JPH0597773A - Production of carbonate ester - Google Patents
Production of carbonate esterInfo
- Publication number
- JPH0597773A JPH0597773A JP3261767A JP26176791A JPH0597773A JP H0597773 A JPH0597773 A JP H0597773A JP 3261767 A JP3261767 A JP 3261767A JP 26176791 A JP26176791 A JP 26176791A JP H0597773 A JPH0597773 A JP H0597773A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- metal
- alkaline earth
- alcohol
- carbon monoxide
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 carbonate ester Chemical class 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 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
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 229910001361 White metal Inorganic materials 0.000 claims description 5
- 239000010969 white metal Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract 1
- 229910001507 metal halide Inorganic materials 0.000 abstract 1
- 150000005309 metal halides Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 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
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Abstract
Description
【０００１】[0001]
【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。周知の如く、炭酸エステルはポリ
マーや医農薬製造中間体及び溶剤として工業的に重要な
化合物である。FIELD OF THE INVENTION The present invention relates to a method for producing a carbonic acid ester. As is well known, carbonic acid esters are industrially important compounds as polymers, intermediates for producing pharmaceuticals and agricultural chemicals, and solvents.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】炭酸エ
ステルの製造方法としては、従来アルコールにホスゲン
を反応させる方法が工業的に行われている。しかしなが
ら、この方法は毒性の高いホスゲンを使用すること、或
いはアルコールとホスゲンの反応により腐食性の強い塩
酸が大量に副生することなどの欠点がある。従って、従
来よりホスゲンを使用しない炭酸エステルの製造法が数
多く提案されている。その中でも一般的な方法として、
エステル化しようとするアルコールを触媒の存在下で一
酸化炭素及び酸素と反応させる方法が挙げられる。使用
される触媒には大別して、主触媒としてパラジウム化合
物を用いるものと、銅化合物を用いるものとの二つがあ
る。前者の例としては、特公昭61−8816号公報が代表的
なものであるが、このパラジウム系触媒はその高い活性
にもかかわらず、高価なパラジウム化合物が金属として
析出し、失活し易いという、実用上重大な欠点を有して
いる。他方、後者の例としては、代表的な例として塩化
第一銅を用いるもの（特公昭60−58739 号公報) 及び塩
化第二銅を用いるもの（特公昭45−11129 号公報) があ
る。これら銅系触媒はパラジウム系触媒に比較し、安定
性には優っているものの、活性は低い為、実用的な反応
速度を得る為には、高濃度で触媒を使用し、高い一酸化
炭素分圧で反応させる必要がある。さらに高濃度の第二
銅イオンが著るしい腐食作用を示す為、反応器等の材質
に大きな制約を受け、工業的に満足のいくものとは言え
ない。2. Description of the Related Art Conventionally, a method of reacting alcohol with phosgene has been industrially carried out as a method for producing a carbonic acid ester. However, this method has drawbacks such as the use of highly toxic phosgene, or the production of a large amount of highly corrosive hydrochloric acid as a by-product due to the reaction between alcohol and phosgene. Therefore, many methods for producing carbonic acid ester without using phosgene have been proposed. Among them, as a general method,
A method of reacting the alcohol to be esterified with carbon monoxide and oxygen in the presence of a catalyst can be mentioned. The catalyst used is roughly classified into two types, one using a palladium compound as the main catalyst and one using a copper compound. As an example of the former, Japanese Examined Patent Publication No. 61-8816 is representative, but despite the high activity of this palladium-based catalyst, an expensive palladium compound precipitates as a metal and is easily deactivated. , Has a serious drawback in practical use. On the other hand, examples of the latter include those using cuprous chloride (Japanese Patent Publication No. 60-58739) and those using cupric chloride (Japanese Patent Publication No. 45-11129). Although these copper-based catalysts are superior in stability to palladium-based catalysts, their activity is low, so in order to obtain a practical reaction rate, use a catalyst at a high concentration and a high carbon monoxide content. It is necessary to react with pressure. Further, since a high concentration of cupric ion shows a remarkable corrosive action, it is not industrially satisfactory because it is greatly restricted by the material of the reactor and the like.
