TW593271B - Production of tertiary butyl acetate from MTBE - Google Patents

Abstract

Disclosed is a process for the production of t-butyl acetate and coproduction of methyl acetate or ethyl acetate, directly from MTBE or ETBE, by contacting a mixture of acetic acid, acetic anhydride, and MTBE, or alternatively, ETBE, with an acid catalyst. Unlike the art, disclosed is a route employing a tert-butyl ether as starting material for the desired production or coproduction of tert-butyl acetate. Also unlike the art, acetic anhydride is employed to react with the water of formation from the esterification reaction to control formation of t-butyl alcohol.

Description

593271

V. Description of the invention (l) Cross-reference of the application The provisional application is filed (u.s. The invention was originally based on Serial No. 60/210, 551 on June 9, 2000). FIELD OF THE INVENTION The present invention is related to the manufacture of esters. Related background information on the background considerations of the production of triethyl butyrate acetate is included in the following text, which is incorporated herein by reference: US 3,102,905, US 3,644,497 'us 5,866,714, us 5,994,578, PCT WO 99/54276, state 3,678, 〇99. "Reaching the excessive reaction material, the reaction of isobutene with acid is the technique 2 c III ('VuAc ^ is generally based on isobutane and": C of the west "Euhua acetic acid emulsified preparation. Contains the product acetic acid / Yizhi Acetic acid, isobutylene, and by-product isobutylene dihydrate j: a reaction mixture of the unreacted feed ingredients-generally fed into μ; the reacted feed, and the purified product acetate Various factors will affect the production of tertiary acid-butyric acid, ^ 3 the operating conditions of the limiting distillation column (for example, temperature, feed point " ^ product collection rate, etc.), and feed tower Blocking or contact of reactants in the medium = Zhongya often occurs in the tower (isobutadiene) dimerization and / or cleaning of steam and steam, ¥ conform to the knitting, and finally need to be shut down 21 to ^ ethoxylation target The first a's of acetic acid is produced from different sources, and it is made of a material that is more widely used than pure isobutylene. Because of 5327271 V. Description of the invention (2) This can reduce or avoid the old problems caused by the previous technology, and use The cost of pure isobutylene is high. The present invention provides a higher cost than the current use. Compared with this isobutylene, fluorenyl tertiary butyl ether ("MTBE") or ethyl tertiary butyl ether (", ETBE "), which is easily available and lower cost, is used as the main raw material to manufacture Advantages of tert-butyl acetate. The route of the present invention is also made using acetic anhydride, and hydrolyzes acetic acid- 曱 S if necessary. 'SUMMARY OF THE INVENTION This article discloses a method of using '' The mixture is contacted with an acidic catalyst, and a method for producing tertiary butyl acetate and co-production of methyl acetate (MeAc) or ethyl acetate (EtAc) from M ΤΒ Ε or Ε Τ Β Ε. The catalyst may be Strong acidic ion exchange resins, such as macroreticular resins. The reaction pressure is usually maintained at about 1 to 5 atmospheres, and the reaction temperature is between about 10 to 10 〇 T: and the preferred temperature range is 40 to 7 0 ° C. However, those skilled in the art need to understand that the reaction conditions (including pressure and temperature) can be changed with the optimum equipment engineering design and process operation. It is better to purify the tertiary butyl acetate containing fractional distillation or general techniques. (T-BuAc), M e A c or E t A c Detailed description of the invention t - B u A c - as the preferred path via lines purified fraction lean isobutoxy, for example, chemical grade isobutylene _ However, since the separation of isobutylene from other close-boiling hydrocarbons of.

