WO2009151021A1 - Procédé de fabrication de propylène glycol - Google Patents

Procédé de fabrication de propylène glycol Download PDF

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Publication number
WO2009151021A1
WO2009151021A1 PCT/JP2009/060444 JP2009060444W WO2009151021A1 WO 2009151021 A1 WO2009151021 A1 WO 2009151021A1 JP 2009060444 W JP2009060444 W JP 2009060444W WO 2009151021 A1 WO2009151021 A1 WO 2009151021A1
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Prior art keywords
oxide
catalyst
copper
propylene glycol
group
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PCT/JP2009/060444
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English (en)
Japanese (ja)
Inventor
成利 吉村
修二 小澤
寛 河野
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三井化学株式会社
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Priority to JP2010516842A priority Critical patent/JP5486491B2/ja
Publication of WO2009151021A1 publication Critical patent/WO2009151021A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration

Definitions

  • the present invention relates to a method for producing propylene glycol using glycerin as a raw material.
  • Propylene glycol is a compound in which the hydroxyl group at the 1-position of glycerin is converted to hydrogen, but it has low toxicity to organisms and is tasteless and odorless. Widely used in fields such as pharmaceuticals, cosmetics and foodstuffs. Generally, propylene glycol is produced by oxidizing propylene derived from petroleum called a fossil raw material to form propylene oxide, and then hydrating it.
  • WO 2007/099161 pamphlet discloses a method of hydrogenating glycerin at a specific reaction temperature and a specific reaction pressure in the presence of a catalyst.
  • the catalyst used in the reaction include a catalyst containing copper, particularly a catalyst made of copper oxide, zinc oxide and alumina.
  • WO 2007/010299 pamphlet describes a fixed bed continuous reactor in the presence of a catalyst in a specific reaction temperature, a specific reaction pressure, a specific hydrogen to raw material quantity ratio, a specific reaction time and a gas phase.
  • a method of using and hydrogenating glycerin is disclosed.
  • a mixture catalyst containing copper oxide and zinc oxide is exemplified. According to this method, it is described in the pamphlet of WO2007 / 010299 that propylene glycol can be obtained in a high yield. However, in this method, it is necessary to vaporize the glycerin in the vaporizer before introducing it into the reactor, and the energy consumption for carrying out the reaction increases, so the method is economically disadvantageous and efficient. It's hard to say.
  • German Patent No. 102007003188 discloses that in the presence of a catalyst containing 20 to 60% by weight of copper oxide, 30 to 70% by weight of zinc oxide and 1 to 10% by weight of manganese oxide, 180 to 240%.
  • a process for the production of propylene glycol is disclosed in which glycerol is reacted with hydrogen at 20 ° C. and 20-100 bar.
  • the reaction format is limited to a batch reaction using an autoclave, and the patent document does not describe anything in an economically advantageous fixed bed continuous reactor or the like.
  • Chinese Patent Application No. 10101149 describes a catalyst having copper, zinc and manganese (and aluminum) (metal element weight ratio is 16 to 48:24 to 48: 0.15 to 4: 0 to 8). Is used to produce propylene glycol by hydrogenating glycerin at 200 to 250 ° C. and 2.5 to 5 MPa.
  • An object of the present invention is to provide a method for producing propylene glycol in a high yield that does not require a step of vaporizing glycerin in a method for producing propylene glycol using glycerin as a raw material.
  • the present inventors have found that (a) at least one of copper and copper oxide, (b) zinc oxide, and (c) groups 2 to 6 of the periodic table.
  • the present inventors have found that the above problems can be solved by using a catalyst containing an oxide of at least one element selected from the group consisting of Group 8 to Group 10 elements. It came.
  • the gist of the present invention is as follows. (a) at least one of copper and copper oxide, (b) zinc oxide, and (c) at least one selected from the group consisting of elements of Groups 2 to 6 and Groups 8 to 10 of the Periodic Table
  • a method for producing propylene glycol comprising the step of catalytically hydrogenating glycerin to obtain propylene glycol in the presence of a catalyst containing an oxide of a seed element.
