TW200934748A - Method for producing alkylated aromatic compound and method for producing phenol - Google Patents

Abstract

The invention aims at providing a process for the production of alkylated aromatic compounds which is suppressed in the formation of hydrocarbon by-products as compared with conventional processes and a process for the production of phenol which comprises the steps of the above process and which is not increased in the number of steps as compared with the conventional cumene process. A process for the production of alkylated aromatic compounds by reacting an aromatic compound with a ketone and hydrogen in a continuous-flow fixed bed reactor provided with a catalyst zone filled with a catalyst containing both a solid acid substance and a Cu-containing catalyst composition, wherein the catalyst zone is composed of an upstream-side catalyst layer and a downstream-side catalyst layer which layers are distinguishable from each other and the upstream-side catalyst layer consists of a Cu-containing catalyst composition (A1) and the downstream-side catalyst layer consists of both a Cu-containing catalyst composition (A2) and a solid acid substance (B) with the (A2):(B) weight ratio being 0.5:1 to 0.001:1.

Description

200934748. VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a counterpart substance by using a sulfonate a ketone and a ruthenium (6), and packaging the method The method of making phenol. Note 1 ^ 3 in part of the step stone, the present invention uses a solid Cu-containing catalyst composition as a catalyst, according to the single - reaction _ = substance, conjugate, ketone money ride reaction i silking (four) Weixiang And a method for converting the method of (4) sub-cloth (four), [prior art] a method for producing cumene by reacting benzene with propylene, a method for producing cumene hydroperoxide by oxidation, and C is too arrogant: the method of producing hydrazine and decomposing and producing acetone and acetone, respectively, is a well-known method for the second reaction, which is generally known as the "iso-biphenyl method" and is the mainstream of the phenol manufacturing method. The cumene system has a combination of C-type characteristics, which is advantageous in the same situation, but when the obtained acetone supply is too = the price difference between propylene, it leads to the effect of guiding the unfavorable direction. deterioration. "There is a strict difference between the miscellaneous and the mergers that are transferred to the favorable direction. For example, there are proposals to obtain from n-butene and stupid: the first Ding Zhaoji benzene oxidation, acid decomposition, while obtaining the transfer of B Method (": J documents, patent document 2). In this method, because of the oxidation of the second butylbenzene, the selectivity of the target second butylbenzene hydrogen peroxide is only 097143629 3 200934748 • degree, others The by-products are higher than the acetophenone, so the phenol manufacturing method is not as good as the cumene method. In addition, there are proposals to make the ring protected by cyclohexene and stupid stupid into a wide-ranging, acid-decomposing The method of obtaining phenol and cyclohexanide is because the method is helium gas. The obtained cyclohexanone is subjected to deargonization to obtain phenol, so that formally avoidable/use of field 1J is produced. However, the ring is stupid. The oxidation reaction causes the target ring to be stupid, and the yield of hydrogen is reduced, which reduces the industrial value. Therefore, the cumene method with the highest yield of related oxidation and acid decomposition maintains superiority. To avoid the two purchases of raw materials and the merger Point 'Proposal has a method of combining and using various methods to use the raw material of cumene method. It can be easily converted into isopropanol by using hydrogenation, and dehydrated by 1 isopropyl alcohol. Responsive, and then reverse with benzene 3

Process of cumene. In other words, (4) There is a process in which (4) is re-processed as a foreign material method (see Patent Document 3). However, this method has a problem of increasing two steps of a hydrogenation step and a dehydration step.提案 A method for obtaining cumene by directly reacting isopropanol obtained by hydrogenation of acetone with benzene has been proposed (refer to Specials 4 to 6). In particular, Patent Document 6 describes a process for treating cumene obtained by combining (4) as a different (four) and using benzene to react. However, even with this method, the hydrogenation step is increased compared to the original cumene method. On the other hand, in the case where the conventional cumene method step is not increased, 097143629 4 200934748 combines the produced acetone for reuse (also a method in which C-, stupid, and hydrogen are directly reacted). There is disclosed a method of preparing an alkylated aromatic compound by reacting an aromatic compound with a ketone and hydrogen in the presence of a solid acid substance and a steel-containing catalyst composition (see Patent Document 7). but

