WO2004048297A1 - 水素化反応方法 - Google Patents
水素化反応方法 Download PDFInfo
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- WO2004048297A1 WO2004048297A1 PCT/JP2003/015134 JP0315134W WO2004048297A1 WO 2004048297 A1 WO2004048297 A1 WO 2004048297A1 JP 0315134 W JP0315134 W JP 0315134W WO 2004048297 A1 WO2004048297 A1 WO 2004048297A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group
Definitions
- the present invention relates to a heterogeneous catalytic hydrogenation method.
- Heterogeneous catalytic hydrogenation is a complex reaction involving three phases: gas-liquid-solid surface, and heretofore disclosed what kind of gas-liquid flow conditions can achieve high productivity. Technology is not found.
- a catalyst containing nickel metal or copper metal is brought into contact with the above raw materials together with hydrogen gas in advance to desulfurize the oil or fat or fatty acid ester.
- a technology has been disclosed that a low sulfur content raw material having a sulfur content of 0.6 ppm or less has the same reduction reactivity as when a raw material having the same sulfur content obtained by distillation of the raw material is used.
- the hydrogenation reaction itself adopts a conventionally known method using a liquid phase suspended bed or a fixed bed reaction system, and a raw material having a reduced sulfur content is used. It merely describes hydrogenation to the corresponding alcohol in the presence of a copper-based ester reduction catalyst according to a conventionally known method.
- Heterogeneous catalytic hydrogenation is a complex reaction involving three phases: gas-liquid-solid surface. Conventionally, under which conditions high productivity can be obtained, Did not.
- a zinc-chromium-based or zinc-chromium-aluminum-based composite metal oxide catalyst is used to hydrogenate unsaturated aldehydes, unsaturated fatty acids or unsaturated fatty acid esters.
- unsaturated alcohol is produced by the above method, there is a method in which the copper content and the nickel content in the composite metal oxide catalyst are not more than a certain amount (Japanese Patent Application Laid-Open No. 2000-89430). (See claims 1 and 2, paragraphs 0022 and 0023).
- the catalyst having a specific composition has a breaking strength of 20 to 500 kg / cm 3 , a transverse breaking strength of 2 to 10 kg per cm, and a bulk specific gravity of 1.0 to 1.8. Is preferred. This method focuses only on the importance of the copper content and the nickel content in the catalyst, and the breaking strength of the catalyst, but does not describe the gas-liquid flow state in the reaction system.
- An object of the present invention is to provide a heterogeneously catalyzed hydrogenation reaction method which can be generally applied to hydrogenation of various raw materials and has high productivity. Disclosure of the invention
- the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, using a solid catalyst-filled tubular reactor in which both hydrogen gas and a liquid-phase hydrogen-containing material flow down from above, the irrigation flow in the hydrogen I spoon reaction under the conditions, 0. 0 0 5 X 1 0- 3 ⁇ 0 in the reaction conditions dynamic liquid phase retained amount per unit catalyst outer surface area. 1 4 X 1 0-3 m 3 Zm
- it was found that the use of a solid catalyst having a minimum catalyst strength of 1.0 kg or more per catalyst resulted in high productivity in the hydrogenation reaction of various raw materials.
- the present invention has been completed by further studies based on such findings, and provides a heterogeneous catalytic hydrogenation method shown below.
- Item 1 Solid flow of hydrogen gas and liquid phase containing hydrogenated substance
- Catalyst strength A-2 ⁇
- ⁇ represents the average value of the minimum crushing strength measured for 100 pieces of the above catalyst in accordance with the method described in “Crushing strength test method” of JISZ8841-1993. Indicates the standard deviation value of the minimum crushing strength.
- a heterogeneous catalytic hydrogenation reaction method wherein the catalyst strength determined by the above is 1.0 kg or more.
- An organic compound in which the substance to be hydrogenated contains at least one group selected from the group consisting of an ester group, a carbon-carbon double bond, an aromatic ring, a nitrile group, an acid amide group and a imide group.
- the heterogeneous catalytic hydrogenation reaction method according to the above item 1, wherein Item 3.
- the hydrogenation reaction is a reduction reaction of a saturated or unsaturated fatty acid alkyl ester to a saturated alcohol, a reduction reaction of an unsaturated fatty acid alkyl ester to an unsaturated alcohol, a fatty acid of an aliphatic or alicyclic dicarponic acid dialkyl ester.
- Item 1 The heterogeneous system according to Item 1, which is a reduction reaction to an aliphatic or alicyclic diole, a reduction reaction of a dicarboxylic anhydride to a lactone-based compound, or a reduction reaction of a lactone-based compound to an aliphatic diol.
- Catalytic hydrogenation reaction method is a reduction reaction of a saturated or unsaturated fatty acid alkyl ester to a saturated alcohol, a reduction reaction of an unsaturated fatty acid alkyl ester to an unsaturated alcohol, or a reaction of an aliphatic or alicyclic dicarboxylate dialkyl ester.
- Hydrogenation reaction is hydrogenation reaction of carbon-carbon double bond, nuclear hydrogenation reaction of aromatic compound, hydrogenation reaction of nitrile compound to amine, acid amide compound to amine Item 1.
- Item 6 The heterogeneous catalyst according to any one of Items 1 to 5 above, wherein the total content of chlorine atoms and sulfur atoms contained in the hydrogenated substance subjected to the hydrogenation reaction is 5 pm or less.
- Item 7 The solid catalyst according to any one of the above items 1 to 6, wherein the solid catalyst supports at least one selected from the group consisting of copper, zinc, nickel, ruthenium, palladium, platinum, mouth dies, and oxides thereof.
- the solid catalyst is at least one selected from the group consisting of copper, zinc, nickel, ruthenium, palladium, platinum, orifice and oxides thereof, and chromium, molybdenum, tungsten, magnesium, barium, aluminum 9.
- Item 9 The heterogeneous system according to any one of Items 1 to 8, wherein the solid catalyst is a solid catalyst supporting at least one selected from the group consisting of copper, chromium, zinc, nickel, ruthenium, and oxides thereof. Catalytic hydrogen reaction method.
- the shape of the solid catalyst is at least one selected from the group consisting of a cylinder, a hollow cylinder, a trilobe, a tetralobe, and a sphere, and the minimum length is 1 to 10 mm.
- Item 10 The heterogeneous catalytic hydrogenation reaction method according to any one of Items 1 to 9 above. Claim 1 1 dissolved hydrogen concentration in the liquid phase of the reaction column is, 0. 0 1 ⁇ 5.
- Item 12 In the steady state of the hydrogenation reaction, when the dissolved hydrogen concentration in the liquid phase is 1 m below the highest point of the catalyst layer in the reaction tower, 10 to 100% of the saturated hydrogen concentration in the liquid phase Item 2.
- Item 1 3 Hydrogenation reaction is
- the dissolved hydrogen concentration in the liquid phase is adjusted to 10 to 60% of the saturated hydrogen concentration in the liquid phase at a point lm below the highest point of the catalyst layer in the reaction tower.
- the heterogeneous catalytic hydrogenation reaction method as described in the above. Item 14 Hydrogenation reaction is
- FIG. 1 is a schematic diagram showing the perfusate flow conditions of the present invention.
- FIG. 2 is a plan view of a solid catalyst having a trilobal column shape, and R indicates a minimum length.
- FIG. 3 is a plan view of a solid catalyst having a four-leaf column shape, and L indicates a minimum length.
- FIG. 4 is a schematic diagram of a reaction apparatus used in each of the examples and comparative examples. The meanings of the symbols used in FIGS. 1 to 4 are as follows.
- the substance to be hydrogenated used as a raw material in the hydrogenation reaction of the present invention is at least selected from the group consisting of an ester group, a carbon-carbon double bond, an aromatic ring, a nitrile group, an acid amide group and an imide group.
