TW200418769A - Process for preparing tert-butanol - Google Patents

Abstract

The invention relates to a process for preparing tert-butanol by reaction of a homogeneous mixture comprising water; tert-butanol and an isobutene-containing hydrocarbon mixture over an acidic ion-exchange resin at from 30 to 120 DEG C, wherein the homogeneous mixture contains, at a proportion by mass of isobutene of above 10%, from 30 to 80% of the maximum amount of water made possible by the solubility of water in the mixture of tert-butanol and the isobutene-containing hydrocarbon mixture.

Description

200418769 ⑴ 发明, Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for preparing tertiary butanol by adding water to isobutene in the presence of an acidic ion exchanger. [Previous technology] Tertiary butanol (TBA) is an important product on a large industrial scale. It can be used as a solvent and an intermediate for the preparation of methyl methacrylate. It is also used to prepare peroxides with at least one third butyl group, such as Precursor of peroxyketal, perester or dialkyl peroxide. These compounds can be used as oxidants and initiators for radical reactions such as olefin polymerization or polymer cross-linking. When isolating pure isobutene in the isobutene mixture, tertiary-butanol can act as an intermediate. Furthermore, it is a reagent for introducing a third butyl group. The alkali metal salt is a strong test and can be used in many synthesises. Tertiary-butanol can be prepared by adding water to isobutene and acid-catalyzing it. Industrial isobutene will usually further contain other olefins such as 2-butene. If these starting materials are used, the conditions used in the industrial process are that no olefins other than the only isobutylene will be hydrated, and the secondary reactions of these olefins such as homogeneous oligomerization or heterogeneous oligomerization will be substantially Completion is suppressed. Such methods are usually performed in the liquid phase and can be divided into two groups: a) the method in which the reaction is performed in an aqueous catalyst solution, and b) in which a multiphase using a solid catalyst insoluble in the reaction phase Catalytic method. Homogeneous catalysis uses sulfuric acid, heteropolyacid, p-toluenesulfonic acid or other strong acids as catalysts. Usually these highly active homogeneous catalysts will become homogeneous with the reaction product form -5- (2) (2) 200418769, so that the catalyst cannot be removed mechanically. In some methods ' additional solvents may be used. If the third-butanol is to be isolated from the reaction solution by distillation, its yield will be reduced due to the reverse reaction and the formation of by-products. Heterogeneous catalysis is often performed using an acidic ion exchanger as a catalyst. European patent EP 0 5 7 9 1 5 3 discloses a use of a sulfonated polymer (polystyrene sulfonic acid or polyvinyl sulfonic acid having a gram molecular weight of 100 to 1 0 0 0 0 g / mole Acid) solution as catalyst. Isobutylene or isobutene-containing starting materials and catalysts pass through the reactor countercurrently. The output from the reactor consists of two phases, which are separated into the upper organic phase containing the tributanol and the catalyst phase. This organic phase can be isolated by distillation to separate the third-butanol. Water will be added to the catalyst phase to replace the consumed water, and then the catalyst phase can be recycled to the reactor. The use of a solid acidic catalyst that is insoluble in the starting material and the product to hydrate isobutene to form tertiary butanol has the advantage that the reaction mixture is acid-free and can be separated into tertiary butanol after treatment. No loss due to re-dissociation or other secondary reactions. This reaction takes place on the surface of the catalyst. In order for the reaction to occur, the two reactants must be simultaneously on the active site of the catalyst. This is quite difficult for water and immiscible isobutylene or isobutene-containing hydrocarbon mixtures. To obtain the desired conversion, it is often necessary to use a solvent to make it feasible to obtain a homogeneous mixture of water and isobutylene feed mixture. For this purpose, the German patent DE E 3 0 3] 7 02 discloses that -6-(3) 200418769 uses methanol as water and isobutene or isobutene-containing hydrocarbons. As a result, tertiary-butanol and methyl tertiary-o can be obtained together. In European Patent EP 0 010 99 3, the atomic aliphatic carboxylic acid is used as a solvent for the two starting materials. Butyl vinegar is formed as a by-product, so it must be hydrolyzed to a carboxylic acid. German patent DE 0 3 0 3 1 7 0 2 is the use of ring Patent 4 3 2 7 2 31 1 is the use of a new form of diversity. These solvents must be separated from tertiary-butanol. Furthermore, there is a danger of decomposition during prolonged operation in the equipment. International Publication Application No. WO 9 9/3 3 7 7 5 In the reactor of the unveiling series, a mixture of a hydrocarbon mixture containing water and a third isobutene containing isobutylene is cation-crosslinked to prepare a third monobutanol. Methods. In separate reactor at 65 ° C. Part of the middle reactor from the first reactor produces the same reactor inlet. The circulation rate (recycled to the first intermediate product divided by the amount of the feed mixture) is 1. The third-butanol at the inlet of the first reactor in the third mixture (the sum of isobutene and any other hydrocarbons) Its weight ratio is 0.5 to 3.5. A portion of the mixture from the first reactor will be introduced into a single two reactor without intermediate introduction of water. The crude product from the final reactor will be passed through if necessary, with a portion of the tertiary-butanol recyclable solvent obtained from the butyl ether product ranging from 1 to 6. The carbons of these acids are the tertiary tertiary-butanol And butanidine, and the solvents used in American alcohols such as neopentyl glycol show a reaction on a multi-stage alcohol and isobutylene or resin change. The reaction temperature is low and will be recycled to a reactor of 8 to 10, and The unrecirculated path in the alcohol and hydrocarbon feed mixture flows through another collection by distillation. Go to the first reaction (4) (4) 200418769 vessel. The disadvantage of this method is the lower space-time yield. According to Practical Examples 1 to 6, the first monobutanol production rate of the first reactor (with product recycling operation) is 0.07 8 to 0.085 kg per liter of catalyst per hour (isobutene concentration at the outlet is 8.3 to 16.2% mass ratio, conversion rate 60.2 to 66.1%) 〇 German patent DE 3 0 2 5 2 6 2 is disclosed by the use of water / isobutan / TBA three-component mixture to prepare TBA. This method is preferably performed in the miscible channels of this system, but it can also be performed in multiphase and homogeneous regions outside the miscible channels. The operating range of this method is illustrated by a triangle diagram. Due to the triple mixture, the composition of the mixture is widely variable in multiphase and homogeneous phases. 