JPH08117765A - Oxidative decomposition of formate - Google Patents
Oxidative decomposition of formateInfo
- Publication number
- JPH08117765A JPH08117765A JP25535194A JP25535194A JPH08117765A JP H08117765 A JPH08117765 A JP H08117765A JP 25535194 A JP25535194 A JP 25535194A JP 25535194 A JP25535194 A JP 25535194A JP H08117765 A JPH08117765 A JP H08117765A
- Authority
- JP
- Japan
- Prior art keywords
- formate
- oxygen
- catalyst
- platinum group
- sodium
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 238000006864 oxidative decomposition reaction Methods 0.000 title claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000354 decomposition reaction Methods 0.000 abstract description 11
- 150000004675 formic acid derivatives Chemical class 0.000 abstract description 11
- 229910052763 palladium Inorganic materials 0.000 abstract description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 3
- -1 amine salt Chemical class 0.000 abstract description 3
- 229910052741 iridium Inorganic materials 0.000 abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 239000010948 rhodium Substances 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract 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 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052790 beryllium Inorganic materials 0.000 abstract description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052792 caesium Inorganic materials 0.000 abstract description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- 229910052701 rubidium Inorganic materials 0.000 abstract description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 229910052712 strontium Inorganic materials 0.000 abstract description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000004280 Sodium formate Substances 0.000 description 8
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 8
- 235000019254 sodium formate Nutrition 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリオールの製造時に副
生されるギ酸ソーダやあるいは化学工場等の廃液中に含
まれるギ酸塩を温和な条件下で、高転化率に酸化分解す
る方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for oxidatively degrading sodium formate produced as a by-product during the production of a polyol or a formate contained in a waste liquid of a chemical factory under mild conditions at a high conversion rate. Is.
【０００２】[0002]
【従来の技術】ギ酸塩は種々の化学品の合成する製造プ
ロセスから多量に排出され、ＣＯＤ、ＢＯＤの規制対象
物であることから、簡便な分解方法が望まれている。従
来、触媒を用いてギ酸塩を接触分解する方法としては、
特開昭４７−２５０５６号、特開昭４８−９６５１２号
に記載される如く、パラジウムあるいはニッケル触媒の
存在下、極性溶媒の中でギ酸塩を分解する方法が知られ
ている。しかしながら、特開昭４７−２５０５６号記載
の方法では、還元下で行う反応中にパラジウム触媒の触
媒活性が低下し、反応後、酸素により触媒を再生しなけ
ればならず煩雑な操作を必要とする。さらに特開昭４８
−９６５１２号記載の方法ではニッケル触媒の存在下、
ギ酸塩を分解するが、この方法では反応温度が高温であ
り、分解速度が遅い等の欠点を有している。以上のよう
な問題点を解決し、安全で且つ温和な条件下で高分解率
を達成できる方法が望まれている。2. Description of the Related Art A large amount of formate is discharged from a manufacturing process for synthesizing various chemicals and it is a regulated object of COD and BOD. Therefore, a simple decomposition method is desired. Conventionally, as a method of catalytically decomposing formate using a catalyst,
As described in JP-A-47-25056 and JP-A-48-96512, a method of decomposing a formate salt in a polar solvent in the presence of a palladium or nickel catalyst is known. However, in the method described in JP-A-47-25056, the catalytic activity of the palladium catalyst is lowered during the reaction carried out under reduction, and the catalyst must be regenerated with oxygen after the reaction, which requires a complicated operation. . Furthermore, JP-A-48
-96512, in the presence of a nickel catalyst,
Although the formate is decomposed, this method has drawbacks such as a high reaction temperature and a slow decomposition rate. There is a demand for a method capable of solving the above problems and achieving a high decomposition rate under safe and mild conditions.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来技術に
おけるギ酸塩の分解法の種々の欠点を解決し、各種の化
学品プロセスから副生されるギ酸塩や各種の廃水中に含
まれるギ酸塩を、温和な条件下で簡便且つ安全に、しか
も高分解率で酸化分解するギ酸塩の酸化分解法を提供す
るものである。DISCLOSURE OF THE INVENTION The present invention solves various drawbacks of the conventional method for decomposing formate, and the formate contained in various wastewaters and formate produced as a by-product from various chemical processes. It is intended to provide a method for oxidative decomposition of a formate, which oxidizes and decomposes a salt simply and safely under mild conditions and at a high decomposition rate.
【０００４】[0004]
【課題を解決するための手段】本発明者等は上記従来技
術の問題点を解決すべく鋭意検討を行い、ギ酸塩を白金
族触媒の存在下、溶液中において酸素もしくは酸素を含
有するガスまたは過酸化水素等と反応させ、温和な条件
下で、短時間に高分解率を達成できる酸化分解法を見い
だし本発明を成すに至った。さらに詳しくはギ酸塩の溶
液をパラジウム、白金、ルテニウム、ロジウム、イリジ
ウムの白金族触媒の存在下１０〜２００℃で酸素もしく
は酸素を含有するガスまたは過酸化水素と反応させ、ギ
酸塩を容易に且つ簡便に酸化分解する方法に関する。Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems of the prior art, and formic acid in the presence of a platinum group catalyst in a solution containing oxygen or a gas containing oxygen or The present invention has been accomplished by finding an oxidative decomposition method that can achieve a high decomposition rate in a short time under mild conditions by reacting with hydrogen peroxide or the like. More specifically, a formate solution is reacted with oxygen or an oxygen-containing gas or hydrogen peroxide at 10 to 200 ° C. in the presence of a platinum group catalyst of palladium, platinum, ruthenium, rhodium, or iridium to easily and formate the formate salt. The present invention relates to a simple oxidative decomposition method.
【０００５】本発明に供するギ酸塩としてはナトリウ
ム、カリウム、カルシウム、マグネシウム、リチウム、
ベリリウム、ルビジウム、ストロンチウム、バリウム、
セシウム等のアルカリ金属及びアルカリ土類金属塩並び
にギ酸アンモニウム、ギ酸アミン塩等が挙げられる。上
記ギ酸塩は通常は水溶液中で分解されるが、ギ酸塩の水
溶液中に有機化合物が存在しても何等差し支えない。The formate salts used in the present invention include sodium, potassium, calcium, magnesium, lithium,
Beryllium, rubidium, strontium, barium,
Examples thereof include alkali metal and alkaline earth metal salts such as cesium, ammonium formate, and amine formate salts. The formate salt is usually decomposed in an aqueous solution, but there is no problem even if an organic compound is present in the aqueous formate solution.
【０００６】本発明に使用される白金族触媒はパラジウ
ム、白金、ルテニウム、ロジウム、イリジウム金属を一
種以上活性炭、炭素繊維、活性炭素繊維等の炭素材、シ
リカ、アルミナ、シリカアルミナ、ゼオライト等の担体
に対して０．０１〜２０重量％、好ましくは０．０５〜
１０重量％担持した触媒が好ましい。本発明におけるギ
酸塩と酸素もしくは酸素を含有するガスまたは過酸化水
素との反応は上記白金族触媒の存在下で反応温度１０〜
２００℃、好ましくは２０〜１５０℃の範囲で行われ
る。The platinum group catalyst used in the present invention is one or more of palladium, platinum, ruthenium, rhodium, and iridium metal, carbon material such as activated carbon, carbon fiber, activated carbon fiber, carrier such as silica, alumina, silica-alumina and zeolite. 0.01 to 20% by weight, preferably 0.05 to
A catalyst loaded with 10% by weight is preferred. In the present invention, the reaction of the formate with oxygen or a gas containing oxygen or hydrogen peroxide is carried out at a reaction temperature of 10 to 10 in the presence of the platinum group catalyst.
It is performed at 200 ° C, preferably in the range of 20 to 150 ° C.
【０００７】また、本発明におけるギ酸塩と酸素もしく
は酸素を含有するガスまたは過酸化水素との反応は常圧
で充分であるが加圧下で行っても何等差し支えない。本
発明におけるギ酸塩と酸素のモル比は０．５以上であり
使用されるギ酸塩の種類、触媒の種類、反応条件等を勘
案して適宜選択されるが一般的には０．５〜１００の範
囲、好ましくは０．５〜５０の範囲で行われる。さら
に、本発明におけるギ酸塩と過酸化水素のモル比は１以
上であり、使用されるギ酸塩の種類、触媒の種類、反応
条件等を勘案して適宜選択されるが一般的には１〜２０
の範囲、好ましくは１〜１０の範囲で行われる。尚、ギ
酸塩と酸素もしくは酸素を含有するガスまたは過酸化水
素との反応は回分式、半回分式あるいは連続式の何れの
方法でも実施し得る。以下に本発明の実施例を示す。In the present invention, the reaction between the formate salt and oxygen or a gas containing oxygen or hydrogen peroxide is sufficient under normal pressure, but it may be carried out under pressure. The molar ratio of formate salt to oxygen in the present invention is 0.5 or more and is appropriately selected in consideration of the type of formate salt used, the type of catalyst, the reaction conditions and the like, but generally 0.5 to 100. In the range of, preferably in the range of 0.5 to 50. Further, the molar ratio of formate salt to hydrogen peroxide in the present invention is 1 or more and is appropriately selected in consideration of the type of formate salt used, the type of catalyst, the reaction conditions, etc. 20
In the range of, preferably in the range of 1-10. The reaction between the formate salt and oxygen or a gas containing oxygen or hydrogen peroxide can be carried out by any of a batch system, a semi-batch system and a continuous system. Examples of the present invention will be shown below.
【０００８】[0008]
実施例１ 粒径１〜２ｍｍの活性炭に１．０重量％パラジウムを担
持した触媒を内径４０ｍｍの反応器に１ｌ充填した。反
応器を７０℃に加熱し、酸素ガスを２００ｌ／時間の流
速で反応器に供給し、さらにギ酸ナトリウム１５．６重
量％を含有する水溶液を常圧下２２５ｇ／時間の流速で
反応器に供給した。反応後のギ酸ナトリウムの分解率は
９８．７％であり、重炭酸ナトリウムの収率は９０．３
％、炭酸ナトリウムの収率は７．５％であった。Example 1 A reactor having an inner diameter of 40 mm was charged with 1 l of a catalyst in which 1.0 wt% palladium was supported on activated carbon having a particle diameter of 1 to 2 mm. The reactor was heated to 70 ° C., oxygen gas was supplied to the reactor at a flow rate of 200 l / hour, and an aqueous solution containing 15.6% by weight of sodium formate was further supplied to the reactor at a flow rate of 225 g / hour under normal pressure. . The decomposition rate of sodium formate after the reaction was 98.7%, and the yield of sodium bicarbonate was 90.3.
%, The yield of sodium carbonate was 7.5%.
【０００９】実施例２ 実施例１で使用したと同一の触媒、反応器を５０℃に加
熱し、空気を流速４６０ｌ／時間で供給しながらギ酸ア
ンモニウム１０．１重量％を含有する水溶液を２ｋｇ／
ｃｍ2 の加圧下、２１０ｇ／時間の流速で反応器に供給
した。反応後のギ酸アンモニウムの分解率は９６．３％
であり、重炭酸アンモニウムの収率は９３．４％、炭酸
アンモニウムの収率は２．５％であった。Example 2 The same catalyst as used in Example 1, the reactor was heated to 50 ° C., and 2 kg of an aqueous solution containing 10.1% by weight of ammonium formate was supplied while air was supplied at a flow rate of 460 l / hour.
It was fed into the reactor at a flow rate of 210 g / hour under a pressure of cm 2 . The decomposition rate of ammonium formate after the reaction is 96.3%
The yield of ammonium bicarbonate was 93.4%, and the yield of ammonium carbonate was 2.5%.
【００１０】実施例３ 実施例１で使用したと同一の触媒、反応器を使用して６
０℃に加熱した反応器にギ酸ナトリウム１１．９重量％
過酸化水素７．３重量％を含有する水溶液を常圧下１０
００ｇ／時間の流速で供給した。反応後のギ酸ナトリウ
ムの分解率は９８．１％であり、重炭酸ナトリウムの収
率は９０．６％、炭酸ナトリウムの収率は７．２％であ
った。また、過酸化水素は全く検出されなかった。Example 3 Using the same catalyst and reactor as used in Example 1, 6
Sodium formate 11.9% by weight in reactor heated to 0 ° C
An aqueous solution containing 7.3% by weight of hydrogen peroxide was added under atmospheric pressure for 10
It was supplied at a flow rate of 00 g / hour. The decomposition rate of sodium formate after the reaction was 98.1%, the yield of sodium bicarbonate was 90.6%, and the yield of sodium carbonate was 7.2%. Moreover, hydrogen peroxide was not detected at all.
【００１１】実施例４ 粒径１〜２ｍｍの活性炭に１．０重量％の白金を担持し
た触媒を実施例１に使用した反応器に１ｌ充填した。５
０℃に加熱し、反応器に酸素を５００ｌ／時間の流速で
供給し、さらにギ酸ナトリウム５．５重量％を含有する
水溶液を常圧下で２００ｇ／時間の流速で供給した。反
応後のギ酸ナトリウムの分解率は９５．９％であり、重
炭酸ナトリウムの収率は９４．０％、炭酸ナトリウムの
収率は１．４％であった。Example 4 1 liter of a catalyst prepared by loading 1.0% by weight of platinum on activated carbon having a particle size of 1 to 2 mm was charged in the reactor used in Example 1. 5
The mixture was heated to 0 ° C., oxygen was supplied to the reactor at a flow rate of 500 l / hour, and an aqueous solution containing 5.5% by weight of sodium formate was further supplied at a flow rate of 200 g / hour under normal pressure. The decomposition rate of sodium formate after the reaction was 95.9%, the yield of sodium bicarbonate was 94.0%, and the yield of sodium carbonate was 1.4%.
【００１２】比較例１ 実施例１で使用した同一の反応器に１〜２ｍｍの市販の
ニッケル−ケイソウ土触媒（日揮化学製）を充填し実施
例１と同一の条件で行った。その結果、ギ酸ナトリウム
の転化率は１１．６％であり重炭酸ナトリウムの収率は
１１．６％であった。Comparative Example 1 The same reactor used in Example 1 was charged with 1-2 mm of a commercially available nickel-diatomaceous earth catalyst (manufactured by JGC Chemical Co., Ltd.) and the same conditions as in Example 1 were used. As a result, the conversion rate of sodium formate was 11.6% and the yield of sodium bicarbonate was 11.6%.
【００１３】[0013]
【発明の効果】本発明の方法により、各種の化学品プロ
セスから副生されるギ酸塩や各種の廃水中に含まれるギ
酸塩を、温和な条件下で簡便且つ安全に、しかも高分解
率で酸化分解することが出来る。Industrial Applicability According to the method of the present invention, the formate produced as a by-product from various chemical processes and the formate contained in various waste waters can be easily and safely treated under mild conditions with a high decomposition rate. Can be oxidatively decomposed.
Claims (2)
下、酸素あるいは酸素を含有するガスと反応させること
を特徴とするギ酸塩の酸化分解法。1. A method for oxidative decomposition of formate, which comprises reacting a solution containing formate with oxygen or a gas containing oxygen in the presence of a platinum group catalyst.
下、過酸化水素と反応させることを特徴とするギ酸塩の
酸化分解法。2. A method for oxidative decomposition of formate, which comprises reacting a solution containing formate with hydrogen peroxide in the presence of a platinum group catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25535194A JPH08117765A (en) | 1994-10-20 | 1994-10-20 | Oxidative decomposition of formate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25535194A JPH08117765A (en) | 1994-10-20 | 1994-10-20 | Oxidative decomposition of formate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08117765A true JPH08117765A (en) | 1996-05-14 |
Family
ID=17277588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25535194A Pending JPH08117765A (en) | 1994-10-20 | 1994-10-20 | Oxidative decomposition of formate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08117765A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1127864A2 (en) * | 2000-02-26 | 2001-08-29 | Oxeno Olefinchemie GmbH | Improved process for the hydroformylation of olefins by reducing the concentration of formic acid |
| KR100490865B1 (en) * | 2001-12-11 | 2005-05-19 | 국보산업 주식회사 | Method of Treating wastewater using catalytic wet oxidation process |
-
1994
- 1994-10-20 JP JP25535194A patent/JPH08117765A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1127864A2 (en) * | 2000-02-26 | 2001-08-29 | Oxeno Olefinchemie GmbH | Improved process for the hydroformylation of olefins by reducing the concentration of formic acid |
| EP1127864A3 (en) * | 2000-02-26 | 2002-04-17 | Oxeno Olefinchemie GmbH | Improved process for the hydroformylation of olefins by reducing the concentration of formic acid |
| KR100490865B1 (en) * | 2001-12-11 | 2005-05-19 | 국보산업 주식회사 | Method of Treating wastewater using catalytic wet oxidation process |
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