JPH0662485B2 - Method for producing carboxylic acid - Google Patents
Method for producing carboxylic acidInfo
- Publication number
- JPH0662485B2 JPH0662485B2 JP61005748A JP574886A JPH0662485B2 JP H0662485 B2 JPH0662485 B2 JP H0662485B2 JP 61005748 A JP61005748 A JP 61005748A JP 574886 A JP574886 A JP 574886A JP H0662485 B2 JPH0662485 B2 JP H0662485B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- acid
- catalyst
- reaction
- sulfuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 55
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 16
- 150000003464 sulfur compounds Chemical class 0.000 description 12
- -1 ester is contained Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 description 1
- ZQZXWCZCICKWEQ-UHFFFAOYSA-N 1-chloro-2-methylbutan-2-ol Chemical compound CCC(C)(O)CCl ZQZXWCZCICKWEQ-UHFFFAOYSA-N 0.000 description 1
- JNOZGFXJZQXOSU-UHFFFAOYSA-N 1-chloro-2-methylpropan-2-ol Chemical compound CC(C)(O)CCl JNOZGFXJZQXOSU-UHFFFAOYSA-N 0.000 description 1
- NPMHELYJLOUPIZ-UHFFFAOYSA-N 2,2,3,4-tetramethylpentanoic acid Chemical compound CC(C)C(C)C(C)(C)C(O)=O NPMHELYJLOUPIZ-UHFFFAOYSA-N 0.000 description 1
- OWEMTCOXFULTNW-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanoic acid Chemical compound CC(C)C(C)(C(C)C)C(O)=O OWEMTCOXFULTNW-UHFFFAOYSA-N 0.000 description 1
- FOTVZXLILUCNDJ-UHFFFAOYSA-N 2,5,5-trimethylhexanoic acid Chemical compound OC(=O)C(C)CCC(C)(C)C FOTVZXLILUCNDJ-UHFFFAOYSA-N 0.000 description 1
- SXJBHJCKWQIWHA-UHFFFAOYSA-N 2-ethyl-2,3,3-trimethylbutanoic acid Chemical compound CCC(C)(C(O)=O)C(C)(C)C SXJBHJCKWQIWHA-UHFFFAOYSA-N 0.000 description 1
- YJMLTIGYXZLKLY-UHFFFAOYSA-N 2-ethyl-4,4-dimethylpentanoic acid Chemical compound CCC(C(O)=O)CC(C)(C)C YJMLTIGYXZLKLY-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N 2t-nonene Natural products CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 150000001935 cyclohexenes Chemical group 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YCBSHDKATAPNIA-UHFFFAOYSA-N non-3-ene Chemical compound CCCCCC=CCC YCBSHDKATAPNIA-UHFFFAOYSA-N 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、カルボン酸の製造方法に関し、さらに詳し
く言うと、硫酸触媒の存在下にオレフィンまたはアルコ
ールと水とを反応させる、いわゆるコッホ反応利用のカ
ルボン酸の製造法方法において、不純物である硫黄化合
物などの生成量を低減させることのできるカルボン酸の
製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a carboxylic acid, more specifically, a so-called Koch reaction utilizing an olefin or alcohol with water in the presence of a sulfuric acid catalyst. In the method for producing a carboxylic acid, the method for producing a carboxylic acid capable of reducing the amount of impurities such as a sulfur compound produced.
［従来の技術およびその問題点］ 従来より、硫酸触媒の存在下に、オレフィンまたはアル
コールと一酸化炭素と水とを反応さるコッホ反応は周知
であるが、得られる反応生成物中には、硫酸エステルな
どの硫黄化合物が含まれるために、得られるカルボン酸
は悪臭がしたり、着色したりするなどの欠点がある。[Prior Art and its Problems] The Koch reaction in which an olefin or alcohol is reacted with carbon monoxide and water in the presence of a sulfuric acid catalyst is well known, but the reaction product obtained contains sulfuric acid. Since the sulfur compound such as ester is contained, the obtained carboxylic acid has drawbacks such as bad odor and coloring.