In the prior art, a hydrocarbon-based by-product is formed in a large amount, and thus a manufacturing method as a workability is not enough. Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 专利 Patent Document 7 ·· The present invention is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention has an object to provide a direct reaction between acetone, benzene and hydrogen. A method for producing cumene and having a hydrocarbon by-product formation amount smaller than that of the conventionally known alkylated aromatic compound; the present invention also provides that the method is included in a partial step and the step is not conventionally known as isopropyl A method for producing phenol which is increased by the benzene method. (Means for Solving the Problem) The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that, by using a catalyst, a solid acid substance and a catalyst composition containing Cu are used, and the catalyst is filled in a special order. And according to a single reaction step, using aromatic compounds such as propylene, etc., and argon as starting materials, corresponding alkylated aromatic compounds such as cumene can be obtained with little by-product and high yield by hydrocarbon by-product. . That is, the method for producing an alkylated aromatic compound of the present invention is to carry out aromatic compound, _ and hydrogen by using a flow-through fixed bed reactor having a catalyst-filled portion containing a solid acid substance and a Cu-containing catalyst composition. a method for preparing a base-forming aromatic compound by a reaction; the catalyst-filled portion is composed of a catalyst layer which can be distinguished from the upstream side and the downstream side; and the catalyst layer on the upstream side is composed of a Cu-containing catalyst composition (A1) is configured; the catalyst layer on the downstream side is composed of a Cu-containing catalyst composition (A2) and a solid acid substance (B); and the weight of the Cu-containing catalyst composition (A2) and the solid acid substance (B)比❹[(A2):(8)], is 0. 5 : 1~〇. 〇〇1 : 1. The Cu-containing catalyst composition (A1) and the Cu-containing catalyst composition (A2) are preferably at least one metal selected from the group consisting of Zn and Cr, and a Cu-containing catalyst composition. Further, the above-mentioned Cu-containing catalyst composition (A1) and the Cu-containing catalyst composition (A2) are preferably a catalyst composition of 糸a Cu and Zn, and the amount of zn to Cu is preferably 0 by atomic ratio. 70~l6Q. The above aromatic compound is preferably benzene. 097143629 6 200934748 The above ketone is preferably acetone. That is, it is preferable that the above aromatic compound is the above-mentioned ketone-based propylene. Preferably, the above solid acid material (B) is one having an oxygen 1 〇 16 16 member ring-zeolite compound, particularly preferably having oxygen 10 or a port. 4 W shell ring fine pore zeolite compound The above zeolite compound is preferably composed of a heart stone, M-22> Fu Shi, Si Xian Shi Shi, ZSM-5 zeolite, ZSM-12 zeolite and γ 刑 ' 'Fei'i At least one zeolite compound selected from the group consisting of vermiculite. The method for producing phenol of the present invention includes the steps of: oxidizing cumene to convert to isopropanol hydrogen peroxide (8), causing cumene hydroperoxide to undergo acid decomposition and combining with the propyl group. 9 (C) a step of reacting C-generated in the above step (b) with hydrogen and benzene to synthesize cumene; and ❹(4) recycling the cumene obtained in the above step (4) to the step in the step (4) Wherein step (c) is carried out in accordance with the method for producing an alkylated aromatic compound described above. (Effect of the Invention) According to the method for producing an alkylated aromatic compound of the present invention, an aromatic compound such as acetone or the like, and hydrogen as a starting material can be used in a single reaction step, and a higher yield can be obtained by a conventional technique. An alkylated aromatic compound such as cumene is obtained in 097143629 7 200934748. Further, the manufacturing method of the excipient compound is included in the manufacturing method of the age in the partial step, and the number of steps of the cumene method is not increased, and the acetone produced by the combination can be re-scented. Moreover, the cumene obtained by the method for producing a silkified aromatic compound does not have any problem with the cumene obtained from propylene or isopropanol and II. The technology of the times can produce the hope that both the knowledge and the economy are obviously superior. [Embodiment] The method for producing the alkylated aromatic compound of the present invention is a flow-through fixed wire having a catalyst-filled portion (which contains a solid acid substance and a Cu-containing catalyst composition). A method for producing an alkylated aromatic compound by reacting an aromatic compound and (4) hydrogen; wherein the catalyst-filled portion is composed of a catalyst layer capable of forming an upstream side and a downstream side; and the upstream catalyst layer is composed of The Cu-containing catalyst composition (A1) is composed; the downstream catalyst layer is composed of a Cu-containing catalyst composition (A2) and a solid acid substance (B); and the above-mentioned cerium-containing Cu catalyst composition (A2) The weight ratio to the solid acid substance (B) [(A2) : (B)] is 0. 5 : 〇. 〇〇 1 : 1. The method for producing an alkylated aromatic compound of the present invention is a fixed bed reaction carried out using a fixed bed reactor. In the fixed bed reaction, the method of filling the solid acid substance and the composition containing the Cu catalyst has a considerable influence on the reaction results. Further, the fixed bed reaction apparatus used in the present invention is taken up before the flow-through fixed bed reaction apparatus having a catalyst-filled portion, and the rest is not particularly limited. For example, an adiabatic fixed bed reactor or a multi-tube heat can be used. 097143629 200934748 Replacement fixed bed reactor, continuous bed fixed bed reactor, radial fixed bed reactor, laminar fixed bed reactor, thin layer fixed bed reactor, tubular fixed bed reactor, etc. According to the production method of the present invention, it is considered that first, a ketone such as acetone is reduced by hydrogen by a function of a composition containing a Cu catalyst to form an alcohol such as isopropyl alcohol, and isopropyl alcohol is used as a function of a solid acid substance. An alcoholic reaction with an aromatic character such as benzene produces an alkylation reaction. In the φ fixed bed reaction, it is preferred to use a suitable catalyst type in each stage of the reaction, and it is preferred to use a catalyst and to suppress a non-targeted side reaction as a preferred filling method. In particular, when the hydrogen pressure and temperature are increased in order to increase the reaction rate, a poor side reaction which is not found at a low hydrogen pressure or a low reaction temperature may occur, which is a common situation in general chemical reactions; In this case, there is a case where the catalyst filling method has a large influence on the reaction results.触 The catalyst-filled portion of the fixed bed reactor used in the present invention distinguishes the catalyst layers on the upstream side and the downstream side, i.e., has two catalyst layers distinguishable. The catalyst layer (upstream side catalyst layer) on the inlet side of the reactor is composed of a Cu-containing catalyst composition (A1), and the catalyst layer on the outlet side of the reactor (the downstream side catalyst layer j is a solid acid substance (B) ) is a main component and is composed of a composition of 0.5: mu 1 .丄 by weight ratio [(A2) : (β)] with the Cu-containing catalyst composition (A2). -513116 discloses that it belongs to the fixed bed anti-097143629 9 200934748 and that the catalyst-filled portion of the reactor is composed of two distinguishable catalytic strips, but the Cu-containing catalyst of the relevant downstream side catalyst layer The weight ratio between the composition (A2) and the solid acid substance (B) has not been examined. In the above publication, there is no embodiment in which the weight ratio [(A2): (B)] of the present invention is present. In the above-mentioned publication, the "produced in the above-mentioned publication" related to the production of cumene is not discussed or described. However, the process of producing a large amount of by-products such as propane is not suitable for industrial use. And found that if the solid acid substance (B) and

