JPH02256651A - Production of carbonic ester - Google Patents
Production of carbonic esterInfo
- Publication number
- JPH02256651A JPH02256651A JP63317424A JP31742488A JPH02256651A JP H02256651 A JPH02256651 A JP H02256651A JP 63317424 A JP63317424 A JP 63317424A JP 31742488 A JP31742488 A JP 31742488A JP H02256651 A JPH02256651 A JP H02256651A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- oxygen
- alcohol
- carbon monoxide
- copper
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000002148 esters Chemical class 0.000 title abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- -1 carbonate ester Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010457 zeolite Substances 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、炭酸エステルの製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a carbonate ester.
炭酸エステルはポリマーや医農薬製造原料及び溶剤とし
て工業的に重要な化合物である。Carbonic esters are industrially important compounds as raw materials and solvents for producing polymers and pharmaceuticals and agricultural chemicals.
（従来の技術）
炭酸エステルの製造法としてはアルコールにホスゲンを
反応させる方法（特公昭５８−５０９７７、特公昭５９
−４９２など）があるが、この方法では毒性の高いホス
ゲンを使用することや、炭酸エステルに塩素イオンが混
入し、その除去が困難でホスゲンを使用しない炭酸エス
テルの製造法としては、塩化第二銅を含む触媒の存在下
に液相でアルコールと一酸化炭緊及び酸素を反応させる
方法（特公昭５Ｂ−３３８５７など）が知られている。(Prior art) As a method for producing carbonic ester, there is a method of reacting alcohol with phosgene (Japanese Patent Publication No. 58-50977, Japanese Patent Publication No. 59-59).
-492, etc.), but this method requires the use of highly toxic phosgene, and chloride ions are mixed into the carbonate ester, which is difficult to remove. A method is known in which alcohol is reacted with carbon monoxide and oxygen in a liquid phase in the presence of a catalyst containing copper (Japanese Patent Publication No. 5B-33857, etc.).
この方法では、ハライド化合物による反応装置材質の腐
食が問題上なり、グラスライニング以外に工業的な材質
は見当らない、また、触媒のスラリー化、触媒活性低下
などの問題点も抱えている。This method has the problem of corrosion of the reactor material due to halide compounds, and there are no industrial materials other than glass lining, and it also has problems such as slurrying of the catalyst and reduction in catalyst activity.
気相条件下の反応（ＵＳ４６２５０４４、Ｗ０８？−１
０７６０１）でもやはり触媒中のハロゲンによる反応装
置材質の腐食が間頭となり、ハステロイＣ等の高価な特
殊金属が必要である。また、炭酸エステルにハロゲンが
混入する可能性があるといった問題を掬えている。さら
に反応中にハロゲンが減少し、触媒活性の低下は免れな
い。Reaction under gas phase conditions (US4625044, W08?-1
07601), corrosion of the reactor material due to the halogen in the catalyst still occurs, and expensive special metals such as Hastelloy C are required. Additionally, there is a problem that halogen may be mixed into the carbonate ester. Furthermore, halogen is reduced during the reaction, inevitably resulting in a decrease in catalyst activity.
（発明が解決しようとしている謀Ｒ）
本発明は、アルコールと一酸化炭素及び酸素を反応させ
て炭酸エステルを製造する方法において、毒性の高いホ
スゲンや装置腐食の原因となるハロゲン及びハロゲン誘
導体が存在しない反応系における炭酸エステルの新しい
製造方法を提供することを目的とする。(Conspiracy to be Solved by the Invention) The present invention provides a method for producing carbonic ester by reacting alcohol with carbon monoxide and oxygen, in which highly toxic phosgene and halogens and halogen derivatives that cause equipment corrosion are present. The purpose of the present invention is to provide a new method for producing carbonate esters in a reaction system that does not require the following steps.
帽１を解決するための手段）
本発明者らは、鋭意研究を重ねた結果、意外にも、金属
鋼の存在下にアルコールと一酸化炭素及び酸素を反応さ
せることによって炭酸エステルが製造できることを見い
出し、本発明に到った。Means for Solving Problem 1) As a result of extensive research, the present inventors surprisingly discovered that carbonate esters can be produced by reacting alcohol with carbon monoxide and oxygen in the presence of metal steel. This heading led to the present invention.