- An organic compound containing one group is at least selected from the group consisting of an ester group, a carbon-carbon double bond, an aromatic ring, a nitrile group, an acid amide group and an imide group.
- the substance to be hydrogenated includes (1) fats and oils, saturated or unsaturated fatty acids derived from fats and oils, alkyl esters of the saturated or unsaturated fatty acids, (2) unsaturated fatty acids or alkyl esters thereof, and (3) aliphatic dicarbones.
- Acid dialkyl ester reaction product of aliphatic dicarboxylic acid and aliphatic diol (oligomer), (4) alicyclic dicarboxylate dialkyl ester, (5) dicarboxylic anhydride, (6) containing carbon-carbon double bond (Unsaturated fatty acids, unsaturated alcohols, etc.), (7) a compound containing an aromatic nucleus of an aromatic compound, (8) a nitrile conjugate, an acid amide compound, and (9) an acid imide compound. .
- the hydrogen reaction according to the present invention includes a reduction reaction of a saturated or unsaturated fatty acid alkyl ester to a saturated alcohol, a reduction reaction of an unsaturated fatty acid alkyl ester to an unsaturated alcohol, a dialkyl aliphatic or alicyclic dicarboxylate.
- Hydrogenation reaction of acid amide compound to amine, hydrogenation reaction of acid imide compound to pyrrolidine compound and amine are recommended.
- lower alkyl refers to an alkyl group having 1 to 4 carbon atoms, unless otherwise specified.
- the method of the present invention comprises a saturated alcohol having 8 to 22 carbon atoms from a raw material selected from the group consisting of a saturated or unsaturated fatty acid, its triglyceride and its lower alkyl ester.
- a saturated alcohol having 8 to 22 carbon atoms from a raw material selected from the group consisting of a saturated or unsaturated fatty acid, its triglyceride and its lower alkyl ester.
- coconut oil, palm oil, palm oil, olive oil, soybean oil, low-elsin rapeseed oil are used as a raw material for producing a saturated alcohol having 8 to 22 carbon atoms.
- Used frying oil such as beef tallow, lard, chicken fat, fish oil, etc., having 8 to 22 carbon atoms of saturated or unsaturated fatty acid triglyceride (oil or fat), or having 8 to 22 carbon atoms obtained from these fats or oils.
- Examples include at least one selected from unsaturated fatty acids and lower alkyl esters of saturated or unsaturated fatty acids having 8 to 22 carbon atoms.
- lower alkyl esters of the saturated or unsaturated fatty acids are preferred as the raw material for the reduction reaction.
- a specific carbon number component can be concentrated and separated by distillation or cooling solid fractionation at the stage of fatty acid lower alkyl ester (especially methyl ester) or fatty acid to obtain a reduction reaction raw material.
- a copper-based solid catalyst described below is usually used.
- the method of the present invention produces an unsaturated alcohol having 16 to 22 carbon atoms from a raw material selected from the group consisting of unsaturated fatty acid, its triglyceride and its lower alkyl ester.
- a raw material selected from the group consisting of unsaturated fatty acid, its triglyceride and its lower alkyl ester.
- Examples of the unsaturated alcohol to be produced include unsaturated alcohols having 16 to 22 carbon atoms and having at least one or more (particularly 1 to 3) unsaturated bonds in the molecule. Specific examples include elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and the like.
- Raw materials for producing the unsaturated alcohol include coconut oil, palm kernel oil, palm oil, olive oil, soybean oil, rapeseed oil, safflower oil, corn oil, cottonseed oil, sunflower oil, rice bran oil, linseed oil Etc .; used frying oil such as soybean oil, rapeseed oil, safflower oil, corn oil, cottonseed oil, sunflower oil, olive oil, rice bran oil, etc .; carbon number of tallow, ginger, chicken fat, fish oil, etc.
- lower alkyl esters of the unsaturated fatty acids, particularly methyl esters, are preferred as the raw material for the reduction reaction.
- the unsaturated fatty acid can be obtained by hydrolyzing the fat or oil according to a conventional method.
- the unsaturated fatty acid alkyl ester can be obtained by esterifying the unsaturated fatty acid thus obtained with a lower alcohol (for example, d-C alcohol such as methyl alcohol). It can also be obtained by transesterification with a C 1 -C 4 alcohol.
- a raw material selected from the group consisting of unsaturated fatty acids, their triglycerides and their lower alkyl esters is distilled or, if necessary, subjected to a cooling solid fractionation operation to obtain an iodine value of 40 to 20. It is preferable to use 0 as a reduction reaction raw material.
- ester of unsaturated fatty acid and unsaturated alcohol (ester of long-chain unsaturated fatty acid and long-chain unsaturated alcohol, ie, wax ester) generated during the reduction reaction or distillation of the reduction reaction product is also reduced. It can be used as a reaction raw material.
- the method of the present invention can be used to produce an aliphatic diol having 3 to 22 carbon atoms from an aliphatic dicarboxylic acid dialkyl ester, hydroxyalkanoic acid, its lower alkyl ester, lactone and the like.
- aliphatic diols having 3 to 22 carbon atoms to be produced include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane.
- the raw materials include (a) an aliphatic dicarboxylic acid having 3 to 22 carbon atoms which may have at least one double bond (particularly 1 to 2). Di-lower alkyl ester, (b) lower alkyl ester of aliphatic monocarboxylic acid having 3 to 22 carbon atoms having l hydroxyl groups, (c) having at least one (particularly 1 to 2) double bond
- Examples thereof include an oligoester formed by a reaction with an aliphatic group or (d) a lactone obtained from an aliphatic monocarboxylic acid having 3 to 22 carbon atoms having one hydroxyl group.
- Examples of the lower alkyl group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and a methyl group is particularly preferable.
- the raw material for 1,3-propanediol is 1-hydroxypropanoic acid, which is a water adduct to the double bond of acrylic acid lower alkyl ester (eg, methyl ester).
- Alkyl esters eg, methyl esters
- a demethyl alcohol condensate of 1-hydroxypropanoic acid lower ester can also be used.
- a condensate (particularly, an oligomer) of 1-hydroxypropanoic acid and its reduction product, 1,3-propanediol can also be used.
- examples of the raw material of 1,4-butanediol include di-lower alkyl maleate, di-lower alkyl succinate, and carboxylactone. Is done.
- alkyl group examples include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group.
- the substitution position is not particularly limited.
- 1,6-hexanediol as raw materials, specifically, di-lower alkyl adipate, ⁇ -force prolactone, 1-hydroxycaproic acid and / or 1-hydroxycaproic acid lower
- Examples include oligo sesame obtained by subjecting an alkyl ester to dehydration esterification condensation and / or transesterification, and 1,6-hexanediol and 1-hydroxycabronic acid and ⁇ or 1-hydroxycabronic acid lower alkyl ester.
- oligoesters of 1,6-hexanediol and adipic acid are examples of 1,6-hexanediol and adipic acid.
- the method of the present invention can be used to produce an alicyclic diol having 8 to 12 carbon atoms from an alicyclic dicarponic acid di (C i -C ⁇ ) alkyl ester.
- alicyclic diol having 8 to 12 carbon atoms to be produced include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexane.
- examples include sandimethanol, 1,5-decalin dimethanol, and 2,6-decalin dimethanol.
- the starting materials include alicyclic dicarponates (C i—) which may have at least one (particularly 1 to 2) double bonds in the molecule.
- C10 ) alkyl esters are exemplified.
- Alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, n-hexyl, n- Linear or branched aliphatic group such as butyl group, n-butyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl An alicyclic group such as a hexyl group is exemplified.
- a 1,4-hexahydrophthalic acid di (C i -C 10 ) alkyl ester is exemplified. .
- 1,5-decalin dimethanol or 2,6-decalin dimethanol as raw materials, specifically, 1,5-decalin dicarboxylic acid di (C i -C 4 ) alkyl
- the ester include 2,6-decalin dicarboxylic acid di (C i -C 4 ) alkyl ester.
