JPH03218919A - Method of recoverying alkali metal - Google Patents
Method of recoverying alkali metalInfo
- Publication number
- JPH03218919A JPH03218919A JP1208190A JP1208190A JPH03218919A JP H03218919 A JPH03218919 A JP H03218919A JP 1208190 A JP1208190 A JP 1208190A JP 1208190 A JP1208190 A JP 1208190A JP H03218919 A JPH03218919 A JP H03218919A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- water
- alkali
- reaction product
- hydroxybenzoic 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.)
- Pending
Links
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 39
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 alkali metal salt Chemical class 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 239000004280 Sodium formate Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
《産業上の利用分野》
本発明は反応生成物からアルカリ金属を回収する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION <<Industrial Application Field>> The present invention relates to a method for recovering alkali metals from reaction products.
さらに詳しくは、アルカリ金属成分をアルカリ源として
再利用できる重炭酸塩の形態で回収する方法に関する。More specifically, it relates to a method for recovering alkali metal components in the form of bicarbonate which can be reused as an alkali source.
《従来技術》
フェノールのアルカリ金属塩と一酸化炭素を常圧あるい
は加圧下、炭酸のアルカリ金属塩またはギ酸のアルカリ
金属塩の存在下、１００〜３５０℃の温度で反応させる
とヒドロキシ安息香酸のアルカリ金属塩を主成分とする
反応生成物が得られることは公知である。<Prior art> When an alkali metal salt of phenol and carbon monoxide are reacted at a temperature of 100 to 350°C under normal pressure or increased pressure in the presence of an alkali metal salt of carbonic acid or an alkali metal salt of formic acid, an alkali of hydroxybenzoic acid is formed. It is known that reaction products containing metal salts as main components can be obtained.
たとえば、特公昭４３−１４９３１号公報、特公昭４３
−２２５８６号公報、特公昭４３−１１２１１号公報、
特公昭４３−２２５８７号公報、特公昭４３−２２９７
１号公報、特公昭４４−３１３３３号公報、特公昭４３
−１３６１８号公報等に開示されている。For example, Japanese Patent Publication No. 43-14931, Publication No. 43-14931,
-22586 Publication, Special Publication No. 11211/1973,
Special Publication No. 43-22587, Special Publication No. 43-2297
Publication No. 1, Special Publication No. 44-31333, Special Publication No. 43
-13618, etc.
そしてこの反応生成物からヒドロキシ安息香酸を得る一
般的方法としては反応生成物を水に溶解し、硫酸などの
鉱酸を加える方法が採用されている。A general method for obtaining hydroxybenzoic acid from this reaction product is to dissolve the reaction product in water and add a mineral acid such as sulfuric acid.
《発明が解決しようとする課題》
しかし、この方法ではアルカリ金属塩と少なくとも当量
の鉱酸が必要なことと、得られた中性のアルカリ金属の
鉱酸塩は、当該反応あるいは他の用途のアルカリ源とし
て再使用できないという欠点がある。[Problem to be solved by the invention] However, this method requires at least an equivalent amount of mineral acid to the alkali metal salt, and the obtained neutral alkali metal mineral acid salt is difficult to use in the reaction or other applications. It has the disadvantage that it cannot be reused as an alkali source.
一方、反応生成物からアルカリ源を回収する方法として
は、ヒドロキシ安息香酸カリウムからたとえば、イオン
交換樹脂膜を用いヱ゛電解透析を行ない水酸化カリウム
として回収する方法、亜硫酸ガスにより亜硫酸水素カリ
ウムあるいは硫酸を用いて硫酸カリウムとしたのち、さ
らに水酸化カルシウムと反応させて水酸化カリウムとす
る方法などが知られている。On the other hand, methods for recovering the alkali source from the reaction product include, for example, recovering potassium hydrogen sulfite or sulfuric acid from potassium hydroxybenzoate by performing electrolytic dialysis using an ion exchange resin membrane, and recovering potassium hydrogen sulfite or sulfuric acid using sulfur dioxide gas. A known method is to use potassium sulfate to form potassium sulfate, which is then further reacted with calcium hydroxide to form potassium hydroxide.
しかし、これらの方法はいずれも経済的に満足しうる方
法ではなく、実用に供されていないのが現状である。However, none of these methods are economically satisfactory and are currently not in practical use.
そこで、本発明者らは、鋭意研究の結果、次の知見を得
た。As a result of intensive research, the present inventors obtained the following knowledge.
■当該反応生成物の水溶液に炭酸ガスを吹き込むことに
よりアルカリ金属の重炭酸塩が生成すること
■特定の有機溶媒の水溶液に対する溶解度の差がアルカ
リ金属の重炭酸塩とヒドロキシ安息香酸、ギ酸のアルカ
リ金属塩との間で大きいこと■水に対する溶解度の差が
ヒドロキシ安息香酸とギ酸のアルカリ金属塩との間で大
きいことこれらの知見を基にさらに研究を重ねた結果、
本発明を完成するに至った。■ Bicarbonate of an alkali metal is produced by blowing carbon dioxide gas into an aqueous solution of the reaction product. ■ The difference in solubility in an aqueous solution of a specific organic solvent is that of bicarbonate of alkali metal, hydroxybenzoic acid, and alkali of formic acid. The difference in solubility in water is large between hydroxybenzoic acid and alkali metal salts of formic acid.Based on these findings, further research revealed that
The present invention has now been completed.
《発明の構成》
すなわち、本発明は
「フェノールのアルカリ金属塩と一酸化炭素とを炭酸ア
ルカリ塩またはギ酸アルカリ塩の存在下反応させて得ら
れる反応生成物からアルカリ金属を回収する方法におい
て、反応生成物を水と水に易溶な有機溶媒との混合物に
溶解し、ついてこの溶液に炭酸ガスを吹き込み、生成す
るヒドロキン安息香酸を水と水に易溶な有機溶媒との混
合物の溶液として得る一方、副生ずるアルカリ金属の重
炭酸塩を固体として析出回収することを特徴とするアル
カリ金属の回収方法」
である。<<Structure of the Invention>> That is, the present invention provides a method for recovering an alkali metal from a reaction product obtained by reacting an alkali metal salt of phenol with carbon monoxide in the presence of an alkali carbonate or an alkali formate. The product is dissolved in a mixture of water and an organic solvent that is easily soluble in water, and then carbon dioxide gas is blown into this solution to obtain hydroquine benzoic acid as a solution of a mixture of water and an organic solvent that is easily soluble in water. On the other hand, there is a method for recovering alkali metals which is characterized by precipitating and recovering by-produced alkali metal bicarbonate as a solid.
以下に本発明のアルカリ金属の回収方法について詳述す
る。The method for recovering alkali metals of the present invention will be described in detail below.
本発明の回収方法が適用されるのはフェノールのアルカ
リ金属塩と一酸化炭素とから反応生成物であるヒドロキ
シ安息香酸を製造するプロセスである。The recovery method of the present invention is applied to a process for producing hydroxybenzoic acid, which is a reaction product, from an alkali metal salt of phenol and carbon monoxide.
ヒドロキシ安息香酸は公知の方法によって得られるもの
であり、フェノールのアルカリ金属の種類、反応時の圧
力、温度、触媒として存在する炭酸のアルカリ金属塩の
種類、有無やギ酸のアルカリ金属塩の種類、有無などに
は限定されない。Hydroxybenzoic acid is obtained by a known method, and depends on the type of alkali metal in phenol, the pressure and temperature during the reaction, the type and presence or absence of an alkali metal salt of carbonic acid present as a catalyst, the type of alkali metal salt of formic acid, It is not limited to the presence or absence.
ただし、アルカリ金属としては価格の点からカリウムか
ナトリウムを使用することが実用的である。However, from the viewpoint of cost, it is practical to use potassium or sodium as the alkali metal.
本発明に用いられる有機溶媒は、ヒドロキシ安息香酸を
溶解するが、アルカリ金属の重炭酸塩をほとんど溶解せ
ず、しかも水に易溶な溶媒であり、このような性質を持
ち合わせない有機溶媒の使用は本発明の目的を達成し得
ない。The organic solvent used in the present invention is a solvent that dissolves hydroxybenzoic acid, but hardly dissolves alkali metal bicarbonate, and is easily soluble in water. Use of an organic solvent that does not have these properties cannot achieve the purpose of the present invention.
具体的にはメタノール、エタノール、ｎ−プロパノール
、１−プロパノール、エチレングリコルなどのアルコー
ル類、アセトン、メチルエチルケトンなどのケトン類、
テトラヒド口フラン、ジオキサンなどのエーテル類、ア
セトニトリル、プロピオニトリルなどのニトリル類、ピ
リジン、ルチジン、トリメチルアミン、エチルアミン、
ジェチルアミン、トリエチルアミン、プロビルアミンな
どのアミン類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ
−ジエチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミ
ド、ヘキサメチルホスホルトリアミドなどのアミド類、
ジメチルスルホキシド、ジエチルスルホキシド、ジフェ
ニルスルホキシドなどのスルホキシド類、ジフエニルス
ルホン、スルホランなどのスルホン類などがあげられる
。Specifically, alcohols such as methanol, ethanol, n-propanol, 1-propanol, and ethylene glycol; ketones such as acetone and methyl ethyl ketone;
Ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, pyridine, lutidine, trimethylamine, ethylamine,
Amines such as diethylamine, triethylamine, probylamine, N,N-dimethylformamide, N,N
- Amides such as diethylformamide, N,N-dimethylacetamide, hexamethylphosphorotriamide,
Examples include sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, and diphenyl sulfoxide, and sulfones such as diphenyl sulfone and sulfolane.
これらの有機溶媒は単独で用いても良いが、前記有機溶
媒の２種以上の混合物または水に不溶な有機溶媒、たと
えばヘキサン、ベンゼンなどとの混合物として用いても
良い。These organic solvents may be used alone, or may be used as a mixture of two or more of the organic solvents, or as a mixture with an organic solvent insoluble in water, such as hexane or benzene.
当該反応生成物に水と水に易溶な有機溶媒とを混合する
順序は基本的には、どちらを先に行なっても良い。Basically, water and an organic solvent easily soluble in water may be mixed into the reaction product in any order.
従って反応溶媒として本発明に使用可能な有機溶媒を適
当量用いている場合には、反応生成物に水を加えるだけ
で良い。Therefore, when an appropriate amount of an organic solvent that can be used in the present invention is used as a reaction solvent, it is sufficient to simply add water to the reaction product.
しかし、反応溶媒として本発明に使用出来ない有機溶媒
を用いている場合には最初に水を加え分液させて水層を
分離した後に水層に本発明に使用可能な有機溶媒を混合
する方が好ましい。However, if an organic solvent that cannot be used in the present invention is used as a reaction solvent, it is preferable to first add water and separate the aqueous layer, and then mix the aqueous layer with an organic solvent that can be used in the present invention. is preferred.
もし、本発明に使用できない有機溶媒に水と本発明に使
用できる有機溶媒とを混合し炭酸ガスを吹き込んだ場合
、その後の分離操作に非常に手間がかかる場合がある。If water and an organic solvent that can be used in the present invention are mixed with an organic solvent that cannot be used in the present invention and carbon dioxide gas is blown into the mixture, the subsequent separation operation may be very time-consuming.
本発明における水の使用量は当該反応生成物を溶解する
が、アルカリ金属の重炭酸塩を溶解しない範囲であり、
本発明における有機溶媒の使用量はヒドロキシ安息香酸
を溶解するが、アルカリ金属の重炭酸塩を溶解しない範
囲である。The amount of water used in the present invention is within a range that dissolves the reaction product but does not dissolve the alkali metal bicarbonate,
The amount of organic solvent used in the present invention is within a range that dissolves hydroxybenzoic acid but does not dissolve alkali metal bicarbonate.
これらは使用する有機溶媒の種類などにより変化するの
は当然であるが、水と水に易溶な有機溶媒との混合物の
使用量は当該反応生成物１重量部に対し通常は２．０重
量部以上であり、好ましくは５．０〜３０重量部である
。It goes without saying that these will vary depending on the type of organic solvent used, but the amount of the mixture of water and an organic solvent that is easily soluble in water is usually 2.0 parts by weight per 1 part by weight of the reaction product. part or more, preferably 5.0 to 30 parts by weight.
また前記混合物中の水と水に易溶な有機溶媒の組成は、
有機溶媒１重量部に対し通常は水が０．０１重量部以上
、好ましくは０．１〜０．５重量部である。Furthermore, the composition of water and water-soluble organic solvent in the mixture is as follows:
The amount of water is usually 0.01 part by weight or more, preferably 0.1 to 0.5 part by weight, per 1 part by weight of the organic solvent.
使用する水が過小な場合、すなわち、使用する有機溶媒
が過剰な場合は、反応生成物が溶解せず、析出するヒド
ロキシ安息香酸と混在し、両者の分離が面倒になる。If too little water is used, that is, if an excessive amount of organic solvent is used, the reaction product will not be dissolved and will be mixed with precipitated hydroxybenzoic acid, making separation of the two difficult.
また、水が過剰な場合は析出するアルカリ金属の重炭酸
塩が水と水に易溶な有機溶媒との混合物に溶解してしま
い、ヒドロキシ安息香酸との分離が面倒になる。Furthermore, if water is excessive, the precipitated alkali metal bicarbonate will be dissolved in a mixture of water and an organic solvent that is easily soluble in water, making separation from hydroxybenzoic acid difficult.
逆に有機溶媒が過小な場合は、析出するヒドロキシ安息
香酸を十分に溶解できず、同じく析出するアルカリ金属
の重炭酸塩と混在し、両者の分離が面倒になる。On the other hand, if the amount of organic solvent is too small, the precipitated hydroxybenzoic acid cannot be sufficiently dissolved and is mixed with the alkali metal bicarbonate that is also precipitated, making it difficult to separate the two.
当該反応生成物を炭酸ガスと接触させる方法としては、
前記方法によって調製された溶液を良く攪拌しながら、
その中に炭酸ガスあるいはこれを含むガスを導入すれば
良く、この際の圧力および温度は常圧あるいは加圧、常
温あるいは加熱、冷却のいずれでも差しつかえない。The method of bringing the reaction product into contact with carbon dioxide gas is as follows:
While thoroughly stirring the solution prepared by the above method,
Carbon dioxide gas or a gas containing carbon dioxide gas may be introduced into it, and the pressure and temperature at this time may be normal pressure, pressurization, room temperature, heating, or cooling.
接触時間は、圧力、温度によって異なるが、通常３０分
〜１時間程度である。The contact time varies depending on pressure and temperature, but is usually about 30 minutes to 1 hour.
本発明に使用される炭酸ガスは純粋なものが好ましいが
、化学工業あるいは関連工業の製造プラント、たとえば
有機化合物の酸化装置から排出される炭酸ガスを含む廃
ガスあるいはそれを濃縮したものでも差しつかえない。The carbon dioxide used in the present invention is preferably pure, but it may also be waste gas containing carbon dioxide discharged from manufacturing plants in the chemical industry or related industries, such as oxidation equipment for organic compounds, or concentrated waste gas. do not have.
炭酸ガスとの接触後、析出したアルカリ金属の重炭酸塩
は口別分離されるが、この結晶中には微量のアルカリ金
属の炭酸塩が含まれているほかは、他の不純物が含まれ
ていないので、乾燥後、そのままアルカリ源として使用
することができる。After contact with carbon dioxide gas, the precipitated alkali metal bicarbonate is separated separately, but apart from a trace amount of alkali metal carbonate, this crystal contains no other impurities. Therefore, after drying, it can be used as an alkali source.
一方、口液を蒸発濃縮して水に易溶な有機溶媒を除去す
ると、主にヒドロキシ安息香酸を含む水溶液か得られる
が、この水溶液を冷却すればヒドロキシ安息香酸の結晶
が析出する。On the other hand, when the oral fluid is evaporated and concentrated to remove the organic solvent that is easily soluble in water, an aqueous solution containing mainly hydroxybenzoic acid is obtained, but when this aqueous solution is cooled, crystals of hydroxybenzoic acid precipitate.
この結晶を水洗後乾燥すれば、着色の少ない高純度のヒ
ドロキシ安息香酸が得られる。If the crystals are washed with water and then dried, highly pure hydroxybenzoic acid with little coloring can be obtained.
ここで得られた口液および洗浄液にはヒドロキシ安息香
酸のアルカリ金属塩、ギ酸のアルカリ金属塩、フェノー
ルなどが含まれているが、これはさらに酸処理して蒸留
あるいは抽出などの操作で回収することができる。The oral fluid and washings obtained here contain alkali metal salts of hydroxybenzoic acid, alkali metal salts of formic acid, phenol, etc., which are further treated with acid and recovered through operations such as distillation or extraction. be able to.
《発明の効果》
本発明の利点はアルカリ金属を重炭酸塩として回収でき
るので当該反応や他の反応のアルカリ源として再利用で
きる点にある。<<Effects of the Invention>> The advantage of the present invention is that the alkali metal can be recovered as bicarbonate and thus can be reused as an alkali source for this reaction or other reactions.
次に本発明を実施例をあげて説明する。Next, the present invention will be explained by giving examples.
実施例 １
内容積１０００ｒｒｌのステンレス製オ〜トクレブにフ
ェノールのナトリウム塩５８ｇと炭酸ナトリウム５３ｇ
およびギ酸ナトリウム３４ｇを入れ、一酸化炭素を常温
で７５ｋｇ／ｃｍ２Ｇ入れて、２６０℃で１３時間反応
させた。Example 1 58 g of sodium salt of phenol and 53 g of sodium carbonate were placed in a stainless steel autoclave with an internal volume of 1000 rrl.
Then, 34 g of sodium formate and 75 kg/cm2G of carbon monoxide were added at room temperature, and the mixture was reacted at 260° C. for 13 hours.
反応終了後、液温か室温付近になってからオ−トクレー
ブを開け、反応生成物をアセトンで洗浄し、得られた結
晶を水 １８０ｇに溶解させ、さらにアセトン１０００
ｇを加えてよく攪拌しながら炭酸ガスをｌｊｌ／分の速
度で室温下パブリングさせた。After the reaction is completed, the autoclave is opened after the temperature of the liquid reaches room temperature, the reaction product is washed with acetone, the obtained crystals are dissolved in 180 g of water, and then dissolved in 1000 g of acetone.
g was added thereto, and while stirring well, carbon dioxide gas was bubbled at a rate of ljl/min at room temperature.
析出した結晶を濾別し、アセトンで洗浄し乾燥後９５ｇ
の固体が得られた。Separate the precipitated crystals by filtration, wash with acetone, dry and weigh 95g.
of solid was obtained.
ナトリウムの回収は仕込みナトリウムに対して５６．５
モル％であり炉液に溶解しているギ酸ナトリウムの分を
差し引くと７５．４モル％であった。炉液からアセトン
を減圧下加熱除去することにより析出した固体を炉別し
水で洗浄、乾燥させＰ−ヒドロキシ安息香酸４１ｇを得
た。Sodium recovery is 56.5% compared to the sodium charged.
The amount was 75.4 mol% after subtracting the amount of sodium formate dissolved in the furnace liquid. Acetone was removed from the furnace solution by heating under reduced pressure, and the precipitated solid was separated from the furnace, washed with water, and dried to obtain 41 g of P-hydroxybenzoic acid.
炉液を硫酸でＰＨ１にして析出した固体を水で洗浄し乾
燥させＰ−ヒドロキシ安息香酸１８ｇを得た。The furnace solution was adjusted to pH 1 with sulfuric acid, and the precipitated solid was washed with water and dried to obtain 18 g of P-hydroxybenzoic acid.
実施例 ２
内容積ＩＣＩＱＯｍｊ！のステンレス製オートクレープ
にフェノールのカリウム塩６０ｇと炭酸カリウム６３ｇ
およびジフェニルエーテル２１０ｇを入れ、常温で一酸
化炭素５０ｋｇ／ｃｍ２Ｇを圧入し、２４０℃で４時間
攪拌しながら反応させた。Example 2 Internal volume ICIQOmj! 60g of potassium salt of phenol and 63g of potassium carbonate in a stainless steel autoclave.
and 210 g of diphenyl ether were added, and 50 kg/cm2G of carbon monoxide was pressurized at room temperature, followed by reaction at 240°C for 4 hours with stirring.
反応終了後、水２００ｇを加え、攪拌静置後、水層を分
離し水層にエタノール１０００ｇを加え、析出した結晶
を炉別した。After the reaction was completed, 200 g of water was added, and after stirring and standing, the aqueous layer was separated, 1000 g of ethanol was added to the aqueous layer, and the precipitated crystals were separated in a furnace.
得られた結晶をエタノールで洗浄し乾燥させ８４ｇの固
体を得た。The obtained crystals were washed with ethanol and dried to obtain 84 g of solid.
カリウム回収率は仕込みカリウム量に対して６２％であ
った。The potassium recovery rate was 62% based on the amount of potassium charged.
炉液よりエタノールを減圧下留去し得られた固体とその
際の炉液を硫酸でｐｎ−ｘにして得られた固体はともに
Ｐ−ヒドロキシ安息香酸であり、フェノールのカリウム
塩に対する回収率は８２％であった。The solid obtained by distilling ethanol off from the furnace liquid under reduced pressure and the solid obtained by pn-xing the furnace liquid at that time with sulfuric acid are both P-hydroxybenzoic acid, and the recovery rate for the potassium salt of phenol is It was 82%.
Claims (1)
カリ塩またはギ酸アルカリ塩の存在下反応させて得られ
る反応生成物からアルカリ金属を回収する方法において
、反応生成物を水と水に易溶な有機溶媒との混合物に溶
解し、ついでこの溶液に炭酸ガスを吹き込み、生成する
ヒドロキシ安息香酸を水と水に易溶な有機溶媒との混合
物の溶液として得る一方、副生するアルカリ金属の重炭
酸塩を固体として析出回収することを特徴とするアルカ
リ金属の回収方法。A method for recovering alkali metals from a reaction product obtained by reacting an alkali metal salt of phenol with carbon monoxide in the presence of an alkali carbonate or an alkali formate. Hydroxybenzoic acid is dissolved in a mixture with a solvent, and then carbon dioxide gas is blown into this solution to obtain hydroxybenzoic acid as a solution of a mixture of water and an organic solvent that is easily soluble in water. A method for recovering alkali metals, characterized by precipitating and recovering them as a solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1208190A JPH03218919A (en) | 1990-01-22 | 1990-01-22 | Method of recoverying alkali metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1208190A JPH03218919A (en) | 1990-01-22 | 1990-01-22 | Method of recoverying alkali metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218919A true JPH03218919A (en) | 1991-09-26 |
Family
ID=11795636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1208190A Pending JPH03218919A (en) | 1990-01-22 | 1990-01-22 | Method of recoverying alkali metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218919A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006315981A (en) * | 2005-05-11 | 2006-11-24 | Ueno Technology:Kk | Method for producing 3,5-di-tert-butyl-4-hydroxybenzoic acid |
-
1990
- 1990-01-22 JP JP1208190A patent/JPH03218919A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006315981A (en) * | 2005-05-11 | 2006-11-24 | Ueno Technology:Kk | Method for producing 3,5-di-tert-butyl-4-hydroxybenzoic acid |
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