JPH089001B2 - Regeneration method of palladium supported catalyst - Google Patents
Regeneration method of palladium supported catalystInfo
- Publication number
- JPH089001B2 JPH089001B2 JP63315389A JP31538988A JPH089001B2 JP H089001 B2 JPH089001 B2 JP H089001B2 JP 63315389 A JP63315389 A JP 63315389A JP 31538988 A JP31538988 A JP 31538988A JP H089001 B2 JPH089001 B2 JP H089001B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- supported catalyst
- acid
- reaction
- catalyst
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 68
- 238000011069 regeneration method Methods 0.000 title claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title description 20
- 229910052763 palladium Inorganic materials 0.000 title description 8
- -1 aromatic halogen compound Chemical class 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000012736 aqueous medium Substances 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 description 27
- 238000005695 dehalogenation reaction Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
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- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
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- 230000007423 decrease Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
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- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
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- DBIOVBYLTPWVSW-UHFFFAOYSA-N 2-ethylpiperidin-4-one;hydrochloride Chemical compound Cl.CCC1CC(=O)CCN1 DBIOVBYLTPWVSW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-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
- FDOQKGWUMUEJLX-UHFFFAOYSA-N 4,5-dichlorophthalic acid Chemical compound OC(=O)C1=CC(Cl)=C(Cl)C=C1C(O)=O FDOQKGWUMUEJLX-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical group CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 238000004811 liquid chromatography Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPLDORJJVPSYGH-UHFFFAOYSA-M sodium;2-carboxy-3,4-dichlorobenzoate Chemical compound [Na+].OC(=O)C1=C(Cl)C(Cl)=CC=C1C([O-])=O HPLDORJJVPSYGH-UHFFFAOYSA-M 0.000 description 1
- DSGYKFHTOCXJAB-UHFFFAOYSA-M sodium;2-carboxy-4,5-dichlorobenzoate Chemical compound [Na+].OC(=O)C1=CC(Cl)=C(Cl)C=C1C([O-])=O DSGYKFHTOCXJAB-UHFFFAOYSA-M 0.000 description 1
- RLCCWSGPYQLVSW-UHFFFAOYSA-M sodium;3-chlorophthalate;hydron Chemical compound [Na+].OC(=O)C1=CC=CC(Cl)=C1C([O-])=O RLCCWSGPYQLVSW-UHFFFAOYSA-M 0.000 description 1
- XLKHCFJHGIAKFX-UHFFFAOYSA-M sodium;4-chlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C=C1 XLKHCFJHGIAKFX-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite 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
- Y02P20/584—Recycling of 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］ 本発明はパラジウム担持触媒の再生法に係り、特に芳
香族ハロゲン化合物を、パラジウム担持触媒を用いて脱
ハロゲン二量化し、芳香族化合物の二量体を製造する方
法において、使用したパラジウム担持触媒を再生する方
法に関する。Description: TECHNICAL FIELD The present invention relates to a method for regenerating a palladium-supported catalyst, and in particular, an aromatic halogen compound is dehalogenated and dimerized by using a palladium-supported catalyst to obtain a diamine of an aromatic compound. It relates to a method for regenerating a palladium-supported catalyst used in a method for producing a monomer.
［従来の技術］ 芳香族化合物の二量体は、種々の工業原料として有用
なものであり、例えば、3,4,3′,4′−ビフェニルテト
ラカルボン酸アルカリ金属塩は、耐熱性ポリイミド樹脂
原料として非常に有用なものである。[Prior Art] Dimers of aromatic compounds are useful as various industrial raw materials. For example, alkali metal salts of 3,4,3 ', 4'-biphenyltetracarboxylic acid are heat-resistant polyimide resins. It is a very useful raw material.
従来、芳香族ハロゲン化合物を脱ハロゲン二量化して
ビフェニル化合物を製造する方法としては、例えばパラ
ジウム担持触媒、水及びメタノールの存在下に脱ハロゲ
ン二量化せしめる方法（特公昭59−14015号）、さら
に、この方法の改良法として、メタノールの代りに、多
価アルコール又はホルムアルデヒドを用いる方法（特開
昭62−26238号）、ギ酸又はギ酸塩を用いる方法（Synth
esis communications 538,（1978）、特開昭61−137838
号及び特開昭61−167642号等）、一酸化炭素を用いる方
法（特開昭61−293932号）等が知られている。Conventionally, as a method for producing a biphenyl compound by dehalogenating an aromatic halogen compound, for example, a method of dehalogenating dimerization in the presence of a palladium-supported catalyst, water and methanol (JP-B-5914015), As a modified method of this method, a method using polyhydric alcohol or formaldehyde instead of methanol (JP-A-62-26238), a method using formic acid or formate salt (Synth
esis communications 538, (1978), JP-A-61-137838
And JP-A-61-167642) and a method using carbon monoxide (JP-A-61-293932).
［発明が解決しようとする課題］ 上記製造方法では、いずれもパラジウム担持触媒を用
いているが、パラジウム担持触媒の触媒活性は使用を重
ねるに従い次第に低下する。例えば、バッチ反応により
繰返し脱ハロゲン二量化反応を行なう場合、同一条件下
の反応では、バッチを重ねる毎、確実に反応内容が悪化
し、目的とするビフェニル化合物等のビアリール化合物
の収率が低下してくるのが実情であった。[Problems to be Solved by the Invention] In each of the above production methods, a palladium-supported catalyst is used, but the catalytic activity of the palladium-supported catalyst gradually decreases with repeated use. For example, when the dehalogenation dimerization reaction is repeatedly carried out by a batch reaction, under the same conditions, the reaction content is surely deteriorated every time batches are repeated, and the yield of the target biphenyl compound such as a biphenyl compound is lowered. It was the reality.