- the heterogeneous catalytic hydrogenation reaction of the present invention is carried out using a copper-based solid catalyst described below. Is preferred.
- the present invention can be used to produce an intramolecular esterification reaction product, a captyrolactone-based compound, from a dicarboxylic anhydride.
- a captyrolactone-based compound from a dicarboxylic anhydride.
- the aptyrolactone-based compound include arptyrolactone, phthalide, hexahydrofuride and the like.
- a nickel-based solid catalyst described below or a noble metal-based solid catalyst described below is used. Is preferably used to carry out the heterogeneous catalytic hydrogenation reaction of the present invention.
- the present invention is applicable to a reaction for hydrogenating a carbon-carbon double bond.
- the method of the present invention can be used to produce a fat and oil from fats and oils which are glycerides of unsaturated fatty acids, and the carbon-carbon duplex slightly remaining in a saturated alcohol having 8 to 22 carbon atoms. It can be applied to the process of hydrogenating bonds to reduce iodine value and produce high quality saturated alcohol. In these cases, it is usually preferable to carry out the heterogeneous catalytic hydrogenation reaction of the present invention using a nickel-based solid catalyst.
- the method of the present invention comprises the steps of: starting from an unsaturated alcohol containing a conjugated double bond in the liver (C 16 —c 22 , particularly c 18 ) as a raw material, hydrogenating a conjugated gen in the unsaturated alcohol to a monoene,
- the present invention can be applied to a process for producing an unsaturated alcohol containing no gen compound.
- Such unsaturated alcohols are excellent in stability over time and heat resistance.
- a process for producing a succinic anhydride by hydrogenating maleic anhydride delta 4 - tetrahydrofuran Yuru anhydride process for producing Kisahidorofu Yurusan anhydride to be hydrogenated
- delta 4 Process of hydrogenating dialkyl tetrahydrophthalate (straight or branched C1-13) ester to produce dialkylhexahydrophthalate (straight or branched C1-13) ester Applicable to In this case, it is usually preferable to carry out the heterogeneous catalytic hydrogenation reaction of the present invention using a nickel-based solid catalyst described below or a noble metal-based solid catalyst described below.
- This invention is applicable to the nuclear hydrogenation reaction of an aromatic compound.
- the aromatic compound as a raw material include a compound containing a benzene ring and a naphthalene ring.
- Cyclohexanedicarboxylic carboxylic acid di (C ⁇ one c 13) alkyl cycloheteroalkyl as a raw material, terephthalic acid di (C i- C 1 3) alkyl, isophthalic acid di (C i- c 13) ⁇ alkyl, Examples thereof include di (C i -C ⁇ ) alkyl terephthalate.
- Examples of the C 13 alkyl group include a methyl group, an ethyl group, and an n-pro Straight chain such as pill, iso-propyl, n-butyl, sec-butyl, iso-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl And alicyclic groups such as linear or branched aliphatic groups, cyclopentyl groups, cyclohexyl groups, 2-methylcyclohexyl groups, 3-methylcyclohexyl groups, and 4-methylcyclohexyl groups. .
- the raw materials used are raw tecole, resorcinol, hydroquinone, 4,4'-biphenol, bisphenol A, Bisphenol Z and the like are exemplified.
- alicyclic diamines such as methylenebis (cyclohexylamine), o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine , 4,4′-methylenedianiline and the like.
- the method of the present invention can be applied to a heterocyclic hydrogenation reaction of a complex ring compound having at least one (particularly 1 to 5) unsaturated bonds.
- heterocyclic compounds include pyridine compounds such as pyridine and methyl nicotinate, quinoline compounds such as quinoline, and furan compounds such as furfuryl aldehyde and furan carboxylic acid.
- piperidine from pyridine methylhexahydronicotinate from methyl nicotinate, decahydroquinoline from quinoline, tetrahydrofurfuryl alcohol from furfurylaldehyde capra, Tetrahydrofurfurylcarboxylic acid can be produced from furancarboxylic acid.
- the heterogeneous catalytic hydrogenation reaction of the present invention is usually performed using a nickel-based solid catalyst described below or a noble metal-based solid catalyst described below. Is preferred.
- the method of the present invention is applicable to the hydrogenation reaction of nitrile compounds to amines.
- the nitrile compound as a raw material is not particularly limited, but specific examples thereof include butyronitrile, laurylonitrile, and stearonitrile.
- the method of the present invention can be applied to a hydrogenation reaction of an acid amide compound to an amine.
- the acid amide as a raw material is not particularly limited, but specific examples thereof include butyric amide, lauric amide, and stearic amide.
- the heterogeneous catalytic hydrogenation of the present invention is usually carried out from a nitrile compound or an acid amide compound using a nickel-based solid catalyst described below or a noble metal-based solid catalyst described below.
- the amine is produced by the reaction.
- the present invention can be applied to a hydrogenation reaction of an acid imide to a pyrrolidine compound diamine.
- a hydrogenation reaction of an acid imide to a pyrrolidine compound diamine for example, the ⁇ 4 Tetorahido port phthalate Imido and Z or to Kisahido port phthalate I Mi de hydrogenated, it is possible to manufacture the O Kuta tetrahydroisoquinoline indole.
- a copper-based solid catalyst described below or a noble metal-based solid catalyst described below it is usually preferable to use a copper-based solid catalyst described below or a noble metal-based solid catalyst described below to produce a pyrrolidine compound amine from the acid imide compound by the heterogeneous hydrogenation reaction of the present invention.
- the hydrogenation reaction is a reduction reaction of a saturated (unsaturated) fatty acid alkyl ester to a saturated alcohol, and a hydrogenation reaction of an unsaturated fatty acid alkyl ester to an unsaturated alcohol.
- the reaction and the nuclear hydrogenation reaction of aromatic compounds are particularly suitable for the present invention.
- the above-mentioned various compounds can be used.
- the total content of chlorine atoms and sulfur atoms is 5 ppm or less, preferably 3 ppm or less, particularly It is preferably at most 1 ppm, more preferably at most 0.3 ppm.
- catalyst poisoning by chlorine atoms is completely different from catalyst poisoning by sulfur atoms. That is, the sulfur compound reacts extremely quickly with the catalyst metal under the hydrogenation reaction conditions, and is localized at the top of the catalyst layer as a metal sulfide.
- a chlorine atom may take a behavior called migration.
- metal chlorides produced by reacting with the catalyst metal tend to dissolve in the reaction solution and diffuse downward in the catalyst layer, expanding the poisoned area (catalyst inactive area).
- the reaction of the organochlorine compound with the catalyst is delayed, and as a result, reaches the lower portion of the catalyst layer and behaves in the same manner as the above migration.
- the present inventors have found that a raw material having a total content of chlorine atoms and sulfur atoms of 5 ppm or less is effective in the presence of two types of poisoning substances having completely different behaviors of sulfur and chlorine. It is a thing.
- the cause of the chlorine atom is included when inorganic compounds such as salt (NaCl) and hydrochloric acid salt are mixed, and when organic chlorine compounds are mixed.
- Contamination of salt is a fundamental problem, especially when the substance to be hydrogenated is derived from a natural product such as a plant, because many of the natural products require salt for the activity of producing the substance to be hydrogenated.
- Chlorine atoms may be mixed in due to the use of hydrochloric acid for the neutralization of the transesterification catalyst or the esterification catalyst.
- Inorganic compounds can generally be reduced and removed by washing with water.
- chlorine compounds may react with the raw materials to form organic chlorine compounds.
- high temperatures are heated together with the blood and gravy of slaughtered beef and pork, so that some of the salt is made organic and the fatty acids derived from tallow and lard convert organic chlorine.
- the recovered vegetable frying oil (commonly known as vegetable No. 2 oil) contains organic chlorine as a result of contact with food containing salt at high temperatures.
- Fatty acids derived from coconut oil also contain naturally occurring organic chlorine.
