WO2009142245A1 - 酢酸n-プロピルの製造方法 - Google Patents
酢酸n-プロピルの製造方法 Download PDFInfo
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- WO2009142245A1 WO2009142245A1 PCT/JP2009/059285 JP2009059285W WO2009142245A1 WO 2009142245 A1 WO2009142245 A1 WO 2009142245A1 JP 2009059285 W JP2009059285 W JP 2009059285W WO 2009142245 A1 WO2009142245 A1 WO 2009142245A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/283—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- the present invention relates to a method for producing n-propyl acetate by hydrogenation reaction of a raw material liquid containing allyl acetate.
- saturated esters such as n-propyl acetate, isobutyl acetate, and n-butyl acetate are frequently used as solvents and reaction solvents and are industrially important compounds.
- These saturated esters are generally produced by an esterification reaction by condensation of the corresponding alcohol and carboxylic acid.
- the equilibrium state of the reaction cannot be tilted toward the product (saturated ester) side, resulting in a high raw material conversion rate and reaction rate. It is industrially difficult to obtain.
- the latent heat of vaporization of water is extremely larger than the latent heat of vaporization of other organic compounds, there is a difficulty in consuming a large amount of energy for separating water by distillation.
- unsaturated esters containing an unsaturated group such as an allyl group, a methacryl group, or a vinyl group at the alcohol site of the ester are industrially produced through an oxidative carboxylation reaction between a corresponding olefin and a carboxylic acid. Can be produced.
- unsaturated group-containing esters can be produced by reacting the corresponding olefin, oxygen and carboxylic acid in the gas phase in the presence of a palladium catalyst, and there are many known references in this regard.
- Patent Document 1 describes that allyl acetate can be industrially produced in a very high yield and a high space-time yield by reacting propylene, oxygen and acetic acid in the gas phase in the presence of a palladium catalyst. ing.
- Patent Document 2 discloses a method for producing acetic acid-n-propyl by hydrogenating allyl acetate using a hydrogenation catalyst, that is, a nickel catalyst as a hydrogenation catalyst.
- Patent Document 3 describes a method for producing n-propyl acetate using a silica-supported palladium catalyst, an alumina-supported palladium catalyst, sponge nickel, and the like.
- the conversion rate of allyl acetate can be almost 100%, and the selectivity of n-propyl acetate is 99.0% or more.
- the raw material gas consisting of propylene, oxygen and acetic acid is passed in the gas phase in the presence of a palladium catalyst to synthesize allyl acetate, the resulting reactor outlet gas is cooled. It is described that it is separated into a non-condensed component and a condensed component, and the crude allyl acetate liquid that is the condensed component is distilled to obtain an allyl acetate-containing liquid containing allyl acetate from the top of the column. Hydrogenation as a liquid makes it possible to obtain the target product n-propyl acetate.
- the present invention has been made in view of the above circumstances.
- an allyl acetate-containing liquid produced from propylene, oxygen, and acetic acid and obtained through a purification process such as distillation is used as a raw material liquid in the presence of a hydrogenation catalyst.
- the problem is to suppress deterioration of the hydrogenation catalyst to a level that can be used industrially.
- the above-mentioned allyl acetate-containing liquid contains a formyl group-containing compound such as acrolein, propionaldehyde, 2-methylcrotonaldehyde, an acryloyloxy group-containing compound such as acrylic acid, allyl acrylate, and the like.
- a formyl group-containing compound such as acrolein, propionaldehyde, 2-methylcrotonaldehyde
- an acryloyloxy group-containing compound such as acrylic acid, allyl acrylate, and the like.
- the inventors have conceived that the deterioration of the hydrogenation catalyst during the hydrogenation reaction can be suppressed by setting these concentrations contained in the raw material liquid to a certain amount or less, and the present invention has been completed. That is, the present invention relates to the following [1] to [6].
- a method for producing n-propyl acetate by hydrogenation reaction of a raw material liquid containing allyl acetate, wherein the concentration of the formyl group-containing compound and the concentration of the acryloyloxy group-containing compound in the raw material liquid are each 100 ppm by mass A method for producing n-propyl acetate, characterized by: [2] The method for producing n-propyl acetate according to [1], wherein the raw material liquid includes an allyl acetate-containing liquid produced from propylene, oxygen and acetic acid.
- an allyl acetate-containing liquid produced from propylene, oxygen, and acetic acid and obtained through a purification process such as distillation is used as a raw material liquid to carry out a hydrogenation reaction in the presence of a hydrogenation catalyst.
- a hydrogenation catalyst When producing n-propyl, the deterioration of the hydrogenation catalyst can be suppressed to an industrially usable level, so the frequency of catalyst replacement can be reduced and the production cost of n-propyl acetate can be reduced. It becomes.
- FIG. 3 is a process diagram showing an example of a process for producing n-propyl acetate by hydrogenating a raw material liquid containing allyl acetate.
- FIG. 4 is a process diagram showing a process for producing n-propyl acetate by hydrogenating a raw material liquid containing allyl acetate in Examples. It is the graph which plotted the yield retention with respect to the amount of impurities in a reaction feed solution.
- the method for producing n-propyl acetate of the present invention is a method for producing n-propyl acetate by hydrogenating a raw material liquid containing allyl acetate, wherein the concentration of the formyl group-containing compound in the raw material liquid and The concentration of the acryloyloxy group-containing compound is 100 mass ppm or less.
- the raw material liquid is not particularly limited as long as it contains allyl acetate, but hereinafter, allyl acetate-containing liquid produced from propylene, oxygen and acetic acid and obtained through a purification step such as distillation in the present invention. Is used as a raw material liquid, and a case where this is subjected to a hydrogenation reaction will be exemplified and described in detail with reference to the drawings.
- propylene used for the raw material gas here.
- lower saturated hydrocarbons such as propane and ethane may be mixed, it is preferable to use high-purity propylene.
- oxygen is not particularly limited, and may be diluted with an inert gas such as nitrogen or carbon dioxide, for example, air.
- inert gas such as nitrogen or carbon dioxide, for example, air.
- high-purity oxygen particularly oxygen having a purity of 99% or more is used. It is preferable.
- the raw material gas supplied to the reactor 11 contains acetic acid, propylene, and oxygen, and may further contain nitrogen, carbon dioxide, rare gas, or the like as a diluent as necessary.
- the preferred ratio of each gas in the total amount of the raw material gas is 4 to 20 vol% for acetic acid, more preferably 6 to 10 vol%, and 5 to 50 vol% for propylene, more preferably 10 to 40 vol%.
- the ratio is 1 to 7: 0.5 to 2.
- the catalyst charged in the reactor 11 may be any catalyst as long as it has the ability to react propylene, acetic acid and oxygen to obtain allyl acetate.
- a supported solid catalyst containing the following components (a) to (c) is preferable.
- the component (a) may be palladium having any valence, but is preferably metallic palladium.
- the “metal palladium” referred to here is palladium having a valence of zero.
- Metallic palladium can be usually obtained by reducing divalent and / or tetravalent palladium ions using hydrazine, hydrogen or the like as a reducing agent. At this time, not all palladium may be in a metal state. There is no restriction
- soluble salts in water such as nitrates, carbonates, sulfates, organic acid salts, halides having at least one element selected from copper, lead, ruthenium and rhenium should be used.
- chlorides that are easily available and excellent in water solubility are preferable.
- copper is mentioned as a preferable element in the said element.
