TWI269789B - Preparation of acrolein and/or acrylic acid - Google Patents

Abstract

Acrolein and/or acrylic acid are prepared from propane and/or propene by a process comprising the following steps: (a) separation, of propane and/or-propene from a propane- and/or propene-containing gas mixture by absorption in an absorbent, (b) separation of the propane and/or propene from the absorbent to give a gas B and (c) use of the gas B obtained in stags (b) for an oxidation of propane and/or propene to acrolein and/or acrylic acid, no heterogeneously catalyzed dehydrogenation of propane-without supply of oxygen being carried out between steps (b) and (c).

Description

1269789 A7 B7 V. INSTRUCTIONS (The present invention relates to a process for preparing acrolein and/or acrylic acid from propane and/or propylene. Propionate and acrylic acid are the main chemicals. Therefore, acrylic acid is especially used for the preparation of polymers. Monomer, the polymer is used as a binder, for example, as an aqueous medium dispersion. According to the desired application of the polymer, acrylic acid can also be esterified prior to polymerization. Acrolein is, for example, preparation of glutaraldehyde, methionine, folic acid. And an important intermediate for acrylic acid. A number of processes for the preparation of acrolein and/or acrylic acid from propane and/or propylene are known. DE-A 33 13 573 and ΕΡ-Α-0 117 146 disclose the conversion of propane to propionium. A method of aldehyde and/or acrylic acid. A two-stage or three-stage method of dehydrogenating propane to propylene in the first stage and oxidizing propylene to acrolein in the second stage is described. The second component formed in the dehydrogenation reaction, such as molecular hydrogen separation of propane, is not carried out in the second stage. The oxidation system is carried out under the condition that the hydrogen is not significantly oxidized. In the third stage, the (tetra) aldehyde can be further It can be converted into C (4). It can also be separated from the unconverted propane and C by absorption and / or after the release of the adsorbent, and then recycled to the first stage (dehydrogenation stage). The Japanese patent 凊 爪 人 i i (2) 6311 discloses a method for preparing an unsaturated carboxylic acid, such as propionic acid, by gas phase catalytic oxidation of propane in the presence of a composite metal oxide catalyst, and wherein the propylene is oxygenated and if necessary The dilution gas core ratio will maintain a high yield of the starting mixture and will remain within the defined range 'especially to maintain the conversion at a specific level. The unconverted propane will be separated by oxidation after separation by a separate separator. Out, including pressure change adsorption single 疋 ' and recycled to gas phase catalytic oxidation. -4- 1269789

78-178 discloses a method in which the unconverted smoke of the oxidation process is absorbed in the absorbent and the stripping agent is stripped with the stripping medium. : t = the hydrocarbon is added to the gas mixture in the amount of the mixture outside the combustible range. The purpose of the present invention is to provide an economy and the catalyst used can be used for a long time without regeneration (4) and / Or a method for preparing propylene and field/propionic acid by propylene gas phase catalysis. It has been found that the object of the present invention is to separate propane and/or propylene from an absorbent by absorbing the acrylic and/or propylene in a mixture containing a mixture of propylene and/or propylene gas, followed by propane and / or propylene is oxidized to propionaldehyde and / or acrylic acid. The present invention is therefore directed to a process for the preparation of acrylic acid and/or acrylic acid from propylene oxide or acetonide, which process comprises the following steps: (a) by adsorbing a gaseous mixture containing propane and/or propylene oxide In the absorbent, separating propane and/or propane, (b) separating propane and/or propionate from the absorbent to obtain a gas B containing propane and/or propylene, and (c) using the gas obtained in the step (b) B. Conversion of propane and/or propylene to acrolein and/or acrylic acid, and in the absence of oxygen supply between step (b) and step (c), heterogeneous catalytic dehydrogenation of propane is not carried out. Preferred embodiments of the invention are illustrated by the following description and accompanying drawings. Since the propylene and/or propylene are adsorbed prior to oxidation, the residue of the absorbent remains in the gas B. Unexpected discovery did not occur during the oxidation process - 5 - This paper scale applies to China National Standard (CNS) A4 specification (2i〇x297 dongdong) 1269789 A7 ------------B7 V. Invention Explanation (3) The problem has been. Therefore, no substantial decrease in the activity of the oxidation catalyst was observed, and the oxidation catalyst can be operated for a long period of time without regeneration. Furthermore, no problems associated with oxidation of the desired absorbent residue in the oxidation stage have been observed. The problem with the residue of the absorbent usually does not occur in the case of using high boiling hydrocarbons, especially bismuth bond as an absorbent, which can be removed, for example, by water cooling or by adsorption. According to the method of DE_A 33 13 573, propane and propane recovered by adsorption or separation are recycled to the heterogeneously catalyzed dehydrogenation of propane. In heterogeneously catalyzed dehydrogenation of the pit, the catalyst may be deactivated by, for example, coking. Therefore, the dehydrogenation catalyst needs to be regenerated. Therefore, the absorbent fed with the gas stream does not cause a problem because it is ashed with coking. On the other hand, the catalyst used for oxidation to propionic acid and/or propionic acid generally does not require frequent regeneration because the additional regeneration cost due to the fact that the absorbent contains feed gas is greater than the cost of dehydrogenation. An advantage of the novel method is that the oxidizing catalyst can be used for a long time without regeneration. A novel method which differs from the method of DE-A 33 13 573 is the adsorption of the separated propylene and/or propylene into the oxidation stage. In contrast to the conditions in the process of DE_A 33 13 573, the present invention is based on the separation of propional and/or propionate from an absorbent and oxidation to acrolein and/or acrylic acid, and non-heterogeneous catalytic dehydrogenation without oxygen supply. . In the present invention, the gas B may also be a gas mixture. In the step (a), a gas mixture A comprising any desired amount of propane and/or propylene may be used. Preferably, the gas mixture A has a molar ratio of 〇·· j 〇〇 to 100:0, preferably 10:90 to 90:10, and usually 80: 2〇 to 40 -6-. National Standard (CNS) A4 Specification (210X297 mm) 1269789 A7 _________ B7 V. Invention Description (4) "" — : 60 propane and propylene. The carrier is good, and the rolling mixture A contains at least one component different from propane and/or propylene, and is not particularly limited. Therefore, another component depends on the gas mixture. In particular, it comprises a second selected from the group consisting of nitrogen, hydrogen, carbon oxides such as carbon monoxide or carbon dioxide, other second components resulting from the dehydrogenation of propane, and gas phase oxidation of propylene to propionaldehyde and/or acrylic acid. a component or at least one component of a second component produced by oxidation of propylene to propionaldehyde and/or propionate. Typically, the other ingredients contain at least hydrogen, nitrogen, carbon oxides or mixtures thereof. Suitable absorbents in step (a) are in principle all absorbents which absorb propane and/or propylene. The absorbent is preferably an organic solvent, and the organic solvent is preferably hydrophobic and/or high in boiling point. Preferably, the boiling point of such solvents (at atmospheric pressure) is at least 120 Torr, preferably at least 18 Torr, especially from 2 Torr to 35 Torr: and most preferably from 250 to 300 ° C, more preferably 260 to 290 ° C. Preferably, the flash point (at 1 atm atmospheric pressure) exceeds 11 〇χ:. In general, suitable absorbents are relatively non-polar organic solvents such as aliphatic hydrocarbons which preferably do not contain externally acting polar groups, but aromatic hydrocarbons may also be employed. Generally, the absorbent needs to have a very high boiling point and a very high solubility to propane and/or propylene. An example of an absorbent is a scorpion te, such as CVC2. - an alkane or CVCso olefin, or an aromatic hydrocarbon such as an alkane distillation intermediate oil fraction, or an ether having a large group on an oxygen atom, or a mixture thereof, may also be added to a polar solvent, for example, mDF_A43 〇 8 〇87 = reveal 1,2-dimethyl ester of phthalic acid. have! Esters of benzoic acid and phthalic acid of linear alkanols of up to 8 carbon atoms, such as n-butyl benzoate, methyl benzoate, ethyl benzoate, dimethyl phthalate and phthalic acid Diethyl ester, and hot oil This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1269789 A7 B7 V. Description of invention (5) Such as biphenyl, diphenyl ether and biphenyl and diphenyl ether a mixture, or a chloro derivative thereof and a triaryl olefin, such as 4-methyl-4 benzyldiphenylmethane and its isomer 2-methyl-2'-benzyldiphenylmethane, 2-methyl- 4. Benzyldiphenylmethane, and 4-methyl-2-benzyldiphenylmethane, and mixtures of such isomers are suitable. Suitable absorbents are solvent mixtures comprising biphenyl and diphenyl ether, preferably a co-sorried mixture, especially comprising about 25 wt% biphenyl and about 75 wt% diphenyl ether, such as commercially available. Biphenyl. Usually, the solvent mixture contains an added solvent such as dimethyl phthalate in an amount of from 0.1 to 25 % by weight based on the total solvent mixture. Other particularly suitable absorbents are Xin Shao, Shao Shao, Yan Fu, Qi - Burn, 12 Burn, 13 Burning, 14 Burning, 15 Burning, 16 Rules, 17 Burning, and 18 Entertainment. ^, and the most suitable one is fourteen. If the absorbent used has the above-mentioned boiling point on the one hand, on the other hand, the molecular weight is not too high, which is optimum. Preferably, the molecular weight of the absorbent is 幺3 00 g/mole. It is also possible to use a liquid chain of 8 to 10 carbon atoms as described in DE-A 33 13 573. Examples of suitable commercially available products are the products of Haltertmann, such as Halpasols i, such as Halpasol 250/340 i and Halpasol 250/275 i, and printing inks designated PKWF and Printosol. The adsorption step is not subject to any particular limitation. All processes and conditions familiar to those skilled in the art can be used. Preferably, the gas mixture is contacted with the absorbent at from 1 to 50, preferably from 2 to 20, more preferably from 5 to 10 bar and from 0 to 100 ° C, especially from 30 to 50 ° C. This adsorption can be carried out in a column or cooling unit. The steps of co-current flow or reverse flow can be used. Suitable absorption towers are, for example, tray towers (with a bulb holder and/or a screen tray), columns with stacked fillings (for example filling of sheet steel with a surface area of 100 to 500 m2/m3, for example -8- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789

Mellapak 250 Y)' and the optional filling tower (9) are filled with Raschig filling). However, it is also possible to use a trickle and spray tower, a graphite block absorber surface absorber, such as a film and a thick film absorber, and a plate washer, a cross spray washer and a rotating wire m, preferably also with or without absorption The contents are carried out in a bubble column. The separation of the propylene and/or propylene by the absorbent can be carried out by stripping, steaming and/or. The separation of the acrylic acid and/or the propionate from the absorbent of the step (8) is preferably carried out by gas or a molecular oxygen (e.g., air) which is inert to the new step (4). In this paper, the stripping can be carried out in a general manner, changing the pressure and/or temperature, and preferably in the range of ο·1 to 10, especially 1 to 5, more preferably! Up to 2 bar and 0 to 20 CTC, especially 2 (^1 〇〇χ, more preferably 3 (^5 〇χ. Another gas for gas extraction is, for example, steam, but the best is oxygen/nitrogen ^物, such as air. When the gas or oxygen content exceeds 1% by volume of oxygen / nitrogen / compound; it can be added at any time before or during the stripping process to reduce the gas explosion range. This purpose is most suitable The gas is a specific heat energy of 2 〇 1 = >29·^ 'such as 甲烧,乙烧, 丙境, 丁烧, pentane, hexane, benzene, methanol, ethanol, ammonia, carbon dioxide or water. The bubble column containing no content is also most suitable for gas extraction. The separation of the propylene and/or propyl hydrazine from the absorbent can also be carried out by steaming, which can be used with a tower familiar to those skilled in the art and containing a packed filler. Optionally, the filling or equivalent content. The preferred distillation conditions are pressures of 〇〇1 to 5, especially 〇1 to 3, more preferably 1 to 2 bar, and temperature (bottom) of 5 〇 to 3 〇. 〇. (:, especially 15〇 to 25〇-9-

1269789 A7

When the gas mixture a contains water, the adsorption is better with the condensation of water (liquid and water cooling): the board is well-considered with water cooling to follow the adsorption step, so that the loss of the absorbent is small. Typically, step (c) is carried out immediately after step (b), i.e., there are no other steps or intermediate stages in between. However, the absorbent may be separated by, for example, water cooling after step (b) and before step (4). The oxidation of propylene and/or propane to acrolein and/or acrylic acid in step (C) can be carried out according to all methods known to those skilled in the art without any limitation. In the step (4), the propylene oxide can be oxidized to C, HI and/or propionate in one or two stages or the propylene can be oxidized to propionate and/or propionate or . The liquid simultaneously oxidizes propane and propylene to propionaldehyde and/or acrylic acid. Oxidation can be carried out in a random manner by selective heterogeneous catalytic meteorological oxidation with molecular oxygen to obtain a gas mixture containing propylene and/or propylene. If necessary, the oxidized propane and/or propylene may be indirectly heat exchanged to the reaction temperature required for the oxidation reaction. In a preferred embodiment, step (c) of the novel process is carried out by oxidizing propylene to aldehyde and/or acrylic acid. In principle, the inductive catalytic gas phase oxidation of propane to acrylic acid by molecular oxygen is carried out in a two-step process, with the first step forming acrolein and the second step converting acrolein to acrylic acid. In a second sequential step, the reaction sequence is carried out in a previously known manner such that step (c) of the novel process can be carried out in successively arranged oxidation zones, which may also be selected in an optimum manner in each oxidation zone. Oxidation catalyst used. Therefore, for the -10-th

