JPH0692907A - Production of carbonic acid ester - Google Patents
Production of carbonic acid esterInfo
- Publication number
- JPH0692907A JPH0692907A JP4242341A JP24234192A JPH0692907A JP H0692907 A JPH0692907 A JP H0692907A JP 4242341 A JP4242341 A JP 4242341A JP 24234192 A JP24234192 A JP 24234192A JP H0692907 A JPH0692907 A JP H0692907A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- carbonic acid
- catalyst
- reaction
- production
- 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
Links
- 150000004651 carbonic acid esters Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004917 carbon fiber Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 18
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 17
- 238000005311 autocorrelation function Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- -1 Carbonate ester Chemical class 0.000 description 10
- GZVBAOSNKYQKIT-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC.COCOC GZVBAOSNKYQKIT-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 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
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一酸化炭素、酸素及び
アルコールから、効率よく炭酸エステルを製造する方法
に関する。炭酸エステルはポリカーボネートやイソシア
ネートの製造原料として、また、種々の有機合成原料と
して非常に有用な化合物である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing carbonic acid ester from carbon monoxide, oxygen and alcohol. Carbonic acid ester is a very useful compound as a raw material for producing polycarbonate and isocyanate, and as a raw material for various organic synthesis.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
炭酸エステルはホスゲンとアルコールから製造されてい
るが、ホスゲンの毒性が非常に強いこと、腐食性のハロ
ゲンを含んだ化合物が副生することから、ホスゲンを用
いない炭酸エステルの製造法が望まれていた。このた
め、触媒を用いて、一酸化炭素、酸素及びアルコールか
ら炭酸エステルを製造する方法が提案されている。例え
ば（Ind. Eng. Chem. Prod. Res. Dev.,19,396 (198
0).）では、液相において、塩化第一銅を触媒として炭
酸エステルを得ている。しかし、このような反応方式で
は反応液中に、反応生成物である水が蓄積してしまい、
その水と触媒が反応することで触媒が変質し、失活が起
こり易いという欠点を有していた。また、種々の有機配
位子、有機塩基助触媒を上記銅塩に添加した液相反応も
提案されているが、蒸留等による炭酸エステルの分離精
製の際に困難を生じるという欠点があった。2. Description of the Related Art Conventionally, the problems to be solved by the invention
Carbonic acid ester is produced from phosgene and alcohol, but since phosgene is extremely toxic and a compound containing corrosive halogen is produced as a by-product, a method for producing carbonic acid ester without phosgene is desired. It was Therefore, a method of producing a carbonic acid ester from carbon monoxide, oxygen and alcohol using a catalyst has been proposed. For example (Ind. Eng. Chem. Prod. Res. Dev., 19,396 (198
In 0).), Carbonate ester is obtained in the liquid phase using cuprous chloride as a catalyst. However, in such a reaction method, water as a reaction product is accumulated in the reaction solution,
The reaction between the water and the catalyst causes the catalyst to change in quality and is easily deactivated. Further, a liquid phase reaction in which various organic ligands and organic base cocatalysts are added to the copper salt has been proposed, but it has a drawback that difficulty occurs in separating and refining a carbonic acid ester by distillation or the like.
【０００３】これらの欠点を克服するために接触気相反
応による炭酸エステル合成が提案されている。すなわ
ち、接触気相反応では、生成した炭酸エステル及び水は
直ちに効率よく触媒から除去されるために触媒の変質の
問題を回避でき、また生成物中への上記有機配位子、有
機塩基助触媒の混入を回避できるため分離精製プロセス
を簡略化することができる。例えば、特公表６３−５０
３６０号では、活性炭の担体に塩化第二銅を担持した触
媒を用いた接触気相反応が提示されている。しかし反応
条件が数十気圧と厳しく、かつ触媒活性が充分ではな
い。本発明の目的は、このような問題点を解決し、穏や
かな反応条件下において効率よく炭酸エステルを製造す
る方法を提供することである。In order to overcome these drawbacks, carbonic acid ester synthesis by catalytic gas phase reaction has been proposed. That is, in the catalytic gas phase reaction, the generated carbonic acid ester and water are immediately and efficiently removed from the catalyst, so that the problem of catalyst deterioration can be avoided, and the organic ligand and organic base cocatalyst in the product can be avoided. It is possible to simplify the separation and purification process since it is possible to avoid the contamination. For example, Japanese Patent Publication 63-50
No. 360 proposes a catalytic gas phase reaction using a catalyst in which cupric chloride is supported on a carrier of activated carbon. However, the reaction conditions are as severe as several tens of atmosphere, and the catalytic activity is not sufficient. An object of the present invention is to solve such problems and provide a method for efficiently producing a carbonate ester under mild reaction conditions.
