JPH0468297B2 - - Google Patents
Info
- Publication number
- JPH0468297B2 JPH0468297B2 JP62303258A JP30325887A JPH0468297B2 JP H0468297 B2 JPH0468297 B2 JP H0468297B2 JP 62303258 A JP62303258 A JP 62303258A JP 30325887 A JP30325887 A JP 30325887A JP H0468297 B2 JPH0468297 B2 JP H0468297B2
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- methanol
- activated carbon
- adsorption
- orthocresol
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 123
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 68
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 42
- 238000001179 sorption measurement Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 239000002351 wastewater Substances 0.000 claims description 21
- 150000002989 phenols Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 description 33
- 230000008929 regeneration Effects 0.000 description 27
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 ortho-methylated phenol compound Chemical class 0.000 description 8
- 239000003245 coal Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-M sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
ïŒç£æ¥äžã®å©çšåéïŒ
æ¬çºæã¯ãããšããŒã«ãŸãã¯ïŒããã³ãªã«ãœã¯
ã¬ãŸãŒã«ãšã¡ã¿ããŒã«ãéå±é
žåç©ã®ååšäžã«æ°
çžæ¥è§Šåå¿ãè¡ãªãããªã«ãäœã¡ãã«åããšããŒ
ã«ååç©ã補é ããæ¹æ³ã«ãããŠã補é å·¥çšãã
æåºãããããšããŒã«ç³»å»æ°ŽãããããšããŒã«ã
ãã³ãªã«ãäœã¡ãã«åããšããŒã«ååç©ãçµæžç
ã«ååããæ¹æ³ã«é¢ãããã®ã§ãããDetailed Description of the Invention (Field of Industrial Application) The present invention involves carrying out a gas phase contact reaction between phenol or/and orthocresol and methanol in the presence of a metal oxide to produce an ortho-methylated phenol compound. The present invention relates to a method for economically recovering phenol and ortho-methylated phenolic compounds from phenolic wastewater discharged from a manufacturing process.
æ¬çºæã®æ¹æ³ã«ããååãããããšããŒã«ãã
ã³ãªã«ãäœã¡ãã«åããšããŒã«ååç©ã¯ãããã
ãå·¥æ¥åæãšããŠæçšã§ãããäŸãã°ãããšããŒ
ã«ã¯ããšããŒã«æš¹èããã³ã¯ã¬ãŸãŒã«é¡ã®åæã§
ãããïŒïŒïŒâãã·ã¬ããŒã«ã¯ããªããšãã¬ã³ãš
ãŒãã«ã®åæããã³èŸ²è¬åäœã®åæã§ããïŒïŒïŒ
âãã·ãªãžã³ã®åæã§ãããäžæ¹ããªã«ãœã¯ã¬ãŸ
ãŒã«ã¯å»è¬ã蟲è¬çã®åæãšããŠæçšã§ããã Both the phenol and the ortho-methylated phenol compound recovered by the method of the present invention are useful as industrial raw materials. For example, phenol is a raw material for phenolic resins and cresols, and 2,6-xylenol is a raw material for polyphenylene ether and agricultural chemical ingredients.
- It is a raw material for xylidine, while orthocresol is useful as a raw material for medicines, agricultural chemicals, etc.
ïŒåŸæ¥ã®æè¡ïŒ
ããšããŒã«ãŸãã¯ïŒããã³ãªã«ãœã¯ã¬ãŸãŒã«ãš
ã¡ã¿ããŒã«ãšãæ°çžã§æ¥è§ŠãããŠãªã«ãäœã¡ãã«
åããšããŒã«ååç©ã補é ããæ¹æ³ã¯å
¬ç¥ã§ã
ããå·¥æ¥çã«å®æœãããŠããã(Prior Art) A method for producing an ortho-methylated phenol compound by bringing phenol or/and orthocresol into contact with methanol in a gas phase is known and is practiced industrially.
ãã®åå¿ã¯ãã¡ãã«åã«ããã¡ãã«åãšçã¢ã«
ã®æ°Žãçæããåå¿ã§ãããåå¿åŸã®æ··åç©ã¯ã
æªåå¿ããšããŒã«ãæªåå¿ã¡ã¿ããŒã«ããã³ãªã«
ãäœã¡ãã«åããšããŒã«ååç©çãå«ãããã®æ··
åç©ããååŠéè«çã«çæããæ°Žãç³»å€ã«æåºã
ãå¿
èŠãããããéåžžãåè¿°ã®åå¿åŸã®æ··åç©ã
ããèžæºã«ããæ°Žãšã¡ã¿ããŒã«ãããšããŒã«é¡ã
ãåé¢ããããã«ãèžæºã«ããæ°Žãšã¡ã¿ããŒã«ã
åé¢ãããããããã¯åè¿°ã®åå¿åŸã®æ··åç©ã
ããèžæºã«ããã¡ã¿ããŒã«ãåé¢åŸãããšããŒã«
é¡ãšæ°Žãäºå±€åé¢ããæ°Žå±€ãç³»å€ã«é€å»ããæ¹æ³
çãããã This reaction is a reaction in which methylation produces water in the same molar amount as the methylation, and the mixture after the reaction is
Contains unreacted phenol, unreacted methanol, ortho-methylated phenol compounds, etc. It is necessary to discharge the water produced stoichiometrically from this mixture to the outside of the system, but normally water and methanol are separated from the phenols by distillation from the mixture after the above-mentioned reaction, and then water and methanol are separated from the phenols by distillation. Methods include separating methanol, or separating methanol from the mixture after the above reaction by distillation, separating phenols and water into two layers, and removing the aqueous layer from the system.