1269789 A7 B7 V. INSTRUCTION DESCRIPTION (8) -- an emulsification zone (propylene-acrolein), preferably a catalyst containing a combined element _--multimetal oxide, but for the second reaction zone (C It is generally preferred that the acrylic acid is a catalyst mainly composed of a multi-metal oxide containing a combined element Μ〇_β. The corresponding multi-metallization catalyst of the dioxide region has been widely described and is familiar with the art. For example, 0 253 409 points to the corresponding U.S. patent on page 5. Preferred I catalyst fluids in the oxidation zone are disclosed in DE_A 44 31 957 & de a 44 31 949. 2. The application in the above publication. Therefore, the product mixture of the first oxidation zone is transferred to the second oxidation zone without treatment with an intermediate. The simplest form of the oxidation zone is therefore a tube bundle reactor, wherein The catalyst content varies along the respective catalyst tubes until the end of the first reaction step. The reaction is described in, for example, ep_a_〇9H 313, ερ_α·〇979 813, ΕΡ-Α-0 990 636 and DE-A 28 30 765. If necessary, the catalyst in the catalyst tube contains It is interrupted by an inert bed. However, it is better to know that this dioxide zone is in the form of a two-tube bundle system connected in parallel. These may be present in the reactor and transferred from one bundle to another bundle by being unsealed. In the catalyst tube, a bed of inert material that can be assembled at will is formed. Although the heat transfer medium generally flows around the catalyst tube, the heat transfer medium does not reach the inert bed of the device as described above. The tube bundle can thus advantageously be encapsulated in separate reactors. Thus, the two tube bundles are stored in the intermediate condenser to reduce any subsequent combustion of the acrolein in the product gas mixture leaving the first oxidation zone. Replacement of the tube bundle reactor with a salt-cooled and/or evaporatively cooled plate heat exchanger as described in pp. A-199 29 487 and DE_A 199 52 964. -11 - This paper scale applies to the Chinese National Standard (CNS) A4 size (210X 297 mm) 1269789 A7 ____^_____ V. Description of the invention (9) The reactor temperature in the first oxidation zone is therefore 3〇〇 to 45〇.^, preferably 3 20 to 390 (^ In the first oxidation zone The reaction temperature is therefore from 2 Torr to 3 Torr, and is usually from 220 to 290 ° C. The reaction pressure in the oxidation zone is preferably from 〇. 5 to 5, and more preferably from 1 to 3 atm. The gas content of the oxidation catalyst of the reaction gas (liter (S, T, P) / lh) is usually 15 〇〇 to 2500 1 Γ 1, or reaches AOOOh-1. The propane content (liter (ST p... VII) is usually 5〇 to 3〇〇h_1, especially 1〇〇 to 2〇〇h_1. In principle, the design of the oxidation zone can be as described in DE_A 198 37 517, DEA 199 10 506, DE-A 199 10 508 and DE-A 198 37 519. Typically, if a multi-zone reaction system is desired, the reaction gas mixture and the amount of catalyst will be externally heated in the dioxide zone in a manner known per se. In accordance with the present invention, a novel process is preferred, with propane propane as a preferred inert diluent gas for propylene oxidation catalyzed by propylene. All of the molecular oxygen required for the emulsification can be previously added to the gas B in a total amount. However, it is also possible to add oxygen to the gas after the first oxidation zone. Preferably, the molar ratio of molecular oxygen in the first oxidation zone is i: 1 soil 1 · 3 and is usually i : :2. Preferred in the second oxidation zone is acrylic acid: the molecular oxygen molar ratio is 1: 〇 5 to 1: 2. In the oxidation zone, molecular oxygen over 1 usually has an advantageous effect on the dynamics of gas phase oxidation. Even if the catalytic gas phase oxidation of the C-inclusion is dynamically controlled to propionic acid, the propane is therefore theoretically subject to a molar excess relative to the molecular oxygen, for example in the first oxidation zone. At this point, excess propylene will actually act as a diluent gas. ...,] It is also known in the upper oxidation zone that the conversion of propylene to acrylic acid is not -12-

1269789 A7 B7 V. INSTRUCTIONS (1〇) Homogeneous catalytic gas phase oxidation. At this time, a two-reaction step occurs in an oxidation reactor containing a catalyst which can catalyze the reaction in the two reaction steps. The amount of catalyst herein may also vary continuously or abruptly with the progress of the reaction in the reaction zone. In a specific example of the step (C) in the form of a parallel oxidation zone, the product gas mixture from the first oxidation zone, if necessary, from the oxide of carbon and the mixture in the mixture, if necessary before the second oxidation zone of the channel The vapor is partially or completely separated. A by-product in the first oxidation zone is formed. Preferably, the step of not requiring such separation is selected. Suitable sources of molecular oxygen required in the oxidation step (C) are pure molecular oxygen and molecular oxygen diluted with an inert gas such as carbon dioxide, carbon monoxide, noble gases, nitrogen and/or saturated hydrocarbons. In a conventional manner, air is used as an oxygen source to replace at least a portion of the desired molecular oxygen. The gas B fed to the oxidation step (c) of the novel process preferably contains only propane and propionate substantially, and the additional air is used as the molecular oxygen source for oxidation. If necessary, the gas B fed to the step (c) can be cooled in a direct manner by adding cooling air. If the desired product is propionaldehyde, the second oxidation zone may not be used in step (c). The oxidation of propane to acrolein and/or acrylic acid in step (c) may also be carried out as described in ΕΡ_Α-0 117 146, US-A-5 198 578 and US-A-5 183 936, or similar to DE-A 33 13 573, CA-A-1 217 502, US-A-3 161 670, US-A-4 53 2 3 65 and WO 97/3 6849. A suitable division is also described in ΕΡ-Α-0 293 ?24, ΕΡ-Α-0 253 409, DE-A 44 31 957, DE 195 08 532 or DE-A 41 32 263. The preferred method is a method of operating with different gases in the oxidation. The oxidation of acrolein to acrylic acid can be as described in WO 00/39065, by -13 - the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 _______B7 V. Description of invention (11) Fluidized bed The reactor is carried out. The oxidation of the pits to propionic acid and/or acrylic acid can also be carried out using a plate type heat exchanger reactor as described in DE_a 99 52 964. In another preferred embodiment, step (c) of the novel process is carried out by oxidation of propane to acrolein and/or acrylic acid. In this oxidation, propane is converted to acrolein and/or acrylic acid in one or more stages on a suitable catalyst. All methods known to those skilled in the art can be used for this purpose. A suitable method is described, for example, in JP-A-10 36 311. Propane heterogeneous catalytic gas phase oxidation to acrolein and/or acrylic acid suitable for use as a multi-metal oxide material of the following formula (I)

MoVbM1cM2d〇n (I) wherein M1 is Te and/or Sb Μ2 is composed of Nb, Ta, W, Ti, Α1·Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni' Pd, Pt, La At least one of Bi, B, Ce, Sn, Zn, Si and In, b is 0.01 to 1 c is > 〇 to 1, preferably o. oi to 1, d is > 〇 to 1, preferably O.oi to 1, n is the number of valences and frequencies determined by the elements other than oxygen in (1). The stoichiometric equivalent of (1) is much known as the metalloid material, for example, ΕΡ-Α-0 608 838? ΕΡ-Α-0 529 853, JP-A 7-232 071, JP-A 1〇.

57813, JP_A 2000-37623, JP-A 10_3631 1, WO 00/29105, Proceedings ISO 99, Rimini (Italy), Sept. 10-11, 1999, G -14 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 dong) 1269789 A7 _ B7 V. Description of invention (12)

Centi and S. Perathoner Ed., SCI Pub. 1999, ΕΡ-Α-0 767 164, Catalysis Today 49__ (1999), 141-153, EP-A-0 962 253, Applied. Catalysis A: General 1 9 4 to 1 9 5 (2000), 479 to 485, JP-A 11/169716, ΕΡ_Α_0 895 809, DE-A. 198 35 247, JP-A 8-57319, JP-A 10-28862, JP-A 11-43314 , JP-A 11-57479, WO 00/29106, JP-A 10-330343, JP-A 11-285637, JP-A 10-310539, JP-A 11-42434, JP-A 11-343261, JP- A 11-343262, WO 99/03825, JP-A 7-53448, JP-A 2000-51693 and JP-A 11-263745. The following multimetal oxides (I), (II) and (III) are especially suitable. In the multimetal oxide material (I) of the formula (1), Μ1 is Te and/or Sb, and Μ2 is Nb, Ta, W, Ti, Al, Zr, Cr, Mn, Fe, Ru, Co, Rh, At least one of Ni, Pd, Pt, Bi, B and Ce elements; b is 0.01 to 1; c is 0.01 to 1; (1 is 0.01 to 1; and η is a price point of an element other than oxygen in the formula (I) And the number of frequency determinations. The preparation of the multimetal oxide material (I) is preferably carried out by subjecting a mixture of elemental sources constituting the multimetal oxide material (I) to fluid heat treatment, and separating and removing the new type The solid is converted into an active oxide by heat treatment. In the multimetal oxide material (I), Μ1 is preferably Te, Μ2 is preferably Nb, b is preferably from 0.1 to 0.6, and c is preferably from 0.05 to 0.4. d is preferably from 0.01 to 0.6. The heat treatment is preferably carried out at 350 to 700 ° C, and the heat treatment is preferably carried out under an oxygen-containing gas at 150 to 400 ° C, followed by an inert gas at 350 to 700 The stoichiometry of the multimetal oxide material (I) is disclosed in ΕΡ-Α-0 608 838, WO 00/29106, JP-A 1 1/169716 and ΕΡ-Α-0 962 253. -15- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7 B7 V. INSTRUCTIONS (13) Fluid thermal preparation of multi-metal oxide active material precursors is well known to those skilled in the art (eg , Applied Catalysis A: 194 to 195 (2000). 479-485, Kinetics and Catalysis, Sister, No. 3 (1999), 401 to 404, Chem. Commun. (1999), 517 to 518, JP-A 6/ 227819 and JP-A 2000/26123 需 This article needs to know that in the high pressure tank (autoclave), in the presence of super-atmospheric vapor, and often at >100 to 600 ° C heat treatment to form the desired multi-metal oxide A preferred homogeneous mixture of materials of material (I). The pressure range is generally up to 500, preferably up to 250 atm. Temperatures in excess of 600 ° C and vapor pressures in excess of 500 atm can also be used, but the application technique is extremely poor. The heat treatment of the fluid is preferably carried out in the presence of steam and liquid water. This is possible with a temperature range of > 100 to 3 74·15 ° C (the critical temperature of water). The phase can flow the entire amount of the starting compound Floating liquid and / or the amount of the solution, however, also possible to make a homogeneous mixture of the starting compound is completely absorbed in the storage step of the water vapor and the balance. Preferably, the fluid heat treatment is carried out at > 100 to 300 ° C, preferably 150 to 250 ° C (e.g., 160 to 180 ° C). The amount of the latter in the high pressure crucible is therefore at least 1% by weight, based on the total amount of water and the source of the elements constituting the desired multimetal oxide material (I). Usually, the above amount does not exceed 90% by weight. It is usually from 3 to 60, or from 5 to 30, and usually from 5 to 15 by weight. /〇. During the heat treatment of the fluid, stripping may or may not be performed. Fluid Heat Preparation The most suitable starting compound (source) for the variant is that it can form oxides and/or hydroxides with water at superatmospheric pressure. Oxide of elemental composition-16- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7 B7 V. Invention description (14) and/or hydroxide can also be attached or used exclusively A starting compound for the preparation of fluid heat. Therefore, the element source can be utilized in a subdivided state. Suitable source constituents may be those which form oxides and/or hydroxides upon heating (if required in air). The oxide and/or hydroxide of the elemental composition may be attached or used exclusively as such a starting compound. Suitable elements 〇 〇 source is, for example, oxidized 4 mesh, such as antimony trioxide, 4 mesh acid salt such as heptamolybdic acid hydrate and hydrazine compound such as chlorinated 4 mesh. Suitable starting compounds with the use of element V are, for example, oxetyl pyruvate oxygen, acid salts such as ammonium montanoate, oxidation signals such as pentoxide (V2 〇 5), vanadium chloride such as vanadium tetrachloride (VC14), and oxy-vanadium such as V0C13. Conveniently, the vanadium starting compound used is a vanadium containing an oxidation state of +4. Appropriate elements of the source are oxidative bonds, such as oxidized women, metals, halogenated women, such as TeCl2, and benzoic acid, such as the original acid H6Te06. Preferably, the starting compound is a cerium halide such as SbCl3, cerium oxide such as antimony trioxide (Sb203), citric acid such as HSb(OH)6, and cerium oxide salt such as cerium oxide sulfate (Sb02) S04. For example, it is oxidized, such as pentoxide (Nb205), oxyhalogenated ruthenium such as NbOCl3, ruthenium halide such as NbCl5, and a complex compound of ruthenium with an organic vanadic acid and/or a dicarboxylic acid, such as an oxalate and an alkoxide. The sharp solution used in ΕΡ-Α-0 895 809 is also suitable as a source. For all other possible elements M2, the most suitable starting compounds are their halides, nitrates, formates, oxalates, acetates, carbonates and/or hydroxides. Suitable starting compounds are often also oxo compounds, such as tungstates, or acids derived therefrom. Usually, the amine salt is also used as the -17- paper scale for the Chinese National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 B7 5. Inventive Note (15) Starting compound. Other suitable starting compounds are the polyanions of the Anderson class, for example, Polyhedron 6, No. 2 (1987), 213-218, and the Applied Catalysis A: General 1 94- 1 95 (2000), 479- It has been used in 485 to prepare a suitable multimetal oxide (I) or in the second document described therein. Another applicable literature source for the polyanions of the Anderson class is Kinetics and Catalysis, 4_0_ (1999) 9 401-404. Another polyanion suitable for use as the starting compound is, for example, the Dawson or Keggin class. Preferred starting compounds are those which are converted to their oxides at elevated temperatures in the presence or absence of oxygen and which may release gaseous compounds. The fluid heat treatment itself therefore takes hours to days. Usually 4 8 hours. Preferably, the application technique is to coat Teflon inside an autoclave intended for use as a fluid heat treatment. If necessary, the autoclave containing the liquid aqueous mixture may be evacuated prior to fluid heat treatment. An inert gas (N 2 'rare gas) can then be filled before the temperature rises. The two measurements can also be omitted. The aqueous mixture can also be flushed with an inert gas prior to heat treatment of the fluid. For the above-described application techniques, an inert gas system is used to generate a superatmospheric pressure in the autoclave prior to heat treatment of the fluid. Newly formed during the heat treatment of the fluid, and solid after the fluid heat treatment (after the fluid heat treatment, the autoclave can be cooled to room temperature, or slowly lowered to room temperature, even if it is allowed to stand for a relatively long period of time) The desired treatment is preferably carried out at 350 to 700 ° C, usually 400 to 650 ° C or 400 to 60 (TC), which can be carried out in an oxidation, reduction or inert gas. Suitable oxidizing gases are, for example, air, Molecular oxygen-rich air, or oxygen-deficient air. Better -18- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7