The weight ratio of the Cu catalyst composition (A2) [(A2): (B)] is 0.5:1 to 0.001:1 (preferably 0.4:1 to 0.002:1), and the by-product of hydrocarbons such as propane can be reduced, and If it exceeds the above range, the by-product of hydrocarbons increases. Further, the catalyst layer on the upstream side is composed of a CU catalyst-containing composition (A1), and the catalyst layer on the downstream side is composed of a solid acid substance (B), and the catalyst layer on the downstream side is not included in the catalyst layer. When the Cu catalyst composition (A2) is used, the following problems occur.合成 The synthesis reaction of an alcohol such as isopropyl alcohol by reduction of a ketone such as acetone is an equilibrium reaction, and the equilibrium is toward the alcohol side at a low temperature, but when it is, for example, a ketone-based acetone and an alcohol-based isopropyl alcohol, if it exceeds about At 80 〇C, a reverse reaction from isopropanol to acetone is initiated. The temperature is increased more and the acetone concentration is increased (Harry j. K. lb, J. Am. Chem. Soc., 67, 1084 (1945)). When there is a residual of propyl ketone, the ketone is mixed into the discharged water when the produced water is separated by the oil-water separation device using the outlet of the reactor. If the discharge water is directly discharged, it will result in a decrease in the original unit. The loss of economic benefits is large. Therefore, in this case, it is necessary to 097143629 10 200934748. From the method of discharging water t·steaming method (4), the ketone and other ketones are 100% converted. It is expected that C-benefits will be rich, and by containing the inclusions (10) in the above-mentioned catalyst layer in the above-mentioned range, even if the above-mentioned equilibrium is more or less in the __ condition, the reaction can still be carried out in the downstream side. The conversion to alcohol reduces the amount of the reaction at the outlet of the reaction. The catalyst-filled portion of the solid-bed reaction I used in the present invention is such that the above-mentioned 'containing (tetra) acid substance and eu-catalyst-containing composition, the catalyst-filled portion is distinguished by the contact between the upstream side and the downstream side. In the medium layer, the catalyst-filled portion distributes the CU catalyst-containing composition (10) in the catalyst layer on the upstream side, and distributes the solid acid substance (8) and the Cu-containing catalyst composition (A2) in the catalyst layer on the downstream side. ). The catalyst layer on the downstream side may be a solid acid substance (8) belonging to an acid catalyst component and a catalyst composition (10) containing cu, and may be of a size corresponding to a catalyst particle size; or The two can be subdivided and mixed, and the 're-lion's size is the same as the centimeter size; or the body acid substance (8) can be used as a carrier, and the catalyst composition (A2) is carried thereon. Further, in the present invention, the Cu catalyst-containing composition (A1) and the Cu-containing catalyst composition (A2) may be the same catalyst composition, and different catalyst compositions may be used. It is preferable to use the same catalyst composition from the Cu catalyst composition (A1) and the Cu catalyst composition (A2) from the viewpoint of the controllability of the reaction. The Cu-containing catalyst compositions (A1) and (A2) used in the present invention may contain 097143629 200934748

A metal type other than Cu, and a metal type other than Cu may be Zn, Cr, A1 or the like. Among them, Zn and Cr are preferred, and Zn is preferred. The metal species other than the Cu may be contained in one type or in two or more types. 01〜1。 The amount of the amount of the metal, the atomic ratio of the amount of the Cu is preferably 0. 01~1. 60, particularly preferably 0.7 (M. 50 is preferred. The metal system φ other than Cu contained in the Cu catalyst composition (Al) or (A2) is selected from the group consisting of Zn and Cr. In the case of at least one metal, the metal content is from the viewpoint of activity and selectivity, and the amount of the metal relative to Cu is preferably 〇· 〇1 to 1.60, especially 〇. 7( M. 50 is preferable. In particular, when the metal-based Zn other than Cu contained in the Cu catalyst composition (A1) or (A2) is contained, the Zn content is Zn from the viewpoint of activity and selectivity. The amount of Cu is preferably 〇.70~1.60, especially 0.8. (M. 50 is better than the amount of Cu. If it is less than 〇70, there will be an activity and selectivity is insufficient; If it exceeds 1.60, the activity is insufficient. Further, the Cu content in the Cu-containing catalyst composition (Al) and (A2) is preferably 5 to 80% by weight, especially 1〇. ~50% by weight is preferred. If it is active The amount of Cu is too small, because the amount of catalyst used needs a large amount, and the reactor is too large', so that the equipment cost is not economical. In addition, when the CU catalyst composition (Al), (A2) contains Zn, Cr , A1 and other metal types, if

When the Cu content is too large, an appropriate atomic ratio cannot be maintained with other metal species such as Zn. 097143629 12 200934748 The Cu-containing catalyst compositions (Al) and (A2) may contain metals other than Zn, Cr, and A1, and other metals such as Fe, etc., insofar as the effects of the present invention are not impaired. When such a content is contained, the content is 10% by weight or less based on cu 1 〇〇 by weight %'. • In addition, in the Cu-containing catalyst composition (Al) and (A2) used in the present invention,