ãããã«ãããæ°ŽâããšããŒã«ã®å
±æ²žæ¡ä»¶ã¯ã
æ°Ž90.8ééïŒ
ãå
±æ²žæž©åºŠ99.5âãæ°ŽâïŒïŒïŒâã
ã·ã¬ããŒã«ã®å
±æ²žæ¡ä»¶ã¯ãæ°Ž88.5ééïŒ
ãå
±æ²žæž©
床99âã§ãããæ°Žã«å¯ŸããããšããŒã«é¡ã®æº¶è§£åºŠ
ã¯ãããšããŒã«7.8ééïŒ
ããªã«ãœã¯ã¬ãŸãŒã«2.2
ééïŒ
ãïŒïŒïŒâãã·ã¬ããŒã«0.6ééïŒ
ã§ãã
ãããããšããŒã«é¡ãšæ°Žã®åé¢ã¯æ¥µããŠå°é£ã§ã
ããéåžžãç³»å€ãžæåºãããçæå»æ°Žã¯ãããšã
ãŒã«é¡ãå°éå«æããããšãšãªãããã®å»æ°Žäžã«
å«ãŸããããšããŒã«é¡ã¯éåžžã«é«äŸ¡ã§ããããšã
ããã«ãããšããŒã«ã¯æ°Žè³ªæ±æ¿é²æ¢æ³ã§èŠå¶ãã
ãŠãããèŠå¶æ¿åºŠã¯éåžžã«ãã³ããã®ãå®ç¶ã§ã
ãã In any case, the water-phenol azeotropic condition is
The azeotropic conditions for water-2,6-xylenol are 90.8% by weight of water, azeotropic temperature of 99.5°C, and 88.5% by weight of water, and azeotropic temperature of 99°C. Orthocresol 2.2
% by weight and 0.6% by weight of 2,6-xylenol, it is extremely difficult to separate phenols from water, and normally the produced wastewater discharged outside the system will contain a small amount of phenols. The phenols contained in this wastewater are extremely expensive;
Furthermore, phenol is regulated by the Water Pollution Control Law, and the regulated concentration is actually very strict.
åŸæ¥ãããšããŒã«ç³»å»æ°Žã®åŠçæ¹æ³ã¯ãççŒçŒ
åŽåŠçã掻æ§æ±æ³¥åŠçã溶åªæœåºæ³ãåžçæ³ãäž
è¬çã«ç¥ãããŠããã Conventionally, combustion incineration treatment, activated sludge treatment, solvent extraction method, and adsorption method are generally known as methods for treating phenolic wastewater.
å·¥æ¥çã«æçšãªããšããŒã«é¡ãååããæ¹æ³ãš
ããŠã¯ã溶åªæœåºæ³ãåžçæ³ããããã溶åªæœåº
æ³ã§ã¯ãããšããŒã«é¡ã®ååã¯å¯èœã§ããããã
ãšããŒã«é¡ãååããåŸã®å»æ°Žã¯ãããšããŒã«é¡
ãæ®ã€ãŠããã掻æ§æ±æ³¥ãããã¯çŒåŽåŠçãå¿
èŠ
ãšãªãããšããŸãã溶åªãäžéšå»æ°ŽåŽãžåé
ãã
ãããã溶åªã®è£çµŠãå¿
èŠãšãªããšããããçµæž
æ§ãæªãã Methods for recovering industrially useful phenols include solvent extraction and adsorption methods. Although it is possible to recover phenols using the solvent extraction method, the wastewater after the phenols have been recovered is It is not economical because some of the solvent remains and requires activated sludge or incineration treatment, and some of the solvent is also distributed to the wastewater side, making it necessary to replenish the solvent.