ここで用いられる銅は、銅単体でも担体に担持したもの
でもよい、担体に担持する場合は、担持量は通常０．０
５〜５０ ｗ ｔ％の範囲で使用される。ａ４の使用量
は、例えば液相法では、０．１ｍｍｏ １／Ｊ（メタ
ノ−ｎ＞ 〜 ５ ０ ０ ０ｍｍ ｏ ＋ ／
−ＩＣメタノ−１）である。The copper used here may be copper alone or supported on a carrier. When supported on a carrier, the amount supported is usually 0.0
It is used in a range of 5 to 50 wt%. For example, in the liquid phase method, the amount of a4 used is 0.1 mmo 1/J (methanol-n> ~ 5000 mm o + /
-IC methanol-1).
固体担体としてはシリカ、アルミナ、シリカ−アルミナ
、ゼオライト、珪藻土、チタニア、ジルコニア、マグネ
シア、活性炭、グラファイト、樹脂などが用いられ触媒
担体としての機能を有するものであればよい。As the solid carrier, silica, alumina, silica-alumina, zeolite, diatomaceous earth, titania, zirconia, magnesia, activated carbon, graphite, resin, etc. can be used as long as it has a function as a catalyst carrier.
固体担持触媒は、銅金属塩を水または有機溶媒に溶解し
、この溶液に該固体担体を加え担持させた後、還元およ
び、加熱処理することにより得ることができる。The solid-supported catalyst can be obtained by dissolving a copper metal salt in water or an organic solvent, adding the solid support to this solution to support the solution, and then reducing and heat-treating the catalyst.
銅金属塩としては、ハロゲン化物、カルボン酸塩、Ｔｉ
Ｉ４酸塩、硫酸塩、酸化物、水酸化物などが用いられる
。Examples of copper metal salts include halides, carboxylates, Ti
I4 acid salts, sulfates, oxides, hydroxides, etc. are used.
本発明における反応基質であるアルコールとしては、メ
タノール、エタノール等の飽和脂肪族アルコール、アリ
ルアルコール等の不飽和脂肪族アルコール、シクロヘキ
サノールのような環式脂肪族アルコール、エチレングリ
コール、ベンジルアルコールなどのような炭素原子数１
〜１０のアルコールが用いられる。Alcohols that are reaction substrates in the present invention include saturated aliphatic alcohols such as methanol and ethanol, unsaturated aliphatic alcohols such as allyl alcohol, cycloaliphatic alcohols such as cyclohexanol, ethylene glycol, benzyl alcohol, etc. number of carbon atoms is 1
~10 alcohols are used.
一酸化炭素及び酸素は、純粋な状態で用いても、窒素、
ヘリウム、アルゴン、二酸化炭素等反応に不活性なガス
で希釈して用いても良いし、酸素源としては空気を用い
ても良い０反応は、常圧または加圧下で行なわれ、反応
系内の一酸化炭素分圧は０．１〜５６気圧、酸素分圧は
０．０５〜４気圧、アルコール分圧は０．１〜４０気圧
の範囲が好ましい。Even when carbon monoxide and oxygen are used in their pure state, nitrogen,
The reaction may be diluted with an inert gas such as helium, argon, or carbon dioxide, and air may be used as the oxygen source.The reaction is carried out under normal pressure or increased pressure, and the Preferably, the carbon monoxide partial pressure is in the range of 0.1 to 56 atm, the oxygen partial pressure is in the range of 0.05 to 4 atm, and the alcohol partial pressure is in the range of 0.1 to 40 atm.
本発明の反応は５０〜２００℃好ましくは９０〜１５０
℃の温度範囲で行なわれ、通常１００気圧以下の反応圧
で行なわれる。The reaction of the present invention is carried out at 50-200°C, preferably 90-150°C.
The reaction is carried out at a temperature range of 100°C and usually at a reaction pressure of 100 atmospheres or less.
（触媒の調製方法）
塩化第二銅二水和物２．５ｇｔｔｌｉ水２２ｍ１に溶か
し、これに１２〜１６メツシユの粒度の活性炭２０ｇを
加え１６時間漫潰、ついで８０℃の熱風乾燥機で１６時
間、時々かきまぜながら水分を蒸発させた。その後４０
０℃で２時間水素雰囲気で加熱処理を行い触媒調製を行
なった。(Catalyst preparation method) 2.5 g of cupric chloride dihydrate was dissolved in 22 ml of water, and 20 g of activated carbon with a particle size of 12 to 16 mesh was added thereto, crushed for 16 hours, and then heated in a hot air dryer at 80°C for 16 hours. , and allowed the water to evaporate while stirring occasionally. then 40
The catalyst was prepared by heat treatment at 0°C for 2 hours in a hydrogen atmosphere.
