JPS60161974A - Preparation of tetrachlorophthalic anhydride - Google Patents
Preparation of tetrachlorophthalic anhydrideInfo
- Publication number
- JPS60161974A JPS60161974A JP59014528A JP1452884A JPS60161974A JP S60161974 A JPS60161974 A JP S60161974A JP 59014528 A JP59014528 A JP 59014528A JP 1452884 A JP1452884 A JP 1452884A JP S60161974 A JPS60161974 A JP S60161974A
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- mixture
- cacl2
- chlorine
- cocl2
- 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
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 title claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 12
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 12
- 239000001110 calcium chloride Substances 0.000 claims abstract description 12
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012495 reaction gas Substances 0.000 abstract description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 3
- 235000011148 calcium chloride Nutrition 0.000 abstract 3
- 229910052799 carbon Inorganic materials 0.000 abstract 3
- 229910002249 LaCl3 Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- -1 inorganic acid salts Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution 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
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance 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
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、無水フタル酸と塩素とを、２００〜４００℃
の範囲の温度で、塩化コバルトを必須成分とし、更に塩
化カルシウム、塩化バリウムおよび塩化ランタンよシな
る群から選ばれた成分を一種もしくは二種以上含有する
混合物を活性炭に担持せしめた触媒上に送入して、気相
で反応させることによシ高純度のテトラクロロ無水７タ
ル酸を高収率で製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides phthalic anhydride and chlorine at a temperature of 200 to 400°C.
At a temperature in the range of The present invention relates to a method for producing high-purity tetrachloroheptatalic anhydride in high yield by reacting the same in the gas phase.
テトラクロロ無水７タル酸は、顔料中間体、難燃性ポリ
エステル等の用途があシ、その製造方法もすでに知られ
ている。その一般的な製造方法は液相法であシ、例えば
ヨード等を触媒にしてクロルスルホン酸あるいは発煙硫
酸等の溶媒中で無水フタル酸を塩素化してテトラクロロ
無水フタル酸をえる方法が知られている（例えば西ドイ
ツ特許第１，９３４，１７４号）。又気相で行う方法と
しては、斉藤ら、有機合成化生協会誌第２２巻第６６３
頁（１９６４年）、同じく第２２巻第７８３頁（１９６
４年）また特開昭３８−２５３６５号公報に記載されて
いる様に、無水フタル酸と塩素を、不活性担体上に塩化
第２鉄及び塩化カリウムを担持させた触媒上で反応させ
る製法も提案されている。前者の場合、液相中で腐蝕性
物質を取シ扱うため、装置の腐蝕が著るしい等の欠点を
有している。又後者の場合、昇華性の塩化第２鉄を触媒
に使うため、飛散してきた塩化第２鉄によシ製品が茶色
系に着色するのが避けられないし、又テトラクロロ無水
フタル酸以外に副生物として７〜ｌＯ重量係のへキサク
ロルベンゼン等が混入してくるため、煩雑な精製工程を
必要とする等の欠点を有している。Tetrachloroheptatalic anhydride has uses such as pigment intermediates and flame-retardant polyesters, and its production method is already known. The general manufacturing method is a liquid phase method. For example, a method is known in which phthalic anhydride is chlorinated in a solvent such as chlorosulfonic acid or fuming sulfuric acid using iodine as a catalyst to obtain tetrachlorophthalic anhydride. (eg West German Patent No. 1,934,174). In addition, as for the method carried out in the gas phase, see Saito et al., Journal of the Society for Organic Synthesis, Vol. 22, No. 663.
(1964), also Vol. 22, p. 783 (196
4) There is also a production method in which phthalic anhydride and chlorine are reacted over a catalyst in which ferric chloride and potassium chloride are supported on an inert carrier, as described in JP-A No. 38-25365. Proposed. In the former case, since corrosive substances are handled in the liquid phase, there are drawbacks such as significant corrosion of the equipment. In the latter case, since sublimable ferric chloride is used as a catalyst, it is inevitable that the product will be colored brown due to the scattered ferric chloride. Since hexachlorobenzene and the like of 7 to 10 weight percent are mixed in as living organisms, it has drawbacks such as the need for complicated purification steps.