äžæ¹ãåžçæ³ã«ã¯æš¹èã«ããåžçã掻æ§çã«ã
ãåžçããããæš¹èåžçæ³ã¯ãé«äŸ¡ãªæš¹èã䜿çš
ããããšã«ããæš¹èã®è£çµŠè²»ãé«ããçµæžæ§ãæª
ãã掻æ§çåžçæ³ã¯ãããšããŒã«ãåžçãã掻æ§
çã®åçãã©ã®ãããªæ¹æ³ã§è¡ãããšããç¹ãšã
åçãã掻æ§çã®æ§èœãã©ã®çšåºŠå埩ããããšã
ãç¹ãéèŠãšãªãã掻æ§çã®åçæ¹æ³ã¯ãçŸåšå
ç±åçæ³ãåºãçšããããŠããããã®ä»ã¢ã«ã«ãª
åçã溶åªåçããããç¹éæ51â54895å·ã«ã
ãã°ã120ã150âã®æ°Žèžæ°ãçšããäœæž©å ç±åç
æ³ã§ã¯ãåççïŒåççåžçéïŒæ°çåžçéïŒã
äœãã700ã1000âã®é°å²æ°ã§è¡ãé«æž©å ç±åç
æ³ã§ã¯ãæ°Žæ§ã¬ã¹ååå¿ã«ãããé«äŸ¡ãªæŽ»æ§çã®
æ倱ã倧ãããèšåã倧巟ã«å¢å ããçµæžçã§ã¯
ãªãããŸããã¢ã«ã«ãªãçšããåçæ¹æ³ã¯ãæäœ
ãç¹éã§æœåºåŸã®ã¢ã«ã«ãªåŠçãåé¡ãšãªãã On the other hand, adsorption methods include adsorption with resin and adsorption with activated carbon.Resin adsorption methods are not economical due to the high cost of replenishing the resin due to the use of expensive resins. The activated carbon adsorption method is based on two points: how to regenerate activated carbon that has adsorbed phenol;
What is important is how much the performance of the regenerated activated carbon is recovered. Currently, the heating regeneration method is widely used as a method for regenerating activated carbon, and other methods include alkali regeneration and solvent regeneration. According to JP-A No. 51-54895, the regeneration rate (adsorption amount of recycled coal/adsorption amount of new coal) is low in the low-temperature heating regeneration method that uses steam at 120 to 150°C, and that In the thermal regeneration method, there is a large loss of expensive activated carbon due to the water gasification reaction, and the amount of equipment required increases significantly, making it uneconomical. In addition, the regeneration method using alkali requires complicated operations and poses a problem in alkali treatment after extraction.
溶åªåçæ¹åŒã®å®éšäŸã¯ãåå·¥åäŒç¬¬18åç§å£
倧äŒSHâ317ïŒ1984ïŒã§çºè¡šãããŠãããããšã
ãŒã«æ°Žæº¶æ¶²ã®åžç掻æ§çã®åççšæº¶åªã®æ€èšã§
ã¯ãã¡ã¿ããŒã«ããã³ãŒã³ããã«ãšã³ãã¢ã»ã
ã³ããšã¿ããŒã«äžãåççïŒåççåžçéïŒæ°ç
åžçéïŒãäžçªè¯å¥œãªãã®ã89ïŒ
ã®ãšã¿ããŒã«ã§
ãããäžçªæªãã®ã69ïŒ
ã®ã¡ã¿ããŒã«ã§ãã€ãã
ãŸãããšã¿ããŒã«åççã®åçåæ°ã®åœ±é¿ã®æ€èš
ã§ã¯ãåçåæ°ïŒåã§åçç80ïŒ
ã§ãã€ãããŸ
ããåå·¥åäŒç¬¬19åç§å£å€§äŒSGâ317ïŒ1985ïŒã®
å®éšäŸã§ã¯ãåçš®åžç質ã®ãšã¿ããŒã«åçã®æ€èš
ã«ãããã¢ã³ãã©ããã³âïŒâã¹ã«ãã³é
žãããª
ãŠã ã®å Žåã¯ãåççã40ïŒ
ã§ãã€ãã An experimental example of the solvent regeneration method was presented at the 18th Autumn Conference of the Japan Chemical Industry Association SH-317 (1984). The best regeneration rate (regenerated coal adsorption amount/new coal adsorption amount) was 89% ethanol, and the worst was 69% methanol.
In addition, when examining the influence of the number of regenerations of ethanol recycled coal, the regeneration rate was 80% after four regenerations. In addition, in an experimental example at the 19th Autumn Conference of the Japan Association of Chemical Engineers SG-317 (1985), the regeneration rate of ethanol for various adsorbates was investigated, and in the case of sodium anthraquinone-2-sulfonate, the regeneration rate was 40%.