Gas 2 = in a gas: 'that is, for example, a gas molecule and/or a rare gas. Of course, the heat treatment can also be carried out at a low pressure. If heat treatment is carried out in a gas, the gas may be a stationary biting gas. #把;' Usually, heat treatment can be carried out for 24 hours or longer. # Heat treatment is preferably in the range of 150 to 4:, or 25 to 35. (:, first in an oxidizing (oxygen) gas (for example, in air). The heat treatment is further carried out in an inert gas at 350 to 7 ° C or 400 to 650 ° C or 400 to 600 ° C. The heat treatment of the catalyst precursor generated by the heat of the mud can also be carried out in this manner, that is, the precursor material is first ingot, heat treated, and then converted into pieces. In the application technique, the solid prepared in the fluid heat treatment is more It is good to be converted into fragments for subsequent heat treatment. 'The stomach is used in the preparation of the multimetal oxide material (1). The starting compound used is the same as that used in the preparation of the multimetal oxide (I), and is generally dry mixed. The heat treatment of the composite is carried out in the same manner as the solid prepared by heat treatment of the heat treatment fluid, and the multimetal oxide material (I) generally has a high selectivity for the formation of acrylic acid, and the catalyst is heterogeneously catalyzed under the same conditions. The gas phase oxidation to acrylic acid also has a high activity. The multimetal oxide material (I) can be converted (for example, pulverized into powder or chips) or can be converted into a molding before use. The catalyst can be solid. Bed, moving bed or fluidized bed. The X-ray diffraction pattern of the multimetal oxide material (I) is thus substantially equivalent to ΕΡ-Α-0 529 853, DE-A 198 35 247 and ΕΡ-Α-0 608 838. The multi-metal oxide material (I) can also be used in a state diluted with, for example, a fine colloidal material such as cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, or oxygen. CNS) A4 specification (21GX 297 public) 1269789 A7 B7 V. Description of invention (17 The overall dilution ratio may reach 9 (diluent): 丨 (active material). It means that the possible overall dilution ratio is also 6 (diluent) :i (active material) and release agent: 1 (active material). The diluent can be added before and/or after calcination. Therefore, the diluent is added before the heat treatment of the fluid. If it is added before calcination, it needs The diluent is selected to be substantially recovered during the calcination process. The same fluid heat treatment is also carried out in the case of the treatment, such as addition. Therefore, for example, in the case of oxide calcination at a corresponding high temperature, Indeed. Suitable for propane oxidation The medium is a multi-metal oxide material (π), and the material < is of the above formula (1)' and its _-ray diffraction pattern has reflections h, i and k, and its peak 値 is at a diffraction angle (2Θ) 22 · 2±0·4. (h), 27.3±0.4. (1) and 28·2±0·4〇(k), where - reflection h is the highest intensity in the X-ray diffraction pattern, and its half width Not more than 0 · 5 〇, - the intensity of the reaction i and the intensity of the reflection k, pki, are 〇65 ^ r $ 〇85 , where R is the intensity ratio defined by the formula R^Pi/CP. + p^ and - The half width of the reaction i and the reflection k is 1 in each case. . Preferably, '0.67 S R s 0.75 and preferably R = 〇.70 to 0.75 or R = 0.72. The preferred multi-metal oxide material (H) is those in which M1 is Te. Further, among these multimetal oxide materials (II), it is more preferable that M2 is Nb, Ta, W and/or Ti. Preferably, Μ2 is Nb. -20- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1269789 A7 -------______ V. Invention description (18 ) ' ----- Multi-metal oxide material ( 11) The chemical dosage system W is preferably from 〇 to 〇6. In a corresponding manner, the preferred range of the chemical dose coefficient e is (4) illusion or 〇.〇5 to 0.4, and the preferred J of JLd is 〇.〇ι14〇" to 〇6. The most preferred multi-metal oxide material (11) is one in which the stoichiometric coefficient is within the above preferred range. Further, the appropriate chemical dosage of the multi-metal oxide material is disclosed in the above-mentioned prior art, in particular, the disclosure of JP-A 7-53448. A specific method for preparing a multimetal oxide material (11) is disclosed, for example, in PCT-A 11 43314, in which the relevant multimetal oxide material (η) is proposed for use in the combustion of heterogeneously catalyzed oxygen dehydrogenation to ethylene. catalyst. After the slave, a multi-metal oxide material of the formula i-phase and other phases (e.g., k-phase) is first produced in a manner previously known and disclosed in the prior art publication of the description. The proportion of the i-phase in the mixture can be varied by selectively removing other phases under the microscope, such as phase addition, or washing the multimetal oxide material with a suitable liquid. Suitable such liquids are, for example, organic acids (e.g., oxalic acid, formic acid, acetic acid, citric acid, and tartaric acid), inorganic acids (e.g., nitric acid), aqueous solutions of alcohols, and aqueous solutions of hydrogen peroxide. Further, 7-232071 discloses a method of preparing a multimetal oxide material (η). The multimetal oxide material (II) is prepared by the preparation method of DE-A 198 35 247. Accordingly, a very homogeneous, preferably fine, anhydrous blend is prepared from a suitable source of its elemental composition, and the blend is at 35 to 7 ° C, or 4 to 650 C or 400. The heat treatment was carried out at 600 °C. The heat treatment can be carried out in an oxidation reduction or an inert gas. Suitable oxidizing gases are, for example, air, oxygen rich in molecular oxygen, or oxygen deficient air. Preferably, the heat treatment is in the inert gas -21 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7

It is carried out in the body, that is, for example, a nitrogen molecule or a rare gas (four) row. Usually, the heat is carried out at atmospheric pressure (〖atm). Of course, the heat treatment can also be carried out under low pressure or super atmospheric pressure. The right is heat treated in the emulsion' and the gas can be a stationary gas or a flowing gas. Usually, the heat treatment can be carried out for 24 hours or longer. The β heat treatment is preferably carried out first in an oxidized (oxygen) gas (for example, in total gas) at 15 〇 to 4 〇 (rc, or 25 〇 to 35 〇χ:), and then the heat treatment is better than inertia = In the gas, it is between 350 and 700. (: or 4〇〇 to 65〇Ό*4〇〇 to 6〇〇. It is held under the armpit. The heat treatment can also make the catalyst precursor material ingot before heat treatment ( If necessary, after the crushing, and if necessary, adding 5 to 2% by weight of fine graphite), followed by heat treatment, and then conversion to fragments. Preparation of the starting compound in the multimetal oxide material (π) The thorough mixing may be carried out in an anhydrous or wet state. If it is carried out in an anhydrous state, the starting compound is preferably used in a fine powder state, and after mixing, calcination (heat treatment) of any composition is carried out. However, it is preferred to sufficiently mix in a wet state. Generally, the starting compounds are mixed with each other in an aqueous solution and/or a suspended liquid state, and then the aqueous material is dried and calcined after drying. Preferably, the aqueous material is an aqueous solution, or the aqueous liquid is better, and dried. Process system is followed by preparation of an aqueous mixture Spray drying (extrusion temperature is usually 1 〇〇 to 15 〇 1, spray drying can be carried out in the same direction or reverse method), the method requires special uniform dry blending, especially when the aqueous material to be spray dried is an aqueous solution Or a suspension. The source of a suitable starting compound of the multimetal oxide material (π) is the compound of the above description of the multimetal oxide material (I). The multimetal oxide material (11) may be a multimetal oxide material. (1) Pull conversion -22· This paper scale applies to China National Standard (CNS) Α4 specification (210X297 public) 1269789 A7 B7 V. Invention description (2〇) Molded 'can be used in such a way. Multi-metal The oxide material (π) can be formed by coating on a support as described below, or by using and/or ingot, both of which are fine metal oxide materials ( II) and fine precursor materials of multi-metal oxides. In the same manner as the multi-metal oxide material (I), the multi-metal oxide material (II) can also be used in a state of being diluted with a fine material. Spherical, solid The cylinder and the hollow cylinder (annular). The largest shape of the above shape is usually 1 to 10 mm. In the case of a cylinder, the length is preferably 2 to 103⁄4 m' and the outer diameter is preferably 4 to 1 〇. In the case of a ring, the thickness of the wall is usually 1 to 43⁄4 m. The length of the ring-shaped unsupported catalyst may be 3 to 6 mm, the outer diameter is 4 to 8 mm, and the wall thickness is 1 to 2. Mm. However, the size of the annular unsupported catalyst may also be 7 mm X 3 mm X 4 mm, or 5 mm X 3 mm X 2 mm (outer diameter X length X inner diameter). X-ray diffraction pattern The definition of the intensity of reflection is defined herein by the definitions described in De_a 198 3 5 247 and DE_A 100 51 419 and DE_A 100 46 6 72. The Central Bureau of Standards of the Ministry of Economic Affairs, the employee consumption cooperative, prints this meaning when viewed along the axis of the intensity perpendicular to the 2 axis. If a 1 is the reflection peak 1 and B 1 is the X-ray diffraction pattern line, the left side of the a 1 peak is significant. The minimum peak (with reflection shoulder minimum is not considered) and B 2 corresponds to the next significant minimum peak on the right side of a 1 and C1 is a straight line extending from the peak a1 perpendicular to the 2 Θ axis and connecting B 1 and B 2 When the line intersects, the intensity of the reflection 1 is the length of the straight line segment A1 C 1 extending from the peak a 1 to the point C 1 . The minimum peak of performance means that the slope of the curve tangent in the reference region of reflection 1 changes from negative to positive, or -23- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7 _____ B7 V. INSTRUCTIONS (21) The slope approaches the point of 〇, and the coordinates of the 2 β-axis and the intensity axis are used to specify this slope. In this paper, the half-width is equivalent to the length of the straight line segment α1.1 when the straight line segment existing between the two points of the intersection point Η1 and Η2 is parallel to the 2 Θ axis. In each case, Ηι and Η 2 are parallel intersections for the left side of a 1 And the point on the right, and the line of the _ ray diffraction pattern is as defined above. An exemplary procedure for determining the half width and strength is also shown in Figure 6 of DE_A 100 46 672. In addition to the reflections h, i and k, the X-ray diffraction pattern of the catalytically active multimetal oxide material (II) is generally advantageous. Other reflections containing peaks at the following diffraction angles (2 Θ ): 9.0 ± 0 · 4 〇 (1), 6.7 ± 0.4. (〇), and 7.9±0·4〇(ρ) χ The χ-ray diffraction pattern of the catalytically active oxide material of formula (1) has the following reflection of the peak of the diffraction angle (2 β ): 45.2 0·4°(q) 〇 Often, the X-ray diffraction pattern of the multimetal oxide material (II) also contains reflections of 29.2±0·4 ο(ιη) and 35·4±0·4 ο(η). The multi-metal oxide material (II) can be a χ-ray diffraction pattern of 2 Θ = 50.0 ± 0.3. The peak position does not have a reflection, that is, the k_ phase is not included. However, the multi-metal oxide material (11) may also contain a k-phase, and its χ-ray diffraction pattern generally also contains reflections of the following diffraction angles (2 Θ ): 36.2 ± 0.4 〇, and 50.0 ± 0.4. -24- This paper scale applies to China National Standard (CNS) A4 specification (210X297 Gongdong) 1269789 A7 _________B7 V. Invention description (22) If reflection h is the intensity 100, then i, 1, m, η, ο, p and q should have the following strengths at the same strength level: i: 5 to 9 5, often 5 to 80, some examples 1 〇 to 60; 1 : 1 to 30; m: 1 to 40; η : 1 to 40 ; 〇: 1 to 3 0 ; ρ : 1 to 30 and q : 5 to 6 0. The right X ray diffraction pattern contains additional reflections other than those described above, and its half width is usually S 1 . . In this paper, all data based on X-ray diffraction pattern are used with C u - K to emit radiation as X-radiation (Siemens diffractometer Θ - /9 D-5000, tube voltage: 4 0 k V, tube current: 4 0 mA, pore V20 (variable), collimator V20 (variable), secondary monochromator aperture (〇 · 1 mm), detector aperture (0 6 mm), measurement interval (2 Θ ) : 0 · 02. The measurement time per step: 24 seconds, the detector · · scintillation counter) is related to the X-ray diffraction pattern generated. The specific surface area of the multimetal oxide material (II) is usually 30 m 2 /g (BET surface area, nitrogen). Another catalyst suitable for propane oxidation is a catalyst (III) comprising a support and a catalytically active oxide material of the above formula (I) coated on the surface of the support, preferably oxidized by the formula (I) The material is M1 is Te. Further, it is preferable that M2 is Nb, Ta, W and/or Ti. Preferably, M2 is Nb. -25- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1269789 V. Description of invention (a) Catalyst (III) The chemical dose coefficient b of the multi-oxide material of formula (I) is preferably 0^1 to 0.6. In a corresponding manner, the preferred range of the stoichiometric coefficient 〇 is 0.01 to 1 or 0.05 to 0.4, and the preferred d of d is 1 to 〇.6. The most preferable metal oxide material (11) is one in which the chemical dose coefficient b, C & d are both within the above preferred range. Furthermore, the appropriate chemical dosage of the oxide material of formula (I) is disclosed in the above publication, in particular ΕΡ-Α-0 608 838, WO 00/29106, JP-A 11/16q71a and EP-A-0 962 Revealed in 253. It is also preferable to apply the above-mentioned multimetal oxide material (H) which is an oxide material of the formula (I) to a support for preparing a catalyst (ΙΠ). The support is preferably chemically inert, i.e., it does not substantially play any role in the catalytic gas phase oxidation of propane to acrylic acid. The most suitable support materials are alumina, cerium oxide, cerium salt such as limestone, kaolin, stearate, pumice, aluminum silicate and magnesium silicate, lanthanum carbide, zirconium dioxide and cerium oxide. The surface of the object can be smooth or rough. The surface of the support is preferably crude, as high surface roughness generally increases the adhesion of the coated active material coating. Typically, the support has a surface roughness R of from 5 to 200 microns and is typically from 2 Å to 100 microns (according to DIN 4?68, sheet !, using D1N-ISO measuring surface available from H〇mmd (Germany)) The variable Hommel tester measures. Further, the support material may be porous or non-porous. The support material is preferably non-porous (the total pore volume is $1% by volume based on the volume of the support) 〇 This paper scale is suitable for Guansuixian (CNS) A4 specification (2lGX297 Gongdong) -26- 1269789 A7 _ _B7__;__ V. Description of invention (24) The thickness of the coating of active oxide material present on the coating catalyst is usually It is from 10 to 1000 mm. However, it may also be from 50 to 700 microns, from 100 to 600 microns or from 300 to 500 microns, or from 150 to 400 microns. Possible coating thicknesses are also from 10 to 500 microns, from 100 to 500 microns. Or 150 to 300 microns. In principle, any desired shape of the support can be applied. The length direction is usually from 1 to 10 mm. However, the support is preferably a sphere or a cylinder, especially a hollow cylinder (ring The support ball preferably has a diameter of 1.5 to 4 mm and is used as a support. The length of the cylinder is preferably from 2 to 10 mm, and the outer diameter thereof is preferably from 4 to 10 mm. If it is annular, the wall thickness is usually preferably 4 mm. The length of the appropriate annular support is also preferably 3 to 6 mm, outer diameter 4 to 8 mm, and wall thickness 1 to 2 mm. However, the measurement of the annular support may also be 73⁄4 m X 3 mm X 4 mm, or 5 mm X 3 mm X 2 mm (outer diameter) X length X inner diameter) The preparation of the catalyst (III) can be carried out in a very simple manner by a pre-formed active oxide material, which is then turned into a fine state and finally coated with a liquid binder. The surface of the support is carried out. Therefore, the surface of the support is wetted with a liquid binder in a very simple manner, and the active material is made by contacting the surface with a fine active oxide material of the formula (I). The coating adheres to the wetted surface. Finally, the coated support is dried. Of course, the process can be repeated after a period of time to thicken the thickness of the coating. At this point, the coated structure becomes a new support. Material, etc. Catalytic active oxidation of formula (1) to be applied to the surface of the support The thickness of the material is suitable for the desired coating thickness. For example, at least 50% of the total number of powder particles pass through the screen size of 1 to 2 microns and the longest dimension exceeds 5 inches.