  • the oxide (c) in the catalyst is an oxide of at least one element selected from the group consisting of magnesium, calcium, barium, scandium, titanium, vanadium, chromium, molybdenum, tungsten, iron, cobalt, and nickel. Is desirable.
  • the weight ratio of at least one of copper and copper oxide (a) to zinc oxide (b) (at least one of copper and copper oxide (a): zinc oxide (b)) in the catalyst is 6: 1 to 6:35. It is desirable to be in the range.
  • the weight ratio of at least one of copper and copper oxide (a) to the oxide (c) in the catalyst is 100: 1 to 1 It is also desirable to be in the range of 5: 1.
  • the catalytic hydrogenation is preferably performed at a reaction temperature of 100 to 350 ° C. and a hydrogen pressure of 1 to 30 MPa.
  • the present invention (a) at least one of copper and copper oxide, (b) zinc oxide, and (c) an element of Groups 2 to 6 and Groups 8 to 10 of the periodic table.
  • a catalyst containing an oxide of at least one element selected from the group propylene glycol can be produced from glycerin in high yield without vaporizing glycerin.
  • This effect is particularly achieved by using an oxide of at least one element selected from the group consisting of magnesium, calcium, barium, scandium, titanium, vanadium, chromium, molybdenum, tungsten, iron, cobalt and nickel as the oxide (c).
  • This is remarkably achieved by using the containing catalyst. Therefore, the production method of the present invention has great industrial utility value.
  • the present invention is described in detail below.
  • the catalyst used in the present invention includes (a) at least one of copper and copper oxide, (b) zinc oxide, and (c) groups 2 to 6 and groups 8 to 10 of the periodic table.
  • a catalyst comprising an oxide of at least one element selected from the group consisting of elements (hereinafter also simply referred to as oxide (c)).
  • the preparation method of the said catalyst is not specifically limited, The following methods etc. are mentioned.
  • Various salts of copper, various salts of zinc and various salts of at least one element selected from the group consisting of elements of Groups 2 to 6 and Groups 8 to 10 of the periodic table (2) a catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b) prepared by a known method And a method of mixing a substance containing the oxide (c) or a catalyst prepared by a known method.
  • One of the preferred embodiments of the catalyst used in the present invention is selected from the group consisting of various salts of copper, various salts of zinc, and elements of Groups 2 to 6 and Groups 8 to 10 of the periodic table. It is a catalyst produced by a known method using various salts of at least one element as a raw material.
  • the catalyst used in the present invention is at least one selected from copper nitrate, sulfate, carbonate, acetate, chloride, oxide, hydroxide, and the like, At least one selected from nitrates, sulfates, carbonates, acetates, chlorides, oxides and hydroxides of zinc; Furthermore, nitrates, sulfates, carbonates, acetates, chlorides, oxides of at least one element selected from the group consisting of elements of Groups 2 to 6 and Groups 8 to 10 of the Periodic Table It can be produced by a known method such as a coprecipitation method, an impregnation method or a kneading method using at least one selected from hydroxides and the like as raw materials.
  • a coprecipitation method for example, an aqueous solution containing copper nitrate, zinc nitrate, and nitrate of a group 2 element in the periodic table is reacted in the presence of a base, and copper, zinc, To produce a coprecipitate containing elements of Group 2 of the periodic table. Thereafter, the catalyst used in the present invention can be produced by drying and calcining the coprecipitate.
  • various salts of copper used, various salts of zinc, and various salts of at least one element selected from the group consisting of elements of Groups 2 to 6 and Groups 8 to 10 of the periodic table By changing the quantitative ratio, the content of at least one of copper and copper oxide (a), zinc oxide (b) and oxide (c) in the catalyst used in the present invention can be adjusted.
  • the weight ratio of at least one of copper and copper oxide (a) and zinc oxide (b) contained in the catalyst used in the present invention (at least one of copper and copper oxide (a): zinc oxide (b) )
  • the weight ratio of at least one of copper and copper oxide (a) and oxide (c) contained in the catalyst used in the present invention Is not particularly limited, but is preferably in the range of 100: 1 to 1.5: 1, and more preferably in the range of 100: 1 to 4: 1.
