JPS6234029B2 - - Google Patents
Info
- Publication number
- JPS6234029B2 JPS6234029B2 JP54136738A JP13673879A JPS6234029B2 JP S6234029 B2 JPS6234029 B2 JP S6234029B2 JP 54136738 A JP54136738 A JP 54136738A JP 13673879 A JP13673879 A JP 13673879A JP S6234029 B2 JPS6234029 B2 JP S6234029B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- nitric acid
- acetate
- iodide
- allyl acetate
- 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.)
- Expired
Links
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 10
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- -1 iodide ions Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000004348 Glyceryl diacetate Substances 0.000 description 3
- XYAUIVRRMJYYHR-UHFFFAOYSA-N acetic acid;propane-1,2,3-triol Chemical compound CC(O)=O.OCC(O)CO XYAUIVRRMJYYHR-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 235000019443 glyceryl diacetate Nutrition 0.000 description 3
- 239000001087 glyceryl triacetate Substances 0.000 description 3
- 235000013773 glyceryl triacetate Nutrition 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 229960002622 triacetin Drugs 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- SRPSOCQMBCNWFR-UHFFFAOYSA-N iodous acid Chemical compound OI=O SRPSOCQMBCNWFR-UHFFFAOYSA-N 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、沃素イオンおよび硝酸の存在下に酢
酸アリルを液相で酢酸および分子状酸素と反応さ
せてグリセリン酢酸エステルを製造する方法に関
するものであり、得られるグリセリン酢酸エステ
ルを加水分解することにより容易にグリセリンを
製造することができる。
従来、グリセリンはその大半が天然油脂のケン
化または加水分解により製造され、また合成グリ
セリンの大部分はプロピレンからエピクロルヒド
リンを経由するいわゆるエピクロルヒドリン法に
より製造されている。
近年、グリセリンの合成を目的として、酢酸ア
リルを酢酸および分子状酸素と反応させてグリセ
リン酢酸エステルを製造する方法が数多く報告さ
れている（特公昭46−43205、特開昭51−11704、
同52−89613、同53−147021等）。しかしながらこ
れらの方法には各々欠点があり、工業的実施を妨
げる要因となつている。たとえば、パラジウムま
たはパラジウム化合物および含窒素酸素化合物を
触媒とする方法には低沸点副生物の生成量が大き
く選択性が低いという欠点があり、沃素、カルボ
ン酸陰イオンおよびある種の陽イオンよりなる触
媒を使用する方法あるいは沃素および錫またはセ
リウム化合物よりなる触媒を使用する方法には触
媒活性が低いという欠点がある。
本発明者は上記実情に鑑み、酢酸アリルを酢酸
および分子状酸素と反応させてグリセリン酢酸エ
ステルを得る方法において、活性および選択性の
すぐれた触媒を開発すべく種々検討を行なつた結
果、沃素イオンおよび硝酸よりなる触媒系が活
性、選択性ともに良好であることを見い出し、本
発明に到達したものである。
以下に本発明を詳細に説明する。
本発明方法は、酢酸アリルに対して過剰量の酢
酸を使用し、液相で行なわれる。通常は過剰量の
酢酸が反応溶媒を兼ねるが、所望により適宜反応
に不活性な有機溶媒を使用することができる。こ
の場合、酢酸アリルの液相中の濃度が低いと反応
速度が小さくなるので、0.5mol／以上であるこ
とが望ましい。
沃素イオンは、反応系内において一義的に存在
するのではなく、硝酸あるいは分子状酸素により
更に硝酸が高酸化状態に酸化された形態の窒素酸
化物が沃素イオンを酸化してI2、I2O、IO-、IO2 -
等のより高次の酸化状態にある沃素化合物種が形
成され、これらが酢酸アリルに作用してアセトキ
シル化が進行し、高酸化状態にある沃素化合物種
は還元されて低次の酸化状態にある沃素イオンま
たは沃素化合物になると考えられる。従つて、本
発明方法においては、上記反応機構に組みこまれ
て沃素イオンを生成し得る沃素化合物を反応系に
供給すればよく、たとえば沃素単体、沃化水素、
沃化リチウム、沃化ナトリウム、沃化カリウム、
沃化マグネシウム、沃化銅等の金属沃化物、次亜
沃素酸またはその塩、沃素酸またはその塩、過沃
素酸またはその塩などが挙げられる。沃素イオン
は反応系内において、１グラムイオン／以下、
好ましくは0.05〜0.2グラムイオン／となるよ
うに用いられる。
硝酸は、反応系内において１モル／以下、好
ましくは0.05〜0.2モル／となるように使用さ
れる。
分子状酸素は純粋な状態で使用することもでき
るが、窒素、アルゴン等の反応に不活性なガスに
より希釈して使用することもできる。また、本発
明方法においては酸素分圧が高いほうが効率よく
反応を進めることができるので、常圧で反応を行
なうこともできるが、むしろ加圧して酸素分圧を
高めて反応を行なうことが好ましい。好適な酸素
分圧は0.1〜100Kg／cm2である。反応温度は通常、
常温〜200℃、好ましくは90〜140℃で行なわれ
る。
本発明方法により得られるグリセリン酢酸エス
テルは、そのままで溶剤として使用することも可
能であり、また加水分解することにより容易にグ
リセリンを得ることができる。
次に本発明を実施例により更に具体的に説明す
る。
実施例 １
チタンで内張りした内容積200c.c.のオートクレ
ーブに酢酸100ml、酢酸アリル10ml（約93ｍ
mol）、沃化カリウム3.32ｇおよび濃硝酸２ml（硝
酸として約27ｍmolを仕込み、酸素６容量％を含
有する窒素を50Kg／cm2Ｇまで圧入して130℃で２
時間反応させた。オートクレーブを室温まで冷却
したのち放圧し、反応生成液をガスクロマトグラ
フイーにより分析したところ、トリアセチン3.09
ｍmol、モノアセチンおよびジアセチン12.55ｍ
molが生成していた。上記反応生成液の入つたオ
ートクレーブを再び酸素含有率６容量％の窒素で
50Kg／cm2Ｇまで加圧し、130℃で８時間反応を行
なつたのち放冷、放圧し、得られた反応生成液を
ガスクロマトグラフイーで分析した。その結果、
トリアセチンの生成量は16.1ｍmolでありモノア
セチンおよびジアセチンの生成量は12.0ｍmolで
あつた。
実施例 ２
還流冷却器を備えた内容積100c.c.のガス吹込口
付ガラス製反応器に酢酸50ml、酢酸アリル５ml
（約46ｍmol）、沃化カリウム1.66ｇおよび濃硝酸
１ml（硝酸として約13ｍmol）を仕込み、130℃
の油浴中に反応器を浸して、酸素ガスを毎分40N
mlの流速で流通させながら90分間反応を行なつ
た。反応終了後、反応生成液をガスクロマトグラ
フイーで分析した結果、トリアセチン0.24ｍ
mol、モノアセチンおよびジアセチン4.52ｍmol
が生成していた。
実施例３〜５、比較例１〜６
沃化カリウムおよび濃硝酸のかわりに表−１に
記載した触媒を使用し、表−１に記載した反応温