この欠点を解消するために、通常、コッホ反応の生成物
から硫酸触媒を分離して得た粗製脂肪酸を蒸留するに先
だって酸化剤を接触させる精製操作が提案されている
（たとえば特公昭48-16897号公報参照）。In order to eliminate this drawback, a purification operation in which an oxidizing agent is contacted with the crude fatty acid obtained by separating the sulfuric acid catalyst from the product of the Koch reaction is usually proposed (for example, JP-B-48-16897). (See the official gazette).
しかしながら、精製操作は、工業的製法として、できる
ことなら酸化剤のような新たな成分を添加しない方が好
ましいので、この後処理工程として酸化剤添加のような
精製操作を省こうとすると、硫酸触媒の濃度を低下させ
て、カルボン酸中に混入する硫黄化合物の生成する量を
減少させねばならず、そうすると、カルボン酸の生成も
抑制されてしまう。However, the refining operation is an industrial production method, and it is preferable not to add a new component such as an oxidizing agent if possible. Therefore, if it is attempted to omit the refining operation such as adding an oxidizing agent as a post-treatment step, the sulfuric acid catalyst Must be reduced to reduce the amount of sulfur compounds mixed in the carboxylic acid, which in turn suppresses the generation of carboxylic acids.
［発明の目的］ この発明は前記事情に基いてなされたものである。[Object of the Invention] The present invention has been made based on the above circumstances.
この発明の目的は、酸化剤を使用する生成操作を採用す
ることなく、生成するカルボン酸中に混入する硫黄化合
物の量を低減させると共に、硫酸触媒を使用したときと
同様にカルボン酸の収率が高い、コッホ反応利用のカル
ボン酸の製造方法を提供することである。The object of the present invention is to reduce the amount of sulfur compounds mixed in the carboxylic acid to be produced without adopting a production operation using an oxidizing agent, and to obtain the yield of the carboxylic acid in the same manner as when a sulfuric acid catalyst is used. It is intended to provide a method for producing a carboxylic acid utilizing the Koch reaction, which has a high temperature.
［前記目的を達成するための手段］ 前記目的を達成するためのこの発明の要旨は、オレフィ
ンまたはアルコールと、一酸化炭素と、水とを反応させ
るカルボン酸の製造方法において、硫酸およびリン酸か
らなる触媒または硫酸、リン酸および金属化合物からな
る触媒を使用することを特徴とするカルボン酸の製造方
法である。[Means for Achieving the Above-mentioned Object] The gist of the present invention for achieving the above-mentioned object is to provide a method for producing a carboxylic acid in which an olefin or an alcohol, carbon monoxide, and water are reacted with each other. And a catalyst composed of sulfuric acid, phosphoric acid and a metal compound are used.
この発明の方法に使用するオレフィンは、いわゆるコッ
ホ反応に使用することができる全ての公知の原料を使用
することができる。たとえばエチレン、プロピレン、ｎ
−ブチレン、イソブチレン、ジイソブチレン、１−ヘキ
セン、２−ヘキセン、３−ヘキセン、１−ヘプテン、２
−ヘプテン、３−ヘプテン、１−オクテン、２−オクテ
ン、３−オクテン、４−オクテン、１−ノネン、２−ノ
ネン、３−ノネン、４−ノネンおよびヘキサデセンなど
の直鎖状または分岐鎖を有するオレフィン、並びにシク
ロヘキセン、およびメチル基、エチル基などのアルキル
基あるいはビニル基などを置換したシクロヘキセンなど
のシクロオレフィンが挙げられる。さらにまた、ブタジ
エンなどのジオレフィン、アリクロライド、メタクリル
クロライドなどのハロゲン化オレフィンも使用すること
ができる。この発明では、前記各種のオレフィンの一種
を選択し、あるいは二種以上の混合物や異性体混合物の
状態で使用することもできる。As the olefin used in the method of the present invention, all known raw materials that can be used in the so-called Koch reaction can be used. For example ethylene, propylene, n
-Butylene, isobutylene, diisobutylene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2
-Has a straight or branched chain such as heptene, 3-heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene and hexadecene. Examples thereof include olefins, cyclohexene, and cycloolefins such as cyclohexene substituted with an alkyl group such as a methyl group or an ethyl group or a vinyl group. Furthermore, diolefins such as butadiene and halogenated olefins such as alichloride and methacryl chloride can also be used. In the present invention, one of the above-mentioned various olefins may be selected or used in the form of a mixture of two or more kinds or an isomer mixture.