本発明者らは、上記の欠点を改良するために鋭意検討し
た結果、無水フタル酸と塩素とを、２００〜４００℃の
範囲の温度で、塩化コバルトを必須成分とし、更に塩化
カルシウム、塩化バリウムおよび塩化ランタンよりなる
群から選ばれた成分を一種もしくは二種以上含有する混
合物を活性炭に担持せしめた触媒上に送入して、気相で
反応させることによって高収率でしかも高純度のテトラ
クロロ無水フタル酸が製造できることを見い出し本発明
を完成させた。As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors have found that phthalic anhydride and chlorine are combined at a temperature in the range of 200 to 400°C with cobalt chloride as an essential component, and calcium chloride and barium chloride. A mixture containing one or more components selected from the group consisting of The present invention was completed by discovering that chlorophthalic anhydride can be produced.
本発明における触媒としては、活性炭上に塩化コバルト
を主成分とし、更に塩化カルシウム、塩化バリウムおよ
び塩化ランタンよシなる群から選ばれた成分を一種もし
くは二種以上含有する混合物を担持させたものが使用さ
れるが、混合物の担持量としては活性炭１００重量部に
対して、塩化コバルト、塩化カルシウム、塩化バリウム
、塩化ランタンの混合物の全担持量が５〜１００重量部
、好ましくは１０〜７０重量部の範囲とするのが良い。The catalyst used in the present invention is one in which cobalt chloride is the main component and a mixture containing one or more components selected from the group consisting of calcium chloride, barium chloride, and lanthanum chloride is supported on activated carbon. The amount of the mixture supported is 5 to 100 parts by weight, preferably 10 to 70 parts by weight, of the mixture of cobalt chloride, calcium chloride, barium chloride, and lanthanum chloride per 100 parts by weight of activated carbon. It is best to set it within the range of .
又塩化コバルトに対する塩化カルシウム、塩化バリウム
および塩化ランタンよシなる群から選ばれた一種もしく
は二種以上の混合物の分子比は１ ： ０．５〜１．５
、好ましくはｌ ： ０．５〜１．０が良い。そして、
これらの塩化コバルト、塩化カルシウム、塩化バリウム
、塩化ランタンは必ずしも最初から塩化物の形で担持さ
れる必要はなく、水酸化物、炭酸塩、硝酸塩などの無機
酸塩あるいは酢酸塩、安息香酸塩などの有機酸塩などと
して加えられても良い。これらは反応前の塩素処理ある
いは反応中に塩素によって塩素化され容易に塩化物にな
る。なお、本発明触媒においては活性炭を使用している
が、活性炭と本質的に同種の木炭、骨炭、血炭などの炭
質物も使用できる。Furthermore, the molecular ratio of one or a mixture of two or more selected from the group consisting of calcium chloride, barium chloride, and lanthanum chloride to cobalt chloride is 1:0.5 to 1.5.
, preferably l: 0.5 to 1.0. and,
These cobalt chloride, calcium chloride, barium chloride, and lanthanum chloride do not necessarily need to be supported in the form of chloride from the beginning, but inorganic acid salts such as hydroxide, carbonate, nitrate, acetate, benzoate, etc. It may also be added as an organic acid salt. These are easily converted into chlorides by chlorination before the reaction or by chlorine during the reaction. Although activated carbon is used in the catalyst of the present invention, carbonaceous materials such as charcoal, bone charcoal, blood charcoal, etc. that are essentially the same as activated carbon can also be used.