- copper chlorides include, but are not limited to, cuprous chloride, cupric chloride, copper acetate, copper nitrate, acetylacetocopper, copper sulfate, and the like.
- the component (c) is preferably an alkali metal acetate, and more specifically, lithium, sodium, and potassium acetates can be mentioned. More preferred are sodium acetate and potassium acetate, and most preferred is potassium acetate.
- the amount of the component (c) supported is not particularly limited, but is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the carrier.
- an alkali metal acetate may be added to the reactor 11 by a method such as adding an aqueous solution or a solution of acetic acid to the raw material gas.
- the carrier for supporting the catalyst component is not particularly limited as long as it is a porous substance generally used as a carrier.
- Silica, alumina, silica-alumina, diatomaceous earth, montmorillonite, titania and the like are preferable, and silica is more preferable.
- carrier Specific examples include powders, spheres, and pellets, but are not limited thereto.
- the particle diameter of the carrier is not particularly limited, but is preferably 1 to 10 mm, and more preferably 3 to 8 mm.
- the pore structure of the carrier preferably has a pore diameter of 1 nm to 1000 nm, more preferably 2 nm to 800 nm.
- the method for supporting the component (a), the component (b), and the component (c) on the carrier is not particularly limited, and the component may be supported by any method. Specifically, for example, a method of impregnating a carrier with an aqueous solution of the component (a) such as a palladium salt and the component (b) and then treating with an aqueous solution of an alkali metal salt can be mentioned. At this time, it is preferable to subject the carrier impregnated with the catalyst solution to an alkali treatment without drying.
- the treatment time with the alkali metal salt aqueous solution is a time required for the catalyst component salt impregnated on the support to be completely converted into a compound insoluble in water, and 20 hours is usually sufficient.
- the metal salt of the catalyst component precipitated on the surface layer of the catalyst carrier by the alkali metal salt treatment is treated with a reducing agent to form a zero-valent metal.
- the reduction treatment is performed in the liquid phase by adding a reducing agent such as hydrazine or formalin. Thereafter, the catalyst carrier is washed with water until chlorine ions or the like are not detected, dried, supported with alkali metal acetate, and further dried.
- reaction mode in which propylene, oxygen and acetic acid are reacted in the presence of a catalyst
- a conventionally known reaction mode can be selected.
- the catalyst used it is preferred to do so.
- the above-mentioned supported solid catalyst it is practically advantageous to adopt a fixed bed flow reaction in which the catalyst 11 is filled in the reactor 11 as the reaction format.
- the material of the reactor 11 is not particularly limited, but is preferably composed of a material having corrosion resistance.
- reaction temperature there is no restriction
- the temperature is preferably 100 to 300 ° C, more preferably 120 to 250 ° C.
- reaction pressure There is no restriction
- the raw material gas is preferably passed through the catalyst at a space velocity of 10 to 15000 hr, particularly 300 to 8000 hr in the standard state.
- the reactor outlet gas 12 containing the produced allyl acetate is obtained.
- the reactor outlet gas 12 is fed to the condensate component separation tank 13, and from the bottom of the condensate component separation tank 13, a crude allyl acetate solution 14 containing allyl acetate, acetic acid, and water as main components is present as the condensate.
- the non-condensed component 15 mainly composed of propylene, oxygen and carbon dioxide gas is obtained.
- the non-condensed component 15 is preferably recycled as a reaction raw material from the upper part of the condensed component separation tank 13 to the reactor 11.
- an absorption tower using acetic acid and water as absorption liquids may be provided.
- the crude allyl acetate solution 14 is purified to remove impurities such as by-products.
- a part or all of the crude allyl acetate solution 14 is supplied to the oil / water separation layer 16, and an oil layer containing a large amount of allyl acetate is supplied to the first distillation column 17.
- the 1st distillation tower bottom liquid 18 containing many high boiling components, such as an acetic acid, acrylic acid, allyl acrylate, and diacetates, and the second containing many low boiling components, such as acrolein, propionaldehyde, and water
- One distillation column top liquid 19 is extracted and removed. These removed liquids may be used as boiler fuel, or may be reused by returning to the allyl acetate production process.
- a first distillation column middle distillate containing allyl acetate as a main component that is, an allyl acetate-containing solution 20 is obtained.
- the allyl acetate purity of the allyl acetate-containing liquid 20 is usually 95% or more.
- the concentrations of acrolein, propionaldehyde, 2-methylcrotonaldehyde, acrylic acid, and allyl acrylate contained in the allyl acetate-containing solution 20 are the reaction conditions of the allyl acetate production process and the distillation conditions of the first distillation column 17. Usually, the total amount is 0.1 to 1.0% by mass. Hereinafter, normal operating conditions of the first distillation column 17 are shown. The first distillation column 17 is operated at an operating pressure of atmospheric pressure + ⁇ , and the allyl acetate-containing liquid 20 having an increased purity is distilled from the middle stage of the column in the range of 100 to 110 ° C.
- a first distillation column bottom liquid 18 mainly composed of acetic acid is withdrawn at a column bottom temperature of 120 to 140 ° C.
- components from the top of the distillation column are condensed by a condenser (not shown) to become a first distillation column top liquid 19.
- a part of the liquid may be refluxed to the first distillation column 17.
- the first distillation column top liquid 19 may be separated into two layers, an aqueous layer and an oil layer, and each may be returned as reflux.
- the first distillation column 17 is configured in the range of 20 to 80 actual stages, and the reflux ratio is operated in the range of 1 to 200.
- the allyl acetate-containing liquid 20 thus obtained is then sent to a hydrogenation reactor 21 filled with a hydrogenation catalyst, and separately recycled to the hydrogenation reactor 21, and a hydrogenation reaction. It is mixed with an inert solvent (hereinafter referred to as a diluting solvent, not shown) to obtain a raw material liquid. Then, this raw material liquid is hydrogenated by hydrogen contained in the supply gas 23 as shown in the following formula (2) to generate n-propyl acetate.
- a part of the produced n-propyl acetate is contained in the recycle liquid 22 and recycled as a diluting solvent to the hydrogenation reactor 21, and the rest is contained in the hydrogenation reaction liquid 24. It is supplied to the distillation column 25.
- the entire amount may be supplied to the second distillation column 25.
- the recycle liquid 22 contains unreacted allyl acetate, by-products and the like in addition to n-propyl acetate as a reaction product.
- the supply gas 23 supplied to the hydrogenation reactor 21 may contain an inert diluent gas such as nitrogen or a rare gas, if necessary, in addition to the hydrogen gas.
- the “inert solvent for the hydrogenation reaction” refers to a solvent that does not substantially affect the hydrogenation reaction of allyl acetate.
- the above-mentioned raw material liquid supplied to the hydrogenation reactor 21 has a formyl group (—CHO) -containing compound concentration and an acryloyloxy group (—O—CO—CH ⁇ CH 2) -containing compound concentration of 100 masses each. It is necessary to be below ppm. That is, as a result of investigations by the present inventors, it is possible to suppress the deterioration of the hydrogenation catalyst by keeping the concentration of easily polymerizable substances such as formyl group-containing compounds and acryloyloxy group-containing compounds and reducing substances in the raw material liquid low. It became clear that it was important in terms.