もっとも、前記各種のオレフィンの中でも、炭素数４〜
15の直鎖状または分岐鎖を有するオレフィンが好まし
く、特にジイソブチレンが好ましい。However, among the various olefins mentioned above, the number of carbon atoms is 4 to
Olefins having 15 straight or branched chains are preferred, and diisobutylene is particularly preferred.
また、前記アルコールとしては、たとえばエタノール、
ｎ−プロパノール、イソプロパノール、ｎ−ブタノー
ル、イソブタノール、tert−ブタノールなどの脂肪族ア
ルコール；ｎ−ヘキサノール、sec −ヘキサノール、te
rt−ヘキサノール、ヘプタノール、オクタノールなどの
高級アルコール、およびこれらの混合物を使用すること
ができる。さらに、シクロペンタノール、シクロヘキサ
ノールなどの環状アルコールなども使用することができ
る。また、２−モノクロルメチル−２−プロパノール、
２−モノクロルメチル−２−ブタノールなどのハロヒド
リンも原料として使用することができる。炭素数４以上
の脂肪族アルコールが好ましい。Further, as the alcohol, for example, ethanol,
Aliphatic alcohols such as n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol; n-hexanol, sec-hexanol, te
Higher alcohols such as rt-hexanol, heptanol, octanol, and mixtures thereof can be used. Furthermore, cyclic alcohols such as cyclopentanol and cyclohexanol can also be used. Also, 2-monochloromethyl-2-propanol,
A halohydrin such as 2-monochloromethyl-2-butanol can also be used as a raw material. Aliphatic alcohols having 4 or more carbon atoms are preferred.
一酸化炭素は、純粋のものが最も好ましいが、水性ガ
ス、発生炉ガス、コークス炉ガスなどから得られる一酸
化炭素含有ガスも使用することができる。The carbon monoxide is most preferably pure, but carbon monoxide-containing gas obtained from water gas, generator gas, coke oven gas or the like can also be used.
水は、純粋のものが最も好もしく、蒸留水、イオン交換
水などを使用することができる。Pure water is most preferable, and distilled water, ion-exchanged water or the like can be used.
この発明で使用する触媒は、硫酸およびリン酸または硫
酸、リン酸および金属化合物からなる。硫酸およびリン
酸よりなる触媒を使用すると、生成物中の硫黄化合物の
含有量を低減することができ、硫酸およびリン酸にさら
に金属化合物を加えてなる触媒は、生成物中の硫黄化合
物の含有量を低減する効果の外に生成カルボン酸の収率
の向上を図ることができる。The catalyst used in this invention consists of sulfuric acid and phosphoric acid or sulfuric acid, phosphoric acid and metal compounds. The use of a catalyst composed of sulfuric acid and phosphoric acid makes it possible to reduce the content of sulfur compounds in the product, and a catalyst prepared by adding a metal compound to sulfuric acid and phosphoric acid can reduce the content of sulfur compounds in the product. In addition to the effect of reducing the amount, the yield of carboxylic acid produced can be improved.
前記硫酸は、触媒中の濃度として、通常、30〜90重量％
が好ましく、特に40〜80重量％が好ましい。The sulfuric acid is usually contained in the catalyst at a concentration of 30 to 90% by weight.
Is preferable, and 40 to 80% by weight is particularly preferable.
また、前記リン酸の、触媒中の濃度としては、通常５〜
70重量％であり、好ましくは15〜55重量％である。The concentration of the phosphoric acid in the catalyst is usually 5 to
It is 70% by weight, preferably 15 to 55% by weight.