1269789

The active material powder having a particle ratio of less than 10% is suitable for a coating having a thickness of from 1 Å to 10 μm. In principle, the distribution of the largest size of the powder particles corresponds to the Gaussian distribution produced during preparation. In order to carry out the coating method on an industrial scale, the process principle disclosed in 〇 96 71 is preferably used. Among them, the support to be coated is firstly placed at a good inclination (the inclination angle is in principle, and $9〇◦, usually $3〇. to S90. The inclination angle is the angle of the central axis of the rotating container with respect to the horizontal) Rotating in a container (such as a turntable or paint bucket). The rotating container delivers, for example, a spherical or cylindrical support to two metering devices that are separated by a specific distance. The first of a metering device preferably corresponds to a nozzle (e.g., operating with compressed air &lt;sprinkler nozzle) through which the spray is rolled into a support in the carousel and is wetted by a liquid binder in a controlled manner. The second dosage device is positioned outside of the spray cone that is sprayed with the &lt;liquid binder and is used to feed the fine oxide active material (e.g., via a rocking belt or powder spiral). The support ball that is wetted in a controlled manner will grasp the supplied active material powder, and when it rolls, the coating will adhere tightly to the surface of the support such as a cylinder or a sphere. If necessary, the support that is sprayed in a compact manner can be passed through the spray nozzle. After one pass, it is wetted in a controlled manner so that it can adhere to other parts of the fine oxide active material in another movement, and so on (the principle does not require intermediate drying). Subtle oxide active materials and liquid binders are in principle continuously and simultaneously fed. The liquid binder can be removed by the action of, for example, a heat exchanger, such as N2 or 2 gas, after termination of coating. The coating method is known as continuous coating of the two and -28 - the paper scale is suitable for the country (four) quasi (four) ten Μ specifications (four)> <297 public love) 1269789 A7

Continuous application of other primers to the surface of the support provides satisfactory adhesion. ^ The above coating step is important for the wetting of the surface of the precoated support in a controlled manner. In short, it means that the surface of the support to be coated is preferably wetted to absorb the liquid binder, but not on the surface of the support. If the surface of the support is too wet, the fine active oxide material is prepared as a separate agglomerate rather than deposited on the surface. The details of this document are found in DE-A 29 09 671. The final removal of the liquid binder used above can be carried out in a controlled manner, such as by evaporation and/or sublimation. In the simplest case, it can be carried out by the action of a hot gas having a temperature τ of usually 50 to 30 (TC, and often 15 〇 1).炊&amp; and, if only pre-drying, can be carried out by hot gas action. The final drying can be carried out, for example, in a drying oven of any type (e.g., a conveyor dryer) or a counter. The temperature used in the preparation of the oxide active material should exceed the calcination temperature used. Of course, drying can also be carried out in equipment other than the drying oven. Regardless of the type and shape of the support, the following bonding agents can be used in the coating process: water, monohydrogen alcohols such as ethanol, methanol, propanol and butanol, polyalcohols such as ethylene glycol, U4-butanediol,丨, 6-hexanediol or glycerol, monobasic 1 polybasic organic carboxylic acid, propionic acid, oxalic acid, malonic acid, glutaric acid, or maleic acid, amino alcohol such as ethanolamine or diethanolamine, and single A functional or polyfunctional organic guanamine such as formamide. Preferably, the binder is also contained in an amount of from 2 to 9 % by weight of water and from 1 to 80% by weight in water, and its atmospheric pressure 下 - lower point or sublimation point is &gt; 100 ° C 'better> 15 ( TC's organic component solution -29 _ This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) --:------- 1269789 A7 B7 V. Invention Description-&quot;) &quot; ~--- The salty organic compound is preferably selected from the above-mentioned possible organic binders. The organic fraction of the above organic ubiquitin agent is from 10 to 50, preferably from 20 to 30 weight ❶/❶. The organic components used in C are monosaccharides and oligosaccharides such as glucose, fruit, sucrose or lactose, and polyethylene oxide and polyacrylate. The preparation of the catalytically active oxide material of formula (I) can be carried out in a manner known in the prior art, i.e., can be carried out, for example, in fluid heat and in a general manner. In one of the latter cases, the catalytically active oxide material of formula (1) is prepared by a suitable source of a very homogeneous &lt;RTI ID=0.0&gt;&gt; °C or 400 to 650X: or 400 to 60 (rC; heat treatment. The heat treatment can be carried out in the multimetal oxide material (π) as described above. The sufficient mixing of the starting compound in the multimetal oxide material (π) In the above, the above-mentioned preparation step of the catalytically active oxide material of the formula (I), the source of the appropriate elemental constituents in the example of the multimetal oxide material (1) is as described above. a starting compound or a source thereof. Preferred is a coated catalyst having a multimetal oxide material (II) as a catalytically active oxide material of the formula (I). However, 'substantially an amorphous structure, And in the X-ray diffraction pattern, the state (I) active oxide material of WO 00/29106 having a broad reflection of the peak 値 at a 2 β angle of about 22 and about 27. is also suitable for manufacturing. Coating the catalyst. However, 'in the X-ray diffraction pattern 2 The position of the peak is 22 1 +〇3. , 28.2±0.3, 36.2 soil 03, 45.2±0.3, and 50·0±0·3. ΕΡ-Α-0 529 853 and ΕΡ-Α-0 608 838, formula (1) Active oxide material is also applicable. -30- This paper scale is applicable to China National Standard (CNS) Α4 specification (210 X 297 mm) 1269789 A7 B7 V. Invention description (28) ——&quot; Coating The catalyst can be applied not only to the active oxide material by applying the final fine active oxide material of formula (1) to the surface of the wetted support, but also to apply the fine precursor material to the wetted support. Surface (using the same coating method and binder) and calcined after drying of the coated support. Such suitable fine precursor materials are, for example, first oxidized by the desired activity of formula (1) The elemental constituent material of the material is prepared. Such a suitable fine front material is a source material of an active oxide material such as oil type (1), which is firstly made into a very uniform, and preferably fine, dry blending. a compound (for example, by spray drying an aqueous suspension or solution of the source) and allowing fine dry blending (If necessary, add 5 to 2% by weight of fine graphite in the ingot) at 15 to 350X, preferably from 250 to 35 (at rC, in an oxidized (oxygen) gas (for example, in air) The heat treatment is carried out for several hours, and if necessary, it can be subjected to final grinding. After the precursor material is coated with the support, it is calcined, and preferably in an inert gas (all other gases are also suitable), at 36 〇 to 7〇 (rc or 400 to 650X: or 400 to 600X: under the above &lt; Multi-metal oxide material or as a catalytic active oxide material including a multi-metal oxide material catalyst (π) touch The medium (ΠΙ) can also be used to oxidize propane. Herein, propylene can be oxidized in the presence of propane. If propane is used as the diluent gas, part of the propane can also be oxidized to acrylic acid. There are no restrictions on the step of propane oxidation. It can be carried out according to all methods known to those skilled in the art. For example, the method described in 6 〇 8 838 or WO 00/29106 can be used, that is, the catalyst and its reaction temperature are, for example, 200 to 550 C or 230 to 480 ° C or 300 to 440 ° C in the step ( c) The composition of the gas B in the middle is as follows: · 31 - This paper scale is suitable for the goods (UisJS) A4 specification (210X297^^) 1269789 A7 B7 V. Invention description (29) 1 to 1 5, Preferably, 1 to 7 vol% of propane, 4 4 to 9.9 vol% of air, and 0 to 55% by volume of vapor. Other possible compositions for feeding the gas mixture of the gas B in the step (c) are: 70 to 9.5 vol% of propane, 5 to 30,000 vol% of molecular oxygen, and 0 to 25% by volume of vapor. The plate heat exchanger reactor described in DE-A 199 52 964 is also suitable for the oxidation of propane. In another embodiment of the invention, the oxidation of propane is carried out according to the method described in DE-A 198 37 517, DE-A 198 37 518, DE-A 198 37 519 and DE-A 198 3 7 520. The product gas mixture leaving the propane oxidation and/or propane oxidation in the novel process step (c) does not exclude the inclusion of the desired product acrolein and/or acrylic acid, but in principle comprises acrolein and/or acrylic acid, not Molecular oxygen, propane, propylene, molecular nitrogen, vapor formed as a by-product and/or continuously used as a diluent, formed as a by-product and/or continuously used as a diluent oxide, and a small amount of other lower aldehydes , hydrocarbons and other inert gases. The desired product, acrolein and/or acrylic acid, can be separated from the product gas mixture in a manner known per se, for example by azeotropic separation, fractional distillation (solvent or non-agent A) or crystallization. Suitable for example, partial condensation of propionate, absorption of propionate in water or high boiling hydrophobic organic solvent, or attachment of acrolein to water or aqueous solution of lower carboxylic acid, followed by processing of the absorbent, The product gas mixture can also be partially condensed, for example, Ep_A_〇1 7-32- This paper size is applicable to the standard B (standard) (CNS) Μ specification (21G>&lt;297 dongdong)--- - 1269789 A7 B7 5. Description of the invention (30) 146, DE-A 43 08 087, DE_A 43 35 172, DE_A 44 36 243, DE_A 199 24 532 and DE_A 199 24 533 In the best specific example of the novel method, step (c) After the desired product has been taken and separated, in steps (a) and (b), unreacted propane and/or propylene are separated from the remaining gas mixture in accordance with the invention and recycled to step (c). The gas mixture A used in the step (a) of the novel process may also be a gas mixture having a composition of a gas mixture prepared by catalytically dehydrogenation of propane to propylene. Herein, dehydrogenation can also be carried out by oxidation, i.e., with or without oxygen supply, especially without substantially supplying oxygen. When oxygen is supplied for dehydrogenation, there are two differences. In one case, all of the hydrogen formed by oxidation of excess oxygen, so that the product gas no longer contains any hydrogen, but contains excess oxygen (oxidative dehydrogenation). In the second case, only enough oxygen is added to supply the reaction, so the product gas does not contain oxygen, but may contain hydrogen (self-heating step). Dehydrogenation of propane can be carried out catalytically or homogeneously (uncatalyzed). The dehydrogenation of propane can be carried out, for example, as described in DE_A 33 13 573 and ΕΡ-Α-0 117 146. In principle, the dehydrogenation of oxidative propane can be carried out by molecular oxygen, such as propane homogenization and/or heterogeneous catalytic oxygen dehydrogenation to propylene. If the first reaction zone is designed for homogeneous oxygen dehydrogenation, it can in principle be as 118-83-3 798 283, CN_A_1 105 352, Applied Catalysis 70(2) (1991), 175-187, Catalysis Today (1992), It is carried out as described in 673-678, and DE-A-1 9 6 22 33 1, but it is also possible to use air as a source of oxygen. The temperature of homogeneous oxygen dehydrogenation is preferably selected from 300 to 700 ° C, preferably from 400 to -33 - This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 _ B7 V. Description of invention ( 31) 600 ° C, and preferably 400 to 500 ° C. The operating pressure can be from 0.5 to 100, especially from 1 to 10 bar. The residence time is usually 0.1 or 0.5 to 20, preferably 0.1 or 0.5 to 5 seconds. The reactor used may be a tubular furnace or a tube bundle reactor, such as a reverse flow tubular furnace in which a discharged gas is used as a heat transfer medium, or a tube bundle reactor in which a salt melt is used as a heat transfer medium. The ratio of propane to oxygen in the starting mixture is preferably from 0.5:1 to 40:1, especially from 1:1 to 6:1, preferably from 2:1 to 5:1. The starting mixture may also comprise substantially inert ingredients such as water, carbon dioxide, carbon monoxide, but noble gases and/or propylene, which may also be recycled components. In this paper, the components recycled to stage (a) are referred to as recycle gases. If the dehydrogenation of propane is designed as a heterogeneously catalyzed oxygen dehydrogenation, in principle, for example, US-A 4 788 371, CN-A 1073893, Catalysis Letters 23_ (1994), 103-106, W. Zhang, Gaodeng Xuexiao Huaxue Xuebao 1 4 (1993), 566, Z. Huang, Shiyou Huagong 2 1 (1992), 592, WO 97/36849, DE-A 197 53 817, US-A 3 862 256, US-A 3 887 631, DE -A 195 30 454, US-A 4 341 664, J. of Catalysis Ml (1997), 560-569, J. of Catalysis 167 (1997), 550-559, Topics in Catalysis i (1996), 265-275 , US-A 5 086 032, Catalysis Letters 10. (1991), 181-192, Ind. Eng. Chem. Res. 35. (1996), 14-18, US-A 4 255 284, Applied Catalysis A: General 100 (1993), 111-130, J. of Catalysis 148. (1 994), 56-67, V. Cortes Corberan and S. Vic Bellon (Ed.), New Developments in Selective Oxidation II, 1994, Elsevier Science BV ·, page 3 0 5 -3 1 3, 3rd World Congress on -34- This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1269789 A7 B7 V. Invention description (32)

Oxidation Catalysis, R.K. Grasselli, S.T. Oyama AM

Gaffney and J.E. Lyons (Ed.), 1997, Elsevier Science B V, p. 375, et al. • Air can also be used as an oxygen source. Preferably, however, the source of oxygen comprises at least 90, more preferably 95 mole percent oxygen, to 100 moles. / ❶ Oxygen source meter. There is no particular limitation on the catalyst suitable for the heterogeneous oxygen desorption. All oxygen dehydrogenation catalysts known to those skilled in the art and capable of oxidizing propane to propylene are suitable. In particular, all of the oxygen dehydrogenation catalysts listed in the above publications can be used. Preferred catalysts include, for example, oxygen degassing catalysts including Mo VNb oxide or pyrophosphate, and all have a getter. Particularly suitable catalysts are catalysts of mixed metal oxides including v Te, yttrium and X as important components, wherein X is selected from the group consisting of saying, narration, tungsten, lanthanum, aluminum, lanthanum, chrome, arsenic, iron, and , alum, nickel, palladium, platinum, rhodium, ruthenium, boron, indium and bismuth. Other particularly suitable oxygen dehydrogenation catalysts are the multi-metal oxide materials of DE-A-197 53 817 or the multi-metal oxide catalyst A, the multi-metal oxide materials listed in the above publication = multi-metal oxide touch Media A is the best. This means that the most suitable active material is the multi-metal oxide material (IV) of the formula IV, Μ^ΜΟ^Μ^Οχ (IV), wherein Μ1 is Co, Ni, Mg, Ζη, Μη and/or Cu, Μ2 is W, V, Te, Nb, P, Cr, Fe, Sb, Ce, Sn and/or "a is 0.5_1·5 'b is 0-0·5 and X is oxygen in addition to formula (IV) The number of valences and the number of frequencies determined by the element. -35-

