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WO2025225693A1 - Procédé de production d'additif pour produits cosmétiques - Google Patents

Procédé de production d'additif pour produits cosmétiques

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Publication number
WO2025225693A1
WO2025225693A1 PCT/JP2025/015886 JP2025015886W WO2025225693A1 WO 2025225693 A1 WO2025225693 A1 WO 2025225693A1 JP 2025015886 W JP2025015886 W JP 2025015886W WO 2025225693 A1 WO2025225693 A1 WO 2025225693A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylic acid
water
acetone
isopropanol
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/015886
Other languages
English (en)
Japanese (ja)
Inventor
弥万里 松本
宏和 丹羽
淳志 岡村
直央 井形
拓海 林
悠子 鳥羽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Publication of WO2025225693A1 publication Critical patent/WO2025225693A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to a method for producing cosmetic additives. More specifically, it relates to a method for producing cosmetic additives using renewable bio-based raw materials that exhibit performance equivalent to or superior to that of cosmetic additives derived from fossil raw materials.
  • Cosmetics such as skin cosmetics and hair cosmetics, may contain thickeners, such as polymers and surfactants, as cosmetic additives to retain active ingredients and improve usability.
  • thickeners such as polymers and surfactants
  • Acrylic polymers containing (meth)acrylic acid as a structural unit are sometimes used as the thickener, as they have a high thickening effect, gel with only a small amount, and provide a fresh, excellent usability (see, for example, Patent Documents 1 and 2).
  • a method for producing such acrylic polymers is disclosed, for example, in Patent Document 3.
  • Patent documents 4 and 5 disclose methods for producing acrylic acid derived from biomass raw materials, which are used to make acrylic polymers. These methods involve using isopropanol obtained by fermentation as a raw material, vaporizing it by heating, and then partially oxidizing it in the presence of oxygen using a partial oxidation catalyst to produce acrylic acid or acrolein.
  • an objective of the present invention is to provide a method for producing cosmetic additives using biomass raw materials that have performance equivalent to or superior to that of conventional cosmetic additives derived from fossil raw materials.
  • the inventors focused for the first time on ethanol as a starting material for the monomers that make up the main chains of cosmetic additives, and investigated a method for producing cosmetic additives derived from bio-based materials, in which natural polymers, which have a poor feel when used, are used as cosmetic additives, and instead, obtain cosmetic additives from ethanol, which has traditionally been used primarily as a fuel.
  • the inventors came up with a production method that can reduce the production costs of acrylic acid using bioethanol, which is produced in large quantities, as a starting material.
  • the present invention has also found that by using bioacrylic acid obtained from bioethanol through a specific process (bioethanol ⁇ bioacetone ⁇ bioisopropanol ⁇ biopropylene ⁇ bioacrylic acid) as a monomer, this low-cost bioacrylic acid derived from bioethanol through a specific process does not cause problems with usability or issues associated with impurities (e.g., coloration or odor), and is equally or even more suitable as a raw material acrylic acid for cosmetic additives than conventional acrylic acid derived from fossil feedstocks. Furthermore, the present invention has found that by using acrylic acid derived from biomaterials with a water content below a specific amount as a raw material, cosmetic additives with an excellent usability can be obtained. Based on these findings, the present invention has been completed to solve the above problems.
  • bioacrylic acid obtained from bioethanol through a specific process bioethanol ⁇ bioacetone ⁇ bioisopropanol ⁇ biopropylene ⁇ bioacrylic acid
  • the present invention provides a method for producing a cosmetic additive containing an acrylic polymer derived from a biomaterial, comprising the following steps (i) to (v), wherein the acrylic acid added in step (v) includes the acrylic acid obtained in step (iv): Step (i) of obtaining acetone from bioethanol; Step (ii) of obtaining isopropanol from the acetone; (iii) obtaining propylene from the isopropanol; Step (iv) of obtaining acrylic acid from the propylene; Step (v) of polymerizing a monomer containing acrylic acid and/or a salt thereof to obtain an acrylic polymer.
  • the above production method preferably further comprises the following step (vi): Step (vi) of drying the acrylic polymer.
  • the total content of ethanol and acetaldehyde in the acetone be 20,000 ppm or less.
  • the ethanol content in the above isopropanol be 20,000 ppm or less.
  • the raw material used to obtain the isopropanol preferably contains the hydrogen obtained in step (i) above.
  • the bioethanol be obtained by fermenting one or more genetically modified or non-genetically modified plant materials selected from the group consisting of sugar cane, corn, and sugar beet.
  • the water content of the acrylic acid and/or its salt added in step (v) is 4000 ppm or less.
  • step (v) in addition to the acrylic acid and/or its salt obtained in the above step (iv), other acrylic acid (salt) may be used in combination in the monomer, and the acrylic acid and/or its salt obtained in the above step (iv) may account for 1 mol % or more of the total amount of acrylic acid (salt) subjected to the above step (v).
  • the above-mentioned cosmetic additive is preferably a thickener.
  • the present invention also provides a method for producing cosmetics containing the cosmetic additive obtained by the above-mentioned production method.
  • the present invention also provides a method for producing a cosmetic additive containing an acrylic polymer, which comprises step (v) of polymerizing acrylic acid and/or a salt thereof, wherein the acrylic acid and/or a salt thereof is derived from a biomaterial and has a water content of 4000 ppm or less.
  • the polymerization is preferably carried out by precipitation polymerization.
  • the method for producing a cosmetic additive of the present invention it is possible to use renewable biomass raw materials to produce cosmetic additives that have performance (such as usability and transparency) equivalent to or superior to that of cosmetic additives derived from conventional fossil raw materials. Because biomass raw materials already absorb CO2 from the air during their production process, producing cosmetic additives using bioethanol as a raw material can aim to produce carbon-neutral, high-performance cosmetic additives. Furthermore, the cosmetic additives obtained by the method for producing a cosmetic additive of the present invention can be produced inexpensively with impurity levels equivalent to or even reduced compared to cosmetic additives derived from fossil raw materials.
  • 1 is a flow sheet showing steps (1) to (8) in a method for producing acrylic acid according to one embodiment of the present invention.
  • 1 is a flow sheet showing steps (9) to (11) in a method for producing acrylic acid according to one embodiment of the present invention.
  • biomass raw materials refer to raw materials derived from living organisms.
  • the bio-raw materials may be animal-derived bio-raw materials (e.g., wool), but renewable plant raw materials are preferably used.
  • bio-raw materials derived from plant components containing natural polymers such as sugars, starch, and cellulose are preferably used.
  • bioethanol, bioacetone, bioisopropanol, biopropylene, and bioacrylic acid refer to ethanol, acetone, isopropanol (also known as 2-propanol or isopropyl alcohol), propylene, and acrylic acid that use biomaterials as their raw materials or as upstream raw materials, and are no different in chemical structure from known ethanol, acetone, isopropanol, propylene, and acrylic acid, except for the amount of carbon isotope 14C .
  • ethanol, acetone, isopropanol, propylene, and acrylic acid are obtained from bio-based raw materials, they may be referred to as bioethanol, bioacetone, bioisopropanol, biopropylene, and bioacrylic acid, respectively.
  • a cosmetic additive derived from a biomaterial means that the acrylic polymer contained as a cosmetic additive contains a monomer derived from a biomaterial as the monomer that constitutes the main chain.
  • the first aspect of the method for producing a cosmetic additive of the present invention (sometimes referred to as the "production method of the present invention") is a method for producing a cosmetic additive containing an acrylic polymer derived from a biomaterial.
  • the production method of the present invention comprises at least the following steps (i) to (v).
  • the acrylic acid added in step (v) includes the acrylic acid obtained in step (iv).
  • bioethanol The present invention is the first to focus on bioethanol as a raw material for cosmetic additives, and its greatest feature is that cosmetic additives are obtained from bioethanol, which has traditionally been used mainly as fuel.
  • Bioethanol is expected to exceed 113 billion liters (approximately 89 million tons) in 2022. This is equivalent to approximately 3% of the approximately 4.6 trillion liters of petroleum production, and as a bio-raw material it is available in large quantities at low cost.
  • Bioethanol is primarily used as fuel (approximately 85% is used for automobiles, etc.), and is also used in industry as a solvent, and in food-related applications such as beverages and disinfectants. While there are examples of bioethanol being used to make chemical products such as ethyl esters, this invention is characterized by its use as a starting material for cosmetic additives, instead of as a fuel.
  • Bioethanol can be obtained from glucose, sucrose, or the like by known fermentation methods. For example, it can be obtained using molasses (blackstrap molasses) obtained after separating refined sugar as the fermentation raw material, according to the following reaction formula: C6H12O6 ⁇ 2CH3CH2OH + 2CO2
  • one molecule of glucose is broken down into two molecules of pyruvic acid by multiple enzymes in the glycolytic pathway.
  • the reactions specific to alcoholic fermentation take place.
  • One molecule of carbon dioxide is removed from one molecule of pyruvic acid, producing acetaldehyde.
  • Acetaldehyde is then quickly reduced to ethanol by electrons from reduced NADH.
  • ethanol obtained from biomaterials can be used, but preferably ethanol obtained from plant materials is used, and more preferably bioethanol obtained from the fermentation of one or more plant materials selected from the group consisting of sugarcane, corn, and sugar beet.
  • Sugarcane, corn, and sugar beet may be further crushed or juiced before fermentation.
  • the plant raw materials may be genetically modified plants (typically genetically modified corn) or non-genetically modified plants, but the production method of the present invention goes through the route of bioethanol, acetone, isopropanol, propylene, and acrylic acid, so unlike when bioethanol is directly used or eaten, there are no genetic modification restrictions and a wide range of genetically modified plant raw materials can be used, which is preferable.
  • the fact that the ethanol is bioethanol can be confirmed by the 14 C/ 12 C determined by radiocarbon dating. Traceable ethanol is also available.
  • the compounds acetone, isopropanol, propylene, and acrylic acid obtained sequentially from bioethanol in this invention can also be confirmed as being derived from biomaterials by the 14 C/ 12 C determined by radiocarbon dating or by recording the acquisition and production pathways.
  • Bioacrylic acid can be produced by the above steps (i) to (iv).
  • the method for producing acrylic acid (bioacrylic acid) including the above steps (i) to (iv) may be referred to as the "method for producing acrylic acid of the present invention.”
  • Step (i) is a step of obtaining acetone (bioacetone) from bioethanol, and preferably includes an acetone synthesis step (1) in which bioethanol is reacted with water (a) to obtain a mixed gas (A) containing acetone, water vapor, carbon dioxide, and hydrogen; an acetone separation step (2) in which an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A); and an acetone distillation step (3) in which the acetone-containing aqueous solution is distilled to separate acetone and water (c).
  • the method for producing acrylic acid of the present invention may also include a hydrogen separation step (4) in which hydrogen is separated from the mixed gas (B).