以äžã®åŠãã溶åªåçæ¹åŒã«é¢ããŠãã掻æ§ç
ã®åççãäœãããšãåé¡ç¹ãšãªã€ãŠãããç¹ã«
ã¡ã¿ããŒã«ã䜿çšããå Žåã¯ãååã§69ïŒ
ã§ã
ããç¹°è¿ã䜿çšãããšãåççã¯éåžžã«äœããçµ
æžæ§ãæªããšèšããªããã°ãªããªãããŸããã¢ã³
ãã©ããã³âïŒâã¹ã«ãã³é
žãããªãŠã ã®åžçã®
å Žåã¯ããšã¿ããŒã«ã«ããåççã¯40ïŒ
ã®äœãã§
ãããåžçç©è³ªã«ãã€ãŠã¯ãã¡ã¿ããŒã«åçã®å Ž
åã¯ã極端ã«åççãäœäžãããšå€æããªããã°
ãªããªãã As mentioned above, the problem with the solvent regeneration method is that the regeneration rate of activated carbon is low. In particular, when methanol is used, the regeneration rate is 69% the first time, and when used repeatedly, the regeneration rate is extremely low, making it uneconomical. In addition, in the case of adsorption of sodium anthraquinone-2-sulfonate, the regeneration rate with ethanol is as low as 40%, and depending on the adsorbent, it is judged that the regeneration rate will be extremely reduced in the case of methanol regeneration. There must be.
ãŸããå
·äœçã«å«ããšããŒã«ç³»å»æ°Žãžã®é©çšå®
éšäŸã¯ãªããã¡ã¿ããŒã«çã®æº¶åªåçã«ãã掻æ§
çåžçæ¹åŒã¯ãå·¥æ¥çã«æªç¢ºç«ã®åéã§ãã€ãã Furthermore, there have been no concrete experimental examples of application to phenol-containing wastewater, and the activated carbon adsorption method by regenerating solvents such as methanol has remained an unestablished industrial field.
ïŒçºæã解決ããããšããåé¡ç¹ïŒ
åèšã®ããã«ãåŸæ¥ã®æè¡ã«ãããŠã¯ãããšã
ãŒã«ãã®ãã®ãšæ°Žãšã®åãªãæ··åç©ã察象ãšãã
ããšããŒã«æ°Žæº¶æ¶²ã®æŽ»æ§çåžçãè¡ãªããã¡ã¿ã
ãŒã«æº¶åªã«ããåçãè¡ãªã€ãããåççãäœ
ããå·¥æ¥çã«ã¯å°åºæºè¶³ããã¬ãã«ã§ã¯ãªãã€
ãã(Problems to be Solved by the Invention) As mentioned above, in the conventional technology, an aqueous solution of phenol, which is a simple mixture of phenol itself and water, was adsorbed on activated carbon and regenerated using a methanol solvent. However, the regeneration rate was low and was not at a level that was industrially satisfactory.
ïŒåé¡ç¹ã解決ããããã®æ段ïŒ
æ¬çºæè
ãã¯ãããšããŒã«ãŸãã¯ïŒããã³ãªã«
ãœã¯ã¬ãŸãŒã«ãšã¡ã¿ããŒã«ãéå±é
žåç©ã®ååšäž
ã«æ°çžæ¥è§Šåå¿ãè¡ãªãããªã«ãäœã¡ãã«åããš
ããŒã«ååç©ã補é ããæ¹æ³ã«ãããŠã補é å·¥çš
ããæåºãããå«ããšããŒã«ç³»å»æ°Žã察象ã«ãã
ãšããŒã«ãŸãã¯ïŒããã³ãªã«ãäœã¡ãã«åããšã
ãŒã«ååç©ã®ååãè¡ãªã€ããšãããé©ãã¹ãã
ãšã«ã掻æ§çã®åççã¯å€§å·Ÿã«åäžãã䜿çšãã
ããšã«å£åããããšãªããé£ç¶äœ¿çšã§ããããšã
åã€ãã(Means for Solving the Problems) The present inventors have proposed a method for producing an ortho-methylated phenol compound by carrying out a gas phase contact reaction between phenol or/and orthocresol and methanol in the presence of a metal oxide. When we recovered phenols and/or ortho-methylated phenolic compounds from phenol-containing wastewater discharged from manufacturing processes, we were surprised to find that the regeneration rate of activated carbon was greatly improved, making it easier to use. It was found that it could be used continuously without deteriorating.
æ¬çºæã¯ãäžèšã®ç¥èŠã«åºããŠãªããããã®
ã§ãããšããŒã«ãŸãã¯ïŒããã³ãªã«ãœã¯ã¬ãŸãŒã«
ãšã¡ã¿ããŒã«ãéå±é
žåç©ã®ååšäžã«æ°çžæ¥è§Šå
å¿ãè¡ãªãããªã«ãäœã¡ãã«åããšããŒã«ååç©
ã補é ããæ¹æ³ã«ãããŠã補é å·¥çšããæåºãã
ãå«ããšããŒã«ç³»å»æ°Žã掻æ§çåžçãè¡ãªãã次
ã«ãã¡ã¿ããŒã«ãçšããŠåžçç©è³ªãè±çããããš
ãç¹åŸŽãšããããšããŒã«ãŸãã¯ïŒããã³ãªã«ãäœ
ã¡ãã«åããšããŒã«ååç©ã®ååæ¹æ³ã§ããã The present invention was made based on the above findings, and includes a method for producing an ortho-methylated phenol compound by carrying out a gas phase contact reaction of phenol or/and orthocresol and methanol in the presence of a metal oxide. This is a method for recovering phenol and/or ortho-methylated phenol compounds, which is characterized by adsorbing phenol-containing wastewater discharged from a manufacturing process with activated carbon, and then desorbing the adsorbed substance using methanol.