触媒の調製方法については、特に制限がなく、たとえば
硫酸とリン酸とを通常の混合操作により予め混合してお
いて硫酸およびリン酸含有の触媒液を調製しておき、触
媒使用時に、この触媒液をそのまま、あるいは稀釈して
使用し、さらに、この触媒液に金属化合物を添加混合し
てからこの金属化合物含有の触媒液を反応系に添加する
ようにしても良い。The method for preparing the catalyst is not particularly limited, and, for example, sulfuric acid and phosphoric acid are mixed in advance by a normal mixing operation to prepare a catalyst solution containing sulfuric acid and phosphoric acid. The liquid may be used as it is or diluted, and further, the metal compound may be added to and mixed with the catalyst liquid, and then the catalyst liquid containing the metal compound may be added to the reaction system.
また、硫酸とリン酸と金属化合物とを予め混合調製して
おき、この金属化合物含有の触媒液を前述のようにして
使用しても良い。Alternatively, sulfuric acid, phosphoric acid, and a metal compound may be mixed and prepared in advance, and the catalyst liquid containing the metal compound may be used as described above.
さらにまた、原料であるオレフィンまたはアルコール、
一酸化炭素および水の混合物に、硫酸、リン酸必要に応
じて金属化合物それぞれを同時にあるいは順次に添加し
ても良い。なお、順次に添加する場合、触媒成分の添加
順序に制限がない。そしてまた、反応容器中に触媒成分
を添加しておき、そこに原料を添加するようにしても良
い。Furthermore, the raw material olefin or alcohol,
Sulfuric acid and phosphoric acid may be added to the mixture of carbon monoxide and water at the same time or sequentially as required. In addition, when they are added sequentially, there is no limitation on the order of adding the catalyst components. Further, the catalyst component may be added to the reaction vessel and the raw material may be added thereto.
いずれにしても、オレフィンまたはアルコールと一酸化
炭素と水とが反応する際に、硫酸およびリン酸からなる
触媒または硫酸とリン酸と金属化合物とからなる触媒が
存在するような状態となっていれば良い。In any case, when the olefin or alcohol, carbon monoxide, and water react with each other, a catalyst containing sulfuric acid and phosphoric acid or a catalyst containing sulfuric acid, phosphoric acid and a metal compound is present. Good.
前記金属化合物としては、たとえば酸化第１銅、酸化第
１銀、硫酸銀、酸化第１金などのほかに金属銅、二価の
銅化合物と金属銅との混合物などを使用することができ
るが、好ましいのは酸化第１銅、酸化第１銀である。As the metal compound, for example, in addition to cuprous oxide, silver (I) oxide, silver sulfate, gold (I) oxide, etc., metallic copper, a mixture of a divalent copper compound and metallic copper, etc. can be used. Preferred are cuprous oxide and silver oxide.
触媒の一成分として、前記金属化合物特に酸化第１銅を
使用するときは、この金属の使用量は、硫酸とリン酸と
の混合物の重量に対して、通常0.1 〜４重量％であり、
好ましくは0.2 〜２重量％である。When the metal compound, particularly cuprous oxide, is used as one component of the catalyst, the amount of the metal used is usually 0.1 to 4% by weight based on the weight of the mixture of sulfuric acid and phosphoric acid.
It is preferably 0.2 to 2% by weight.
触媒の使用量は、オレフィンまたはアルコールの供給量
0.3 モルに対して75ｍｌ以上であればよい。The amount of catalyst used is the amount of olefin or alcohol supplied
It may be 75 ml or more with respect to 0.3 mol.
前記触媒の存在下における、これらオレフィンまたはア
ルコールと一酸化炭素と水との反応は、回分式、半回分
式、連続式のいずれの形式で、反応系で所定反応温度、
所定反応圧力下で、行なうことができる。The reaction of these olefins or alcohols with carbon monoxide and water in the presence of the catalyst is a batch system, a semi-batch system, or a continuous system, at a predetermined reaction temperature in the reaction system,
It can be performed under a predetermined reaction pressure.