  • the catalytic reaction proceeds in a high yield.
  • the oxide (c) described above is an oxide of at least one element selected from the group consisting of magnesium, calcium, barium, scandium, titanium, vanadium, chromium, molybdenum, tungsten, iron, cobalt, and nickel. Is desirable, and is more desirably an oxide of at least one element selected from the group consisting of magnesium, iron, tungsten, vanadium, cobalt, and nickel.
  • the catalyst used in the present invention contains a fourth component other than at least one of copper and copper oxide (a), zinc oxide (b) and oxide (c) to the extent that this reaction is not inhibited. May be.
  • This component includes alkali metals such as sodium, potassium and cesium, elements other than those of Group 2 to Group 6, Group 8 to Group 10 of the periodic table selected in oxide (c), and These oxides are mentioned. Inclusion of the fourth component in the catalyst is expected to improve the sustainability of the catalyst effect and improve the stability of the catalyst.
  • a preferred embodiment of the catalyst used in the present invention is also a catalyst obtained by mixing a substance or catalyst containing an oxide (c) of at least one element selected from the group consisting of elements of Group 10 to Group 10 It is one of.
  • the catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b) used in the present invention was produced by the above known methods (coprecipitation method, impregnation method, kneading method, etc.). Catalysts and commercially available products (for example, F10G manufactured by JGC Chemical Co., Ltd., Shift Max 210 manufactured by Zude Chemie Catalysts Co., Ltd., etc.) can be used.
  • the substance or catalyst containing the oxide (c) for example, the following can be used.
  • Periodic Table Group 2 to Group 6, Group 8 to Group 10 Oxides (2) Mixtures of Multiple Oxides of These Elements (for example, N made by Sud Chemie Catalyst Co., Ltd.) -150, N850, etc.) (3) at least one of copper and copper oxide and an oxide (c) of at least one element selected from the group consisting of elements of Groups 2 to 6 and Groups 8 to 10 of the periodic table Catalyst, that is, a catalyst produced by the above-mentioned known methods (coprecipitation method, impregnation method, kneading method, etc.), a commercially available catalyst (for example, N-140, N-840 manufactured by Zude Chemie Catalysts Co., Ltd.) ).
  • the weight ratio of at least one of copper and copper oxide (a) to zinc oxide (b) contained in the catalyst used in the present invention (at least one of copper and copper oxide (a): zinc oxide (b))
  • it is preferably in the range of 6: 1 to 6:35, more preferably in the range of 5: 1 to 5:15, and in the range of 3: 1 to 3: 7. More desirably, it is particularly desirable to be in the range of 2: 1 to 2: 4.
  • the weight of at least one of copper and copper oxide (a) refers to the weight of at least one of copper and copper oxide when the substance or catalyst containing oxide (c) contains at least one of copper and copper oxide.
  • the weight ratio of at least one of copper and copper oxide (a) and oxide (c) contained in the catalyst used in the present invention Is not particularly limited, but is preferably in the range of 100: 1 to 1.5: 1, more preferably in the range of 100: 1 to 4: 1, and in the range of 100: 1 to 5: 1. More desirably.
  • the catalytic reaction proceeds in a high yield.
  • the weight of at least one of copper and copper oxide (a) refers to the weight of at least one of copper and copper oxide when the substance or catalyst containing oxide (c) contains at least one of copper and copper oxide. The sum of the weight of copper and copper oxide in the catalyst containing (a) and zinc oxide (b) and the weight of copper and copper oxide in the substance or catalyst containing oxide (c).
  • the oxide (c) described above is an oxide of at least one element selected from the group consisting of magnesium, calcium, barium, scandium, titanium, vanadium, chromium, molybdenum, tungsten, iron, cobalt, and nickel. Is desirable, and is more desirably an oxide of at least one element selected from the group consisting of magnesium, iron, tungsten, vanadium, cobalt, and nickel.
  • the catalyst used in the present invention contains a fourth component other than at least one of copper and copper oxide (a), zinc oxide (b) and oxide (c) to the extent that this reaction is not inhibited. May be.