1. The composition of this mixture in the homogeneous phase, that is, in the single-phase region, starts with the composition having the largest amount of water (the solubility of water in the mixture can be limited by the water separator), and has a low water content. The mixture ends (less than about 5% relative to the solubility limit). Therefore, with the help of German patent D Ε 3 0 2 5 2 6 2, this isobutene-containing / water / third-butanol triple mixture with a variable isobutene ratio in the hydrocarbon mixture is in homogeneous contact. In the presence of the vehicle, a large space for possible binding is left, and tertiary butanol can be obtained with high selectivity and a satisfactory reaction rate. However, in order to obtain a high reaction rate and selectivity, it is preferable to use a mixture whose water content is close to the solubility limit in the German patent DE E 3 2 5 2 6 2. (5) (5) 200418769 [Summary of the Invention] Since the known method using an acidic cation exchange resin as a catalyst can provide simple operations, but is not satisfactory in terms of space-time yield and / or selectivity, An object of the present invention is to provide a method for preparing tertiary-butanol from isobutene or an isobutene-containing mixture with good space-time yield and selectivity at high isobutene conversion. It was surprisingly found that when a homogeneous mixture containing water, third-butanol and isobutene or an isobutene-containing hydrocarbon mixture was reacted on an acidic ion exchange resin to form a third-butanol, Containing less water than is feasible based on the water solubility of the triple mixture, the reaction rate, selectivity and space-time yield will increase. Accordingly, the present invention provides a loan from 30 to 120. (: A method for reacting a homogeneous reaction mixture containing water, a third-butanol and an isobutene-containing hydrocarbon mixture on an acidic ion exchange resin to prepare a third monobutanol, wherein the homogeneous reaction mixture At the beginning of the reaction, the isobutene has a mass ratio of more than 10% and a water ratio of 30 to 80% based on the water solubility of the skin mixture. The water ratio of the reaction mixture should preferably be lower, such as 50 to 80%, 60 to 30%, or 70 to 80%. In each case these numbers are based on the maximum number of major quantities defined by the solubility of water in the homogeneous reaction mixture. According to the reaction of isobutene with water The law of mass action of the reaction to form TBA, Equation 1 is applicable: CB = K * Cj * Cw (Equation 1) -9- (6) 200418769 CB: Mole C of the third-butanol in the reaction mixture !: Reaction mixture Molar concentration Cw in isobutene: Molar concentration in water in the reaction mixture K: Equilibrium constant The following equation applies to the rate of tertiary-butanol formation in the reaction of tertiary monobutanol / water. Puigjaner, F. Recase ns Inhibition by Liquid — Phas e — Hydration of Isobutene alcohol: Kinetic and Equilibrium Studies, Res. 1 998, Issue 27, 2224 -2231 Μ): r = k (C) * Cw-CB / K) :( 1+ c * CB) nn = l ^ 2 r: The reaction rates k and c are increased at a constant temperature, specific catalyst and catalyst quantity according to this formula, and the concentration of water that generates the third-butanol is increased. According to this, the international publication application No. WO 99/33775 and the German patent DE 030 25 homogeneous solution are to use the largest possible amount of water. Therefore, it was even more surprising to find that the use of a water-saturated mixture with a lower water content at a tri-butanol ratio may result in a large tertiary-butane reaction rate. If a homogeneous mixture of isobutene-containing hydrocarbons (ie, a homogeneous mixture of radon butanol and water is exchanged for acidic ions, if the parameters are fixed, the reaction concentration of tertiary-butanol / isobutane is homogeneous (E V e 1 〇, L · Product in the tot-Butyl Ing · Eng. Chem. ...... (Equation 2) is a constant. The reaction rate will follow the application No. 262 Case No. Liquid, or using alcohol to achieve the most liquid I), the reaction on the third resin, the rate is determined by time and -10- (7) (7) 200418769. If you want to depend on the water content of the ion exchange resin used At the timing, the initial rate of TBA formation can be reduced or increased. When starting with a resin with a low water content, the rate of tertiary-butanol formation will initially decrease, but will become constant only after 2-6 days. During this period, the catalyst will absorb water, which can be easily measured from the water balance. The amount of water absorbed by the catalyst depends on the water concentration of the reaction mixture and the distance of this water concentration from the solubility limit. As the solubility limit is approached, the more water the catalyst absorbs. As the water absorbed by the catalyst increases, the rate of reaction to form tertiary-butanol decreases under the same conditions elsewhere. This may be due to hydration and / or the water-swelling layer of the catalyst inhibiting the quality The transfer of (especially isobutylene) causes the acid strength of the active site to decrease. Therefore, the water content of the starting mixture in a long-term operation can affect the reaction rate of tertiary-butanol formation in two ways, that is, by The concentration effect that can increase the rate (refer to Equation 2) and the effect of absorbing water by the catalyst that can reduce the rate. The economic efficiency of industrial methods can be determined not only by the initial rate, but also by the steady state (that is, the long-term operation of the equipment) The composition of the homogeneous mixture of the method of the present invention is explained using a phase diagram. Figure 1 shows water, third-butanol, and isobutene-containing hydrocarbons in a triangular coordinate system (coordinates from 0 to 100% by mass). Phase diagram of a hydrocarbon mixture. The hydrocarbon mixture (raffinate I) contains 45% isobutene and 55% saturated and monounsaturated C4-hydrocarbons. The phase diagram can be applied in the temperature range of 20 to 80 ° C And the pressure higher than the saturation pressure of the hydrocarbon mixture. In this area, there is essentially no pressure and temperature dependent properties. In other components of the isobutylene-containing hydrocarbon mixture, the figure only slightly changes, so it can be changed slightly. Applicable to -11 > (8) 200418769 to explain the present invention. From the vertex W of the triangle through the maximum 値] v! The curve of the other vertex K represents the line of the homogeneous region and the polyphase region. Below the curve, the 'mixture is polyphase The curve is the area of a homogeneous solution. This curve can also show the maximum ratio of water in the three-component system. In the method of the present invention, the reactor feed is preferably based on the KM section curve, The MD line segment and the DK line segment are bounded. Because of the low water content specified by the present invention, the precise composition of the reactants is within this area. MD means KB is vertical. When it decreases from the M point under a certain hydrocarbon / tertiary-butanol ratio, the composition of the mixture can be expressed. When the temperature range is from 40 to 90 ° C, the maximum water content of the two-component mixture (second monobutanol /; isobutylene raffinate I) can be determined for K Μ) of interest by The following is calculated. It is also valid if isobutene-containing hydrocarbon mixtures have different sets of equations. lnXw = 〇〇〇 5 7 0 ΧΒ-0.8215 ... (Equation 3 or