【０００３】[0003]
【課題を解決するための手段】本発明者等は上述の状況
に鑑み、工業的に炭酸エステルを合成する為に、より有
利な方法を鋭意探索してきたが、以下に示す触媒系の使
用により上述の問題点が解決できる事を見出し、本発明
を完成した。即ち、本発明は、アルコールと一酸化炭素
及び酸素とを、下記(a) および(b)からなる触媒、又は
(a), (b)および(c) からなる触媒の存在下に、反応させ
ることを特徴とする炭酸エステルの製造法を提供するも
のである。 (a) 白金族金属ないし白金属金属を担持した固体触媒 (b) アルカリ金属又はアルカリ土類金属の弱酸塩 (c) アルカリ金属又はアルカリ土類金属のハロゲン化物 本触媒系を、従来より知られている触媒系と比較すると
以下の特徴が挙げられる。In view of the above situation, the inventors of the present invention have eagerly searched for a more advantageous method for industrially synthesizing a carbonic acid ester, but by using the catalyst system shown below, The present invention has been completed by finding that the above problems can be solved. That is, the present invention, alcohol and carbon monoxide and oxygen, the catalyst comprising the following (a) and (b), or
The present invention provides a method for producing a carbonic acid ester, which comprises reacting in the presence of a catalyst consisting of (a), (b) and (c). (a) Solid catalysts carrying platinum group metals or white metal metals (b) Weak acid salts of alkali metals or alkaline earth metals (c) Halides of alkali metals or alkaline earth metals This catalyst system has been conventionally known. The following characteristics can be mentioned in comparison with the existing catalyst system.
【０００４】(A) パラジウムを主触媒とする他の触媒系
との比較 本発明の触媒系と、同様にパラジウムを主触媒とする他
の触媒系との最大の違いは、他の触媒系ではパラジウム
の他に、第二銅イオン、第二鉄イオン等の酸化性陽イオ
ンと共存させているのに対し、本発明の触媒系で共存す
るのは、酸化性を持たないアルカリ又はアルカリ土類金
属イオンのみである点である。従って本発明では、パラ
ジウム金属が酸化され、二価の陽イオンとして、溶液中
に溶出する事がなく、従って他の触媒系のように、溶存
パラジウムイオンが、副生する水の影響その他の要因に
より金属として析出し、失活する事や、器壁等へ付着し
て、ロスする事がない。さらにパラジウムイオン、第二
銅イオン等の酸化性陽イオンが溶液中に存在する事によ
る、反応器等への腐食も避ける事ができる。これらの特
徴は、工業的には、非常に大きな長所となる。 (A) Other catalyst system with palladium as main catalyst
Comparison with the catalyst system of the present invention, the biggest difference between other catalyst systems also similarly palladium as the main catalyst, other catalyst systems other than palladium, such as cupric ion, ferric ion In contrast to the coexistence with an oxidizing cation, the catalyst system of the present invention coexists only with an alkali or alkaline earth metal ion having no oxidizing property. Therefore, in the present invention, the palladium metal is not oxidized and does not elute into the solution as a divalent cation. Therefore, like other catalyst systems, the dissolved palladium ion has an influence of water by-produced and other factors. As a result, it will not be deposited as a metal and will not be deactivated, nor will it be attached to the vessel wall or the like and lost. Furthermore, it is possible to avoid corrosion to the reactor and the like due to the presence of oxidizing cations such as palladium ions and cupric ions in the solution. These characteristics are industrially very advantageous.
【０００５】(B) 銅を主触媒とする触媒系との比較 先に述べたように銅を主触媒とした場合、実用的な反応
速度を得る為には、高い触媒濃度 (通常数百〜数千mmol
／リットル）を必要とする事から、第二銅イオンの酸化
性による腐食も著しいものになるが、本発明では先に述
べたように、そのような腐食の問題を避ける事ができ
る。又、白金属を主触媒にしている事で当然、一酸化炭
素分圧も銅系のように高くする必要がない。 (B) Comparison with catalyst system using copper as main catalyst As described above, when using copper as the main catalyst, in order to obtain a practical reaction rate, a high catalyst concentration (usually several hundred to Thousands of mmol
/ Liter), the corrosion due to the oxidizing property of the cupric ion becomes significant, but the present invention can avoid such a corrosion problem as described above. Further, since the white metal is used as the main catalyst, naturally, it is not necessary to increase the carbon monoxide partial pressure as in the copper system.
【０００６】以上に述べたように本発明は、従来の触媒
系において問題となっていた点を解決するものであり、
本発明により炭酸エステルを工業的に有利に製造する事
ができる。As described above, the present invention solves the problems in the conventional catalyst system,
According to the present invention, carbonic acid ester can be industrially advantageously produced.
