JP4852266B2 - Production method of monohydroxyacetone - Google Patents
Production method of monohydroxyacetone Download PDFInfo
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- JP4852266B2 JP4852266B2 JP2005190850A JP2005190850A JP4852266B2 JP 4852266 B2 JP4852266 B2 JP 4852266B2 JP 2005190850 A JP2005190850 A JP 2005190850A JP 2005190850 A JP2005190850 A JP 2005190850A JP 4852266 B2 JP4852266 B2 JP 4852266B2
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- Prior art keywords
- catalyst
- monohydroxyacetone
- copper
- silica
- glycerin
- Prior art date
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- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- -1 nitrogen Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、医農薬中間体原料として有用なモノヒドロキシアセトンの製造法に関する。 The present invention relates to a method for producing monohydroxyacetone useful as a raw material for intermediates for pharmaceuticals and agricultural chemicals.
触媒の存在下で、グリセリンを気相接触反応せしめてモノヒドロキシアセトンを製造する方法は公知であり、有毒なクロムを構成元素とする銅クロマイトを触媒として使用する方法が報告されており（例えば、特許文献１参照）、モノヒドロキシアセトンが収率５０％〜８０％程度で得られている。
本発明は、グリセリンを気相で反応させてモノヒドロキシアセトンを製造するにあたり、有毒なクロムを用いなくても、従来製法と同等の収率でモノヒドロキシアセトンを製造する方法を提供することを課題とする。 It is an object of the present invention to provide a method for producing monohydroxyacetone in a yield equivalent to that of a conventional production method without using toxic chromium when producing monohydroxyacetone by reacting glycerin in a gas phase. And
本発明は、触媒の存在下で、グリセリンを気相接触反応せしめてモノヒドロキシアセトンを製造する方法において、触媒としてシリカに担持した銅及び／又は酸化銅を用いることを特徴とするモノヒドロキシアセトンの製造法に関する。 The present invention relates to a method for producing monohydroxyacetone by reacting glycerin in a gas phase in the presence of a catalyst, and using copper and / or copper oxide supported on silica as a catalyst. It relates to the manufacturing method.
本発明によれば、有毒なクロムを用いなくても、触媒としてシリカに担持した銅及び／又は酸化銅を用いることで、従来技術と同等の収率でモノヒドロキシアセトンを製造することができることから、本発明の製造方法は工業的利用価値大なるものである。 According to the present invention, monohydroxyacetone can be produced in a yield equivalent to that of the prior art by using copper and / or copper oxide supported on silica as a catalyst without using toxic chromium. The production method of the present invention has a great industrial utility value.
以下に本発明を詳細に説明する。
本発明に使用する触媒は活性成分を銅及び／又は酸化銅とし、その担体をシリカとするものである。本触媒は、銅の硝酸塩、硫酸塩、炭酸塩、酢酸塩、塩化物、酸化物及び／又は水酸化物を、銅及び／又は酸化銅の原料化合物として用いることができ、従来法の調製方法、例えば、共沈法、含浸法、混練法によって調製される。含浸法により調製された銅及び／又は酸化銅をシリカに担持させた触媒が好ましい。銅及び／又は酸化銅がシリカに担持された触媒において、銅及び／又は酸化銅の担持量は特に制限はないが、シリカに対して通常０．１〜２５重量％ 、好ましくは３〜７重量％ である。また、助触媒として、アルカリ金属、アルカリ金属を含有してもよく、シリカに対して、通常０．００１〜１重量％ 、好ましくは０．０１〜０．５％の使用量である。また、触媒の形状は粉末状、円柱状、球状、粒状など、所望の形状に成形して反応に使用される。触媒の成形方法としては、あらかじめシリカを上記所望の形状に成形し、当該成形されたシリカを用いて含浸法により触媒を調製して成形触媒を得る方法が挙げられる。
The present invention is described in detail below.
The catalyst used in the present invention has copper and / or copper oxide as the active ingredient and silica as the carrier. In this catalyst, copper nitrate, sulfate, carbonate, acetate, chloride, oxide and / or hydroxide can be used as a raw material compound of copper and / or copper oxide. For example, it is prepared by a coprecipitation method, an impregnation method, or a kneading method. A catalyst in which copper and / or copper oxide prepared by an impregnation method is supported on silica is preferable. In the catalyst in which copper and / or copper oxide is supported on silica, the supported amount of copper and / or copper oxide is not particularly limited, but is usually 0.1 to 25% by weight, preferably 3 to 7% by weight with respect to silica. %. Moreover, as a co-catalyst, you may contain an alkali metal and an alkali metal, and they are 0.001-1 weight% normally with respect to a silica, Preferably it is the usage-amount of 0.01-0.5%. The catalyst is shaped into a desired shape such as powder, column, sphere, or granule and used for the reaction. Examples of the method for forming the catalyst include a method in which silica is formed into the desired shape in advance and a catalyst is prepared by an impregnation method using the formed silica to obtain a formed catalyst.