Xw = EXP [0.05 7 0 XB ~ 0.8215] · ...

Xw: water content, expressed in mass% Xb: second monobutanol content, expressed in mass% In the process of the present invention, the fibrous liquid fed to the homogeneous reactor will be lower than the largest possible 値 (line segment KM). The area of the boundary between the amount and the triangle is the homogeneous solution. When the composition of the area is as shown in Figure 1, the mixture and the bottom line are started. When the water concentration region (the line segment k / contains 45% of the experimental equation) , This equation 3b) the water content is based on the water solubility of the third-butanol-12-(9) (9) 200418769 and the isobutylene-containing hydrocarbon mixture to calculate the possible water amount of 3 0-80%, Especially 50 to 80%, 60 to 80% or 70 to 80%, which can be measured by simple experiments or calculated using equation 3a / b. According to the present invention, the The isobutene concentration is higher than 10% by mass, particularly higher than 5% by mass. Therefore, the reactor feeds are those which are preferably at a temperature of 35 ° C to 70 ° C. A mixture whose components in the range of C degrees do not move at all from the thermal equilibrium of isobutylene, water, and TBA. As for the starting material, it is feasible to use isobutene-containing hydrocarbon mixtures or other pure isobutene. The isobutene-containing hydrocarbon mixture preferably does not include any acetylene derivatives, diene less than 5,000 Ppm, and may not contain any other olefins having one or more branches on the olefinic double bond. For example, the isobutene-containing mixtures for industrial use include light petroleum alcohol fractions from refineries, C4 fractions from FCC units or steam crackers, Fischer-Tropsch: mixtures for synthesis, butane dehydrogenation reaction mixtures, Mixtures of skeletal isomerization reactions of linear butenes, olefin metathesis reactions or other industrial processes. These mixtures can be used in the method of the invention after removing several unsaturated compounds. For example, a suitable isobutene mixture can be obtained from the 01 residue of a steam cracker by extracting butadiene or selectively hydrogenating it to linear butene. This feed (the raffinate I or the selectively hydrogenated C4 cracked fraction) contains n-butane, isobutane, three linear butenes, and isobutene, and is the preferred starting material for the process of the present invention. -13- (10) 200418769 Raffinate I, hydrogenated c4 cracked fractions or similar mixtures can be selectively hydroisomerized in the reaction tower to obtain isobutene (probably 1-butene) and isobutene The concentration of buto isobutene in the hydrocarbon mixture can be in a wide range. However, for the economic benefit of the method, it is more appropriate to use a mass ratio different from 30%, preferably greater than 40%. As for the catalyst, it can be used. An acidic ion exchanger that is insoluble in the starting product mixture. Under reaction conditions, it is not possible to introduce acidic products into the product due to hydrolysis or other reactions. This will result in a yield in the processing of the reaction mixture. A suitable catalyst must be able to catalyze the hydration reaction of isobutene. It must be able to catalyze unbranched olefins. Furthermore, they must also be completely oligomerized with olefins. A suitable catalyst is a solid ion having a sulfonic acid group. For example, ion exchange resins which are more effectively used include resins of aldehyde condensates or polymerized oligomers of aromatic vinyl compounds. Examples of aromatic vinyls that can be used for the preparation of oligomers for polymerization are: styrene, vinyltoluene, vinylnaphthalene, vinylmethylstyrene, vinylchlorobenzene, vinylxylene and, in particular, these The oligomer combined with styrene and divinylbenzene can be used as an ion exchanger with sulfonic acid group. These resins can be prepared in the form of gels, macroporosity, or hydrocarbon-like components. In this way, the mixture of the alkane varies within the range. Hydrocarbon mixtures with high butene concentrations are also insoluble. This catalyst must be mixed because of the loss. However, it is almost impossible to catalyze the exchange of resins by using phenol / sulfonation to obtain compounds such as real ethylbenzene and vinylbenzene. The precursor of the formed polyresin sponge. -14-(11) (11) 200418769 In particular, suitable resins in the form of styrene-diethylbenzenebenzene can be purchased under the following trade names: D u 〇] ite C 2 0, D u ο 1 it C 2 6, A mber 1 yst 1 5, A mbel · 1 yst 3 5, A mber 1 ite IR — 1 2 0, amber 1 ite 2 0 0, Dowex 50, Lewatit SPC 118, LewatitSPC 108, Lewatit K2611 (taken from Bayer), Lewatit K2631, OC 1501 (taken from Bayer), Lewatit K2621, Lewatit K2629, Le watit K24 31. The characteristics of these resins, in particular, specific area, porosity, stability, swelling or shrinkage, and exchange capacity can be changed by the preparation method used. In the present invention, the ion exchange resin is preferably used in the form of their fluorene. And its ion exchange capacity is preferably 2 to 7 equivalents / kg, especially 3 to 6 equivalents / kg (relative to wet commercial resins). It is preferable to use macroporous resins, such as Lewatit S PC 1 1 8. Lewatit SPC 108 or Lewatit K2631. The particle size of industrial resins is usually in the range of 0.5 to 2 mm. The particle size distribution can be narrow or wide. For example, an ion exchange resin (monodisperse resin) having a very uniform particle size can be used. When several reactors are used, resins with the same or different particle