- the most preferable method is to use these chlorine-free raw materials, but it can be selected in consideration of raw material prices and supply stability.
- Sulfur atoms may be mixed in due to the use of P-toluenesulfonic acid or sulfuric acid in the ester exchange catalyst neutralization or esterification catalyst. These compounds can generally be reduced and removed by washing with water.
- protein-derived sulfur compounds such as cystine are mixed.
- Beef tallow, lard, palm oil, palm oil, and palm kernel oil contain such a protein-derived sulfur compound.
- the sulfur compound is mixed with the fatty acid and methyl ester supplied to the present invention. Sulfur compounds from these proteins are reduced by distillation. Can be reduced.
- sulfur compound content is often influenced by the upstream raw material production process, and raw material selection is the preferred method.
- carbon - used in the reaction for hydrogenating carbon-carbon double bond delta 4 - tetrahydrofuran Yuru acid anhydride and delta 4 -
- a conjugated diene of compound anhydride Manufactured by a Diels-Alder reaction of maleic acid, but sulfur compounds such as carbon disulfide are often mixed in butadiene-isoprene of the conjugated conjugate, and it is preferable to select raw materials.
- reaction raw material for nuclear hydrogenation of an aromatic compound it is preferable to select a deep desulfurized raw material of extremely low sulfur content for a petroleum-based one.
- sulfur compounds such as thiophene are often contained in a large amount, and it is preferable that they are not used in the present invention.
- solid catalyst used in the present invention known solid catalysts used in hydrogenation reactions can be used. Among them, copper, zinc, nickel, ruthenium, palladium, platinum, rhodium and their oxides are exemplified. Solid catalysts supporting at least one member selected from the group consisting of products are exemplified. Further, such a solid catalyst includes, as a co-catalyst, at least one metal selected from the group consisting of chromium, molybdenum, tungsten, magnesium, barium, aluminum, calcium, zirconium, manganese, nickel, silicon and oxides thereof. May be further carried.
- Examples of the carrier used for such a solid catalyst include silica, alumina, silica alumina, titania, diatomaceous earth, terra alba, activated carbon, carbon, graphite, zeolite, clays such as montmorillonite, and carriers such as alkaline earth silicates. You.
- the solid catalyst used in the present invention is a known catalyst. These catalysts can be used as they are, but are preferably subjected to a suitable activation treatment such as a reduction treatment before use. Activation treatment such as reduction treatment can be performed by a commonly used method.
- Copper-based catalysts include copper, copper-zinc, copper-chromium, copper-zinc-chromium and these One or more catalysts selected from the following oxides; and copper-based catalysts, with addition of polybutene, tungsten, magnesium, barium, aluminum, iron / steam, zirconia, gaynes and their oxides
- a solid catalyst supporting the modified catalyst is exemplified.
- solid catalysts supported on alkaline earth metal silicates in the form of copper-calcium-silicic acid, copper-manganese monosilicate, copper-barium monosilicate, copper-calcium-barium-silicate, copper-calcium-barium-manganese-silicate. Is exemplified.
- copper-based solid catalysts can be suitably used for a reduction reaction of a saturated or unsaturated fatty acid ester to a saturated alcohol.
- the notation “M 1 -M 2 oxide” such as the above-mentioned copper-chromium oxide refers to a catalyst containing an oxide of metal Ml and an oxide of metal M 2.
- copper-chromium oxide refers to a catalyst comprising copper oxide and chromium oxide.
- M1-M2-M3 oxide such as copper-zinc-aluminum oxide refers to the oxide of metal M1, the oxide of metal M2, and the oxide of metal M3.
- “copper-zinc-aluminum oxide” refers to a catalyst containing copper oxide, zinc oxide, and aluminum oxide. The same applies to other similar expressions.
- zinc catalyst examples include zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxide, zinc-iron oxide, zinc-iron-aluminum oxide, and the like. Is done. These zinc-based solid catalysts can be suitably used for the reduction reaction of unsaturated fatty acid ester to unsaturated alcohol.
- nickel-based catalyst examples include nickel-diatomaceous earth and nickel-chromium oxide. These nickel-based solid catalysts can be suitably used for a hydrogenation reaction of a double bond or a nuclear hydrogenation reaction.
- Noble metal-based solid catalysts containing ruthenium, palladium, platinum, rhodium or oxides thereof include silica, alumina, silica-alumina, titania, activated carbon, carbon, graphite, and other such carriers.
- a solid catalyst supporting an oxide of the metal is exemplified. These noble metal-based solid catalysts are effective catalysts for various hydrogenation reactions, and are particularly effective for hydrogenation reactions of double bonds and nuclear hydrogenation reactions.
- the shape of the solid catalyst used in the present invention is preferably a cylinder, a hollow cylinder, a three-lobe pillar, a four-leaf pillar, and a three-dimensional shape, or the like. Solid catalysts having two or more different shapes may be used. No.
- a solid catalyst with a minimum length of about 1 to about L O mm is recommended.
- the "minimum length" means, for example, for a spherical catalyst having a diameter of 5 mm, the minimum length is 5 mm, and the diameter is 3 mm x height. For a 5 mm cylindrical catalyst, its minimum length is 3 mm.
- the minimum length of the hollow cylinder is 3 mm which is larger than the inner diameter.
- the size (R) shown in Fig. 2 is the minimum length for trilobular columns
- the size (L) shown in Fig. 3 is the minimum length for tetralobular columns (both height (axial direction)). Length) is larger than R or L).
- the productivity tends to decrease because the external surface area of the solid catalyst in the reactor becomes small. If the diameter is less than 1 mm, the solid catalyst is too clogged, and the pressure loss tends to be large, so that it tends to be difficult to form a perfusate flow.
- the method for producing these solid catalysts is not particularly limited. Conventionally known methods such as a molding method, an extrusion molding method, and a melt granulation method can be exemplified. Specifically, powders and pastes are compressed by a tableting machine, a granulator, an extrusion molding machine, a spherical molding machine in oil, or the like. It can be easily manufactured.
- the solid catalyst of the present invention is filled with a solid catalyst having a catalyst strength of 1.0 kg or more per catalyst.
- the catalyst strength in the present invention is defined as the strength obtained by measuring the minimum crushing strength individually for 100 catalysts, calculating the average value A and the standard deviation value ( ⁇ ), and obtaining the equation ⁇ 2 ⁇ . is there. In the present invention, it is important that the strength of the catalyst is not less than 1.0 kg, particularly 1.5 to 4.0 kg.
- the minimum crushing strength is measured in accordance with JIS Z—8841–1993, “3.1 Method of crushing strength test method”.
- the “minimum crushing strength” refers to the crushing strength measured by compressing the solid catalyst of the cylinder, hollow cylinder, trilobe, and tetralobe used in the invention in the longitudinal direction (axial direction).
- Degree of crushing is the smaller of the crushing strengths measured by compressing from the degree and the lateral direction (radial direction, that is, the direction perpendicular to the axis direction).
- it has the shape of a hollow cylinder, a trilobular pillar, a tetralobular pillar, etc., it is horizontal (perpendicular to the axial direction).
- the consolidation strength is called the minimum consolidation strength. If the above catalyst strength is less than 1.0 kg, there is a tendency for catalyst outflow due to damage to the catalyst and, in particular, a tendency to block the reaction vessel and connecting pipes. Also, even if the catalyst has a high average value (A), if the standard deviation value ( ⁇ ) is large, that is, if the ratio of catalysts with low strength is large, these weak catalysts will be damaged, and catalyst loss and equipment loss will occur. Solid catalysts, which tend to be clogged and take into account variations in strength, are effective. This does not occur within the scope of the present invention.