反応温度は、通常−10〜80℃であり、好ましくは０〜30
℃である。反応温度は−10℃より低いと、反応速度が低
下するので好ましくなく、80℃よりも高いと、硫酸スラ
ッジ、硫酸エステルなどが増加することがあるので好ま
しくない。The reaction temperature is usually −10 to 80 ° C., preferably 0 to 30.
℃. If the reaction temperature is lower than -10 ° C, the reaction rate is lowered, which is not preferable, and if it is higher than 80 ° C, sulfuric acid sludge, sulfuric acid ester, etc. may increase, which is not preferable.
反応圧力は、通常０〜100 Ｋｇ／ｃm2Ｇまで十分であ
り、好ましくは10〜15Ｋｇ／ｃm2である。10〜15Ｋｇ／
ｃm2の反応圧力にすると、前記低濃度の硫酸を使用する
ことによるカルボン酸の収率の低下を防止することがで
きるからである。The reaction pressure is usually sufficient to 0~100 Kg / cm 2 G, preferably 10-15 kg / cm 2. 10-15 kg /
This is because the reaction pressure of cm 2 can prevent the decrease in the yield of carboxylic acid due to the use of the low concentration sulfuric acid.
反応時間は、通常10〜120 分で十分である。A reaction time of 10 to 120 minutes is usually sufficient.
この発明の方法では、コッホ反応により目的物であるカ
ルボン酸、副生成物としてオレフィン重合物などが生成
するのであるが、たとえばジイソブチレンを原料とする
場合、2,2,4,4 −テトラメチルペンタン酸、2,2,3,4 −
テトラメチルペンタン酸、２−エチル−2,3,3 −トリメ
チルブタン酸、2,5,5 −トリメチル−ヘキサン酸、２−
エチル−4,4 −ジメチル−ペンタン酸、２−イソプロピ
ル−3,2 −ジメチルブタン酸などの混合物であるところ
の、炭素数９のカルボン酸を主成分とするカルボン酸混
合物が、目的生成物として得られる。In the method of the present invention, a Koch reaction produces a carboxylic acid which is a target product, and an olefin polymer as a by-product.For example, when diisobutylene is used as a raw material, 2,2,4,4-tetramethyl is used. Pentanoic acid, 2,2,3,4-
Tetramethylpentanoic acid, 2-ethyl-2,3,3-trimethylbutanoic acid, 2,5,5-trimethyl-hexanoic acid, 2-
A carboxylic acid mixture containing a carboxylic acid having 9 carbon atoms as a main component, which is a mixture of ethyl-4,4-dimethyl-pentanoic acid, 2-isopropyl-3,2-dimethylbutanoic acid, etc. can get.
反応の終了後、得られる反応生成液からたとえばｎ−ヘ
キサンなどの有機溶媒で抽出し、水洗し、抽出溶媒を除
去することによって、目的とするカルボン酸を得ること
ができる。After completion of the reaction, the desired carboxylic acid can be obtained by extracting the reaction product solution with an organic solvent such as n-hexane and washing with water to remove the extraction solvent.
この発明の方法では、反応生成液中には、触媒の一成分
である硫酸に由来する硫黄化合物の生成が少なく、した
がって、カルボン酸中への硫黄化合物の混入も少なくな
って、着色、悪臭のないカルボン酸を得ることができ
る。According to the method of the present invention, the reaction product liquid contains less sulfur compounds derived from sulfuric acid, which is one component of the catalyst, and therefore less of the sulfur compounds is mixed into the carboxylic acid. No carboxylic acid can be obtained.
前記触媒を使用すると何故硫黄化合物の生成を抑制する
ことができるのか、その詳細な理由は不明である。The detailed reason why the production of sulfur compounds can be suppressed by using the catalyst is unknown.
