JPH0219346A - Production of carbonic acid ester - Google Patents
Production of carbonic acid esterInfo
- Publication number
- JPH0219346A JPH0219346A JP63168594A JP16859488A JPH0219346A JP H0219346 A JPH0219346 A JP H0219346A JP 63168594 A JP63168594 A JP 63168594A JP 16859488 A JP16859488 A JP 16859488A JP H0219346 A JPH0219346 A JP H0219346A
- Authority
- JP
- Japan
- Prior art keywords
- earth metal
- aliphatic alcohol
- production
- copper salt
- salt
- 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 abstract description 8
- 150000004651 carbonic acid esters Chemical class 0.000 title description 2
- -1 alkaline-earth metal salt Chemical class 0.000 claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract description 4
- 229940045803 cuprous chloride Drugs 0.000 abstract description 4
- 239000000543 intermediate Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910002090 carbon oxide Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910001361 White metal Inorganic materials 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000010969 white metal Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 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
- 229910052786 argon Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005752 Copper oxychloride Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- MUJRNJDKBBSXSE-UHFFFAOYSA-N calcium;butan-1-olate Chemical compound [Ca+2].CCCC[O-].CCCC[O-] MUJRNJDKBBSXSE-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas 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
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は触媒の存在下に脂肪族アルコールを一酸化炭素
および酸素と反応させて炭酸エステルを製造する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a carbonic ester by reacting an aliphatic alcohol with carbon monoxide and oxygen in the presence of a catalyst.
〔従来の技術及び発明が解決しようとする課題〕炭酸エ
ステルは、医農薬製造用中間体やエンジニアリングプラ
スチックス製造用中間体および溶媒として工業上有用な
物質である。炭酸エステルの製造法としては■銅塩触媒
の存在下にアルコールを一酸化炭素および酸素と反応さ
せて製造する方法（特公昭６Ｏ−５８７３９） 、■パ
ラジウムと銅塩と複素架橋環式第三級アミンよりなる触
媒存在下、アルコールを一酸化炭素および酸素と反応さ
せて製造する方法（特公昭６１−８８１６゜特公昭６ｌ
−４３３３８）などが知られている。特に■の方法では
助触媒としてアルカリ金属アルコキシド又はアルカ゛す
金属水酸化物を用いることが提案されている。[Prior Art and Problems to be Solved by the Invention] Carbonic esters are industrially useful substances as intermediates and solvents for producing pharmaceuticals and agricultural chemicals, intermediates for producing engineering plastics, and solvents. Methods for producing carbonic esters include: ■ A method of producing alcohol by reacting it with carbon monoxide and oxygen in the presence of a copper salt catalyst (Japanese Patent Publication No. 6O-58739), ■ Palladium, copper salt, and hetero-bridged cyclic tertiary A method of producing alcohol by reacting it with carbon monoxide and oxygen in the presence of an amine catalyst (Special Publication No. 61-8816゜Special Publication No. 61)
-43338) are known. In particular, in method (2), it has been proposed to use an alkali metal alkoxide or alkali metal hydroxide as a cocatalyst.
しかし、これらの製造方法にはそれぞれ次の様な問題点
が残されている。即ち上記■の方法は一酸化炭素の燃焼
損失が大きいこと、及び反応速度が小さいために巨大な
反応容器を用いるか、あるいは高い一酸化炭素分圧およ
び酸素分圧が必要であることであり、父上記■の方法は
一酸化炭素の燃焼損失が大きいこと、及び炭酸ニス５チ
ルの生成量が少ないことなどである。However, each of these manufacturing methods still has the following problems. In other words, method (1) above has a large combustion loss of carbon monoxide and a low reaction rate, so it requires the use of a huge reaction vessel or high partial pressures of carbon monoxide and oxygen. The disadvantages of method (2) above are that the combustion loss of carbon monoxide is large and the amount of varnish carbonate produced is small.