- the catalyst strength determined by the above equation ⁇ 2 ⁇ is based on the fact that the minimum compaction strength of 97.5% or more of the solid catalyst is 1 kg or more in arbitrary 100 catalysts. It is a representation of the total. Hydrogenation reaction method
- the heterogeneous catalytic hydrogenation reaction method of the present invention comprises the steps of: using an undesired S hydrogenation material as a raw material in the presence of the above-mentioned catalyst, and performing an upward reaction between hydrogen gas and the hydrogenation material under perfusate flow conditions. It is a method of flowing down in parallel flow, and the details are described below.
- the perfusate flow of the present invention is defined as a liquid phase (that is, a liquid hydrogenated substance) flows down in a film form on the solid catalyst by the action of gravity, and is parallel to a film liquid phase flowing down on the surface of the solid catalyst particles.
- a liquid phase that is, a liquid hydrogenated substance
- Fig. 1 shows an example.
- the liquid phase 100 flows in the form of a film along the surface of the solid catalyst particles 102, flows down in the form of a film along the surface of the solid catalyst i 103 under the solid catalyst particles 102, and further flows in a solid form. It flows down in a film along the surface of the solid catalyst particles 104 below the catalyst particles 103 (and the solid catalyst particles following it).
- the liquid phase 100 flows in a film along the surface of the solid catalyst particles 110 adjacent to the solid catalyst particles 102, and the solid catalyst particles 1 1 1 (and subsequent solid catalyst particles 1 11 Particles) along the surface of the particles.
- FIG. 1 shows an example in which a spherical solid catalyst is used, the above description also applies to solid catalysts of other shapes.
- Such irrigation flow conditions vary depending on the tube diameter, feed rate and hydrogen gas supply rate, hydrogen gas pressure, and catalyst dimensions;
- the raw material supply rate per reactor cross-sectional area lm 2 is under the reaction conditions, 0. 4 ⁇ 4 0 m 3 Zh about (preferably l ⁇ 3 0 m 3 Zh extent, more preferably about 2 ⁇ 3 0 m 3 / h ⁇ , hydrogen gas feed rate per reactor cross-sectional area lm 2 is under the reaction conditions, 4 ⁇ 4 0 0 0 m 3 /7 !! about (preferably Is 10 to 2 0 0 0 m 3 / h, more preferably about ⁇ flow is obtained within the range of about 40 ⁇ 1000m 3 / h.
- the hydrogen gas supply rate is higher than this, a part of the liquid phase (substance to be hydrogenated) becomes a spray flow that flows as droplets, and the high productivity of the present invention cannot be obtained.
- Larger feed rates result in pulsating flow.
- the solid catalyst collides and crushes due to a phenomenon of increasing pressure loss and a phenomenon of fluidization of the solid catalyst, which is not preferable for the heterogeneous catalyst hydrogenation reaction method of the present invention.
- the supply amount of the raw material increases, the raw material becomes a continuous phase, and the gas is dispersed to form a bubble flow that flows as bubbles, so that the high productivity of the present invention cannot be obtained.
- the dynamic liquid phase retention amount per unit tactile surface area is changed under the reaction conditions after the time when the hydrogenation reaction is in a steady state.
- 0. 005X 10- 3 ⁇ 0. 14X 10- 3 m 3 / m 2 approximately, preferably 0. 05X 10-3 ⁇ 0. 12X 10- 3 m 3 is important is Zm 2 about. If the dynamic liquid phase retention amount per catalyst external surface area is greater than 0.14X10-3 mV m 2 , a pulsatile flow will tend to occur where the liquid phase retention volume is too high and the liquid phase retention volume is low. There, whereas, 0. 005X 10- 3 m 3 or Zm 2 than less the Most feeding rate is too small theoretically high productivity can not be obtained, the gas flow rate is large to Kisugi to form a spray stream of the aforementioned would.
- Dynamic liquid phase retained amount per unit catalyst outer surface area to be adjusted to 0. 005X 10- 3 ⁇ 0. 14X 10- 3 m 3 Zm 2 approximately ranges, in particular employing the ⁇ flow conditions In addition, it can be carried out by adjusting the size (minimum length) and shape of the solid catalyst to be filled.
- the “catalyst outer surface area” of the present invention is the outer surface area of the solid catalyst, and is the surface area of the solid catalyst particles when viewed macroscopically.
- the outer surface area of the catalyst is, for example, in the case of a cylindrical catalyst having a radius of r and a height of !!!, the sum of the area 2 ⁇ r 2 of the upper and lower circles and the side area 27 rh, For example, in the case of a sphere with a radius r, it is 4 Ttr 2 .
- the above terms will be used to distinguish them from the microscopic surface area of the catalyst containing pores.
- “per unit catalyst external surface area” means a total of the catalyst external surface areas of a plurality of catalysts packed in the reaction tower per 1 m 2 .
- the “dynamic liquid phase holding amount” in the present invention is a value obtained by subtracting the static holding amount from the total hold-up amount.
- reaction solution near the catalyst point where the solid catalysts come into contact with each other is almost completely shaded by the solid catalyst and the surface tension, etc. It is stationary and has little contribution to production and is not taken into account. This is called a static holding amount.
- the liquid phase (substance to be hydrogenated) 100 is shaded by the solid catalyst 102 in the space between the solid catalyst 102 and the solid catalyst 103. Due to factors such as surface tension and the like, they stay in the space between the solid catalyst 102 and the solid catalyst 103 and are almost still. The amount of liquid phase that has stayed and is almost stationary is called static liquid phase retention.
- the dynamic liquid phase holding amount per outer surface area of the catalyst of the present invention indicates the total amount of liquid phase flowing down along the surface of each catalyst in a film in parallel with the descending hydrogen gas. Therefore, the sum of the static liquid phase holding amount and the dynamic liquid phase holding amount is the total hold-up amount.
- the dynamic liquid is measured by measuring the weight (W) of the liquid discharged from the lower part of the reaction tower. The amount of phase retention can be measured. That is, W is the dynamic liquid phase holding amount.
- the dynamic fluid phase holding amount 0. 0 0 5 X 1 0- 3 ⁇ 0 per catalyst outer surface area as described above.
- the concentration of dissolved hydrogen in the liquid phase is preferably from 0.01 to 5.0 kmO I Zm 3 , particularly preferably from 0.3 to 5.0 ⁇ O kmol Zm 3 .
- the dissolved hydrogen concentration in the liquid phase is changed to the saturated hydrogen concentration in the liquid phase at a point lm below the highest point of the catalyst layer in the reaction tower. It is preferably adjusted to 10 to 100%.
- reaction is particularly intense, for example, (1) translation, saturated or unsaturated fatty acid derived from fats and oils, alkyl ester of the saturated or unsaturated fatty acid, (2) unsaturated fatty acid or its alkyl ester, (6) Hydrogenation of large amounts of double bonds, such as hydrogenation of double bonds in compounds containing carbon-carbon double bonds (unsaturated fatty acids, unsaturated alcohols, etc.), (7) aromatics Nuclear hydrogenation processes such as hydrogenation of compounds, (1) fats and oils, saturated fatty acids derived from fats and oils, alkyl esters of the saturated fatty acids, (2) unsaturated fatty acids or (3) aliphatic dicarboxylic acid dialkyl ester, reaction product of aliphatic dicarboxylic acid and aliphatic diol (oligomer), (4) hydrogenation reaction of alicyclic dicarboxylic acid dialkyl ester, etc.
- the concentration of dissolved hydrogen in the liquid phase is adjusted to the value of the saturated hydrogen concentration in the liquid phase at a point 1 m below the highest point of the catalyst layer in the reaction tower. Preferably, it is adjusted to 10 to 60%.
- a process of selecting a catalyst having a low reaction activity to maintain reaction selectivity such as a process for producing an unsaturated alcohol from an unsaturated carboxylic acid ester;
- the process of selecting mild reaction conditions such as the process of hydrogenating to monoene and producing unsaturated alcohols that do not contain conjugated compounds; carbon remaining in saturated alcohols with 8 to 22 carbon atoms—
- the dissolved hydrogen concentration is adjusted to 50 to 100% of the saturated hydrogen concentration in the liquid phase at a point lm below the highest point of the catalyst layer in the reaction tower.