しかし、硫黄化合物の生成を制御する機構についての理
論的解明がなされていなくとも、この発明の方法による
と、硫黄化合物の生成を抑制して、悪臭、着色のない、
しかも高収率でカルボン酸を製造することができるので
あるから、この発明の方法は、工業的に有利なカルボン
酸の製造方法と言える。However, according to the method of the present invention, even if a theoretical elucidation of the mechanism for controlling the production of the sulfur compound has not been made, the production of the sulfur compound is suppressed, and there is no bad odor or coloring.
Moreover, since the carboxylic acid can be produced in a high yield, the method of the present invention can be said to be an industrially advantageous method for producing a carboxylic acid.
［発明の効果］ この発明によると、 (1) 副反応生成物である硫黄化合物の生成量が少なく
て、それだけ着色、悪臭の少ないカルボン酸を製造する
ことができ、 (2) 硫酸触媒を使用した場合と同様に高収率でカルボ
ン酸を製造することができる、 などの優れた利点を有するカルボン酸の製造方法を提供
することができる。EFFECTS OF THE INVENTION According to the present invention, (1) a carboxylic acid having a small amount of a sulfur compound as a by-product, which is less colored and malodorous, can be produced, and (2) a sulfuric acid catalyst is used. As in the case of the above, it is possible to provide a method for producing a carboxylic acid, which has excellent advantages such as the ability to produce a carboxylic acid in a high yield.
［実施例］ 次にこの発明の実施例および比較例を示してこの発明を
さらに詳述する。EXAMPLES Next, the present invention will be described in more detail by showing Examples and Comparative Examples of the present invention.
（実施例１〜５、比較例１〜３） 第１表に示す濃度の硫酸およびリン酸（比較例ではリン
酸を使用せず。）の水溶液と第１表に示す量の酸化第１
銅とからなり、第１表に示す触媒量の触媒を、反応容器
内に仕込み、この反応容器内を十分に一酸化炭素で置換
してから、これを攪拌しながら、飽和になるまで一酸化
炭素を吸収させた。次いで、反応容器内の一酸化炭素圧
を15Ｋｇ／ｃm2に維持しつつ、この反応容器内に、第１
表に示す反応条件で、ジイソブチレンと一酸化炭素とを
反応させた。なお、反応中に消費されて減少した一酸化
炭素は、その分新たに補給した。1.5 時間の反応時間の
経過後、ジイソブチレンの補給を停止し、そのままさら
に１時間攪拌した。その後、等量の水を加えた。(Examples 1 to 5 and Comparative Examples 1 to 3) Aqueous solutions of sulfuric acid and phosphoric acid having concentrations shown in Table 1 (phosphoric acid was not used in Comparative Examples) and amounts of oxidation shown in Table 1 were used.
A catalyst consisting of copper and having a catalytic amount shown in Table 1 was charged into a reaction vessel, and the inside of the reaction vessel was sufficiently replaced with carbon monoxide. Absorbed carbon. Then, while maintaining the carbon monoxide pressure in the reaction vessel at 15 Kg / cm 2 , the first
Diisobutylene was reacted with carbon monoxide under the reaction conditions shown in the table. The carbon monoxide consumed and reduced during the reaction was newly replenished. After the reaction time of 1.5 hours had elapsed, the replenishment of diisobutylene was stopped, and stirring was continued for 1 hour. Then, an equal amount of water was added.
このようにして得られた反応混合物を、実施例１，２お
よび比較例１，２については水で稀釈せずにそのまま、
実施例３〜５および比較例３については水で３倍に稀釈
した後、ｎ−ヘキサン200 ｍｌで３回抽出を繰返した。The reaction mixture thus obtained was used as is for Examples 1 and 2 and Comparative Examples 1 and 2 without dilution with water.
In Examples 3 to 5 and Comparative Example 3, after diluting with water three times, extraction with 200 ml of n-hexane was repeated three times.
抽出液中に混入する若干の硫酸を水洗により除去し、ｎ
−ヘキサンを蒸留により除去して第１表に示す組成のカ
ルボン酸混合物を得た。Some sulfuric acid mixed in the extract was removed by washing with water,
-Hexane was removed by distillation to obtain a carboxylic acid mixture having the composition shown in Table 1.
