WO2016136692A1 - Catalyseur pour la production d'ester alkylique d'acide gras, procédé pour la production dudit catalyseur et procédé pour la production d'ester alkylique d'acide gras utilisant ledit catalyseur - Google Patents

Catalyseur pour la production d'ester alkylique d'acide gras, procédé pour la production dudit catalyseur et procédé pour la production d'ester alkylique d'acide gras utilisant ledit catalyseur Download PDF

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WO2016136692A1
WO2016136692A1 PCT/JP2016/055135 JP2016055135W WO2016136692A1 WO 2016136692 A1 WO2016136692 A1 WO 2016136692A1 JP 2016055135 W JP2016055135 W JP 2016055135W WO 2016136692 A1 WO2016136692 A1 WO 2016136692A1
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catalyst
fatty acid
alkyl ester
acid alkyl
producing
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PCT/JP2016/055135
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Japanese (ja)
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研司 野中
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日本ケッチェン株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a fatty acid alkyl ester production catalyst, a production method thereof, and a production method of an aliphatic alkyl ester using the catalyst, and more specifically, esterification or transesterification reaction of a fatty acid and / or glyceride with an alcohol.
  • the present invention relates to a catalyst for producing a fatty acid alkyl ester, a method for producing the same, and a method for producing a fatty acid alkyl ester using the catalyst.
  • Fatty acid alkyl esters are used as raw materials for various chemicals, resins, detergents, and surfactants. In recent years, they have been used as alternative fuels for petroleum-based fuels, especially biodiesel fuels, from the viewpoint of reducing environmental impact and carbon neutrality. The use as is expanding.
  • the biodiesel fuel is a general term for fuels that are mainly modified by chemical treatment of vegetable oils and fats to be suitable for diesel engines.
  • fatty acid methyl ester (FAME) obtained by transesterification of a vegetable oil containing triglyceride and methanol is known.
  • FAME fatty acid methyl ester
  • methods for producing a fatty acid alkyl ester in addition to a homogeneous base catalyst method and an acid catalyst method, methods such as an enzyme method and a supercritical methanol method are known.
  • the base catalyst method is a method in which an oil and fat containing fatty acid glycerides and a lower alcohol such as metalanol are contacted in the presence of a base catalyst (caustic soda or the like) to obtain a fatty acid alkyl ester by a transesterification reaction.
  • a base catalyst such as copper or the like
  • the reaction proceeds under relatively mild conditions, but when free fatty acids are present in the raw oil and fat, soap (consumption of the base catalyst) and water (inactivation of the base catalyst) are neutralized with the base catalyst. ) Is formed and the transesterification reaction is inhibited.
  • the saponification of the produced ester is promoted together with the base catalyst, resulting in a decrease in the ester yield.
  • a saponification reaction does not occur with an acid catalyst (sulfuric acid or the like)
  • water produced by an esterification reaction between an existing free fatty acid and an alcohol inactivates the acid catalyst, like a base catalyst.
  • a homogeneous catalyst it is difficult to separate the product and the catalyst, and a waste disposal facility for the catalyst solution is also required.
  • the solid acid catalyst functions as a catalyst for each of the ester exchange reaction of glyceride and the esterification reaction of free fatty acid, and has an advantage that the product after the reaction and the catalyst can be easily separated.
  • Patent Document 1 proposes a solid acid catalyst exhibiting a super strong acid having an argon adsorption heat of 15 to 22 kJ / mol.
  • a super strong acid when used, the transesterification proceeds, but the catalyst is easily deactivated, and there is also a problem that a side reaction such as isomerization occurs.
  • Patent Document 2 discloses an esterification reaction catalyst that exhibits solid acidity with Hammett's acidity function (H 0 ) of ⁇ 3 to ⁇ 9 in which molybdenum oxide is supported on a zirconia support.
  • H 0 Hammett's acidity function
  • the main component of the support is zirconia, which is difficult to control the pore structure, most of the reaction occurs only on the outer surface of the catalyst and has a problem in reaction efficiency.
  • the catalyst component is easily dissolved during the reaction process, and there is a problem in the activity stability of the catalyst.
  • Patent Document 3 is a group consisting of inorganic porous carriers such as silica and alumina, at least one metal element selected from Group 6 of the periodic table, and manganese, iron, cobalt, nickel, copper, zinc, gallium, and tin.