  • Step (ii) is a step of obtaining isopropanol (bioisopropanol) from the acetone (bioacetone). It preferably includes a step of reacting the acetone obtained in the acetone distillation step (3) with hydrogen to obtain a mixed gas containing isopropanol, and more preferably includes an isopropanol synthesis step (5) in which the acetone is reacted with the hydrogen obtained in the hydrogen separation step (4) to obtain a mixed gas (C) containing isopropanol.
  • the raw material for obtaining the isopropanol includes the hydrogen obtained in step (i).
  • Step (ii) also preferably includes an isopropanol separation step (6) in which isopropanol is separated from the mixed gas (C).
  • Step (iii) is a step of obtaining propylene (biopropylene) from the isopropanol (bioisopropanol), and preferably includes a propylene synthesis step (7) in which the isopropanol obtained in the isopropanol separation step (6) is dehydrated to obtain a mixed gas (D) containing propylene and water, and a propylene separation step (8) in which propylene and water (d) are separated from the mixed gas (D).
  • a propylene synthesis step (7) in which the isopropanol obtained in the isopropanol separation step (6) is dehydrated to obtain a mixed gas (D) containing propylene and water
  • a propylene separation step (8) in which propylene and water (d) are separated from the mixed gas (D).
  • Step (iv) is a step of obtaining acrylic acid (bioacrylic acid) from the propylene (biopropylene), and preferably includes an acrylic acid synthesis step (9) in which the propylene obtained in the propylene separation step (8) is oxidized to obtain a mixed gas (E) containing acrylic acid, an acrylic acid absorption step (10) in which the mixed gas (E) is brought into contact with a collection liquid to obtain an acrylic acid-containing solution, and an acrylic acid purification step (11) in which the acrylic acid-containing solution is purified to obtain acrylic acid. More preferably, the acrylic acid absorption step (10) is a step in which the mixed gas (E) is brought into contact with water (e) to obtain an aqueous solution containing acrylic acid.
  • steps (1) to (11) are a preferred embodiment of steps (i) to (iv) leading up to the production of bioacrylic acid.
  • identical elements in the drawings are designated by the same reference numerals, and redundant explanations will be omitted.
  • the dimensional proportions in the drawings have been exaggerated for the sake of explanation and may differ from the actual proportions.
  • only one device and step is depicted in Figures 1 and 2, but multiple devices may be connected in series or parallel.
  • the reaction and purification in each step may be continuous or batchwise, with continuous being preferred.
  • FIGS. 1 and 2 are flow sheets showing steps (1) to (8) and steps (9) to (11), respectively, of one embodiment of the method for producing acrylic acid of the present invention.
  • the following are connected by piping: acetone synthesis reactor 1 in which step (1) is performed; acetone separation column 2 in which step (2) is performed; acetone distillation column 3 in which step (3) is performed; hydrogen separation unit 4 in which step (4) is performed; isopropanol synthesis reactor 5 in which step (5) is performed; isopropanol separation unit 6 in which step (6) is performed; propylene synthesis reactor 7 in which step (7) is performed; propylene separation unit 8 in which step (8) is performed; acrylic acid synthesis reactor 9 in which step (9) is performed; acrylic acid absorption column 10 in which step (10) is performed; acrylic acid distillation column 11A in which step (11A) is performed; and acrylic acid crystallization unit 11B in which step (11B) is performed.
  • piping 90 shown in FIG. 1 and piping 90 shown in FIG. 2 are the same piping, propylene separation unit 8 and acrylic acid synthesis reactor 9 are connected to each other. This allows the acetone synthesis reactor 1 to the acrylic acid crystallizer 11B to be connected in series. As a result, steps (1) to (11) can be carried out in a continuous flow.
  • each step with a pipe may be connected to perform steps (1) to (11) as a continuous flow, as will be described later, one or more of the steps may be performed at different locations, and instead of connecting the steps with a pipe, the raw materials may be transported by other means (e.g., rail, ship, truck, etc.). In such cases, the raw material piping in Figures 1 and 2 may be interpreted as other means of transportation.
  • raw materials ethanol and water (a) are supplied to an acetone synthesis reactor 1 through a pipe 12.
  • the mixed gas (A) obtained in the acetone synthesis reactor 1 is supplied to the acetone separation tower 2 via pipe 20.
  • an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A).
  • water (b) may be supplied to the acetone separation tower 2 via pipe 21, and the mixed gas (A) may be brought into contact with the water (b) to produce an acetone-containing aqueous solution.
  • the acetone-containing aqueous solution obtained in the acetone separation tower 2 is supplied to the acetone distillation tower 3 via pipe 30.
  • the acetone-containing aqueous solution is distilled to separate acetone and water (c).
  • the water (c) can be supplied (reused) via pipe 31 to at least one selected from the acetone synthesis reactor 1, the acetone separation tower 2, and the acrylic acid absorption tower 10.
  • reuse means that the water is reused in a process other than the process in which it is generated. Before being reused, the water may be subjected to other treatments, such as removing impurities, or may not be subjected to other treatments. Furthermore, water generated in a process subsequent to the process in which the reused water was used is also considered reused when it is reused in a further process.
  • the mixed gas (B) obtained in the acetone separation column 2 is supplied to the hydrogen separation device 4 via piping 40.
  • hydrogen is separated from the mixed gas (B).
  • Acetone obtained in the acetone distillation column 3 can be supplied to the isopropanol synthesis reactor 5 via pipe 50, and hydrogen obtained in the hydrogen separation unit 4 can be supplied via pipe 41.
  • unreacted hydrogen obtained in the isopropanol separation unit 6, which will be described later, can be supplied to the isopropanol synthesis reactor 5 via pipe 61.
  • the hydrogen supplied to the isopropanol synthesis reactor 5 may be fresh, and the hydrogen may be supplied to the isopropanol synthesis reactor 5 via a pipe (not shown) separate from pipe 41.
  • the isopropanol synthesis reaction "CH 3 C( ⁇ O)CH 3 +H 2 ⁇ CH 3 CH(OH)CH 3 " produces a mixed gas (C) containing the product isopropanol (also known as 2-propanol or isopropyl alcohol) and unreacted hydrogen.
  • the mixed gas (C) obtained in the isopropanol synthesis reactor 5 is supplied to the isopropanol separation device 6 via piping 60.
  • isopropanol is separated from the mixed gas (C).
  • unreacted hydrogen can be separated from the mixed gas (C).
  • the isopropanol obtained in the isopropanol separation device 6 is supplied to the propylene synthesis reactor 7 via a pipe 70.
  • the mixed gas (D) obtained in the propylene synthesis reactor 7 is supplied to the propylene separation unit 8 via pipe 80.
  • propylene and water (d) are separated from the mixed gas (D).
  • the water (d) can be recycled via pipe 81 to at least one selected from the acetone synthesis reactor 1, the acetone separation tower 2, and the acrylic acid absorption tower 10.
  • propylene obtained in the propylene separation device 8 is supplied to the acrylic acid synthesis reactor 9 via a pipe 90. Furthermore, oxygen is supplied to the acrylic acid synthesis reactor 9 via a pipe 91.
  • the mixed gas (E) obtained in the acrylic acid synthesis reactor 9 is supplied to the acrylic acid absorption tower 10 via pipe 100. Furthermore, water can be supplied to the acrylic acid absorption tower 10 via pipe 101 as a liquid for capturing acrylic acid from the mixed gas (E). In the acrylic acid absorption tower 10, the mixed gas (E) is brought into contact with a capturing liquid (preferably water (e)) to obtain an acrylic acid-containing solution (preferably an aqueous acrylic acid-containing solution). The mixed gas (F) that is not absorbed (dissolved) in water is discharged via pipe 102. If necessary, the mixed gas (F) is cooled and separated into a condensate and gas components. The condensate may be returned to the acrylic acid absorption tower 10.
  • a capturing liquid preferably water (e)
  • an acrylic acid-containing solution preferably an aqueous acrylic acid-containing solution
  • the mixed gas (F) that is not absorbed (dissolved) in water is discharged via pipe 102. If necessary, the mixed gas (F) is cooled and separated into
  • the gas components may be returned to the acrylic acid synthesis reactor 9.
  • the liquid (capture liquid) for capturing acrylic acid from the mixed gas (E) is typically water, but other liquids can also be used.
  • the aqueous acrylic acid-containing solution will be referred to as an acrylic acid-containing solution.
  • the following description of "acrylic acid-containing aqueous solution" should not be construed as meaning that the liquid for collecting acrylic acid (collection liquid) is limited to water, but rather that the collection liquid may consist of a liquid other than water, or may consist of a mixture of water and a liquid other than water.
  • the acrylic acid-containing aqueous solution obtained in the acrylic acid absorption tower 10 is supplied to an acrylic acid purification apparatus via pipe 110.
  • an acrylic acid purification apparatus is exemplified by an acrylic acid distillation tower 11A and an acrylic acid crystallizer 11B, which are arranged in this order.
  • the acrylic acid purification apparatus may also consist solely of the acrylic acid distillation tower 11A.
  • the acrylic acid purification apparatus consists solely of the acrylic acid distillation tower 11A
  • the acrylic acid-containing aqueous solution obtained in the acrylic acid absorption tower 10 is supplied to the acrylic acid distillation tower 11A via pipe 110, and the acrylic acid crystallizer 11B and pipes 113, 114, and 120 are not included in the acrylic acid production system.
  • the acrylic acid purification apparatus may consist only of the acrylic acid crystallizer 11B.
  • the acrylic acid-containing aqueous solution obtained in the acrylic acid absorption tower 10 is supplied to the acrylic acid crystallizer 11B via pipe 114.
  • the acrylic acid purification apparatus consists only of the acrylic acid crystallizer 11B, the acrylic acid production system does not include the acrylic acid distillation tower 11A and pipes 110, 111, and 112.
  • the acrylic acid-containing aqueous solution is distilled to separate roughly purified acrylic acid and water (f).
  • the water (f) can be recycled via pipe 112 to at least one selected from the acetone synthesis reactor 1, the acetone separation column 2, and the acrylic acid absorption column 10.
  • the roughly purified acrylic acid is supplied to the acrylic acid crystallizer 11B via pipe 111.
  • the partially purified acrylic acid is separated by crystallization into purified acrylic acid and mother liquor.
  • the mother liquor may be returned to the acrylic acid distillation column 11A or the acrylic acid absorption column 10.
  • acrylic acid is produced from the raw material ethanol through steps (1) to (11). Next, each of steps (1) to (11) will be explained.
  • step (1) ethanol and water (a) are reacted to obtain a mixed gas (A) containing acetone, water vapor, carbon dioxide, and hydrogen.
  • the raw material, ethanol includes bioethanol (biomass ethanol) derived from biomass feedstocks from the perspective of carbon neutrality.
  • the bioethanol content is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, relative to 100% by mass of raw material ethanol. Whether the ethanol is bioethanol or derived from fossil fuels can be confirmed using radiocarbon dating.