この発明による方法は、以下の実施例によりさらに詳し
く説明するが、この発明は実施例に何ら限定されるもの
ではない。The method according to the invention will be explained in more detail with reference to the following examples, but the invention is not limited to the examples in any way.
実施例 ｌ
上記調製法により調製した触媒１５・ｍｌ（６゜５ｇ、
４． ８ （Ｃｕ）ｍｍ ｏ ｌ ）を、高圧気相
用Ｕ字型反応管に充填し、 １５０℃、２０．４気圧、
１０７００ ｈ−１（７）空間速度（ＣＯ／ ０２／
Ｎ２／ メ９ノール（モル比）＝３７／３１５７／３）
で２時間反応させた。生成物の定量は、ガスクロマトグ
ラフ法によフた。その結果０．７７ｇのジメチルカーボ
ネートを得た。Example 1 15 ml (6°5 g,
4. 8 (Cu) mmol) was filled into a U-shaped reaction tube for high pressure gas phase, and the temperature was 150°C, 20.4 atm,
10700 h-1 (7) Space velocity (CO/ 02/
N2/men9ol (molar ratio) = 37/3157/3)
The mixture was allowed to react for 2 hours. The product was quantified by gas chromatography. As a result, 0.77 g of dimethyl carbonate was obtained.
（メタノールからの副生成物として０．０７ｇの蟻酸メ
チルが検出された。）
実施例 ２
実施例 １と同じ触媒２． ５ｇ（１，８５（Ｃｕ）ｍ
ｍｏｌ）を粉末状に砕き、３８ｍ１のメタノールととも
に３２０ｍ１のオートクレーブに仕込んだ、さらに２０
気圧のＣ０１１気圧の０２．４気圧のＡｒを張り込み、
１３０℃で７０分間反応させた。その結果０．８０ｇの
ジメチルカーボネートを得た。 （メタノールからの副
生成物としてｏ、ｏｏ３ｇのメチラールが検出された。(0.07 g of methyl formate was detected as a by-product from methanol.) Example 2 Same catalyst as Example 1 2. 5g (1,85(Cu)m
mol) was crushed into powder and charged into a 320 ml autoclave with 38 ml of methanol.
Atmospheric pressure C011 atm 02.4 atm Ar is charged,
The reaction was carried out at 130°C for 70 minutes. As a result, 0.80 g of dimethyl carbonate was obtained. (3 g of methylal was detected as a by-product from methanol.
）実施例 ３
銅粉１ ｇ （１５，７ｍｍｏ １）を３８ｍ１のメタ
ノールとともに３２０ｍ１のオートクレーブに仕込んだ
、さらに７．２気圧のＣ０１０，９気圧の０２．４気圧
のＮ２を張り込み、 １３０℃で７０分間反応させた。) Example 3 1 g (15.7 mmo 1) of copper powder was charged into a 320 ml autoclave with 38 ml of methanol, and further charged with 7.2 atm of CO10, 9 atm of N2, and 7.0 atm of N2 at 130°C. Allowed to react for minutes.
その結果０．０１４ｇのジメチルカーボネートを得た。As a result, 0.014 g of dimethyl carbonate was obtained.
（メタノールからの副生成物として０．００２ｇのメ
チラールが検出された。）比較例
活性炭２．５ｇを用い実施例 ３と同じ条件で反応を行
なったが、ジメチルカーボネートの生成は、認められな
かった。(0.002 g of methylal was detected as a by-product from methanol.) Comparative Example A reaction was carried out using 2.5 g of activated carbon under the same conditions as in Example 3, but no formation of dimethyl carbonate was observed. .
（発明の効果）
金属鋼の存在下にアルコールと一酸化炭嚢及び酸素を温
和な条件で反応装置を腐食させることなく炭酸エステル
を得ることができる。腐食がないので反応装置は安価な
汎用の材質、例えば５Ｕｓ−３１６Ｌ等を使用すること
が可能である。また、不純物の混入の恐れもなく高い純
度の炭酸エステルを得ることが可能となった。(Effects of the Invention) A carbonic acid ester can be obtained in the presence of metal steel using alcohol, a carbon monoxide bag, and oxygen under mild conditions without corroding the reactor. Since there is no corrosion, it is possible to use inexpensive general-purpose materials such as 5Us-316L for the reactor. Furthermore, it has become possible to obtain highly pure carbonate ester without fear of contamination with impurities.