- the polymer when the hydrogenation reaction is continued for a raw material liquid in which at least one of the formyl group-containing compound concentration and the acryloyloxy group-containing compound concentration exceeds 100 ppm by mass, the polymer is coated on the surface of the hydrogenation catalyst, resulting in catalytic activity. Reduce. When the catalytic activity decreases, the conversion rate of allyl acetate decreases, and as a result, allyl acetate as a substrate and acetic acid-1-propenyl (cis isomer, trans isomer) isomerized from allyl acetate are mixed in the reaction product liquid. It will be.
- Allyl acetate and 1-propenyl acetate have a small boiling point difference from n-propyl acetate and are difficult to separate by distillation, and it is difficult to separate and purify them during subsequent purification. As a result, the purity of the product n-propyl acetate is reduced.
- the formyl group-containing compound concentration and the acryloyloxy group-containing compound concentration are determined by analyzing the raw material liquid by gas chromatography (GC).
- the formyl group-containing compound is a so-called aldehyde compound, and specifically includes acrolein, propionaldehyde, 2-methylcrotonaldehyde, and the like.
- the acryloyloxy group-containing compound is acrylic acid or an ester thereof, and specific examples include acrylic acid and allyl acrylate.
- the total concentration is 100 mass ppm or less in the raw material liquid, and even when a plurality of acryloyloxy group-containing compounds are present, the total concentration is 100 masses in the raw material liquid. It is made to become below ppm. Actually, the content is set to 0.01 to 100 ppm by mass.
- the preferred formyl group-containing compound concentration and acryloyloxy group-containing compound concentration of the raw material liquid are each independently 0 to 80 mass ppm, more preferably 0 to 50 mass ppm.
- a method for adjusting the formyl group-containing compound concentration and the acryloyloxy group-containing compound concentration of the raw material liquid to 100 ppm by mass or less, respectively, a method of adjusting the reaction conditions of the allyl acetate production process, the distillation conditions (temperature of the first distillation column 17) The number of stages, the number of distillation columns, etc.), the method of adjusting the amount of the above-mentioned dilution solvent used, and the like. By combining these appropriately, the concentration of each is 100 ppm by mass or less. Good. Below, an example of the method of reducing the amount of a formyl group containing compound and an acryloyloxy group containing compound according to distillation tower conditions is described.
- the impurity concentration in the allyl acetate-containing liquid 20 obtained from the middle column of the column is reduced by increasing the reflux ratio and increasing the amount of extraction at the column top and column bottom. It becomes possible to do. Further, as an equipment solution, the number of columns is increased, internal efficiency with high efficiency is adopted, the extraction position of the allyl acetate-containing liquid 20 is set to an appropriate number, or a plurality of distillation columns are used. For example, increasing the degree of purification. Of course, it is necessary to find an optimum condition because excessive facilities and inefficient operating conditions lower the economy.
- the composition of the feedstock to the first distillation column 17 is 64% by mass of allyl acetate, 22% by mass of acetic acid, 13% by mass of water, and 500 mass ppm of propionaldehyde and 440 mass of acrolein as the formyl group-containing compound.
- the concentration of the formyl group-containing compound and the acryloyloxy group-containing compound in the middle stage extraction liquid can be 100 to 1000 ppm by mass.
- the concentration of the formyl group-containing compound and the acryloyloxy group-containing compound at the time of supply to the hydrogenation reactor 21 is reduced to 100 ppm by weight or less by providing a distillation column or diluting the liquid with the recycle liquid 22 or the like. It becomes possible.
- the allyl acetate-containing liquid 20 is mixed with the recycle liquid 22 and a diluting solvent is used as a raw material liquid.
- the allyl acetate-containing liquid 20 is not necessarily combined with the recycle liquid 22 and the diluting solvent. It is not necessary to be mixed, it may be mixed with only the recycle liquid 22 to be a raw material liquid, may be mixed with only a diluting solvent to be a raw material liquid, or may not be mixed with these alone. It may be said.
- the concentration of the formyl group-containing compound and the concentration of the acryloyloxy group-containing compound in the raw material liquid at the time of being supplied to the hydrogenation reactor 21 is 100 mass ppm or less, respectively. It is.
- the calorific value is extremely large (for example, the calorific value associated with hydrogenation of 1 kg of allyl acetate is 1607 kJ). Therefore, when only allyl acetate is reacted, the exotherm associated with the hydrogenation causes reaction in the reaction system. The temperature rises significantly, and this can accelerate the hydrocracking reaction. In order to suppress this extreme temperature rise, it is preferable to carry out the hydrogenation reaction by diluting allyl acetate with a diluent solvent inert to the hydrogenation reaction.
- the concentration of allyl acetate in the raw material liquid at the time when it is supplied to the hydrogenation reactor 21 is preferably in the range of 1 to 50% by mass, more preferably 3 to 30% by mass, and most preferably 5%. The range is from mass% to 15 mass%. If the concentration of allyl acetate is less than 1% by mass, an extreme temperature rise due to heat generation can be sufficiently suppressed, but the concentration of allyl acetate becomes too low, resulting in low productivity. On the other hand, when the concentration of allyl acetate exceeds 50% by mass, it is difficult to sufficiently suppress an extreme temperature rise due to heat generation.
- the temperature inside the reactor cannot be controlled (for example, the reactor temperature is set to 0 ° C. to It becomes impossible to control within the preferred range of 200 ° C.).
- Such a diluting solvent is not particularly limited, but an organic solvent having no ethylenic carbon double bond (C ⁇ C bond) is preferable from the viewpoint that it is difficult to undergo a hydrogenation reaction.
- saturated esters such as ethyl acetate, n-propyl acetate, butyl acetate, isopropyl acetate, n-propyl propionate, ethyl propionate, butyl propionate, isopropyl propionate, cyclohexane, n-hexane, n- Hydrocarbons such as heptane; Aromatic hydrocarbons such as benzene and toluene; Ketones such as acetone and methyl ethyl ketone; Halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and methyl chloride; Diethyl ether, Di- ethers such as n-propyl ether; alcohols such
- saturated esters, hydrocarbons, and ketones are preferable from the viewpoint of being less susceptible to hydrogenation reaction and less likely to cause hydrogenolysis of allyl acetate. Further, since n-propyl acetate produced by the reaction is inactive to the hydrogenation reaction, the recycle liquid 22 containing this can be used as a diluting solvent.
- the hydrogen gas used for the supply gas 23 is not particularly limited. Usually, commercially available ones may be used, but it is preferable to use ones having high purity. Further, the amount of hydrogen gas to be supplied is preferably more than the theoretical amount of hydrogen gas necessary for producing n-propyl acetate from allyl acetate. A range of 1.1 to 3.0 times mol of the theoretical amount is more preferable, and a range of 1.1 to 2.0 times mol of the theoretical amount is particularly preferable. When the amount of hydrogen gas supplied is equal to or less than the theoretical amount, when a side reaction such as a hydrocracking reaction occurs, the amount of hydrogen consumed by the side reaction is insufficient for the original reaction. In addition, when the supply amount of hydrogen gas is extremely large, it is economically disadvantageous.
- the hydrogenation catalyst is an element selected from Group 8, Element 9 and Group 10 elements of the Periodic Table (according to the International Pure and Applied Chemistry Union Inorganic Chemical Nomenclature Revised Edition (1989), the same shall apply hereinafter). That is, a catalyst containing iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum is preferred. Preferable elements include palladium, rhodium, ruthenium, nickel and platinum, and palladium, rhodium and ruthenium are particularly preferable.