O: \ 71 \ 71653.ptd Page 6 593271 V. Description of the invention (3) Not easy ’Therefore, chemical grade isobutene will cause problems in terms of cost and usability. One method of preparing and purifying isobutylene is to catalyze the cleavage of mtβE acid, and then relatively easily separate isobutene from methanol (Me0Η) from the residual μTΒΕ. This pure isobutylene can be used in an acetamidine oxidation reactor. (See us 3, 102, 95). The present invention provides a direct way to sell t-BuAc with low cost ... The 50-H reaction uses acetic acid as a solvent and a reactant, and is acid-catalyzed by adding acetic anhydride (Ac: 20) and MTBE 'to prepare t-Bu Ac with a co-product ^ [eAc. The Me Ac can be purified for sale, hydrolyzed to methanol and acetic acid for recycling, or used as a carbonization raw material for the manufacture of A c20. In addition, ETBE can be used instead of MTBE to produce t-BuAc and EtAc. Reaction j

eq.l) ΜΤΒΕ —— > isobutylene + Me〇HH eq. 2) isobutylene + HOAc- > t-BuAc H + eq. 3) MeOH -f- HOAc- > MeAc + H, 0 ^-eq .4) Ac2〇 + H2〇 一-> 2H〇Ac MTBE + Ac2〇— > t-BuAc + MeAc t-B u A c There will be various competitive reactions in manufacturing, resulting in poor response, or reducing Product yield required. Under the conditions of the acetamidine oxidation reaction, the third butyl alcohol formed by the reaction of water with isobutylene is used in the present invention by using

593271 V. Description of the invention (4) A c: 2 0 is controlled as a reactant. The formation of t-B u Ο Η will compete with the required formation of t-B u A c and therefore represents a decrease in the efficiency of the host substance. Another example of poor reaction efficiency is the formation of diisobutylene (D 丨 B) through the dimerization of isobutylene. The D I B formed in the reaction step of the method of the present invention is minimized by using known control techniques, including: reducing the isobutene concentration in contact with the acid catalyst, operating at low temperature, and controlling the catalyst activity. The reaction of M T B E and A c: 20 in acetic acid is acid-catalyzed and can be performed in a batch or continuous manner. Reactive distillation can be used to drive the required reaction to completion by adding AqO / HOAc to the top of the distillation or defenta tower. MTBE was fed to the bottom of the tower, and MeAc was extracted as distillate, and a mixture of ribs and Qiyi BuAc was taken as the residual stream. Pure t-BuAc can be recovered from the residue of the reactive distillation column by careful consideration. The acetic acid stream from the top of the reactive distillation column can be purified and sold, for example, by carbonylation to be used as Ac: 20, and amidine is hydrolyzed to MeOH and HOAc; among them, HOAc can be used to produce AC. The preferred reactor using M · manufacturing t-BuAc is a column flow and fixed catalyst bed design. Sterile acid catalysts can be selected from the general sources listed, such as zeolites, amphiphilic polybasic acids, and strong acidic ion exchange resins (IER). A preferred heterogeneous catenary is a strong acidic ion exchange tree. For example, the purification of the crude product of Buhm tBuAc involves fractional distillation.

The following examples demonstrate preferred specific examples of the invention. But 孰 know you Φ +…, from the inventor J n: The technology represents the technology that the inventor has found to be used for making too much work. Experimental operation is not optimal. Revealing a specific body = nutritional changes, and will get the same or similar two: Jin ^ 丨-叼 + from the color of the present invention ^ 3271 V. Description of the invention (5) Analysis of samples obtained during the operation of God or scope experiment The values in the system are reaction conditions, product analysis, and rolling phase chromatography. The temperature of the catalyst bed t is for various results. The next known measurement. The highest catalyst bed temperature is 1. The preheating / cooling agent used for different catalysts and the amount of catalyst is set to high 〇 t. The data listed in Tables I and II in Goby's Examples I and II are taken from the products of the reaction. The words A and B represent reactants. 〃 and * Liquid inverse conversion at temperature = 100% (the amount of product _ person) / (selectivity of B to feed = = the amount of B produced by the actual amount of β found in the product ) X 100%