本発明者は上記事情に鑑み、芳香族ハロゲン化合物の
脱ハロゲン二量化反応において、使用したパラジウム担
持触媒を効率的に再生する方法を提供することを目的と
する。In view of the above circumstances, the present inventor aims to provide a method for efficiently regenerating a palladium-supported catalyst used in a dehalogenation dimerization reaction of an aromatic halogen compound.
［課題を解決するための手段及び作用］ 請求項（１）のパラジウム担持触媒の再生法は、少な
くとも１個のハロゲン原子を芳香核炭素に有する芳香族
ハロゲン化合物を、水、還元剤及びハロゲン受容体の存
在下、パラジウム担持触媒を用いて脱ハロゲン二量化す
る方法において、反応に用いたパラジウム担持触媒を70
〜200℃の温度の水媒体中で懸濁洗浄処理することを特
徴とする。[Means and Actions for Solving the Problems] The method for regenerating a palladium-supported catalyst according to claim (1) is directed to an aromatic halogen compound having at least one halogen atom in an aromatic nucleus carbon, water, a reducing agent and a halogen acceptor. In the method of dehalogenation and dimerization using a palladium-supported catalyst in the presence of a catalyst, the palladium-supported catalyst used in the reaction is
It is characterized in that the suspension washing treatment is carried out in an aqueous medium at a temperature of ~ 200 ° C.
請求項（２）のパラジウム担持触媒の再生法は、請求
項（１）の方法により、70〜200℃の温度の水媒体中で
懸濁洗浄処理した後のパラジウム担持触媒を、次いで、
ハロゲン化水素酸中に浸漬処理することを特徴とする。According to the method for regenerating the palladium-supported catalyst of claim (2), the palladium-supported catalyst after being subjected to suspension washing treatment in an aqueous medium at a temperature of 70 to 200 ° C. according to the method of claim (1),
It is characterized in that it is immersed in hydrohalic acid.
即ち、本発明者らは反応に用いたパラジウム担持触媒
を効率的に再生する方法を提供すべく鋭意検討を重ねた
結果、特定温度の水媒体中で、使用済のパラジウム担持
触媒を懸濁洗浄処理することにより、また、更に、処理
後ハロゲン化水素酸中に浸漬処理することにより、活性
低下した触媒が再生されることを見出し、本発明を完成
させた。That is, as a result of repeated intensive studies to provide a method for efficiently regenerating the palladium-supported catalyst used in the reaction, the present inventors suspended and washed the used palladium-supported catalyst in an aqueous medium at a specific temperature. The present invention has been completed by finding that the catalyst whose activity has been lowered is regenerated by the treatment, and further by the immersion treatment in hydrohalic acid after the treatment.
以下に本発明を詳細に説明する。 The present invention will be described in detail below.
請求項（１）の再生法においては、少なくとも１個の
ハロゲン原子を芳香核炭素に有する芳香族ハロゲン化合
物を、水、還元剤及びハロゲン受容体の存在下、パラジ
ウム担持触媒を用いて脱ハロゲン二量化する脱ハロゲン
二量化反応に使用した後のパラジウム担持触媒を70〜20
0℃の温度の水媒体中で懸濁洗浄することにより、触媒
活性を再生、向上させる。即ち、前述の如く、このよう
な脱ハロゲン二量化反応で使用したパラジウム担持触媒
はその触媒活性が低下しており、これをそのまま同一条
件の脱ハロゲン二量化反応の触媒として繰り返し使用し
た場合には、反応成績が大幅に低下するため、本発明方
法に従って、パラジウム担持触媒を水媒体中にて懸濁洗
浄処理することにより触媒活性を向上、再生する。In the regeneration method of claim (1), an aromatic halogen compound having at least one halogen atom in an aromatic carbon is dehalogenated with a palladium-supported catalyst in the presence of water, a reducing agent and a halogen acceptor. The palladium-supported catalyst after being used in the dehalogenation dimerization reaction to be quantified is 70 to 20
The catalyst activity is regenerated and improved by suspension washing in an aqueous medium at a temperature of 0 ° C. That is, as described above, the catalyst activity of the palladium-supported catalyst used in such a dehalogenation dimerization reaction is lowered, and when this is repeatedly used as it is as a catalyst for the dehalogenation dimerization reaction under the same conditions, Since the reaction results are significantly reduced, the catalyst activity is improved and regenerated by subjecting the palladium-supported catalyst to suspension washing treatment in an aqueous medium according to the method of the present invention.
懸濁洗浄処理は、通常、触媒が分散可能な必要量の脱
塩水を仕込んだ撹拌容器中にパラジウム担持触媒を混合
し撹拌することにより行なわれるが、その際の温度は70
〜200℃、好ましくは80〜150℃であり、圧力は通常、常
圧〜200kg/cm2、好ましくは常圧〜100kg/cm2であり、更
に、必要に応じて不活性ガスの存在下に実施される。ま
た、処理時間は通常５分〜５時間、好ましくは20分〜３
時間である。Suspension washing treatment is usually carried out by mixing and stirring the palladium-supported catalyst in a stirring vessel charged with a necessary amount of demineralized water in which the catalyst can be dispersed, and the temperature at that time is 70
To 200 ° C, preferably 80 to 150 ° C, the pressure is usually atmospheric pressure to 200 kg / cm 2 , preferably atmospheric pressure to 100 kg / cm 2 , and, if necessary, in the presence of an inert gas. Be implemented. The processing time is usually 5 minutes to 5 hours, preferably 20 minutes to 3
It's time.
懸濁洗浄処理の温度があまり低い場合、又は、処理時
間が極端に短い場合は、触媒の再生効果がないので好ま
しくない。この懸濁洗浄処理は２回以上に分けて実施し
ても良い。If the temperature of the suspension washing treatment is too low, or if the treatment time is extremely short, there is no catalyst regeneration effect, which is not preferable. This suspension washing treatment may be performed twice or more.
なお、本発明においては、上記の懸濁洗浄処理に先立
ち、予め、常温で同様の懸濁洗浄処理を行なうことによ
り、触媒に付着した反応液を除去しておくことが好まし
い。In the present invention, it is preferable to remove the reaction liquid adhering to the catalyst by carrying out the same suspension cleaning treatment at room temperature in advance, prior to the above suspension cleaning treatment.
請求項（２）の再生法は、請求項（１）の方法により
70〜200℃の温度の水媒体中で懸濁洗浄処理した後のパ
ラジウム担持触媒を、引き続きハロゲン化水素酸中に浸
漬処理する。The reproduction method of claim (2) is based on the method of claim (1).
The palladium-supported catalyst, which has been subjected to suspension washing treatment in an aqueous medium at a temperature of 70 to 200 ° C., is subsequently immersed in hydrohalic acid.
使用するハロゲン化水素酸としては、通常、塩酸、臭
化水素酸、ヨウ化水素酸が挙げられ、特に塩酸が好まし
い。ハロゲン化水素酸の濃度は、通常0.001〜20重量
％、好ましくは0.1〜10重量％である。また、ハロゲン
化水素酸による浸漬処理の処理温度は、通常５〜70℃、
好ましくは10〜40℃であり、処理時間は５分〜24時間と
するのが好ましい。処理後のパラジウム担持触媒は、例
えば、苛性アルカリ、炭酸アルカリなどのアルカリで系
内のpHを８〜13とした後、濾別することにより回収する
ことができる。この場合、pHが８未満でも13を超えて
も、濾液へのパラジウムの溶出ロスが大きく経済的に不
利である。The hydrohalic acid to be used usually includes hydrochloric acid, hydrobromic acid and hydroiodic acid, with hydrochloric acid being particularly preferred. The concentration of hydrohalic acid is usually 0.001 to 20% by weight, preferably 0.1 to 10% by weight. The treatment temperature of the dipping treatment with hydrohalic acid is usually 5 to 70 ° C.
The temperature is preferably 10 to 40 ° C., and the treatment time is preferably 5 minutes to 24 hours. The treated palladium-supported catalyst can be recovered by, for example, adjusting the pH of the system to 8 to 13 with an alkali such as caustic alkali or alkali carbonate, and then filtering. In this case, even if the pH is less than 8 or more than 13, the elution loss of palladium in the filtrate is large and it is economically disadvantageous.
このような懸濁洗浄処理後の浸漬処理により再生され
たパラジウム担持触媒は、処理前の触媒に比べてその活
性が著しく高いものである。従って、この触媒を用いて
同様な芳香族ハロゲン化合物の脱ハロゲン二量化反応を
繰り返し実施した場合には、従来以上に良好な反応成績
を得ることができる。The palladium-supported catalyst regenerated by the immersion treatment after such suspension washing treatment has a significantly higher activity than the catalyst before treatment. Therefore, when the same dehalogenation dimerization reaction of an aromatic halogen compound is repeatedly carried out using this catalyst, a better reaction result than ever can be obtained.
以下に、本発明のパラジウム担持触媒の再生法の適用
対象である脱ハロゲン二量化反応について説明する。The dehalogenation dimerization reaction to which the palladium-supported catalyst regeneration method of the present invention is applied will be described below.
該脱ハロゲン二量化反応における出発物質としては、
少なくとも１個のハロゲン原子を芳香核炭素に有する芳
香族ハロンゲ化合物が使用される。芳香核炭素にある少
なくとも１個のハロゲン原子としては、ヨウ素、臭素及
び塩素が挙げられるが、臭素及び塩素が好ましく、特に
安価な塩素を用いるのが好適である。芳香族化合物の芳
香核に置換しているハロゲン原子が２以上の場合、該ハ
ロゲン原子は各々同一あるいは異なっていても良い。ま
た、置換するハロゲン原子数は６個まで可能で、ハロゲ
ン原子数が多い場合には、二量化と共に脱ハロゲン化が
起こり得るが、ハロゲン原子数は１〜２個、特に１個が
好ましい。この芳香族化合物の核炭素には前記の少なく
とも１個のハロゲン原子以外の置換基を有することがで
きるが、ハロゲン原子の隣接炭素に他の置換基を有する
場合、あるいは複数のハロゲン原子が隣接する場合に
は、ビアリール化合物の収率が低下する場合がある。As the starting material in the dehalogenation dimerization reaction,
Aromatic halonge compounds having at least one halogen atom on the aromatic carbon are used. Examples of the at least one halogen atom in the aromatic nucleus carbon include iodine, bromine and chlorine, but bromine and chlorine are preferable, and particularly inexpensive chlorine is preferably used. When the aromatic nucleus of the aromatic compound has two or more halogen atoms, the halogen atoms may be the same or different. Further, the number of halogen atoms to be substituted can be up to 6, and when the number of halogen atoms is large, dehalogenation may occur together with dimerization, but the number of halogen atoms is preferably 1 to 2, particularly preferably 1. The nuclear carbon of this aromatic compound may have a substituent other than at least one halogen atom described above, but in the case where the carbon adjacent to the halogen atom has another substituent, or a plurality of halogen atoms are adjacent to each other. In some cases, the yield of the biaryl compound may decrease.
本発明に係る反応においては、アルカリ水溶液に可溶
な原料を用いることが有利であり、そのためには、通常
１〜２個のカルボキシル基又は水酸基で置換された芳香
族ハロゲン化合物が望ましい。なお、芳香族化合物とし
ては、通常単環式化合物が使用される。In the reaction according to the present invention, it is advantageous to use a raw material that is soluble in an alkaline aqueous solution, and for that purpose, an aromatic halogen compound substituted with 1 to 2 carboxyl groups or hydroxyl groups is usually desirable. A monocyclic compound is usually used as the aromatic compound.
原料として用いられる芳香族ハロゲン化合物の具体例
としては、例えばクロロベンゼン、ｐ−クロロブロモベ
ンゼン、ｐ−クロロジフェニル、ｐ−クロロフェノー
ル、ｐ−クロロアニソール、ｐ−クロロベンズアミド、
ｐ−クロロアニリン、ｐ−クロロニトロベンゼン、ｐ−
クロロベンゾフェノン、ｐ−クロロアセトフェノン、ｐ
−クロロベンゼンスルホン酸ナトリウム塩、ｐ−クロロ
安息香酸及びそのリチウム、ナトリウム、カリウム等の
アルカリ金属塩、ｐ−クロロベンゾニトリル、ｍ−ブロ
モ安息香酸及びそのリチウム、ナトリウム、カリウム等
のアルカリ金属塩、β−クロロナフタリン、４−クロロ
オルソキシレン、４−クロオルソフタル酸及びそのリチ
ウム、ナトリウム、カリウム等のアルカリ金属塩、４−
クロロフタル酸無水物、及び4,5−ジクロロフタル酸等
が挙げられ、これらは１種を単独で、或いは２種以上を
混合して使用することができる。Specific examples of the aromatic halogen compound used as a raw material include, for example, chlorobenzene, p-chlorobromobenzene, p-chlorodiphenyl, p-chlorophenol, p-chloroanisole, p-chlorobenzamide,
p-chloroaniline, p-chloronitrobenzene, p-
Chlorobenzophenone, p-chloroacetophenone, p
-Chlorobenzenesulfonic acid sodium salt, p-chlorobenzoic acid and its alkali metal salts such as lithium, sodium and potassium, p-chlorobenzonitrile, m-bromobenzoic acid and its alkali metal salts such as lithium, sodium and potassium, β -Chloronaphthalene, 4-chloroorthoxylene, 4-chloroorthophthalic acid and its alkali metal salts such as lithium, sodium and potassium, 4-
Examples thereof include chlorophthalic anhydride and 4,5-dichlorophthalic acid. These can be used alone or in combination of two or more.
特に、４−クロロオルソフタル酸、そのアルカリ金属
塩、又はその酸無水物を単独で或いはそれらの１種を主
成分とする混合物を用いた場合には、耐熱性ポリイミド
原料である3,4,3′,4′−ビフェニルテトラカルボン酸
アルカリ金属塩が得られるので有利である。Particularly, when 4-chloroorthophthalic acid, an alkali metal salt thereof, or an acid anhydride thereof is used alone or in a mixture containing one of them as a main component, it is a heat-resistant polyimide raw material. Advantageously, an alkali metal salt of 3 ', 4'-biphenyltetracarboxylic acid is obtained.
水は、前記芳香族ハロゲン化合物が水溶性である場
合、これを溶解した水溶液として、又は直接反応系に添
加して用いられる。使用する水の量は、通常芳香族ハロ
ゲン化合物、パラジウム触媒、還元剤及びハロゲン受容
体を含む反応成分に対し少なくとも0.1容量％以上、好
ましくは１容量％以上である。芳香族ハロゲン化合物が
アルカリ水溶性である場合は、溶媒量使用するのが好適
である。一方、芳香族ハロゲン化合物が非水溶性の場
合、多量の水の使用はかえってビアリール化合物の収率
を低下させることがあるので、水の使用量は１〜60容量
％の範囲から選択して用いるのが好ましい。水の使用量
が前記範囲より少ないか、もしくは水を添加しない場合
は、ビアリール化合物の収率及び選択率が低下し好まし
くない。When the aromatic halogen compound is water-soluble, water is used as an aqueous solution in which the aromatic halogen compound is dissolved or added directly to the reaction system. The amount of water used is usually at least 0.1% by volume, preferably 1% by volume or more, based on the reaction components containing the aromatic halogen compound, the palladium catalyst, the reducing agent and the halogen acceptor. When the aromatic halogen compound is water-soluble in alkali, it is preferable to use a solvent amount. On the other hand, when the aromatic halogen compound is water-insoluble, use of a large amount of water may rather lower the yield of the biaryl compound, so the amount of water used is selected from the range of 1 to 60% by volume. Is preferred. If the amount of water used is less than the above range or if water is not added, the yield and selectivity of the biaryl compound decrease, which is not preferable.
本発明に係る脱ハロゲン二量化反応で用いる還元剤と
しては、通常、アルコール類、一酸化炭素、クロロホル
ム、ホルムアルデヒド類等が挙げられ、なかでもアルコ
ール類が特に好ましい。アルコール類としては、例え
ば、メタノール、エタノール、プロパノールなどの１価
アルコール、エチレングリコール、プロピレングリコー
ル、1,2−ブタンジオール、1,3−プロパンジオール、1,
4−ブタンジオール等の２価アルコール、グリセリン等
の３価アルコール、ペンタエリスリトール等の４価アル
コールが挙げられ、なかでもエチレングリコール、プロ
ピレングリコール、1,2−ブタンジオール、グリセリン
等の２価又は３価アルコールが好適である。ホルムアル
デヒド類としては、通常、パラホルムアルデヒド、ホル
マリンが挙げられる。Examples of the reducing agent used in the dehalogenation dimerization reaction according to the present invention generally include alcohols, carbon monoxide, chloroform, formaldehydes and the like, and among them, alcohols are particularly preferable. Examples of alcohols include monohydric alcohols such as methanol, ethanol and propanol, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-propanediol, 1,
Examples thereof include dihydric alcohols such as 4-butanediol, trihydric alcohols such as glycerin, and tetrahydric alcohols such as pentaerythritol. Among them, dihydric or trihydric compounds such as ethylene glycol, propylene glycol, 1,2-butanediol, and glycerin. Polyhydric alcohols are preferred. Examples of formaldehydes usually include paraformaldehyde and formalin.
このような還元剤の使用量は、通常原料の芳香族ハロ
ゲン化合物１モルに対して、0.01〜50モル、好ましくは
0.1〜10モルである。還元剤として一酸化炭素を使用す
る場合には、通常、その分圧が0.1〜6kg/cm2、好ましく
は、１〜10kg/cm2となるように調節される。一酸化炭素
は純粋ガスとして用いても、また、混合ガス、例えば、
窒素ガスなどの他のガスとの混合ガスとして用いても良
い。The amount of such reducing agent used is usually 0.01 to 50 mol, preferably 1 to 50 mol, preferably 1 mol of the aromatic halogen compound.
It is 0.1 to 10 mol. When carbon monoxide is used as the reducing agent, the partial pressure is usually adjusted to 0.1 to 6 kg / cm 2 , preferably 1 to 10 kg / cm 2 . Carbon monoxide may be used as a pure gas, or it may be a mixed gas such as
It may be used as a mixed gas with other gas such as nitrogen gas.
また、ハロゲン受容体としては、脱ハロゲン二量化の
際に生じるハロゲン原子を受容できる物質であれば良
く、通常は、塩基性物質が用いられる。この塩基性物質
としては、例えば、アンモニア、アルカリ金属化合物、
アルカリ土類金属化合物等が挙げられる。これらの中で
もアルカリ金属化合物又はアルカリ土類金属化合物が好
適であり、具体的にはアルカリ金属又はアルカリ土類金
属の水酸化物、炭酸、硝酸、リン酸、ホウ酸等の無機酸
塩、酢酸、フタル酸等の有機酸塩、及びアルコキシド類
等が挙げられる。The halogen acceptor may be any substance that can accept a halogen atom generated during dehalogenation dimerization, and a basic substance is usually used. Examples of the basic substance include ammonia, alkali metal compounds,
Examples thereof include alkaline earth metal compounds. Among these, alkali metal compounds or alkaline earth metal compounds are preferable, and specifically, alkali metal or alkaline earth metal hydroxides, carbonic acid, nitric acid, phosphoric acid, inorganic acid salts such as boric acid, acetic acid, Examples thereof include organic acid salts such as phthalic acid and alkoxides.
特に好ましい具体例は、水酸化リチウム、水酸化ナト
リウム、水酸化カリウム、水酸化マグネシウム、水酸化
カルシウム、水酸化バリウム等の水酸化物、炭酸ナトリ
ウム、炭酸カリウム、炭酸水素ナトリウム等の炭酸塩、
ナトリウムメトキシド、ナトリウムエトキシド、カリウ
ムターシャリーブチレート等のアルコキシドであるが、
炭酸塩は水酸化物に比べ反応収率がやや低い場合もある
ので、水酸化物がより好ましい。Particularly preferred specific examples are lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, hydroxides such as barium hydroxide, sodium carbonate, potassium carbonate, carbonates such as sodium hydrogen carbonate,
Alkoxides such as sodium methoxide, sodium ethoxide, potassium tertiary butyrate,
Hydrocarbons are more preferred because carbonates may have a slightly lower reaction yield than hydroxides.
このようなハロゲン受容体を併用することにより、ビ
アリール化合物類をより高収率で得ることが可能とな
る。これらハロゲン受容体の使用量は出発原料である芳
香族ハロゲン化合物中に含まれるハロゲン原子数及びカ
ルボキシル基等の酸性置換基の有無などによっても異な
り、特に限定されるものではないが、通常は、芳香族ハ
ロゲン化合物１モルに対し0.01〜100モル、好ましくは
0.1〜20モルの範囲で用いられる。ハロゲン受容体の使
用量が上記範囲外の場合には、ビアリール化合物の収率
が低下する等の不具合が生じ、好ましくない。By using such a halogen acceptor in combination, it becomes possible to obtain the biaryl compounds in a higher yield. The amount of these halogen acceptors used depends on the number of halogen atoms contained in the starting aromatic halogen compound and the presence or absence of an acidic substituent such as a carboxyl group, and is not particularly limited, but usually, 0.01-100 mol, preferably 1 mol, of aromatic halogen compound
It is used in the range of 0.1 to 20 mol. If the amount of the halogen acceptor used is outside the above range, problems such as a decrease in the yield of the biaryl compound occur, which is not preferable.
本発明に係る脱ハロゲン二量化反応で使用するパラジ
ウム担持触媒としては、金属パラジウムを、例えば、活
性炭、シリカ、アルミナ、シリカアルミナ、酸化チタ
ン、マグネシア、珪藻土、グラファイト、炭酸バリウ
ム、炭酸カルシウム、ゼオライト等の担体に担持させた
ものが挙げられ、特にパラジウム−活性炭触媒が好適で
ある。金属パラジウムは、通常、パラジウム担体に対し
て0.1〜20重量％、特に0.5〜10重量％程度担持されてい
るのが好適である。Examples of the palladium-supported catalyst used in the dehalogenation dimerization reaction according to the present invention include metallic palladium, for example, activated carbon, silica, alumina, silica-alumina, titanium oxide, magnesia, diatomaceous earth, graphite, barium carbonate, calcium carbonate, zeolite and the like. The carrier supported on the carrier is exemplified, and a palladium-activated carbon catalyst is particularly preferable. It is preferable that the palladium metal is usually supported on the palladium carrier in an amount of 0.1 to 20% by weight, particularly 0.5 to 10% by weight.
パラジウム担持触媒の使用量は、通常、芳香族ハロゲ
ン化合物１モルに対し、パラジウム原子換算で100〜0.0
01ミリグラム原子、好ましくは30〜0.1ミリグラム原子
である。The amount of the palladium-supported catalyst used is usually 100 to 0.0 in terms of palladium atom based on 1 mol of the aromatic halogen compound.
It is 01 milligram atom, preferably 30-0.1 milligram atom.
なお、本発明においては、少量の助触媒を併用するこ
ともできる。例えば、パラジウム担持触媒は、パラジウ
ムに対して20％以下の少量のルテニウム、金、ニッケ
ル、セリウム等を助触媒として含んでいても差し支えな
い。In the present invention, a small amount of cocatalyst can be used together. For example, the palladium-supported catalyst may contain a small amount of ruthenium, gold, nickel, cerium or the like, which is 20% or less with respect to palladium, as a cocatalyst.
本発明に係る脱ハロゲン二量化反応は、溶媒の存在下
又は非存在下のいずれでも実施し得るが、溶媒を使用す
る場合、溶媒としては反応に不活性な溶媒が用いられ
る。この溶媒としては、例えば、テトラヒドロフラン、
ジオキサン等のエーテル化合物、アセトン、ジエチルケ
トン、メチルエチルケトン等のケトン化合物及びエチレ
ングリコールジアセテート等のエステル化合物等から選
択される１種又は２種以上が用いられる。かかる溶媒の
使用量は、特に限定されるものではないが、通常、芳香
族ハロゲン化合物１重量部に対し、0.01〜100重量部の
範囲で用いられる。The dehalogenation dimerization reaction according to the present invention can be carried out in the presence or absence of a solvent. When a solvent is used, a solvent inert to the reaction is used. Examples of the solvent include tetrahydrofuran,
One or more selected from ether compounds such as dioxane, ketone compounds such as acetone, diethyl ketone and methyl ethyl ketone, and ester compounds such as ethylene glycol diacetate are used. The amount of such a solvent used is not particularly limited, but is usually 0.01 to 100 parts by weight per 1 part by weight of the aromatic halogen compound.
脱ハロゲン二量化反応の温度は、通常20〜250℃、好
ましくは50〜200℃であり、圧力は通常、常圧〜200kg/c
m2、好ましくは常圧〜100kg/cm2である。また、反応時
間は原料の種類、触媒量、反応温度等に応じて適宜決定
されるが、通常10分〜24時間の範囲である。The temperature of the dehalogenation dimerization reaction is usually 20 to 250 ° C, preferably 50 to 200 ° C, and the pressure is usually atmospheric pressure to 200 kg / c.
m 2 , preferably atmospheric pressure to 100 kg / cm 2 . The reaction time is appropriately determined depending on the type of raw material, the amount of catalyst, the reaction temperature, etc., but is usually in the range of 10 minutes to 24 hours.
本発明に係る脱ハロゲン二量化反応は、回分法、半回
分法又は連続法のいずれでも実施することができる。回
分法で実施する場合には、反応器に所定量の芳香族ハロ
ゲン化合物、水、還元剤、ハロゲン受容体及びパラジウ
ム担持触媒、さらに必要に応じて溶媒を仕込み、撹拌
下、所望の反応温度に加熱し反応を行なわせることがで
きる。The dehalogenation dimerization reaction according to the present invention can be carried out by either a batch method, a semi-batch method or a continuous method. When carrying out by the batch method, a reactor is charged with a predetermined amount of an aromatic halogen compound, water, a reducing agent, a halogen acceptor and a palladium-supported catalyst, and if necessary, a solvent, and the mixture is stirred at a desired reaction temperature. The reaction can be carried out by heating.
反応終了後の混合物は、通常、濾過によりパラジウム
担持触媒を分離した後、得られたビアリール化合物の性
状に応じて、例えば、蒸留、晶析又は酸析などの方法に
よって目的化合物を回収する。After the reaction, the mixture is usually filtered to separate the palladium-supported catalyst, and then the target compound is recovered by a method such as distillation, crystallization or acid precipitation depending on the properties of the obtained biaryl compound.
［実施例］ 以下に実施例及び比較例を挙げて本発明をより具体的
に詳細に説明するが、本発明はその要旨を超えない限
り、以下の実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
実施例１ ［触媒の再生処理］ 内容積500mlのパイレックス製ビーカーに、４−クロ
ロフタル酸の脱ハロゲン二量化反応に８回繰り返し使用
したパラジウム担持触媒32.5g（活性炭8.42g、Pd443mg
を含有する。）及び脱塩水375mlを入れ、30℃にて30分
間撹拌した後、No.5Cの濾紙（東洋濾紙（株）製）にて
濾別した。引き続き、500mlの４つ口フラスコに脱塩水3
50ml及び濾別した触媒を入れ、還流下で２時間撹拌を行
なった後、50℃迄冷却し、No.5Cの濾紙にて濾別した。
この濾別した触媒を、1000mlのパイレックス製ビーカー
に7.3重量％塩酸400mlと共に入れ、30℃で2.5時間撹拌
を行なった。次いで、25重量％苛性ソーダ水溶液を滴下
し、内容物のpHを11とし、更に室温で10分間撹拌を続け
た後No.5Cの濾紙にて濾別した。Example 1 [Regeneration of catalyst] 32.5 g of palladium-supported catalyst (8.42 g of activated carbon, Pd 443 mg of Pd) was repeatedly used in a dehalogenation dimerization reaction of 4-chlorophthalic acid in a beaker made of Pyrex with an internal volume of 500 ml eight times.
Contains. ) And deionized water (375 ml) were added, the mixture was stirred at 30 ° C. for 30 minutes, and then filtered with No. 5C filter paper (manufactured by Toyo Roshi Kaisha, Ltd.). Continuously, add 3 ml of demineralized water to a 500 ml 4-neck flask.
After adding 50 ml of the catalyst separated by filtration and stirring under reflux for 2 hours, the mixture was cooled to 50 ° C. and filtered with No. 5C filter paper.
The catalyst separated by filtration was put in a 1000 ml Pyrex beaker together with 400 ml of 7.3% by weight hydrochloric acid, and the mixture was stirred at 30 ° C. for 2.5 hours. Then, a 25 wt% caustic soda aqueous solution was added dropwise to adjust the pH of the contents to 11, and the mixture was further stirred at room temperature for 10 minutes and then filtered off with a No. 5C filter paper.
［二量化反応］ 1.5Lのステンレス製誘導撹拌機付きオートクレーブ
に、上記再生処理を施したパラジウム−活性炭担持触媒
の全量と、４−クロロフタル酸モノナトリウム塩を主成
分とする白色粉末300.0g（４−クロロフタル酸モノナト
リウム塩740.6m mol、３−クロロフタル酸モノナトリウ
ム塩146.6m mol、4,5−ジクロロフタル酸モノナトリウ
ム塩45.6m mol、3,4−ジクロロフタル酸モノナトリウム
塩31.8m mol及びフタル酸モノナトリウム塩344.1m mol
を含む。）と、25重量％苛性ソーダ水溶液537.3g（335
8.4m mol）と、脱塩水334.3gとグリセリン23.99g（260.
5m mol）とを入れ、窒素雰囲気下で撹拌しつつ加熱し、
108℃で５時間反応を行なった後、液体クロマトグラフ
ィーにより分析を行ない、原料の転化率及び所望とする
ビフェニルテトラカルボン酸４ナトリウム塩（以下、
「Ｓ−BTC塩」と略す。）の収率を求めた。[Dimerization reaction] To a 1.5 L stainless steel autoclave with an induction stirrer, the total amount of the palladium-activated carbon-supported catalyst subjected to the above-mentioned regeneration treatment and white powder 300.0 g (4 -Chlorophthalic acid monosodium salt 740.6 mmol, 3-chlorophthalic acid monosodium salt 146.6 mmol, 4,5-dichlorophthalic acid monosodium salt 45.6 mmol, 3,4-dichlorophthalic acid monosodium salt 31.8 mmol and phthal Acid monosodium salt 344.1 mmol
including. ), And 537.3 g (335%
8.4mmol), deionized water 334.3g and glycerin 23.99g (260.
5m mol), and heat while stirring under a nitrogen atmosphere,
After performing the reaction at 108 ° C. for 5 hours, analysis by liquid chromatography was performed, and the conversion rate of the raw material and the desired biphenyltetracarboxylic acid tetrasodium salt (hereinafter,
Abbreviated as "S-BTC salt". ) Was determined.
結果を第１表に示す。 The results are shown in Table 1.
なお、転化率、収率は下記式により算出した。 The conversion rate and the yield were calculated by the following formulas.
原料の転化率（モル％） Ｓ−BTC塩収率（モル％） 実施例２ 触媒再生処理の加熱下での水媒体中への懸濁洗浄処理
を1.5Lステンレス製誘導撹拌機付きオートクレーブを用
い、窒素雰囲気下150℃、5kg/cm2−Ｇで２時間行なった
こと以外は実施例１と同様に再生処理し、同様に二量化
反応を行なって、原料の転化率及びＳ−BTC塩の収率を
求めた。Raw material conversion (mol%) S-BTC salt yield (mol%) Example 2 A catalyst regenerating treatment was carried out by suspension washing treatment in an aqueous medium under heating, using an autoclave equipped with a 1.5 L stainless steel induction stirrer under a nitrogen atmosphere at 150 ° C. and 5 kg / cm 2 -G for 2 hours. Regeneration was carried out in the same manner as in Example 1 except that the dimerization reaction was carried out in the same manner as above, and the conversion rate of the raw materials and the yield of the S-BTC salt were determined.
結果を第１表に示す。 The results are shown in Table 1.
実施例３ 触媒再生処理の加熱下での懸濁洗浄処理を80℃で行な
ったこと以外は実施例１と同様に再生処理し、同様に二
量化反応を行なって、原料の転化率及びＳ−BTC塩の収
率を求めた。Example 3 Regeneration treatment was carried out in the same manner as in Example 1 except that the suspension washing treatment under heating of the catalyst regeneration treatment was carried out at 80 ° C., and the dimerization reaction was conducted in the same manner as in Example 1 to convert the raw material and the S The yield of BTC salt was determined.
結果を第１表に示す。 The results are shown in Table 1.
実施例４ 触媒再生処理の7.3重量％塩酸中への浸漬処理を５時
間行なったこと以外は実施例１と同様に再生処理し、同
様に二量化反応を行なって、原料の転化率及びＳ−BTC
塩の収率を求めた。Example 4 The regeneration treatment was performed in the same manner as in Example 1 except that the catalyst regeneration treatment was performed by dipping in 7.3 wt% hydrochloric acid for 5 hours. BTC
The salt yield was determined.
結果を第１表に示す。 The results are shown in Table 1.
比較例１ 触媒再生処理の加熱下での水媒体中への懸濁洗浄処理
を行なわなかったこと以外は実施例１と同様に処理し、
同様に二量化反応を行なって、原料の転化率及びＳ−BT
C塩の収率を求めた。Comparative Example 1 The same treatment as in Example 1 was carried out except that the suspension washing treatment in an aqueous medium under heating in the catalyst regeneration treatment was not performed.
Similarly, a dimerization reaction is performed to convert the raw material and the S-BT.
The yield of C salt was determined.
結果を第１表に示す。 The results are shown in Table 1.
実施例５ 触媒再生処理の7.3重量％塩酸中への浸漬処理を行な
わなかったこと以外は実施例１と同様に再生処理し、同
様に二量化反応を行なって、原料の転化率及びＳ−BTC
塩の収率を求めた。Example 5 Regeneration treatment was performed in the same manner as in Example 1 except that the catalyst regeneration treatment was not performed by dipping in 7.3 wt% hydrochloric acid, and a dimerization reaction was performed in the same manner as in Example 1 to convert the raw material and the S-BTC.
The salt yield was determined.
結果を第２表に示す。 The results are shown in Table 2.
比較例２ 触媒再生処理の加熱下での水媒体中への懸濁洗浄処理
及び塩酸中での浸漬処理を行なわなかったこと以外は実
施例１と同様に処理し、同様に二量化反応を行なって、
原料の転化率及びＳ−BTC塩の収率を求めた。Comparative Example 2 The same dimerization reaction was carried out as in Example 1 except that the suspension washing treatment in an aqueous medium under heating in the catalyst regeneration treatment and the dipping treatment in hydrochloric acid were not conducted. hand,
The conversion of raw materials and the yield of S-BTC salt were determined.
結果を第２表に示す。 The results are shown in Table 2.
第１表及び第２表より、本発明の方法によれば、パラ
ジウム担持触媒が高度に再生され、触媒活性の高いパラ
ジウム担持触媒が得られ、得られたパラジウム担持触媒
は反応に再使用し、良好な反応成績を得ることができる
ことが明らかである。From Table 1 and Table 2, according to the method of the present invention, the palladium-supported catalyst was highly regenerated, a palladium-supported catalyst having high catalytic activity was obtained, and the obtained palladium-supported catalyst was reused in the reaction, It is clear that good reaction results can be obtained.
［発明の効果］ 以上詳述した通り、本発明のパラジウム担持触媒の再
生法によれば、脱ハロゲン二量化反応に用いたパラジウ
ム担持触媒を、容易かつ効率的に再生し、著しく触媒活
性が高められたパラジウム担持触媒を得ることが可能と
される。しかして、再生されたパラジウム担持触媒は、
脱ハロゲン二量化に有効に再使用することができ、高い
転化率及び収率にて脱ハロゲン二量化反応を実施するこ
とが可能とされる。このように、本発明の方法によれ
ば、高価なパラジウム担持触媒を繰り返し再使用するこ
とが可能とされ、工業的、経済的に極めて有利である。 [Effects of the Invention] As described in detail above, according to the method for regenerating a palladium-supported catalyst of the present invention, the palladium-supported catalyst used in the dehalogenation dimerization reaction is easily and efficiently regenerated, and the catalytic activity is significantly enhanced. The obtained palladium-supported catalyst can be obtained. Then, the regenerated palladium-supported catalyst is
It can be effectively reused for dehalogenation dimerization, and it is possible to carry out the dehalogenation dimerization reaction with high conversion and yield. Thus, according to the method of the present invention, an expensive palladium-supported catalyst can be repeatedly reused, which is extremely advantageous industrially and economically.
特に、請求項（２）の方法に従って、懸濁洗浄処理し
た後のパラジウム担持触媒を、ハロゲン化水素酸中に浸
漬処理することにより、パラジウム担持触媒を著しく高
度に再生することが可能とされる。In particular, according to the method of claim (2), the palladium-supported catalyst after the suspension washing treatment is dipped in hydrohalic acid so that the palladium-supported catalyst can be remarkably regenerated. .
フロントページの続き (72)発明者 高井 正樹 神奈川県横浜市緑区鴨志田町1000番地 三 菱化成株式会社総合研究所内 (56)参考文献 特公 昭42−20480（ＪＰ，Ｂ１)Front page continuation (72) Inventor Masaki Takai 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Co., Ltd. Research Institute (56) Reference Japanese Patent Publication No. 42-20480 (JP, B1)
Claims (2)
素に有する芳香族ハロゲン化合物を、水、還元剤及びハ
ロゲン受容体の存在下、パラジウム担持触媒を用いて脱
ハロゲン二量化する方法において、反応に用いたパラジ
ウム担持触媒を70〜200℃の温度の水媒体中で懸濁洗浄
処理することを特徴とするパラジウム担持触媒の再生
法。1. A method of dehalogenating an aromatic halogen compound having at least one halogen atom in an aromatic nucleus carbon in the presence of water, a reducing agent and a halogen acceptor, using a palladium-supported catalyst, to carry out a reaction. A method for regenerating a palladium-supported catalyst, which comprises subjecting the palladium-supported catalyst used in step 1 to suspension washing treatment in an aqueous medium at a temperature of 70 to 200 ° C.
理した後のパラジウム担持触媒を、次いで、ハロゲン化
水素酸中に浸漬処理することを特徴とする特許請求の範
囲第１項に記載の再生法。2. The palladium-supported catalyst, which has been subjected to suspension washing treatment in an aqueous medium at a temperature of 70 to 200 ° C., is then subjected to immersion treatment in hydrohalic acid. Regeneration method described in paragraph.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63315389A JPH089001B2 (en) | 1988-12-14 | 1988-12-14 | Regeneration method of palladium supported catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63315389A JPH089001B2 (en) | 1988-12-14 | 1988-12-14 | Regeneration method of palladium supported catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02160048A JPH02160048A (en) | 1990-06-20 |
| JPH089001B2 true JPH089001B2 (en) | 1996-01-31 |
Family
ID=18064809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63315389A Expired - Lifetime JPH089001B2 (en) | 1988-12-14 | 1988-12-14 | Regeneration method of palladium supported catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089001B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004275936A (en) * | 2003-03-18 | 2004-10-07 | Nippon Paper Industries Co Ltd | Method for washing activated carbon catalyst for oxidizing white liquor, and white liquor oxidizing apparatus equipped with washing mechanism |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5321168A (en) * | 1993-09-16 | 1994-06-14 | Exxon Chemical Patents Inc. | Activation of cobalt preformer catalyst for oxo process |
-
1988
- 1988-12-14 JP JP63315389A patent/JPH089001B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004275936A (en) * | 2003-03-18 | 2004-10-07 | Nippon Paper Industries Co Ltd | Method for washing activated carbon catalyst for oxidizing white liquor, and white liquor oxidizing apparatus equipped with washing mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02160048A (en) | 1990-06-20 |
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