【０００７】以下本発明をより具体的に説明する。本発
明において使用される触媒は、下記(a) および(b) 、又
は(a), (b)および(c) の組合せからなる。 (a) 白金族金属ないし白金属金属を担持した固体触媒 (b) アルカリ金属又はアルカリ土類金属の弱酸塩 (c) アルカリ金属又はアルカリ土類金属のハロゲン化物 (a), (b), (c) 各々につき以下に具体例を挙げる。(a)
成分の白金族金属としては、ルテニウム、ロジウム、パ
ラジウム等が挙げられるが、特にパラジウムが好ましい
活性を示す。それらは、金属微粒子そのもの、いわゆる
ブラックの形態でも使用できるが、通常は、担体に担持
した形で用いられる。担体としては、活性炭、グラファ
イト、アルミナ、シリカ、マグネシア等の通常の触媒担
体が使用されるが、特に活性炭が好ましい活性を示す。
白金属金属の担体への担持率は、通常 0.1〜50重量％、
好ましくは 0.5〜10重量％のものが用いられる。The present invention will be described in more detail below. The catalyst used in the present invention comprises the following (a) and (b), or a combination of (a), (b) and (c). (a) Solid catalyst supporting platinum group metal or white metal (b) Weak acid salt of alkali metal or alkaline earth metal (c) Halide of alkali metal or alkaline earth metal (a), (b), ( c) Specific examples are given below. (a)
Examples of the platinum group metal of the component include ruthenium, rhodium, palladium, and the like, with palladium showing particularly preferable activity. Although they can be used in the form of metal fine particles themselves, so-called black, they are usually used in the form of being supported on a carrier. As the carrier, a usual catalyst carrier such as activated carbon, graphite, alumina, silica, magnesia, etc. is used, and activated carbon shows particularly preferable activity.
The loading rate of the white metal metal on the carrier is usually 0.1 to 50% by weight,
Preferably, 0.5 to 10% by weight is used.
【０００８】(b) 成分のアルカリ金属又はアルカリ土類
金属の弱酸塩としては、リチウム、ナトリウム、カリウ
ム、ルビジウム、セシウム、ベリリウム、マグネシウ
ム、カルシウム、バリウム等の酢酸、プロピオン酸、ピ
バリン酸、安息香酸などのカルボン酸塩、炭酸、ホウ
酸、リン酸などの無機塩、フェノール、クレゾール、パ
ラクロロフェノールなどのフェノール類の塩及びこれら
の混合物等が挙げられる。(c) 成分のアルカリ金属又は
アルカリ土類金属のハロゲン化物としては、リチウム、
ナトリウム、カリウム、ルビジウム、セシウム、ベリリ
ウム、マグネシウム、カルシウム、バリウム等の塩化
物、臭化物、ヨウ化物及びこれらの混合物等が挙げられ
る。Examples of the weak acid salt of the alkali metal or alkaline earth metal of the component (b) include acetic acid such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, barium, propionic acid, pivalic acid, benzoic acid. And the like, inorganic salts such as carbonic acid, boric acid and phosphoric acid, salts of phenols such as phenol, cresol and parachlorophenol, and mixtures thereof. As the alkali metal or alkaline earth metal halide of the component (c), lithium,
Examples thereof include chlorides such as sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium and barium, bromides, iodides, and mixtures thereof.
【０００９】各触媒成分の使用濃度としては、(a) 成分
については、使用量が多いほど反応速度の面では有利で
あるから、使用する反応装置の撹拌能力、除熱能力等の
機械的特性によって適切な量を使用すれば良い。(b) 成
分については１〜1000mmol／リットル、好ましくは５〜
500mmol ／リットル程度の濃度で使用される。(c) 成分
については１〜1000mmol／リットル、好ましくは５〜50
0mmol ／リットル程度の濃度で使用される。Regarding the concentration of each catalyst component to be used, as for component (a), the larger the amount used, the more advantageous in terms of reaction rate. Therefore, the mechanical characteristics such as stirring ability and heat removal ability of the reactor used Depending on the amount, you can use an appropriate amount. The component (b) is 1 to 1000 mmol / liter, preferably 5 to
It is used at a concentration of about 500 mmol / liter. About component (c), it is 1-1000 mmol / liter, preferably 5-50.
It is used at a concentration of about 0 mmol / liter.
【００１０】本発明の反応物質であるアルコールとして
は、例えばメタノール、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、フェノール等の芳香族アルコール、その他ジオー
ル、ポリオール等が挙げられるが、好ましくは炭素数が
１〜20のアルコールが用いられ、中でもメタノールが好
ましい。反応ガスである一酸化炭素及び酸素は、それら
の高純度ガスのみならず、窒素、アルゴン、二酸化炭素
等の本発明の反応に対し不活性なガスで希釈したものを
用いてもよい。従って、酸素源として空気も使用でき
る。本発明の反応は、上記のような触媒の存在下、常圧
又は加圧下で行われ、好ましくは１気圧〜100 気圧であ
る。反応に不活性なガスで希釈する場合は、反応系内の
一酸化炭素分圧は 0.1〜30気圧、酸素分圧は0.05〜10気
圧の範囲に調節される。また反応温度は20〜250 ℃の範
囲である。Examples of the alcohol which is a reactant of the present invention include saturated aliphatic alcohols such as methanol and ethanol, unsaturated aliphatic alcohols such as allyl alcohol, aromatic alcohols such as phenol, and other diols and polyols. However, an alcohol having 1 to 20 carbon atoms is preferably used, and methanol is particularly preferable. As the reaction gases, carbon monoxide and oxygen may be used not only those gases having high purity but also those diluted with a gas inert to the reaction of the present invention such as nitrogen, argon, carbon dioxide and the like. Therefore, air can also be used as an oxygen source. The reaction of the present invention is carried out in the presence of the catalyst as described above under normal pressure or increased pressure, preferably at 1 atm to 100 atm. When diluted with a gas inert to the reaction, the carbon monoxide partial pressure in the reaction system is adjusted to 0.1 to 30 atm and the oxygen partial pressure is adjusted to 0.05 to 10 atm. The reaction temperature is in the range of 20 to 250 ° C.