The operations of Example I are listed in Table I. First, a mixture of 3 47. 8 wt% peracid, 28.9 Wt% Ac20 and 23.9% MTBE was preheated to a temperature of 40 ° C, and fed at a rate of 8.5 g / min with 6 · 〇8 grams (8.61 cc) of Rohm and Haas A-36® micro-mesh ion exchange catalyst bed (operations 1 3-2). Nest the trickle-bed reactor, and then four coolants at the same temperature as the preheating section, and operate at atmospheric pressure. Analysis of the reactor product gave 1.37% isobutylene, .15.24% ethyl acetate, 0.52% third-butyl alcohol, 8.61% third-butyl acetate, 51.77% HO Ac, 7.24% 2'4,4-dimethyl-1-pentene (dimer), ι · 83% 2,4,4-trifluorenyl-2-pentene (dimer) and 4. 33% of all terpolymers and polymers. The conversion and the a-j * of MTBE were 98.6%, and the selectivity to tertiary acetic acid was 27.7%. For operation 17-2 and 17-4 series, 3.71 and 7.4 g / min, respectively

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V. Description of the invention (6) The preheating / reactor cooling rate is reduced to 1.86 g / min. 2 1 wt% acetic acid, 27.4 wt%. The rate of Ac20 is higher than the rate of acetic acid oxygen catalyzed by other M® I ER Feed the same raw material into the reactor and lower it to 35 ° C, and feed the operations 1 7-6 to operations 21-2, 21-4, and 21-6 using 47 acetate needles and 25 · 2 wt% The mixture of MTBE was only about 10% less (Moore). The data from the operation of Example 1 are combined in the following Table I: Μ · ΤΒΕ becomes a-butyl acetate-17-2 40 17-4 40 17-6 35 2U2 35 21-4 40 21-6 40 3.71 7.40 1.86 1.86 1.86 3.66 97.6 72.7 96.1 92.52 94.9 97.4 28.9 56.3 48.2 45.4 35.7 36.2 2.42 3.06 2.50 2.06 1.99 2.77 15.34 11.72 15.23 15.34 15.73 15.07 0.55 6.47 0.90 1.87 1.27 1.83 0.24 < 0.1 0.11 0.78 1.15 0.63 8.82 12.81 14.49 13.93 11.23 11.68 8.83 5.97 6.79 8.65 7.24 5.92 0.68 2.05 1.70 1.97 2.02 Operation No. 13-2 Temperature, t 40 Feed rate, g / min 1.85 MTBE conversion,% 98.6 Selectivity to t-BuAc,% 27.6 Isobutylene, wt% 1.37 Acetic acid Methyl ester, wt% 15.24 MTBE, wt% 0.33 tert-butyl alcohol, wt% 0.52 tert-butyl acetate, wt ° / 〇8.61 all dimers, wt% 9.07 all terpolymers, wt% 4.33

Rohm and Haas A-36® Amberlyst_36 macroreticular ion exchange resin The total amount of polymer collected in each operation is about 2-I5wt ° /. And the conversion of MTBE is about 72 to 99%. Example 2 Example 2 lists the various operations suspended in Table 1 1

Page 10 5327271 V. Description of the invention (7) A mixture containing 2 3 · 6 6 wt% Μ TBE, 4 7 · 0 1 wt% acetic acid, and 2 8. 4 7 wt% acetic acid if is fed into a mixture containing 6. 11 Grams (10.7 cc) of Rohm and Haas DPT-1 ® strongly acidic ion exchange resin in a jacketed trickle-bed trickle bed reactor. The feed flow rate and preheating / reactor coolant temperature that are changed according to the series of operations are listed in Table II below: Table II: MTBE to Acetyl Acetate-A-36® DPT-1 Catalyzed by Butyl Ester Operation number 33-2 33-4 33-6 37-2 37-4 37-7 37-9 41-1 41-3 Temperature. ° c 40 40 40 40 40 40 35 35. 35 Feed rate, g / min 3.75 2.90 2.20 1.36 0.65 0.31 1.36 1.36 0.68 ΜΊΈΕ conversion,% 69.8 72.3 75.2 87.9 93.6 96.5 75.7 78.8 88.8 Selectivity to t-BuAc,% 68.7 69.8 72.3 73.5 75.9 73.2 74.4 75.7 79.5 Isobutylene, wt% 2.58 2.86 2.80 2.78 2.50 2.22 2.16 2.20 2.20 Acetic acid acetate, wt% 11.08 11.41 12.06 13.74 14.80 15.02 11.65 12.2 13.91 ΜΤΊΒΕ, wt% 7.16 6.55 5.86 2.85 1.52 0.83 5.74 5.03 2.85 Tertiary-butyl alcohol, wt. 0/0 0 0 0 0 0 0 0 0 0 0 3 0 0 Acetic acid tertiary-butyl alcohol, wt% 14.95 15.75 16.96 20.14 22.13 22.02 17.58 18.60 22.57 acetic acid, wt% 52.33 51.14 51.50 52.33 52.17 52.58 50.81 51.49 50.91 Acetic anhydride, wt% 8.22 7.54 6.66 2.39 0.063 0 6.79 5.52 2.89 All dimers, wt% 0.29 0.25 0.27 0.63 0.94 1.53 0.56 0.21 0.30 As shown in Table II, the dimer content is about 0.2 to 2 1 W t%, # ΜΤΒΕ car special 4 daggers about 69 to 94% conversion. The data illustrate the manufacture of tertiary-butyl acetate and methyl malate from MTBE, acetic acid and acetic anhydride. The reactant was used as the main raw material. The reaction is performed using a strong acid catalyst. The range of conditions is proven, and a range of results is obtained. Tables I and II show the major conversions, i.e., MTBE conversions of about 69% to about 99%. The main loss of efficiency is the dimerization of isobutene (the intermediate formed in this process) into agglomerates