Cu and other metals which may be optionally contained are preferably contained in the form of a metal oxide. The method for producing the catalyst compositions (A1) and (A2) is not particularly limited, and for example, it can be prepared by a wet method. The wet type system is, for example, an impregnation method and a co-precipitation method, and among these, the co-precipitation method is preferred because higher activity can be obtained. Specific examples of the production method of the Cu-containing catalyst composition (A1) and (A2) by the co-precipitation method are as follows: an aqueous solution of an aqueous acid salt solution in which copper, zinc, and a metal element are mixed, and is exposed to a basic compound. In the aqueous solution, the precipitated precipitate is washed and recovered, and the collected precipitate is dried, and then calcined. The acid salt of each metal element is subjected to a reaction with the test compound to obtain a precipitate, which is dried and calcined to form an oxide of each metal element, and is left unrestricted. Examples of such acidic salts include nitrates, sulfates, and hydrochlorides. The compound which is in contact with each metal element is, for example, a carbonate or a bicarbonate which is a metal money: a metal carbonate. The method of contacting the aqueous acid salt solution of each metal element with the aqueous solution of the test compound can be controlled by reading the range of η, and there is no limitation of _, for example, 097143629 13 200934748 A method in which an aqueous solution and an acidic salt aqueous solution of each metal element are simultaneously mixed, and a method of mixing an aqueous solution of an aqueous solution of each metal element acid salt in a water solution of the test compound is added. In the solution, a method of adding an aqueous solution of the test compound is added. The temperature at which the aqueous acid salt solution of each metal element is brought into contact with the aqueous solution of the test compound is not particularly limited as long as it is in the range of 10 to 80 °C. φ The precipitate obtained by reacting the acid salt of each metal element with the basic compound is usually washed with water in a temperature range of from room temperature to 50 ° C, and then in a temperature range of from 100 to 160 ° C. Drying is carried out in an air or inert gas atmosphere. After drying, the catalyst of the present invention can be obtained by calcination. The calcination system can be carried out at a temperature in the range of 200 to 470 °C. The calcination temperature is preferably 45 or less. In addition, the optimum calcination temperature is 300 C or more because the decomposition of the precipitate can be sufficiently carried out. Calcination is usually carried out in the presence of air or an inert gas. The calcined catalyst can be used directly in the reaction, and the calcined catalyst can be treated in a liquid phase or a gas phase by using a reducing gas such as hydrogen or carbon monoxide, and then used in the reaction. The media composition (Al) and (A2) may be formed by sintering in a ceramic carrier such as mullite or cordierite or a cerium oxide fiber cloth or a spongy metal, in addition to ingot molding or extrusion molding. It is used for the reaction on a porous plate or the like and formed into a honeycomb shape. 097143629 14 200934748 Furthermore, the composition containing Cu catalyst (Α1;), (%(:12, etc.) is added to the right, PbS〇4, FeCl2, which is extracted, a heterometal, an alkali metal salt, or BaS〇4, etc., may have a k-liter activity and selectivity, and may be added as needed. The shape of the CU catalyst composition (9), (10) is Any shape such as spherical, cylindrical, extruded, broken, etc. And = can be tied to the scope of the fresh coffee, as long as the size of the reactor is re-selected ^ The invention makes (4) the bribes f (8), _ in the catalyst with the function of ❹ 只要 as long as it is generally known as "solid acid For example, a zeolite compound, dioxoxane, oxygen (10), ion-supported oxidization, W〇3-supported zirconia, etc., are used. In particular, an inorganic crystalline porous compound mainly composed of lanthanum and aluminum is used. The buddha compound is a preferred silking catalyst from the viewpoint of heat resistance and the selection of the target alkylated aromatic compound. The stone compound is an aromatic compound and a standard alkylated aromatic compound used as a raw material. The compounding control of the compound is different from the preferred zeolite compounding system. For example, when benzene is used as the aromatic compound, and the ketone is used to produce cumene which is a fluorinated aromatic compound, the zeolite is used. The compound preferably uses a zeolite compound having pores of oxygen 1 to 16 ring members. The zeolite compound having pores of 10 to 16 ring members of the oxygen may, for example, be a ferrierite, a zeolite, a ZSM-5 zeolite, or a ZSM- 11 zeolite, Z SM-12 Buddha stone, NU 87 / Fu Shi, Θ 1 Buddha stone, water scale we good stone (weinebeneite), χ zeolite, Υ type zeolite, USY type zeolite, mordenite, dealuminated silk phoenix stone, 097143629 15 200934748 Zeolite, MCM-22 zeolite, MCM-36 zeolite, zeolite of MCM~u, *, sodium chabazite, potassium zeolite, cloverite, VPI-5 zeolite, τ 佛石, etc. Among these zeolite compounds, preferably The isopropanol % _ pores are particularly preferred to use zeolites having oxygen 10 or 12-membered ring pores. The zeolite compound having oxygen 10 or 12-membered ring pores is J. For example, γ Zeolite, USY zeolite, mordenite, dealuminated silk Buddha, /5 Buddha stone,

MCM-22 zeolite, MCM-56 zeolite, ZSM-12 zeolite, ZSM_5 zeolite, etc., of which, from the viewpoint of cumene selectivity, it is preferably zeolite-free, MCM22 zeolite, mercerized Fossil, ZSM-5 zeolite, ZSM. -12 Buddha stone, γ type zeolite, especially stone > Fu Shi, MCM-22 zeolite is preferred. The literature on the reaction of benzene with propylene for alkylation (e.g., US 4992606, US5453554, Erdoel Erdgas Khole, 113, 84, 1997) predicts that the special zeolite, MCM-22 zeolite, and MCM-56 zeolite are preferred structures. Related; 5 zeolite and MCM-22 zeolite, from the point of view of catalyst activity and iso-p-propylbenzene selectivity, there are some literatures indicating that MCM-22 zeolite is superior to zeolite (for example, US5453554), but also pointed out The literature with little difference in effect (eg, Journal of Catalysis, 191, 163-173, 2000), the difference between good and bad is not clear. The composition ratio of cerium to aluminum (矽/aluminum) of the zeolite compounds is preferably in the range of 2/1 to 200/1, particularly from the viewpoint of activity and thermal stability, preferably 5/M00. /1. And 'the aluminum atom contained in the zeolite skeleton can also be used, using Ga, Ti, 097143629 16 200934748