  • the bioethanol content can be measured as follows. 1. The ethanol used in the raw gas is burned and converted entirely into carbon dioxide. 2. Carbon dioxide is separated and purified using a vacuum line. 3. The carbon dioxide produced from ethanol is completely reduced with hydrogen using iron as a catalyst to produce graphite. 4. Using a 14 C-AMS measuring device (for example, manufactured by NEC Corporation), the ratio of the 14 C concentration to the 13 C concentration ( 14 C/ 13 C) of the graphite derived from ethanol is measured. 5.
  • a 14 C-AMS measuring device for example, manufactured by NEC Corporation
  • the ratio of 14 C concentration to 13 C concentration was measured for oxalic acid (hereinafter also referred to as the standard sample) from the same year that the raw material ethanol was produced, provided by the National Institute of Standards ( NIST ), using the same methods as in 1 to 4 above. 6.
  • the 14 C/ 13 C value of graphite derived from raw ethanol is divided by the 14 C/ 13 C value of the standard sample, and the result is multiplied by 100 to obtain the bioethanol content.
  • Water (a) is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. can be used. These waters may also be groundwater, river water, or treated versions of these. Water obtained by the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (a).
  • the state of these metal elements (metal (Me), iron, and zirconium) is not particularly limited, and for example, a metal oxide containing the metal element, a metal oxide supported on a carrier, a carrier containing the metal element, or a metal element supported on a carrier can be used as the catalyst.
  • the metal oxide may be a composite metal oxide.
  • Examples of the crystal structure of the composite metal oxide include spinel, perovskite, magnetoplumbite , and garnet types, with the spinel type being preferred.
  • the composite metal oxide is preferably an iron composite oxide (also known as ferrite) represented by the general formula MeO.nFe2O3 (Me represents at least one metal selected from the group consisting of magnesium, calcium, manganese, and zinc, and n represents an integer of 1 to 6 ), and specific examples include MgFe2O4 and ZnFe2O4 .
  • the carrier examples include activated carbon, silica (SiO 2 ), alumina (Al 2 O 3 ), zeolite, silica-calcia, zirconia (ZrO 2 ), ceria (CeO 2 ), and magnesia (MgO). Of these, activated carbon, silica-calcia, zirconia, ceria, and magnesia are more preferred, and zirconia is particularly preferred.
  • the shape of the carrier is not particularly limited, and examples include spherical, pellet, and honeycomb shapes.
  • the BET specific surface area of the carrier is preferably 20 to 200 m 2 /g, and more preferably 40 to 200 m 2 /g. Using a carrier with a high specific surface area is preferred because it makes it easier for the catalyst components to be supported in a dispersed state, thereby increasing catalytic activity.
  • the state of the zirconium element contained in the catalyst is not particularly limited, and may be contained as a compound containing zirconium alone as the metal, as an element of a composite metal oxide containing other metal elements, or as a support.
  • An example of a compound containing zirconium alone as the metal is zirconium oxide (ZrO 2 ).
  • Examples of composite metal oxides containing other metal elements include composite metal oxides of zirconium and Sn, Pb, Zn, Cu, Fe, Mn, In, etc.
  • zirconium oxide (ZrO 2 ) or composite metal oxides of zirconium, Zn, and Fe are preferred as the support, and zirconium oxide (ZrO 2 ) is more preferred from the viewpoint of catalyst performance.
  • the amount of metal (Me) in the catalyst is preferably 0.4 to 0.7 mol, more preferably 0.4 to 0.6 mol, and even more preferably 0.45 to 0.55 mol per mol of iron. When the amount of metal (Me) is within the above range, good catalytic activity is obtained.
  • the amount of zirconium in the catalyst is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.5 mol, and may be 0.1 to 0.4 mol per mol of iron. When the amount of zirconium is within the above range, the durability of the catalyst can be improved.
  • the total content of the metal (Me), iron, and zirconium in the catalyst is preferably 50 to 100% by mass, and more preferably 80 to 100% by mass, based on 100% by mass of the catalyst.
  • the acetone synthesis reaction can be carried out in either a batch or continuous manner, but from the standpoint of productivity, a continuous method is preferred.
  • the acetone synthesis reaction is preferably carried out as a gas-phase reaction. Reaction formats for gas-phase reactions include fixed beds, moving beds, and fluidized beds, but the simpler fixed bed format is preferred.
  • ethanol gas and water vapor may be mixed and then supplied to the acetone synthesis reactor to come into contact with the catalyst, or ethanol gas and water vapor may be supplied separately to the acetone synthesis reactor to come into contact with the catalyst.
  • Ethanol gas and water vapor can be obtained by heating ethanol and water, respectively, in a vaporizer.
  • an inert gas such as nitrogen or helium may also be supplied to the acetone synthesis reactor.
  • the concentration of ethanol gas is preferably 3 to 66 mol%, and more preferably 5 to 50 mol%, relative to the total amount of gas supplied to the acetone synthesis reactor (100 mol%).
  • the molar ratio of water vapor to ethanol gas is preferably 0.5 to 10, and more preferably 1 to 5.
  • the reaction pressure in the acetone synthesis reaction may be reduced, normal, or increased, but is preferably 0.07 to 2 MPa, and more preferably 0.1 to 1 MPa.
  • the reaction temperature in the acetone synthesis reaction is preferably 250 to 600°C, more preferably 300 to 550°C, and even more preferably 330 to 500°C.
  • the space velocity in the acetone synthesis reaction is preferably 300 to 10,000 (1/h), more preferably 400 to 8,000 (1/h), and even more preferably 500 to 6,000 (1/h).
  • step (2) In the acetone separation step (2) (also referred to as "step (2)"), an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A) obtained in the above step (1). As a result, water vapor and acetone gas are condensed, and the acetone aqueous solution and the mixed gas (B) are separated (gas-liquid separation). In this case, it is preferable to bring the liquid component obtained by condensation into contact with the gas component by stirring or the like, because the acetone gas remaining in the gas component dissolves in water and the recovery rate of acetone can be improved.
  • Water (b) may be supplied to the acetone separation device as needed, separate from the water vapor in the mixed gas (A). Supplying water (b) can improve the acetone absorption efficiency in the acetone separation device. Water (b), together with condensed water from the water vapor, serves as a solvent for the acetone-containing aqueous solution. Water (b) is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. can be used. Water obtained in the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (b).
  • the pressure during the separation operation is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa.
  • the temperature during the separation operation is preferably 0 to 90°C, more preferably 0 to 50°C, and even more preferably 5 to 40°C.
  • step (3) In the acetone distillation step (3) (also referred to as "step (3)"), the acetone-containing aqueous solution obtained in the above step (2) is distilled to separate acetone and water (c).
  • the distillation can be carried out by a known method. Examples of the distillation method include thin film distillation and rectification. The distillation can be carried out either batchwise or continuously, but from the viewpoint of productivity, the continuous method is preferred.
  • the purity of the acetone obtained in step (3) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, from the viewpoint of improving the isopropanol yield in the isopropanol synthesis step (5) described below and the isopropanol purity in the isopropanol separation step (6).
  • the acetone obtained above is used in the next step (ii), it is preferable that the aldehydes, alcohols, and ketones (excluding acetone) in the acetone have been reduced.
  • Ethanol and acetaldehyde in particular are preferably reduced, as they may turn into acetic acid after passing through steps (ii) to (iv).
  • the total content of ethanol and acetaldehyde in acetone is preferably 20,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 5,000 ppm or less.
  • water (c) can be reused as water used in the method for producing acrylic acid of this embodiment (at least one selected from the group consisting of water (a) in step (1), water (b) in step (2), and water (e) in step (10)).
  • step (4) hydrogen is separated from the mixed gas (B) containing carbon dioxide and hydrogen obtained in the above step (2).
  • the method used for separation is not particularly limited, and known methods such as physical absorption, chemical absorption, membrane separation, cryogenic separation, and compression liquefaction can be appropriately used.
  • Physical absorption is a method of separating and recovering carbon dioxide from mixed gases without chemical reaction, using physical mechanisms such as adsorption (e.g., adsorption onto an adsorbent such as activated carbon) or dissolution (e.g., dissolution into an organic solvent).
  • adsorption e.g., adsorption onto an adsorbent such as activated carbon
  • dissolution e.g., dissolution into an organic solvent
  • a preferred example of physical adsorption is pressure swing adsorption (PSA).
  • PSA pressure swing adsorption
  • Chemical absorption involves reacting (absorbing) carbon dioxide with a basic substance, primarily an amine or alkali, converting it into a form such as bicarbonate, which is then separated and recovered from the mixed gas. Carbon dioxide can be recovered by heating or reducing the pressure of the absorbent after absorbing the carbon dioxide.
  • Membrane separation is a method of separating and recovering hydrogen or carbon dioxide from mixed gases by selectively allowing the passage of hydrogen or carbon dioxide through a separation membrane.
  • separation membranes include polymeric membranes, dendrimer membranes, amine-containing membranes, and inorganic membranes such as zeolite membranes. Separation membranes may contain metal atoms, such as Pd.
  • the purity of the hydrogen obtained in step (4) is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more, from the viewpoint of improving the catalytic activity of the catalyst in the isopropanol synthesis step (5) described below.
  • step (5) In the isopropanol synthesis step (5) (also referred to as "step (5)"), the acetone obtained in the step (3) above is reacted with hydrogen (preferably the hydrogen obtained in the step (4) above) to obtain a mixed gas (C) containing isopropanol.
  • Other catalysts include solid catalysts containing metal elements such as Ba, Co, Cr, Cu, Fe, Mn, Ni, Pd, Pt, Zn, Zr, Ru, and Rh.
  • solid catalysts containing at least one metal element selected from the group consisting of Pt, Ru, Ni, Fe, and Co are preferred, and it is more preferred to use at least one solid catalyst selected from the group consisting of Ru catalysts, Ni-Pt catalysts, Ru-Pt catalysts, and Ni-Ru catalysts.
  • the catalyst may be in the form of a metal element, alloy, oxide, or the like.
  • the catalyst may also be in the form of a mixture of metal elements, a mixture of metal elements and metal oxides, a mixture of metal oxides, or a mixed metal oxide.
  • the catalyst may also be a metal element supported on a carrier such as activated carbon, silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), zirconia (ZrO 2 ), ceria (CeO 2 ), magnesia (MgO), or diatomaceous earth.
  • silica (SiO 2 ) or zirconia (ZrO 2 ) is preferred as the carrier.
  • the catalyst may be used alone or in combination of two or more.
  • the isopropanol synthesis reaction can be carried out in either a batch or continuous mode, but from the perspective of productivity, a continuous mode is preferred.
  • the isopropanol synthesis reaction is preferably carried out as a gas-phase reaction.
  • Gas-phase reaction formats include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed format is preferred.
  • acetone gas and hydrogen can be mixed and then supplied to the isopropanol synthesis reactor to contact the catalyst, or acetone gas and hydrogen can be supplied separately to the isopropanol synthesis reactor to contact the catalyst.
  • Acetone gas can be obtained by heating acetone in a vaporizer.
  • an inert gas such as nitrogen or helium can also be supplied to the isopropanol synthesis reactor.
  • the molar ratio of hydrogen to acetone gas (hydrogen/acetone gas) supplied to the isopropanol synthesis reactor is preferably 1 to 10, more preferably 1 to 5.
  • the reaction pressure in the isopropanol synthesis reaction may be reduced, normal, or increased, but is preferably 0.1 to 2 MPa, more preferably 0.1 to 1 MPa.
  • the reaction temperature in the isopropanol synthesis reaction is preferably 20 to 200°C, more preferably 25 to 150°C. A lower reaction temperature is advantageous in terms of equilibrium, but tends to make hydrogenation less likely to proceed. On the other hand, a higher reaction temperature tends to prevent an increase in acetone hydrogenation conversion due to equilibrium constraints.
  • the space velocity in the acetone synthesis reaction is preferably 200 to 50,000 (1/h), more preferably 1,000 to 20,000 (1/h), and even more preferably 2,000 to 10,000 (1/h).
  • step (6) isopropanol separation step (6)
  • acetone separation step (6) also referred to as "step (6)"
  • isopropanol is separated from the mixed gas (C) obtained in the step (5).
  • the mixed gas (C) may contain hydrogen used in the step (5) in addition to isopropanol. More specifically, in the step (6), the mixed gas (C) is supplied to an isopropanol separation apparatus, and the mixed gas (C) is cooled in the apparatus. This condenses the isopropanol, and isopropanol (liquid) is separated from gas components such as hydrogen (gas-liquid separation). The hydrogen contained in the gas components may be reused in the isopropanol synthesis step (5).
  • the pressure in the separation operation is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa.
  • the temperature in the separation operation is preferably 0 to 50°C, more preferably 5 to 40°C.
  • the isopropanol obtained by separation may be supplied directly to the next step (7), or, if necessary, may be further purified by distillation before being supplied to the next step (7).
  • the purity of the isopropanol obtained in step (6) is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 93% by mass or more, from the viewpoint of improving the propylene yield in the propylene synthesis step (7) described below and the propylene purity in the propylene separation step (8).
  • ethanol in the isopropanol obtained above may turn into acetic acid through steps (iii) to (iv), it is preferably reduced.
  • the ethanol content in the isopropanol is preferably 20,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 5,000 ppm or less.
  • Step (7) the isopropanol obtained in the step (6) is subjected to a dehydration reaction to obtain a mixed gas (D) containing propylene and water.
  • the shape of the catalyst is not particularly limited, and examples include tablet, ring, spherical, cylindrical extruded, trilobe extruded, and granular shapes. Among these, spherical, tablet, and extruded shapes are preferred because they have high catalytic strength and can be uniformly packed into a reaction tube.
  • the catalyst may be one of the above, which has been subjected to acid treatment and/or calcination as necessary.
  • Acid treatment is performed by immersing the catalyst (e.g., a gamma-alumina catalyst) in acid to adjust the acid strength of the catalyst.
  • acids used in acid treatment include aqueous solutions of hydrochloric acid, nitric acid, boric acid, etc., and carboxylic acids such as acetic acid, formic acid, and oxalic acid.
  • a catalyst with an average pore diameter of 30 to 150 ⁇ , calculated statistically based on the relationship between pore diameter and pore volume, and a standard deviation of 10 to 40 ⁇ is preferably used.
  • the propylene synthesis reaction can be carried out in either a batch or continuous manner, but from the standpoint of productivity, a continuous method is preferred.
  • the propylene synthesis reaction is preferably carried out as a gas-phase reaction. Reaction formats for gas-phase reactions include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed format is preferred.
  • isopropanol can be heated in a vaporizer and supplied to the propylene synthesis reaction as isopropanol gas.
  • an inert gas e.g., nitrogen, helium, argon
  • nitrogen, helium, argon may also be supplied to the propylene synthesis reactor.
  • the reaction temperature in the propylene synthesis reaction is preferably 150 to 500°C, more preferably 180 to 400°C.
  • the reaction pressure in the propylene synthesis reaction may be reduced, normal, or increased, but is preferably a pressure at which a gas-phase reaction can be maintained.
  • propylene separation step (8) In the propylene separation step (8) (also referred to as “step (8)"), propylene and water (d) are separated from the mixed gas (D) obtained in the step (8). More specifically, the mixed gas (D) is supplied to a propylene separation apparatus, and water is condensed by pressurization and cooling. This allows separation into a gas phase mainly consisting of propylene and an aqueous phase mainly consisting of water (d).
  • the water (d) can be reused as water (at least one selected from the group consisting of water (a) in step (1), water (b) in step (2), and water (e) in step (10)) used in the method for producing acrylic acid according to this embodiment.
  • the pressure when the pressurized state is established is preferably 0.5 to 5 MPaG from the viewpoint of separation and purification costs. Furthermore, the reaction product (gaseous) can be easily liquefied simply by cooling it to 20 to 50°C.
  • the propylene obtained by separation may be supplied directly to the next step (9), or, if necessary, may be further purified by distillation before being supplied to the next step (9).
  • the purity of the propylene obtained in step (8) is preferably 90% by mass or more, more preferably 93% by mass or more, and even more preferably 95% by mass or more, from the viewpoint of improving the yield of acrylic acid in the acrylic acid synthesis step (9) described below and the purity of acrylic acid in the acrylic acid separation step (11).
  • step (9) In the acrylic acid synthesis step (9) (also referred to as “step (9)"), the propylene obtained in the above step (8) is subjected to an oxidation reaction to obtain a mixed gas (E) containing acrylic acid.
  • a mixed gas (E) containing acrylic acid For the acrylic acid synthesis reaction (propylene oxidation reaction) "CH 2 ⁇ CHCH 3 +1.5O 2 ⁇ CH 2 ⁇ CHCOOH +H 2 O", a known method (for example, the method described in Japanese Patent Nos. 3,948,837 and 3,938,646) can be appropriately adopted.
  • propylene is oxidized by contacting it with a molecular oxygen-containing gas such as oxygen or air in the presence of a known catalyst.
  • the oxidation reaction is usually carried out in two stages.
  • the catalyst used in the first stage reaction is one that can produce acrolein through the gas phase oxidation of propylene gas, and there are no particular restrictions on the catalyst used in the second stage reaction, as long as it can produce acrylic acid through the gas phase oxidation of acrolein gas.
  • the catalyst used in the first-stage reaction may be a solid catalyst containing at least one element selected from the group consisting of Fe, Co, Ni, Mo, Bi, Al, and Si, preferably containing at least one element selected from the group consisting of Fe, Mo, and Bi, and more preferably containing a composite oxide containing Fe, Mo, and Bi.
  • the catalyst used in the second-stage reaction may be a solid catalyst containing at least one element selected from the group consisting of V, Mo, Cu, W, Sb, Al, and Si, preferably containing at least one element selected from the group consisting of Mo, V, and W, and more preferably containing Mo and V.
  • the acrylic acid synthesis reaction can be carried out in either a batch or continuous manner, but from the standpoint of productivity, a continuous method is preferred.
  • the reaction temperature in the acrylic acid synthesis reaction is usually in the range of 200 to 400°C.
  • the mixed gas (E) obtained in the above step (9) is contacted with an absorbent (typically water (e)) for collecting acrylic acid from the mixed gas (E) to obtain an aqueous solution containing acrylic acid.
  • the mixed gas (E) may contain acrylic acid, the molecular oxygen-containing gas used in the above step (9), unreacted components (propylene, acrolein), and by-products (e.g., acetone, acetic acid, furfural, formaldehyde, etc.).
  • the liquid for collecting acrylic acid from the mixed gas (E) is typically water, but other liquids can also be used.
  • the aqueous solution containing acrylic acid should be read as an acrylic acid-containing solution.
  • a collecting liquid for acrylic acid in the mixed gas (E) at least one of water and an organic solvent is used.
  • an organic solvent such as methyl isobutyl ketone, diisopropyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, n-propyl acetate, n-butyl acetate, diphenyl ether, and diphenyl ether is used.
  • water or diphenyl ether, more preferably water, is used as the collecting liquid.
  • the water (e) used as the collection liquid for absorbing acrylic acid is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. can be used. These waters may be groundwater, river water, or treated versions of these.
  • the water obtained in the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (e).
  • the method for contacting the mixed gas (E) with water (e) is not particularly limited, and any known contact method can be used as appropriate. Specific examples of contact methods include cross-current contact using bubble cap trays, uniflat trays, perforated plate trays, jet trays, bubble trays, or Venturi trays; and countercurrent contact using turbogrid trays, dual flow trays, ripple trays, Kittel trays, or structured packings such as gauze, sheet, or grit, or random packing.
  • step (11) the acrylic acid-containing aqueous solution obtained in the step (10) is purified to obtain acrylic acid.
  • the aqueous acrylic acid solution may contain acrylic acid, acetic acid, water, and other impurities (maleic acid, propionic acid, furfural, formaldehyde, etc.).
  • the method for purifying acrylic acid is not particularly limited, and known techniques such as distillation and crystallization can be used as appropriate.
  • Purification may involve only distillation (acrylic acid distillation step (11A)), only crystallization (acrylic acid crystallization step (11B)), or a combination of distillation (acrylic acid distillation step (11A)) and crystallization (acrylic acid crystallization step (11B)).
  • the acrylic acid distillation step (11A) and the acrylic acid crystallization step (11B) are combined in this order.
  • distillation may be performed only once or multiple times in combination.
  • crystallization may be performed only once or multiple times in combination.
  • distillation and crystallization may be performed continuously or batchwise.
  • water (f) is separated from the aqueous acrylic acid solution by distillation.
  • Azeotropic distillation using an azeotropic solvent is preferred.
  • azeotropic solvents include heptane, toluene, ethyl methacrylate, methyl isobutyl ketone, n-propyl acrylate, methyl acetate, and n-butyl acetate.
  • Toluene, methyl isobutyl ketone, methyl acetate, and n-butyl acetate are preferred, and toluene is even more preferred.
  • multiple azeotropic solvents may be a mixture of these solvents.
  • Water (f) can be reused as water (at least one selected from the group consisting of water (a) in step (1), water (b) in step (2), and water (e) in step (10)) used in the method for producing acrylic acid according to this embodiment.
  • the water obtained by the method as the water used in the method. That is, it is preferable to reuse at least one selected from the group consisting of water (c) and water (d) as at least one selected from the group consisting of water (a) and water (e).
  • the mixed gas (A) is contacted with water (b) (water (b) is supplied) in the acetone separation step (2), it is preferable to reuse at least one selected from the group consisting of water (c) and water (d) as at least one selected from the group consisting of water (a), water (b), and water (e).
  • the acrylic acid purification step (11) includes an acrylic acid distillation step (11A)
  • the reuse described above not only reduces the cost of water procurement but also reduces the total amount of wastewater discharged from the production process, thereby reducing the environmental burden and suppressing wastewater treatment costs, thereby providing an acrylic acid production method that is excellent in both environmental and economic terms.
  • water (Y) encompasses both “a form in which water (Y) is only water (X)” and “a form in which water (Y) is composed of water (X) and water other than water (X) (e.g., tap water, industrial water, pure water).”
  • Reusing water (X) as water (Y) preferably refers to "a form in which water (Y) is only water (X).”
  • water (a) to water (f) may each contain 25% by mass or less (preferably 20% by mass or less, more preferably 18% by mass or less) of impurities other than H 2 O.
  • Water (c) is preferably reused as water (a) and/or water (b), and more preferably reused as water (a). This reduces the amount of wastewater, and if unreacted ethanol remains in water (c) from the acetone synthesis step (1), the unreacted ethanol can be reused again for acetone synthesis without being discarded, thereby improving the yield of acetone synthesis from raw material ethanol.
  • the content of methyl propyl ketone in water (c) is 5000 ppm or less and the content of methyl isobutyl ketone is 500 ppm or less; more preferably, the content of methyl propyl ketone in water (c) is 3000 ppm or less and the content of methyl isobutyl ketone is 200 ppm or less.
  • the water can be suitably reused as water (a) and/or water (b).
  • Water (d) is preferably reused as at least one selected from the group consisting of water (a), water (b), and water (e), more preferably reused as water (a) and/or water (b), and even more preferably reused as water (a).
  • This has the effect of reducing the amount of wastewater and enabling the reuse of acetone, a small amount of by-product produced during the isopropanol dehydration reaction, without being discarded together with the wastewater.
  • the isopropanol content in water (d) is preferably 10,000 ppm or less, more preferably 5,000 ppm or less. When the isopropanol content is within the above range, it can be suitably reused as at least one selected from the group consisting of water (a), water (b), and water (e).
  • Water (f) is preferably reused as water (e). This reduces the amount of wastewater and enables the recovery of acrylic acid remaining in water (f), thereby improving the production efficiency of acrylic acid.
  • the impurities contained in water (f) preferably include components used in distillation step 11 (A), and it is preferable that the amount of these components is not more than a predetermined amount.
  • the distillation step is azeotropic distillation using an azeotropic solvent
  • the content of the azeotropic solvent components in water (f) is preferably 1000 ppm or less, and more preferably 500 ppm or less.
  • the content of the azeotropic solvent components is within the above range, it can be suitably reused as water (e).
  • steps (1) to (11) are preferably carried out in a continuous flow. This eliminates the need for ancillary equipment such as intermediate tanks, allowing for a simpler production facility, thereby shortening production time and reducing facility costs. Furthermore, wastewater generated within the process can be used in other steps within the process, reducing the overall amount of wastewater produced, resulting in reduced wastewater treatment costs.
  • an acrylic acid production system having an acetone reactor, an acetone separation column, an acetone distillation column, a hydrogen separation unit, an isopropanol synthesis reactor, an isopropanol separation unit, a propylene synthesis reactor, a propylene separation unit, an acrylic acid synthesis reactor, an acrylic acid absorption column, and an acrylic acid distillation column and/or an acrylic crystallization unit.
  • the propionic acid content in the acrylic acid obtained by propylene oxidation and purification is preferably 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less, and the acetic acid content is preferably 1500 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less.
  • the low propionic acid (and even more preferably acetic acid) content in the acrylic acid reduces the odor (acid odor) of the resulting cosmetic additive. Furthermore, the yield of the cosmetic additive (the ratio of the acrylic acid used to the cosmetic additive obtained) is improved.
  • the acrylic acid namely protoanemonin, allyl acrylate, allyl alcohol, aldehydes (particularly furfural), maleic acid, and benzoic acid
  • one or more, more preferably two or more, even more preferably three or more, even more preferably four or more, particularly preferably five or more, and especially preferably all six are each present at 0 to 20 ppm (by mass, the same applies hereinafter). More preferably, each is present at 0 to 10 ppm, even more preferably 0 to 5 ppm, even more preferably 0 to 3 ppm, particularly preferably 0 to 1 ppm, and most preferably N.D. (below detection limit).
  • aldehydes may increase in acrylic acid derived from bio-based raw materials, so it is preferable to control this content.
  • Control methods include the use of an aldehyde treatment agent or crystallization.
  • the total amount of protoanemonin, allyl acrylate, allyl alcohol, aldehyde, maleic acid, and benzoic acid is preferably 100 ppm or less, more preferably 0 to 20 ppm, even more preferably 0 to 10 ppm, and especially preferably 0 to 5 ppm.
  • Moisture in acrylic acid promotes the formation of acrylic acid dimers, and the increase in acrylic acid dimers increases the amount of residual monomers in cosmetic additives.
  • cosmetic additives and cosmetics using them tend to have excellent thickening properties and a smooth texture.
  • a high water content in acrylic acid affects the precipitation behavior of the precipitate during precipitation polymerization, making it more likely that clumps will form, resulting in residual particles when the cosmetic additive is dissolved in water, which can affect the texture of the cosmetic additive.
  • the water content of the acrylic acid obtained in step (iv) is preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less (5000 ppm or less), and particularly preferably 0.45% by mass or less (4500 ppm or less), and may be 0.4% by mass or less (4000 ppm or less), 0.3% by mass or less (3000 ppm or less), or 0.25% by mass or less (2500 ppm or less).
  • the amount of acrylic acid dimer in the acrylic acid (salt) supplied to step (v) described below is preferably 1,000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less.
  • the amount of acrylic acid dimer in the acrylic acid (salt) supplied to step (v) described below is, for example, 1 ppm or more.
  • step (v) impurities in the acrylic acid (salt) be N.D., but it is difficult to completely remove them even through steps (i) to (iv). Therefore, a certain amount of the acrylic acid contained therein may be used in step (v), and impurities in the acrylic acid (salt) (for example, acetic acid and propionic acid in the acrylic acid (salt)) may be removed in step (v) and/or step (vi) by heating in the cosmetic additive manufacturing process.
  • impurities in the acrylic acid (salt) for example, acetic acid and propionic acid in the acrylic acid (salt)
  • an acrylic polymer can be produced via the following step (v) using bioacrylic acid obtained by the above steps (i) to (iv).
  • an acrylic polymer can be produced via the following step (v) using acrylic acid and/or a salt thereof derived from a biomaterial having a water content of 4000 ppm or less.
  • the production methods of the present invention preferably include the following step (vi), and when the polymerization method is suspension polymerization or precipitation polymerization, it is preferable to include step (vi) after the filtration step. Step (v) of polymerizing a monomer containing acrylic acid and/or a salt thereof to obtain an acrylic polymer; Step (vi) of drying the acrylic polymer
  • the acrylic acid and/or its salt obtained in step (iv) is used as the monomer for the acrylic polymer.
  • the acrylic acid and/or its salt derived from a biomaterial having a water content of 4000 ppm or less is used as the monomer.
  • the acrylic polymer is a crosslinked polymer obtained by optionally crosslinking a monomer composition containing acrylic acid (salt) as the main component.
  • the acrylic polymer may contain a graft component.
  • the acrylic polymer may be a homopolymer of acrylic acid (salt) (polyacrylic acid (salt)) or a copolymer of acrylic acid (salt) and another monomer.
  • the content of acrylic acid (salt) in 100% by mass of the monomers that make up the acrylic polymer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more; it may be 99% by mass or more, or even 100% by mass.
  • the content of acrylic acid in 100% by mass of acrylic acid (salt) used as a monomer constituting the acrylic polymer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, and may even be 100% by mass.
  • the acrylic acid (salt) to be polymerized may be solely the acrylic acid and/or its salt obtained in step (iv) above, or may be used in combination with other acrylic acids (salts).
  • acrylic acids (salts) to be used in combination include acrylic acids (salts) derived from fossil feedstocks and other bio-acrylic acids (salts) obtained from sources other than bioethanol.
  • the ratio of the acrylic acid and/or its salt obtained in the above step (iv) in combination with other acrylic acid (salt) can be determined appropriately, but from the viewpoints of performance, sustainability, and renewability, the higher the ratio of the acrylic acid and/or its salt obtained in the above step (iv) to be used, the more preferable it is, and the acrylic acid and/or its salt obtained in the step (iv) is preferably 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more relative to 100% by mass of the total amount of acrylic acid (salt) to be subjected to the step (v).
  • the upper limit depends on the production capacity of the acrylic acid obtained in the above step (iv), but may be less than 100 mol%, 95 mol% or less, or 90 mol% or less.
  • a method for using the acrylic acid and/or its salt obtained in step (iv) above in combination with another acrylic acid (salt) includes mixing the acrylic acid and/or its salt obtained in step (iv) above with another acrylic acid (acrylic acid derived from a fossil raw material) and/or its salt.
  • the acrylic acid obtained in step (iv) above is preferably used in step (v) shortly after purification; the interval between steps (iv) and (v), particularly including transportation and storage, is preferably within 10 days, more preferably within 5 days, even more preferably within 2 days, and particularly preferably within 1 day.
  • the water content of the acrylic acid (salt) added in step (v) is preferably 0.5% by mass or less (5000 ppm or less), more preferably 0.45% by mass or less (4500 ppm or less), even more preferably 0.4% by mass or less (4000 ppm or less), and particularly preferably 0.3% by mass or less (3000 ppm or less), and may be 0.25% by mass or less (2500 ppm or less).
  • a polymerization inhibitor may be added to the acrylic acid (salt) used in step (v).
  • the amount of polymerization inhibitor added is, for example, 1 to 300 ppm, preferably 10 to 200 ppm, and more preferably 20 to 80 ppm.
  • a preferred polymerization inhibitor is p-methoxyphenol.
  • the monomer composition used to obtain the acrylic polymer may essentially consist solely of acrylic acid (salt) as a monomer, or may contain other monomers copolymerizable with acrylic acid (salt).
  • examples of such other monomers include, but are not limited to, methacrylic acid, maleic acid, itaconic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamide, and salts thereof. These monomers may be used alone or in a suitable mixture of two or more types. Among these, itaconic acid is preferred when used in combination with other monomers, as it can be obtained by fermentation and contributes to the use of bio-based raw materials.
  • the proportion of acrylic acid (salt) in the monomer composition is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 90 to 100 mol%, relative to the total amount of monomers (100% by mass). Furthermore, the proportion of the other monomers in the monomer composition is, for example, 0 to 50 mol%, and preferably 5 to 45 mol%.
  • a crosslinking agent is used.
  • the crosslinking agent may be added before or after the polymerization of the monomer composition.
  • examples of the above crosslinking agent include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol di(meth)acrylate.
  • crosslinking agents examples include compounds having two or more ethylenically unsaturated groups in one molecule, such as tol triallyl ether neoallyl, N,N'-methylene bis(meth)acrylamide, triallyl isocyanurate, trimethylolpropane di(meth)allyl ether, triallylamine, tetraallyloxyethane, and glycerol propoxy triacrylate.
  • Compounds having two ethylenically unsaturated groups in one molecule such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate, are preferred. Only one type of crosslinking agent may be used, or two or more types may be used.
  • the polymerization method for the monomer composition is not particularly limited, and any known or commonly used method can be used.
  • Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these, precipitation polymerization is preferred from the standpoint of achieving superior thickening properties for the cosmetic additive and superior usability of the cosmetic.
  • a solvent may be used in the polymerization of the above-mentioned monomer composition.
  • a hydrophobic organic solvent can be used as the solvent for the polymerization of the above-mentioned monomer composition.
  • hydrophobic organic solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, aliphatic ketones, and aliphatic esters.
  • Aliphatic hydrocarbons include, for example, aliphatic hydrocarbons with 5 or more carbon atoms, such as n-pentane, n-hexane, and n-heptane.
  • Alicyclic hydrocarbons include, for example, cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane.
  • Aromatic hydrocarbons include, for example, benzene, toluene, and xylene.
  • Aliphatic alcohols include, for example, aliphatic alcohols with 4 or more carbon atoms, preferably 4 to 6 carbon atoms, such as n-butyl alcohol and n-amyl alcohol.
  • Aliphatic ketones include, for example, aliphatic ketones with 4 or more carbon atoms, preferably 4 to 6 carbon atoms, such as methyl ethyl ketone.
  • Aliphatic esters include, for example, aliphatic esters with 4 or more carbon atoms, preferably 4 to 6 carbon atoms, such as ethyl acetate.
  • hydrophobic organic solvents such as hydrophobic organic solvents
  • hydrophobic organic solvents may be used alone or in a mixture of two or more types.
  • each of the hydrophobic organic solvents listed above may be used alone or in a mixture of two or more types.
  • a solvent for polymerizing the above-mentioned monomer composition that is a combination of at least one selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons with at least one selected from the group consisting of aliphatic ketones and aliphatic esters, and it is even more preferable to use a combination of an alicyclic hydrocarbon and an aliphatic ester.
  • the mass ratio of the aliphatic hydrocarbons and alicyclic hydrocarbons to the aliphatic ketones and aliphatic esters used in the solvent for polymerizing the above-mentioned monomer composition is preferably 100/0 to 50/50, and more preferably 90/10 to 70/30.
  • the mass ratio of alicyclic hydrocarbon to aliphatic ester (mass of alicyclic hydrocarbon/mass of aliphatic ester) used in the solvent for polymerizing the above-mentioned monomer composition is preferably 100/0 to 50/50, and more preferably 90/10 to 70/30.
  • a polymerization initiator can be used to polymerize the above monomer composition.
  • a radical polymerization initiator is preferably used as the polymerization initiator.
  • Preferred radical polymerization initiators are thermal polymerization initiators, such as peroxide-based polymerization initiators and azo compound-based polymerization initiators.
  • peroxide-based polymerization initiators examples include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, and diisopropylbenzene hydroperoxide.
  • azo compound polymerization initiators examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,3-dimethylbutyronitrile), 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis(2,3,3-trimethylbutyronitrile), 2,2'-azobis(2-isopropylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and dimethyl-2,2'-azobisisobutyrate.
  • One or more of the above polymerization initiators may be used.
  • the supply time when supplied at a uniform rate is, for example, when the monomer is supplied over 60 to 350 minutes and the polymerization initiator is supplied over 80 to 400 minutes, preferably when the monomer is supplied over 90 to 300 minutes and the polymerization initiator is supplied over 100 to 350 minutes.
  • the monomer is supplied over 45 to 300 minutes and the polymerization initiator is supplied over 60 to 350 minutes, preferably when the monomer is supplied over 45 to 250 minutes and the polymerization initiator is supplied over 60 to 300 minutes, and more preferably when the monomer is supplied over 45 to 200 minutes and the polymerization initiator is supplied over 60 to 250 minutes. In either case, it is preferable to supply the polymerization initiator for a longer period than the monomer.
  • the cosmetic additive By carrying out step (vi) of drying the acrylic polymer, the cosmetic additive can be obtained as a powder. Furthermore, at the same time, impurities remaining in the obtained acrylic polymer (monomers such as acrylic acid (salt), and those exemplified and explained as impurities that may be contained in bioacrylic acid) can be removed.
  • the drying can be carried out under normal pressure or under reduced pressure.
  • the drying temperature is, for example, 60 to 120°C, preferably 80 to 110°C. A drying temperature of 120°C or less makes it less likely that the acrylic polymer will deteriorate, and can prevent a decrease in viscosity and a deterioration in feel. A drying temperature of 60°C or higher improves the productivity of the drying process and allows for sufficient removal of the solvent.
  • the neutralization rate of the acid groups in the acrylic polymer is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less.
  • Neutralization may also be performed in an unneutralized form (neutralization rate of 0 mol%).
  • Neutralization may be performed on the monomer (monomer composition containing acrylic acid (salt)), on the acrylic polymer after polymerization, or on both.
  • neutralization salts include alkali metal salts of (poly)acrylic acid, such as sodium, potassium, and lithium, ammonium salts, and amine salts.
  • acrylic acid (boiling point 141°C) may volatilize during polymerization or drying.
  • the volatilized acrylic acid may be discarded, but from the viewpoints of the environment, CO2 reduction, and carbon neutrality, it is preferable to capture and recycle the volatilized acrylic acid.
  • Acrylic acid can be captured by known means such as absorption with water or alkaline water or cooling.
  • the captured bioacrylic acid or its aqueous solution e.g., alkaline aqueous solution
  • the acrylic acid (salt) used in step (v) may be used in combination with other bioacrylic acids derived from fossil raw materials or from sources other than bioethanol, as long as at least a portion of the monomers constituting the main chain of the acrylic polymer in the cosmetic additive contain a monomer derived from bioethanol, a portion of the acetone in step (ii), the isopropanol in step (iii), and the propylene in step (iv) may contain acetone, isopropanol, or propylene derived from fossil raw materials or from biomaterials other than bioethanol, respectively.
  • acetone, isopropanol, or propylene derived from fossil raw materials or from biomaterials other than bioethanol can be used in combination in cases where the crops used as raw materials for bioethanol are poor in harvest, or when treating surplus or by-products of compounds derived from fossil raw materials generated in the production of other compounds.
  • the amounts of carbon isotopes C and C vary depending on the type of plant raw material, or whether the raw material is fossil or non-fossil.
  • cosmetic additives with various amounts of C and C can be produced. Measuring the amounts of C and C enables traceability (identification) of the cosmetic additive after production.
  • the proportion of bioethanol-derived acrylic acid (salt) among the monomers constituting the main chain of the final cosmetic additive is preferably 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, and 70 mol% or more, in this order.
  • the acrylic polymer (cosmetic additive) obtained in step (v) or step (vi) may be subjected to a classification step to uniformize the particle size.
  • the above steps (i) to (vi) may be connected and carried out continuously, or may be carried out individually. Furthermore, the individual purification of acetone, isopropanol, propylene, or acrylic acid described in the above steps (i) to (iv) may be omitted. Furthermore, the above steps (i) to (vi) may be carried out by the same producer, or some or all of them may be carried out by different producers. For example, the tasks may be shared as follows:
  • steps (i) to (vi) may be carried out at the same location or at different locations.
  • “same location” we mean a location within an industrial site that is close enough to be connected by pipeline. If carried out at different locations, transportation methods other than pipelines, such as long-distance transportation by tanker, truck, rail, etc., may be used.
  • steps (v) and (vi) be carried out at the same location, and it is also preferable that steps (i) to (vi) be carried out at a maximum of four locations, even at a maximum of three locations, or even at two locations, and it is particularly preferable that all steps be carried out at a single location.
  • step (iv) is an exothermic reaction accompanied by oxidation
  • the heat generated in step (iv) can be used for heating, such as polymerization in step (v) and drying in step (vi), resulting in a more CO2 -reducing and environmentally friendly method for producing cosmetic additives.
  • the heat can be supplied to steps (v) and (vi) as high-pressure steam through a pipeline.
  • step (iii) and step (iv) are gas-phase reactions and the isopropanol dehydration reaction in step (iii) also produces a high yield of biopropylene
  • step (i) and/or step (ii) may be carried out at a location separate from steps (iii) to (vi).
  • ethanol used or produced in steps (i) to (v) are handled as liquids or gases.
  • propylene may be cooled and liquefied before handling, or may be handled as a gas.
  • Transport e.g., pipeline transport
  • storage e.g., storage in a tank with a liquid cooling or circulation mechanism
  • a cooling medium may be produced by recovering latent heat from the propylene and used for cooling in steps after step (iv).
  • the polyacrylic acid obtained in step (v) from liquid acrylic acid is in the form of a slurry. Therefore, transport and storage methods suitable for the slurry state are selected between steps (v) and (vi).
  • step (iv) and step (v) be carried out within a certain time period (especially including transportation and storage) of 10 days or less, and further preferably within 5 days, 2 days, or 1 day.
  • steps (i) to (vi) may be carried out at multiple locations, by multiple manufacturing companies, or by methods with different conditions within the scope of the present invention.
  • methods with different conditions within the scope of the present invention correspond to, for example, cases where raw materials that differ in whether they have been refined are used together in the next step, or cases where raw materials obtained using different catalysts are used together in the next step.
  • the cosmetic additive obtained by the production method of the present invention (sometimes referred to as the "cosmetic additive of the present invention") contains at least an acrylic polymer obtained via step (v).
  • the cosmetic additive has, for example, the following properties.
  • the ratio of bio-based raw materials can be specified by the 14 C (radiocarbon)/ 12 C (carbon) ratio of the resulting acrylic polymer. While acrylic acid (salt)-based cosmetic additives obtained from conventional fossil raw materials (particularly petroleum, and even more preferably propylene) have a 14 C/ 12 C ratio of less than 1.0 ⁇ 10 ⁇ 14 , the acrylic polymer in the cosmetic additive of the present invention has a 14 C/ 12 C ratio of preferably 1.0 ⁇ 10 ⁇ 14 or more, more preferably 1.0 ⁇ 10 ⁇ 13 or more, even more preferably 5.0 ⁇ 10 ⁇ 13 or more, and particularly preferably 1.0 ⁇ 10 ⁇ 12 or more.
  • 14 C/ 12 C can be measured by isotope mass spectrometry or the like, as described, for example, in US Patent Nos. 3,885,155, 4,427,884, 5,438,194, and 5,661,299.
  • the specific measurement procedure is as follows. 1. Cosmetic additives are burned and converted into carbon dioxide. 2. Carbon dioxide is separated and purified using a vacuum line. 3. Carbon dioxide produced from cosmetic additives is reduced with hydrogen using iron as a catalyst to produce graphite. 4. Using a 14 C-AMS measuring device, the ratio of the 14 C concentration to the 12 C concentration ( 14 C/ 12 C) of graphite derived from cosmetic additives is measured.
  • radioactive carbon can be adjusted by the ratio of bio-based raw materials (especially bioethanol) used.
  • the stable carbon isotope ratio ( ⁇ 13 C) measured by accelerator mass spectrometry can be adjusted appropriately within the range of 0 to -40% (per mille).
  • the stable carbon isotope ratio ( ⁇ 13 C) can be adjusted depending on the type of plant used as the raw material, and can be adjusted appropriately by adjusting the raw material to C3 plants (wheat, potato, rice, etc.) with ⁇ 13 C ⁇ -20% and C4 plants (corn, etc.) with ⁇ 13 C ⁇ -20%.
  • C3 plants wheat, potato, rice, etc.
  • C4 plants corn, etc.
  • the cosmetic additive of the present invention has the advantage that the bioacrylic acid obtained is highly pure, resulting in a low level of residual monomer.
  • the residual monomer is controlled to, as an example of a means for achieving the above-mentioned polymerization, typically 500 ppm or less, preferably less than 500 ppm, more preferably 0 to 450 ppm, even more preferably 0 to 400 ppm, even more preferably 0 to 300 ppm, and particularly preferably 0 to 200 ppm.
  • the residual monomer can be appropriately controlled by the polymerization initiator used during polymerization and the subsequent drying conditions, etc.
  • the cosmetic additive of the present invention has a purity of acrylic acid obtained by the method for producing acrylic acid of the present invention that is equal to or higher than that of conventional fossil raw materials, so there is no increase in the amount of impurities. Furthermore, there are no problems with coloration or odor.
  • Typical impurities in cosmetic additives other than residual monomers include acetic acid and propionic acid, and the total content thereof is preferably 1000 ppm or less, more preferably 800 ppm or less, even more preferably 600 ppm or less, even more preferably 500 ppm or less, even more preferably 400 ppm or less, and particularly 300 ppm or less.
  • the total content of acetic acid, propionic acid, and residual monomers (especially acrylic acid), which are responsible for the acidic odor of cosmetic additives, is preferably 1500 ppm or less, more preferably 1200 ppm or less, and even more preferably 1000 ppm or less.
  • the viscosity of an aqueous solution prepared to have a cosmetic additive concentration of 0.5% by mass and a pH of 7.3 to 7.8 with a 50% by mass aqueous sodium hydroxide solution is preferably 40,000 to 100,000 mPa s, more preferably 45,000 to 90,000 mPa s, and even more preferably 50,000 to 80,000 mPa s.
  • the viscosity is measured using a Brookfield viscometer at 25°C and a rotation speed of 4 rpm.
  • the YI (Yellow Index) is preferably 20 or less, more preferably 15 or less, and may be 10 or less.
  • Cosmetic additives that do not cause turbidity are preferred. Transparent cosmetic products and products with various visual effects have been developed, and as long as the cosmetic additive does not cause turbidity, the visual effect can be freely selected.
  • Cosmetic additives that have a fresh feel when used are preferred.
  • the feel of the cosmetic when used and the texture when applied to the skin are important characteristics of the cosmetic.
  • a fresh and light feel and a moist and heavy feel.
  • there are few cosmetic additives that can provide a fresh and light feel and there is a high demand in the market.
  • a less preferred feel is a sticky feel, which many people find unpleasant.
  • the manufacturing method of the present invention uses biomass raw materials to produce cosmetic additives with performance equal to or better than that of conventional cosmetic additives derived from fossil raw materials. Furthermore, because the manufacturing method of the present invention uses inexpensive bioethanol as the biomass raw material, it allows for efficient and inexpensive production. Furthermore, because the manufacturing method of the present invention produces cosmetic additives using acrylic acid (salt) with few impurities, the cosmetic additives of the present invention have few impurities.
  • the cosmetic additives of the present invention can be used as known or conventional cosmetic additives.
  • examples of such additives include thickeners, gelling agents, texture improvers, moisturizers, film-forming agents, UV absorbers, antibacterial agents, emulsifiers, surfactants, and dispersants.
  • the above additives may be used alone or in combination with two or more types.
  • Cosmetics can be produced using the cosmetic additive of the present invention.
  • the cosmetic contains at least the cosmetic additive of the present invention.
  • the cosmetic may contain other ingredients in addition to the cosmetic additive of the present invention.
  • the other ingredients mentioned above include, for example, solvents (e.g., water, organic solvents, etc.), oils, lower alcohols, polyhydric alcohols, thickeners, humectants, surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants), fatty acid alkanolamides, antioxidants, antioxidant aids, powder ingredients (e.g., organic powders, pigments, colorants, etc.), natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, chelating agents, sugars and their derivatives, amino acids and their derivatives, organic amines, polymer emulsions, pH adjusters (acids, alkalis, etc.), vitamins, preservatives/antibacterial agents, anti-inflammatory agents, various extracts, activators, blood circulation promoters, antiseborrheic agents, anti-inflammatory agents, fragrances, etc.
  • solvents e.g., water, organic
  • the above-mentioned cosmetics include known or commonly used cosmetics, such as skin cosmetics, hair cosmetics, and bath cosmetics.
  • topical preparations are applied to the skin, nails, hair, etc. of the human body, and can be used to treat various diseases by blending them with active pharmaceutical ingredients, for example.
  • Cosmetics are also applied to the skin, nails, hair, etc. of the human body, but are used for cosmetic purposes. Even when used as an "topical preparation," they may actually be used in the same manner and dosage as cosmetics. Therefore, in this specification, the term "cosmetics" includes such topical preparations. Examples include antiperspirants, skin cleansers, topical skin preparations, hair cleansers, and topical hair preparations.
  • Medicinal uses of topical preparations include hair growth agents, hair restorers, analgesics, disinfectants, anti-inflammatory agents, cooling agents, and skin anti-aging agents.
  • the above-mentioned skin cosmetics can be used on the scalp, face (including lips, eyebrows, and cheeks), hands, fingers, nails, and any part of the body.
  • skin cleansing products such as cleansing gel, cleansing cream, cleansing foam, facial cleanser, eye makeup remover, facial cleanser, liquid soap (body soap), hand soap, gel soap, shaving cream, nail polish remover, and acne treatment cosmetics
  • skin care products such as skin cream, scalp treatment, skin milk, milk lotion, emulsion, facial pack, body powder, essence, shaving lotion, and massage lotion
  • makeup products such as foundation, liquid foundation, oil-based foundation, makeup base, face powder, blusher, lip balm, rouge paste, lip gloss, eye cream, mascara, eyebrow pencil, and eyelash cosmetics
  • antiperspirants such as deodorants
  • UV protection products such as sunscreens and suntanning agents
  • deodorant products such as sunscreens and suntanning agents.
  • the above-mentioned hair cosmetics include eyelash cosmetic products; hair cleansers such as shampoos and rinse-in shampoos; hair styling products such as hair wax, hair curl retainers, setting agents, hair creams, hair sprays and hair liquids; hair coloring products such as hair dyes, hair color sprays, hair color rinses and hair color sticks; hair care products such as hair tonics, hair treatment essences and hair packs; and hair rinses or hair conditioning products such as oil rinses, cream rinses, treatment rinses, hair conditioners and hair treatments.
  • Examples of the above-mentioned bath cosmetics include foam baths.
  • the form of the cosmetic is not particularly limited, but may be any of a solution, emulsion, cream, solid, semi-solid, paste, gel, powder, multi-layered, mousse, water-in-oil, or oil-in-water emulsion composition (emulsion composition).
  • the cosmetic of the present invention can also be formulated by known methods in the form of, for example, a liquid, suspension, emulsion, cream, ointment, gel, liniment, lotion, aerosol, powder, spray, sheet in which a sheet such as a nonwoven fabric is impregnated with the cosmetic of the present invention, or stick.
  • the content of the cosmetic additive of the present invention in the cosmetic is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, relative to the total amount (100% by mass) of the cosmetic.
  • the content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less.
  • the product was then purified to obtain acetone with a purity of over 95% by mass.
  • the impurities included ethanol and acetaldehyde at a total of 4,000 ppm, with the majority of the remainder being water.
  • step (ii) isopropanol was synthesized by reacting a gas of hydrogen/acetone with a purity of 95% or higher (2.7/1 molar ratio) at 0.5 MPa and 100°C in the presence of a catalyst consisting of spherical silica (particle size 1.7-4 mm) carrying 5% nickel and 5% ruthenium by mass, yielding isopropanol with a purity of 98% by mass.
  • the ethanol content in the isopropanol was 2,200 ppm, with the majority of the remaining impurities being water and acetone.
  • step (iii) the above-mentioned gas, 98% pure by mass, consisting of isopropanol/oxygen/nitrogen (6.8/12.5/80.7 vol.%), was reacted at 325°C in the presence of a catalyst consisting of 10% by mass of tungsten oxide supported on spherical gamma-alumina with a particle size of 2 to 4 mm, to obtain propylene.
  • step (iv) the propylene was oxidized at 325°C in the presence of a bismuth molybdenum catalyst (acrolein production catalyst) with a particle size of 5-7 mm to obtain acrolein, and the acrolein was then reacted at 275°C in the presence of a molybdenum vanadium catalyst with a particle size of 5-7 mm to obtain acrylic acid.
  • acrolein production catalyst a bismuth molybdenum catalyst
  • acrolein production catalyst acrolein production catalyst
  • acrolein molybdenum vanadium catalyst with a particle size of 5-7 mm to obtain acrylic acid.
  • the water content of the bioacrylic acid was 2,300 ppm.
  • Example 1 (Production of cosmetic additives from bioacrylic acid) A thermometer, a reflux condenser, and a separable glass flask equipped with a stirrer were charged with 43.4 g of ethyl acetate and 173.6 g of cyclohexane, and the temperature was raised to 70 ° C. under stirring.
  • the monomer solution and the initiator solution started dropping simultaneously, the monomer solution was added dropwise for 180 minutes, and the initiator solution was added dropwise for 210 minutes. After the completion of all the dropwise addition, the reaction solution was kept at 70°C for an additional 150 minutes to mature and complete the polymerization (precipitation polymerization). Subsequently, the reaction solution was filtered to recover the polymer precipitate, which was then dried under reduced pressure at 90°C for 3 hours and then at 105°C for 5 hours to obtain cosmetic additive 1 of Example 1.
  • Example 2 (Production of a cosmetic additive using both bioethanol-derived acrylic acid and fossil-derived acrylic acid) Polymerization was carried out under the same conditions as in Example 1, except that a mixture of 16.5 g of acrylic acid A derived from fossil materials obtained in Production Example 2 and 16.5 g of bioacrylic acid obtained in Production Example 1 was used instead of 33.0 g of bioacrylic acid obtained in Production Example 1. After completion of the polymerization, drying was carried out under the same conditions as in Example 1, and cosmetic additive 2 of Example 2 was obtained.
  • Comparative Example 1 (Production of a cosmetic additive using acrylic acid derived from fossil raw materials) Polymerization was carried out under the same conditions as in Example 1, except that acrylic acid A derived from fossil raw materials obtained in Production Example 2 was used instead of the bioacrylic acid obtained in Production Example 1. After completion of the polymerization, drying was carried out under the same conditions as in Example 1, and a cosmetic additive 3 of Comparative Example 1 was obtained.
  • Comparative Example 2 (Production of cosmetic additives using acrylic acid derived from fossil raw materials) Polymerization was carried out under the same conditions as in Example 1, except that 33.0 g of acrylic acid B derived from fossil materials obtained in Production Example 3 was used instead of 33.0 g of bioacrylic acid obtained in Production Example 1. The water content in the total acrylic acid was 5000 ppm. The formation of coarse particles was confirmed during polymerization. Furthermore, after polymerization, stickiness to the filter paper increased, requiring significantly longer filtration times. Drying was carried out under the same conditions as in Example 1, and cosmetic additive 4 of Comparative Example 2 was obtained.
  • the cosmetic additives prepared in the Examples and Comparative Examples were mixed with the various components shown in Table 1 to prepare moisturizing gels adjusted to a pH of 5.8 to 6.0.
  • the moisturizing gels also contained 1,3-butylene glycol (manufactured by Daicel Corporation), glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), EDTA-2Na (manufactured by Chubu Cherest Co., Ltd.), potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sodium hyaluronate (manufactured by Kewpie Corporation), and phenoxyethanol (manufactured by Yokkaichi Synthetic Co., Ltd.).
  • the cosmetic additive of Comparative Example 3 had significantly low thickening properties, so the amount added was increased to prepare the moisturizing gel.
  • the units of addition amounts shown in Table 1 are "% by mass.”
  • Viscosity Measurement A measurement aqueous solution was prepared so that the concentration of the cosmetic additive was 0.5% by mass and the pH was adjusted to 7.3 to 7.8 using a 50% by mass aqueous sodium hydroxide solution. The viscosity was measured using a B-type viscometer (product name "TVB-10", manufactured by Toki Sangyo Co., Ltd., rotor No. M4) at 25°C and a rotation speed of 4 rpm.
  • B-type viscometer product name "TVB-10", manufactured by Toki Sangyo Co., Ltd., rotor No. M4
  • the moisturizing gel using the cosmetic additive of the example obtained by the manufacturing method of the present invention using bioethanol, a biomass raw material was evaluated as having a superior feel (usability) and transparency compared to the moisturizing gel using the cosmetic additive derived from fossil raw materials.
  • the cosmetic additives of the examples obtained by the manufacturing method of the present invention using bioethanol, a biomass raw material can be used in a variety of cosmetics in addition to the moisturizing gel mentioned above.
  • Formulation examples are shown below as reference cosmetics, but cosmetics using the cosmetic additives of the present invention are not limited to these.
  • the pH of each reference cosmetic was measured at 25°C using a glass electrode pH meter (model: LAQUA F-72, manufactured by Horiba, Ltd.), and the viscosity was measured using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.) with a rotor No. 4 at a rotation speed of 12 rpm for 1 minute.
  • a cosmetic serum was prepared by mixing the cosmetic additive 1 prepared in Example 1 with the various components shown in Table 3.
  • Other components used included 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), xanthan gum: Eco Gum T (manufactured by CP Kelco U.S., Inc.), (acrylates/alkyl acrylate (C10-30)) crosspolymer: Carbopol ETD2020 (manufactured by Lubrizol Corporation), sodium hydroxide: sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), phospholipids and others: LiNPOSOME-V-MC (manufactured by Lilac Pharma Co., Ltd.), and phenoxyethanol: Phenoxyethanol-S (manufactured by Yokkaichi Chemical
  • Cosmetic additive 1 prepared in Example 1 was mixed with the various components shown in Table 4 to prepare a gel.
  • Other components included 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), glycerin: concentrated glycerin for cosmetics (manufactured by Miyoshi Oil & Fats Co., Ltd.), xanthan gum: Echo Gum T (manufactured by CP Kelco U.S., Inc.), (hydroxyethyl acrylate/sodium acryloyldimethyl taurate) copolymer: SEPINOV EMT10 (manufactured by SEPPIC), squalane: olive squalane (manufactured by Kokyu Alcohol Kogyo Co., Ltd.), and meadowfoam oil: CROPURE.
  • 1,3-butylene glycol 1,3-butylene glycol (UK) (manufactured by Daicel Corporation)
  • MEADOWFOAM manufactured by Croda
  • dimethicone KF-96A-10CS
  • sodium hydroxide sodium hydroxide
  • niacinamide nicotinamide
  • phenoxyethanol phenoxyethanol-S
  • Cosmetic additive 1 prepared in Example 1 was mixed with the various components shown in Table 5 to prepare a disinfectant gel.
  • Other components used included glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), ethanol: 99.5% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), TEA: triethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sodium hyaluronate: Hyaluronic Acid HA-LQ (manufactured by Kewpie Corporation), 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), and phenoxyethanol: Phenoxyethanol-S (manufactured by Yokkaichi Chemical Co., Ltd.).
  • a styling gel was prepared by mixing the cosmetic additive 1 prepared in Example 1 with the various components shown in Table 6. Other components used included: glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), ethanol: 99.5% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), EDTA-2Na: Chelest 2B-SD (manufactured by Chubu Chelest Co., Ltd.), PVP: CV-8896 (manufactured by Nippon Shokubai Co., Ltd.), AMP: 2-amino-2-methyl-1-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), PEG-40 hydrogenated castor oil: NIKKOL HC-40 (manufactured by Nikko Chemicals Co., Ltd.), and fragrance: CITRUS GREEN BC181504 (manufactured by Toyotama Fragrance Co., Ltd.), and fragrance:
  • Cosmetic additive 1 prepared in Example 1 was mixed with the various components shown in Table 7 to prepare a sunscreen gel.
  • EDTA-2Na Chel
  • EHS (manufactured by DSM), diisopropyl sebacate: FineNeo-iPSE (manufactured by Nippon Fine Chemical Co., Ltd.), dimethicone: KF-96A-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.), (Acrylates/C10-30 alkyl acrylate crosspolymer: Carbopol ETD2020 (manufactured by Lubrizol Corporation), xanthan gum: Echo Gum T (manufactured by CP Kelco U.S., Inc.), potassium hydroxide: potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), sodium hyaluronate: Hyaluronsan HA-LQ (manufactured by Kewpie Corporation), titanium oxide, others: DIS-AB-10W (manufactured by Sakai Chemical Industry Co., Ltd.), 1,3-butylene glycol: 1,3-butylene
  • a method for producing a cosmetic additive containing an acrylic polymer derived from a biomaterial comprising the following steps (i) to (v), wherein the acrylic acid added in step (v) includes the acrylic acid obtained in step (iv): Step (i) of obtaining acetone from bioethanol; Step (ii) of obtaining isopropanol from the acetone; (iii) obtaining propylene from the isopropanol; Step (iv) of obtaining acrylic acid from the propylene; Step (v) of polymerizing a monomer containing acrylic acid and/or a salt thereof to obtain an acrylic polymer.
  • [Appendix 2] The method according to Appendix 1, further comprising the following step (vi): Step (vi) of drying the acrylic polymer.
  • [Appendix 3] The method according to appendix 1 or 2, wherein the total content of ethanol and acetaldehyde in the acetone is 20,000 ppm or less.
  • [Appendix 4] The production method according to any one of Appendices 1 to 3, wherein the ethanol content in the isopropanol is 20,000 ppm or less.
  • [Appendix 5] The production method according to any one of Appendices 1 to 4, wherein the raw material for obtaining isopropanol contains the hydrogen obtained in the step (i).
  • Appendix 6 The production method according to any one of Appendices 1 to 5, wherein at least a portion of the water generated in the steps up to obtaining the acrylic acid is reused in at least one of the steps using water.
  • Appendix 7 The method of any one of Appendices 1 to 6, wherein the bioethanol is obtained by fermenting one or more genetically modified or non-genetically modified plant materials selected from the group consisting of sugar cane, corn, and sugar beet.
  • Appendix 8 The production method according to any one of Appendices 1 to 7, wherein the water content in the acrylic acid and/or a salt thereof added in the step (v) is 4000 ppm or less.
  • Appendix 12 A method for producing a cosmetic additive containing an acrylic polymer, comprising a step (v) of polymerizing acrylic acid and/or a salt thereof, wherein the acrylic acid and/or a salt thereof is acrylic acid derived from a biomaterial and has a water content of 4000 ppm or less.
  • Appendix 13 The method for producing a cosmetic additive according to Appendix 12, wherein the polymerization is carried out by precipitation polymerization.
  • Appendix 14 The method for producing a cosmetic additive according to Appendices 12 or 13, wherein a hydrophobic organic solvent is used in the polymerization.

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  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne un procédé de production, à partir d'une matière première issue de la biomasse, d'un additif pour produits cosmétiques dont les performances sont équivalentes ou supérieures à celles d'un additif pour produits cosmétiques classique issu de combustibles fossiles. Un procédé de production d'un additif pour produits cosmétiques selon la présente invention consiste à produire un additif pour produits cosmétiques qui contient un polymère acrylique issu d'une matière première biologique, ce procédé comprenant une étape (i) consistant à obtenir de l'acétone à partir de bioéthanol, une étape (ii) consistant à obtenir de l'isopropanol à partir de l'acétone, une étape (iii) consistant à obtenir du propylène à partir de l'isopropanol, une étape (iv) consistant à obtenir de l'acide acrylique à partir du propylène, et une étape (v) consistant à polymériser un monomère contenant de l'acide acrylique et/ou un sel de celui-ci pour obtenir un polymère acrylique. L'acide acrylique introduit à l'étape (v) contient l'acide acrylique obtenu à l'étape (iv).
PCT/JP2025/015886 2024-04-26 2025-04-24 Procédé de production d'additif pour produits cosmétiques Pending WO2025225693A1 (fr)

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JP2024072891 2024-04-26

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011136237A1 (fr) * 2010-04-26 2011-11-03 株式会社日本触媒 Poly(acide acrylique) ou sel de celui-ci, résine absorbant l'eau à base de poly(acide acrylique) ou de sel de celui-ci et son procédé de production
JP2023167854A (ja) * 2022-05-13 2023-11-24 株式会社日本触媒 アセトン水素化触媒及びイソプロパノールの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011136237A1 (fr) * 2010-04-26 2011-11-03 株式会社日本触媒 Poly(acide acrylique) ou sel de celui-ci, résine absorbant l'eau à base de poly(acide acrylique) ou de sel de celui-ci et son procédé de production
JP2023167854A (ja) * 2022-05-13 2023-11-24 株式会社日本触媒 アセトン水素化触媒及びイソプロパノールの製造方法

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