- the hydrogenation catalyst may be an element (or compound) alone or may be supported on a carrier if necessary. In the hydrogenation reaction using a fixed bed reactor described later, it is more preferable that the catalyst is supported on a support because a large metal surface area can be obtained upon contact between the hydrogenation catalyst and allyl acetate. .
- a substance for example, a porous substance
- a support for supporting the catalyst can be used without particular limitation.
- a support include silica, alumina, titanium oxide, diatomaceous earth, carbon, or a mixture thereof. These carriers are preferably formed into pellets or spheres for easy handling.
- the specific surface area of the support is not particularly limited, but is preferably one having a high specific surface area from the viewpoint of facilitating good dispersion of the catalyst metal. More specifically, a specific surface area value measured by the BET method is preferably 10 to 1000 m 2 / g, more preferably 30 to 800 mm 2 / g, particularly 50 to 500 mm 2 / g.
- the total pore volume of the carrier is not particularly limited, but is 0.05 to 6.5 ml / g, more preferably 0.1 to 5.0 ml / g (particularly 0.5 to 3.0 ml / g). It is preferable.
- the shape of the carrier is not particularly limited, and can be appropriately selected from known shapes. From the point of uniformity of the internal pressure of the hydrogenation reactor 21, pellets, spheres, hollow cylinders, spoke wheels, and a foam having a monolith catalyst support in the form of a honeycomb with parallel flow channels or an open pore system. Ceramics are preferable, and pellets and spheres are particularly preferable in consideration of simplicity of manufacturing.
- the support can be used without excessive pressure drop when the catalyst supported on the support is stacked on the catalyst layer, and when stacked, the support has a very high geometric surface area compared to the total capacity of the stack. It is preferable to have. From such a point, the carrier preferably has an outer dimension in the range of 0.5 to 5.0 mm, and more preferably an outer dimension in the range of 1.0 to 4.5 mm.
- the hydrogenation reaction can be carried out by either a gas phase reaction or a liquid phase reaction.
- the hydrogenation reactor 21 can be a fixed bed type reaction apparatus, a moving bed type reaction apparatus, a fluidized bed type reaction apparatus, or the like. It is.
- a gas phase reaction it is preferable to consider the following. In general, the heat of reaction accompanying hydrogenation is extremely large.
- the temperature at which the reactant is introduced into the hydrogenation reactor 21 is set to be equal to or higher than the boiling point of the reactant.
- the reaction temperature of the reactant to the hydrogenation reactor 21 can be made lower than its boiling point, and therefore, there is an advantage that it is easy to maintain a suitable reaction temperature (for example, 200 ° C. or less). is there.
- specific examples of the structure of the hydrogenation reactor 21 include a fixed bed type, a fluidized bed type, and a stirring bed type. From the viewpoint of easy separation of the catalyst and the product after the reaction, a fixed bed type reactor is most preferable among them.
- the fluid flow in the liquid phase reaction using a fixed bed reactor is a gas-liquid two-phase flow of a liquid containing a raw material and a gas containing hydrogen gas.
- the gas-liquid two-phase flow is divided into three types of gas-liquid counter-current type, gas-liquid downward co-current type, and gas-liquid upward co-current type depending on how the raw material gas and liquid flow. Any of them can be used in the present invention, but the gas-liquid downward co-current type is most preferable from the viewpoint that hydrogen necessary for the reaction and the catalyst can be efficiently contacted.
- the most preferable reaction mode of the hydrogenation reactor 21 is a gas-liquid two-phase liquid phase reaction from the viewpoint of increasing the space-time yield while suppressing hydrocracking.
- the direction of flow is a gas-liquid downward co-current type.
- a hydrogenation reaction is performed as a liquid phase reaction of an adiabatic system using a raw material liquid diluted with the above-mentioned dilution solvent from the viewpoint of suppressing the hydrogenolysis reaction. It is preferable to carry out. Thereby, the allyl acetate concentration in the raw material liquid can be lowered, and measures such as cooling the hydrogenation reactor 21 become unnecessary.
- the form of the hydrogenation reactor 21 is not particularly limited. When a gas-liquid downward co-current reaction mode using a fixed bed reactor is used, use a reactor with a cooling jacket, a multi-tubular reactor with a cooling jacket, an adiabatic reactor, etc. Is preferred. In view of the construction cost of the hydrogenation reactor 21 and the conversion rate of allyl acetate, an adiabatic reactor is preferable.
- the reaction temperature of the hydrogenation reaction may vary depending on the type of raw material, but is preferably 0 to 200 ° C, particularly preferably 40 to 150 ° C. If the reaction is less than 0 ° C, a sufficient reaction rate tends to be difficult to obtain, and if it exceeds 200 ° C, hydrogenolysis tends to proceed.
- the reaction pressure of the hydrogenation reaction is a gas phase reaction
- sufficient activity can be obtained even at normal pressure. For this reason, it is preferable to carry out at normal pressure.
- the reaction can be accelerated under a pressurizing condition as necessary as long as the allyl acetate can be vaporized at a temperature of 200 ° C. or lower.
- the gas-liquid downward co-current type is preferable as the raw material gas and liquid flow method as described above.
- the reaction pressure is preferably in the range of 0.05 to 10 MPaG, more preferably in the range of 0.3 to 5 MPaG.
- the reaction pressure is less than 0.05 MPaG, the hydrogenation reaction tends not to be sufficiently promoted.
- the reaction pressure exceeds 10 MPaG, the hydrocracking reaction tends to occur.
- the gas-liquid downward co-current reaction mode is most preferable as described above.
- the hydrogenation reaction liquid 24 obtained from the hydrogenation reactor 21 is supplied to the second distillation column 25.
- moisture content The liquid 27 is extracted, and the high-purity n-propyl acetate product 28 is extracted from the middle column of the second distillation column 25. In this way, a high purity n-propyl acetate product 28 can be obtained.
- the concentration of the formyl group-containing compound and the concentration of the acryloyloxy group-containing compound in the raw material solution are By setting it as 100 mass ppm or less, deterioration of a hydrogenation catalyst can be suppressed and catalyst activity can be maintained.
- the method for producing n-propyl acetate according to the present invention is a method in which a crude allyl acetate solution obtained from propylene, oxygen and acetic acid is used as a raw material solution containing an allyl acetate solution which has been purified through a purification step such as distillation. Is particularly useful.
- the composition ratio of the condensate obtained in each of the following examples was determined by gas chromatography (GC). The measurement conditions at that time are shown below.
- GC condition ⁇ Equipment: GC-17A (manufactured by Shimadzu Corporation) ⁇ Detector: Flame ionization detector ⁇ Measurement method: Internal standard method (Internal standard substance: 1,4-dioxane) ⁇ Injection temperature: 200 °C -Temperature rising condition: held at 40 ° C for 10 minutes, then heated at 5 ° C / min, then held at 200 ° C for 30 minutes.
- -Column TC-WAX (manufactured by GL Science Inc.), inner diameter 0.25 mm, film thickness 0.25 ⁇ m, length 30 m
- Example 1 In the flow shown in FIG. 2, a stainless steel cylindrical reactor 36 (internal volume 80 cc) having an inner diameter of 20 mm ⁇ is loaded with a supported palladium catalyst (alumina carrier, 3 mm diameter ⁇ 3 mm length pellet, palladium content 0.3 as a hydrogenation catalyst). 80% of mass%, “PGC catalyst” manufactured by NV Chemcat Co., Ltd.) was filled to form a catalyst packed bed 37, and the pressure of the reactor 36 was adjusted to 0.8 MPaG with hydrogen gas.