sizes (particle size distribution) or can be installed. This ion exchange resin may also use a shaped object, such as a cylinder, a ring, or a ball, as needed. If it is through the reactor at a high linear rate, it is more advantageous to use -15- (12) (12) 200418769 with a larger particle size to reduce the low pressure drop. If it is passed through the reactor at a low linear rate, it is more advantageous. Use smaller particle sizes to achieve the most appropriate conversion. In order to avoid the elimination of acidic groups from the resin during operation (this will make the processing process in the method not operate normally), and to maintain high catalyst activity after a long period of operation, this ion exchange resin can be pretreated, for example Rinse first with water, TBA or TBA / water mixture in the temperature range of 40 to 120 ° C. Since water is consumed through the hydration of isobutylene, the water content in the reaction mixture is reduced. In order to obtain the highest possible yields and reaction rates, further water infeed is necessary. When using only one reactor, this can be achieved by feeding water at various points along the tubular reactor. However, in practice, it is difficult to accurately introduce the required amount of water and immediately form a homogeneous solution. Therefore, it is technically simple and advantageous to continuously connect several reactors and introduce the required amount of water between the reactors. As the tertiary-butanol concentration increases after the reaction, the water solubility in the reactor output will also increase. Therefore, more water can be added between the reactors than has been reacted by the previous reactor. According to the present invention, the water that has been consumed can be replaced, and furthermore, only less water is needed than the solubility limit is reached. In the case of the last reactor, this may deviate depending on the needs, so the final reactor can be supplied with a water-saturated solution or a mixture containing more water than the corresponding solubility. The advantage of this method is that when the reactor volume is sufficiently large, the isobutene conversion will increase slightly at low isobutene concentrations-16- (13) (13) 200418769; but it also has the disadvantage that the third one The alcohol / water ratio is less helpful, especially when a high proportion of anhydrous tertiary butanol is desired. The amount of water in the starting material mixture is derived from the tertiary butanol / water solution (except the start-up phase), which can Obtained during the process itself. If this amount of water is insufficient, additional water must be fed. Pure water or a mixture of water and tertiary butanol can be introduced between the reactors. It is also feasible to recycle a portion of the TBA obtained after the reaction to prepare a homogeneous mixture with water and an isobutylene-containing hydrocarbon mixture. Water can be introduced between the reactors to change the reaction equilibrium. According to the invention, only a homogeneous solution can be fed into the reaction. Therefore, the water or water / tertiary-butanol solution must be mixed with the initial hydrocarbon mixture or reactor output so that it can form a homogeneous phase before entering the first or subsequent reactor Solution. This can be done, for example, with a fixed mixer. The required water concentration in the reactor feed can be set by measuring the amount of the individual streams after measuring the water content of the individual streams. The process of the present invention can be carried out in a batch or continuous operation in a reactor conventionally used for solid / liquid contact reactions. When using a continuously operating flow reactor ' a fixed bed is usually used, but it is not necessary. If a fixed-bed flow reactor is used, the liquid can flow up or down. Generally, it is better to flow down. Furthermore, the reactor can be operated in a product recycle or single path manner. When using a tubular reactor, the ratio of the length of the catalyst bed to the diameter can vary depending on the geometric space of the reactor or the degree of its decoration. Therefore, under a certain amount of catalyst and space velocity (L H S V), different evacuation tube speeds will be reached. In a reactor where a portion of the reaction mixture is to be recycled, it is typically operated at an exhaust tube speed of 13 to 26 meters / hour. If the reactor is operated in a single path, the evacuation tube speed is typically in the range of 1 to 13 meters per hour. Accordingly, when the reactor is operated in a product recycling manner, its catalyst space velocity (LH S V) is 0.3 to 10 h -1, particularly 1 to 5 h -1. If the reactor is operated in a single path, its space velocity is in the range of 0.1 to 5.0 h-1, especially 0.4 to 3 h_]. The process according to the invention can be carried out in one reactor or in a series of successive reactors, in particular two, three or four reactors (they have decreasing temperatures depending on the direction of flow). If the first or several reactors are carried out in a product recycling mode, the recycling factor (the ratio of the pumped amount of the entire tour to the fresh feed) can be set between 0.1 · 10. The recycling factor of the first reactor is preferably 1 to 4, especially 2 to 3.5. In a preferred method variant, the first reactor is operated in a product recirculation mode, while the other reactor is operated in a single pass. The number of reactors used depends on the required conversion, typically 2 to 10, especially 2 to 4. Each reactor can be performed in an adiabatic or substantially isothermal manner (i.e., the temperature rise is less than 10 ° C). Excessive temperature rises should be avoided because they have an adverse effect on the equilibrium (redissociation). -18- (15) (15) 200418769 The temperature at which the method of the present invention is performed is in the range of 30 to 120 ° C. The reaction rate is too slow at lower temperatures, and the incidence of secondary reactions such as hydrocarbon oligomerization increases at higher temperatures. Therefore, the reactor is preferably operated at 35 to 70 ° C. The temperature of different reactors may be the same or different within the specified range. In a process variable, the temperature decreases sequentially from one reactor to the other with the flow direction. This is because the equilibrium position becomes more favorable when the temperature decreases, and a higher conversion rate can be achieved in this way. However, it is not appropriate to lower the temperature below 35 ° C because the reaction at that time appears too slow for industrial processes. For example, in the case of four consecutive reactors, it is more feasible to make the first one react at an average temperature of 67 to 70 ° C, the second one at an average temperature of 53 to 561, and the third One was at an average temperature of 42 to 46 ° C, while the fourth was at an average temperature of 42 to 38 ° C. At the respective reaction temperatures, the reaction of the present invention can be carried out at a pressure equal to or higher than the vapor pressure of the starting hydrocarbon mixture, preferably at a pressure lower than 40 bar. To avoid vaporization problems in the reactor, this pressure should be 2 to 4 bar higher than the vapor pressure of the reaction mixture. The total conversion of isobutene depends on the form and quantity of catalyst used, the reaction conditions set and the number of reaction stages. Based on economic benefits, the isobutene conversion rate is maintained within the range of 50 to 95%, preferably within the range of 70 to 90% KI. Meanwhile, in order to maintain high space-time production, it is more appropriate to use hydrocarbons having an isobutene content of not less than 20% ', preferably not less than 40%. The reaction mixture leaving the last reactor will pass through a distillation column which is at or below the pressure of the last reactor, but with a pressure of at least -19- (16) 200418769 operating at 1 bar. The product from the top of the distillation is a hydrocarbon containing unreacted "inert" hydrocarbons which will be introduced with the starting material. The product obtained at the bottom is a tertiary-butanol aqueous solution. The separated hydrocarbon mixture can be processed to obtain more production. For example, if raffinate I or selectively hydrogenated c4 is used as the starting material, the top product will contain unreacted isobutene along with olefins as well as isobutane and n-butane. Residual isobutylene can be separated from this mixture by reacting with methyl tertiary-butyl ether. In the residual liquid, linear butene can also be used to separate 1-butene into di-n-butene and their high-carbon oligomers if necessary. Another use free of isobutylene is reprocessing to produce pure 1-butene. Part of the obtained third-butanol aqueous solution can be recycled in the process. The other parts are used as such or processed to produce an azeotropic mixture of pure butanol and water and tertiary butanol. At the same time, a stream containing water and tertiary-butanol (which is processing the crude tertiary-obtained) may also be recycled to the first reactor. The recycling factor of the third-butanol recycled in this manner is from 0.1 to 1.7. A diagram of four reactors which can carry out the process of the present invention continuously is shown in FIG. A hydrocarbon mixture containing isobutene! (E.g., Ϊ), the output 20 from the first reactor 3 and the third-butanol / water mixture 2 containing recirculation] 8 and, if appropriate, water reaches the first reactor 3. Part of the reactor output 4 will go to the first reactor 3, and the other part will be mixed with water 5 through the butene mixture to make the linear butyl methanol reverse retention and conversion. The third one will be another butanol. The best way is to briefly recycle the residual liquid in the loop 19. The second -20- (17) (17) 200418769 reactor 6 will be recycled. The reactor output 7 will pass through the reactor 9 together with the water 8. The reaction solution 10 and water 11 react in a reactor 12. The reactor output will be fractionated in column 14. The product 15 obtained at the top is a hydrocarbon mixture containing hydrocarbons which are inert under the reaction conditions and a small amount of unreacted isobutylene. Basically, the bottom product 16 is composed of tertiary-butanol and water. A part (1 8) of this product will be recycled to the first reactor 3, while the other part (1 7) is used as such or processed in a distillation zone (not shown) to produce a third-butadiene Alcohol / water azeotrope and / or tertiary-butanol. The following examples illustrate the invention, but do not limit its scope. The scope of the invention is defined by the invention description and the scope of patent application. [Embodiment] Examples: The raffinate streams used in Examples 1 to 6 have the following components: n-butane: 8.2% isobutane: 2 · 3% 1-butane! ) ¾. J 0. J% 2-butene (cis + trans) 14.2% isobutene: 45.0% The isobutene content in the raffinate is typically in the range of 30 to 60%. The liquid stream will react with water and recycled TBA as a solubilizer in existing production equipment. The feed into the reactor of the production equipment -21-(18) 200418769