本発明はこの様な先行技術をふまえて、アルコール、−
酸化炭素、酸素から炭酸エステルを製造する方法におい
て、更に一酸化炭素の燃焼損失等による選択率の低下を
低減し、かつ高められた量の炭酸エステルを得る方法を
提供することを目的とする。The present invention is based on such prior art, alcohol, -
It is an object of the present invention to provide a method for producing carbonic ester from carbon oxide and oxygen, which further reduces the decrease in selectivity due to combustion loss of carbon monoxide, and obtains an increased amount of carbonic ester.
本発明者等は、パラジウム・銅レドックス触媒系を用い
てアルコール、−酸化炭素、酸素より炭酸エステルを得
る反応について鋭意努力して助触媒の探索をおこなった
ところ、塩基性アルカリ土類金属塩が助触媒として、炭
酸エステルの生成量を増加させる点と一酸化炭素の燃焼
損失を低減させる点で優れていることを見いだして、本
発明に到ったものである。The present inventors have made extensive efforts to search for co-catalysts for the reaction of producing carbonic acid esters from alcohol, -carbon oxide, and oxygen using a palladium-copper redox catalyst system, and found that basic alkaline earth metal salts were found. The present invention was developed based on the discovery that the cocatalyst is excellent in increasing the amount of carbonate ester produced and reducing the combustion loss of carbon monoxide.
即ち本発明は、■白金属化合物、■銅塩および、（３）
塩基性アルカリ土類金属塩からなる触媒の存在下に脂肪
族アルコールを一酸化炭素および酸素と反応させること
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。That is, the present invention comprises (1) a white metal compound, (2) a copper salt, and (3)
The present invention provides a method for producing a carbonate ester, which is characterized by reacting an aliphatic alcohol with carbon monoxide and oxygen in the presence of a catalyst consisting of a basic alkaline earth metal salt.
脂肪族アルコールとしては飽和脂肪族アルコール、例え
ば、メタノール、エタノール、ブタノールなどが使用さ
れ、通常は溶媒を兼ねて過剰量使用される。As the aliphatic alcohol, saturated aliphatic alcohols such as methanol, ethanol, butanol, etc. are used, and are usually used in an excess amount to also serve as a solvent.
白金属化合物としては、ルテニウム、ロジウム、パラジ
ウムなどの化合物が用いられ、なかでも、パラジウムが
好ましい。As the white metal compound, compounds such as ruthenium, rhodium, and palladium are used, and among them, palladium is preferable.
白金属化合物は単体としても、或いはハロゲン化物、硝
酸塩、硫酸塩、燐酸塩、酢酸塩、スルホン酸塩などの金
属塩としても使用される。The platinum metal compound can be used alone or as a metal salt such as a halide, nitrate, sulfate, phosphate, acetate, or sulfonate.
又、活性炭、グラファイト、アルミナ、シリカアルミナ
、珪藻土、アスベスト、イオン交換樹脂、珪酸塩、ポリ
ビニールピリジン、マグネシア、カルシア等の担体に担
持しても使用される。It can also be used when supported on carriers such as activated carbon, graphite, alumina, silica alumina, diatomaceous earth, asbestos, ion exchange resins, silicates, polyvinylpyridine, magnesia, and calcia.
銅塩は、塩化第一銅、塩化第二銅などのハロゲン化物の
ほか、オキシ塩化銅や硝酸塩、硫酸塩、スルホン酸塩、
酢酸塩、安息香酸塩、蓚酸塩、燐酸塩などが使用される
。Copper salts include halides such as cuprous chloride and cupric chloride, as well as copper oxychloride, nitrates, sulfates, sulfonates,
Acetate, benzoate, oxalate, phosphate, etc. are used.
塩基性アルカリ土類金属塩としては、水酸化ベリリウム
、ベリリウムメトキシド、ベリリウムエトキシド、水酸
化マグネシウム、マグネシウムメトキシド、マグネシウ
ムイソプロポキシド、水酸化カルシウム、カルシウムメ
トキシド、カルシウムブトキシド、水酸化ストロンチウ
ム、水酸化バリウムなどが使用される。Basic alkaline earth metal salts include beryllium hydroxide, beryllium methoxide, beryllium ethoxide, magnesium hydroxide, magnesium methoxide, magnesium isopropoxide, calcium hydroxide, calcium methoxide, calcium butoxide, strontium hydroxide, Barium hydroxide is used.