- a supported palladium catalyst alumina carrier, 3 mm diameter ⁇ 3 mm length pellet, palladium content 0.3 as a hydrogenation catalyst.
- PPC catalyst 80% of mass%, “PGC catalyst” manufactured by NV Chemcat Co., Ltd.
- Hydrogen gas is circulated in the reactor 36 from the hydrogen gas supply pipe 32 at a rate of 16.6 Nl / hr, the electric furnace set temperature of the reactor 36 is set to 80 ° C., and then the reaction supply liquid is supplied from the upper part of the reactor 36.
- each substance of acrolein, propionaldehyde, 2-methylcrotonaldehyde, acrylic acid, and allyl acrylate is not added to the reaction supply liquid, and the concentration thereof is 0 mass ppm.
- the reaction mixture obtained from the reactor outlet gas 33 was condensed by a condenser 38, and the obtained condensate 34 was analyzed using GC under the above-described conditions.
- symbol 35 is non-condensable gas in the figure.
- Table 1 shows the yield when 3 hours passed from the start of the reaction and the yield when 100 hours passed.
- the yield when 100 hours passed from the start of the reaction with respect to the yield when 3 hours passed from the start of the reaction was expressed as a percentage to obtain the yield retention rate, that is, the amount of impurities added to the reaction feed solution, that is, containing the formyl group Plotted against compound concentration and acryloyloxy group-containing compound (FIG. 3).
- Example 2 Supported palladium catalyst as a hydrogenation catalyst (egggar activated carbon carrier, crushed product (4-8 mesh), palladium content 0.5% by mass, manufactured by NV Chemcat Co., Ltd. “0.5% Pd carbon particles (W) LA Allyl acetate was hydrogenated in the same manner as in Example 1 except that “type”) was used. The results are shown in Table 1 and FIG.
- Example 3 Example 1 except that a supported platinum catalyst (alumina carrier, 3 mm diameter ⁇ 3 mm long pellet, platinum content 0.3 mass%, “HDMax 800 Tab” manufactured by Zude Chemie Catalysts Co., Ltd.) was used as the hydrogenation catalyst. In this way, allyl acetate was hydrogenated. The results are shown in Table 1 and FIG.
- Example 4 Except for using a supported nickel catalyst (diatomite carrier, diameter 5.2 mm ⁇ length 4.6 mm, cylindrical molded product, nickel content 50 mass%, “N111” manufactured by JGC Chemical Co., Ltd.) as the hydrogenation catalyst
- a supported nickel catalyst diatomite carrier, diameter 5.2 mm ⁇ length 4.6 mm, cylindrical molded product, nickel content 50 mass%, “N111” manufactured by JGC Chemical Co., Ltd.
- the present invention can be applied to a method for producing n-propyl acetate by hydrogenation reaction of a raw material liquid containing allyl acetate.
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Abstract
Description
本願は、2008年5月21日に、日本に出願された特願2008-133403号に基づき優先権を主張し、その内容をここに援用する。
しかしながら、このようなエステル化反応では、副生物である水を系外に取り除かなければ、反応の平衡状態を生成物(飽和エステル類)側に傾けることができず、高い原料転化率や反応速度を得ることは工業的に困難である。また、水の蒸発潜熱は他の有機化合物の蒸発潜熱に比べて極端に大きいため、蒸留による水の分離には多大のエネルギーを消費する等の困難性もある。
特に、パラジウム触媒の存在下、相当するオレフィン、酸素およびカルボン酸を気相で反応させることによって不飽和基含有エステルを製造できることは周知であり、これに関しては多くの公知文献がある。例えば特許文献1には、プロピレンと酸素と酢酸とをパラジウム触媒の存在下、気相で反応させることにより、極めて高収率、かつ高空時収率で酢酸アリルを工業的に生産できると記載されている。
例えば特許文献2には、水素化反応の触媒、すなわち水素化触媒としてニッケル触媒を用いて酢酸アリルを水素化し、酢酸-n-プロピルを製造する方法が開示されている。特許文献3には、シリカ担持型パラジウム触媒、アルミナ担持型パラジウム触媒、スポンジニッケルなどを用いて酢酸n-プロピルを製造する方法が記載されている。特許文献3によると、酢酸アリルの転化率はほぼ100%を達成でき、また酢酸n-プロピルの選択率は99.0%以上を達成している。ここで、特許文献3には、プロピレン、酸素および酢酸からなる原料ガスをパラジウム触媒の存在下、気相のまま通過させ酢酸アリルを合成する場合において、得られた反応器出口ガスを冷却して非凝縮成分と凝縮成分に分離し、その凝縮成分である粗酢酸アリル液を蒸留し、塔頂から酢酸アリルを含む酢酸アリル含有液を得ることが記載されており、この酢酸アリル含有液を原料液として水素化することで、目的製品である酢酸n-プロピルを得ることが可能とされている。