  • a solid acid catalyst for producing a fatty acid alkyl ester is disclosed that carries at least one metal element selected from the group consisting of at least one non-metallic element of boron or silicon. The catalyst exhibits a certain activity in transesterification and esterification reactions. However, particularly when the proportion of free fatty acids in the raw material is high, the elution of the supported active ingredient is not sufficient, and further improvement in the stability of the catalytic activity has been demanded.
  • An object of the present invention is to solve the problems in conventional fatty acid alkyl ester production catalysts, improve the yield of fatty acid alkyl esters, and have high stability, a method for producing the same, and fatty acid alkyl esters using the catalyst It is to provide a manufacturing method.
  • the present inventors have conducted extensive research focusing on optimization of a support component having catalytic activity and a catalyst pore structure, and as a result, a porous support containing alumina. It was found that a catalyst having a specific amount of a specific active metal component and a specific pore structure was extremely effective for transesterification and esterification of fats and oils, and thus completed the present invention.
  • the present invention contains a porous carrier containing alumina and at least two elements selected from Group 6 of the periodic table carried thereon, an average pore diameter of 9.5 to 27 nm, all fine particles.
  • the pore volume is 0.5 to 1.0 ml / g
  • the specific surface area is 120 to 300 m 2 / g
  • the ratio of the pore volume with an average pore diameter of ⁇ 1.5 nm to the total pore volume is 15 to 70%
  • the fatty acid alkyl ester production catalyst is characterized in that the ratio of the pore volume having an average pore diameter of ⁇ 5 nm to the total pore volume is 60% or more.
  • the method for producing a fatty acid alkyl ester production catalyst of the present invention comprises a step of impregnating a porous support containing alumina with a compound solution of at least two elements selected from Group 6 of the periodic table, and then the presence of oxygen. This method includes a step of baking at 400 to 750 ° C. below.
  • the method for producing a fatty acid alkyl ester of the present invention is a method in which fatty acid and / or glyceride and alcohol are reacted at a temperature of 100 to 250 ° C. and a pressure of 0.1 to 6.0 MPa in the presence of the catalyst.
  • the fatty acid alkyl ester production catalyst according to the present invention is not only capable of producing a fatty acid alkyl ester stably and at a higher yield than conventional solid acid catalysts, but also glycerin produced as a by-product in the process of transesterification. It is also possible to obtain a product with high purity and high added value.
  • the alumina-containing porous carrier used for the catalyst of the present invention is based on alumina.
  • the crystal structure of alumina in the carrier is not particularly limited.
  • alumina hydrates such as ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ type transition alumina, bayerite, dibsite, boehmite, pseudoboehmite, etc. Or a mixture thereof.
  • Alumina-containing porous carrier is an alumina hydrate powder obtained from commercially available boehmite, pseudoboehmite or the like, neutralization reaction of acidic and / or basic aluminum compounds, and alumina obtained from a sol-gel method using aluminum alkoxide as a starting material Hydrate gels and powders thereof can be obtained by kneading, molding, drying, and calcination.
  • the content of alumina in the carrier is preferably 75% by mass or more, particularly 80 to 100% by mass, based on the carrier and aluminum oxide.
  • 25 masses of silica, titania, zirconia, boria, magnesia, zinc oxide, diphosphorus pentoxide, zeolite, clay mineral, or any mixture thereof can be used for this carrier in order to modify the chemical properties of the carrier surface. % Or less, particularly preferably 1 to 20% by mass. In that case, it is preferable to add silica, titania and boria, particularly silica and boria.
  • the hydrate is kneaded to satisfy a desirable condition as the pore structure of the finished catalyst described later. Then, the moisture content is adjusted (55 to 70% as loss on ignition) and formed into a desired shape (pellet, sphere, extrudate, etc.).
  • Sodium oxide and organic molding aids (cellulosic aids, starches, etc.) may be added.
  • the molded product is usually 640 to 900 ° C. (instead of the ambient temperature, not the ambient temperature), preferably 660 to 890 ° C., more preferably 680 to 870 ° C. for 0.1 to 10 hours in air.
  • the support is calcined for 0.5 to 8 hours, more preferably 1 to 5 hours.
  • the carrier obtained in the above step is loaded with at least two elements selected from Group 6 of the periodic table.