æ¬çºæã«é©çšããã觊åªã¯ãéå±æåãšããŠã
éããããžãŠã ããã³ã¬ã³ããã°ãã·ãŠã ãã¯ã
ã ãã€ã³ãžãŠã ã®åç¬ãŸãã¯çµåããããããã
ãã«ããããã®æåã«ã¢ã«ã«ãªéå±ãã¢ã«ã«ãªå
é¡éå±ãåžåé¡éå±çãæ·»å ããŠäœ¿çšããå Žåã
ããã The catalyst applied to the present invention has, as a metal component,
Iron, vanadium, manganese, magnesium, chromium, and indium may be used alone or in combination, and alkali metals, alkaline earth metals, rare earth metals, etc. may be added to these components.
æ¬çºæã«ãããïŒïŒïŒâãã·ã¬ããŒã«ãŸãã¯ïŒ
ããã³ãªã«ãœã¯ã¬ãŸãŒã«ã®è£œé ã®å ŽåãäŸçµŠåæ
äžã®ããšããŒã«ãŸãã¯ïŒããã³ãªã«ãœã¯ã¬ãŸãŒã«
ã«å¯Ÿããã¡ã¿ããŒã«ã®ã¢ã«æ¯ã¯ã觊åªçš®ã«ããç°
ãªãããïŒïŒïŒã20ã§ããããŸããæ°Žèžæ°ãŸãã¯
äžæŽ»æ§ã¬ã¹ã¯å¿
èŠã«å¿ããŠå°å
¥ã§ããããæ°Žèžæ°
ã®å ŽåãããšããŒã«ãŸãã¯ïŒããã³ãªã«ãœã¯ã¬ãŸ
ãŒã«ã«å¯Ÿããã¢ã«æ¯ã¯ïŒïŒïŒã15ã奜ãŸããã 2,6-xylenol or/in the present invention
and for the production of orthocresol, the molar ratio of methanol to phenol or/and orthocresol in the feedstock varies depending on the catalyst species, but ranges from 1:1 to 20. Further, water vapor or an inert gas can be introduced as necessary, but in the case of water vapor, the molar ratio to phenol and/or orthocresol is preferably 1:0 to 15.
åå¿æž©åºŠã¯è§Šåªçš®ã«ããç°ãªããã250ã600â
ã®ç¯å²ã奜ãŸããã The reaction temperature varies depending on the catalyst type, but is between 250 and 600â.
A range of is preferred.
åå¿ã®å§åã¯ãåžžå§ã§ãæžå§ãŸãã¯å å§äžã§ã
å®æœå¯èœã§ããã The reaction can be carried out at normal pressure, reduced pressure or increased pressure.
ãªã«ãäœã¡ãã«åããšããŒã«ååç©ã®è£œé å·¥çš
ããæåºãããå«ããšããŒã«å»æ°Žäžã«ã¯ãå°éã®
ã¡ã¿ããŒã«å«æãããŠããå Žåã¯ããããããèž
æºæäœçã«ãããã¡ã¿ããŒã«ãé€å€ããŠããããš
ãæãŸãããã¡ã¿ããŒã«ãé€å€ããåŸã掻æ§çåž
çãè¡ãªãããšã«ãããããšããŒã«ããªã«ãœã¯ã¬
ãŸãŒã«ããã³ïŒïŒïŒâãã·ã¬ããŒã«ã®æå¹æåã®
åžçéãå¢å ããçµæžçã§ããããšãããã«ãå»
æ°Žã®åŠçåŸã®æåºæ¡ä»¶æ¬¡ç¬¬ã§ã¯ãCODãäœæžã
ãå¿
èŠãããããšãªã©ã®çç±ã«ããã If the phenol-containing wastewater discharged from the manufacturing process of the ortho-methylated phenol compound contains a small amount of methanol, it is desirable to remove the methanol in advance by distillation or the like. By performing activated carbon adsorption after excluding methanol, the amount of adsorption of the active ingredients of phenol, orthocresol and 2,6-xylenol is increased, and it is economical, and depending on the discharge conditions after wastewater treatment. , due to reasons such as the need to reduce COD.