[2]前記原料液は、プロピレンと酸素と酢酸とから製造された酢酸アリル含有液を含むことを特徴とする[1]に記載の酢酸n-プロピルの製造方法。
[3]前記ホルミル基含有化合物が、アクロレイン、プロピオンアルデヒド、2-メチルクロトンアルデヒドから選ばれる少なくとも1種であることを特徴とする[1]または[2]に記載の酢酸n-プロピルの製造方法。
[4]前記アクリロイルオキシ基含有化合物が、アクリル酸および/またはアクリル酸アリルであることを特徴とする[1]または[2]に記載の酢酸n-プロピルの製造方法。
[5]前記水素化反応には、周期律表の8族元素、9族元素および10族元素からなる群から選ばれる少なくとも1種の元素を含有する化合物を水素化触媒として用いることを特徴とする[1]ないし[4]のいずれかに記載の酢酸n-プロピルの製造方法。
[6]前記水素化触媒が、パラジウム、ロジウム、ルテニウム、ニッケルおよび白金の群から選ばれる少なくとも1種を含有する化合物であることを特徴とする[5]に記載の酢酸n-プロピルの製造方法。
原料液としては、酢酸アリルを含有するものであれば特に制限はないが、以下、本発明について、プロピレンと酸素と酢酸とから製造され、蒸留などの精製工程を経て得られた酢酸アリル含有液を原料液に使用して、これを水素化反応する場合を例示し、図面を参照して詳細に説明する。
プロピレンと酸素と酢酸とを原料として、酢酸アリルを製造する際の反応式を下記式(1)に示す。この反応により酢酸アリルを製造する場合、図1に示すように、まず、プロピレンと酸素と酢酸とを含有する原料ガスを、触媒が充填された反応器11に供給する。
酢酸、プロピレン、酸素の比率としては、モル比にして、酢酸:プロピレン:酸素=1:0.25~13:0.15~4の比率が好ましく、より好ましくは、酢酸:プロピレン:酸素=1:1~7:0.5~2の比率である。
(a)パラジウム
(b)銅、鉛、ルテニウムおよびレニウムから選ばれる少なくとも1種以上の元素を有する化合物
(c)アルカリ金属酢酸塩およびアルカリ土類金属酢酸塩から選ばれる少なくとも一種以上の化合物
(a)成分の原料には特に制限はない。金属パラジウムを用いることはもちろんのこと、金属パラジウムに転化可能なパラジウム塩を用いることも可能である。金属パラジウムに転化可能なパラジウム塩の例としては、塩化パラジウム、塩化ナトリウムパラジウム、硝酸パラジウム、硫酸パラジウムなどがあるが、これらに限定されるものではない。
担体と(a)成分との比率としては、質量比にして、担体:(a)成分=1:0.1~5.0の比率が好ましく、より好ましくは、担体:(a)成分=1:0.3~1.0の比率である。
(a)成分および(b)成分の比率としては、モル比にして、(a)成分:(b)成分=1:0.05~10が好ましく、より好ましくは(a)成分:(b)成分=1:0.1~5である。
(c)成分の担持量については特に制限はないが、担体100質量部に対して1~30質量部の担持量であることが好ましい。また、希望する担持量とするために、アルカリ金属の酢酸塩を、例えば、水溶液または酢酸の溶液として原料ガスに添加する等の方法によって反応器11中に加えてもよい。
担体の粒子直径としては特に制限はないが、好ましくは1~10mmであり、より好ましくは3~8mmである。管状反応器に触媒を充填して反応を行う場合、粒子直径が1mm未満では、原料ガスを流通させるときに大きな圧力損失が生じ、有効にガス循環ができなくなる恐れがある。また粒子直径が10mmを超えると、触媒内部まで原料ガスが拡散できなくなり、有効に触媒反応が進まなくなる恐れがある。
担体の細孔構造は、その細孔直径が1nm~1000nmにあることが好ましく、2nm~800nmの間がより好ましい。
具体的には、例えばパラジウム塩などの(a)成分と、(b)成分との水溶液を担体に含浸させた後、アルカリ金属塩の水溶液で処理する方法が挙げられる。この際、触媒液が含浸された担体を乾燥することなくアルカリ処理するのが好ましい。アルカリ金属塩水溶液による処理時間は、担体に含浸させた触媒成分の塩が、水に不溶な化合物に完全に変換されるのに必要な時間であり、通常20時間で十分である。
例えば、上述した担持型固体触媒を用いる場合は、当該触媒を反応器11に充填した固定床流通反応を反応形式として採用することが実用上有利である。
反応器11の材質については特に制限はないが、耐食性を有する材料で構成されたものが好ましい。
反応圧力としては特に制限はない。設備の点から0.0~3.0MPaG(ゲージ圧)であることが実用上有利であり、より好ましくは0.1~1.5MPaGである。
また、原料ガスは、標準状態において、空間速度10~15000hr、特に300~8000hrで触媒に通すのが好ましい。
なお、凝縮成分分離槽13を設ける代わりに、酢酸、水を吸収液とする吸収塔を設けてもよい。
ついで、粗酢酸アリル液14を精製して、副生成物などの不純物を除去する。
具体的には、図1に示すように、粗酢酸アリル液14の一部又は全量を油水分離層16に供給して、酢酸アリルを多く含む油層を第1の蒸留塔17に供給する。
そして、酢酸、アクリル酸、アクリル酸アリル、ジアセテート類等の高沸成分を多く含有する第1の蒸留塔塔底液18と、アクロレイン、プロピオンアルデヒド、水分等の低沸成分を多く含有する第1の蒸留塔塔頂液19とをそれぞれ抜出し、除去する。これら除去された液は、ボイラー燃料として使用しても良いし、また酢酸アリル製造プロセス内に戻して再利用しても良い。
一方、第1の蒸留塔17の塔中段からは、酢酸アリルを主成分とする第1の蒸留塔中段留出液、すなわち、酢酸アリル含有液20が得られる。この酢酸アリル含有液20の酢酸アリル純度は、通常、95%以上となる。また、酢酸アリル含有液20に含有されるアクロレイン、プロピオンアルデヒド、2-メチルクロトンアルデヒド、アクリル酸、アクリル酸アリルの濃度は、酢酸アリル製造プロセスの反応条件や、第1の蒸留塔17の蒸留条件などにもよるが、通常、合計で0.1~1.0質量%となる。
以下、第1の蒸留塔17の通常の運転条件を示す。第1の蒸留塔17は大気圧+αの操作圧にて運転され、塔中段からは100~110℃の範囲で純度の高められた酢酸アリル含有液20を留出する。塔底からは、酢酸を主成分とする第1の蒸留塔塔底液18を120~140℃の塔底温度で抜き出す。また蒸留塔塔頂からの成分は凝縮器(図示省略)により凝縮され、第1の蒸留塔塔頂液19となる。その液の一部は第1の蒸留塔17へ還流させてもよい。このとき、第1の蒸留塔塔頂液19を水層と油層に二層分離させ各々を還流として戻しても良い。通常、第1の蒸留塔17は20段~80段の実段数の範囲で構成され、還流比は1~200の範囲で運転される。
リサイクル液22は、反応生成物である酢酸n-プロピルの他、未反応の酢酸アリル、副生物などを含むものである。また、水素化反応器21に供給される供給ガス23は、水素ガス以外にも必要に応じて窒素または希ガスなどの不活性の希釈ガスを含んでいてもよい。なお、「水素化反応に不活性な溶媒」とは、酢酸アリルの水素化反応に実質的に影響を与えない溶媒をいう。
すなわち、本発明者らの検討により、ホルミル基含有化合物、アクリロイルオキシ基含有化合物などの易重合性物質や還元性物質の原料液中の濃度を低く抑えることが、水素化触媒の劣化を抑制する点で重要であることが明らかとなった。特に、ホルミル基含有化合物濃度およびアクリロイルオキシ基含有化合物濃度の少なくとも一方が100質量ppmを超える原料液について水素化反応を継続した場合、水素化触媒の表面を重合物が被覆し、結果として触媒活性を低下させる。触媒活性が低下すると、酢酸アリルの転化率は低下し、その結果、基質の酢酸アリルや、酢酸アリルが異性化した酢酸-1-プロペニル(cis体、trans体)が反応生成液中に混在することとなる。酢酸アリルや酢酸-1-プロペニル(cis体、trans体)は、酢酸n-プロピルとの沸点差が小さく蒸留による分離は困難であり、後の精製時にこれらを分離精製することは難しい。結果として、製品の酢酸n-プロピルの純度は低下することとなる。