【０００４】本発明者らは、一酸化炭素、酸素及びアル
コールを接触気相反応させることによる炭酸エステルの
製造法について、鋭意検討を重ねた結果、二価の銅塩を
活性炭素繊維に担持した触媒を用いれば、穏やかな反応
条件下、特に低圧下において、触媒活性、選択性ともに
高くきわめて有利に炭酸エステルが得られることを見い
だし、本発明を完成するに至った。The inventors of the present invention have conducted extensive studies as to a method for producing a carbonic acid ester by catalytically reacting carbon monoxide, oxygen and an alcohol with each other, and as a result, have carried a divalent copper salt on activated carbon fiber. It has been found that the use of a catalyst makes it possible to obtain a carbonate ester with very high catalytic activity and high selectivity under mild reaction conditions, especially under low pressure, and thus completed the present invention.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、二
価の銅塩を活性炭素繊維に担持した触媒の存在下で、一
酸化炭素、酸素及びアルコールを接触気相反応させるこ
とを特徴とする炭酸エステルの製造方法である。以下
に、この発明の方法を詳しく説明する。この発明で用い
られる触媒は、二価の銅塩を活性炭素繊維（以下ＡＣＦ
と記述）に担持したものである。本発明における二価の
銅塩としては、上述の塩化第二銅や臭化第二銅等のハロ
ゲン化銅または、硝酸銅が好ましく用いられる。ＡＣＦ
は、その原料をピッチ、ポリアクリルアミド、セルロー
スあるいはフェノールとする何れのＡＣＦでもよい。比
表面積が高いＡＣＦ、すなわち７００ｍ2 ／ｇより大き
な比表面積を有するＡＣＦが担体として好ましい。また
ＡＣＦの形状は適当なバインダー等を加え、成形するこ
とによりフェルト状、ペレット状等任意の形状を用いる
ことができる。接触気相反応の場合においては一般的に
ペレット状が取扱の点で好ましい。これらＡＣＦに対す
る銅担持量は０. １〜３０重量％の範囲が活性の点で好
ましい。That is, the present invention is characterized by carrying out catalytic gas phase reaction of carbon monoxide, oxygen and alcohol in the presence of a catalyst having a divalent copper salt supported on activated carbon fibers. Is a method for producing a carbonate ester. The method of the present invention will be described in detail below. The catalyst used in this invention is a divalent copper salt containing activated carbon fiber (hereinafter referred to as ACF).
And description). As the divalent copper salt in the present invention, the above-mentioned copper halide such as cupric chloride and cupric bromide or copper nitrate is preferably used. ACF
May be any ACF whose raw material is pitch, polyacrylamide, cellulose or phenol. ACF having a high specific surface area, that is, ACF having a specific surface area larger than 700 m 2 / g is preferable as the carrier. The shape of the ACF may be an optional shape such as a felt shape or a pellet shape by adding an appropriate binder or the like and molding. In the case of catalytic gas phase reaction, pellets are generally preferable in terms of handling. The amount of copper supported on these ACFs is preferably in the range of 0.1 to 30% by weight from the viewpoint of activity.
【０００６】本製造法に用いるアルコールは、メタノー
ル、エタノール等の脂肪族アルコール、の他、不飽和ア
ルコール、多価アルコールがあげられるが、好ましくは
炭素数１〜４のアルコールである。Alcohols used in this production method include aliphatic alcohols such as methanol and ethanol, unsaturated alcohols and polyhydric alcohols, with alcohols having 1 to 4 carbon atoms being preferred.
【０００７】原料ガスである一酸化炭素及び酸素は、二
酸化炭素、窒素及び他の反応に不活性なガスで希釈して
用いても良い。反応は、好ましくは加圧下で行う。その
際の一酸化炭素分圧は０. ５〜５０気圧、好ましくは３
〜３０気圧であり、酸素分圧は０. １〜１０気圧、好ま
しくは０. ３〜５気圧の範囲である。Carbon monoxide and oxygen, which are raw material gases, may be diluted with carbon dioxide, nitrogen and other gases inert to the reaction. The reaction is preferably carried out under pressure. The carbon monoxide partial pressure at that time is 0.5 to 50 atm, preferably 3
-30 atm and oxygen partial pressure in the range of 0.1-10 atm, preferably 0.3-5 atm.
【０００８】反応温度は５０〜１８０℃の範囲で行う。
反応温度が低いと活性が充分でなく、反応温度が高いと
一酸化炭素の燃焼反応による二酸化炭素の生成量が増え
るため、好ましくは９０〜１３０℃の範囲で行う。The reaction temperature is 50 to 180 ° C.
If the reaction temperature is low, the activity is not sufficient, and if the reaction temperature is high, the amount of carbon dioxide produced by the combustion reaction of carbon monoxide increases, so the temperature is preferably in the range of 90 to 130 ° C.