ãªã«ãäœã¡ãã«åããšããŒã«ååç©ã®è£œé å·¥
çšãäŸãã°ãïŒïŒïŒâãã·ã¬ããŒã«ããªã«ãœã¯ã¬
ãŸãŒã«ã®è£œé å·¥çšããæåºãããå»æ°Žäžã«ã¯ãã¡
ã¿ããŒã«ãããšããŒã«ãïŒïŒïŒâãã·ã¬ããŒã«ã
ãªã«ãœã¯ã¬ãŸãŒã«ã®æçšæåã®ä»ã«ã埮éã®äžçŽ
ç©ãå«æãããŠãããäžçŽç©ãšããŠã¯ãäŸãã°ã
ã¢ããœãŒã«ãïŒïŒïŒâãã·ã¬ããŒã«ãïŒïŒïŒâã
ã·ã¬ããŒã«ãïŒïŒïŒïŒïŒâããªã¡ãã«ããšããŒ
ã«ãã®é
žãé
¢é
žçãããã Methanol, phenol, 2,6-xylenol,
In addition to the useful components of orthocresol, it contains trace amounts of impurities. Examples of impurities include:
Examples include anisole, 2,4-xylenol, 2,5-xylenol, 2,4,6-trimethylphenol, formic acid, and acetic acid.
掻æ§çåžçã®éã¯ãåºå®åºæ¹åŒãŸãã¯ç§»ååºæ¹
åŒã®è£
眮ãéåžžæ¡çšãããã䜿çšãã掻æ§çã¯ã
ç²ç¶çãç Žç çãéžæããããé液éã«å¯Ÿãã掻
æ§çã®éã¯ç¹ã«éå®ã¯ãããªãã掻æ§çã®éãå€
ãå Žåã¯ãåœç¶ãªããåžçéãå€ãããã掻æ§ç
ã®åçåæ°ãå°ãªããªãããåžçèšåã倧ãããª
ããäžæ¹ã掻æ§çã®éãå°ãªãå Žåã¯ãåžçéã
å°ãªãã掻æ§çã®åçåæ°ãå€ããªãããåžçèš
åã¯å°ãããªããåžçããã³è±çã®æäœåæ°ã¯å¢
å ãããäŸãã°ãåºå®åºæ¹åŒã§äºå¡ã§é£ç¶çã«å
æããŠåŠçããå Žåã¯ã掻æ§çã®åçæé以äžã«
ãªãããã«åžçæéãéžã¶å¿
èŠã¯ããããåºå®åº
æ¹åŒã§äžå¡ã§åžçãåçãç¹°è¿ãå Žåã¯ãåžçæ
éãç¹ã«éå®ããªããŠããããåžçããéã®åžç
枩床ãåžçå§åã¯ãåžžæž©ãåžžå§ã§è¡ãããã For activated carbon adsorption, fixed-bed or moving-bed equipment is usually employed. The activated carbon used is
Granular coal, crushed coal is selected. The amount of activated carbon relative to the amount of liquid passed is not particularly limited. When the amount of activated carbon is large, the amount of adsorption is naturally large, so the number of times the activated carbon is regenerated is reduced, but the adsorption equipment becomes larger. On the other hand, when the amount of activated carbon is small, the amount of adsorption is small and the number of times the activated carbon is regenerated increases, but the adsorption equipment becomes smaller and the number of adsorption and desorption operations increases. For example, when using a fixed bed method and processing by continuously switching between two columns, it is necessary to select an adsorption time that is longer than the regeneration time of activated carbon, but when using a fixed bed method and repeating adsorption and regeneration using one column, There is no need to particularly limit the adsorption time. The adsorption temperature and adsorption pressure during adsorption are normal temperature and normal pressure.
ã¡ã¿ããŒã«ã«ããè±çã®éã¯ã䜿çšã¡ã¿ããŒã«
éãäœæžãããããã¡ã¿ããŒã«æ¿åºŠãé«ãæ¹ãæ
ãŸãããã¡ã¿ããŒã«äœ¿çšéã¯ãããšããŒã«ããªã«
ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒïŒâãã·ã¬ããŒã«ã®åå
çã®é¢ãããå€ãæ¹ãããããè±çã«æéããã
ããè£
çå¹çãæªåãããäžæ¹ãã¡ã¿ããŒã«äœ¿çš
éãå°ãªããšãè±çæéã¯çããè£
眮å¹çã¯é«ãŸ
ãããããšããŒã«ããªã«ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒ
ïŒâãã·ã¬ããŒã«ã®ååçãäœäžãããååçã
ã»ãŒ100ïŒ
ã«è¿ãçµæžçãªã¡ã¿ããŒã«éã®æ¡ä»¶ãš
ããŠã¯ãè±ç液äžã®ããšããŒã«ããªã«ãœã¯ã¬ãŸãŒ
ã«ããã³ïŒïŒïŒâãã·ã¬ããŒã«ã®æ¿åºŠãïŒééïŒ
以äžã§ããããšã奜ãŸããã When desorbing with methanol, it is desirable to have a high methanol concentration in order to reduce the amount of methanol used. It is better to use a larger amount of methanol in view of the recovery rate of phenol, orthocresol, and 2,6-xylenol, but desorption takes time and attachment efficiency deteriorates. On the other hand, if the amount of methanol used is small, the desorption time will be short and the equipment efficiency will be increased.
The recovery rate of 6-xylenol decreases. The conditions for an economical amount of methanol with a recovery rate close to 100% are that the concentration of phenol, orthocresol, and 2,6-xylenol in the desorption solution is 1% by weight.
It is preferable that it is below.
ããšããŒã«ããªã«ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒïŒâ
ãã·ã¬ããŒã«ãå«ãè±ã¡ã¿ããŒã«æ¶²ã¯ãåé¢æ¿çž®
æäœãè¡ãããšãªãããªã«ãœã¯ã¬ãŸãŒã«ããã³
ïŒïŒïŒâãã·ã¬ããŒã«ã補é ããå·¥çšãžåŸªç°ãã
ãã Phenol, orthocresol and 2,6-
The demethanolized liquid containing xylenol is recycled to the process for producing orthocresol and 2,6-xylenol without performing a separation and concentration operation.
ãªã«ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒïŒâãã·ã¬ããŒã«
ã補é ããå·¥çšããæåºãããäžçŽç©ãå€æ°å«æ
ããå«ããšããŒã«ç³»å»æ°Žã掻æ§çåžçããéã®æž
念ã¯ãããšããŒã«é¡ã®æçšæåã®åžçãšå
±ã«ãäž
çŽç©ãåããŠåžçããã¡ã¿ããŒã«æº¶åªã«ããåç
ãç¹°è¿ãããéãäžçŽç©ã®èç©ã«ãããåççã
極端ã«äœäžãã掻æ§çãå
šé亀æããªããã°ãªã
ãªãç¶æ
ãšãªããçµæžæ§ããªããªãããšã§ãã€
ãã There are concerns when adsorbing phenolic wastewater containing many impurities discharged from the process of manufacturing ortho-cresol and 2,6-xylenol with activated carbon. When regeneration using a methanol solvent is repeated, the regeneration rate is extremely reduced due to the accumulation of impurities, and the activated carbon must be completely replaced, making it uneconomical.
ãšããããäžèšè£œé å·¥çšå»æ°Žã«é©çšããå Žå
ã¯ã掻æ§çåççã90ïŒ
ã§ãåŸæ¥ã®æè¡äŸãšæ¯èŒ
ãããšå€§å·Ÿã«åäžããæ°çŸåã®ã¡ã¿ããŒã«æº¶åªã«
ããåçåæ°ã«ãããŠãå£åããªãããã®çŸè±¡
ã¯ãå«ããšããŒã«ç³»å»æ°ŽãããšããŒã«ããªã«ãœã¯
ã¬ãŸãŒã«ãïŒïŒïŒâãã·ã¬ããŒã«ããã³äžçŽç©ã
å«ãå€æåã«ãããçžäºäœçšãèµ·ããããšæšå¯ã
ããã However, when applied to wastewater from the above manufacturing process, the activated carbon regeneration rate was 90%, which is a significant improvement compared to conventional techniques, and does not deteriorate even after several hundred regenerations using methanol solvent. This phenomenon is presumed to be due to interaction between the multiple components of the phenol-containing wastewater, including phenol, orthocresol, 2,6-xylenol, and impurities.
ïŒçºæã®å¹æïŒ
æ¬çºæã«ãããŠã¯ãããšããŒã«ãŸãã¯ïŒããã³
ãªã«ãäœã¡ãã«åããšããŒã«ååç©è£œé å·¥çšãã
æåºãããå«ããšããŒã«ç³»å»æ°Žã掻æ§çåžçãã
ã¡ã¿ããŒã«æº¶åªãçšããŠè±çããããšã«ããã掻
æ§çãç¹°è¿ã䜿çšããŠãã掻æ§çã®åžçæ§èœãå£
åããããšãªããåççã¯90ïŒ
ãšå€§å·Ÿã«åäžãã
é·æé£ç¶äœ¿çšãã§ããã(Effects of the Invention) In the present invention, phenol-containing wastewater discharged from the phenol or/and ortho-methylated phenol compound manufacturing process is adsorbed with activated carbon,
By desorbing using methanol solvent, the adsorption performance of activated carbon does not deteriorate even if the activated carbon is used repeatedly, and the regeneration rate is greatly improved to 90%.
Can be used continuously for a long time.