また、本発明の触媒には、助触媒として塩基性アルカリ
土類金属塩を用いたときに、銅塩の溶解度を向上させる
ためにアルカリ土類金属ノ１０ゲン化物を併用すること
もできる。Furthermore, when a basic alkaline earth metal salt is used as a cocatalyst, an alkaline earth metal decogenide can be used in combination with the catalyst of the present invention in order to improve the solubility of the copper salt.
アルカリ土類金属ハロゲン化物としては、アルカリ土類
金属の塩化物、臭化物、ヨウ化物などが使用される。As the alkaline earth metal halide, chlorides, bromides, iodides, etc. of alkaline earth metals are used.
本発明の実施に当っては、通常は過剰量の原料の脂肪族
アルコールや、反応によって生成する炭酸エステルが溶
媒を兼ねて使用されるが、別に溶媒を使用することもで
きる。溶媒としては、ベンゼン、トルエン、キシレン等
の芳香族炭化水素、オクタン、デカン等の脂肪族炭化水
素、ジブチルエーテル、テトラヒドロフラン、エチレン
グリコールジメチルエーテル、テトラエチレングリコー
ルジメチルエーテル等のエーテル、酢酸エチル、安息香
酸メチル等のエステル、アセトニ） ＋Ｊル、ベンジエ
） ＩＪル等のニトリル、Ｎ−メチルピロリドン、Ｎ、
Ｎ−ジメチルホルムアミド等のアミド、エチレンジメチ
ルウレア等の尿素などが用いられる。In carrying out the present invention, an excess amount of aliphatic alcohol as a raw material or a carbonate ester produced by the reaction is usually used as a solvent, but a separate solvent can also be used. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, ethers such as dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, ethyl acetate, and methyl benzoate. esters, acetonyl), nitriles such as IJ, N-methylpyrrolidone, N,
Amides such as N-dimethylformamide, ureas such as ethylenedimethylurea, and the like are used.
本発明方法は回分式あるいは液相連続式で通常以下の条
件で実施される。温度条件は５０〜２００℃であり、−
酸化炭素分°圧が０．５〜２０ｋｇ／ｃｍ２、酸素分圧
が０．０５〜１０ｋｇ／ｃｍ２の範囲で使用される。The method of the present invention is carried out either batchwise or continuously in a liquid phase under the following conditions. The temperature conditions are 50 to 200℃, -
The carbon oxide partial pressure is used in the range of 0.5 to 20 kg/cm2, and the oxygen partial pressure is used in the range of 0.05 to 10 kg/cm2.
白金属化合物の使用量は、通常、反応溶液ｉｆにつき０
．０００１〜１０ｇの範囲で使用される。金属銅または
その塩の使用量は白金属化合物の０．５〜１００００重
量倍の範囲で使用される。塩基性アルカリ土類金属塩の
使用量は白金属化合物の０．５〜２００００重量倍の範
囲で使用される。アルカリ土類金属塩を併用する場合は
白金属化合物の０．５〜２００００重量倍の範囲の使用
量が好ましい。The amount of platinum metal compound used is usually 0 per reaction solution if
．． It is used in the range of 0001 to 10g. The amount of metallic copper or its salt used is in the range of 0.5 to 10,000 times the weight of the platinum metal compound. The basic alkaline earth metal salt is used in an amount of 0.5 to 20,000 times the weight of the white metal compound. When an alkaline earth metal salt is used in combination, the amount used is preferably 0.5 to 20,000 times the weight of the white metal compound.
本発明の方法によれば炭酸エステルの生成量を増加させ
、しかも選択率の低下を低減させることが出来る。According to the method of the present invention, it is possible to increase the amount of carbonate ester produced and to reduce the decrease in selectivity.
次に発明の詳細について以下に例示するいくつかの実施
例で説明するが、これらの実施例は本発明を限定するも
のではない。Next, the details of the invention will be explained with reference to some examples illustrated below, but these examples are not intended to limit the invention.