なお、ホルミル基含有化合物濃度およびアクリロイルオキシ基含有化合物濃度は、原料液をガスクロマトグラフィー(GC)で分析することにより求められる。
なお、ホルミル基含有化合物が複数種存在する場合はその合計濃度が原料液中100質量ppm以下となるようにし、アクリロイルオキシ基含有化合物が複数種存在する場合もその合計濃度が原料液中100質量ppm以下となるようにする。現実的には0.01~100質量ppmとする。また、原料液の好ましいホルミル基含有化合物濃度およびアクリロイルオキシ基含有化合物濃度は、それぞれ独立に0~80質量ppmで、さらに好ましくは0~50質量ppmである。
以下に、蒸留塔条件により、ホルミル基含有化合物、アクリロイルオキシ基含有化合物量を低減する方法の一例を記す。
まず、第1の蒸留塔17の操作条件として、還流比を上げることや、塔頂、塔底の抜き出し量を増加させることにより、塔中段から得られる酢酸アリル含有液20中の不純物濃度を低減することが可能となる。また、設備的な解決方法としては、塔の段数を増加させること、段効率の高いインターナルスを採用すること、酢酸アリル含有液20の抜き出し位置を適切な段数とすること、或いは蒸留塔を複数本とし、精製度合いを高めることなどが挙げられる。もちろん、過剰な設備や非効率な運転条件では経済性を低下させるため、最適条件を見出す必要がある。
更に、抽出塔を組み入れることや、その他当業者が考え得る分離プロセス、例えば吸着工程や、膜分離工程などを利用することなども考えられる。
例えば、第1の蒸留塔17への供給原料の組成が、酢酸アリル64質量%、酢酸22質量%、水13質量%であり、且つホルミル基含有化合物として、プロピオンアルデヒド500質量ppm、アクロレイン440質量ppm、アクリル酸アリル4500質量ppm、アクリル酸2000質量ppmを含有する液を、実段数60段、油層還流比130、水層還流比3、D/F(=中段抜出量/蒸留塔供給量)0.6とすることで、中段抜出液中のホルミル基含有化合物、アクリロイルオキシ基含有化合物の濃度は100~1000質量ppmとすることが可能となる。さらに蒸留塔を設けたり、当該液をリサイクル液22などにより希釈することで、水素化反応器21に供給する時点でのホルミル基含有化合物、アクリロイルオキシ基含有化合物の濃度を100重量ppm以下とすることが可能となる。
ただし、酢酸アリルの水素化反応の反応温度を低く抑える観点からは、希釈溶媒で希釈して、水素化反応を行うことが好ましい。すなわち、酢酸アリルの水素化反応においては、反応温度は低い方が水素化分解反応の抑制が容易なため、好ましい。水素化反応は、発熱量が極めて大きい(例えば、酢酸アリル1kgの水素化に伴う発熱量は1607kJである。)ため、酢酸アリルのみを反応させると、その水素化に伴う発熱によって反応系内の温度が著しく上昇し、これが原因となって水素化分解反応が促進される可能性がある。この極端な温度上昇を抑制するには、酢酸アリルを水素化反応に不活性な希釈溶媒で希釈して、水素化反応を行うことが好ましい。
酢酸アリルの濃度が1質量%未満では、発熱による極端な温度上昇は十分に抑制できるものの、酢酸アリルの濃度が低くなりすぎ、その結果、生産性が低くなる。他方、酢酸アリルの濃度が50質量%を超えると、発熱による極端な温度上昇を十分に抑制することが困難となる。更に断熱式の液相反応(特に、断熱式の気液2相流の液相反応。)を採用した場合は、反応器内の温度を制御できなくなる(例えば、反応器の温度を0℃~200℃の好適な範囲に制御できなくなる。)可能性が増大する。
具体的には、酢酸エチル、酢酸n-プロピル、酢酸ブチル、酢酸イソプロピル、プロピオン酸n-プロピル、プロピオン酸エチル、プロピオン酸ブチル、プロピオン酸イソプロピル等の飽和エステル類、シクロヘキサン、n-ヘキサン、n-ヘプタン等の炭化水素類;ベンゼン、トルエン等の芳香族炭化水素類;アセトン、メチルエチルケトン等のケトン類;四塩化炭素、クロロホルム、塩化メチレン、塩化メチル等のハロゲン化炭化水素類;ジエチルエーテル、ジ-n-プロピルエーテル等のエーテル類;エタノール、n-プロパノール、イソプロパノール、n-ブタノール、sec-ブタノール等のアルコール類;N-メチル-2-ピロリドン、N、N-ジメチルアセトアミド等のアミド類を挙げることができる。これらの中でも、水素化反応を受けにくく、かつ酢酸アリルの水素化分解反応を起こしにくいという点からは、飽和エステル類、炭化水素類、ケトン類が好ましい。
また、反応で生成した酢酸n-プロピルは水素化反応に不活性であるので、これを含むリサイクル液22を希釈溶媒とすることも可能である。
水素化触媒としては、元素(ないし化合物)単独でも、また必要に応じて担体に担持させてもよい。後述の固定層反応装置を用いた場合の水素化反応においては、担体に担持されている方が、水素化触媒と酢酸アリルとの接触の際に大きな金属表面積を得ることができる点からより好ましい。
これらの担体はペレット状、球状に成形されたものであると取り扱いが簡便となり好ましい。
担体の比表面積は特に制限されないが、触媒金属の良好な分散を容易とする点からは、高い比表面積を有するものが好ましい。より具体的には、BET法による比表面積の値が10~1000m2/g、更には30~800mm2/g特に、50~500mm2/gのものが好ましい。また、担体の全細孔容積は、特に制限されないが、0.05~6.5ml/g、更には0.1~5.0ml/g(特に0.5~3.0ml/g)であることが好ましい。
担体の形状は特に制限されず、公知の形状から適宜選択することが可能である。水素化反応器21の内圧の均一性の点からは、ペレット状、球状、中空円柱状、スポーク車輪、および平行なフローチャネルを有する蜂の巣状の形のモノリス触媒担体または開放性孔系を有する発泡セラミックが好ましく、造り方の簡便性を考慮すると、ペレット状、球状が特に好ましい。
担体は、担体に担持した触媒を触媒層にばら積みした場合、圧力低下が過大になり過ぎることなしに使用でき、かつ、ばら積みした場合、ばら積みの総容量に比べて非常に高い幾何学的表面積を有することが好ましい。このような点から、上記担体は0.5~5.0mmの範囲の外寸であることが好ましく、1.0~4.5mmの範囲の外寸であることが更に好ましい。
気相反応の場合、水素化反応器21の構造形式は、固定層型反応装置、移動層型反応装置、流動層型反応装置等の使用が可能であるが、固定層反応装置が最も一般的である。
また、気相反応の場合には、以下のことを考慮することが好ましい。一般に水素化に伴う反応熱は極めて大きい。また、気相反応の場合、水素化反応器21への反応物質の投入温度は、その反応物質の沸点以上に設定される。この場合、空時収率を高くしようとすると、水素化に伴う発熱量が増加し、水素化反応器21内の温度が好適な反応温度(例えば200℃)を超えて上昇し、副反応である水素化分解反応が加速してしまう恐れがある。この対策として、空時収率を低くして発熱量を抑制する、あるいは冷却などによる温度制御が挙げられる。
この点、液相反応の場合には、水素化反応器21への反応物質の投入温度をその沸点より低くすることができ、したがって好適な反応温度(例えば200℃以下)に保ち易いという利点がある。
液相反応の場合、水素化反応器21の構造形式の具体例としては、固定層型、流動層型、攪拌層型等を挙げることができる。反応後の触媒と生成物の分離の容易性の点からは、これらの中で固定層型反応装置が最も好ましい。
上述したことを総合すると、水素化分解を抑制しつつ空時収率を高くする点から、水素化反応器21の最も好ましい反応形態は、気液2相流の液相反応であり、その流体の流れ方は気液下向並流式となる。
一方、気液2相流の液相反応の場合、溶存水素濃度を確保する点から加圧することが好ましい。気液2相流の液相反応で反応器内の水素濃度を十分に確保する点からは、原料の気体と液体の流れ方は、上述したように気液下向並流式が好ましい。