- the dissolved hydrogen concentration and the saturated hydrogen concentration refer to the concentration at the temperature and pressure of the hydrogenation reaction, respectively.
- the “saturated hydrogen concentration in the liquid phase” indicates the maximum hydrogen concentration that can be dissolved in the reaction substrate itself, and the hydrogen gas and the liquid phase can be sufficiently dissolved under the set reaction conditions without a catalyst. Is the saturated hydrogen concentration obtained by contacting
- the dissolved hydrogen concentration of the present invention is the concentration of hydrogen in a liquid phase that comes into contact with a solid catalyst together with a substance to be hydrogenated as a result of gas phase hydrogen molecules being dissolved in the liquid phase.
- the dissolved hydrogen concentration is preferably set to 10 to 100% with respect to the saturated hydrogen concentration.
- the actual value is 100%.
- the reaction amount between the reaction substrate and the hydrogen molecule is very large, and the dissolved hydrogen concentration tends to be low. According to the study of the present inventors, it was found that maintaining the concentration of dissolved hydrogen in the liquid phase at 10% or more at the lm point in the upper part of the reaction tower was advantageous for obtaining high productivity.
- the dissolved hydrogen concentration range and the ratio of the dissolved hydrogen concentration to the saturated hydrogen concentration are affected by an extremely large number of factors, various methods can be adopted.For example, considering the following factors, It can be done easily. That is, regarding the solid catalyst, the selection of a low-activity catalyst, the reduction of the active species concentration of the catalyst, the reduction of the catalytic surface area, and the reduction of the dynamic liquid phase retention amount tend to increase the hydrogen concentration. Regarding the hydrogen gas supply method, increasing the hydrogen pressure and increasing the hydrogen flow rate tend to increase the dissolved hydrogen concentration. As for the method of supplying hydrogenated substances, reducing the concentration of the reaction substrate and the amount of the supply of the reaction raw material tend to increase the dissolved hydrogen concentration. Therefore, the relationship between these factors and the above-mentioned dissolved hydrogen concentration (and the ratio of the dissolved hydrogen concentration to the saturated hydrogen concentration) is determined in advance under the set reaction conditions. It can be easily carried out by appropriately selecting these conditions according to the type of product.
- the reaction temperature and reaction pressure of the hydrogenation reaction are not particularly limited as long as the hydrogenation reaction can be completed, but the reaction temperature is usually 50 to 350 as a condition for obtaining a practical reaction rate. And preferably in the range of about 50 to 300, and the reaction pressure is generally recommended to be in the range of normal pressure to about 35 MPa, preferably about 0.9 to 30 MPa.
- the above hydrogenation reaction is usually carried out without a solvent, but when the raw materials and Z or the reaction product have a high melting point and are difficult to handle, improve the reactivity and selectivity, and efficiently use the heat of reaction.
- a solvent can be used for removal or the like.
- the reaction If the melting point of the reaction product is low, the reaction The use of the product itself is also an effective method. In the case of a nuclear hydrogenation reaction in which the heat of reaction is extremely large, a method of diluting with a solvent or a reaction product itself and supplying the diluted solution can be employed.
- the solvent is generally inert to the hydrogenation reaction, and can be appropriately selected from solvents which do not react with the raw materials and the reaction products.
- water alcohols having 1 to 10 carbon atoms, diols such as ethylene glycol and propylene glycol, ether solvents such as diglyme and triglyme, ether alcohols such as methyl propylene glycol and butyl cellulose, and carbon atoms 5 to 10 paraffins, cycloparaffin hydrocarbons and the like can be used.
- aromatic hydrocarbons such as toluene and xylene can be used.
- the amount of the solvent used is not particularly limited, but is in the range of 0.05 to 0.5 parts by weight, preferably 0.1 to 5 parts by weight, based on 1 part by weight of the material to be hydrogenated, on a weight basis. It is in the range of 0 parts by weight.
- the reaction tower used in the present invention may be of any shape that forms a uniform irrigation flow when filled with a solid catalyst.
- a facility such as a Pakarecap-type dispersion plate for uniformly supplying a supply liquid to the solid catalyst may be provided at the upper part.
- the length and it diameter of the reactor can be selected as appropriate according to the type of raw material, type of reaction, production volume, equipment construction cost / operability, etc., but generally the diameter is about 2 to 200 cm. It is preferable to use a reactor having a length of about 3 to 100 cm, particularly about 2 to 20 m, particularly about 3 to 15 m.
- a multi-tube reactor can be used as the reactor.
- the diameter is about 2 to 2 Ocm, preferably 2 to about 0 cm, and the length of the catalyst layer is 2 to 2 cm.
- a process of connecting piping for introducing hydrogen gas for cooling in the middle of the reaction tower is used, or a heat exchanger that removes heat during the most intense reaction is connected in series. It is preferred to select a process to connect to Example
- the equipment shown in Fig. 4 is used. That is, the reactor 1 having a diameter of 40 cm and a catalyst height of lm of 40 mm, and the reactors 2, 3 and 4 having a height of 40 cm and a height of 3 m passing through a high pressure gas-liquid separator 5, 7 and 8 And connected in series.
- a bubble-cap type dispersion plate (not shown) was installed horizontally at the top of each reaction tower.
- the reactor 1 having a catalyst filling height of lm since the reactor 1 having a catalyst filling height of lm was used, a device capable of measuring the concentration of dissolved hydrogen at a point 1 m below the highest point of the catalyst layer of the reaction tower was obtained.
- an integrated reaction tower equipped with a redispersion device may be used.
- reaction tower 4 High-pressure gas-liquid connected to the last part (that is, reaction tower 4) of the reaction tower (reactor tower 4) consisting of reactors 1, 2, 3, and 4 (catalyst packed bed 11: total height of L4 is 10 m) Collected from separator 9 The conversion of the final reaction product taken was measured.
- a low-pressure gas-liquid separator 6 is installed at the bottom of the high-pressure gas-liquid separator 5 connected to the reactor 1 with a catalyst filling height of 1 m, and moves from the high-pressure gas-liquid separator 5 to the next reactor 12.
- the dynamics per unit catalyst external surface area under perfusate flow conditions The liquid phase retention was measured.
- the catalyst outer diameter surface area was obtained by measuring the dimensions (diameter and height) of 10 catalysts used, obtaining an average value of the dimensions, and calculating from the average value.
- a low-pressure gas-liquid separator 6 was installed at the bottom of the high-pressure gas-liquid separator 5 connected to the reactor 1 with a catalyst filling height of 1 m, and a certain amount of the reaction liquid (liquid phase) was withdrawn in a sealed state.
- the amount of dissolved hydrogen gas was calculated by measuring the amount of dissolved hydrogen gas at high pressure based on changes in the pointer of the installed pressure gauge.
- the dissolved hydrogen concentration becomes enthusiastic according to the reaction situation in the reactor 1 (that is, the point lm from the highest point of the catalyst layer). I have.
- the liquid phase in the reactor 1 is transferred to the low-pressure gas-liquid separator 6, the hydrogen molecules dissolved in the liquid phase are released in a gaseous state, and the pointer of the pressure gauge 6 1 is attached. Appears as a change (pressure increase). From the space volume and the pressure increase of the low-pressure gas-liquid separator 6, the dissolved hydrogen concentration of the liquid phase in the high-pressure gas-liquid separator 5 was calculated.
- a point 1 m below the highest point of the catalyst layer at the top of the reaction tower is abbreviated as “1 m point at the top of the reaction tower”.
- the catalyst-free reaction solution collected by the method described in 4) above was batch-converted with a stirrer. Hydrogen gas was supplied to the flask while stirring, and the saturated hydrogen concentration of the liquid phase at the temperature and the pressure was measured.