実施例１
テフロン加工した撹拌機付き３８０ｍｆのオートクレー
ブに塩化パラジウム９．３ｍｍｏｌ 、塩化第一銅７．
５ｍｍｏＩ 、塩化マグネシウム７．５ｍｍｏ１ 、７
ダネシウムメトキシド７、５ｍｍｏｌおよびメタノール
４０ｍ１を挿入し、オートクレーブ内を窒素で置換した
。次いで窒素を５．７ｋｇ／ｃｍ” −酸化炭素を３
．６ｋｇ／ｃｍ２．３３ｍｏ１％の酸素を含む酸素・ア
ルゴン混合ガスを２．７ｋｇ／ｃｍ２圧大したのち、オ
ートクレーブを１３０℃に保ち、１時間反応させたのち
、常温まで冷却し放圧して、反応ガスおよび反応生成液
をガスクロマトグラフィーにより分析し、炭酸ジメチル
の生成量及び−酸化炭素の反応量を定堡した。その結果
得られた炭酸ジメチルは１２゜Ｑｍｍｏｌであり、Ｓ
ＣＯ−ＤＭＣ（注）は６３％であった。Example 1 9.3 mmol of palladium chloride and 7.0 mmol of cuprous chloride were placed in a 380 mf autoclave equipped with a Teflon-treated stirrer.
5 mmol, magnesium chloride 7.5 mmol, 7
Danesium methoxide 7.5 mmol and methanol 40 ml were inserted, and the inside of the autoclave was purged with nitrogen. Then nitrogen at 5.7 kg/cm” and carbon oxide at 3
．． After increasing the pressure of oxygen/argon mixed gas containing 6 kg/cm2.33 mo1% oxygen to 2.7 kg/cm2, the autoclave was kept at 130°C and reacted for 1 hour, then cooled to room temperature and depressurized to release the reaction gas. The reaction product liquid was analyzed by gas chromatography to determine the amount of dimethyl carbonate produced and the amount of carbon oxide reacted. The resulting dimethyl carbonate was 12°Qmmol, S
CO-DMC (note) was 63%.
（注）
一酸化炭素の炭酸ジメチルへの選択率（Ｓ ＣｏＤＭＣ
）は、下式に従って示される。(Note) Selectivity of carbon monoxide to dimethyl carbonate (S CoDMC
) is shown according to the formula below.
比較例１
実施例１において塩化マグネシウムとマグネシウムメチ
ラートの代わりに塩化カリウム１５ｍｍｏｌ及びカリウ
ムメトキシド１５＋ｔ＋ｍｏｌを使用した以外は、同じ
操作を行った。その結果得られた炭酸ジメチルは４．２
ｍｍｏｌ であり、Ｓ ＣｏＣｏ−１ｌは２４％であっ
た。Comparative Example 1 The same operation as in Example 1 was performed except that 15 mmol of potassium chloride and 15+t+mol of potassium methoxide were used instead of magnesium chloride and magnesium methylate. The resulting dimethyl carbonate is 4.2
mmol and S CoCo-1l was 24%.
実施例２〜６
塩化第一銅と塩化マグネシウムとマグネシウムメトキシ
ドの量を変えたこと以外は実施例１と同じ操作を行った
。その結果は表−１に示す通りであった。Examples 2 to 6 The same operation as in Example 1 was performed except that the amounts of cuprous chloride, magnesium chloride, and magnesium methoxide were changed. The results were as shown in Table-1.
実施例７
塩化マグネシウムの使用量を３．Ｑｍｍｏｌ 、マグネ
シウムメトキシドの代わりに水酸化マグネシムウを７．
５ｍｍｏｌ、−酸化炭素の分圧を２．７ｋｇ／ｃ＋＋＋
”、酸素・アルゴン混合ガスの分圧を４ ｋｇ／ｃｍ”
、窒素の分圧を１３．３ｋｇ／ｃｍ２に変えたこと以外
は実施例１と同じ操作を行った。その結果、得られた炭
酸ジメチルは１８．３ｍｍｏｌであり、Ｓ ＣＯ−ＤＭ
Ｃは５９％であった。Example 7 The amount of magnesium chloride used was 3. Qmmol, magnesium hydroxide instead of magnesium methoxide 7.