【０００９】[0009]
【実施例】以下、本発明を実施例により更に具体的に説
明するが本発明は、これら実施例に限定されるものでは
ない。なお、原料のアルコールにメタノールを用いて示
した以下の実施例においては得られる炭酸エステルは炭
酸ジメチル（以下ＤＭＣという）である。また、選択率
は、原料の一酸化炭素及びメタノールに対して、それぞ
れ以下の式を用いて算出した。 Ｓ(CO)＝Ｒ(DMC) ／｛Ｒ(DMC) ＋Ｒ(CO2) ｝ × １００ Ｓ(CH3OH) ＝２Ｒ(DMC) ／｛２Ｒ(DMC) ＋２Ｒ(DME) ＋３Ｒ(DMM) ｝ × １００ ここで、Ｓ(CO) ：原料の一酸化炭素に対する選択率
（％）、Ｓ(CH3OH) ：原料のメタノールに対する選択率
（％）、Ｒ(DMC) ：ＤＭＣ生成量（mmol）、Ｒ(CO2) ：
二酸化炭素生成量（mmol）、Ｒ(DME) ：ジメチルエーテ
ル生成量（mmol）、Ｒ(DMM) ：ジメトキシメタン（メチ
ラール）生成量（mmol）である。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The carbonate ester obtained in the following examples in which methanol was used as the alcohol of the raw material was dimethyl carbonate (hereinafter referred to as DMC). Further, the selectivity was calculated using the following formulas for the raw material carbon monoxide and methanol. S (CO) = R (DMC) / {R (DMC) + R (CO 2 )} × 100 S (CH 3 OH) = 2R (DMC) / {2R (DMC) + 2R (DME) + 3R (DMM)} × Where S (CO): selectivity (%) of carbon monoxide for the raw material, S (CH 3 OH): selectivity (%) of methanol for the raw material, R (DMC): production amount of DMC (mmol), R (CO 2 ):
Carbon dioxide production (mmol), R (DME): dimethyl ether production (mmol), R (DMM): dimethoxymethane (methylal) production (mmol).
【００１０】実施例１ （炭酸エステル製造） 塩化第二銅（０. ３１８ｇ）をエタノール（１００ｍ
ｌ）に溶解した溶液中にピッチ系ＡＣＦ（大阪ガス製・
ＦＮ−２００・ＣＦ−２０）１. ８８ｇを浸漬し、エタ
ノールを留去することによってＣｕＣｌ2 ／ＡＣＦ触媒
（Ａ−１）を調製した。触媒の化学分析による銅の担持
量は１. ４重量％であった。流通反応器の内径１０ｍｍ
のハステロイＢ製反応管に触媒を５ｍｌ（重量約１ｇ）
充填した。反応は一酸化炭素を毎分６０ｍｌ（ＳＴ
Ｐ）、空気を毎分１０ｍｌ（ＳＴＰ）、メタノールを毎
分１７ｍｌ（ＳＴＰ）流し、反応圧７気圧、反応温度で
１２５℃で行った。生成物の分析はオンラインガスクロ
により、反応中約１時間毎に行った。反応開始後、約１
０時間で反応は定常状態に達した。ＤＭＣは４. ６mmol
／ｇ−触媒・ ｈで生成した。銅１モルあたりの活性で表
すと５. ７×１０-3mol ／mol-Cu・ sec.となる。ＤＭＣ
以外の生成物は、ＣＯ2 、ジメチルエーテル（ＤＭＥ）
及びジメトキシメタン（ＤＭＭ）であり、原料のＣＯに
対するＤＭＣ選択率は７６％、メタノールに対する選択
率は９７％であった。Example 1 Production of Carbonic Acid Ester Cupric chloride (0.318 g) was added to ethanol (100 m).
Pitch-based ACF (manufactured by Osaka Gas
CuCl 2 / ACF catalyst (A-1) was prepared by immersing 1.88 g of FN-200 / CF-20) and distilling off ethanol. The amount of copper supported by the chemical analysis of the catalyst was 1.4% by weight. Flow reactor inner diameter 10 mm
5 ml of catalyst in a Hastelloy B reaction tube (about 1 g in weight)
Filled. The reaction is 60 ml of carbon monoxide per minute (ST
P), 10 ml of air per minute (STP) and 17 ml of methanol per minute (STP) were flown at a reaction pressure of 7 atm and a reaction temperature of 125 ° C. The analysis of the product was performed by online gas chromatography about every hour during the reaction. About 1 after starting the reaction
The reaction reached a steady state at 0 hours. DMC is 4.6 mmol
/G-catalyst.h. The activity per mol of copper is 5.7 × 10 −3 mol / mol-Cu · sec. DMC
Other products are CO 2 , dimethyl ether (DME)
And dimethoxymethane (DMM), the DMC selectivity to the raw material CO was 76%, and the selectivity to methanol was 97%.