- the principle of measuring the pneumatic strength is as follows: a solid catalyst particle, which is the substance to be measured, is placed on a stationary sample table with a diameter of 25 mm, and a movable pressurized surface with a diameter of 5 mm is placed from above. It is processed at a speed of 1 mmZ seconds and measures the strength when it is pressed against the substance to be measured and breaks.
- the compressive strength measured by compressing from the lateral direction was lower than the compressive strength measured by compressing from the longitudinal direction.
- the crushing strength was defined as “minimum crushing strength”.
- catalyst strength (kg) ⁇ -2 ⁇
- ⁇ indicates the average value of the minimum crushing strength
- ⁇ indicates the standard deviation value of the minimum crushing strength
- the values of the raw material supply rate, the hydrogen gas rate, and the dynamic liquid phase holding amount are values under the reaction conditions.
- Reactors 1, 2, 3 and 4 were filled with a cylindrical copper-chromium oxide catalyst (bulk specific gravity: 1.1 kg / liter) manufactured by a tableting machine having a diameter of 3 mm and a height of 3 mm. Hydrogenation was performed in advance to activate the catalyst. More specifically, after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 150 ° C. in a nitrogen stream. Over a period of 10 hours, gradually increase the hydrogen gas concentration so that the hydrogen gas becomes 100% gradually. A nitrogen-hydrogen mixed gas was flowed. After the hydrogen gas reached 100%, the temperature was increased to 220. Immediately before the supply of the raw material was started by operating the hydrogen gas circulator 16, the hydrogen gas supply rate was set to be equal to the predetermined rate below.
- a cylindrical copper-chromium oxide catalyst bulk specific gravity: 1.1 kg / liter
- Palm kernel oil-derived methyl laurate (vulcanization ⁇ Yuryou 0. 05ppm, chlorine content 0. 20 ppm), placed in a raw material tank T, reactor cross-sectional area lm 2 per raw material supply rate 1 ⁇ 3 ⁇ in the reaction column cross-sectional area lm 2 per hydrogen gas velocity 80 OMV, temperature 220, pressure 18 MPa, the reactor 1, 2, 3 and successively to 4 via the high-pressure gas-liquid separator 5, 7 and 8
- the raw material and hydrogen gas were supplied, and the system was operated for 500 hours under perfusate flow conditions to obtain a crude product of lauryl alcohol as a hydrogenation product.
- the dynamic liquid phase retention amount per unit catalyst external surface area was 0.09 ⁇ 10 ⁇ 3 mVm 2 .
- Dissolved hydrogen concentration was 0. 8 kmo IZm 3.
- Example 2 The same as in Example 1 except that at a hydrogen gas velocity of 5000 m 3 Zh per reactor cross section lm 2 , the raw material supply rate was set to 5 Om 3 ⁇ per reactor cross section lm 2 which is a flow rate at which a pulsating flow occurs. Operated.
- Dynamic liquid phase retained amount per unit catalyst outer surface area was 0. 1 5X 10- 3 mVm 2.
- the pressure in the high-pressure gas-liquid separator 9 in the reactor 4 decreased, and conversely, the pressure in the hydrogen gas pipe supplied to the reactor 1 increased.
- the reaction was stopped, the reaction tower was opened, and the catalyst was inspected. As a result, the catalyst at the bottom of each reaction tower was crushed, and the bottom pipes were almost closed.
- Reactors 1 to 4 were filled with a cylindrical copper-chromium oxide catalyst having a diameter of 3 mm and a height of 3 mm.
- the reaction was carried out in the same manner as in Example 1 except that this catalyst was used.In 200 hours, the pressure of the high-pressure gas-liquid separator 9 of the reactor 4 was reduced. Pressure is rising. The reaction was stopped, the reaction tower was opened, and the catalyst was inspected. As a result, the catalyst at the bottom of each reaction tower was crushed, and the bottom piping was almost closed.
- Reactors 1 to 4 were charged with a cylindrical copper-chromium oxide catalyst having a diameter of 3 mm and a height of 3 mm.
- the operation was performed in the same manner as in Example 1 except that this catalyst was used. After 100 hours, the pressure of the high-pressure gas-liquid separator 9 of the reactor 4 was reduced. Pressure is rising. The reaction was stopped, the reaction tower was opened, and the catalyst was inspected. As a result, the catalyst at the bottom of each reaction tower was partially crushed, and the bottom pipe was almost closed.
- Example 2 Hydrogenation reaction of unsaturated fatty acid alkyl ester to saturated alcohol Unsaturated fatty acid obtained by distilling a fatty acid obtained by hydrolyzing palm oil and fractionating the solid by cooling (Iodine value 98.3, glc composition C14: 0.6%, C16: 5.0%, C18F0: 1.8%, C18F1: 74.5%, C18F2: 18.0%, C20F 1: 0.1
- the notation (Fn) such as Fl, F2, etc. indicates that the unsaturated fatty acid has n double bonds.
- the same applies to the following description which is esterified with methyl alcohol and p-toluenesulfonate.
- the methyl ester (0.5% sulfur content, 0.7 ppm chlorine content) washed with ⁇ and washed with ⁇ was used as a raw material.
- Dynamic liquid phase retained amount per unit catalyst outer surface area was 0. 10X10- 3 m 3 Zm 2. Dissolved hydrogen concentration in the liquid phase was 0. 7 kmo lZm 3.
- 500 ml of the reaction liquid phase obtained here was put into a 1000 ml batch type autoclave, hydrogen gas was supplied under stirring, heated to 220 ° C, and the saturated hydrogen concentration at 18 MPa was measured. It was 5 kmo 1 / m 3 . That is, the concentration of dissolved hydrogen in the liquid phase at a point 1 m above the reaction tower was 47% of the saturated hydrogen concentration in the liquid phase.
- Example 3 Beef tallow Z Fatty acid mixed with lard fat ⁇ ! (Iodine value 57.0, g 1 cMC 12: 0.1%, C14: 2.2%, C16F0: 22.6%, C16F1: 4.8%, C18F0: 13. ⁇ %, C18Fi: 46.3%, Cl8F2: 5.1%, C18F3: 0.6%, C20F2: 0.4%, fatty acids of CI 5, fatty acids of C17 and fatty acids of C19 The total of 4.2%) was esterified with methyl alcohol and p-toluenesulfonic acid, and the methyl ester (sulfur content 2.5 ppm, chlorine content 1.0 ppm) washed with ⁇ was used as a raw material.
- the reaction tower cross-sectional area lm 2 per feeding rate of 1 Om 3 Bruno h, except for using anti ⁇ sectional area lm 2 per hydrogen gas velocity 100 Om 3 / h as in Example 1 The operation was continuously performed for 500 hours under the conditions of perfusate flow to produce a crude beef and pig mixed fat alcohol. Table 3 shows the reaction results.
- the dynamic liquid phase retention amount per unit catalyst external surface area was 0.08 ⁇ 10 ⁇ 3 mVm 2 .
- the dissolved hydrogen concentration in the liquid phase was 1.1 kmo 1 Zm 3 .
- Vegetable No.2 oil (Iodine value 119.5, g 1 ct C: 0.4%, C16: 12.0%, C16F1: 0. ⁇ %, C18: 4.3%, C18F1: 40.8%, C 18F2: 34.1%, C18F3: 7.3%, C20Fl: 0.4%) were transesterified with methyl alcohol and sodium hydroxide, neutralized with 10% hydrochloric acid, and washed with water to obtain methyl ester. (Sulfur content 3.3 ppm, chlorine content 4.2 ppm) were used as raw materials.
- Example 2 The operation was continuously performed for 500 hours under the perfusate flow conditions in the same manner as in Example 1 except that the raw materials were used, to produce a crude vegetable oil-reduced alcohol.
- Each reaction column was filled with a latex-type copper oxide-calcium silicate catalyst (bulk specific gravity 1.5 kg / l) manufactured by a tableting machine having a diameter of 3 mm and a height of 3 mm.