This paper scale is suitable for agglomeration (CNS) A4 size (x 297 mm) 1269789 Description of invention (33 In principle, the appropriate active material (IV) can be made from a suitable source of its elemental composition; = a very homogeneous, finely dried blend, calcined at 450 to 1 ° C. The appropriate source of the multimetal oxide active material composition is an oxide compound, and / or can, from to; Γ 2: heating compounds converted to oxides. These are especially heart, nitrogen (tetra), formate, oxalate, citrate, acetate, carbonic acid = material = salt, Ammonium salt and/or hydroxide. Preparation of multi-metal oxide material 枓 (IVX starting material can be dry mixed, for example, fine powder, or wet, such as using water as a solvent. Multi-metal oxide material (IV) can be used. The powder is used and formed to obtain a specific catalyst geometry, which can be formed before and after the final calcination. It can also be used to support the catalyst or to apply the preformed inert catalyst carrier to pulverize the active material or precursor. Forming of materials. Traditionally 'usable Porous or single-pore oxidized, oxygen-cut, di-oxidized, zirconia, tantalum carbide or niobate as support materials, may have regular or irregular shape for the support. Oxygen removal from propane heterogeneous catalysis In terms of hydrogen reaction, the reaction temperature is preferably from 200 to 600 ° C, especially from 250 to 500 ° C, more preferably from 350 to 44 (rc, operating pressure is preferably from 0.5 to 10, especially from 1 to 10, more preferably Bar. Operating pressures above 1 bar, for example, [· 5 to 丨〇 bar, are particularly advantageous. As a result, the heterogeneous catalytic oxygen dehydrogenation of propane is carried out on a fixed bed. The latter should be loaded into the tube of the tube bundle reactor. The average residence time of the reaction gas mixture in the catalyst bed is preferably from 0.5 to 20 seconds, as described in EP-A-0700893 and EP-A-0700714, and the ratio of the ratio of propylene to oxygen is Required conversion rate and -36- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1269789

Catalyst selectivity varies and should be self-contained 5 : 1 to 40 : 1, especially from 1:1 to 6 : i , better from 2 : 1 to 5 : 1. As a result, the propane selectivity decreases as the propane conversion increases. Therefore, the reaction of propane on propylene is more efficient than that of propylene and a relatively low conversion of propylene. The conversion rate of propylene is particularly preferably from 5 to 40%, more preferably from i 〇 to 3%. Here, the term propane conversion represents the proportion of propane conversion supplied. The selectivity is particularly preferably from 5 9 to 98%, more preferably from 80 to 98%, and the term selectivity refers to the number of propylene moles produced per propane-converted propane, expressed as a percentage. Preferably, the starting mixture for the dehydrogenation of propylene oxide contains from 5 to 95% by weight of propane, based on 100% by weight of the starting mixture. The starting mixture of the dehydrogenation reaction of the deuterated milk other than propane and oxygen may in turn comprise, in particular, inert ingredients such as water, carbon dioxide, carbon monoxide, nitrogen, inert gases and/or propylene. Heterogeneous oxygen dehydrogenation can also be carried out in the presence of a diluent such as a vapor. Any desired reactor sequence known to those skilled in the art can be used for homogeneous oxidative dehydrogenation or heterogeneous catalytic oxygen dehydrogenation. For example, the reaction can be carried out in two or more stages of introduction of oxygen in a single stage or period. It is also possible to use homogeneous and heterogeneous catalytic oxygen dehydrogenation combined with each other. As for possible components, the propane oxygen dehydrogenation product mixture may contain, for example, the following components: propene, propane, carbon dioxide, carbon monoxide, water, nitrogen, oxygen, ethane, ethylene, methane, acrolein, propionic acid, epoxy B. Alkanes, butane, acetic acid, formic acid, formic acid, propylene propylene and butene. The preferred product mixture of propane oxygen dechlorination is based on 100% by weight of the product mixture in each case, containing: 5 to 10% by weight of propylene, 1 to 2% by weight of carbon monoxide, 1 to 3 parts by weight - 37-

1269789

% carbon dioxide, 4 to 1% by weight of water, up to 1% by weight of nitrogen, 〇 [to 〇 $ wt% acrolein, ... wt% acrylic acid, 〇〇 5 to 〇 2 wt% acetic acid, 0.01 to 0.05 wt% formaldehyde, Weight% oxygen, 〇〇% by weight Other components mentioned above, the balance being propane. By the means, the propane dehydrogenation of the gas mixture A can also be carried out as described in De_a U 13 573 or as described below, in the absence of oxygen in the presence of heterogeneously catalyzed decarburization. The local dehydrogenation reaction mixes the volume, so the conversion can be increased by reducing the product partial pressure. This can be achieved in a simple manner, e.g. by dehydrogenation under reduced pressure or by premixing a substantially inert diluent gas, such as a vapor, which is typically a gas inert to the dehydrogenation reaction. Another advantage of dilution with steam is that the coking of the catalyst used is generally reduced because the vapor reacts with the resulting coke in accordance with the principle of coking gasification. Further, the vapor may be present in the downstream oxidation step (4) as a diluent gas. Alternatively, the vapor may be partially or completely separated (e.g., by condensation) prior to the step, and when the gas mixture thus produced is reused in the oxidation step (c), the proportion of the diluent gas N2 may be increased. Other diluents suitable for the dehydrogenation of propane are, for example, carbon monoxide, carbon dioxide, nitrogen and noble gases such as He, Ne&amp;Ar. All of the diluents listed may be present in their own right or in a very broad mixture. Preferably, the diluent is in principle also a diluent suitable for the oxidation step (c). Generally, it is preferably a diluent which is inert in each stage (i.e., having a chemical change of less than 5, preferably less than 3, and more preferably less than !% by mole). In principle: Dehydrogenation catalysts known from the prior art are suitable for the dehydrogenation of propane. It can also be roughly divided into two groups, that is, the oxidized ones (for example, chromium oxide and/or -38-

1269789 A7 ___ B7 V. INSTRUCTIONS (36) Alumina) and inclusive of at least one deposited on a general oxidative support are in principle compared to precious metals (eg, pins). In particular, W0 99/46039, US-A 4 788 371, ΕΡ-Α-0 705 136, WO 99/29420, US_A 4 220 091, US-A 5 430 220, US-A 5 877 369, ΕΡ- All dehydrogenation catalysts recommended in Α-0 117 146, DE-A 199 37 196, DE-A 199 37 105 and DE-A 199 37 107. In particular, the catalysts of Example 1, Example 2, Example 3, and Example 4 of -£-A 1&quot; 37 1〇7 can be used. These are elements containing 10 to 99.9% by weight of a dioxide hammer, 〇 to 60% by weight of alumina, cerium oxide and/or titanium dioxide, and 0.1 to 10% by weight of at least one element of the first or second major group of the periodic table, An element of the third minor group, an element of the eighth sub-family, bismuth and/or tin, provided that the total weight percentage is 100% by weight. In principle, all reactor types and process variables known in the prior art are suitable for propane dehydrogenation. The description of the process variables is contained in, for example, all of the prior art publications relating to dehydrogenation catalysts. A more detailed description of the dehydrogenation process to which the present invention is applicable is also included in Catalytical Studies Division, Oxidative Dehydrogenation and Alternative Dehydrogenation Processes, Study Number 4192 OD, 1993, 430 Ferguson Drive, Mountain View, California, 94043-5272 U.S.A. The general partial heterogeneous catalytic dehydrogenation of propane is exothermic, i.e., the heat (energy) required to produce the desired reaction temperature is supplied to the reaction gas prior to and/or during the catalytic dehydrogenation process. -39- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 A7 B7 V. Inventive Note (37) Furthermore, due to the high reaction temperature required, the general heterogeneous catalytic desorption of propane Hydrogen forms a small amount of high-boiling, high-molecular-weight organic compounds that contain carbon and deposit on the surface of the catalyst, thereby deactivating the latter. In order to minimize the adverse effects, it is possible to dilute with steam to pass the catalytic dehydrogenation of the propane on the surface of the catalyst at a high temperature. Under the conditions obtained, the deposited carbon is partially or completely removed by the gasification principle of coke. Another possibility to remove deposited carbon compounds is to allow the oxygen-containing gas to pass through the dehydrogenation catalyst at high temperatures, thus burning more or less deposited carbon. The reduction of carbon deposits can also be achieved by adding molecular hydrogen to the propane which is to be catalytically dehydrogenated before it is passed through the dehydrogenation catalyst at a high temperature. Of course, it is also possible to add a mixture of vapor and molecular hydrogen to the propane to be catalytically hydrogenated. The addition of molecular hydrogen to the catalytic dehydrogenation of propane also reduces undesired formation of propadiene and acetylene by-products. The appropriate reaction gaseous state for propane dehydrogenation is a fixed bed tubular reactor or tube bundle reactor. This means that the dehydrogenation catalyst is present in the reaction tube or in a reaction tube bundle in a fixed bed. The reaction tube is heated by burning a gas such as a hydrocarbon such as methane in a space surrounding the reaction tube. Preferably, the direct heating profile of the catalytic tube is about 20 to 30% from the start of the fixed bed, and the other lengths are heated to the desired reaction temperature by the radiant heat released during the combustion process. In this way, an almost isothermal reaction can be achieved. The inner diameter of the reaction tube is about 10 to 15 cm. A typical dehydrogenation tube reactor comprises from 300 to 1000 reaction tubes. The temperature inside the reaction tube is from 300 to 700 ° C, preferably from 400 to 700 ° C. The reaction gas is preferably preheated to the reaction temperature before being fed to the tubular reactor. Typically, the product gas mixture exits the reaction tube at 50 to below 100 °C. In the above steps, -40- This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 B7 5. Inventive Note (38) It is better to use oxidized chrome and/or alumina as the main oxidizing agent. Hydrogen catalyst. Usually, it is not necessary to contain a diluent gas, and nitrogen substantially uses pure propane as the starting reaction gas. Dehydrogenation catalysts are usually used without dilution. On an industrial scale, about three tube bundle reactors are operated in parallel. The second reactor is in principle a dehydrogenation mode, but the catalyst system is arranged in one of its reactors. The above steps are used, for example, in the BASF Linde propane dehydrogenation process known in the literature. Furthermore, it is used in a steam activated re-production (STAR) process by Phillips Petroleum C (for example, see US-A 4 902 849, U SA 4 996 3 87 and US-A 5 3 89 342) Developed. The dehydrogenation catalyst used in the STAR process is preferably platinum containing a promoter on a zinc (magnesium) spinel as a support (for example, see US-A 5 073 662). The pre-dehydrogenated propane in the STAR process is diluted with steam relative to the BASF Linde propane dehydrogenation process. The molar ratio of vapor to propane is usually from 4 to 6. The operating pressure is usually from 3 to 8 atm, and the reaction temperature is preferably from 480 to 620 °C. The general catalyst gas mixture has a typical catalyst loading of 0.5 to 10 1Γ1. Propane dehydrogenation can also be designed as a moving bed type. For example, a moving catalyst bed can be encapsulated in a radial flow reactor. The catalyst slowly moves from the top to the bottom while allowing the reaction gas mixture to flow radially. This step is used, for example, in the UOP Oleflex dehydrogenation process. In the dehydrogenation process, because the reactor in the process is semi-insulated, many parallel reactors (typically four seats) can be operated. This avoids excessive temperature differences in the reaction gas mixture at the reactor inlet and at the reactor outlet (in the case of insulation mode operation -41 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 B7 __ 5. Inventive Note (39), the starting mixture of the reaction gas is shaped like a heat transfer medium having a heat content associated with the reaction temperature, and does not achieve a favorable overall conversion. When the catalyst bed leaves the moving bed reactor, it is regenerated and reused. For example, a spherical dehydrogenation catalyst of platinum substantially comprising a spherical alumina support can be used as the dehydrogenation catalyst for the process. Another form of U0P is the addition of rhodium to the propane to be hydrogenated to prevent premature aging of the catalyst. The operating pressure is typically 2 to 5 atm. The molar ratio of moir hydrogen to propane is preferably from 1 to 1. The reaction temperature is preferably from 550 to 650 ° C, and the contact time of the catalyst with the reaction gas mixture is selected from about 2 to 61 Γ 1 . In the fixed bed process, the shape of the catalyst can also be spherical or cylindrical (hollow or solid). Another form of propane dehydrogenation is Proceedings De Witt, Petrochem. Review, Houston, Texas, 1992a, N1, which is stated in a fixed foot bed to make the undiluted propane heterogeneity catalyze the possibility of propane dehydrogenation. Preferably, the two fluidized bed systems operate in close proximity, one of which is in principle a regenerative state. The active material used is chromium oxide on alumina. The operating pressure is usually from 1 to 1.5 atm, and the dehydrogenation temperature is in principle from 550 to 600 °C. The heat required for dehydrogenation is introduced into the reaction system by preheating the dehydrogenation catalyst to the reaction temperature. The operating pressure is usually from 1 to 2 atm, and the reaction temperature is usually from 55 Torr to 600 °C. The above described dehydrogenation step is also known in the literature, as in Snamprogetti-Yarsintez Process 0. As for the other above step, the heterogeneously catalyzed propane dehydrogenation in the absence of oxygen is based on ABB Lummus Crest (cf. Proceedings De Witt, Petrochem. Review, Houston, Texas, 1992, PI) Method of Development - 42 - This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1269789

The present invention is based on the heterogeneous catalysis of the oxygen-containing heterogeneous catalyzed dehydrogenation of the main towel, which is generally converted to a molar conversion of >3 〇Mol% (in principle (4) Mohr%) (in a single pass through the reactor) Subject to the operation. It is preferably sufficient to convert the indole to <5 to $3(), ^25% by mole. This means dechlorination of propane-butan: in the conversion of propane to 10 to 20 mol% (conversion is carried out by reaction: standard). This is especially due to the fact that the remaining amount of unconverted propane is diluted with molecular nitrogen in the downstream oxidation step (C), thereby reducing the formation of propionaldehyde and/or propionic acid by-products. In order to achieve the above conversion of propane, it is preferred to carry out the depropation of propane at an operating pressure of 0 3 to 3 atm. Preferably, the propane to be dehydrogenated is also diluted with steam. Therefore, the amount of hot water in the water can compensate for part of the dehydrogenation and exothermic effect. On the other hand, dilution with helium can reduce the partial pressure of the starting materials and products, and it has the beneficial effect of balancing the dehydrogenation level. Further, as described above, the presence of steam has an advantageous effect on the time-on-stream of the dehydrogenation catalyst. If you need 'molecular hydrogen, you can add it as another ingredient. Molecular hydrogen on the molar ratio of propylene to S 5 in principle. For relatively low propane conversion, the molar ratio of vapor to propane may be from 30, preferably from 0.1 to 2, and more preferably from 5 to 1. In fact, for a single pass of the reaction gas through the reactor, only a relatively small amount of heat is eliminated and a conversion is achieved for a single pass through the reactor, and a relatively low reaction temperature has proven to be sufficient for the low propane conversion step. Therefore, the dehydrogenation ((semi)insulation) of propane is preferably carried out under relatively low propane conversion, ie the reaction gas starting mixture is in principle heated to 500 to 700 ° C (eg direct combustion of the surrounding walls), or 550 to 650 ° C. Usually, a single adiabatic pass through the catalyst bed is sufficient to achieve the desired conversion, but the reaction gas -43- this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789

V. Description of the invention (41 =:!: but to about 30 to 200 °c (depending on the conversion). Containing steam as a pass, the mussel is even better from the viewpoint of the insulation step. The lower the reaction temperature is The longer the running time of the catalyst bed used (times_Gn kiss eam). The original: upper, regardless of whether it is adiabatic or isothermal operation, propane can be in a fixed bed, should be prepared with a mixed bed or fluidized bed, to a relatively low Dehydrogenation of the conversion of propane. It is straightforward to note that the reaction of the reaction gas mixture in the axially and/or lightly flowing through the solid bed reactor «single (four) reactor is sufficient for carrying out the dehydrogenation, especially the adiabatic operation. In the simplest case, 'this is a single-seal reaction volume, for example an inner diameter of 0.1 to 10 meters, preferably 〇 5 to 5 meters, and wherein the catalyst bed system is on a support device (eg, a grid) The container on the column. The reaction volume filled with the catalyst and thermally insulated according to the adiabatic operation flows axially through the reaction gas containing hot propane. The shape of the catalyst may be spherical, ring-shaped or as a strand. The reaction volume in the system is obtained in an extremely economical device, so all the catalyst shapes are preferred. They are all special low pressure dropers. These are special catalyst shapes that produce large void volumes, or constructors in a structural manner (such as a honeycomb). In order to allow the propane-containing reactive gas to flow, the reactor may comprise, for example, casting. And the two cylinders are placed in one of the other inside, and the catalyst bed can be arranged in an annular gap. In the case of insulation, the metal casting is thermally insulated in sequence. DE-A 199 37 107 The catalysts disclosed therein, especially the catalysts disclosed in the examples, are particularly suitable for single pass through propane dehydrogenation catalysts with relatively low propane conversion. • 44 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 Gongdong) 1269789 A7 --------------B7___ V. Invention 5 ( 42~) &quot; ---~ After relatively long-term operation, the above catalyst can be easily In the first stage, the air diluted, for example, with nitrogen is first passed through the catalyst bed at a pressure of 3 Torr to 6 ° C, usually from 〇 to 50 〇. It can be, for example, 50 to 10000 h-1, and the oxygen content of the regeneration gas can be 〇5. ./ .. Volume 20 further downstream of the regeneration zone, air can be used in other apparatus for the same regeneration conditions regeneration gas application techniques, preferably prior to catalyst regeneration with an inert gas (e.g. N 2) rinsing the catalyst.