The feed was used as feed for the laboratory example. Figure 2 shows schematically the laboratory equipment used. The feed (1) is preheated to the required temperature, and then sent to a laboratory reactor (2) which is operated isothermally at 60 ° C, except for Examples 3 and 4, which are at 5 5 Operate at ° C. This reactor includes a fixed catalyst bed having a diameter of 1 cm and a length of 20 cm, with the exception of Examples 3 and 4, where the length is 25 cm. The catalyst used was Amberlyst 35 in H + form. In order to examine the effect of water content more precisely, the amount of catalyst will be intentionally kept low. The product stream (3) was analyzed by gas chromatography analysis. Each component such as n-butane, isobutane, 1-butene, 2-butene (cis + trans) will be listed together with other C4. The reported composition is based on the output of the product at a pseudo-steady state equilibrium reached after 20 to 30 hours. The pressure in the device is 12 bar absolute. Example 1 (according to the present invention)

The number of streams in the following table is the same as in Figure 2. Percentages are mass ratios. In terms of isobutene content, the feed (1) is equivalent to the feed to the first reactor of the production facility. The feed rate was 0.3 kg / hour. -22- (19) 200418769 stream digital stream name mass ratio 2 1.87% isobutylene 1.00% water 1 reactor input 3 3.40% TB A 43.4 9% other c4 0.23% other components 20.72% isobutylene 0.63% water 3 reaction Device output 3 4.9 2% TBA 43.4 9% Other c4 0.24% Other components