Metal, stone compounds other than aluminum such as Fe, Mn, and B. The shape of the so-called homo-substituted boiling solid acid substance (8) to be substituted is not particularly limited, and may be a spherical, cylindrical, extruded, crushed cup, and the particle size is also a compounding reaction. The size of the benefit can be selected within the range of 〇.01~1〇〇mm. Further, these solid acid substances may be used alone or in combination of two or more. ❹ 1 The _catalyst layer is a solid acid substance (8) which is a simple acid group and is used as a carrier and carries a Cu-containing catalyst composition (10). The method for carrying the Cu-containing catalyst composition (A2) may be carried on the solid acid substance (B) by the following method: impregnating the solid acid substance (B) with a Cu nitrate aqueous solution, and a method of performing calcination; or an organic molecule which is generally referred to as a ligand for dissolving Cu in an organic solvent as a complex for bonding, and then impregnating the solid acid substance (B) in the organic solvent and performing stewing The method of burning; or the vapor deposition of a substance in a complex compound by vaporization under vacuum. Further, when the solid acid substance (B) is obtained from the corresponding metal salt, a solid acid substance belonging to the carrier may be simultaneously carried out in the presence of a metal salt as a catalyst composition containing a metal such as Cu or Zn optionally contained ( The coprecipitation method of the synthesis of B) and the support of the Cu-containing catalyst composition (A2). In the practice of the present invention, it is preferable that the Cu-containing catalyst composition (Al), (A2) and the solid acid substance (B) are dehydrated by a known method. In the fixed bed reaction mode according to the present invention, for example, after the Cu-containing catalyst composition (Al), (A2), and 097143629 17 200934748 solid acid substance (8) are filled in the catalyst-filled portion, the catalyst is filled. The Ministry of Health can pass nitrogen, I and other inert gases, and it can be kept at the above temperature for more than 10 minutes. Further, in order to exhibit the activity of the composition containing the Cu catalyst (10) and (10), it is also possible to carry out the treatment under a nitrogen stream after the removal of the money. In the present invention, the aromatic compound may be a compound having a carbon number of 6 to exemplified, and examples thereof include a stupid group such as benzene, f- and diphenyl, a substituted fluorenyl derivative, or naphthalene. A naphthalene homologue such as methylnaphthalene, or a substituent derivative thereof, wherein the ketone system is exemplified by a condensate having a carbon number of 3 to 2 Å, and an object or a non-object can be used. Things. The base group to be bonded to the carbonyl group is exemplified by an alkyl group or an aromatic group, and specific examples thereof include acetone, acetophenone, acetophenone, etc., among which acetone is preferred. Among these, the 'aromatic compound is a reaction in which benzene and a ketone are produced using benzene and ketone to produce cumene, which is the most important industrial match. In this case, the molar ratio of benzene to acetone (benzene/acetone) is preferably 20, especially preferably 1 to 18. If it is less than the above range, the amount of formation of dipropylbenzene or tripropylbenzene will increase. Dipropylbenzene and tripropylbenzene have the possibility of returning to cumene due to transalkylation with benzene in the process of cumene. The reaction temperature of transalkylation is higher. If the amount of benzene and tripropylbenzene is too large, the cost of steam increases, which is not economical. On the other hand, if it is higher than the above range, when the excess benzene is recovered by the subsequent step of the reactor, it is not economical because it causes the load of the distillation column. Further, if the molar ratio of benzene to acetone (benzene/097143629 18 200934748 is a by-product of inhibition of propane, it is acetone) is preferably 3 to 18 (preferably 4 to 18), and more preferably. The characteristic compound of the present invention is reacted with a fine reaction in the presence of hydrogen in the presence of hydrogen to form a hydrogen in the form of a molecule, and may also be a hydrocarbon in accordance with the reverse production line of the ship. #使(四), 苯听进行反应, as long as the theoretical hydrogen can be more than _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Sub 1 5 仏 Mo Er. Although it is desired to reduce the acetone conversion rate to less than 1% by weight, it can be reduced by reducing the amount of hydrogen used to less than i times the mole. In addition, the hydrogen supplied in the present month reaction can be combined with the network. The oxygen atoms present react to form water and can be withdrawn from the reactor outlet with isopropyl. In addition, the hydrogen above the Bingtiantian is preferably not consumed in the first place without side reactions. Tian will add gas 11 to the reaction, usually in continuous supply. There is no special restriction on this method. It can be separated from the reaction by adding hydrogen after the reaction starts. The intermittent supply of re-supply after the time, and the case of the liquid phase reaction can also make the helium dissolved in the dissolved money for supply. In addition, the recovery process A can also supply hydrogen pain ^ _ tablets that are recovered from the tower together with the low-boiling distillate. The pressure of the added wind is generally changed as appropriate with the pressure of the reactor and the method of supplying the gas. There is no particular limitation on the conditions for the implementation of this reaction. The conditions described in ############################################################### The contact between the mixture and the hydrogen can be carried out by any means such as gas-liquid countercurrent, gas-liquid cocurrent flow, and the direction of the liquid or gas can also be set as: liquid drop-gas rise liquid rise_gas drop, liquid gas rise, liquid Any way such as gas drop. The relative reaction temperature is not particularly limited in the present invention, and it is preferably 5 Å to 3 Å, particularly preferably 60 to 200 Å. If the reaction temperature is lower than the above range, since the calcination reaction rate is too low, a large amount of solid acid substance (B) is required, and the reactor is too large, so that it is not suitable for industrial use. On the other hand, if the reaction temperature is higher than the above range, undesired side reactions such as hydrogenation decomposition and transfer reaction are caused, and thus it is not economical. Further, a preferred embodiment of the pressure range is: μ100 () gas pressure, particularly preferably 0. 5~500 gas pressure. Further, in the practice of the present invention, the amount of the catalyst to be used is not particularly limited. For example, when the reaction system is carried out using a fixed bed circulation device, the supply amount of the raw material hydrazine (ketone + aromatic compound) per hour ( The weight) divided by the value of the catalyst weight (ie WHSV) means 'preferably in the range of ~. l~200/hr, especially in the range of 〜. 2~100/hr. Further, the reset ratio of the upstream catalyst layer to the downstream catalyst layer in the 'catalyst filling portion' is not particularly limited, and generally the upstream catalyst layer: the downstream catalyst layer (weight ratio 1) is 1: 〇 M: 100, preferably 1: 〇· 05~1: 50. If the weight ratio of the upstream side catalyst layer is too small, the acetone conversion rate is lowered, which is not economical. The weight ratio of the right upstream side catalyst layer is too large, and the alkylation reaction is not sufficiently carried out by 097143629 20 200934748, and the yield of the alkylated aromatic compound such as cumene is lowered, and thus it is not economical. In the practice of the present invention, a solvent or a gas which is inactive with respect to the catalyst and the reaction reagent may be added to the reaction system, and it may be carried out in a diluted state. - When the catalyst activity decreases after a certain period of time, the activity of the catalyst can be restored by performing regeneration by a known method. In order to maintain the production amount of the alkylated aromatic compound such as cumene for the month b, two or three reactors may be arranged in parallel, and one of the reactors may be regenerated during the period of 'the convenience of the remaining one or two. The reactor rotates the Trojan way. Further, in the case of three reactors, it is also possible to adopt a method in which two other reactors are connected in series to reduce the variation in production amount. As described above, by the method for producing an alkylated aromatic compound of the present invention, cumene can be directly obtained from the by-product C in the production of phenol. The cumene obtained in this manner can be used as a raw material for producing acetone, and can be used in a process for producing phenol by subjecting cumene to oxidation by including the following steps (a) to (4), followed by decomposition. Waiting for it. In addition, there is no problem even if various improvements are provided. Further, the step (c) is carried out in accordance with the method for producing the above-described alkylated aromatic compound. (a) a step of converting cumene to cumene hydroperoxide; '(6) subjecting iso-benzene hydroperoxide to acid decomposition, and synthesizing a desired step; (c) in the above step (8) The resulting (d), a step of reacting with hydrogen and benzene to synthesize cumene; and 097143629 21 200934748 (d) recycling the isopropyl group obtained in the above step (c) to the step in step (a). [Embodiment] Next, the exemplary embodiments of the present invention will be described in more detail, but the present invention is not limited thereto. [Example 1] A fixed bed reactor equipped with a high pressure feed system, a high pressure hydrogen flow meter, a high pressure nitrogen flow meter, an electric furnace, a catalyst-filled reactor, and a back pressure valve is used. The pressurized liquid phase flow reaction is carried out in a vertical laminar flow manner. In a reactor made of SUS316 having an inner diameter of 1 cm, the copper-zinc catalyst (manufactured by Sud Chemie Co., Ltd.) was first filled from the outlet side of the reactor.