  • the loading method there are no particular limitations on the loading method, and various industrial methods such as impregnation method, coating method, spraying method and the like can be applied, but the impregnation method is preferable from the viewpoint of workability and addition efficiency.
  • the impregnation method, adsorption method, equilibrium adsorption method, pore filling method, incipient wetness method, evaporation to dryness method, spray method, etc. are all applicable to the present invention, but from the viewpoint of workability, the pore filling method Is preferred.
  • the order of supporting the Group 6 elements is not particularly limited, and can be sequentially or simultaneously supported. In the case of the impregnation method, a solution in which a solvent-soluble compound of each element is dissolved in various polar organic solvents, water or a water-polar organic solvent mixture can be used, but the most preferable solvent is water.
  • the Group 6 element of the periodic table supported as an active component is at least two selected from chromium, molybdenum, and tungsten.
  • chromium-molybdenum, chromium-tungsten, and molybdenum-tungsten can be used. From the viewpoint of economy and activity, a combination of molybdenum and tungsten is preferable.
  • the supported amount is 8 to 25% by mass, preferably 9 to 20% by mass, more preferably 10 to 18% by mass, based on the oxide catalyst, as the sum of all Group 6 group element oxides. If it is less than 8% by mass, the catalyst activity is low, and if it exceeds 25% by mass, there is no increase in activity.
  • the range of the molar ratio of tungsten to molybdenum is 0.01 to 0.25, preferably 0.02 to 0.23, and more preferably 0.03 to 0.20. If the molar ratio is less than 0.01, the stability of the catalyst activity is lacking, and if it exceeds 0.25, no improvement in the improvement effect on the stability of the transesterification and esterification reaction is observed.
  • the raw material for Group 6 elements of the periodic table examples include chromate, molybdate, tungstate, trioxide, halide, heteropolyacid, heteropolyacid salt, and organometallic compounds including carbonyl compounds.
  • the oxide is 0.01 to 8% by mass, preferably 0.01 to 4% by mass, more preferably, based on the oxide catalyst. Can contain 0.01 to 0.99% by mass of iron, cobalt, nickel (including any mixture thereof).
  • the addition amount range is 0.1 to 10% by mass, preferably 0.5 to 8% by mass as phosphorous oxide based on the oxide catalyst. More preferably, it is 1 to 5% by mass.
  • phosphoric acid examples include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphonic acid, diphosphonic acid, phosphinic acid, and polyphosphoric acid.
  • a drying operation (room temperature to 300 ° C., 0.1 to 24 hours) is performed as necessary, and then a firing operation is performed.
  • a Group 6 element is supported on an alumina-containing support in the form of an oxide.
  • the firing conditions at this time are 350 to 770 ° C. in air, preferably 400 to 730 ° C., more preferably 480 to 680 ° C., and 0.5 to 24 hours, preferably 1 to 12 hours.
  • the average pore diameter is 9.5 to 27 nm, preferably 9.8 to 26 nm, more preferably 10 to 25 nm.
  • the total pore volume is preferably 0.5 to 1.0 ml / g, more preferably 0.6 to 0.8 ml / g.
  • the ratio of the pore volume having an average pore diameter in the range of ⁇ 1.5 nm is 15 to 70% with respect to the total pore volume. It is desirable to have a pore structure that is preferably 18 to 65%, more preferably 20 to 60%. If it is less than 15%, the proportion of fine pores that do not contribute to the reaction or large pores with a small surface area increases, and if it exceeds 70%, the diffusion of fats and oils having a relatively large molecular size into the pores is inhibited. It causes a decrease in activity.
  • the ratio of the pore volume in the range of the average pore diameter ⁇ 5 nm to the total pore volume as an index indicating the shape of the distribution of the total pore diameter in the catalyst is 60% or more, preferably 65% or more, more preferably Is preferably 70% or more. If it is less than 60%, the volume ratio of micropores and giant pores that do not contribute to the reaction increases (including bimodal and multimodal pore distributions), so that the catalytic activity decreases.
  • the pore distribution of the catalyst of the present invention is a unimodal distribution having an average pore diameter and a local maximum point in the vicinity thereof.
  • the pore structure (total pore volume, average pore diameter, pore distribution, etc.) of the catalyst of the present invention is the mercury intrusion method (contact angle 140 °, surface tension 480 dyn / cm), and the specific surface area is the BET method. This is the value obtained.