本発明における触媒成分、塩化コバルト、塩化カルシウ
ム、塩化バリウムおよび塩化ランタンは、従来提案され
ている（特開昭３８−２５３６５号）成分である塩化鉄
等と異なシ、本発明での反応温度２００〜４００℃の範
囲で全く昇華性がないため、本発明では製品中にこれら
の無機塩が夾雑することなく又製品が着色しない利点が
ある。又従来提案された製造法では塩素化さ、れた無水
７タル酸は脱炭酸を受け易く核塩素化された安息香酸ク
ロライド類やヘキサクロルベンゼン等の副生物が多量に
生成し再結晶などの精製工程を必要としたが、本発明で
はすぐれて純度の高いテトラクロル無水フタル酸を高収
率で見られ、製品としてそのま＼使用できるはととなる
という利点もある。The catalyst components in the present invention, cobalt chloride, calcium chloride, barium chloride, and lanthanum chloride, are different from iron chloride, etc., which are components conventionally proposed (Japanese Patent Application Laid-Open No. 38-25365), and the reaction temperature in the present invention is 200%. Since there is no sublimation in the range of -400 DEG C., the present invention has the advantage that the products are not contaminated with these inorganic salts and the products are not colored. In addition, in the conventionally proposed production method, chlorinated anhydrous 7-talic acid is easily decarboxylated, and a large amount of by-products such as nuclear chlorinated benzoic acid chlorides and hexachlorobenzene are produced, resulting in the formation of large amounts of by-products such as recrystallization. Although a purification step was required, the present invention has the advantage that highly pure tetrachlorophthalic anhydride can be obtained in high yield and can be used as is as a product.
反応温度は、無水フタル酸濃度、空間速度などのような
その時の反応条件によって異なるが、生成物の融点が２
５４〜２５８℃と蒸気圧の小さな物質であるため、２０
０℃未満では反応管中で閉塞を起す傾向があシ好ましく
ない。又反応温度が４００℃を起えると、脱炭酸反応が
起シ易くなシ好ましくない。よって２００〜４００ ℃
、とくに３００〜３８０℃の温度範囲が好ましい。The reaction temperature varies depending on the reaction conditions at the time, such as phthalic anhydride concentration, space velocity, etc.
Since it is a substance with a low vapor pressure of 54-258℃,
If the temperature is lower than 0°C, there is a tendency for clogging to occur in the reaction tube, which is undesirable. Furthermore, if the reaction temperature rises to 400°C, the decarboxylation reaction is not likely to occur, which is not preferable. Therefore, 200-400℃
A temperature range of 300 to 380°C is particularly preferred.
本発明での塩素ガスの使用量は反応に必要な理論量の１
〜２倍が最適であるが、さらに３倍以上の塩素ガスを用
いて未反応の塩素ガスを循環使用することもできる。塩
素ガスは窒素、炭酸ガス、塩化水素ガスなどとともに希
釈されて供給されても良い。The amount of chlorine gas used in the present invention is 1 of the theoretical amount required for the reaction.
The optimum amount is 2 times as much, but it is also possible to use 3 times or more of chlorine gas and recycle the unreacted chlorine gas. Chlorine gas may be diluted with nitrogen, carbon dioxide, hydrogen chloride gas, etc. and then supplied.
反応ガスの空間速度は毎時２００〜１０００とするのが
実用的である。又原料ガス中の無水７タル酸の濃度は反
応温度によって異なるが、０．５〜１０容量係が適当で
、とくに１〜３容量係の範囲が好ましい。It is practical that the space velocity of the reaction gas is 200 to 1000 per hour. The concentration of 7-talic anhydride in the raw material gas varies depending on the reaction temperature, but is suitably in the range of 0.5 to 10 volumes, particularly preferably in the range of 1 to 3 volumes.
本発明は固定床反応器でも流動床反応器でも使用できる
。The present invention can be used in fixed bed or fluidized bed reactors.
以下本発明を実施例によシ更に具体的に説明するが、本
発明はこれらに限定されるものではない。The present invention will be explained in more detail below using Examples, but the present invention is not limited thereto.
実施例 １
塩化コバルト（ＣｏＣ４２として） １２．Ｏｙと塩化
バリウム（ＢａＣｌ２・２Ｈ２０として） ｌ ８．１
ｙを含む水溶液１５０ＣＣに４〜６メツシユの活性炭
〔飲用薬品製「白鷺（商標） Ｊ Ｃ−２Ｘ：３６０Ｃ
Ｃを浸し、湯浴上で水分を蒸発乾固せしめて触媒を調製
した。Example 1 Cobalt chloride (as CoC42) 12. Oy and barium chloride (as BaCl2.2H20) l 8.1
Add 4 to 6 meshes of activated carbon to 150 cc of an aqueous solution containing y [Shirasagi (trademark) J C-2X: 360 C manufactured by Orable Pharmaceutical Co., Ltd.
A catalyst was prepared by soaking C and evaporating the water to dryness on a hot water bath.
その担持率は５２重重量％あった。この触媒５０匡を内
径２６輯のニッケル製反応管に充填した。The loading rate was 52% by weight. Fifty square meters of this catalyst was packed into a nickel reaction tube having an inner diameter of 26 mm.
反応管を浸した浴温を３００℃とし、塩素ガスを毎時３
．Ｏ２触媒層に２時間通じ塩素処理を行った。The bath temperature in which the reaction tube was immersed was set to 300°C, and chlorine gas was supplied at 300 °C per hour.
．． The O2 catalyst layer was subjected to chlorine treatment for 2 hours.
ついで、浴温を３２０℃とし、気化させた無水フタル酸
を毎時２．５ｔと塩素ガスを毎時３．Ｏｔと窒素ガス毎
時１１．６１とをよく混合して触媒層に送入し、反応を
行った。生成した固型物は結晶器で僕
捕集し、捕集量を秤量した量、ガスクロマトグラフ（Ｓ
Ｅ ５２ ： １ ｆｆ１ｓ カラム檜温度１１０℃）
で、目的物質テトラクロロ無水フタル酸及び副生物とし
ての核塩素化安息香酸クロライド及びヘキサクロルベン
ゼンを定量した。５時間反応させた結果粗生成物２０．
Ｏｆかえられ、供給無水フタル酸に対して、えられた粗
生成物をテトラクロロ無水フタル酸として収率を算出し
たところ８２．８モル係であった。又粗生成物中の副生
物の含有率は各々核塩素化安息香酸クロライド１．６重
量％、ヘキサクロルベンゼン０．３重量％であった。な
お、テトラクロロ無水フタル酸とこれらの副生物以外は
ガスクロマトグラフィーでピークは認められなかった。Next, the bath temperature was set to 320°C, and 2.5 tons of vaporized phthalic anhydride and 3 tons of chlorine gas were added per hour. Ot and nitrogen gas at 11.61/hr were thoroughly mixed and fed into the catalyst layer to carry out a reaction. The generated solid matter was collected using a crystallizer, and the collected amount was weighed and analyzed using a gas chromatograph (S
E52: 1 ff1s Column hinoki temperature 110℃)
Then, the target substance tetrachlorophthalic anhydride and the by-products nuclear chlorinated benzoic acid chloride and hexachlorobenzene were quantified. After 5 hours of reaction, a crude product of 20.
The yield of the obtained crude product as tetrachlorophthalic anhydride was calculated as 82.8 mol relative to the supplied phthalic anhydride. The content of by-products in the crude product was 1.6% by weight of nuclear chlorinated benzoic acid chloride and 0.3% by weight of hexachlorobenzene. Note that no peaks were observed in gas chromatography except for tetrachlorophthalic anhydride and these by-products.
実施例 ２
反応温度を変えた以外は、実施例１でえられたのと同じ
触媒を使用して、同じ条件で反応させて表１の結果をえ
た。Example 2 The same catalyst obtained in Example 1 was used and the reaction was carried out under the same conditions except that the reaction temperature was changed, and the results shown in Table 1 were obtained.
実施例３〜６および比較例１
触媒成分を変えた以外は、実施例１と同じ様に触媒を調
製し、又反応温度を変えた以外は実施例１と同じ様に反
応を行い表１の結果をえた。Examples 3 to 6 and Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that the catalyst components were changed, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed. I got the results.
Claims (1)
囲の温度で、塩化コバルトを必須成分とし、更に塩化カ
ルシウム、塩化バリウムおよび塩化ランタンよりなる群
から選ばれた成分を一種もしくは二種以上含有する混合
物を活性炭に担持せしめた触媒上に送入して、気相で反
応させることを特徴とするテトラクロロ無水フタル酸の
製造方法。 （２１塩化カルシウム、塩化バリウムおよび塩化ランタ
ンよシなる群から選ばれた一種もしくは二種以上の混合
物が１．塩化コバルトに対し分子比で０．１〜１．５の
範囲存在せしめられてなる特許請求の範囲＋１１記載の
方法。 （３１塩化コバルト、塩化カルシウム、塩化バリウム、
塩化ランタンの全担持量が活性炭１００重量部に対して
５〜１００重量部である特許請求の範囲（１）または（
２１記載の方法。[Claims] (11) 7 Talic anhydride and chlorine are mixed at a temperature in the range of 200 to 400°C, with cobalt chloride as an essential component, and further selected from the group consisting of calcium chloride, barium chloride, and lanthanum chloride. A method for producing tetrachlorophthalic anhydride, characterized by feeding a mixture containing one or more components onto a catalyst supported on activated carbon and reacting in the gas phase. (21 Calcium chloride, barium chloride) 1. The method according to claim 11, wherein one or a mixture of two or more selected from the group consisting of: (31 Cobalt chloride, calcium chloride, barium chloride,
Claim (1) or (1) wherein the total amount of lanthanum chloride supported is 5 to 100 parts by weight per 100 parts by weight of activated carbon.
21. The method described in 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59014528A JPS60161974A (en) | 1984-01-31 | 1984-01-31 | Preparation of tetrachlorophthalic anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59014528A JPS60161974A (en) | 1984-01-31 | 1984-01-31 | Preparation of tetrachlorophthalic anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60161974A true JPS60161974A (en) | 1985-08-23 |
Family
ID=11863632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59014528A Pending JPS60161974A (en) | 1984-01-31 | 1984-01-31 | Preparation of tetrachlorophthalic anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60161974A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307858A (en) * | 1987-05-18 | 1988-12-15 | エルフ アトケム ソシエテ アノニム | Method for producing halogenated imide |
| EP0632032A1 (en) * | 1993-06-02 | 1995-01-04 | Nippon Light Metal Co., Ltd. | Process for purifying tetrachlorophthalic anhydride and high-purity tetrachlorophthalic anhydride |
| US5574172A (en) * | 1993-05-27 | 1996-11-12 | Mitsubishi Chemical Corporation | Process for producing halogenated phthalic anhydride |
-
1984
- 1984-01-31 JP JP59014528A patent/JPS60161974A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307858A (en) * | 1987-05-18 | 1988-12-15 | エルフ アトケム ソシエテ アノニム | Method for producing halogenated imide |
| US5574172A (en) * | 1993-05-27 | 1996-11-12 | Mitsubishi Chemical Corporation | Process for producing halogenated phthalic anhydride |
| EP0632032A1 (en) * | 1993-06-02 | 1995-01-04 | Nippon Light Metal Co., Ltd. | Process for purifying tetrachlorophthalic anhydride and high-purity tetrachlorophthalic anhydride |
| US5493033A (en) * | 1993-06-02 | 1996-02-20 | Nippon Light Metal Company, Ltd. | Process for purifying tetrachlorophthalic anhydride |
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