ShiftMax210 'element mass % Cu 32~35%, Ζη 35~40%, Α1 6~7%, Ζη to Cu atomic ratio 1·〇~1.2) powder (classified 250~500#) 〇. 5g and become The catalyst layer on the upstream side. After being packed into quartz wool, the above-mentioned copper-zinc catalyst 0.5 g and MCM-22C are prepared according to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001, P225, and then compression-molded at 20 MPa, and then The mixture was classified into 250 to 500/i, and Si/Almol ratio = 20) 3.0 g was mixed and filled to form a catalyst layer on the downstream side. After pressurizing to 3 Mpa with hydrogen, a reduction treatment was carried out at 200 ° C for 3 hours from the inlet side of the reactor under a flow of hydrogen of 12.5 ml/min. The mixture of benzene/acetone 097143629 22 200934748 (3/1 mol) was circulated at a ratio of 2.50 g/Hr from the inlet side of the reactor under a hydrogen flow of 12. 5 ml/min. . In the middle of the reactor outlet and the back pressure valve, 200 ml/min of nitrogen was introduced using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the reaction gas was introduced into the injection of the GC using a 0.2 ml sampling tube and subjected to GC analysis to quantify the product. The reaction results are shown in Table 1. In the case of the catalyst layer on the downstream side, when the weight ratio of the acid catalyst (MCM-22)/reduction catalyst (copper-lexomer) is 6, it is lower than that of Comparative Examples 1 and 2 described later. A decrease in propane by-products was found. [Example 2] A fixed bed reaction apparatus provided with a high pressure feed pump, a high pressure hydrogen flow meter, a high pressure nitrogen flow meter, an electric furnace, a catalyst-filled portion reactor, and a back pressure valve was used, in accordance with a vertical layer. The pressurized liquid phase flow reaction is carried out in a flowing manner. In a reactor made of SUS316 having an inner diameter of 1 cm, first from the outlet side of the reactor, a copper-zinc catalyst (manufactured by Sud Chemie, product name _ ShiftMax 210, elemental substance i% Cu 32 to 35%, Zn 35~) was filled. 40%, A1 6~7%,

The atomic ratio of Zn to Cu is 1·〇~1.2) powder (classified as 250~500/z) 〇. 9g and becomes the catalyst layer on the upstream side. After being packed into quartz wool, the above-mentioned copper-zinc catalysts O.lg and MCM-22C are prepared by compressing the catalyst according to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001 and P225, and then grading according to 20 MPa. 0 to 0 〇 β ' 'Si / Almol ratio = 20) 3. 0g mixed and filled, it becomes the catalyst layer on the downstream side. 097143629 23 200934748 After pressurizing to 3 Mpa with argon, a reduction treatment was carried out for 3 hours from 20.0 hours from the inlet side of the reactor under a flow of hydrogen of 12.5 ml/min. The mixture of benzene/acetone (3/1 mol) was circulated at a ratio of 2.50 g/Hr from the inlet side of the reactor under a hydrogen flow of 12. 5 ml/min. In the middle of the reactor outlet and the back pressure valve, 200 ml/min of nitrogen was introduced using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the reaction gas was introduced into the injection of the GC using a 0.2 ml sampling tube, and GC was analyzed to quantify the product. The reaction results are shown in Table 1. In the case where the catalyst layer on the downstream side is in the weight ratio 30 shown by the acid catalyst (MCM-22)/reduction catalyst (copper-zinc catalyst), it is found in comparison with the comparative examples 1 and 2 described later. The sideline production of C. [Example 3] A fixed bed reactor equipped with a high pressure feed pump, a high pressure hydrogen flow meter, a high pressure nitrogen flow meter, an electric furnace, a catalyst-filled portion reactor, and a back pressure valve was used. The pressurized liquid phase flow reaction is carried out in a laminar flow. In a reactor made of SUS316 having an inner diameter of 1 cm, from the outlet side of the reactor, first, a copper-chromium catalyst (manufactured by Sud Chemie, product name G99b, elemental mass 阢11 35%, Cr 31%, Ba 2%) was filled. , Μη 3%, Zn to Cu's original 'sub-ratio 0) powder (classified 250~500#) 0. 9g and become the upstream side of the contact 'media layer. After being packed into quartz wool, the above-mentioned copper-chromium catalysts 0. lg and MCM-22C will be prepared according to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001, P225, and the catalyst is compressed at 20 MPa. And further classified into 250 to 500, Si/Almol ratio = 20) 3.0 g mixed and filled to become a catalyst layer on the downstream side. After pressurizing to 3 MPa with hydrogen, a reduction treatment was carried out at 200 ° C for 3 hours from the inlet side of the reactor under a flow of 12.5 ml/min. The mixture was cooled to 175 ° C under a hydrogen flow of 12. 5 ml / min. At this time, a mixture of stupid / propylene (10/1 mol) was passed from the inlet side of the reactor at a ratio of 2.50 g / Hr. • Introduce 200 ml/min of nitrogen in the middle of the reactor outlet and the back pressure valve using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the reaction gas was introduced into the injection of the GC using a 0.2 ml sampling tube and subjected to GC analysis to quantify the product. The reaction results are shown in Table 1. In the case of the downstream side catalyst layer, when the weight ratio shown by the acid catalyst (MCM-22)/reduction catalyst (copper-complex catalyst) is 30, the propane by-product is found in comparison with the comparative example 3 described later. cut back. Further, by increasing the molar ratio of benzene/acetone to 10, the propane by-product is more inhibited than in Examples 1 and 2, and cumene can be obtained in a high yield. [Example 4] A fixed bed reaction apparatus provided with a high pressure feed pump, a high pressure hydrogen flow meter, a high pressure nitrogen flow meter, an electric furnace, a catalyst-filled portion reactor, and a back pressure valve was used, in accordance with a vertical layer. The pressurized liquid phase flow reaction is carried out in a flowing manner. In a reactor made of SUS316 having an inner diameter of 1 cm, from the outlet side of the reactor, first, a copper-zinc catalyst (manufactured by Sud Chemie Inc.) product name 097143629 25 200934748 *