The achievable conversion rate is: 5. 30%

The ratio of water in the reactor feed to water based on the mass ratio in the miscible channels was 3 5.3 9%. Example 2 (comparative group) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility. The feed rate was 0.3 kg / hour. -23- (20) 200418769 Stream digital stream name quality ratio_ 2 1.58% 2.3 1% 1 reactor input 3 2.9 6% 42.92% 0,23% 20.6 1% 2.00% 3 reactor output 3 4.2 5 % 42.92% 0.23% isobutylene water

TB A other C4 other components isobutylene water

The conversion rate of TB A and other C4 components is: 4.53% The ratio of water to reactor-based water in the miscible channel based on the old ratio of 4.53% is 83.6%. Embodiment 3 (according to the present invention) The flow numbers in the following table are the same as those in FIG. 2. The percentage is the ratio of the side to the side. In view of its isobutene content, the feed (1) is equivalent to the feed that is penetrated into the first reactor of the production equipment. The feed rate was 0.3 kg / small sum. Unlike the other examples, the temperature of the reactor (in the case of production equipment) is 5 5 ° C. Compared with other examples, another difference is that the diameter of the catalyst bed is 1 cm and the length is 25 cm. -24- (21) 200418769 stream digital stream name reactor input reactor output ratio 15.42% isobutylene 2.00% water 4〇 * 21% TB A 42 · 〇6% other c4 other components 1 4.54 % Isobutene K? 2% water 41 · 38% TB A 42 · 〇5% other c4 0 * 3 1% other components § The conversion rate that can be achieved is: 5.73%

The ratio of the water in the reactor feed to the water based on the mass ratio in the miscible primary channel was 4 9.3 8%. Example 4 (comparative group) The flow numbers in the following table are the same as in Figure 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility. The feed rate was 0.3 kg / hour. Unlike the other examples, the temperature of the reactor (in the case of production equipment) is at 5 5 t :. Compared with other embodiments, another difference is that the catalyst bed has a diameter of 1 cm and a length of 25 cm. -25- (22) 200418769 stream digital stream name mass ratio 1 reactor input 15.21% isobutylene 3.31% water 3 9.6 8% TBA 41.49% other C4 0.30% other components 0 reactor output 14.38% isobutylene 3.04% Water 40.77% TBA 41.49% Other C 4 0.31% Other components

Achievable conversion rate is: 5.47%

The ratio of water in the reactor feed to water based on the mass ratio in the miscible channels was 8 4.0 7%. Embodiment 5 (according to the present invention) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. In terms of its isobutene content, the feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 50% by mass. The feed rate was 0.3 kg / hour. -26- (23) (23) 200418769 stream digital stream stream name mass ratio 2 5.3 8% isobutene 1.00% water 1 reactor input 3 3.3 8% TB A 3 9.26% other c4 0.97% other components 23.90% isobutene 0.53% water 3 reactor output 3 5.3 2% TB A 3 9.26% other c4 0.98% The conversion rate achievable by other components is: 5. 8 2% water-to-miscible channels in the feed to the reactor The proportion of water in the place is 35.56%. Example 6 (comparative group) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 50% by mass. The feed rate was 0.3 kg / hour. -27- (24) 200418769 stream digital stream name mass ratio 2 5.0 0% isobutene 2.50% water 1 reactor input 3 2.8 8% TB A 3 8.6 7% other c4 0.96% other components 2 3.8 3% isobutene 2.13% water 3 reactor output 3 4.42% TB A 3 8.6 7% other c4 0.96% other components

Achievable conversion rate is: 4.67%

The ratio of water in the reactor feed to water based on the mass ratio in the miscible channels was 91.09%. Embodiment 7 (according to the present invention) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. In terms of its isobutene content, the feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 60% by mass. The feed rate was 0.3 kg / hour. -28- (25) 200418769 Stream digital stream name quality ratio 3 2.67% isobutylene 1.21% water 1 reactor input 3 3.3 2% TB A 3 1.50% other c4 1.30% other components 3 0.5 2% isobutylene 0.52% Water 3 reactor output 36.14% TB A 3 1.50% other c4 1.32% other components