Claims (1)
応させることを特徴とする炭酸エステルの製造方法。A method for producing carbonate ester, which comprises reacting alcohol with carbon monoxide and oxygen in the presence of metallic copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317424A JPH0813788B2 (en) | 1988-12-15 | 1988-12-15 | Method for producing carbonate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63317424A JPH0813788B2 (en) | 1988-12-15 | 1988-12-15 | Method for producing carbonate ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02256651A true JPH02256651A (en) | 1990-10-17 |
| JPH0813788B2 JPH0813788B2 (en) | 1996-02-14 |
Family
ID=18088075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63317424A Expired - Lifetime JPH0813788B2 (en) | 1988-12-15 | 1988-12-15 | Method for producing carbonate ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813788B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06285375A (en) * | 1992-06-29 | 1994-10-11 | Jgc Corp | Catalyst for production of carbonic diester and production method using the same |
| US5387708A (en) * | 1993-12-10 | 1995-02-07 | The Dow Chemical Company | Production of dialkyl carbonates using copper catalysts |
| CN1102076C (en) * | 1996-10-04 | 2003-02-26 | 千代田化工建设株式会社 | Method for producing diester carbonate |
| US9249082B2 (en) | 2010-02-09 | 2016-02-02 | King Abdulaziz City for Science and Technology (KACST) | Synthesis of dimethyl carbonate from carbon dioxide and methanol |
-
1988
- 1988-12-15 JP JP63317424A patent/JPH0813788B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06285375A (en) * | 1992-06-29 | 1994-10-11 | Jgc Corp | Catalyst for production of carbonic diester and production method using the same |
| US5387708A (en) * | 1993-12-10 | 1995-02-07 | The Dow Chemical Company | Production of dialkyl carbonates using copper catalysts |
| CN1102076C (en) * | 1996-10-04 | 2003-02-26 | 千代田化工建设株式会社 | Method for producing diester carbonate |
| US9249082B2 (en) | 2010-02-09 | 2016-02-02 | King Abdulaziz City for Science and Technology (KACST) | Synthesis of dimethyl carbonate from carbon dioxide and methanol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813788B2 (en) | 1996-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4410722A (en) | Process for preparing oxalic acid diesters using platinum group metals supported on alumina | |
| JPH02256651A (en) | Production of carbonic ester | |
| EP0556806B1 (en) | Process for producing biphenyltetracarboxylic dianhydride | |
| JP2638174B2 (en) | Method for producing carbonate ester | |
| JPH06218284A (en) | Catalyst for synthesizing dicarbonate and production or carbonic diester using the same | |
| EP0284816B1 (en) | Method of producing aldehydes | |
| JP3372197B2 (en) | Method for producing dimethyl carbonate | |
| JP2870738B2 (en) | Method for producing carbonic acid diester | |
| JPH0615505B2 (en) | Oxidative dehydrogenative dimerization of orthophthalic acid ester | |
| JP3139106B2 (en) | Method for producing carbonate ester | |
| JPH0219347A (en) | Production of dimethyl carbonate | |
| JPH05140009A (en) | Production of 1,1,1,2,2,3,4,5,5,5-decafluoropentane | |
| JP3124400B2 (en) | Method for producing carbonic acid diester | |
| JPH04193849A (en) | Production of substituted aromatic carboxylic acid ester | |
| JPH02184655A (en) | Production of carbonic acid ester | |
| JP3139108B2 (en) | Method for producing carbonate ester | |
| JPS62277337A (en) | Method for purifying o-methylacetophenone | |
| JPH02164853A (en) | Production of carbonic acid ester | |
| JPH04297443A (en) | Production of carbonic acid diester | |
| JPH02218647A (en) | Preparation of carbonate ester | |
| JPH04356446A (en) | Production of carbonic acid ester | |
| JPH0313214B2 (en) | ||
| JPH083103A (en) | Production of beta-naphthoic acid | |
| JPH01316341A (en) | Production of omega-hydroxy fatty acid | |
| JPH026438A (en) | Production of carbonic acid ester |