ShiftMax210, element mass Shen 11 32~35%, Zn 35~40%, A1 6~7%, atomic ratio of Zn to Cu 1. (Μ· 2) powder (classified as 250~50〇β) 〇. 9g And become the catalyst layer on the upstream side. After filling the quartz wool, the copper is further

, -Zinc Catalyst 0. lg and MCM-22C will be prepared according to VERIFIED SYNTHESES 0F ZEOLITIC MATERIALS Second Revised Edition 2001 > P225, after compression molding at 20MPa, and then graded into 250~500/z, Si /Almol ratio = 20) 3. 0g is mixed and filled, and φ becomes a catalyst layer on the downstream side. After pressurizing to 3 Mpa with hydrogen, from the inlet side of the reactor at a flow rate of 12. 5 ml/min of hydrogen, according to 20 (TC for 3 hours reduction treatment. Under a hydrogen flow of 12. 5 ml/min 'cooling to 175 ° C, this At the inlet side of the reactor, a mixture of benzene/propion (10/1 mol) was passed at a ratio of 2.50 g/Hr. In the middle of the reactor outlet and the back pressure valve, a high pressure nitrogen flow meter was used to introduce 200 ml. /min nitrogen. A switching valve is placed on the pipeline after the back pressure valve, and the reaction gas is introduced into the injection of the GC using a Φ 0.2 ml sampling tube and GC analysis is performed to quantify the product. The reaction results are shown in Table 1. The downstream side catalyst layer has a weight ratio of 3〇 as shown by the acid catalyst (MCM-22)/reduction catalyst (steel_chromium catalyst), compared with the comparative example 3 described later. It was found that the propane by-product was reduced, and by increasing the molar ratio of benzene/acetone, the propane by-product was more inhibited than in the Example 2, and cumene was obtained in a high yield. [Comparative Example 1] 097143629 26 200934748 Use with high pressure feed pump, high pressure hydrogen flow meter, high pressure nitrogen flow meter, electric furnace, The reactor filled with the medium and the fixed bed reactor of the back pressure valve are subjected to a pressurized liquid phase flow reaction in a vertical laminar flow. - A copper-zinc catalyst is used in a reactor of SUS316 having an inner diameter of 1 cm. (SudChemie Company system, product name shiftMax210, element mass Shen 11 32~35%, Zn 35~40%, A1 6~7%, atomic ratio of Zn to Cu 1.0~1. 2) Powder (classified 250~500 #物) l. 〇g, and point zeolite (catalyzed by the company into a '2" MPa compression molding and then graded to 250 ~ 500 / /, Si / Almol ratio = 12) 1. 〇g mixed and filled. After pressurizing to 3 Mpa with hydrogen, the reduction treatment was carried out from the inlet side of the reactor at a flow rate of 12. 5 ml/min. under a hydrogenation of 200 C for 3 hours. Under a hydrogen flow of 25 m 1 /min, the temperature was lowered to 175. A mixture of benzene/propylene (3/1 mol) was passed from the inlet side of the reactor at a ratio of 5.00 g/Hr. In the middle of the reactor outlet and the back pressure valve, nitrogen of φ 200 ml/min was introduced using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the reaction gas was introduced into the injection of the GC using a 0.2 ml sampling tube and subjected to GC analysis to quantify the product. The results of the reaction are shown in Table 1. "A large amount of propane by-product was found by pressurization. * [Comparative Example 2] A fixed bed equipped with a high-pressure feed pump, a high-pressure hydrogen flow meter, a high-pressure nitrogen flow meter, an electric furnace, a reactor with a catalyst-filled portion, and a back pressure valve 097143629 27 200934748 According to the vertical laminar flow, the pressurized liquid phase flow reaction is performed. In a reactor made of SUS316 having an inner diameter of 1 cm, first, a copper-zinc catalyst (manufactured by Sud Chemie, product name ShiftMax 210, element mass % 〇 1 32 to 35%, Zn 35 to 40) was filled from the outlet side of the reactor. %, A1 6~7%, . Zn to Cu atomic ratio powder (classified 250~500 ") 0.9g and become the catalyst layer on the upstream side. After stuffing into quartz wool, the above copper-zinc Catalyst 2. 5g and MCM-22C will be prepared according to VERIFIED SYNTHESES 0F φ ZEOLITIC MATERIALS Second Revised Edition 2001 > P225, after compression molding at 20MPa, and then graded to 250~500 #物, Si/Almol ratio =20) 3. 0g is mixed and filled to become the catalyst layer on the downstream side. After pressurizing to 3 MPa with hydrogen, the reduction treatment was carried out at 200 ° C for 3 hours from the inlet side of the reactor under a wind flow of 12.5 ml/min. The mixture was cooled to 175 ° C under a hydrogen flow of 12.5 ml/min. At this time, a mixture of benzene/acetone 10 (3/1 mol) was passed from the inlet side of the reactor at a ratio of 2.50 g/Hr. In the middle of the reactor outlet and the back pressure valve, 200 ml/min of nitrogen was introduced using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the product was quantified by introducing a reaction gas into the injection of the GC using a 0.2 ml sampling tube and performing GC analysis. 'The reaction results are shown in Table 1. When the weight ratio of the acid catalyst (MCM-22)/reduction catalyst (copper-zinc catalyst) was 1.2, a large amount of propane by-product was found. 097143629 28 200934748 [Comparative Example 3] A fixed bed reactor equipped with a high-pressure feed pump, a high-pressure hydrogen flow meter, a high-pressure nitrogen flow meter, an electric furnace, a reactor with a catalyst-filled portion, and a back pressure valve, The pressurized liquid phase flow reaction is carried out in a vertical laminar flow manner. In a reactor made of SUS316 having an inner diameter of 1 cm, the copper-zinc catalyst (manufactured by Sud Chemie Co., Ltd.) was first filled from the outlet side of the reactor.

