. The starting product and reaction solvent circulation section includes a distillation column 241 And an evaporator 242. The non-polar reactor effluent leaves the ion exchange column 231 and enters the distillation column 241. The cyclohexane starting product and the acetic acid solvent are released as the top product in the distillation column 241 and are recycled to the oxidation reactor 2 11 For the oxidation reaction. The bottom of the column is sent to the evaporator 242 at will. The attached acetic acid is removed in the evaporator 242 and sent to the reactor 2. 11. The remaining non-polar effluent includes the desired final product of adipic acid and other reactions The by-products are sent to the product recovery and purification unit 250. The product recovery and purification unit 250 includes the first crystallizer 251 and a hydrolyzer-11-This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) ------- 1 ------ (Please read the precautions on the back before filling out this page) Order 1 -_ Line · Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 583169 Economy Printed by the Consumers' Cooperative of the Ministry of Intellectual Property Bureau A7 B7 5. Invention Description (9) 253, and a second crystallizer 255. The first crystallizer 251 is crystallized from the non-polar reactor effluent to obtain the final product of adipic acid. The slurry was filtered off. The crystals remaining on the filter 2 5 2 purified the final adipic acid product. The remaining mother liquor may still contain adipic acid, which is then sent to hydrolysis 253. Water and a hydrolysis catalyst are added to the solution for hydrolysis. The liquid discharged from the hydrolyzer 253 is filtered by the filter 254 to recover the hydrolysis catalyst. The filtrate was sent to a second crystallizer 255. The produced crystal slurry was filtered, and the crystals remaining on the filter 256 were purified adipic acid. The remaining liquid is waste. The following examples provide preferred specific examples to further illustrate the invention, and are not intended to limit the scope of the invention. Examples Non-limiting examples 1-3 are provided below. These examples prove that an ion exchange resin bed is not effective in extracting high amounts of cobalt (about 8,000 ppm) from the reactor effluent without water extraction to reduce the cobalt concentration in the liquid stream in advance. Example 4 illustrates a method that involves phase separation to reduce the amount of cobalt in the reactor effluent before receiving an ion exchange treatment. Example 1 This experiment was performed to demonstrate the use of an ion exchange resin as a reactor product effluent after unreacted CH and a portion of acetic acid (HAc) have been removed. The ingredients of the feed mixture are as follows: -12- The national standard (CNS) A4 specification (2W χ 297 public love) of this paper for weekly use ----------- packing ------- 1 Order ------- line (Please read the precautions on the back before filling this page) 583169 A7

V. Description of the invention (10) Example 1 Weight percentage of feed ingredients 86.21 Acetic acid Water 1.15 Adipic acid 8.83 Succinic acid 0.56 Cobalt (II) 0.76 Iron (Π) 0.031 ----------- pack- -(Please read the notes on the back before filling this page) (II) is cobalt (II) acetate tetrahydrate, iron (II) ferrous acetate. The catalyst content in the mixture was reduced without water extraction before ion exchange treatment. The feed mixture was stirred at 400 rpm and 60 ° C for 30 minutes and mixed to completely dissolve the solid. &Amp; fat used

Resm Tech® CG8 high-capacity, colloidal, sulfonated polyphenylenesulfonium cation exchange resin. Resin preparation: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Pretreatment resin removes fine resin particles to obtain H + resin. Explicitly add enough distilled water to mask the resin for 1 inch from the top of the resin bed. Gently shake the wet resin for 1 minute to ensure complete mixing. Let the mixture stand for 15 minutes. Decant the upper water ’Repeat the wet process. A 10 wt% hydrochloric acid (HC1) solution was added to cover the resin and the resin was loaded. The mixture was gently stirred for i minutes followed by 30 minutes of contact. The resin was decanted with 10 wt% HC1 'and the resin was rinsed with 10 times the bed volume (the resin volume was initially measured). The resin was then contacted with an acetic acid solution containing 2% cobalt for 25 hours to saturate with cobalt. Decant the solution and regenerate the resin. Add 10 wt% HC1 to the resin during regeneration to cover the resin tree for 1 inch. HC1 fluid is connected to resin by magnetic stirring at 200 rpm. -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) '~ 583169 A7 ____ B7 V. Description of the invention (11) 30 minutes. Decant HC1 and repeat acetic acid regeneration. Rinse 4 times with distilled water and let stand for 5 minutes in each rinse. Procedure: Add 14 grams of recycled resin to a 250 ml container containing 40 grams of the feed mixture. The container was stirred at 200 rpm for 6.5 hours to reach the required contact level. After 6.5 hours, a sample was taken and sent to the plasma coupling spectrophotometric analysis to determine the concentration in the feed mixture and the production stream after contact with the ion exchange resin. The following performance results indicate that ion exchange resins are very effective at removing large amounts of cobalt from the reactor effluent. ------------ Loading --- (Please read the precautions on the back before filling this page) Sample sample (ppm) Feed mixture 7560 Ion exchange product 1 Order-1 Example 2- -Line · The experiment in Example 1 was repeated with a chelating isobutyric acid cation exchange resin Amberlite® IRC-71 8 Resin preparation and removal procedures were completed in the same way as in Example 1. The following performance results indicate that Amberlite® IRC-718 resin is far less effective than Resin Tech CG8 polystyrene cation exchange resin. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 2 Sample sample (ppm) Feed mixture 7560 Ion exchange product 466 -14- This paper size applies to China National Standard (CNS) A4 specification mm)-583169 A7 --- --- B7 ____ 5. Description of the invention (12) Example 3 This experiment uses ion exchange resin to remove cobalt from the effluent of adipic acid reactor, which can be called reconstituted feed. Furthermore, the catalyst content in the mixture before the ion exchange treatment was reduced without water extraction. The restructured feed includes the following: ----------- · Installation ------- Ί -------- line Φ (Please read the precautions on the back before filling in this Page) The product of the crude product produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs contains 98.4 wt% adipic acid and 1.6 wt%. Commercial catalyst solids contain the following components: Commercial catalyst solids weight% adipic acid 31.0 glutaric acid 7.50 succinic acid 1.20 other 45.03 15.0 -15- Example 3 Reconstituted feed component weight% acetic acid 76.94 cyclohexane Alkane 12.40 Water 1.01 Commercial catalyst solid 4.87 Commercial crude reactor product 4.70 Cyclohexanone 0.042 Cyclohexanol 0.048 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 male f) 583169 A7-B7 V. Invention Note (13) The reconstituted feed is mixed with a stirrer and heated at 4 ° C for 2 hours to dissolve all solids. The resin used is ResinTech® CG8 cation exchange resin. Resin preparation: The resin is pretreated to remove fine resin particles and obtain Type resin. Clearly say 'add enough water to submerge the resin for 1 inch and soak the resin with distilled water. Stir the wet resin for 1 minute and allow the mixture to stand for 5 minutes to ensure complete mixing. Repeat the wet washing process after decanting the water. Add a 10 wtD / salt solution to cover the resin for 1 inch to load the resin. Stir the mixture for 1 minute, and then contact for 30 minutes. Decant 10 wt% hydrochloric acid 'in a 10-fold bed. (Resin volume in the tower) Rinse the resin with distilled water. Finally, rinse the resin with 10 times the bed volume of glacial acetic acid. Decobalting procedure: Add 5 ml of resin to a # 20 two-stage tower with glass frit (pressurized filter bucket), add The 50 ml feed was placed in a 125 ml conical flask directly under the tower. A line pump was used to connect a feed ring to the tower to make a feed rate of 5 ml per second through the ion exchange bed. See Figure 1. Tower operation 11 hours 6 The contact time recommended by the manufacturer was completed in minutes. Samples were provided for the coupling coupled plasma spectrophotometric analysis to determine the reconstituted feed and the cobalt concentration of both product streams after contact with the ion exchange resin. The following display results again indicate Resin Tech® CG8 cation exchange resin is particularly effective in removing high levels in continuous flow systems. Sample level (ppm) Reconstituted feed 7967 Ion exchange products 2 -16- This paper is sized to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) ▼ Packing ----------- Order -------- Line _ Printed Economy Intellectual Property Bureau employee consumption Printed by the company 583169 A7 B7 V. Description of the invention (14) Example 4 Referring to Figure 2, cyclohexane (CH), acetic acid (HAc), catalyst activator (such as cyclohexanone CHO), catalyst and oxygen (or Air) is fed into the continuous reactor at a predetermined flow rate. The reaction is performed at a pressure in the range of 1-70 kg / cm2, 70.-150. (: The temperature between the ranges is performed at a space velocity of 1-200 h_1 for a period of 1-8 hours. The reactor effluent contains unreacted CH, HAc, catalyst, adipic acid (AA), succinic acid (SA), glutaric acid (GA), MCHA, water and other minor components. The reactor effluent was cooled to the desired temperature range, a small amount of water was added to the liquid stream, and then the liquid was directed to the phase separator. Although not much water is added, the polar phase is greatly expanded, resulting in better interfacial control in the phase separator. The conditions in the phase separator allow virtually all of the catalyst to remain in the underlying polar phase, with a very small amount of carboxylic acid present in the polar phase. The polar phase is sent to the distillation column or flash column for dehydration and recycled to the reactor section. The non-polar phase is cooled to an appropriate temperature and fed to an ion exchange tower to remove the last trace of catalyst. The non-polar phase containing no catalyst was then introduced into the distillation column to remove CH and a single HAc from the overhead product to the reaction section. The bottom liquid stream was transferred to an evaporator to remove excess HAc, and any purified adipic acid crystals were precipitated in the crystallizer. The slurry in this crystallizer is fed into a filter to recover purified adipic acid, and the mother liquor is transferred to a hydrolyzer to convert MCHA to adipic acid. Here, an appropriate amount of a hydrolysis catalyst is added to promote the reaction. After removing the hydrolysis catalyst with a filter, additional adipic acid was recovered through a crystallization / filtration step. The present invention has described specific examples which are considered to be desirable today, but is not intended to limit the present invention. On the contrary, the present invention is intended to cover various modifications and include equivalent devices and structures within the spirit and scope of the accompanying patent application. The following patent application department -17- This paper size applies to China National Standard (CNS) A4 specification (x 297 public love) " ----------- install ------- Γ-order · τ -------- line (please read the precautions on the back before filling this page)