Achievable conversion rate is: 6.58%

The ratio of water in the reactor feed to water based on the mass ratio in the miscible channels was 4 2.88%. Embodiment 8 (according to the present invention) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 60% by mass. The feed rate was 0.3 kg / hour. -29- (26) 200418769 Stream digital stream name quality ratio 3 2.3 4% isobutylene 2.20% water 1 reactor input 3 2.99% TB A 3 1.18% other c4 1.29% other components 3 0.63% isobutylene 1.66% water 3 Reactor output 3 5.24% TB A 3 1.18% other c4 1.29% other components

Achievable conversion rate is: 5.28%

The ratio of water in the reactor feed to water based on the mass ratio in the miscible channels was 7 9.7 2%. Example 9 (comparative group) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 60% by mass. The feed rate was 0.3 kg / hour. -30- (27) 200418769 Stream digital stream name mass ratio 3 2.17% isobutylene 2.71% water 1 reactor input 3 2.8 2% TB A 3 1.02% other c4 1.28% other components 30.6 1% isobutylene 2.21% water 3 Reactor output 3 4.8 8% TB A 3 1.02% other c4 1 1.29% other components

Achievable conversion rate: 4.8 7%

The ratio of the water in the reactor feed to the water based on the mass ratio in the miscible channels was 98.83%. Example 10 (comparative group) The flow numbers in the following table are the same as those in FIG. 2. Percentages are mass ratios. The feed (1) is equivalent to the feed to the first reactor of the production facility, but the isobutene content in the raffinate I is 60% by mass. The feed rate was 0.3 kg / hour. -31 _ (28) 200418769 Stream digital stream name quality ratio 32.84% isobutene 0.70% water 1 reactor input 3 3.4 9% TBA 3 1.66% other c4 1.31% other components 3 1.17% isobutylene 0.20% water 3 reaction Output 3 5.5 7% TBA 3 1.66% other c4 1.40% other components

The achievable conversion rate is: 5.06% The ratio of water in the reactor feed to the miscible channels is 24.79

Comparing Examples 1 and 2, Examples 3 and 4, Examples 5 and 6, and Comparative Examples 7, 8 and 9, respectively, shows that the example with the lowest water content allows the highest reaction of isobutylene to TBA. Conversion rate. Comparative Examples 7, 8 and 10 show that when the water content is as low as the required limit of at least 30% of the water mass ratio at the miscible channels, the attainable conversion rate decreases again. [Schematic description] -32- (29) 200418769 Figure 1 is a phase diagram showing water, tertiary-butanol, and isobutene-containing hydrocarbon mixtures in a triangular coordinate system (coordinates of 0 to 100% by mass). Fig. 2 schematically shows the experimental treasure equipment used in the embodiment of the present case. Fig. 3 is a simplified diagram of an apparatus having four reactors which enables the process of the present invention to be carried out continuously. Main: Component comparison table 1 feed 2 laboratory reactor 3 product stream 1 isobutene-containing hydrocarbon mixture 2 second-butanol / water mixture 3 first reactor 4 reactor output 5 water 6 second Reactor 7 Reactor output 8 Water 9 Reactor 10 Reaction solution 11 Water 12 Reactor 13 Reactor output 14 Tower

-33- (30) 200418769 15 Top product 16 Bottom product 17 Another part 18 Recycling 19 Water 20 Output product Content Bottom product Stream -34

Claims (1)

200418769 拾 Application, patent application scope 1. A method for preparing tertiary-butanol, which is prepared by using an acidic ion-exchange resin containing water, tertiary-butanol and Homogeneous reaction mixture reaction of isobutylene-containing hydrocarbon mixtures, where 'the homogeneous reaction mixture contains more than 1 G% isobutene by mass at the beginning of the reaction' and 30 to 80% based on the water solubility of the reaction mixture The amount of water available. 2. The method according to item 1 of the patent application scope, wherein a part of the third-butanol obtained through the reaction is recycled to prepare the homogeneous reaction mixture. 3. The method according to item 2 of the patent application, wherein the recycling factor used to recycle the third-butanol obtained by the reaction is 0 · 1 to 1.7 ° 4 · The method according to item 1 of the patent application In which, the reaction is performed in a plurality of successively connected reactors. 5. The method according to item 1 of the patent application, wherein the water system is introduced between the reactors. 6. The method according to any one of items 1 to 5 of the scope of patent application, wherein the water content of the homogeneous reaction mixture is 50 to 80% of the maximum amount. 7. The method according to any one of claims 1 to 5, wherein the successively connected reactors decrease the temperature in accordance with the flow direction.