結果を第１表に示す。The results are shown in Table 1.
なお、生成したカルボン酸混合物中の硫黄含有量は、微
量硫黄分析計［三菱化成（株）製］を用いて測定し、リ
ン含有量は、生成したカルボン酸混合物を電気炉で灰
化、捕集した後、指示薬を添加して発色による吸光度を
測定して決定した。The sulfur content in the produced carboxylic acid mixture was measured by using a trace sulfur analyzer [manufactured by Mitsubishi Kasei Co., Ltd.], and the phosphorus content was ashed and captured in an electric furnace of the produced carboxylic acid mixture. After collection, an indicator was added and the absorbance due to color development was measured and determined.
（実施例６） ジイソブチレンの代りに１−オクタノールを使用した外
は前記実施例４と同様にして実施した。 Example 6 The procedure of Example 4 was repeated except that 1-octanol was used instead of diisobutylene.
カルボン酸混合物の収率は55.6％であり、カルボン酸混
合物の組成としては、トリメチル酢酸が20.9重量％、Ｃ
８カルボン酸が10.7重量％、Ｃ９カルボン酸が40.8重量
％、その他のカルボン酸が27.6重量％であり、また、カ
ルボン酸混合物中の硫黄含有量は0.033 重量％であり、
リン含有量は10ppm 以下であった。The yield of the carboxylic acid mixture was 55.6%, and the composition of the carboxylic acid mixture was trimethylacetic acid 20.9% by weight and C
8 carboxylic acids are 10.7% by weight, C 9 carboxylic acids are 40.8% by weight, other carboxylic acids are 27.6% by weight, and the sulfur content in the carboxylic acid mixture is 0.033% by weight,
The phosphorus content was 10 ppm or less.
Claims (4)
素と、水とを反応させるカルボン酸の製造方法におい
て、硫酸およびリン酸からなる触媒または硫酸、リン酸
および金属化合物からなる触媒を使用することを特徴と
するカルボン酸の製造方法。1. A method for producing a carboxylic acid in which an olefin or an alcohol, carbon monoxide and water are reacted with each other, using a catalyst composed of sulfuric acid and phosphoric acid or a catalyst composed of sulfuric acid, phosphoric acid and a metal compound. A method for producing a carboxylic acid, which is characterized.
許請求の範囲第１項に記載のカルボン酸の製造方法。2. The method for producing a carboxylic acid according to claim 1, wherein the metal compound is a metal oxide.
許請求の範囲第２項に記載のカルボン酸の製造方法。3. The method for producing a carboxylic acid according to claim 2, wherein the metal oxide is cuprous oxide.
許請求の範囲第１項から第３項までのいずれかに記載の
カルボン酸の製造方法。4. The method for producing a carboxylic acid according to any one of claims 1 to 3, wherein the reaction is carried out at -10 to 80 ° C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61005748A JPH0662485B2 (en) | 1986-01-14 | 1986-01-14 | Method for producing carboxylic acid |
| US07/915,386 US5223641A (en) | 1986-01-14 | 1992-07-20 | Carboxylic acid mixtures and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61005748A JPH0662485B2 (en) | 1986-01-14 | 1986-01-14 | Method for producing carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62164645A JPS62164645A (en) | 1987-07-21 |
| JPH0662485B2 true JPH0662485B2 (en) | 1994-08-17 |
Family
ID=11619727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61005748A Expired - Fee Related JPH0662485B2 (en) | 1986-01-14 | 1986-01-14 | Method for producing carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662485B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223641A (en) * | 1986-01-14 | 1993-06-29 | Idemitsu Petrochemical Chemical Company, Limited | Carboxylic acid mixtures and process for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948616A (en) * | 1972-09-13 | 1974-05-11 | ||
| US4055802A (en) * | 1976-08-12 | 1977-10-25 | Bell Telephone Laboratories, Incorporated | Electrical identification of multiply configurable circuit array |
-
1986
- 1986-01-14 JP JP61005748A patent/JPH0662485B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62164645A (en) | 1987-07-21 |
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