【００１１】[0011]
【実施例】以下、実施例により、本発明を更に詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。なお、実施例は撹拌槽による回分法によってい
るが、充填槽、滴子槽等による連続反応方式等、従来よ
り固液不均一反応に用いられている反応技術を適用する
事も可能であるのは言うまでもない。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, although the embodiment is based on the batch method using a stirring tank, it is also possible to apply a reaction technique conventionally used for solid-liquid heterogeneous reaction such as a continuous reaction method using a filling tank and a drop tank. Needless to say.
【００１２】実施例１ 容量300ml のオートクレーブに、メタノール50ml、５％
パラジウム／活性炭0.52ｇ、酢酸カリウム0.50ｇを入
れ、COを４atm 、O2を２atm 、N2を19atm 圧入した後、
130℃に昇温し、60分間保持した。冷却後内容物を取り
出し、ガスクロマトグラフ法により分析した。生成した
炭酸ジメチルは0.63ｇ (7.0mmol)であった。Example 1 In an autoclave having a volume of 300 ml, 50 ml of methanol and 5%
Palladium / activated carbon 0.52g, potassium acetate 0.50g, CO 4atm, O 2 2atm, N 2 19atm were injected.
The temperature was raised to 130 ° C. and kept for 60 minutes. After cooling, the contents were taken out and analyzed by gas chromatography. The amount of dimethyl carbonate produced was 0.63 g (7.0 mmol).
【００１３】実施例２ 容量300ml のオートクレーブに、メタノール50ml、５％
パラジウム／活性炭0.52ｇ、酢酸カリウム0.50ｇ、塩化
カリウム0.1ｇを入れ、実施例１に準じて反応した。生
成した炭酸ジメチルは 1.5ｇ (16.7mmol) であった。Example 2 In an autoclave having a volume of 300 ml, 50 ml of methanol and 5%
Palladium / activated carbon (0.52 g), potassium acetate (0.50 g) and potassium chloride (0.1 g) were added, and the reaction was carried out according to Example 1. The amount of dimethyl carbonate produced was 1.5 g (16.7 mmol).
【００１４】比較例１ 容量300ml のオートクレーブに、メタノール50ml、５％
パラジウム／活性炭0.52ｇを入れ、実施例１に準じて反
応した。生成した炭酸ジメチルは0.02ｇ(0.2mmol) であ
った。Comparative Example 1 In an autoclave having a volume of 300 ml, 50 ml of methanol and 5%
Palladium / activated carbon (0.52 g) was added and the reaction was carried out according to Example 1. The amount of dimethyl carbonate produced was 0.02 g (0.2 mmol).
Claims (1)
下記(a) および(b)からなる触媒、又は(a), (b)および
(c) からなる触媒の存在下に、反応させることを特徴と
する炭酸エステルの製造法。 (a) 白金族金属ないし白金属金属を担持した固体触媒 (b) アルカリ金属又はアルカリ土類金属の弱酸塩 (c) アルカリ金属又はアルカリ土類金属のハロゲン化物1. Alcohol and carbon monoxide and oxygen,
A catalyst comprising the following (a) and (b), or (a), (b) and
A method for producing a carbonic acid ester, which comprises reacting in the presence of a catalyst comprising (c). (a) Solid catalyst carrying platinum group metal or white metal (b) Weak acid salt of alkali metal or alkaline earth metal (c) Halide of alkali metal or alkaline earth metal
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261767A JPH0597773A (en) | 1991-10-09 | 1991-10-09 | Production of carbonate ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261767A JPH0597773A (en) | 1991-10-09 | 1991-10-09 | Production of carbonate ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597773A true JPH0597773A (en) | 1993-04-20 |
Family
ID=17366413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3261767A Pending JPH0597773A (en) | 1991-10-09 | 1991-10-09 | Production of carbonate ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597773A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1991
- 1991-10-09 JP JP3261767A patent/JPH0597773A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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