気液2相流の液相反応の場合、反応圧力は0.05~10MPaGの範囲であることが好ましく、更に好ましくは0.3~5MPaGの範囲である。反応圧力が0.05MPaG未満では、水素化反応が十分に促進されにくい傾向があり、他方、反応圧力が10MPaGを超えると、水素化分解反応が起こりやすくなる傾向がある。
水素化反応器21内の水素濃度を十分に確保する点からは、上述したように気液下向並流式の反応形態が最も好ましい。
水素化反応器21から得られた水素化反応液24は、第2の蒸留塔25に供給される。そして、酢酸、プロピオン酸プロピル等の高沸成分を多く含有する第2の蒸留塔塔底液26と、C3ガス、プロピオンアルデヒド、水分等の低沸成分を多く含有する第2の蒸留塔塔頂液27とがそれぞれ抜出され、第2の蒸留塔25の塔中段から高純度の酢酸n-プロピル製品28が抜出される。このようにして、高純度の酢酸n-プロピル製品28を得ることができる。
実施例および比較例中の各語句の定義は下記式による。
収率(%)=(生成した酢酸n-プロピルのモル数)/(反応器に仕込まれた酢酸アリルのモル数)×100
収率保持率(%)=反応開始から100時間経過した際の収率/反応開始から3時間経過した際の収率×100
(GC条件)
・機器:GC-17A(島津製作所製)
・検出器:水素炎イオン化検出器
・測定方法:内部標準法(内部標準物質:1,4-ジオキサン)
・インジェクション温度:200℃
・昇温条件:40℃で10分間保持し、その後5℃/分で昇温し、200℃で30分間保持
・カラム:TC-WAX(GL Science Inc.製)、内径0.25mm、膜厚0.25μm、長さ30m
酢酸アリル:昭和電工(株)製、純度99.6%、酢酸-1-プロペニル3594ppm、酢酸151ppm、水59ppm
酢酸n-プロピル:キシダ化学(株)製、純度99.7%、酢酸イソプロピル459ppm、n-プロパノール2696ppm、水170ppm
アクロレイン:東京化成工業(株)製、純度>90%
プロピオンアルデヒド:和光純薬工業(株)製、純度98+%
2-メチルクロトンアルデヒド:東京化成工業(株)製、純度>95%
アクリル酸:和光純薬工業(株)製、純度98+%
アクリル酸アリル:Alfa Aesar社製、純度90+%
図2に示すフローで、内径20mmφのステンレス製円筒型反応器36(内容積80cc)に、水素化触媒として担持型パラジウム触媒(アルミナ担体、直径3mm×長さ3mmペレット、パラジウム含有量0.3質量%、エヌイーケムキャット(株)製「PGC触媒」)80ccを充填して触媒充填層37とし、反応器36の圧力を水素ガスで0.8MPaGに調整した。水素ガスを水素ガス供給管32から16.6Nl/hrの速度で反応器36内に流通させ、反応器36の電気炉設定温度を80℃とした後、反応器36の上部から、反応供給液(原料液)として酢酸n-プロピル:酢酸アリル=9:1(vol%)の混合液を、液供給管31から400cc/hrの速度で反応器36内に流通させた(固定層型、気液下向並流式)。
なお、反応供給液にはアクロレイン、プロピオンアルデヒド、2-メチルクロトンアルデヒド、アクリル酸、アクリル酸アリルの各物質は添加されておらず、その濃度は0質量ppmである。
反応器出口ガス33から得られる反応混合物を凝縮器38で凝縮し、得られた凝縮液34を、GCを用いて上述した条件で分析した。なお、図中符号35は非凝縮ガスである。反応開始から3時間経過した際の収率と、100時間経過した際の収率とを表1に示す。また、反応開始から3時間経過した際の収率に対する反応開始から100時間経過した際の収率を百分率で表して収率保持率とし、反応供給液に添加した不純物量、すなわち、ホルミル基含有化合物濃度およびアクリロイルオキシ基含有化合物に対してプロットした(図3)。
水素化触媒として担持型パラジウム触媒(椰子ガラ活性炭担体、破砕品(4~8メッシュ)、パラジウム含有量0.5質量%、エヌイーケムキャット(株)製「0.5%Pdカーボン粒(W)LAタイプ」)を用いた以外は実施例1と同様の方法で、酢酸アリルを水素化した。結果を表1および図3に示す。
水素化触媒として担持型白金触媒(アルミナ担体、直径3mm×長さ3mmペレット、白金含有量0.3質量%、ズードケミー触媒(株)製「HDMax800Tab」)を用いた以外は実施例1と同様の方法で、酢酸アリルを水素化した。結果を表1および図3に示す。
水素化触媒として担持型ニッケル触媒(珪藻土担体、直径5.2mm×長さ4.6mm、円柱状成型品、ニッケル含有量50質量%、日揮化学(株)製「N111」)を用いた以外は実施例1と同様の方法で、酢酸アリルを水素化した。結果を表1および図3に示す。
反応供給液として酢酸n-プロピル:酢酸アリル=9:1(vol%)の混合液にアクロレイン20質量ppmを含有させた以外は、実施例1と同様の方法で酢酸アリルを水素化した。結果を表1および図3に示す。
反応供給液として、酢酸n-プロピル:酢酸アリル=9:1(vol%)の混合液に表1に示す種類と量のホルミル基含有化合物、アクリロイルオキシ基含有化合物を含有させたものを使用し、触媒として表1に示すものを使用した以外は、実施例1と同様の方法で酢酸アリルを水素化した。結果を表1および図3に示す(ただし実施例19は図3に示さない)。
12:反応器出口ガス
13:凝縮成分分離槽
14:粗酢酸アリル液
15:非凝縮成分
16:油水分離層
17:第1の蒸留塔
18:第1の蒸留塔 塔底液
19:第1の蒸留塔 塔頂液
20:酢酸アリル含有液
21:水素化反応器
22:リサイクル液
23:供給ガス
24:水素化反応液
25:第2の蒸留塔
26:第2の蒸留塔 塔底液
27:第2の蒸留塔 塔頂液
28:酢酸n-プロピル製品
31:液供給管
32:水素ガス供給管
33:反応器出口ガス
34:凝縮液
35:非凝縮ガス
36:ステンレス製円筒型反応器
37:触媒充填層
38:凝縮器
Claims (6)
- 酢酸アリルを含有する原料液の水素化反応により、酢酸n-プロピルを製造する方法であって、
前記原料液のホルミル基含有化合物濃度およびアクリロイルオキシ基含有化合物濃度が、各々100質量ppm以下であることを特徴とする酢酸n-プロピルの製造方法。 - 前記原料液は、プロピレンと酸素と酢酸とから製造された酢酸アリル含有液を含むことを特徴とする請求項1に記載の酢酸n-プロピルの製造方法。
- 前記ホルミル基含有化合物が、アクロレイン、プロピオンアルデヒド、2-メチルクロトンアルデヒドから選ばれる少なくとも1種であることを特徴とする請求項1または2に記載の酢酸n-プロピルの製造方法。
- 前記アクリロイルオキシ基含有化合物が、アクリル酸および/またはアクリル酸アリルであることを特徴とする請求項1または2に記載の酢酸n-プロピルの製造方法。
- 前記水素化反応には、周期律表の8族元素、9族元素および10族元素からなる群から選ばれる少なくとも1種の元素を含有する化合物を水素化触媒として用いることを特徴とする請求項1ないし4のいずれかに記載の酢酸n-プロピルの製造方法。
- 前記水素化触媒が、パラジウム、ロジウム、ルテニウム、ニッケルおよび白金の群から選ばれる少なくとも1種を含有する化合物であることを特徴とする請求項5に記載の酢酸n-プロピルの製造方法。
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JP2011136937A (ja) * | 2009-12-28 | 2011-07-14 | Showa Denko Kk | 酢酸n−プロピルの製造方法 |
WO2011122367A1 (en) * | 2010-03-31 | 2011-10-06 | Showa Denko K.K. | Method for producing n-propyl acetate and method for producing allyl acetate |
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