5 mmol, - the partial pressure of carbon oxide is 2.7 kg/c+++
", partial pressure of oxygen/argon mixed gas is 4 kg/cm"
The same operation as in Example 1 was performed except that the partial pressure of nitrogen was changed to 13.3 kg/cm2. As a result, the dimethyl carbonate obtained was 18.3 mmol, and S CO-DM
C was 59%.
実施例８
塩化マグネシウムと水酸化マグネシウムの代わりに水酸
化カルシウムだけ７．５ｍｍｏｌ に変えたこと以外は
実施例７と同じ操作を行った。その結果、得られた炭酸
ジメチルは２０．４ｍｍｏｌであり、Ｓ Ｃｏ−ＤＭＣ
は６８％であった。Example 8 The same operation as in Example 7 was performed except that 7.5 mmol of calcium hydroxide was used instead of magnesium chloride and magnesium hydroxide. As a result, the dimethyl carbonate obtained was 20.4 mmol, and S Co-DMC
was 68%.
比較例２
水酸化カルシウムの代わりに水酸化カリウムを１５．
Ｑｍｍｏｌを用いたこと以外は実施例８と同じ操作を行
った。その結果、得られた炭酸ジメチルはｌ、 １ｍｍ
ｏｌであり、Ｓ ＣＯ−ＤＭＣは３％であった。Comparative Example 2 Potassium hydroxide was used instead of calcium hydroxide.
The same operation as in Example 8 was performed except that Qmmol was used. As a result, the dimethyl carbonate obtained was 1, 1 mm.
ol and S CO-DMC was 3%.
Claims (1)
アルカリ土類金属塩からなる触媒の存在下に脂肪族アル
コールを一酸化炭素および酸素と反応させることを特徴
とする炭酸エステルの製造法。A carbonate ester characterized by reacting an aliphatic alcohol with carbon monoxide and oxygen in the presence of a catalyst consisting of (1) a platinum metal compound, (2) a copper salt, and (3) a basic alkaline earth metal salt. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168594A JPH0219346A (en) | 1988-07-06 | 1988-07-06 | Production of carbonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63168594A JPH0219346A (en) | 1988-07-06 | 1988-07-06 | Production of carbonic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0219346A true JPH0219346A (en) | 1990-01-23 |
Family
ID=15870950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63168594A Pending JPH0219346A (en) | 1988-07-06 | 1988-07-06 | Production of carbonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0219346A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081182C (en) * | 1998-03-12 | 2002-03-20 | 华中理工大学 | Liquid phase oxidation and carbonylation process synthesizing dimethyl carbonate |
| CN104098472A (en) * | 2013-04-08 | 2014-10-15 | 泉州恒河化工有限公司 | Method for producing safe and environment-friendly carbonic ester series mixed solvents |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6413058A (en) * | 1987-07-04 | 1989-01-17 | Daicel Chem | Production of carbonic acid ester |
| JPH01287062A (en) * | 1988-02-16 | 1989-11-17 | Daicel Chem Ind Ltd | Production of carbonic acid ester |
-
1988
- 1988-07-06 JP JP63168594A patent/JPH0219346A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6413058A (en) * | 1987-07-04 | 1989-01-17 | Daicel Chem | Production of carbonic acid ester |
| JPH01287062A (en) * | 1988-02-16 | 1989-11-17 | Daicel Chem Ind Ltd | Production of carbonic acid ester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081182C (en) * | 1998-03-12 | 2002-03-20 | 华中理工大学 | Liquid phase oxidation and carbonylation process synthesizing dimethyl carbonate |
| CN104098472A (en) * | 2013-04-08 | 2014-10-15 | 泉州恒河化工有限公司 | Method for producing safe and environment-friendly carbonic ester series mixed solvents |
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