Page 11 593271 V. Description of the invention (8) (Dimer plus trimer). The loss of this insufficient efficiency is due to the irreversible loss of the main raw material, and is between about 1% and about 40%. Although it is desirable to have low amounts of isobutylene and tertiary butyl alcohol in the reaction product, it is expected that both of these materials can be recovered by standard techniques and recycled back to the reactor for the production of tertiary butyl acetate using this method. «

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Claims (1)

Year η repair, I.11. V constitutional 593271 K No. 90113976 Announcement VI. Scope of patent application 1. A method for preparing tertiary-butyl acetate and co-production of methyl acetate from MTBE (methyl tertiary butyl ether), by using acetic acid, acetic anhydride and The mixture of MTBE comes in contact with the acid catalyst. · 2. —A method for preparing tert-butyl acetate from ETBE (ethyl tert-butyl ether) and co-production of methyl acetate by contacting a mixture of acetic acid, acetic anhydride and ETBE with an acid catalyst And up. Where the catalyst is strong acid ion, the catalyst is giant net type, where the catalyst is strong acid ion, and the catalyst is giant net type, where the conversion of MTBE exceeds that of MTBE, and the conversion of ETBE exceeds 3. The method of the first item of the range exchanges the resin. 4. The catalyst as in the method of applying for item 3 of the patent scope. 5. The method according to item 2 of the patent application, sub-exchange resin. 6. The catalyst as in the method of applying for item 5 of the patent scope. 7. Method as claimed in item 1 of the patent scope 6 9% ° 8. Method as claimed in item 7 of the patent scope 7 5% 9. Method as claimed in item 2 of the patent scope 6 9% ° 1 0. As applied for patent The method of scope item 9 wherein the conversion of ETBE exceeds 75%. 1 1. The method according to item 1 of the patent application scope, wherein the selectivity for forming t-BuAc exceeds 25%. O: \ 71 \ 71653-911212.ptc Page 14 593271 _Case No. 90113976 jl 1 > Month \ / Day Amendment_, VI. Patent Application Scope 12. If the method of the second scope of patent application is applied, where t- The selectivity of BuAc exceeds 25%. 1 3. The method according to item 1 of the patent application range, wherein the reaction pressure is maintained at 1 to 5 atmospheres, and the reaction temperature is between 10 and 100 ° C. 14. The method according to item 13 of the scope of patent application, wherein the reaction temperature is between 40 and 70 ° C. 15. The method according to item 2 of the patent application range, wherein the reaction pressure is maintained at 1 to 5 atmospheres, and the reaction temperature is between 10 to 100 ° C. 16. The method according to item 15 of the patent application range, wherein the reaction temperature is between 40 and 70 ° C. O: \ 71 \ 71653-911212.ptc Page 15