度および反応時間で実施例２と同様に反応を行な
つた。結果は表−１に示す。
The present invention relates to a method for producing glycerol acetate by reacting allyl acetate with acetic acid and molecular oxygen in a liquid phase in the presence of iodide ions and nitric acid, and by hydrolyzing the resulting glycerol acetate. Glycerin can be easily produced. Conventionally, most glycerin has been produced by saponification or hydrolysis of natural oils and fats, and most synthetic glycerin has been produced by the so-called epichlorohydrin method in which propylene is converted to epichlorohydrin. In recent years, for the purpose of synthesizing glycerin, many methods have been reported for producing glycerin acetate by reacting allyl acetate with acetic acid and molecular oxygen (Japanese Patent Publication No. 46-43205, Japanese Patent Publication No. 51-11704,
52-89613, 53-147021, etc.) However, each of these methods has drawbacks, which hinder their industrial implementation. For example, methods using palladium or palladium compounds and nitrogen-containing oxygen compounds as catalysts have the disadvantage of producing large amounts of low-boiling by-products and low selectivity. Methods using catalysts or catalysts consisting of iodine and tin or cerium compounds have the disadvantage of low catalytic activity. In view of the above circumstances, the present inventor conducted various studies to develop a catalyst with excellent activity and selectivity in a method for obtaining glycerin acetate by reacting allyl acetate with acetic acid and molecular oxygen. The present invention was achieved by discovering that a catalyst system consisting of ions and nitric acid has good activity and selectivity. The present invention will be explained in detail below. The process of the invention uses an excess of acetic acid relative to allyl acetate and is carried out in the liquid phase. Usually, an excess amount of acetic acid also serves as a reaction solvent, but an inert organic solvent can be used in the reaction if desired. In this case, if the concentration of allyl acetate in the liquid phase is low, the reaction rate will be low, so the concentration is preferably 0.5 mol/or more. Iodine ions do not exist uniquely in the reaction system, but nitrogen oxides, which are nitric acid further oxidized to a highly oxidized state by nitric acid or molecular oxygen, oxidize iodide ions to form I 2 , I 2 O, IO - , IO 2 -
Iodine compound species in a higher oxidation state are formed, and these act on allyl acetate to progress acetoxylation, and the iodine compound species in a higher oxidation state are reduced to a lower oxidation state. It is thought that it becomes an iodine ion or an iodine compound. Therefore, in the method of the present invention, it is sufficient to supply to the reaction system an iodine compound that can be incorporated into the above reaction mechanism to generate iodide ions, such as elemental iodine, hydrogen iodide,
Lithium iodide, sodium iodide, potassium iodide,
Examples include metal iodides such as magnesium iodide and copper iodide, hypoiodic acid or its salts, iodic acid or its salts, and periodic acid or its salts. Iodine ions are contained in the reaction system at a rate of 1 gram ion/or less,
It is preferably used in an amount of 0.05 to 0.2 gram ion/. Nitric acid is used in the reaction system in an amount of 1 mol or less, preferably 0.05 to 0.2 mol/. Molecular oxygen can be used in a pure state, but it can also be used diluted with a gas inert to the reaction, such as nitrogen or argon. In addition, in the method of the present invention, the reaction can proceed more efficiently when the oxygen partial pressure is high, so the reaction can be carried out at normal pressure, but it is preferable to carry out the reaction by increasing the oxygen partial pressure. . A suitable oxygen partial pressure is 0.1-100 Kg/ cm2 . The reaction temperature is usually