After Ik, it is usually preferred to carry out regeneration with pure molecular hydrogen or molecular hydrogen diluted with an inert gas (hydrogen content should be &gt; 1 volume 0 / Torr), and another range of the same conditions. The dehydrogenation of propane (^3 〇mol%) with relatively low propane conversion can in all cases be operated at the same catalyst loading as high propane conversion (&gt; 3 〇mol/〇). The load of the reaction gas in Anhai may be, for example, 1 〇〇 to 10 (9) 〇 1, and usually 100 to 3000 h-1, that is, usually 1 〇〇 to 2000 If 1. The dehydrogenation of propane, which is relatively low propane conversion, can be carried out in an optimal manner in a tray reactor. This will contain more than one catalytic dehydrogenation catalyst bed in a continuous space. The number of the catalyst beds may be from 1 to 20, preferably from 2 to 8, but may also be from 3 to 6. The catalyst bed is preferably arranged in a radial alignment. By means of application technology, a fixed catalyst bed is preferably used in the disk-receiving reactor. In the simplest case, the stationary catalyst beds in the axial furnace reactor are arranged in an axial arrangement or in a circumferential gap of a cylindrical barrier of the copper shaft arrangement on the other side. However, it is also possible to arrange the annular gaps in segments and to allow gas to enter above or below the segments after passing through the segments. -45- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Binding #· 1269789 A7 B7 V. Inventive Note (43) Preferably, the reaction gas mixture is passed from a catalyst bed to a next catalyst bed in a tray reactor by heating it with hot gas. The heat exchanger blades are either intermediately heated by passing them through a tube heated with hot combustion gases. If the tray reactor is additionally adiabatically operated, it is sufficient for the desired propane conversion (幺30 mole%), in particular the catalyst described in DE-A 199 37 107, in particular the specific examples The reaction gas mixture is preheated to a temperature of 450 to 550 ° C before being passed to the dehydrogenation reactor, and is maintained in this temperature range inside the susceptor reactor. This means that the total propane dehydrogenation is carried out at very low temperatures, which proves to be particularly advantageous for the time-on-stream of the stationary catalyst bed of the second regenerant. It is preferable to carry out the above intermediate heating by a direct method (automatic heating step). Thus, a limited amount of molecular oxygen is added to the reaction gas mixture before it flows between the first catalyst bed and/or the downstream catalyst bed. Depending on the dehydrogenation catalyst used, limited combustion of the hydrocarbons contained in the reaction gas mixture, formation of propane dehydrogenation, and/or addition of any coke deposited on the catalyst surface to the reaction gas mixture, or coke Catalysts and/or hydrogen, combustion catalysis (which is preferably also introduced into the reactor bed by (selectively) catalyzed hydrogen (and/or hydrocarbon) combustion by application techniques (such suitable catalysts are for example US-A 4 788 371, US-A 4 886 928, US-A 5 430 209, US-A 5 530 171, US-A 5 527 979 and US-A 5 563 3 14, such a catalyst bed can be packaged Sealed in the tray reactor to change the bed containing the dehydrogenation catalyst. The reaction heat thus released can actually be dehydrogenated by isothermal catalyzed propane dehydrogenation according to the semi-automatic heating mode. When the residence time of the selection increases, it is possible that the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 B7 V. Inventive Note (44) The temperature of propane dehydrogenation is lowered or substantially constant It can especially lengthen the running time in the second regeneration room (long times-on-str Eam). In principle, oxygen should be fed as described above, so the oxygen content in the reaction gas mixture is 0.5 to 10% by weight based on the amount of propane and propylene contained therein. Suitable oxygen source is pure molecule. Oxygen and oxygen diluted with an inert gas such as CO, co2, N2 or a rare metal, especially air. The resulting combustion gas usually has an additional dilution effect and thus promotes heterogeneously catalyzed dehydrogenation of propane. The isothermal nature of hydrogen can be achieved by placing a sealed content (e.g., a ring), preferably but not twitching, into the space between the catalyst beds in the tray reactor prior to introduction. Placed in individual catalyst beds. These contents contain suitable solids or liquids that evaporate or dissolve above a certain temperature, and thus consume heat and condense, and thus release heat, causing the temperature to fall below this temperature. One possibility of heating the reaction gas mixture to the desired reaction temperature in dehydrogenation is also to consume a portion of the propane and/or H2 contained therein by molecular oxygen (eg, in a suitable combustional touch with a specific effect) Above, for example, by simple passage and/or passage, and by the heat of combustion thus released to the desired reaction temperature. The obtained combustion products such as C02 and H20, and any N2 accompanying the molecular oxygen required for combustion are preferably Forming an inert diluent gas. According to the method, it is also possible to carry out propane dehydrogenation of the unconverted propane and optionally propylene after carrying out step (C) and separating the desired product (acrolein and/or acrylic acid), which may be as described above. The step (a) is carried out again for the product gas mixture prepared after dehydrogenation of propane. -47- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm).

Binding line 1269789 A7 B7 V. INSTRUCTIONS (48) Gas streams of other components that can be exothermicly converted (such as C0 or CO/H2 mixtures, such as synthesis gas) are mixed. The purity of these gases is not limited. The exothermic nature of the oxidizing component of PDH can encompass the exothermic nature of the PDH reaction, so less heat can be added externally or, in the best case, no heating is required to cover the enthalpy of the PDH reaction. The PDH is operated at 0.3 to 10, preferably 1 to 5 bar, and 350 to 700 ° C, preferably 400 to 600 ° C. PDH possible reactors are all known to those skilled in the art, such as axial flow devices, such as disk-retaining reactors, and devices that are arranged in a hollow cylindrical state and are a plurality of catalyst beds that radiate, or many independent The device is for example a tubular, dome or sphere device. The number of reactors in the PDH is not limited to three. Preferably, a plurality of reading devices are used, since other gases can be fed in the middle in a simple manner, and thus a more independent catalyst bed can be treated in a special manner, for example regenerated during operation and separated from others. Thus, for example, the reactor containing the catalyst bed to be regenerated is isolated from the main gas stream by means of a suitable closing element, such as a valve or flange in a connecting tube between the sliding valve reactors, and the gas required for regeneration, For example, N 2 , Η 2 , thin air or air or an oxygen-rich gas passes over the catalyst bed and the deposit is removed from the catalyst. It is still fed to the main gas stream in the reactor (which may have a total amount of from 1 to 20, preferably from 2 to 5) and mainly produces the desired product propylene. In a PHD reactor, the catalyst layer can be left on the barrier, a bed of inert material, or a similar support device known to those skilled in the art. There is no limit to the type of catalyst. For example, fragments, spheres, extrudates, rings, cylinders or structural fillings and single crystal types can be used. These shapes are preferably those that provide a small pressure drop. • 51 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1269789 A7 B7 V. Invention Description ------- For the distribution of gas fed to the catalyst bed, you can use the familiar version. Gas distributors known to the skilled artisan, such as screen trays, annular distributors or manifolds, and irregular beds or structural fillings, such as static mixers. A plurality of catalyst layers having different functions can be arranged in the PDH reactor. If a multi-catalyst layer is used, it is preferred to arrange one or more layers of the catalyst layer before the PDH catalyst layer and preferably oxidize thereon, for example, in addition to propionate or propylene, 2. C 0 and/or others. Oxidized component (C0_PC4H2-PC). However, it is also possible to apply an additional catalyst layer upstream of the PDH catalyst layer if the PDH catalyst is economically acceptable to perform this function or propane oxidation loss propane. The PDH catalyst can be operated at a rate of from 1 Torr to 2 Torr per liter of the catalyst bed per hour, preferably from 5 Torr to 10,000, more preferably from 1 00 to 10,000 liters (8 τ p). The gas space velocity of the main oxidizing CO or ruthenium 2 and a lesser propane or propylene catalyst is usually from 5 〇〇〇 to 30,000 liters per liter of the catalyst bed per hour (s.T.P.). The conversion of propionyl is from 1 to 60%, preferably from 2 to 50%, at a propane selectivity of from 80 to 99.5%, usually from 88 to 96%. The conversion of the feed gas c〇, A or other combustion gases is better. The conversion of ruthenium 2 formed during the PDH process is from 1 to 99%, often from 10 to 80%, and most usually from 30 to 70%, depending on the propane conversion. The reaction gas (2) from PDH contains about 20 to 60% by volume of ν2, about 1 to 5% by volume of CO 2 , 0.5 to 45% by volume of water, about 5 to 4 % by volume of propane, and about 1 to 20% by volume. Propylene, about 1 to 2% by volume of Ha and other by-products such as ethane, ethylene, methane and (:4+. PDH reaction gas (2) is at 400 to 650 ° C, more preferably 450 to 6 〇 :. (:, and 0.3 to 1 〇, better prepared at 1 to 5 bar. It is a reverse-cycle gas-52- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - ------- 1269789

After a slow-down process, the resulting off-gas stream (15) can be fed to catalytic or non-catalytic waste incineration, or directly to the atmosphere, depending on its purity. Absorbent mainly containing propane (2 to 30% by volume) and/or polypropylene (2 to 3% by volume), and possibly other components (for example, C〇2, C 2·, C 4+, h20) The flow (16) can be slowly programmed (iet_d〇wn) if needed and re-fed into the desorption section K2. The let-down can be carried out in one or more stages without recovering mechanical energy and recovering mechanical energy (for example, by centrifugal pumping with a turbine or reversible operation). Again, it can be used to heat the gas stream (16) prior to desorption. The heating is preferably carried out by reverse phase flow heat exchange with a flow of W 6 (17). Alternatively, it can be used to heat the gas stream (16) above this temperature. The desorption in the K2 of the propylene and/or propylene can be carried out by distillation or simply flashing or stripping. The desorption is carried out by reducing the pressure to 〇1 to 1 Torr, especially 1 to 5, preferably 1.5 to 3. However, if desorption is carried out by distillation, the separation step can be carried out based on all knowledge known to those skilled in the art. The simplest example of desorption is the solvent contained in a flash or flash evaporation in a device suitable for use in an unsuitable manner. Preferably, the gas stream (16) is heated to 20 to 300 ° C, especially 40 to 200 C ', and preferably 5 (^15 〇 0 C) before flashing. The device should be designed to facilitate the firing of C. Or thermal dynamic separation between propylene and solvent, and fluid separation between gas and liquid. The device may be, for example, a cylinder or a sphere, and other designs known to those skilled in the art. If the device is a cylinder, the cylinder may be Vertically or horizontally. In principle, it is fed into the flash unit between the gas discharge and the liquid discharge. In the simplest case, there is no other content in the device. -56- The paper ruler Family standard ^iTlT secret (210 X 297 mm)

装·# 1269789 A7 ___ B7 V. Description of the invention (61 ~~- — burning, 7.4 vol% propylene, 12.3 vol% 〇2, 46.4 vol. 0/(^2, 1.5 vol% water and 1.6 vol% C〇2 And a small amount of fourteen appearances, and passed to the cooling device not at the top of the desorption tower K 2 . The bottom discharge of the desorbed i K 2 is transported via the pump pi and the heat exchanger w 7 To the top of the adsorption tower K1. The cooling device is a metal tower having the same inner diameter of 80 mm and the same filling device as the adsorption tower κ 1. The water cooling system is operated at 3 〇 ° C. Approximately 120 liters of water is placed on the bed. The two-phase liquid mixture is removed from the bottom of the cooling unit and passed to a phase separator. The phase separator has a diameter of 2 mm and a length of 5003⁄4 m and contains the device in separation. A horizontal container of fine braided metal wire fabric in one-third of the flow direction. The aqueous phase removed from the phase separator D丨 is pumped back to the top of the cooling unit. The average hourly removal of 1 gram from the phase separator Fourteen pits' and pass to the fourteen-burn storage tank. The water lost during the cooling process is condensed water (2 1) The gas stream cooled from the water is heated to 2 ° C before the second stage of oxidation. The oxidation takes place in a tube with an inner diameter of 26 mm and a length of 4 m. The first mold tube is filled with 2.7 m ΕΡ-Α. - The catalyst described in 0 575 879, and the second mold tube is filled with the catalyst described in 3 m ΕΡ-Α-0 017 000. Then 315 liters per hour (STP) of air is passed to the first and the first The separation between the oxidation zone and the oxidation reaction gas (26) and the purification of the fetal acrylic acid are described in ΕΡ-Α-0 982 289. According to this method, an average of 440 grams per hour is included. 99.5% acrylic acid crude acrylic acid (27) -64 - This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)