【００１１】実施例２ ピッチ系ＡＣＦの代わりにＰＡＮ（ポリアクリルニトリ
ル）系ＡＣＦ（東邦レーヨン製ＦＥ−３００）を用い
て、実施例１と同様に触媒（Ａ−２）を調製した。触媒
の化学分析による銅の担持量は２. ８重量％である。こ
の触媒を用い、実施例１と同様に反応を行った。反応開
始後約５時間で定常状態に達した。ＤＭＣは５. ３mmol
／ｇ−触媒・ ｈで生成した。銅１モルあたりの活性で表
すと３. ３×１０-3mol ／mol-Cu・ sec.となる。ＤＭＣ
以外の生成物は、ＣＯ2 、ジメチルエーテル（ＤＭＥ）
及びジメトキシメタン（ＤＭＭ）であり、原料のＣＯに
対するＤＭＣ選択率は７８％、メタノールに対する選択
率は９４％であった。Example 2 A catalyst (A-2) was prepared in the same manner as in Example 1 except that a PAN (polyacrylonitrile) -based ACF (FE-300 manufactured by Toho Rayon) was used instead of the pitch-based ACF. The amount of copper supported by the chemical analysis of the catalyst is 2.8% by weight. Using this catalyst, a reaction was carried out in the same manner as in Example 1. A steady state was reached about 5 hours after the start of the reaction. DMC is 5.3 mmol
/G-catalyst.h. The activity per mol of copper is 3.3 × 10 −3 mol / mol-Cu · sec. DMC
Other products are CO 2 , dimethyl ether (DME)
And dimethoxymethane (DMM), the DMC selectivity to the raw material CO was 78%, and the selectivity to methanol was 94%.
【００１２】比較例１ ＡＣＦの代わりに、活性炭（ツルミコール製ＨＣ３０
Ｓ）を用いて同様に触媒（Ｂ−１）を調製した。触媒の
化学分析による銅の担持量は２. ４％である。この触媒
を用い、実施例１と同様に反応を行った。ＤＭＣは、
１. ８mmol／ｇ−触媒・ｈで生成した。銅１モルあたり
の活性で表すと１. ３５×１０-3mol ／mol-Cu・ sec.と
なる。ＤＭＣ以外の生成物は、ＣＯ2、ジメチルエーテ
ル（ＤＭＥ）及びジメトキシメタン（ＤＭＭ）であり、
原料のＣＯに対するＤＭＣ選択率は８４％、メタノール
に対する選択率は８９％であった。Comparative Example 1 Instead of ACF, activated carbon (HC30 manufactured by Tsurumi Coal) was used.
A catalyst (B-1) was similarly prepared using S). The amount of copper supported by the chemical analysis of the catalyst is 2.4%. Using this catalyst, a reaction was carried out in the same manner as in Example 1. DMC is
It was produced at 1.8 mmol / g-catalyst · h. The activity per mol of copper is 1.35 × 10 −3 mol / mol-Cu · sec. Products other than DMC are CO 2 , dimethyl ether (DME) and dimethoxymethane (DMM),
The DMC selectivity with respect to the raw material CO was 84%, and the selectivity with respect to methanol was 89%.
【００１３】[0013]
【発明の効果】本発明を用いることにより、穏やかな反
応条件下、特に低圧下において、触媒活性、選択性とも
に高く炭酸エステルを製造することができる。INDUSTRIAL APPLICABILITY By using the present invention, a carbonate ester can be produced with high catalytic activity and high selectivity under mild reaction conditions, especially under low pressure.
Claims (1)
の存在下で、一酸化炭素、酸素及びアルコールを接触気
相反応させることを特徴とする炭酸エステルの製造方
法。1. A method for producing a carbonic acid ester, which comprises subjecting carbon monoxide, oxygen and alcohol to a catalytic gas phase reaction in the presence of a catalyst in which a divalent copper salt is supported on activated carbon fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4242341A JPH0692907A (en) | 1992-09-10 | 1992-09-10 | Production of carbonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4242341A JPH0692907A (en) | 1992-09-10 | 1992-09-10 | Production of carbonic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0692907A true JPH0692907A (en) | 1994-04-05 |
Family
ID=17087759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4242341A Pending JPH0692907A (en) | 1992-09-10 | 1992-09-10 | Production of carbonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692907A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703618A1 (en) * | 1987-02-06 | 1988-08-18 | Opel Adam Ag | Rear axle for a motor vehicle |
-
1992
- 1992-09-10 JP JP4242341A patent/JPH0692907A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703618A1 (en) * | 1987-02-06 | 1988-08-18 | Opel Adam Ag | Rear axle for a motor vehicle |
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