- a latex-type copper oxide-calcium silicate catalyst (bulk specific gravity 1.5 kg / l) manufactured by a tableting machine having a diameter of 3 mm and a height of 3 mm.
- the dynamic liquid phase retention amount per unit catalyst external surface area was 0.09 ⁇ 10-3 mVm 2 .
- the dissolved hydrogen concentration per liquid phase volume was 0.8 kmo 1 Zm 3 .
- 500 ml of the liquid phase of the crude reaction product obtained here was put into a separate 1000 ml zitch type autoclave, heated to 190, and the saturated hydrogen concentration at 20 MPa was measured. 6 kmo IZm 3 . That is, the dissolved hydrogen concentration per liquid phase volume at 1 m above the reactor was 50% of the saturated hydrogen concentration in the liquid phase.
- Each reaction column was charged with a tablet-type copper-zinc-aluminum oxide catalyst (bulk specific gravity 1.6 kg / l) manufactured by a tableting machine having a diameter of 3 mm and a height of 3 mm.
- a tablet-type copper-zinc-aluminum oxide catalyst (bulk specific gravity 1.6 kg / l) manufactured by a tableting machine having a diameter of 3 mm and a height of 3 mm.
- Saturated fatty acid methyl obtained by transesterification of palm kernel oil with methyl alcohol and sodium hydroxide and distillation (g1c composition C12: 75%, C14: 25%) (sulfur content 0.2 ppm, chlorine content the amount 0.
- Dynamic liquid phase retained amount per unit catalyst outer surface area was 0. 09x 10 one 3 mVm2.
- Dissolved hydrogen concentration per liquid phase volume was 0. 8kmo lZm 3.
- the liquid phase 50 Oml of the crude reaction product obtained here was put into a separate 1000 ml patch type autoclave, heated to 230, and the saturated hydrogen concentration at 20 MPa was measured. 1.6 kmo IZm was 3 . That is, the dissolved hydrogen concentration per liquid phase volume at 1 m above the reactor was 50% of the saturated hydrogen concentration in the liquid phase.
- Example 7 Hydrogenation of dicarboxylic diester to diol The reaction was carried out continuously for 500 hours under the irrigation flow conditions in the same manner as in Example 1 except that dimethyl sepatate (sulfur content: 0.05 ppm, chlorine content: 0.05 ppm) was supplied. A crude 1,10-decanediol as a diol was obtained. The reaction results are shown in Table 7 below. From Table 7, it can be seen that the reaction proceeded without any abnormalities and exhibited excellent effects.
- the dynamic liquid phase retention amount per unit catalyst external surface area was 0.09 ⁇ 10 3 mVm 2 .
- Dissolved hydrogen concentration in the liquid phase was 0. 6kmo IZm 3.
- Reactors 1 to 4 were filled with a columnar zinc-chromium oxide catalyst (bulk specific gravity 1.4 kg / l) manufactured by a tableting machine with a diameter of 5 mm and a height of 5 mm.
- a columnar zinc-chromium oxide catalyst (bulk specific gravity 1.4 kg / l) manufactured by a tableting machine with a diameter of 5 mm and a height of 5 mm.
- Unsaturated fatty acids obtained by distilling the fatty acids obtained by hydrolyzing palm kernel oil and fractionating them by cooling solids (iodine value 93.4, g 1 c «C12: 0.6%, C14: 0.6% C16: 5 5%, 018: 1.4%, C18F1: 78.5%, C18F2: 11.8%, C18F3: 0.5%, C20F2: 0.3%)
- Product name: PALMAC 750: Acidke was used as a raw material, with methyl alcohol (sulfur content: 0.05 ppm, chlorine content: 0.05 ppm) obtained by esterification of methyl alcohol with methyl alcohol without a catalyst.
- Dynamic liquid phase retained amount per unit catalyst outer surface area was 0. 07X10 one 3 MVM 2.
- the dissolved hydrogen concentration in the liquid phase was 1.5 kmo IZm 3 .
- the direction in which the strength of the packed catalyst was the weakest was the transverse strength.
- Reactors 1-4 were filled with a cylindrical 0.5 wt% ruthenium-alumina catalyst manufactured by a tablet press having a diameter of 3 mm and a length of 3 mm.
- a reduction reaction of a saturated or unsaturated fatty acid alkyl ester to a saturated alcohol a reduction reaction of an unsaturated fatty acid alkyl ester to an unsaturated alcohol, an aliphatic or alicyclic dicarboxylic acid dialkyl ester of an aliphatic or alicyclic diol
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Cited By (4)
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JP2007289855A (ja) * | 2006-04-25 | 2007-11-08 | Sakai Chem Ind Co Ltd | 水素化触媒とその利用とその製造方法 |
JP2009022938A (ja) * | 2007-07-24 | 2009-02-05 | Kao Corp | 水素添加用触媒 |
JP2013128901A (ja) * | 2011-12-22 | 2013-07-04 | Tosoh Corp | 水素化触媒組成物成型体、及びその製造方法 |
CN113403105A (zh) * | 2021-06-10 | 2021-09-17 | 克拉玛依市先能科创重油开发有限公司 | 乙烯裂解焦油为原料的悬浮床加氢装置的开工进油方法 |
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DE102008064280A1 (de) * | 2008-12-20 | 2010-06-24 | Bayer Technology Services Gmbh | Verfahren zur Herstellung von Bis(Para-Aminocyclohexyl)Methan |
CN103100392B (zh) * | 2011-11-09 | 2014-12-31 | 中国石油化工股份有限公司 | 一种加氢裂化催化剂及其制备方法 |
CN103100390B (zh) * | 2011-11-09 | 2015-09-30 | 中国石油化工股份有限公司 | 一种加氢处理催化剂的制备方法 |
WO2013116029A1 (en) * | 2012-02-01 | 2013-08-08 | Invistad North America S.A R.L. | Process for producing dodecane-1, 12-diol by reduction of lauryl lactone produced from the oxidation of cyclododecanone |
DE102014013530A1 (de) | 2014-09-12 | 2016-03-17 | Clariant International Ltd. | Extrudierter Cu-Al-Mn-Hydrierkatalysator |
TWI534131B (zh) | 2014-11-27 | 2016-05-21 | 財團法人工業技術研究院 | 氫化4,4’-二胺基二苯甲烷的觸媒與方法 |
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- 2003-11-27 JP JP2004555059A patent/JP4802497B2/ja not_active Expired - Fee Related
- 2003-11-27 WO PCT/JP2003/015134 patent/WO2004048297A1/ja active Application Filing
- 2003-11-27 EP EP03811941.8A patent/EP1566372B1/en not_active Expired - Fee Related
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Cited By (5)
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JP2007289855A (ja) * | 2006-04-25 | 2007-11-08 | Sakai Chem Ind Co Ltd | 水素化触媒とその利用とその製造方法 |
JP4661676B2 (ja) * | 2006-04-25 | 2011-03-30 | 堺化学工業株式会社 | 水素化触媒とその利用とその製造方法 |
JP2009022938A (ja) * | 2007-07-24 | 2009-02-05 | Kao Corp | 水素添加用触媒 |
JP2013128901A (ja) * | 2011-12-22 | 2013-07-04 | Tosoh Corp | 水素化触媒組成物成型体、及びその製造方法 |
CN113403105A (zh) * | 2021-06-10 | 2021-09-17 | 克拉玛依市先能科创重油开发有限公司 | 乙烯裂解焦油为原料的悬浮床加氢装置的开工进油方法 |
Also Published As
Publication number | Publication date |
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EP1566372A4 (en) | 2007-03-21 |
EP1566372A1 (en) | 2005-08-24 |
EP1566372B1 (en) | 2018-01-10 |
JPWO2004048297A1 (ja) | 2006-03-23 |
JP4802497B2 (ja) | 2011-10-26 |
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