  • This component includes alkali metals such as sodium, potassium and cesium, elements other than those of Group 2 to Group 6, Group 8 to Group 10 of the periodic table selected in oxide (c), and These oxides are mentioned. Inclusion of this component in the catalyst is expected to improve the sustainability of the catalyst effect and the stability of the catalyst.
  • reaction In the production method of the present invention, catalytic hydrogenation is performed on glycerin in the presence of a catalyst containing at least one of copper and copper oxide (a), zinc oxide (b), and oxide (c).
  • the catalyst used in the present invention may be used as it is, but known methods (for example, Catalyst Course 5, Catalyst Design, Chapter 4 for improving handling, improving catalyst stability, improving reaction efficiency, etc.) 116 pages, edited by the Catalysis Society of Japan, Kodansha, published in 1985).
  • the shape of the catalyst and the particle size and shape of the catalyst can be arbitrarily selected depending on the reaction mode and the shape of the reactor.
  • binder can also be used during molding.
  • the binder is used for the purpose of binding solids and enhancing the mechanical strength of the catalyst.
  • Any inorganic or organic substance can be used as the binder as long as it does not inhibit the reaction according to the present invention.
  • Specific examples of the binder include clay, kaolin, talc, bentonite, alumina sol, zirconia sol, silicate, silicon carbide, and organic polymer.
  • propylene glycol is obtained by catalytic hydrogenation of glycerin.
  • the glycerin can be used alone, in an aqueous solution or in a solution with an organic solvent.
  • the amount of water or organic solvent used is not particularly limited, but is usually 5 to 90% by weight with respect to 100% by weight of glycerin. From the viewpoint of volumetric efficiency and reaction rate, it is preferably 10 to 70% by weight.
  • a reaction apparatus for carrying out the production method of the present invention a batch type reaction apparatus (for example, an autoclave), a fixed bed continuous reaction apparatus (equipped with a fixed bed catalyst reactor), a fluidized bed continuous reaction apparatus (fluidized bed catalyst reactor). And a moving bed continuous reaction apparatus (having a moving bed catalytic reactor).
  • a fixed bed continuous reaction apparatus a fluidized bed continuous reaction apparatus or a moving bed continuous reaction apparatus, more preferably a fixed bed continuous reaction apparatus with simple equipment, and a trickle bed. It is further desirable to use a fixed bed continuous reactor.
  • the reactor provided in the continuous reaction apparatus is preliminarily filled with a solid catalyst capable of hydrogenating glycerin, and glycerin and hydrogen are continuously supplied thereto.
  • a solid catalyst capable of hydrogenating glycerin
  • glycerin and hydrogen are continuously supplied thereto.
  • a solid catalyst capable of hydrogenating glycerin and a reaction liquid containing glycerin are charged into the reaction apparatus, and hydrogen is further supplied.
  • an inert gas such as nitrogen may be further supplied to the reactor for adjusting the reaction conditions.
  • glycerin and hydrogen may contain other components to the extent that the effects of the present invention are not impaired.
  • glycerin is a compound derived from a raw material, and causes impurities such as catalyst degradation (for example, long-chain fatty acids, metal salts, sulfur-containing compounds such as sulfuric acid, thiol and thioether, and nitrogen-containing compounds such as amines) May be included.
  • catalyst degradation for example, long-chain fatty acids, metal salts, sulfur-containing compounds such as sulfuric acid, thiol and thioether, and nitrogen-containing compounds such as amines
  • known separation methods such as distillation, adsorption, ion exchange, crystallization, extraction and the like can be used.
  • the amount of the catalyst used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight with respect to 100% by weight of glycerin.
  • the method for charging the catalyst into the reactor is not particularly limited.
  • a catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b) prepared by a known method, and separately prepared by a known method
  • the substance containing the oxide (c) or the catalyst may be mixed before being charged into the reactor.
  • the fixed bed Each may be alternately charged into the reactor so that each catalyst is layered.