It is carried out at room temperature to 200°C, preferably 90 to 140°C. The glycerin acetate obtained by the method of the present invention can be used as it is as a solvent, and glycerin can be easily obtained by hydrolysis. Next, the present invention will be explained in more detail with reference to Examples. Example 1 100 ml of acetic acid and 10 ml of allyl acetate (approximately 93 m
mol), 3.32 g of potassium iodide and 2 ml of concentrated nitric acid (approximately 27 mmol of nitric acid), nitrogen containing 6% oxygen by volume was introduced under pressure to 50 kg/cm 2 G, and the mixture was heated at 130°C
Allowed time to react. After cooling the autoclave to room temperature, the pressure was released and the reaction product liquid was analyzed by gas chromatography, and it was found that triacetin was 3.09.
mmol, monoacetin and diacetin 12.55m
mol was generated. The autoclave containing the above reaction product liquid was heated again with nitrogen containing 6% oxygen by volume.
The pressure was increased to 50 kg/cm 2 G, and the reaction was carried out at 130° C. for 8 hours, then allowed to cool, the pressure was released, and the resulting reaction product liquid was analyzed by gas chromatography. the result,
The amount of triacetin produced was 16.1 mmol, and the amount of monoacetin and diacetin produced was 12.0 mmol. Example 2 50 ml of acetic acid and 5 ml of allyl acetate were placed in a glass reactor equipped with a reflux condenser and a gas inlet with an internal volume of 100 c.c.
(approximately 46 mmol), 1.66 g of potassium iodide and 1 ml of concentrated nitric acid (approximately 13 mmol as nitric acid), and heated to 130°C.
Immerse the reactor in an oil bath with oxygen gas at 40N per minute.
The reaction was carried out for 90 minutes while flowing at a flow rate of 1 ml. After the reaction was completed, the reaction product solution was analyzed by gas chromatography, and it was found that 0.24 m of triacetin was detected.
mol, monoacetin and diacetin 4.52 mmol
was being generated. Examples 3 to 5, Comparative Examples 1 to 6 Reaction was carried out in the same manner as in Example 2 using the catalysts listed in Table 1 instead of potassium iodide and concentrated nitric acid, and at the reaction temperature and reaction time listed in Table 1. I did this. The results are shown in Table-1.
【表】【table】
Claims (1)
を酢酸アリルに対して過剰量の酢酸および分子状
酸素と反応させることを特徴とするグリセリン酢
酸エステルの製造方法。1. A method for producing glycerol acetate, which comprises reacting allyl acetate with an excess amount of acetic acid and molecular oxygen relative to allyl acetate in the presence of iodide ions and nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673879A JPS5661325A (en) | 1979-10-23 | 1979-10-23 | Production of glycerol acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13673879A JPS5661325A (en) | 1979-10-23 | 1979-10-23 | Production of glycerol acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5661325A JPS5661325A (en) | 1981-05-26 |
| JPS6234029B2 true JPS6234029B2 (en) | 1987-07-24 |
Family
ID=15182344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13673879A Granted JPS5661325A (en) | 1979-10-23 | 1979-10-23 | Production of glycerol acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5661325A (en) |
-
1979
- 1979-10-23 JP JP13673879A patent/JPS5661325A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5661325A (en) | 1981-05-26 |
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