ShiftMax210, element mass 1132~35%, Zn 35~40%, A1 6~7%, 原子 Zn to Cu atomic ratio 1·(Μ.2) powder (classified 250~500/z)〇.9g And become the catalyst layer on the upstream side. After being packed into quartz wool, the above-mentioned copper-zinc catalyst 2, 5g and MCM-22C are compressed and molded according to VERIFIED SYNTHESES OF ZEOLITIC MATERIALS Second Revised Edition 2001 and P225, and then classified. 0 to 0 / / / / 'Si / Almol ratio = 20) 3. 0g mixed and filled, it becomes the catalyst layer on the downstream side. After the pressure was pressurized to 3 MPa by hydrogen, the reduction treatment was carried out at 200 ° C for 3 hours from the inlet side of the reactor under a flow of hydrogen of 12.5 ml/min. The mixture was cooled to 175 ° C under a hydrogen flow of 12.5 ml/min. At this time, a mixture of benzene/acetone (10/1 mol) was passed from the inlet side of the reactor at a ratio of 2.50 g/Hr. 'In the middle of the reactor outlet and the back pressure valve, 200 ml/min of nitrogen was introduced using a high pressure nitrogen flow meter. A switching valve was placed in the line after the back pressure valve, and the reaction gas was introduced into the injection of the GC using a 0.2 ml sampling tube and subjected to GC analysis to quantify the product. 097143629 29 200934748 The reaction results are shown in Table 1. When the weight ratio of the acid catalyst (MCM-22)/reduction catalyst (copper-lexomer) was 1.2, a large amount of propane by-product was found.

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Claims (1)

200934748 VII. Applicable scope of the patent: L A method for producing an alkylated aromatic compound, which is a flow-through fixed bed reaction device having a catalyst-filled portion containing a physicochemical substance and a Cu-containing catalyst composition, + 1 composition of a fragrant compound, a ketone, and hydrogen to produce an alkylated aromatic compound, wherein the catalyst-filled portion is composed of a catalyst layer that can be distinguished from the upstream side and the downstream side; The catalyst layer is composed of a catalyst-containing composition (μ); the T & _ layer is composed of a Cu-containing catalyst composition (A 2 ) and an IS body acid substance (B); The weight ratio of the site (A2) to the solid acid (8) [(10): (8)] is 0.5: HU〇. 2. The method for producing an alkylated aromatic compound according to the first aspect of the patent application, wherein the ❹ Lu catalyst composition (A1) and the cu catalyst-containing viscous, (10) are from a constituent group. Select at least two: genus: Cu catalyst composition. The metal and the method of claim 3, wherein the production of the above-mentioned cL-containing alkylated aromatic compound (A2) is composed of Cu and z (A1) and Cu catalyst-containing composition ratio &quot (M shoulder catalyst composition, and the amount according to the atom 4. As in the patent application method, wherein the above aromatic compound is a product of the stupid aromatic compound 097143629 32 200934748 · 5. And a method for producing an alkylated aromatic compound according to the first aspect of the invention, wherein the aromatic compound is benzene, The method for producing an alkylated aromatic compound according to any one of claims 6 to 6, wherein the solid acid substance (B) has oxygen oxime~ΐ6 The method for producing an alkylated aromatic compound according to the seventh aspect of the invention, wherein the zeolite compound is a fossil compound having an oxygen ring or a 12-membered ring pore. 9. If you apply for a patent _ Item 7 (4) Method for producing a fragrance compound] wherein the zeolite compound is composed of a group consisting of stone feldspar, mcm_22 phoenix, mordenite, ZSM-5 zeolite, ZSM-12 buddha and γ type zeolite Selecting at least one zeolite compound. _ ίο. A method for producing a phenol comprising the following steps: (a) a step of converting cumene to cumene hydroperoxide; (b) a step of synthesizing phenol and acetone by acid decomposition of isopropyl hydrogen peroxide; (5) a step of reacting acetone formed in the above step (6) with hydrogen and benzene to synthesize cumene; and (d) following the above steps (c) The cumene obtained is recycled to the step in the step; 097143629 33 200934748 ' It is characterized in that the step (c) is carried out in accordance with the method of any one of claims 1 to 9. 097143629 34 200934748 IV. Designated representative drawings: (1) The representative representative of the case is: None (2) The symbolic symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: no 097143629 2