  • the catalyst used in the present invention When used for the reaction, it may be used for the reaction as it is, or activated by reduction with hydrogen in advance before being used in the reaction, and the metal compound contained in the catalyst is completely or partially obtained. Alternatively, it may be used after being reduced to a metal. In general, this reduction is carried out by bringing the catalyst into contact with hydrogen gas at 100 to 400 ° C.
  • the reduction operation is performed only on the catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b).
  • the catalyst containing the oxide (c) or the catalyst may be mixed with the passed catalyst, or the catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b) and the oxide (c) are included.
  • reduction operations were performed on a catalyst containing at least one of copper and copper oxide (a) and zinc oxide (b), and a catalyst containing at least one of copper and copper oxide and oxide (c), respectively. You may mix two types of catalysts which passed through these reduction
  • reaction is carried out in the liquid phase under continuous conditions or batchwise, at a reaction temperature in the range of 100 to 350 ° C., preferably in the range of 150 to 300 ° C., more preferably in the range of 150 to 250 ° C. it can.
  • the reaction is generally carried out under a hydrogen pressure of 1 to 30 MPa, preferably 2 to 20 MPa, more preferably 3 to 15 MPa under continuous conditions or in a batch system. At a pressure in such a range, the reaction rate is sufficiently high, and propylene glycol can be obtained efficiently.
  • the reaction time is usually 1 to 20 hours in the case of a batch reaction.
  • the feed rate of glycerol per unit weight of the solid catalyst in the reaction is desirably at 0.05Hr -1 or more 100 hr -1 or less, 0.1 hr -1 or more 50 hr - More preferably, it is 1 or less.
  • the average moving linear velocity in the reactor of the reaction solution supplied to the reactor in the continuous reaction is not particularly limited.
  • the same LHSV can vary depending on the reactor shape.
  • it is preferably 2 cm / min to 100 cm / min, and more preferably 5 cm / min to 100 cm / min.
  • the reactor used when a continuous reaction apparatus is used, the reactor used may be a single reactor or a plurality of reactors.
  • the reactors when a plurality of reactors are used, the reactors may be installed in series or in parallel. By installing reactors in series, reaction conditions can be controlled more precisely. Further, by installing the reactors in parallel, for example, the catalytic hydrogenation reaction of glycerol is performed in one reactor, the regeneration operation of the deteriorated catalyst is performed in the other reactor, etc., and these operations are performed while switching. This makes it possible to maintain the production amount of propylene glycol constant.
  • propylene glycol can be produced from glycerin in high yield without vaporizing glycerin.
  • glycerin is vaporized and catalytic hydrogenation is performed in the gas phase. Also good.
  • the conversion rate of glycerin and the yield of propylene glycol were calculated by gas chromatography (gas chromatograph apparatus: GC-14A manufactured by Shimadzu Corporation, column: HP-INNOWAX manufactured by Agilent, detector: FID).
  • the selectivity for propylene glycol was calculated from the conversion and yield.
  • Example 2 to 9 and Comparative Examples 1 and 2 In Examples 2 to 9 and Comparative Examples 1 and 2, the reaction was carried out in the same manner as in Example 1 except that the catalyst used was changed as shown in Table 1. The results are shown in Table 1 together with Example 1. Each catalyst was produced by the coprecipitation method as in Example 1.
  • Example 10 A catalyst having the same composition as the catalyst used in Example 1 was compressed using a tablet press under a reduced pressure of 0.5 mmHg (66.7 Pa) at a pressure of 5 MPa for 5 minutes, and then the catalyst was pulverized and sieved. Went. When the portions that did not pass through the 0.25 mm sieve but passed through the 0.5 mm sieve were collected, the bulk density was 0.85 g / cm 3 . This was used in the reaction as a shaped catalyst.
  • a fixed bed continuous reactor made of Hastelloy C276 having a reaction tube with an inner diameter of 9 mm was filled with 5.0 g (5.9 ml) of the molded catalyst obtained above, and the catalyst packed portion was heated to 195 ° C.
  • the pressure in the reaction tube was kept at 3 MPa.
  • Example 3 instead of the molded catalyst used in Example 10, 5.0 g (5.9 ml) of a molded catalyst obtained by molding a catalyst having the same composition as the catalyst used in Comparative Example 2 in the same manner as in Example 10. The reaction was conducted in the same manner as in Example 10 except that was used. After 5 hours, the liquid flowing out from the reaction tube was collected over 1 hour, and the collected liquid (reactant) was analyzed. As a result, the conversion of glycerin was 76.7% and the yield of propylene glycol was The selectivity for propylene glycol was 93.0%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L’invention concerne un procédé de fabrication de propylène glycol avec un rendement élevé, en utilisant la glycérine en tant que matière première, ledit procédé ne nécessitant pas d’étape d’évaporation de la glycérine. Le procédé de fabrication de propylène glycol est caractérisé en ce qu’il comprend une étape d’obtention de propylène glycol par hydrogénation catalytique de glycérine en présence d’un catalyseur qui contient (a) du cuivre et/ou de l’oxyde de cuivre, (b) de l’oxyde de zinc et (c) un oxyde d’au moins un élément choisi dans le groupe constitué des éléments des groupes 2 à 6 et des éléments des groupes 8 à 10 du tableau périodique.
PCT/JP2009/060444 2008-06-13 2009-06-08 Procédé de fabrication de propylène glycol WO2009151021A1 (fr)

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Application Number Priority Date Filing Date Title
JP2010516842A JP5486491B2 (ja) 2008-06-13 2009-06-08 プロピレングリコールの製造方法

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Application Number Priority Date Filing Date Title
JP2008155667 2008-06-13
JP2008-155667 2008-06-13

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WO2009151021A1 true WO2009151021A1 (fr) 2009-12-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120008989A (ko) * 2010-07-21 2012-02-01 에스케이이노베이션 주식회사 바이오 글리세린으로 1,2-프로필렌 글리콜을 제조하는 방법
JP2013521221A (ja) * 2010-03-03 2013-06-10 ズードケミー インコーポレイテッド 活性酸化ジルコニウム支持触媒を用いた、糖、糖アルコール、又はグリセロールの、価値のある化学物質への変換
WO2021036374A1 (fr) * 2019-08-26 2021-03-04 同济大学 Catalyseur composite et son application dans un procédé de préparation de propylène glycol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007053705A2 (fr) * 2005-10-31 2007-05-10 University Of Missouri Board Of Curators Procede de fabrication d'alcools inferieurs a partir de glycerol
WO2007099161A1 (fr) * 2006-03-03 2007-09-07 Basf Se Procédé de synthèse du 1,2-propanediol
CN101214440A (zh) * 2008-01-14 2008-07-09 南京工业大学 一种用于甘油氢解制1,2-丙二醇的催化剂及其制备方法
JP2009173550A (ja) * 2008-01-21 2009-08-06 Kao Corp 多価アルコールの水素化分解物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007053705A2 (fr) * 2005-10-31 2007-05-10 University Of Missouri Board Of Curators Procede de fabrication d'alcools inferieurs a partir de glycerol
WO2007099161A1 (fr) * 2006-03-03 2007-09-07 Basf Se Procédé de synthèse du 1,2-propanediol
CN101214440A (zh) * 2008-01-14 2008-07-09 南京工业大学 一种用于甘油氢解制1,2-丙二醇的催化剂及其制备方法
JP2009173550A (ja) * 2008-01-21 2009-08-06 Kao Corp 多価アルコールの水素化分解物の製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013521221A (ja) * 2010-03-03 2013-06-10 ズードケミー インコーポレイテッド 活性酸化ジルコニウム支持触媒を用いた、糖、糖アルコール、又はグリセロールの、価値のある化学物質への変換
KR20120008989A (ko) * 2010-07-21 2012-02-01 에스케이이노베이션 주식회사 바이오 글리세린으로 1,2-프로필렌 글리콜을 제조하는 방법
KR101711610B1 (ko) * 2010-07-21 2017-03-02 에스케이이노베이션 주식회사 바이오 글리세린으로 1,2-프로필렌 글리콜을 제조하는 방법
WO2021036374A1 (fr) * 2019-08-26 2021-03-04 同济大学 Catalyseur composite et son application dans un procédé de préparation de propylène glycol

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