1269789 ^ (8) 0114444 patent application, Chinese manual replacement page (93 years 8 invention description (after the dehydrogenation of propane in Wutian, propane especially le# is the dilution gas in step (C). 疋 § when propane dehydrogenation, or Add propylene to Bu Zhi Niu 2: It can also be said that it will still be pure C-burn and / / ^, 仏, to the gas B in the step (C). When the right dilute is converted to acrylic acid ^ v Ding (〇, the gas leaving the operation can be oxygenated: = acrylic, nitrogen and residual oxygen, also contains and components, such as - carbon oxide, citric acid, formaldehyde, acetic acid with propionic acid. In a specific example, (4) the second component will be catalytically oxidized before the dehydrogenation of the propane..., and the molecular sheep _, 乂 may be added, and the gas is heated in dehydrogenation. The oxidation may be carried out in the post-combustion catalyst. ^丁如氧1化崔崔Support#7卜夕 PH丨P d catalyst, such as R〇-2 0 /1 3 or R〇-20/25 (both from BASF). This July car The specific examples are shown in the following Figures i to 7, which are used to illustrate the invention but are not limiting. Figures 1 to 5 show schematic diagrams of a preferred method, wherein For the sake of simplicity, it does not show all the words and discharges. Figure i shows the adsorption and desorption section ^, the oxidation zone S2 (which is the type of propylene oxidized to acrolein and / or acrylic acid), ^ operation section S3 In Figure 1, propane and propylene (if necessary, residual nitrogen) are used in stage S1 from a suitable absorbent containing propane, propylene, hydrogen and an anaerobic oxide (oxidized stone and carbon monoxide) and possibly A mixture of nitrogen and another hydrocarbon is absorbed and desorbed from the absorbent by air stripping. In this way, hydrogen, carbon oxides, other hydrocarbons, and nitrogen are removed. The gas stream containing propylene and possibly propane is re-fed. In the oxidation zone S2, propylene is oxidized therein to acrylic acid and/or acrylic acid. After the oxidation zone S2, the obtained product is fed into the operation section S3, wherein the obtained product is finely divided and/or propylene fo while. The remaining unconverted. 71836-930804 -48- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)

1269789 Γ——— Patent Application No. 090114444 I Replacement Page of Chinese Manual (93, Factory 5, Invention Description (46) 'One propylene and propylene and carbon oxides and any residual nitrogen and oxygen re-feeding In the other figure, the same reference numerals are used for the same meaning as in Fig. 1. Compared with Fig. 1, the propane dehydrogenation section of Fig. 2 is upstream and can be Oxygenation or non-oxygenation. A gas mixture prepared by dehydrogenation of propane and containing hydrogen, carbon oxides and possibly residual nitrogen and hydrocarbons in addition to propane and propylene is fed to the adsorption and desorption section s1. Compared with Fig. 1, the target 3 contains a propylene oxidation section S22 (propane (4) which is oxidized to acrolein and/or acrylic acid) instead of the propylene oxidation section S2. Θ 4 is in (oxygen or unoxygenated The dehydrogenation section S 4 is carried out after § 3 of the operating section, and the gas mixture prepared in this stage is recycled to the adsorption and desorption section S 1 . Figure 5 shows another preferred embodiment of the process in which oxygen is supplied The lower propane dehydrogenation section S 5 system is downstream of the adsorption and desorption section $1. Figures 6 and 7 show In another preferred method, the method of Figure 6 follows the method of Figure 4. In Figure 4, the propane dehydrogenation section 34 contains three reactions, the first of which is the combustion of carbon monoxide before propane dehydrogenation (PDH) (c 〇_pc), before hydrogen dehydrogenation (PDH), hydrogen post-combustion (H^PC) is carried out in a two-pass flow reactor. These post-combustions are used to supply propane dehydrogenation energy. Propane dehydrogenation reaction The number of reactors is not limited to three reactors. In the propane dehydrogenation section S4, propane is fed via a pipeline (3〇). Air can be fed via line (6). The gas mixture prepared after dehydrogenation of propane is passed through the stage. The heat exchanger W and the compressor V in S 1 are fed to the adsorption tower κ丨 and the desorption column κ 2. After desorption in κ 2, the absorbent is recycled back to the adsorption column K1. Exhaust gas (33) is removed from the process and can be passed to the incineration plant E if necessary. To make the -49 - paper size applicable to China National Standard (CNS) A4 specification (210X 297 public)

Binding

71836-930804 Patent No. 090114444 Chinese manual replacement page (93

DESCRIPTION OF THE INVENTION (47 1269789 The separated propane and/or propylene stream is fed to the oxidation section § 2, which here mainly presents four oxidation reactors. However, the number of oxidation reactors is not limited to this number. The desired product acrolein and/or acrylic acid is then processed in stage s 3 and withdrawn via the official line (3 1 ). Unconverted propane and/or propylene is passed through the official line (3 2 ) to recycle the gas, accompanied by The other gas components that have not been separated are adsorbed and recycled to the dehydrogenation section S 4 of the propane gas. In Figure 7, the circulating gas (丨) in the operating section S 3 (the gas system is in the range of 9 〇C and 0·8 to Prepared at 5 bar and further compressed to a pressure of 2 to 1 bar by the aid of a compressor v ) in a heat exchanger opposite the reaction gas (2) of the propane dehydrogenation zone (pdh) S4 Heating to a temperature of from 1 Torr to 65 Torr. [In the example of Figure 7, the pressures listed are absolute pressures here and below. Suitable compressors are known to those skilled in the art. Specific examples, and are described in detail below. The circulating gas stream (1) contains about 4 〇 to 8 〇 vol% of N 2 , about 1 to 5 vol% C02 '〇·1 to 2 vol% CO, 2 to 5% by volume of oxygen, 〇·5 to 25% by volume of water, other oxidation by-products and about 5 to 40% by volume of unconverted propane and about 〇 1 to 3 vol% of unconverted propylene. Fresh propane (3) and preferably water or steam (4) are mixed with the gas before the channel PDHS4 after heating or after. The applicable fresh propylene is suitable for use. Propane gas or liquid. However, a preferred source of propylene is industrial propane (&gt; 9 〇%, especially &gt; 9.5 %, preferably &gt; 9 8 %, S has a small C4 portion of propylene) or pure Propylene (&gt; 9 9 % propane burn content). The molar ratio of water or vapor to propane in the gas stream is 0.05 to 5, preferably 〇. 1 to 2. It is preferably combined with 1 (5), air (6). ) or oxygen-containing gas and in PDH 71836-930804 -50- This paper scale is suitable for wealth _ home standard (CNS) Α 4 specifications (10) χ tearing public Dong 1269789 No. 090114444 patent application Chinese manual replacement page (Year of the year idy Ϋ job 5, invention description (5 〇 (1) cold to more than the circulating gas (1) inflow temperature of at least 5 ° C, preferably at least 50 C, and better at least 1 〇〇 aC temperature The gas stream (1) 3) is further cooled in one or more stages to about 10 to 60 ° C, depending on the temperature at which the countercurrent heat exchanger W 1 flows out. In the multi-stage cooling, the heat exchanger w 2 can be cooled. The production of the gas or the cooling with air and the cooling in the heat exchanger w 3 can be carried out by air or brine cooling, depending on the temperature level. Depending on the pressure, temperature and temperature in the gas flow (4 3) to (4 d) The water content, the water will condense and separate from the gas stream (45) in the separator ai. Suitable gas separators are all specific examples known to those skilled in the art and suitable for this purpose. The cooled and partially dehydrated gas stream (4 6 ) if necessary is compressed at a pressure from the outlet of the separator A i to a pressure of 50 bar. Compression may or may not be intercooled, in one or more stages. Suitable compressors are all known in the art and are suitable for this purpose, such as reciprocating and rotary compressors, screw compressors, diaphragm compressors, rotary multi-blade compressors, turbo compressors, Centrifugal compressors and rotary piston blowers and centrifugal blowers; however, thirteen-wheel compressor live centrifugal compressors are preferred. The selection criteria for the compressor are the pressure increase and the amount of compressed air flow. The multi-stage compression by intercooling condenses water and possibly other condensable components during the intermediate cooling process and separates from the gas stream during or after the intermediate condensation process described above. The gas stream (7) compressed to the final pressure can be re-cooled in one or more stages as described above, which can be repeated for water to be separated from the gas streams (7) to (9) and any other condensable material. The compressor V 1 can be operated with an electric motor or with a steam or gas turbine. The choice is based on the conditions of the infrastructure. Usually, the most economical is the steam leak 71836-930804 -53- This paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1269789 The 0901 H444 patent has the If one to one Chinese manual replacement page (93^8 fetch &gt; V. Description of the invention (51-wheel drive. All of the cold-reduction flow, for example (1 1 ) _ after pressure increase - and (1 2 ), is cycled to PDH until it is required before entering PDH The ratio of water to propane is reached, and the rest is discharged, and if necessary, incinerated. The condensed stream (丨3) can be evaporated before the circulation is discharged, or can be further processed, such as purification, before the cycle. It can be fed into the adsorption column K 1 , wherein the propane and/or propylene are separated from the gas stream. Here, the gas stream (丨0) is contacted with the absorbent, which can absorb the C3 library and possibly absorb other components. Suitable absorbents are all materials known to those skilled in the art, and the above-mentioned absorbents are preferably used. The gas stream (10) is preferably fed back into the absorbent in many stages. The absorption can be in the range of 丨〇 to 丨5. 〇°C, preferably 20 to 80 ° C, and preferably 30 to 60 t:, and 1 to 50, Preferably, it is carried out at 3 to 30' and preferably at 5 to 20 bar. Suitable absorbents K 1 are all known examples known to those skilled in the art, such as Ding Hermische Trennverfahren; Klaus Sattel, VCH, 1988 (ISBN 3-527) -28636-5), preferably a column having contents. Suitable contents are the same as those known to those skilled in the art, such as sieve trays, dual flow trays, bubble cap holders. , cave deck, lattice retainer, valve retainer or include, for example, rings (eg from Raschig), pau ring, Intalox saddle, Beri saddle, super saddle, super toroidal saddle, Interpack Irregular beds of fillers or wire mesh rings, and construction fillers (eg Sulzer_Kerapak or Sulzer filler BX or CY, or fillers such as Montz, and fillers from other manufacturers). The best is Rasch of Raschig Pak 250.YC. It is preferred to obtain high liquid load or irregular density such as non-structural bed or structural filling. Possible irregularity 71836-930804 -54- This paper scale is applicable to China National Standard (CNS) A4 specification ( 210X 297 mm) 1269789

Patent No. 090114444 _ 々 £ £ EE Chinese Manual Replacement Page (93 years _ 士士令) &quot;&quot;&quot;&quot;&quot;&quot;' — ----—一· _' Office; The date of the opening is (^ --- 岔 degree is the free junction area per m 2 per hour should be greater than 5 〇, preferably greater than 8 〇 m3. The content can be metal, ceramic or plastic, or can include many materials The composition of the bed or filler material is important for the absorbent to fully wet the contents. The air flow ratio between the adsorption and the gas (丨〇) adsorption (24) follows the requirements of its thermal dynamics and The number of theoretical plates, the temperature, the pressure, the adsorption of the absorbent, and the degree of separation required. The general ratio is 1: 1 to 5 〇 · 1, especially 1: 1 to 3 0 : 1, and preferably }: 丨 to 2 〇: 丨 (kg / kg), and the theoretical number of plates is generally 1 to 4 〇, especially 2 to 3 〇, and preferably 5 to 2 〇. The definition of the number of theoretical plates is in the technical literature. It has been clarified, for example, Thermische Trennverfahrenff Klaus Sattel, VCH5 1988, (ISBN 3_527-28636-5). 'The right need to be propane and / or propylene The reduced concentration gas stream (14) is fed to the cooling section to reduce the loss of the absorbent. The mode of operation of the cooling is described in more detail in the desorption of the following desorption section. After leaving any cooling section, the gas stream (14) Can be run down slowly. The degree of slowness (let-d〇wn) can be performed by throttling without one or more segments, or in one or more segments of the gas turbine τ丨, and Recycling mechanical energy. In the case of recovering mechanical energy, it is heated by the gas stream (14) entering the turbine. The gas stream can be catalyzed and non-catalyzed by the combustible and oxidative damage contained in its stream, or Direct heating by external feeding, and indirect combustion by heat under steam or external combustion. Slow process (the mechanical energy obtained in the process can be directly used as one of the driving compressors, preferably V丨 or the auxiliary or main device generating electricity) 71836-930804 -55- This paper size applies to the home standard (CNS) A4 regulation 572_1 () X297 public director) 14444 patent application Chinese manual replacement page (August 93) Five invention description (54 for better thermal dynamics Separation, 孰And the contents of the gas stripping can be placed in the steaming hall and the separator which are known to the cooker. The preferred fluid dynamic separation is the content of the separation used for the above adsorption, such as weaving, weaving; It can be additionally integrated in the flash-based device. The grain in the plate 4 is filled with heat, such as a heating tube coil or a heating step. If necessary, air or new propane or the required two processes in the process can be used: (eg steam, steaming process). However, it is better to use the special case for the purpose of flashing. The volatile component is activated by oxygen and/or propylene (when autumn, two: (2: the milk of the segment is volatilized) All the amount of the gas stripping gas stream (10); Bu absorption === air required for enelic acid or acrylic acid, two: 25) is carried out before or after oxidizing propylene to propene adsorption. The compression can be used in the process of detoxification process, and the gas stream (25) can also contain the gas components from C. Best:: fresh in the outside of the gas or other good in the desorption process , the initial gas flow (= or the same direction feeding into the liquid absorbent. If it is inverse (four), the desorber can be the same as the desorption tower described in the literature for the suction (four) process, if the explosion range is passed, then It is preferably a lateral flow. This is the starting point of the (25) heart for the burning tendency of the mixture of the biased gas mixture and the propane-containing and/or propylene-containing gas stream (18) relative to the burning tendency. Gas mixture containing. 57- X 297 mm when the combustible material is too low to burn) 纸张 fiV to 1269 789 Patent Application No. 090114444 Replacement Page of Chinese Manual (93 years)

DESCRIPTION OF THE INVENTION (55 The two gas mixture is defined herein as being rare, so that when the gas is not combustible, the gas is mixed, and if the body is too lateral flow, then all of the starting gas: and not in the text Into, follow the desorption tower at many appropriate points to guide the second two:: • The gas mixture and the desorption adsorption tower can be arranged vertically or horizontally. When the point is at the point. The combustion component is adsorbed to the adsorption problem before entering the desorption tower. 'The initial gas stream is mixed with the starting gas: it is rich in the way before entering the desorption tower, and the substance (9) such as propane, propylene, methane, B Mixing of alkane, butane, water, etc. 'However, the initial gas stream can also be separated, and the starting gas containing no (iv) or propylene can be passed to the bottom of the desorption column to achieve propane and/or propylene in the adsorbent stream. Excellent consumption, and the starting gas rich in propane and/or propylene is passed to the desorption column zone where a combustible gas mixture can be formed. By pumping (P 1 ) to assist in increasing any reverse flow heat exchange (w 6 ) and pressure, the absorbent stream (17) consumed in propane and/or propylene may be further processed in one or more • (eg, It is cooled in W7 and fed back into the absorber K1 via line (24). Usually multiple stages of desorption can be carried out at all pressures and temperatures. However, it is preferred that the pressure is lower than the pressure of absorption and the temperature is higher than the temperature of absorption. In this case, the pressure is 1 to 5, especially 2 to 3 bar, and the temperature is 20 to 200 ° C, especially 30 to 100. (:, and preferably 35 to 70 ° C. The ratio of the absorbent stream (17) to the initial gas stream (25) follows the thermal requirements and depends on the theoretical plate number, temperature, pressure and the deposition properties of the absorbent. And degree of separation 71836-930804 -58- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)