本発明の製造法は、固定床触媒反応器、流動床触媒反応器又は移動床触媒反応器で行うことができる。以下、固定床触媒反応器を用いて行う場合を例として本発明を説明する。本発明の触媒を反応管に充填し、当該反応管にグリセリンを導入して気相接触反応させる。グリセリンは、窒素等の不活性ガス及び／又は水素と共に供給しても、特に支障なく反応を行うことができ、特に水素と共に供給することが好ましい。窒素の使用量としては、グリセリン１モルに対して、通常０．５〜１０モル、好ましくは０．８〜５モルである。水素の使用量としては、グリセリン１モルに対して、通常０．５〜１０モル、好ましくは０．８〜５モルである。 The production method of the present invention can be carried out in a fixed bed catalyst reactor, a fluidized bed catalyst reactor or a moving bed catalyst reactor. Hereinafter, the present invention will be described by taking as an example the case of using a fixed bed catalytic reactor. The catalyst of the present invention is filled in a reaction tube, and glycerin is introduced into the reaction tube to cause a gas phase contact reaction. Even if glycerin is supplied together with an inert gas such as nitrogen and / or hydrogen, the reaction can be carried out without any problem, and it is particularly preferable to supply it together with hydrogen. As usage-amount of nitrogen, it is 0.5-10 mol normally with respect to 1 mol of glycerol, Preferably it is 0.8-5 mol. As usage-amount of hydrogen, it is 0.5-10 mol normally with respect to 1 mol of glycerol, Preferably it is 0.8-5 mol.
グリセリンは単独、水溶液又は有機溶剤との溶液で用いることができる。水又は有機溶剤の使用量は特に制限はないが、グリセリンに対して通常１０〜９０重量％である。 Glycerin can be used alone or in a solution with an aqueous solution or an organic solvent. The amount of water or organic solvent used is not particularly limited, but is usually 10 to 90% by weight with respect to glycerin.
グリセリンと所望により窒素等の不活性ガス及び／又は水素との混合ガスを、空間速度（ＳＶ）１００〜１００００ｈｒ−１、好ましくは３００〜３０００ｈｒ−１で触媒上に通じる。反応温度は通常１５０〜７００℃、好ましくは２００〜５００℃である。反応の圧力は、大気圧以下から数気圧まで用いることができるが、通常大気圧から２気圧付近が至便である。 A mixed gas of an inert gas and / or hydrogen, such as nitrogen, optionally glycerin, space velocity (SV) 100~10000hr -1, preferably leads to the catalyst in 300~3000hr -1. The reaction temperature is usually 150 to 700 ° C, preferably 200 to 500 ° C. The reaction pressure can be from below atmospheric pressure to several atmospheres, but it is usually convenient from atmospheric pressure to around 2 atmospheres.
上記のようにして反応を行った後、反応管から流出するモノヒドロキシアセトンを主成分とする反応ガスを、そのまま冷却及び／又は適当な溶媒に通じて、モノヒドロキシアセトンを含む凝縮物及び／又は溶液を得る。得られた凝縮物又は捕集液から、濃縮、抽出、蒸留等の単位操作を組み合わせてモノヒドロキシアセトンが単離できる。 After carrying out the reaction as described above, the reaction gas mainly composed of monohydroxyacetone flowing out from the reaction tube is directly cooled and / or passed through an appropriate solvent, and the condensate containing monohydroxyacetone and / or Obtain a solution. Monohydroxyacetone can be isolated from the resulting condensate or collected liquid by combining unit operations such as concentration, extraction and distillation.
本発明を更に詳細に説明するために、以下に具体的な実施例を上げるが、本発明はこれらに限定されるものではない。尚、モノヒドロキシアセトンの収率はガスクロマトグラフィーで算出した。 In order to describe the present invention in more detail, specific examples are given below, but the present invention is not limited thereto. The yield of monohydroxyacetone was calculated by gas chromatography.
参考例（触媒の調整）
シリカ粉末を押し出し成形（円柱形、径１．７ｍｍ、長さ５〜２０ｍｍ）したシリカ担体に対して、炭酸銅１．９ｇと２８％アンモニア水４４．０ｇとの溶液を上記シリカ担体１８．７ｇに含浸させた後、１２０℃で３時間乾燥し、次に空気気流中、６００℃で３時間焼成した。このようにして酸化銅をシリカに担持した触媒（触媒中の酸化銅の含有量：６重量％）を得た。
Reference example (catalyst adjustment)
A silica carrier obtained by extruding silica powder (cylindrical shape, diameter 1.7 mm, length 5 to 20 mm) to a solution of 1.9 g of copper carbonate and 44.0 g of 28% ammonia water was used to obtain 18.7 g of the silica carrier. And then dried at 120 ° C. for 3 hours, and then fired in an air stream at 600 ° C. for 3 hours. In this way, a catalyst in which copper oxide was supported on silica (copper oxide content in the catalyst: 6% by weight) was obtained.
実施例１
参考例で得られた触媒１０ｍｌを内径１５ｍｍの反応管に充填し、反応管の触媒充填部を２８５℃に昇温した。この触媒充填部に５０重量％グリセリン水溶液を０．１６６７ｇ／分で、及び水素を４０ｍｌ／分（グリセリン１モルに対して２モル）、窒素を４０ｍｌ／分（グリセリン１モルに対して２モル）で２０分間供給した。反応管から流出する反応生成ガスを水１００ｍｌ中に通じて、モノヒドロキシアセトンを含む捕集液を得た。捕集液中のモノヒドロキシアセトンの収率は８２％であった。
Example 1
10 ml of the catalyst obtained in the reference example was filled in a reaction tube having an inner diameter of 15 mm, and the temperature of the catalyst filling portion of the reaction tube was raised to 285 ° C. 50 wt% aqueous glycerin solution is 0.1667 g / min, and hydrogen is 40 ml / min (2 mol per mol of glycerin) and nitrogen is 40 ml / min (2 mol per mol of glycerin). For 20 minutes. The reaction product gas flowing out from the reaction tube was passed through 100 ml of water to obtain a collection liquid containing monohydroxyacetone. The yield of monohydroxyacetone in the collected liquid was 82%.
実施例２、比較例１〜２
実施例１の触媒、触媒充填部の温度、窒素及び水素の供給量を表１の通りに代えた以外は実施例１と同様にして行った。その結果を表１に示す。
Example 2, Comparative Examples 1-2
The same procedure as in Example 1 was carried out except that the catalyst of Example 1, the temperature of the catalyst filling portion, the supply amounts of nitrogen and hydrogen were changed as shown in Table 1. The results are shown in Table 1.
Claims (1)
A method for producing monohydroxyacetone, characterized in that copper and / or copper oxide supported on silica is used as a catalyst in a method for producing monohydroxyacetone by subjecting glycerol to gas phase contact reaction in the presence of a catalyst.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005190850A JP4852266B2 (en) | 2005-06-30 | 2005-06-30 | Production method of monohydroxyacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005190850A JP4852266B2 (en) | 2005-06-30 | 2005-06-30 | Production method of monohydroxyacetone |
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| Publication Number | Publication Date |
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| JP2007008850A JP2007008850A (en) | 2007-01-18 |
| JP4852266B2 true JP4852266B2 (en) | 2012-01-11 |
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| JP2005190850A Expired - Fee Related JP4852266B2 (en) | 2005-06-30 | 2005-06-30 | Production method of monohydroxyacetone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5177759B2 (en) * | 2008-03-26 | 2013-04-10 | 独立行政法人産業技術総合研究所 | Method for producing cyclic ether and hydroxyketone from polyhydric alcohol |
| CA2729659C (en) * | 2008-07-16 | 2015-11-24 | Michio Ikura | Conversion of glycerol to naphtha-range oxygenates |
| JP5197320B2 (en) * | 2008-11-20 | 2013-05-15 | 花王株式会社 | Method for producing α-aminoketone compound |
| JP6099133B2 (en) * | 2013-03-11 | 2017-03-22 | 株式会社ダイセル | Method for producing ketol compound |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4128692A1 (en) * | 1991-08-29 | 1993-03-04 | Henkel Kgaa | METHOD FOR PRODUCING ACETOL |
| DE4238492C2 (en) * | 1992-11-14 | 1995-06-14 | Degussa | Process for the preparation of 1,2- and 1,3-propanediol |
| JPH08176055A (en) * | 1994-12-27 | 1996-07-09 | Osaka Organic Chem Ind Ltd | Process for producing oxo compound |
| JP2838664B2 (en) * | 1995-01-13 | 1998-12-16 | 大阪有機化学工業株式会社 | Process for producing oxo compound |
| JP3668540B2 (en) * | 1995-09-22 | 2005-07-06 | ダイセル化学工業株式会社 | Method for producing ketone |
| JP2002173457A (en) * | 2000-12-05 | 2002-06-21 | Daicel Chem Ind Ltd | Method for producing ketone compound |
| JP4359447B2 (en) * | 2003-05-14 | 2009-11-04 | 広栄化学工業株式会社 | Method for producing monohydroxyacetone |
| JP2005211881A (en) * | 2004-02-02 | 2005-08-11 | Chisso Corp | Hydroxyketone production catalyst and process for producing hydroxyketone using the catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104722301A (en) * | 2015-03-04 | 2015-06-24 | 浙江工业大学之江学院 | Preparation method of catalyst for preparing dihydroxy acetone by selective oxidation of glycerinum and application method thereof |
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| JP2007008850A (en) | 2007-01-18 |
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