  • the catalyst was treated in air at 450 ° C. for 1 hour to remove volatile components such as moisture, and the analysis obtained here, The measured value is a value based on an oxide catalyst standard. The same heating temperature and time were applied to the measurement of loss on ignition. Further, a fluorescent X-ray analyzer was used for quantification of the supported metal component and the carrier component.
  • fatty acid and / or glyceride used as the raw material in the present invention, various animal and vegetable fats and oils including monoglyceride, diglyceride and triglyceride, and a mixture of fatty acids produced by hydrolysis of such animal and vegetable fats and oils can be used. .
  • fat and oil mixtures examples include soybean oil, rapeseed oil, sunflower oil, cottonseed oil, hemp seed oil, linseed oil, tung oil, evening primrose oil, safflower oil, coconut oil, amazana oil, avocado oil, camelina oil, canola oil, coconut oil, Sesame oil, mustard oil, olive oil, corn oil, safflower oil, peanut oil, macadamia nut oil, brazil nut oil, castor oil, rice oil, jojoba oil, neem oil, palm oil, jatropha oil, carranja oil, orlanchonchi Thorium, Pseudocollistis ellipsoidia, Senedesmus, Botryococcus brownie, Euglena and vegetable oils such as algae oil obtained from these algae, beef tallow, beef bone fat, beef leg oil, pork fat, horse fat Animal oils such as sheep oil, deer oil, chicken oil, butter oil, bone oil, whale oil, shark oil, cod liver oil, sardine
  • restoration may be sufficient.
  • the used waste oil of the above fats and oils, the arbitrary mixtures of waste oil and the said fats and oils can also be used.
  • Alcohol used in the method for producing a fatty acid alkyl ester of the present invention is preferably an alcohol having 1 to 10 carbon atoms.
  • Such alcohols include primary alcohols such as methanol, ethanol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, pentyl alcohol and neopentyl alcohol, and secondary alcohols such as isopropyl alcohol and sec-butyl alcohol.
  • Tertiary alcohols such as tert-butyl alcohol and tert-amyl alcohol
  • polyhydric alcohols such as ethylene glycol, propylene glycol and trimethylene glycol, and any mixture of these alcohols, but primary alcohols are preferred.
  • methanol or ethanol is preferable.
  • the starting fatty acid and / or glyceride and alcohol are heated at a temperature of 100 to 250 ° C, preferably 120 to 230 ° C, more preferably 140 to 210 ° C, and a pressure of 0.1. It is contacted with the catalyst of the present invention at a pressure of ⁇ 6.0 MPa, preferably 0.5-5 MPa, particularly preferably 1.0-4.5 MPa.
  • a pressure of ⁇ 6.0 MPa preferably 0.5-5 MPa, particularly preferably 1.0-4.5 MPa.
  • the reaction time is not limited, and is 0.1 to 100 hours in the case of a batch system, and 0 to 0 in the flow system when the time for contacting the raw oil and fat and alcohol with the catalyst of the present invention is expressed as a mass space velocity (WHSV).
  • WHSV mass space velocity
  • the molar ratio of alcohol to fatty acid is 1.1 to 50, preferably 1.2 to 40, more preferably.
  • Raw oils and fats and alcohols can be used at 1.5 to 30, particularly preferably 3 to 15.
  • the above reaction may be carried out in one stage, but it is also possible to carry out the reaction in a plurality of stages of two or more stages in order to increase the purity of the produced ester.
  • either a batch type or a flow type reactor can be used, but a flow type reactor is preferably used from the viewpoint of reaction efficiency.
  • alcohol, glycerol, and water are removed from a product, and the crude fatty-acid alkylester (A) containing an unreacted fat and free fatty acid is obtained.
  • alcohol and water can be separated by simple distillation, rectification or the like under normal pressure or reduced pressure conditions.
  • various methods such as sedimentation separation, centrifugal separation, electrostatic separation and the like utilizing the specific gravity difference and polarity difference with the fatty acid alkyl ester can be applied.
  • the crude fatty acid alkyl ester (A) thus obtained is reacted in the second stage with alcohol at the same pressure, raw material / alcohol ratio, and mass space velocity as in the first stage.
  • the reaction temperature at this time is 80 to 230 ° C., preferably 60 to 210 ° C., and is preferably equal to or lower than the first stage.
  • side reactions such as the hydrolysis reaction of produced
  • alcohol, water and glycerin are removed by the same method as in the first stage to obtain a crude fatty acid alkyl ester (B).
  • the crude fatty acid alkyl ester (B) is distilled under normal pressure or reduced pressure, and a fraction having boiling points of 100 ° C. or lower and 360 ° C. or higher is removed to obtain a purified fatty acid alkyl ester.
  • This purified fatty acid alkyl ester can be used as it is as various chemical raw materials and biodiesel fuel, but a higher quality fatty acid alkyl ester can be obtained by further rectifying under normal pressure or reduced pressure.
  • a silica-alumina hydrate gel (silica / alumina mass ratio: 1.5 / 98.5) is prepared by adding and mixing aluminum sulfate, sodium aluminate and water glass into a tank containing hot tap water. did. The hydrate gel was separated from the solution, and the impurities were washed and removed using warm water, citric acid was added, and the mixture was heated and kneaded using a kneader to adjust the moisture content to 64.3%. This kneaded product was extruded and calcined in air at 850 ° C. for 1.5 hours to obtain a silica-alumina carrier.
  • Example 1 was the same as Example 1 except that water glass was not used at the time of carrier preparation, the moisture content at the time of molding the alumina hydrate was 62.8%, and the carrier calcination temperature was 800 ° C.
  • Catalyst B was prepared by the method. Table 1 shows the physical properties and chemical composition of Catalyst B.
  • Example 1 With reference to Example 8 (Catalyst H) of Patent Document 3, the alumina support of Example 2 of the present application was impregnated with an ethyl silicate / ethanol solution and dried at 120 ° C. to prepare an alumina support on which ethyl silicate was supported. (Silica / alumina mass ratio: 1.5 / 98.5).
  • molybdic acid was 8.7% by mass of molybdenum trioxide (10% with respect to alumina) and 3.9% by mass of tin dioxide (4.5% with respect to alumina) based on the oxide catalyst.
  • catalyst C was obtained.
  • the physical properties and chemical composition of the catalyst C are shown in Table 1.
  • the purity of the catalyst C of Comparative Example 1 is low.
  • dehydration condensation products with metal rule such as 2-methoxy-1,3-propanediol and 3-methoxy-1,2-propanediol were observed. It is considered to have been higher than necessary, and showed a catalytic action for side reactions such as etherification between glycerol and methanol and hydrolysis of FAME.
  • the purity of glycerin in the catalysts A and B of Examples 1 and 2 is high, and the catalyst of the present invention is excellent in the quality of by-products.
  • the catalyst of the present invention has less acid elution of the supported metal component than the catalyst C of the prior art, and therefore the degree of activity deactivation is low even when using a raw material having an acid property with many free fatty acids. It is thought that the effect which was excellent in activity stability is shown.
  • the present invention can produce fatty acid alkyl esters that can be used for various chemicals, resins, detergents, surfactant raw materials, biodiesel fuel, and the like from various oil and fat raw materials including poor waste oil with high efficiency and low cost. Useful as technology. Further, the purity of glycerin produced as a by-product is high, and it is possible to obtain a product with high added value including the product of the main reaction.

Abstract

L'invention concerne un catalyseur pour la production d'un ester alkylique d'acide gras, qui a un rendement et une stabilité d'activité encore meilleurs que ceux obtenus avec les catalyseurs classiques, un procédé pour la production du catalyseur et un procédé pour la production d'un ester alkylique d'acide gras utilisant ce catalyseur. Le catalyseur contient un support poreux contenant de l'alumine et au moins deux éléments supportés par le support et choisis dans le groupe 6 du tableau périodique des éléments, le catalyseur ayant un diamètre moyen des pores de 9,5 à 27 nm, un volume total des pores de 0,5 à 1,0 ml/g et une surface spécifique de 120 à 300 m2/g. Le rapport du volume des pores ayant un diamètre qui est le diamètre moyen des pores ± 1,5 nm au volume total des pores est de 15 à 70 % et le rapport du volume des pores ayant un diamètre qui est le diamètre moyen des pores ± 5 nm au volume total des pores est supérieur ou égal à 60 %.
PCT/JP2016/055135 2015-02-25 2016-02-23 Catalyseur pour la production d'ester alkylique d'acide gras, procédé pour la production dudit catalyseur et procédé pour la production d'ester alkylique d'acide gras utilisant ledit catalyseur WO2016136692A1 (fr)

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