Claims (1)

583169 Patent Application No. 090113348 Chinese Application for a Replacement Scope of the Patent (Signed Year ^ Month ^ A8 B8 C8 D8 1. A method for removing a catalyst from a reaction mixture, the mixture being formed by a reaction between a glow and an oxidant in an oxidation reactor in the presence of the catalyst, the method comprising the following steps: (a) cooling the reaction mixture and / or adding water To the reaction mixture; (b) separating the reaction mixture into polar and non-polar phases; (c) cycling the polar phase to the oxidation reactor; and (d) transferring the non-polar phase to the ion exchange unit to remove the catalyst. 2. According to the method of item j in the scope of the patent application, the hydrocarbon in the hydrazone is selected from cyclohexane, cyclohexanone, cyclohexanol, cyclohexyl hydroperoxide, and mixtures thereof. 3. The method according to the patent claim μ, wherein the oxidant contains oxygen. 4. According to the method of item i of the patent application, the catalyst in the catalyst contains a compound selected from the group consisting of palladium, iron, manganese and mixtures thereof. 5. The method according to item 1 of the patent application range, wherein the reaction mixture is cooled to a temperature in the range of 30 to 100 ° C. & The method according to claim η, wherein water is added in a range of 0 to 100/0 by weight of the total reaction mixture. 7. A method according to item 5 of the patent application, wherein the reaction mixture is cooled to a temperature in the range of 30 to 50 ° C. 8. The method according to item 6 of the patent application, wherein water is added in a range of 0.1 to 5% by weight of the total reactor effluent. 9. ^ The method of applying for the 15th member of the patent scope, wherein the ion exchange resin-polymer resin has cation exchange and acid resistance, and is selected from the group consisting of chelated isobutyric acid cation exchange resin, and continuous polybenzene; Exchange resin 箬. V blade? This paper size applies to Chinese National Standard (CNS) Α4 size (21〇 X 297 mm) 583169 A8 B8 C8 ι〇 · According to the method of the scope of the patent application No. 9 is: ^ Hui Zhongyang Li Yu X Tree Change Month 丨 for the same kind of preparation! , Colloidal particles, and continuous polyphenylenesulfonium cation exchange tree 11.2: Method for removing catalyst from reaction effluent, the effluent is made up of smoke and: oxidant in oxidation reactor when catalyst exists The internal reaction method includes the following steps: (a) cooling the reactor effluent; and (b) transferring the cooled reactor effluent to the ion exchange unit to remove the catalyst. 12. The method according to item i i of the scope of the Chinese patent, wherein the hydrocarbon is selected from the group consisting of cyclohexane, cyclohexanone, cyclohexanol, cyclohexyl hydroperoxide, and mixtures thereof. 13. A method according to item 丨 丨 in the scope of patent application, wherein the oxidant includes oxygen. 14. The method according to item 丨 丨 of the scope of patent application, wherein the catalyst contains a compound selected from the group consisting of cobalt salts, iron salts, manganese salts and mixtures thereof. 15. The method according to item 丨 丨 of the scope of patent application, wherein the ion exchange resin is a permanent CT resin which has cation exchange and acid resistance, and is selected from chelated isobutyric acid cation exchange resin, and sulfonated polybenzene Ethylene cation exchange resin. 16. The method according to item 5 of the scope of patent application, wherein the cation exchange resin is a high capacity, colloidal, sulfonated polystyrene cation exchange resin. 17. · A device for removing the catalyst in the reaction mixture. The mixture is formed by the reaction of a smoke and an oxidant in the oxidation reactor in the presence of the catalyst. The device includes: a separator for separating the reaction mixture into polar and non-polar Phase; -2- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) k- order 58316S 8 8 8 8 A BCD VI. Patent application scope The distillation column removes excess water from the polar phase and circulates the polar phase back to the oxidation reactor; and the ion exchange unit removes the catalyst from the non-polar phase. 18. · A device for removing a catalyst from a reaction mixture. The mixture is formed by reacting a hydrocarbon with an oxidant in an oxidation reactor in the presence of the catalyst. The device includes: a cooling unit for cooling the reaction mixture; and Ion exchange units are used to remove the catalyst from the reaction mixture. -3- ___ This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm)