JPH062725B2 - Method for producing α-anthraquinone sulfonic acid and recovering the catalyst used therein - Google Patents
Method for producing α-anthraquinone sulfonic acid and recovering the catalyst used thereinInfo
- Publication number
- JPH062725B2 JPH062725B2 JP63278489A JP27848988A JPH062725B2 JP H062725 B2 JPH062725 B2 JP H062725B2 JP 63278489 A JP63278489 A JP 63278489A JP 27848988 A JP27848988 A JP 27848988A JP H062725 B2 JPH062725 B2 JP H062725B2
- Authority
- JP
- Japan
- Prior art keywords
- metal catalyst
- palladium
- anthraquinone
- acid
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 78
- 229910052763 palladium Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 238000006277 sulfonation reaction Methods 0.000 claims description 19
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 150000004056 anthraquinones Chemical class 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkali metal salts Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000005185 salting out Methods 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- WWPPXDOOKMWVDN-UHFFFAOYSA-N 3-amino-3,4-dihydro-1h-1,5-naphthyridin-2-one Chemical compound C1=CC=C2NC(=O)C(N)CC2=N1 WWPPXDOOKMWVDN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 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〕 本発明はアントラキノンを発煙硫酸にてスルホン化させ
てα−アントラキノンスルホン酸を製造し、生成したス
ルホン化混合物に溶解している触媒を回収する方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention produces an α-anthraquinone sulfonic acid by sulfonating anthraquinone with fuming sulfuric acid, and recovers a catalyst dissolved in a sulfonation mixture formed. Regarding the method.
アントラキノンを溶媒にてスルホン化させてα−アント
ラキノンスルホン酸を製造する方法には金属型触媒を必
要とする。従来、高い変換率とα−選択性のスルホン化
反応に達するための色々の触媒と溶媒が開示され、触媒
の回収方法も開示されている。The method for producing α-anthraquinone sulfonic acid by sulfonating anthraquinone with a solvent requires a metal type catalyst. Heretofore, various catalysts and solvents have been disclosed for reaching a high conversion and α-selective sulfonation reaction, and a method for recovering the catalyst has also been disclosed.
Kirm-Othmer,"Encyclopedia of Chemical Technology",
3rd edtion (1978),vol.2,P.729に開示している１−ア
ントラキノンスルホン酸の周知の製造方法はアントラキ
ノンを発煙硫酸に水銀塩の存在下でスルホン化させるも
ので、出発アントラキノンの約45％が変換されると、ジ
スルホン化反応が顕著になるから、スルホン化反応を中
止する必要がある。米国特許第3,763,191号には特にパ
ラジウムまたはそれを含む化合物を用いて実質上より高
い選択性でα−アントラキノンスルホン酸を製造する方
法を記載している。該米国特許の実施例に示すα−選択
性とスルホン化反応の程度はいまだに要求に達していな
い、そして反応混合物に安定されている触媒の回収方法
も記載されていない。また、米国特許第3,792,065号に
は水銀をほとんど避けたα−アントラキノンスルホン酸
を製造する方法を記載している。それには水銀は硫酸塩
の形態で触媒として導入され、還元剤を加えて金属に
し、スルホン化混合物から分離させる。Kirm-Othmer, "Encyclopedia of Chemical Technology",
A well-known method for producing 1-anthraquinonesulfonic acid disclosed in 3rd edtion (1978), vol.2, P.729 is to sulfonate anthraquinone to fuming sulfuric acid in the presence of a mercury salt. When 45% is converted, the disulfonation reaction becomes remarkable, so it is necessary to stop the sulfonation reaction. U.S. Pat. No. 3,763,191 describes a process for producing .alpha.-anthraquinone sulfonic acids with substantially higher selectivity, especially using palladium or compounds containing it. The α-selectivity and degree of sulfonation reaction shown in the examples of said US patent have not yet been met, and no method for recovering a catalyst which is stable in the reaction mixture is described. Also, U.S. Pat. No. 3,792,065 describes a method for producing .alpha.-anthraquinone sulfonic acid which is almost free of mercury. To that, mercury is introduced as a catalyst in the form of a sulphate, a reducing agent is added to the metal and it is separated from the sulphonation mixture.
液体二酸化硫黄の溶媒にてアントラキノンのα−スルホ
ン化を選択的に促進する新規な触媒を日本化学誌1980
(3)P.322-326の川端康治郎等による「液体二酸化硫黄中
での三酸化硫黄によるアントラキノンのα−スルホン化
におけるパラジウムの触媒作用」に記載している、それ
にはスルホン化反応に液体二酸化硫黄とパラジウムを含
む化合物を用いることによりアントラキノンの変換率が
100％、アントラキノンスルホン酸の収率が76％、α−
選択率が99％に達した。川端らは更に可溶化した活性炭
付きパラジウムを水素処理により再沈着させる方法を記
載し、反応混合物のpH値を＞７に調整した後、20気圧の
水素を導入して、可溶化した活性炭付きパラジウムを沈
着させたが、回収した活性炭付きパラジウムを再循環さ
せると、アントラキノンの変換率が70％に低下した。ま
た、活性炭付きパラジウムを除去した後、混合物に空気
または酸素を導入してモノアントラキノンスルホン酸の
塩を沈澱させる。A new catalyst that selectively promotes the α-sulfonation of anthraquinone in a solvent of liquid sulfur dioxide is published in Japan Chemical Journal 1980.
(3) P.322-326, K. Kawabata et al., `` Palladium Catalysis in α-Sulfonation of Anthraquinone by Sulfur Trioxide in Liquid Sulfur Dioxide ''. By using a compound containing sulfur and palladium, the conversion rate of anthraquinone
100%, the yield of anthraquinone sulfonic acid is 76%, α-
The selectivity reaches 99%. Kawabata et al. Describe a method of redepositing solubilized palladium with activated carbon by hydrogen treatment. After adjusting the pH value of the reaction mixture to> 7, hydrogen at 20 atm was introduced to solubilize palladium with activated carbon. However, when the recovered palladium on activated carbon was recycled, the conversion of anthraquinone was reduced to 70%. Further, after removing the palladium with activated carbon, air or oxygen is introduced into the mixture to precipitate the salt of monoanthraquinonesulfonic acid.
本発明はα−アントラキノンスルホン酸を製造する方法
であり、多孔性担体に沈着した金属触媒の存在下、発煙
硫酸にてアントラキノンをスルホン化させて、スルホン
化反応生成混合物を還元剤で処理して可溶化金属触媒等
を再沈着した後、触媒を濾過して、混合物からα−アン
トラキノンスルホン酸生成物を分離する。The present invention is a method for producing α-anthraquinone sulfonic acid, wherein anthraquinone is sulfonated with fuming sulfuric acid in the presence of a metal catalyst deposited on a porous carrier, and the sulfonation reaction product mixture is treated with a reducing agent. After redepositing the solubilized metal catalyst etc., the catalyst is filtered to separate the α-anthraquinone sulfonic acid product from the mixture.
上記スルホン化反応は高変換率と高選択性およびほとん
ど同じ活性を保持する回収触媒により、どんな周知の方
法よりもっと経済的なα−アントラキノンスルホン酸を
製造する方法を提供する。The above sulfonation reaction provides a more economical method of producing α-anthraquinone sulfonic acid than any known method, with the recovery catalyst retaining high conversion and high selectivity and almost the same activity.
本発明はα−アントラキノンスルホン酸生成物、特に１
−アントラキノンスルホン酸を製造する方法、及びスル
ホン化反応生成混合物から可溶化金属触媒を回収する方
法を提供するものである。この方法は金属触媒が存在
下、発煙硫酸にてアントラキノンをスルホン化させて、
還元剤で処理して可溶化金属触媒を加えられた多孔性担
体に沈着させる。一般、本案にて参考文献とする米国特
許第3,763,191号に記載されている金属触媒は本案の製
造法に適用される。適当な触媒として、ルテニウム、ロ
ジウム、パラジウム、オスミウム、イリジウム、白金、
銀、金、コバルト、ニッケル、水銀、タリウム、及びそ
れらを含む化合物が挙げられる。本発明に好ましい触媒
はパラジウム、ロジウム、それらの金属を含む化合物、
特にパラジウムおよびパラジウムを含む化合物、例え
ば、Ｐｄ，ＰｄＯ，Ｐｄ（ＯＡc）2等が挙げられる。最
も好ましい例として、メッシュ番号が60以上の海綿パラ
ジウム粒子を出発触媒として使用する。この製造法に多
孔性担体として適用する材料に、例えば、ＳｉＯ2，Ｔ
ｉＯ2，ＢａＳＯ4，アントラキノン及び炭素が挙げら
れ、特に炭素が好ましい。この製造法にて、ＳＯ３の濃
度が20％以上の発煙硫酸を使ってスルホン化反応生成混
合物中の硫酸の量を減少させる。発煙硫酸中のＳＯ３の
濃度は35−45重量％が好ましい、また、ＳＯ３とアント
ラキノンのモル比は約４：１が好ましい。当業者に周知
の通り、スルホン化反応を影響するものに、例えば、反
応温度、触媒の温度、反応時間が挙げられるが、一般は
目的とする生成物により制御される。パラジウムを触媒
とし、１−アントラキノンスルホン酸を製造する本案の
好ましい実例にスルホン化反応は室温から120℃、好ま
しくは80から100℃で、アントラキノンに対するパラジ
ウム触媒の濃度が0.3−2.0重量％、好ましくは0.35−1.
5重量％で達せられ、約97％の出発アントラキノンが１
−アントラキノンスルホン酸生成物の最適収率に変換す
るところで反応を止める。一般、本製造法に適用する還
元剤は米国特許第3,792,065号に記載している。その詳
しいことは参照して戴きたい。還元剤の例として、ホル
ムアルデヒド、葡萄糖、亜硫酸ナトリウム、亜硫酸カリ
ウム、亜硫酸水素ナトリウム、亜硫酸水素カリウム、二
酸化硫黄、ギ酸、ギ酸ナトリウム、ギ酸カリウム、シュ
ウ酸、シュウ酸の中性またはアルカリ金属塩が挙げら
れ、そのうちホルムアルデヒドが特に好ましい。本発明
の可溶化金属の還元反応は大気圧で、室温から115℃、
好ましくは80は110℃の温度にて攪拌しながら行う。特
に川端らが提案した可溶化金属触媒等を再沈着する前に
スルホン化反応生成混合物のpHを調整することは本製造
法に必要はない。反応混合物から濾過して集めた沈澱金
属担体を酸がなくなるまで水洗いして、乾燥することに
より、金属触媒が得られる。また、母液から慣用の塩析
方法で１−アントラキノンスルホン酸生成物が得られ
る。The present invention relates to α-anthraquinone sulfonic acid products, especially 1
-Provides a method for producing anthraquinone sulfonic acid and a method for recovering a solubilized metal catalyst from a sulfonation reaction product mixture. In this method, anthraquinone is sulfonated with fuming sulfuric acid in the presence of a metal catalyst,
Treatment with a reducing agent deposits the solubilized metal catalyst on the added porous support. Generally, the metal catalysts described in US Pat. No. 3,763,191, which is referred to in the present case, are applied to the production method of the present case. Suitable catalysts include ruthenium, rhodium, palladium, osmium, iridium, platinum,
Included are silver, gold, cobalt, nickel, mercury, thallium, and compounds containing them. Preferred catalysts for the present invention are palladium, rhodium, compounds containing these metals,
In particular, palladium and compounds containing palladium such as Pd, PdO, Pd (OAc) 2 and the like can be mentioned. In the most preferred example, sponge palladium particles having a mesh number of 60 or more are used as a starting catalyst. As a material applied as a porous carrier in this manufacturing method, for example, SiO 2 , T
Examples include iO 2 , BaSO 4 , anthraquinone and carbon, with carbon being particularly preferred. In this method, fuming sulfuric acid having a SO 3 concentration of 20% or more is used to reduce the amount of sulfuric acid in the sulfonation reaction product mixture. The concentration of SO 3 in fuming sulfuric acid is preferably 35-45% by weight, and the molar ratio of SO 3 to anthraquinone is preferably about 4: 1. As is well known to those skilled in the art, those that influence the sulfonation reaction include, for example, reaction temperature, catalyst temperature, reaction time, but are generally controlled by the desired product. In a preferred example of the present invention for producing 1-anthraquinonesulfonic acid using palladium as a catalyst, the sulfonation reaction is from room temperature to 120 ° C, preferably 80 to 100 ° C, and the concentration of the palladium catalyst relative to anthraquinone is 0.3 to 2.0% by weight, preferably 0.35-1.
5% by weight, about 97% of starting anthraquinone is 1
-Stop the reaction at the point where it converts to an optimum yield of anthraquinone sulfonic acid product. Generally, the reducing agents applicable to this manufacturing method are described in US Pat. No. 3,792,065. Please refer to the details. Examples of reducing agents include formaldehyde, glucose, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sulfur dioxide, formic acid, sodium formate, potassium formate, oxalic acid, neutral or alkali metal salts of oxalic acid. Of these, formaldehyde is particularly preferable. The reduction reaction of the solubilized metal of the present invention is carried out at atmospheric pressure from room temperature to 115 ° C.
Preferably 80 is carried out at a temperature of 110 ° C. with stirring. In particular, it is not necessary for this production method to adjust the pH of the sulfonation reaction product mixture before redepositing the solubilized metal catalyst proposed by Kawabata et al. The precipitated metal carrier collected by filtration from the reaction mixture is washed with water until acid-free, and dried to obtain a metal catalyst. Further, the 1-anthraquinonesulfonic acid product is obtained from the mother liquor by a conventional salting-out method.
次に実施例を挙げて本発明を更に詳しく説明する、特に
指定しない限り、部と％は重量を示す。The present invention will now be described in more detail with reference to the examples. Parts and% are by weight unless otherwise specified.
実施例１ 本実施例の目的は海綿パラジウム粒子を触媒として、１
−アントラキノンスルホン酸を製造し、沈着形態で海綿
パラジウム粒子を回収するものである。0.83ｇのメッシ
ュ番号325の海綿パラジウム粒子を攪拌しながら、 機械式攪拌機、温度計、加熱ジャケット付容量500mlの
三瓶口フラスコ中の95mlの25％発煙硫酸に加え、70℃に
加熱して、パラジウムの重量125.5倍、即ち104.5ｇのア
ントラキノンを加えた後、90℃にて90mlの65％発煙硫酸
を徐々に滴下し、５−10分内に約98℃に達し、滴下開始
後から５時間保持する。この際サンプルを取って検査す
ると、約3.4％の出発アントラキノンが未反応のままで
あった。加熱を中止して、室温まで冷却してから、1100
mlの氷水にあけて、フラスコ反応器を100mlの水で洗
い、洗い水と希釈混合物を合併する。この希釈水溶液に
17ｇの活性炭と75ｇの37％ホルマリンを加え、加熱して
約110℃にて45分保持し、未だ熱いうちに濾過して、活
性炭付きパラジウムのケークを得る。このケークを100m
lの熱湯で洗い、不用の可溶性物を溶解してから、また
濾過して乾燥すると活性炭付きパラジウム触媒が得られ
る。これは下記の実施例にて次のスルホン化反応に用い
る。濾液と洗液の混合液から取ったサンプルをＡＡ法で
分析して、可溶化パラジウムの濃度を測定する。瀘液と
洗液の混合液を約85℃に加熱して、ＫCl飽和水溶液を計
約35ｇ加え、攪拌しながら85℃に約１時間保持た後、加
熱を中止して、一夜放置する。１−アントラキノンスル
ホン酸のカリウム塩を濾過して得られたケークを200ml
の３％ＫKl水溶液で洗い乾燥すると、133.5ｇの１−ア
ントラキノンスルホン酸のカリウム塩を得た。これは転
換したアントラキノンの85％である。スルホン化反応生
成物の組成の分析値とパラジウムの損失は表１の通りで
ある。Example 1 The purpose of this example is to use sponge palladium particles as a catalyst.
Producing anthraquinone sulfonic acid and recovering sponge palladium particles in a deposited form. While stirring 0.83 g of mesh number 325 sponge palladium particles, add 95 ml of 25% fuming sulfuric acid in a 500 ml capacity three-necked flask equipped with a mechanical stirrer, thermometer and heating jacket, and heat to 70 ° C to add palladium. The weight is 125.5 times, that is, 104.5 g of anthraquinone is added, then 90 ml of 65% fuming sulfuric acid is gradually added dropwise at 90 ° C, reaching about 98 ° C within 5-10 minutes, and kept for 5 hours after the start of addition. To do. When a sample was taken and inspected at this time, about 3.4% of the starting anthraquinone remained unreacted. Stop heating and allow to cool to room temperature before 1100
Pour into ml of ice water, wash the flask reactor with 100 ml of water and combine the wash water with the diluted mixture. In this diluted aqueous solution
Add 17 g of activated carbon and 75 g of 37% formalin, heat and hold at about 110 ° C. for 45 minutes and filter while still hot to obtain a palladium cake with activated carbon. 100 m of this cake
After washing with hot water of 1 to dissolve the unwanted soluble matter, filtration and drying again, a palladium catalyst with activated carbon is obtained. It is used in the next sulfonation reaction in the examples below. A sample taken from the mixture of the filtrate and the washing solution is analyzed by the AA method to measure the concentration of solubilized palladium. The mixture of the filtrate and the washing liquid is heated to about 85 ° C., a total of about 35 g of a KCl saturated aqueous solution is added, and the mixture is maintained at 85 ° C. for about 1 hour while stirring, then the heating is stopped and the mixture is left to stand overnight. 200 ml of cake obtained by filtering potassium salt of 1-anthraquinone sulfonic acid
After washing with 3% KKl aqueous solution and drying, 133.5 g of potassium salt of 1-anthraquinonesulfonic acid was obtained. This is 85% of the converted anthraquinone. The analytical values of the composition of the sulfonation reaction product and the loss of palladium are shown in Table 1.
実施例２ 本実施例の目的は本発明の方法で回収した触媒の活性が
元来の触媒とほとんど同じであることを示す。前記実施
例１から回収した活性炭付きパラジウム（Ｐｄ−Ｃ
（Ｉ）と称する）で海綿パラジウム粒子を置換し、還元
反応の前に活性炭を加える外は、実施例と同じく操作す
る。また上記工程から回収した活性炭付きパラジウム
（それぞれＰｄ−Ｃ（II）、Ｐｄ−Ｃ（III）と称す
る）を使って反応を二回を行う。スルホン化反応生成物
の組成を分析値とパラジウムの損失は表１の通りであ
る。Example 2 The purpose of this example is to show that the activity of the catalyst recovered by the process of the present invention is almost the same as the original catalyst. Palladium with activated carbon recovered from Example 1 (Pd-C
(I) is used to replace the sponge palladium particles, and activated carbon is added before the reduction reaction. The reaction is performed twice using palladium with activated carbon (referred to as Pd-C (II) and Pd-C (III), respectively) recovered from the above step. The analytical values of the composition of the sulfonation reaction product and the loss of palladium are shown in Table 1.
表１に示す通り、各サイクルから回収した活性炭付きパ
ラジウムの活性は出発の海綿パラジウム粒子とほとんど
同じで、かつ川端らの方法と比べ、可溶化Ｐｄの損失は
顕著に減少した。事実上、実施例２の製造法で11サイク
ル繰り返しても、回収した活性炭付きパラジウムの活性
は新鮮な海綿パラジウム粒子と殆ど同じである。 As shown in Table 1, the activity of palladium with activated carbon recovered from each cycle was almost the same as that of the starting sponge palladium particles, and the loss of solubilized Pd was significantly reduced as compared with the method of Kawabata et al. In fact, the activity of the recovered palladium on activated carbon is almost the same as that of the fresh sponge palladium particles even after 11 cycles of the production method of Example 2.
フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // C07B 61/00 300
Claims (13)
触媒等を回収する方法において (a) パラジウム、ルテニウムまたはこれらの金属を含
んだ化合物よりなる群から選ばれる金属触媒の存在下、
発煙硫酸にてアントラキノンをスルホン化し、 (b) ｐＨ値を７以上に調節せずに、多孔性担体の存在
下、ホルムアルデヒド、ぶどう糖、亜硫酸ナトリウム、
亜硫酸カリウム、亜硫酸水素ナトリウム、亜硫酸水素カ
リウム、二酸化硫黄、ギ酸、ギ酸ナトリウム、ギ酸カリ
ウム、シュウ酸、およびシュウ酸の中性またはアルカリ
金属塩よりなる群から選ばれる還元剤でスルホン化反応
生成混合物を処理して、前記多孔性担体上に前記金属触
媒を沈着させ、 (c) 前記処理した混合物から前記多孔性担体上に沈着
した金属触媒を分離し、 (d) 前記分離した金属触媒から洗浄により酸を除去
し、 (e) 前記金属触媒を分離した後の酸を含む前記混合物
からα−アントラキノンスルホン酸生成物を回収するこ
とを特徴とする方法。1. A method for producing α-anthraquinone sulfonic acid,
In the method of recovering a catalyst and the like (a) in the presence of a metal catalyst selected from the group consisting of palladium, ruthenium or a compound containing these metals,
Sulfonating anthraquinone with fuming sulfuric acid, (b) formaldehyde, glucose, sodium sulfite, in the presence of a porous carrier without adjusting the pH value to 7 or more,
A sulfonation reaction product mixture is prepared with a reducing agent selected from the group consisting of potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sulfur dioxide, formic acid, sodium formate, potassium formate, oxalic acid, and oxalic acid neutral or alkali metal salts. Treating to deposit the metal catalyst on the porous support, (c) separating the metal catalyst deposited on the porous support from the treated mixture, and (d) washing the separated metal catalyst. Removing the acid, and (e) recovering the α-anthraquinone sulfonic acid product from the mixture containing the acid after separating the metal catalyst.
項第１項記載の方法。2. The method according to claim 1, wherein the product is recovered by salting out.
求項第１項記載の方法。3. The method according to claim 1, wherein the separation of the metal catalyst is performed by filtration.
に析出した金属である請求項第１項記載の方法。4. The method according to claim 1, wherein the metal catalyst for sulfonation is a metal deposited on a support.
または第４項記載の方法。5. The method according to claim 1 or 4, wherein the metal is palladium.
請求項第５記載の方法。6. The method according to claim 5, wherein the metal catalyst is sponge palladium particles.
６０以上である請求項第６項記載の方法。7. The method according to claim 6, wherein the sponge palladium particles have a mesh number of 60 or more.
によりアントラキノンの所望する変換度にて中止させる
請求項第１項または第４項記載の方法。8. A process according to claim 1, wherein the sulfonation reaction is stopped at the desired degree of conversion of anthraquinone by addition of ice water or water.
アントラキノンスルホン酸である請求項第１項記載の方
法。9. The α-anthraquinone sulfonic acid is 1-
The method according to claim 1, which is anthraquinone sulfonic acid.
求項第１項記載の方法。10. The method according to claim 1, wherein the reducing agent is formaldehyde.
第１０項記載の方法。11. The method of claim 10 wherein the metal catalyst comprises palladium.
１：25から１：50である請求項第１１項記載の方法。12. The method according to claim 11, wherein the ratio of palladium to formaldehyde is from 1:25 to 1:50.
温度範囲内で行なう請求項第１項記載の方法。13. The method according to claim 1, wherein the treatment with the reducing agent is carried out within a temperature range of 80 to 110 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278489A JPH062725B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing α-anthraquinone sulfonic acid and recovering the catalyst used therein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278489A JPH062725B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing α-anthraquinone sulfonic acid and recovering the catalyst used therein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138167A JPH02138167A (en) | 1990-05-28 |
| JPH062725B2 true JPH062725B2 (en) | 1994-01-12 |
Family
ID=17598040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63278489A Expired - Lifetime JPH062725B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing α-anthraquinone sulfonic acid and recovering the catalyst used therein |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062725B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52125153A (en) * | 1976-04-13 | 1977-10-20 | Agency Of Ind Science & Technol | Treatment of sulfonation reaction mixture of anthraquinone |
-
1988
- 1988-11-02 JP JP63278489A patent/JPH062725B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02138167A (en) | 1990-05-28 |
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