1269789 ^. 替换090114444 Patent application Chinese manual replacement page (93 43⁄4 month especially 5:1 to 40:1, 'The number of theoretical plates is usually 1 to 2 0. The ratio is usually 1: 1 to 5 Q: 5 is preferably from 1 0: 1 to 3 0: 1 (kg/kg), especially from 2 to 15, preferably from 3 to 1 〇. Usually, the turbidity of the helium gas containing propane and/or propylene starts to flow. It can be fed into the oxidation zone S 2 without further treatment. However, it is better to feed the initial gas stream into another process section in the emulsion to reduce the milk, for example, with the 卩1,1#1 The loss of the adsorbent. The absorbent is used for the oxidation of the rare origin of the weeping 8 -, and the separation of the ceremony can be carried out by all the specific examples known to the skilled person. A specific example of this is to cool the dilute starting gas stream with water. In this case, the water is washed from the absorbent to remove the dilute or the cooling can be at the top of the desorbent, on the liquid receiving material, or in the separation. It is carried out in the apparatus. Those skilled in the art know that the contents of the distillation, adsorption and desorption of the agricultural know-how and the above-mentioned adsorption literature Φ can be loaded. It is used in the cooling device to separate. It can also be used for cooling equipment if it is designed for mixing π % knife. It can be used for water cooling. IV, absorbent, after separating propane and/or propylene, water/absorption The mixture of the agent (19) is fed into the phase separator 01, and the treated initial gas stream (10) can be fed into the propylene oxidation section s 2 after preheating in the knead. The phase cutter can be used by those skilled in the art. All specific examples are known and can be used, for example, in liquid/liquid extraction. The simplest case is a device with or without horizontal or vertical extension of the contents, wherein the organic absorbent phase is separated from the cooling water. The diameter to length ratio can be i: i to i: 1 〇〇, especially 疋 1 · 1 to 1 ·· 1 0 ' and preferably 丨: i to 丨: 3. The device can be grounded or operated using an air cushion. In order to be separated from the organic absorbent, the device can be equipped with a round member and extract the organic phase therefrom. For phase separation, the device can be equipped with 71836-930804 Λ -59 - the paper size is accurate (CNS) Α 4 specifications (210Χ297 Public love) 1269789

904114444 Patent f Replacement page (93^β乐) ^. Contents such as woven fabric rotary phase separators, for example, all of which are known to those skilled in the art for this purpose, coiled crucibles, or converter devices board. Of course, the heart can also be used. After the phase 7 is separated, the separated adsorbate can be recycled to the desorption. If the cloud is required, the cold water in front of the cooling device can be twisted or cooled in the heat exchanger (W9). Well, a large amount of water is circulated by the aid of the pump (..., , ). The appropriate addition density in the cooling device is 2 sm. m free junction area is greater than 3 〇 'especially greater than 5 0 ' is better than $ 〇 ^ 80, but less than 1000, especially less than 500, preferably less than 300 m3 of water. Cooling in the water can be used as a condensate (21) and a dilute acid solution (2 2), from the acrylic acid preparation process In order to avoid increasing the concentration, a portion of the circulating cooling water may be removed by flushing stream (23) and fed to an incineration plant or fed to another disposal (eg, a wastewater treatment plant). The temperature of the gas stream of the oxidation zone S2 (18) at a pressure of 1 to 3 bar &lt;90 C, especially &lt; 70 ° C, preferably also adds water to the gas stream. In a manner known to those skilled in the art, premixing the vapor or saturating the gas stream (18) in a water permeator. The composition of the gas stream treated in this manner is 3 〇 to 7 〇 vol% of N 2, 5 to 20 vol% of Ο: 2 to 15 vol% of propylene, 2 to 40 vol. · 5 to 25 vol% water and containing other ingredients such as c 〇 2, methane, ethane, ethylene and C 4 +. It can be fed into the oxidation zone S 2 as described above or as in the patent literature The disclosure of propylene or acrolein can be carried out, for example, in a Deggendorfer-Werft salt bath reactor according to the prior art, or in other reactors. The first oxidation stage becomes acrolein and the second oxygen 71836-930804 -60- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm). 12697: 090114444 Patent application Chinese manual replacement page (93 years)

</ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> heat. The propylene load is preferably 5 to 35 Torr per liter of the catalyst bed per hour, especially 9 to 3 inches, preferably 1 to 25 liters of 0 butyl p) propylene. The separation of the reaction gas (26) of the acrylic acid with the oxidation stage S2 in the stage S3 can be carried out by using, for example, a high boiling point solvent such as diphenyl and dimethyl phthalate, or by adsorption in water or by borrowing It is carried out by partial condensation. The purification of acrylic acid can be carried out by gas distillation or by azeotropic distillation or crystallization. The method described in Figure 7 is suitable for retrofitting existing work wastes for the manufacture of acrolein and/or acrylic acid, and is used in combination with the new acrylic acid. Unexpectedly, it has been found that no oxidation or oxidation catalysts can cause problems other than the absorbent residue often desired in gas B. Further, any oxidation product which may be formed by the absorbent during the oxidation process does not cause a problem. When the absorbent residue causes problems, in principle, it is not the case that a high boiling hydrocarbon (especially an alkane) is used as an absorbent, which can be removed by, for example, water cooling or adsorption. Surprisingly, therefore, the adsorption can be carried out in a novel manner. The adsorption of propane and/or propylene used herein is substantially easier and more economical to handle than the adsorption used in Japanese Patent Publication No. JP-A-10 363 11. Further, an advantage of the present invention is that the existing use of propylene as a starting material, the factory for preparing acrolein and/or acrylic acid can be converted into a more economical use of a more economical firing as a starting material in a preferred manner. The following examples of preferred embodiments of the novel method are used to illustrate the present invention. 71Θ36-930Θ04-61 -

Chinese manual replacement page (93 4 8 $ -__ ^ , foot ^090114444 patent application _ 5, invention description (59). Example acrylic is prepared by the method shown in Figure 7. The following reference numbers are used 7 related. Put 2090 liters (3.7\?) /}1 at a temperature of 30. (: and the pressure of 1.2 5 &amp; 1* prepared from the operating section S3 of the circulating gas (丨) compressed to 2.0 by the compressor v〇 Bar* and heated to 450 ° C in a heat exchange state W 1 countercurrent to the reaction gas (2) from propane dehydrogenation (pDH). Here and the pressures (bar) listed below are absolute in this example Pressure. Circulating gas stream (1) containing 60.3 vol% n2, 1.2 vol% C 〇 2, 0.5 vol% CO, 3.4 vol% 〇2, 丨.9 vol% water, 32·2 volume 0/〇 propane and 0.4 5% by volume of propylene and other oxidation by-products. Before heating, the fresh propylene (3) and vapor (4) of liter (STP) / h are mixed with the circulating gas stream before entering the PDH. The new propane used is industrial grade propane 9 8% propane content and 100 ppm by weight of C/fraction. The molar ratio of vapor to propane in the gas stream is 0.5. In the first reactor of the reactor, the inner diameter of the reactor is 50 mm. The reactor is designed to be self-heating operation. Each reaction contains '1103⁄4 m of south including extrudate (d = 3亳). Meter, 1 = 5 mm) Catalyst bed. In the 4 reactor, the propane system undergoes a conversion of 2% at a propylene selectivity of 92%. The reaction gas of the PDH (2) contains 44.9 vol. %CO2, 16.9 vol% water, 24.0 vol% propane, 5.8 vol% propylene, 5.6 vol. / Η 2 and small amounts of other by-products such as Ethylene, Ethylene, Ethylene Alkane and C4+. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). Food 090114444 patent application f --------------7^—^ Chinese manual Replacement page (August, 1993, the potential of Yat Chang ▲ ▲, the invention description (6 反应 from the PDH reaction gas (2) is prepared at 520 ° C and 1,5 bar *, and cooled to 30 ° C. An average of about 35 grams of water per hour (丨丨) is condensed. The cooled gas stream (6) is compressed to 7. $ bar in a single stage piston compressor and recooled to 3 〇C; It (1 2 ) Combined with condensate (1 1 ), the knife is steamed and mixed with the circulating gas stream (1). The other part (air stream (2 1 )) is fed for cooling. The rest is discharged. Then 2340 liters ( S . Τ · P) / h gas flow (10) to the bottom of the adsorption tower κ 1 (metal wall, inner diameter = 80 mm, tower height 3 m). 6 〇 vol% of the adsorption column is filled with a filling element of Montz (Montz-Pak type B1). The gas stream (10) contains 53.9 vol% nitrogen, 3.3 vol% carbon dioxide, 44 vol% water '28.8 vol% propane, 7.0 vol% propylene, 6.6 vol% hydrogen and a small amount of other by-products such as ethane, ethylene, methane And C 4+. 35 kg/hr of low-C 3 tetradecane (24) was passed to the top of the adsorption column K 1 at 30 °C. The exhaust stream (14) still contained 1 1 50 ppm by volume of propane and 750 ppm by volume of propylene. The exhaust gas stream (1 4) of the adsorption tower is directly down-pressed to a normal temperature and a normal pressure through a pressure control valve, and is incinerated. The thinner adsorbent stream (16) is removed from the bottom of the column 1 and is down-pressed to 2.4 bar via a pressure control valve and fed to the top of the desorption column K2. The desorption column K2 is the same size as the adsorption column 1 and is filled in the same manner as a filling. 1310 liters (S.T.P.) of compressed air was passed to the bottom of the desorption column at 2.45 bar and 30 °C. The desorption tower is at a constant temperature of 40 °C. Gas leaving the desorption column (2190 liters (8. butyl.?) / 11) contains 30.7 vol% C 71836-930804 -63- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 黛Patent application 090114444?丨y f ], 'd丨 Chinese manual replacement page (August, 1993) ί: 六丨 V. Description of the invention (62) Brief description of the drawings Figs. 1 to 5 show schematic diagrams of a preferred method of carrying out the invention. Figures 6 and 7 show a simplified diagram of another preferred method of carrying out the invention. Schematic diagram symbolic description 1 Recirculating gas 2 Reactive gas 3 Propane 4 Water or vapor 5 Rat gas 6 Line 7 Air flow 8 Air flow 9 Air flow 10 Air flow 11 Condensate flow 12 Condensate flow 13 Condensate flow 14 Air flow 15 Exhaust flow 16 Absorbent flow 17 Absorbent stream 18 treated initial gas stream 19 Water/absorbent mixture 20 Adsorbate 71836-930Θ04 -65- This paper scale applies to China National Standard (CNS) Α4 size (210 X 297 mm) 1269789 .~ _ 090114444 No. Patent Statement Specification Replacement Page (93 years 丫Ά7 JSl; ^ r V. Invention Description (63) ...' 2 1 Condensate 22 Dilute Acid Solution 23 Flushing Stream 24 Adsorption 25 Starting Gas Stream 26 Reaction Gas 27 Crude C Dilute acid 3 0 line 3 1 line 32 line 33 exhaust gas 43 gas stream 44 gas stream 45 gas stream 46 gas stream S 1 adsorption and desorption section S2 propylene oxidation section S3 operation section S4 oxygen supply or unoxygenated propane dehydrogenation section S5 oxygen supply Propane dehydrogenation section S22 Propane oxidation section W Heat exchanger W 1 Reverse flow heat exchanger W2 Heat exchanger 71836-930804 -66- This paper size applies China National Standard (CNS) A4 Specification (210 X 297 mm) 12697鹊090114444 Patent Application Replacement Page (August, 1993) V. Invention Description (64 'Μ脚α; W3 Heat Exchanger W4 Heat Exchange W5 heat exchanger W6 reverse flow heat exchanger W7 heat exchanger W9 heat exchanger P 1 Lipu P2 pump D 1 phase separator V compressor V0 compressor VI compressor V2 compressor K1 adsorption tower K2 desorption tower T 1 gas turbine T2 thirsty wheel A 1 separator A2 separator E incineration plant 71Θ36-930Θ04 -67- This paper scale applies to China National Standard (CNS) Α4 specification (210 X 297 mm)

Claims (1)

Patent Application No. A8 Branch Range Replacement (93 years / »f .ό .) r'^.xt Six patent application scope 1 · / Method for producing acrolein and / or acrylic acid from propane and / or propylene The method comprises the steps of: (4) separating propane and/or propylene by adsorbing a gas mixture A containing propane and/or propylene, in the absorbent, and (b) separating propionate and/or c from the absorbent. _, obtaining a gas B containing propane and/or propylene, and (c) using the gas B obtained in the step (b), converting the propane and/or propylene into a propylene and/or a bupropion acid, and In the absence of oxygen supply between step (8) and step (4), no heterogeneous catalytic dehydrogenation of propane is carried out. 2. The method of claim W, wherein step (4) contains at least propylene and/or propylene, at least A gas mixture A selected from the group consisting of hydrogen, nitrogen and other constituents of carbon. 3. The method of claim 1 or 2, wherein at least one Cs-Cw alkane or Cs is used in step (a) -Cw ene is used as an absorbent. 4. As in the method of claim 13th, the method is (b) in the process of firing, flashing and/or steaming. In step (C), in step (C), the separation of C and / or propylene from the absorbent is stripped. Patent application No. 2 or 2, propylene is oxidized to acrolein and/or acrylic acid. 6 · If oxidized to acrolein and/or acrylic acid by the method of claim 1 or 2, 7 The method of item 6, wherein the multimetal oxide material of the formula (1) is used as the material for propane oxidation in the step (c) (1) MoV5MlcM2H〇r 2 Where M is Te and/or Sb M2 is comprised of Nb, Ta, W Ti λι 7 η ', A1, Zr, Cr, Mn, Ga, Fe, Ru, Co, Rh, Ni, Pd, Pt, La pr 〇' At least one of B, Ce, Sn, Zn, Si and ln elements, bcdn is 0.01 to 1 is &gt; 0 to 1, is &gt; 0 to 1, and is the valence and frequency of the element other than oxygen in (1) The number of decisions. The method of claim 1 or 2, wherein the unconverted broth and/or gamma after the step (4) is separated according to steps (4) and (8), and is recycled back to the step (C). The method of claim 1 or 2, wherein the gas A used in the step (4) has a composition of a gas mixture obtained by homogenizing and/or heterogeneously catalytically denitrifying into propylene. 1 0 。 凊 凊 凊 凊 犯 犯 犯 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第 第U. The method of claim 1 or 2, wherein the step is carried out (after the unconverted propane and optionally propylene are subjected to propane dehydrogenation, and the resulting product mixture is subjected to step (a) again. 1 2 The method of claim 1 or 2, wherein the step (c) is performed immediately after the step (b). 1 3. The method of claim 1 or 2, wherein in the step (b) Water cooling is carried out before and after step (c) to separate the absorbent. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm).