JPH04198150A - Oxidation of 2-chloropropionaldehyde - Google Patents
Oxidation of 2-chloropropionaldehydeInfo
- Publication number
- JPH04198150A JPH04198150A JP2325752A JP32575290A JPH04198150A JP H04198150 A JPH04198150 A JP H04198150A JP 2325752 A JP2325752 A JP 2325752A JP 32575290 A JP32575290 A JP 32575290A JP H04198150 A JPH04198150 A JP H04198150A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- chloropropionaldehyde
- chromium
- chloropropionic acid
- oxygen
- 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
- UAARVZGODBESIF-UHFFFAOYSA-N 2-chloropropanal Chemical compound CC(Cl)C=O UAARVZGODBESIF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims description 20
- 230000003647 oxidation Effects 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 10
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 9
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 6
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 abstract description 26
- NDUPDOJHUQKPAG-UHFFFAOYSA-M 2,2-Dichloropropanoate Chemical compound CC(Cl)(Cl)C([O-])=O NDUPDOJHUQKPAG-UHFFFAOYSA-M 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- WDNIVTZNAPEMHF-UHFFFAOYSA-N acetic acid;chromium Chemical compound [Cr].CC(O)=O.CC(O)=O WDNIVTZNAPEMHF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000002904 solvent Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- 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 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 Organic acid salts Chemical class 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GAWAYYRQGQZKCR-REOHCLBHSA-N (S)-2-chloropropanoic acid Chemical compound C[C@H](Cl)C(O)=O GAWAYYRQGQZKCR-REOHCLBHSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- UGWBWPXTGFPEFG-UHFFFAOYSA-N chloro hypochlorite chromium Chemical compound [Cr].ClOCl UGWBWPXTGFPEFG-UHFFFAOYSA-N 0.000 description 1
- BUGMCLNOCJDESP-UHFFFAOYSA-L chromium(2+);diacetate;hydrate Chemical compound O.[Cr+2].CC([O-])=O.CC([O-])=O BUGMCLNOCJDESP-UHFFFAOYSA-L 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material 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
- 238000001577 simple distillation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 150000003682 vanadium compounds Chemical class 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）
本発明は次の反応式１）
％式％）
に従って２−クロロプロピオンアルデヒドを酸化して２
−クロロプロピオン酸を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is based on the following reaction formula 1).
- A method for producing chloropropionic acid.
２−クロロプロピオン酸は工業薬品および農薬製造用中
間体として広範囲な用途を有する重要な化合物である。2-Chloropropionic acid is an important compound with a wide range of uses as an intermediate for the production of industrial chemicals and pesticides.
（従来の技術および発明が解決しようとする課Ｈ）従来
、２−クロロプロピオン酸は工業的には次の反応式２）
％式％）
に従ったプロピオン酸の塩素化反応によって製造されて
いる。しかし、この反応方法では、式から明らかなよう
に消費される塩素の半分は塩化水素の副生に向けられて
おり、塩素の利用率の面において経済的に好ましくない
上に、副生ずる塩化水素は未反応塩素や各種の不純物を
含むために利用価値が低く、また、廃棄に際しても中和
用のアルカリを必要とするという不利益を有す−る。ま
た、この方法で得られる２−クロロプロピオン酸には、
不純物として未反応のプロピオン酸の他に塩素化が更に
進んだ２．２−ジクロロプロピオン酸等のジクロル体が
通常数％含まれるために純度９５％以上とすることが困
難である。特に、これらのジクロル体は単なる蒸留では
２−クロロプロビオン酸との分離が非常に困難であり、
高純度の２−クロロプロピオン酸を必要とする場合には
、例えば−旦メチルエステルに変換してから精密蒸留に
かけ、次いで加水分解の後にメタノールを分離回収する
といった煩雑な操作を必要とするという欠点を有してい
る。更に、このプロピオン酸の塩素化反応は、腐食性の
強い塩化水素を取り扱うために装置に高価な材料を必要
としたり装置の維持に大きな負担をかける等の問題点が
ある。 上記問題点の解決方法として、塩素化法によら
ない即ちジクロル体を生成しない製造方法の採用が考え
られる。それは、例えば特開昭６１−１２６０４６号公
報に開示されているロジウムおよび塩基の存在下に塩化
ビニルと合成ガスとの反応によって製造できる２−クロ
ロプロピオンアルデヒドを、例えば特開昭６２−９６４
４６号公報に開示されている、鉄化合物、クロム化合物
、ニッケル化合物、マンガン化合物、銅化合物およびセ
リウム化合物から成る群から選ばれる少なくとも一種の
金属化合物の存在下、液相において酸素もしくは酸素含
有ガスにより酸化する方法が好適である。この方法は塩
化ビニルを出発原料としているため、基本的にジクロル
体の副生が殆どないという特徴があり好適である。又、
特開平０１−２３３２５７号公報には（１）鉄化合物と
（２）バナジウム化合物、クロム化合物またはクロム化
合物を触媒として式１）の反応を行うと高い選択率で酸
化反応が出来る事が示されている。(Problem H to be solved by the prior art and the invention) Conventionally, 2-chloropropionic acid has been industrially produced by the chlorination reaction of propionic acid according to the following reaction formula 2) % formula %) . However, in this reaction method, as is clear from the equation, half of the chlorine consumed is directed toward the by-product of hydrogen chloride, which is not economically desirable in terms of the utilization rate of chlorine. Since it contains unreacted chlorine and various impurities, it has low utility value, and also has the disadvantage of requiring alkali for neutralization when disposed of. In addition, 2-chloropropionic acid obtained by this method has
It is difficult to obtain a purity of 95% or higher because, in addition to unreacted propionic acid, several % of dichloro compounds such as 2,2-dichloropropionic acid, which has been further chlorinated, are usually contained as impurities. In particular, it is very difficult to separate these dichloro compounds from 2-chloroprobionic acid by simple distillation.
When high-purity 2-chloropropionic acid is required, the disadvantage is that it requires complicated operations, such as first converting it to methyl ester, then subjecting it to precision distillation, and then separating and recovering methanol after hydrolysis. have. Furthermore, this chlorination reaction of propionic acid has problems such as requiring expensive materials for the equipment to handle highly corrosive hydrogen chloride and placing a heavy burden on the maintenance of the equipment. As a solution to the above-mentioned problems, it is possible to adopt a production method that does not involve chlorination, that is, does not generate a dichloride. 2-chloropropionaldehyde, which can be produced by the reaction of vinyl chloride with synthesis gas in the presence of rhodium and a base, as disclosed in, for example, JP-A-62-964;
46, in the presence of at least one metal compound selected from the group consisting of iron compounds, chromium compounds, nickel compounds, manganese compounds, copper compounds and cerium compounds, by oxygen or oxygen-containing gas in the liquid phase. A method of oxidation is preferred. Since this method uses vinyl chloride as a starting material, it is suitable because it is basically characterized in that there is almost no by-product of dichloride. or,
JP-A-01-233257 discloses that when the reaction of formula 1) is carried out using (1) an iron compound and (2) a vanadium compound, a chromium compound, or a chromium compound as a catalyst, an oxidation reaction can be carried out with high selectivity. There is.
しかし、本反応は一般的に溶媒を用いて実施されるが、
２−クロロプロピオンアルデヒド濃度が通常１〜５０重
景％、好ましくは５〜３０重景％で実施され、比較的高
濃度で酸化反応を行うと選択率が著しく低下するという
欠点があった。従って、より好ましくは１〜１５重量％
で反応する必要があった。しかし、選択率が高くても目
的生成物の濃度が低いと、目的物よりも低沸点の溶媒を
用いた場合に、生成物の単位重量当たりに換算した溶媒
回収のエネルギーコストが非常に高くなり、高濃度でも
選択率よく酸化反応できる方法が望まれていた。However, although this reaction is generally carried out using a solvent,
The 2-chloropropionaldehyde concentration is usually 1 to 50% by weight, preferably 5 to 30% by weight, and when the oxidation reaction is carried out at a relatively high concentration, the selectivity is significantly reduced. Therefore, more preferably 1 to 15% by weight
I needed to react. However, even if the selectivity is high, if the concentration of the target product is low, the energy cost of solvent recovery per unit weight of product becomes very high when a solvent with a lower boiling point than the target product is used. There was a desire for a method that could perform oxidation reactions with good selectivity even at high concentrations.
（課題を解決するための手段および作用）本発明者らは
、上記問題点を解決するに当たり鋭意検討を積み重ねた
結果、鉄化合物、クロム化合物及びモリブデン化合物の
共存条件下にて酸化反応すれば、液相溶媒中比較的高い
濃度でも式１）の反応が極めて高い選択率で進行し、前
記問題点が解決できる事を見出し本発明を完成するに至
った。 即ち、本発明は、鉄化合物、クロム化合物及び
モリブデン化合物の存在下、液相において酸素もしくは
酸素含有ガスにより酸化することを特徴とする２−クロ
ロプロピオンアルデヒドの酸化方法である。 本発明の
方法において用いる鉄化合物としては塩化第一鉄、塩化
第二鉄、硫酸第一鉄、硫酸第二鉄、硝酸第二鉄等の二価
または三価の鉄の鉱酸塩や酢酸第一鉄、酢酸第二鉄、安
息香酸第一鉄、蓚酸第一鉄、ナフテン酸鉄等の二価また
は三価の鉄の有機酸塩等が好ましく、またこの他、水酸
化第二鉄や酸化第二鉄等も使用する事ができる。また、
二価または三価の鉄の２−クロロプロピオン酸塩も好ま
しい鉄化合物の例として挙げられる。(Means and effects for solving the problem) As a result of intensive studies in solving the above problems, the present inventors found that if an oxidation reaction occurs under the coexistence conditions of an iron compound, a chromium compound, and a molybdenum compound, The present inventors have found that the reaction of formula 1) proceeds with extremely high selectivity even at a relatively high concentration in a liquid phase solvent, and that the above-mentioned problems can be solved, leading to the completion of the present invention. That is, the present invention is a method for oxidizing 2-chloropropionaldehyde, which is characterized by oxidizing 2-chloropropionaldehyde in a liquid phase with oxygen or an oxygen-containing gas in the presence of an iron compound, a chromium compound, and a molybdenum compound. The iron compounds used in the method of the present invention include divalent or trivalent iron mineral salts such as ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, and ferric nitrate, and ferrous acetate. Organic acid salts of divalent or trivalent iron such as monoferrous, ferric acetate, ferrous benzoate, ferrous oxalate, and naphthenate are preferred; Secondary iron etc. can also be used. Also,
2-chloropropionate of divalent or trivalent iron is also mentioned as an example of a preferred iron compound.
又、クロム化合物の例としては、塩化クロム（■）、塩
化クロム（ＩＩＩ） 、クロムヘキサカルボニル、オキ
シ塩化クロム（■）、酸化クロム（Ｉ［Ｉ）、酸化クロ
ム（■）、硝酸クロム（１）（９水和物）、三フッ化ク
ロム（■）（四水和物）、クロム（ＩＩＩ）アセチルア
セトナート、クロム（Ｉ［Ｉ）三フッ化アセチルアセト
ナート、酢酸クロム（ＩＩＩ） （１水和物）、ナフ
テン酸クロム等の化合物が例示される。Examples of chromium compounds include chromium chloride (■), chromium chloride (III), chromium hexacarbonyl, chromium oxychloride (■), chromium oxide (I[I), chromium oxide (■), and chromium nitrate (1). ) (9hydrate), chromium trifluoride (■) (tetrahydrate), chromium (III) acetylacetonate, chromium (I[I) trifluoride acetylacetonate, chromium (III) acetate (1 Examples include compounds such as hydrate) and chromium naphthenate.
更にモリブデン化合物の例としては、五塩化モリブデン
、二硫化モリブデン、モリブデンヘキサカルボニル、酸
化モリブデン（■）、酸化モリブデン（ＩＶ）アセチル
アセトナート、酢酸モリブデン（Ｕ）二量体、ナフテン
酸モリブデン等の化合物が挙げられる。Furthermore, examples of molybdenum compounds include molybdenum pentachloride, molybdenum disulfide, molybdenum hexacarbonyl, molybdenum oxide (■), molybdenum oxide (IV) acetylacetonate, molybdenum acetate (U) dimer, molybdenum naphthenate, and the like. can be mentioned.
以上の化合物は、粉末状または結晶状で使用できるが、
２−クロロプロピオン酸や２−クロロプロピオンアルデ
ヒド及び又は予め溶媒に溶解させた形で用いることも好
ましい使用方法である。これらの化合物の使用量は通常
、反応液相中に各々の金属に換算して鉄は１０〜２００
００重量ｐｐｍ 、モリブデンは１０〜５０００重量ｐ
ｐｍ、クロムは０．１〜５００重量ρｐｍの範囲で使用
する事が望ましい。この濃度範囲外では、溶媒中に於け
る２−クロロプロピオンアルデヒドが２０重量％を越え
るような比較的高い濃度では、高選択率が得られないか
、高転化率を得る事が出来なくなる。溶媒中に於ける２
−クロロプロピオンアルデヒド濃度、反応温度及び酸素
分圧など他の条件に応じて最適な触媒濃度を任意に選ぶ
事が出来る。特にクロムについては、反応液相中５００
重量ｐｐｗｌを越えると急激な酸化反応が起こり易く、
安定した酸化反応を行うのが難しくなる。また、クロム
の非存在下では、高い転化率を達成できなくなり好まし
くない。The above compounds can be used in powder or crystal form, but
It is also preferable to use 2-chloropropionic acid, 2-chloropropionaldehyde, and/or in the form of a pre-dissolved solution in a solvent. The amount of these compounds used is usually 10-200% of iron in the reaction liquid phase in terms of each metal.
00 ppm by weight, molybdenum is 10-5000 ppm by weight
It is desirable to use chromium in a range of 0.1 to 500 weight ρpm. Outside this concentration range, at relatively high concentrations of 2-chloropropionaldehyde in the solvent exceeding 20% by weight, high selectivity or high conversion cannot be obtained. 2 in solvent
- The optimal catalyst concentration can be arbitrarily selected depending on other conditions such as chloropropionaldehyde concentration, reaction temperature, and oxygen partial pressure. Especially for chromium, 500
When the weight ppwl is exceeded, rapid oxidation reactions tend to occur;
It becomes difficult to perform a stable oxidation reaction. Moreover, in the absence of chromium, a high conversion rate cannot be achieved, which is not preferable.
本発明の方法では、２−クロロプロピオンアルデヒドの
酸化を温度２０〜１２０℃の範囲で行う事が好ましい。In the method of the present invention, 2-chloropropionaldehyde is preferably oxidized at a temperature in the range of 20 to 120°C.
２０℃より低い温度では酸化反応速度が４い上に過酸の
蓄積の恐れがあるために通常は好ましくない。又、１２
０″Ｃより高い温度では、２−クロロプロピオンアルデ
ヒドや２−クロロプロピオン酸の脱塩酸等の副反応が著
しくなり、２−クロロプロピオン酸の収率が低下すると
ともに純度も悪くなる。これらの理由から、用いる温度
は４０〜９０℃が更に好ましい範囲である。Temperatures lower than 20° C. are generally not preferred because the oxidation reaction rate is low and there is a risk of peracid accumulation. Also, 12
At temperatures higher than 0''C, side reactions such as dehydrochlorination of 2-chloropropionaldehyde and 2-chloropropionic acid become significant, resulting in a decrease in the yield and purity of 2-chloropropionic acid.These reasons are Therefore, the temperature used is more preferably in the range of 40 to 90°C.
本発明の方法では、溶媒の不存在下でも酸化は充分進行
するが、酸化に伴う発熱を効率よく除去して良好な反応
成績を得る為に溶媒の存在下で酸化を行うことが好まし
い。このような溶媒としては、酸化反応条件下で変質や
副反応を伴わないものが使用しうる。好ましい例として
は、酢酸、プロピオン酸、酪酸等のカルボン酸があり、
また、このほか、ジメチルスルホキシドや、スルホラン
、アセトン等も挙げられる。これら溶媒中の２−クロロ
プロピオンアルデヒドの濃度は、通常１〜５０重量％程
度である。しかし比較的低濃度での酸化反応は、はぼ定
量的な高転化率且つ高選択率の反応成績が得られるもの
の、反応生成液中の目的物の濃度が低く、溶媒回収のエ
ネルギーコストが高くなり本発明の目的にはそぐわない
。本発明では１５重量％さらには２０重量％を越える比
較的高い濃度域でも、高転化率にて高選択率で酸化反応
させ得る事が特長である。即ち高濃度域でも選択率を損
なう事なく反応させる事が出来る。In the method of the present invention, oxidation proceeds satisfactorily even in the absence of a solvent, but in order to efficiently remove the heat generated by oxidation and obtain good reaction results, it is preferable to carry out oxidation in the presence of a solvent. As such a solvent, one that does not cause deterioration or side reactions under oxidation reaction conditions can be used. Preferred examples include carboxylic acids such as acetic acid, propionic acid, butyric acid,
Other examples include dimethyl sulfoxide, sulfolane, and acetone. The concentration of 2-chloropropionaldehyde in these solvents is usually about 1 to 50% by weight. However, although oxidation reactions at relatively low concentrations can yield quantitatively high conversion rates and high selectivity, the concentration of the target product in the reaction product is low and the energy cost of solvent recovery is high. Therefore, this is not suitable for the purpose of the present invention. The present invention is characterized in that the oxidation reaction can be carried out with high conversion and high selectivity even in a relatively high concentration range exceeding 15% by weight or even 20% by weight. That is, even in a high concentration range, the reaction can be carried out without loss of selectivity.
又、この２−クロロプロピオンアルデヒドの酸化におい
ては、原料や溶媒に由来する水の混入がしばしば見られ
るが、反応系内に水が共存すると反応速度が低下して好
ましくない。しかし、本発明の方法においては、反応系
内の水は完全に除去する必要はなく、通常液相中に１０
重量％以下、特に好ましくは３重量％以下とすれば酸化
は充分に進行する。Further, in the oxidation of 2-chloropropionaldehyde, contamination of water originating from raw materials and solvents is often observed, and the coexistence of water in the reaction system is undesirable because the reaction rate decreases. However, in the method of the present invention, it is not necessary to completely remove water in the reaction system;
Oxidation will proceed sufficiently if the amount is less than 3% by weight, particularly preferably less than 3% by weight.
本発明の方法において、酸化剤としては酸素または酸素
含有ガスが用いられる。酸素含有ガスとしては、最も一
般的には空気が用いられる。これらの酸素含有ガスの圧
力は、反応系内の酸素分圧で０．２ｋｇ ／ｃｍ”−Ｇ
以上、特に５ ｋｇ／ ｃｍ”−Ｇ以上が好ましい。酸
素分圧には特に上限を設ける必要はないが、あまり高圧
にすることは工業的に好ましくないので通常は酸素分圧
１００ ｋｇ／ ｃｍ”−Ｇ以下の範囲で行われる。In the method of the invention, oxygen or an oxygen-containing gas is used as the oxidizing agent. Air is most commonly used as the oxygen-containing gas. The pressure of these oxygen-containing gases is 0.2 kg/cm"-G as the oxygen partial pressure in the reaction system.
Above, 5 kg/cm"-G or above is particularly preferable. Although there is no need to set an upper limit on the oxygen partial pressure, it is industrially undesirable to make the pressure too high, so the oxygen partial pressure is usually 100 kg/cm"-G. - It is carried out in the range below G.
（実施例）
以下、実施例により本発明の方法を更に具体的に説明す
る。(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
裏隻■土
反応溶媒として用いる酢酸に、２−クロロプロピオン酸
の第二鉄塩を鉄として６６６ｐｐｍ、５％ナフテン酸モ
リブデンをモリブデンとして６６．６ｐｐｍ、及び酢酸
クロム（ＩＩ）（１水和物）をクロムとして１３．３ｐ
ｐｍになるように調製して加え、溶解した。In the acetic acid used as a reaction solvent, 666 ppm of ferric salt of 2-chloropropionic acid as iron, 66.6 ppm of 5% molybdenum naphthenate as molybdenum, and chromium (II) acetate (monohydrate) were added. 13.3p as chrome
pm, added and dissolved.
撹拌装置を備えた内容積１００ｍ１のステンレス製オー
トクレーブに、２−クロロプロピオンアルデヒド８ｇと
、上記酢酸溶媒１２ｇを入れ、これに酸素と窒素が１：
１の混合ガスを８０Ｋｇ／ｃｍｚ−Ｇまで圧入し、温水
浴中、撹拌下で５０℃において１時間反応を行わせた。8 g of 2-chloropropionaldehyde and 12 g of the above acetic acid solvent were placed in a stainless steel autoclave with an internal volume of 100 m1 equipped with a stirring device, and oxygen and nitrogen were added in 1:1 ratio.
A mixed gas of No. 1 was injected under pressure to 80 kg/cmz-G, and the reaction was carried out at 50° C. for 1 hour with stirring in a hot water bath.
反応の進行に伴い圧力が低下しないようにボンベから酸
素を補給し、圧力を８０Ｋｇ／ｃｍ”−Ｇに保った。Oxygen was supplied from a cylinder to prevent the pressure from decreasing as the reaction progressed, and the pressure was maintained at 80 kg/cm''-G.
反応終了後、オートクレーブを冷却し、圧を抜いた後に
内容物を取り出し、ガスクロマトグラフにより分析した
。分析の結果、２−クロロプロビオンアルデヒドの転化
率は６３．５％で、２−クロロプロピオン酸への選択率
は９８．４％であった。また、反応液中には２，２−ジ
クロロプロピオン酸の副生は認められなかった。After the reaction was completed, the autoclave was cooled, the pressure was released, and the contents were taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of 2-chloroprobionaldehyde was 63.5%, and the selectivity to 2-chloropropionic acid was 98.4%. Furthermore, no by-product of 2,2-dichloropropionic acid was observed in the reaction solution.
実施１
実施例１の方法において、反応温度を４０℃とし、反応
時間を２時間とした以外は実施例１と同様に反応を行っ
た。その結果、２−クロロプロピオンアルデヒド転化率
５９．８％、２−クロロプロピオン酸選択率９８．７％
の反応成績を得た。又、反応後の液中には２．２−ジク
ロロプロピオン酸の副生は認められなかった。Example 1 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 40° C. and the reaction time was 2 hours. As a result, 2-chloropropionaldehyde conversion rate was 59.8% and 2-chloropropionic acid selectivity was 98.7%.
obtained reaction results. Furthermore, no by-product of 2,2-dichloropropionic acid was observed in the solution after the reaction.
実施拠主
実施例１の方法において、２−クロロプロピオンアルデ
ヒドの仕込を６ｇ、酢酸溶媒の仕込を１４ｇとした以外
は実施例１と同様に反応を行った。その結果、２−クロ
ロプロピオンアルデヒド転化率７９．９％、２−クロロ
プロピオン酸選択率９８．１％の反応成績を得た。又、
反応後の液中には２，２−ジクロロプロピオン酸の副生
は認められなかった。The reaction was carried out in the same manner as in Example 1, except that 6 g of 2-chloropropionaldehyde and 14 g of acetic acid solvent were charged. As a result, a reaction result of 2-chloropropionaldehyde conversion of 79.9% and 2-chloropropionic acid selectivity of 98.1% was obtained. or,
No by-product of 2,2-dichloropropionic acid was observed in the solution after the reaction.
実ｌｌ津（
実施例１の方法において、２−クロロプロピオンアルデ
ヒドの仕込を１．５ｇとし、実施例１で調製した触媒を
含む酢酸溶媒を９ｇと試薬の酢酸９．５ｇを仕込み反応
時間を２時間として実施例１と同様に反応を行った。そ
の結果、２−クロロプロピオンアルデヒド転化率９９．
１％、２−クロロプロピオン酸選択率９９．０％の反応
成績を得た。又、反応後の液中には２，２−ジクロロプ
ロピオン酸は認められなかった。(In the method of Example 1, 1.5 g of 2-chloropropionaldehyde was charged, 9 g of the acetic acid solvent containing the catalyst prepared in Example 1, and 9.5 g of acetic acid as a reagent were charged, and the reaction time was set to 2. The reaction was carried out for the same time as in Example 1. As a result, the 2-chloropropionaldehyde conversion rate was 99.
1% and a 2-chloropropionic acid selectivity of 99.0%. Moreover, 2,2-dichloropropionic acid was not observed in the solution after the reaction.
北較桝工
実施例１の方法において、酢酸中の酢酸クロム（Ｉ［Ｉ
） （１水和物）をクロムとして１１０００ｐｐにな
るように調製して用いた以外は実施例１と同様に反応を
行った。しかし反応途中で急激に温度暴走が起こり安定
的な運転が困難であった。In the method of Example 1, chromium acetate (I[I
The reaction was carried out in the same manner as in Example 1, except that chromium (monohydrate) was prepared to have a concentration of 11,000 pp. However, a sudden temperature runaway occurred during the reaction, making stable operation difficult.
ｌ校医ｌ
実施例１の方法において、酢酸クロム（ＩＩ［）（１水
和物）のみを含まない酢酸溶媒を用いた以外は実施例１
と同様に反応を行った。その結果、２−クロロプロピオ
ンアルデヒド転化率１８．９％、２−クロロプロピオン
酸選択率９９．３χの反応成績を得た。1 School doctor 1 Example 1 in the method of Example 1 except that an acetic acid solvent not containing only chromium acetate (II[) (monohydrate) was used.
The reaction was carried out in the same manner. As a result, a reaction result of 2-chloropropionaldehyde conversion of 18.9% and 2-chloropropionic acid selectivity of 99.3χ was obtained.
比較■１
実施例１の方法において５％ナフテン酸モリブデンのみ
を含まない酢酸溶媒を用いた以外は実施例１と同様に反
応を行った。その結果、２−クロロプロピオンアルデヒ
ド転化率３６．７％、２−クロロプロピオン酸選択率９
０．１％の反応成績を得た。Comparison (1) A reaction was carried out in the same manner as in Example 1 except that an acetic acid solvent containing only 5% molybdenum naphthenate was used. As a result, the 2-chloropropionaldehyde conversion rate was 36.7%, and the 2-chloropropionic acid selectivity was 9%.
A reaction result of 0.1% was obtained.
比較±↓
実ｍ例ｉの方法において２−クロロプロピオン酸の第二
鉄塩のみを含まない酢酸溶媒を用いた以外は実施例工と
同様に反応を行った。その結果、２−クロロプロピオン
アルデヒド転化率４７．８％、２−クロロプロピオン酸
選択率８８．ｏχの反応成績を得た。Comparison ±↓ Example M The reaction was carried out in the same manner as in Example I except that an acetic acid solvent not containing only the ferric salt of 2-chloropropionic acid was used. As a result, the 2-chloropropionaldehyde conversion rate was 47.8%, and the 2-chloropropionic acid selectivity was 88. Oχ reaction results were obtained.
（発明の効果）
本発明の方法により、従来行われていたプロピオン酸の
塩素化法に比較して腐食の少ない環境下で工業的に２−
クロロプロピオン酸を選択性良く製造することができる
。また、これまでに提案されてきた２−クロロプロピオ
ンアルデヒドの酸化方法に比較して、より高い濃度でに
２−クロロプロピオン酸を製造することができる。更に
、得られる２−クロロプロピオン酸中には、２．２−ジ
クロロプロピオン酸が検出されない極めて有益な製造方
法である。(Effects of the Invention) The method of the present invention enables industrial use of 2-
Chloropropionic acid can be produced with good selectivity. Furthermore, compared to the oxidation methods of 2-chloropropionaldehyde that have been proposed so far, 2-chloropropionic acid can be produced at a higher concentration. Furthermore, 2,2-dichloropropionic acid is not detected in the 2-chloropropionic acid obtained, making this a very useful production method.
Claims (1)
ロム化合物及びモリブデン化合物の存在下、液相におい
て酸素もしくは酸素含有ガスにより酸化することを特徴
とする２−クロロプロピオンアルデヒドの酸化方法。 ２、酸化を４０〜９０℃の温度範囲内で行うことを特徴
とする特許請求の範囲第１項に記載の方法。[Claims] Oxidation of 2-chloropropionaldehyde, characterized in that 1,2-chloropropionaldehyde is oxidized with oxygen or an oxygen-containing gas in a liquid phase in the presence of an iron compound, a chromium compound, and a molybdenum compound. Method. 2. The method according to claim 1, characterized in that the oxidation is carried out within a temperature range of 40 to 90°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325752A JPH04198150A (en) | 1990-11-29 | 1990-11-29 | Oxidation of 2-chloropropionaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325752A JPH04198150A (en) | 1990-11-29 | 1990-11-29 | Oxidation of 2-chloropropionaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198150A true JPH04198150A (en) | 1992-07-17 |
Family
ID=18180246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2325752A Pending JPH04198150A (en) | 1990-11-29 | 1990-11-29 | Oxidation of 2-chloropropionaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198150A (en) |
-
1990
- 1990-11-29 JP JP2325752A patent/JPH04198150A/en active Pending
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