ããã«ãå«ããšããŒã«å»æ°Žäžã®ããšããŒã«ãŸã
ã¯ïŒããã³ãªã«ãäœã¡ãã«åããšããŒã«ååç©ã®
æçšæåã100ïŒ
è¿ãååã§ããåæå¹çã®åäž
ãèšãããšãã§ããããšãåŠçæ°Žã¯ããšããŒã«ã
ã»ãšãã©å«æãããŠããªãã®ã§äºæ¬¡åŠçãå¿
èŠãš
ããããšãªããå
Œ
±æ°Žåã«æåºå¯èœãšãªãããšãª
ã©èããå¹æãçºæ®ããã Furthermore, it is possible to recover nearly 100% of the useful components of phenol and/or ortho-methylated phenol compounds in phenol-containing wastewater, improving raw material efficiency, and since the treated water contains almost no phenol, it can be used as a secondary It has remarkable effects such as being able to be discharged into public waters without the need for treatment.
ïŒå®æœäŸïŒ 以äžãå®æœäŸã«ããæ¬çºæã説æããã(Example) The present invention will be explained below with reference to Examples.
第ïŒå³ã®ãããŒã·ãŒãã«ãããããåå¿åšïŒå
ã§ããšããŒã«ããã³ã¡ã¿ããŒã«ããéããããžãŠ
ã ç³»ã®éå±é
žåç©ã®ååšäžã«åå¿ãããåå¿çæ
ç©ã¯ç±äº€æåšïŒã§å·åŽãããã¬ã¹åé¢å¡ïŒã®å¡åº
ããã©ã€ã³ïŒãéããè±æ°Žå¡ïŒã§æ°Žåãèžæºåé¢
ããåŸãè±æ°Žå¡ïŒã®å¡é ããçåºããã¡ã¿ããŒã«
ããã³æ°Žã¯ãã©ã€ã³ïŒãéããã¡ã¿ããŒã«å¡ïŒã§
èžæºåé¢ããããããšããŒã«ç³»æ··åç©ã¯ã©ã€ã³ïŒ
ãéãã次工çšãžç§»ããããã¡ã¿ããŒã«å¡ïŒã®å¡
åºããã¯ã©ã€ã³ïŒãéããããšããŒã«ããªã«ãœã¯
ã¬ãŸãŒã«ããã³ïŒïŒïŒâãã·ã¬ããŒã«ããã®ä»ã¯
ã¬ãŸãŒã«äžçŽç©ãå«ãå«ããšããŒã«å»æ°Žãæåºã
ããããã®å»æ°Žäžã«å«æãããŠããã¡ã¿ããŒã«
ããã¡ã¿ããŒã«èžæºå¡ïŒïŒã§é€å»ããã According to the flow sheet of FIG. 1, phenol and methanol are reacted in the presence of iron and vanadium metal oxides in the reactor 1, the reaction product is cooled in the heat exchanger 2, and the gas separation column 3 Methanol and water are passed through line 4 from the bottom of the column and separated by distillation in dehydration tower 5, and then distilled from the top of dehydration tower 5. Methanol and water are passed through line 6 and separated by distillation in methanol column 7. Line 8 for phenolic mixtures
is passed through to the next process. Phenol-containing wastewater containing phenol, orthocresol, 2,6-xylenol, and other cresol impurities is discharged from the bottom of the methanol column 7 through a line 9. Methanol contained in this wastewater was removed in a methanol distillation column 10.
ã¡ã¿ããŒã«é€å»åŸã®å«ããšããŒã«ç³»å»æ°Žäžã«
ã¯ãããšããŒã«ããªã«ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒïŒ
âãã·ã¬ããŒã«ãåèš2.53ééïŒ
å«ãŸããŠããã
ãã®å»æ°Žãã©ã€ã³ïŒïŒãéããŠãåºå®å±€æ¹åŒã®æŽ»
æ§çåžçèšåïŒïŒãžå°å
¥ããã©ã€ã³ïŒïŒã®åŠç液
äžã®ããšããŒã«é¡ããªãŒã¯ããçŽåã«ãã©ã€ã³ïŒ
ïŒããã®é液ã掻æ§çåžçèšåïŒïŒã«åæããã©
ã€ã³ïŒïŒãéããŠæåºããã次ã«ãã©ã€ã³ïŒïŒã
éããŠãã¡ã¿ããŒã«ã§æŽ»æ§çåžçèšåïŒïŒã«åžç
ããããšããŒã«ããªã«ãœã¯ã¬ãŸãŒã«ããã³ïŒïŒïŒ
âãã·ã¬ããŒã«ãã©ã€ã³ïŒïŒãéããŠè±çããã
è±çã¡ã¿ããŒã«ãããªãã¡ãã©ã€ã³ïŒïŒã®ããšã
ãŒã«é¡æ¿åºŠã6000ppmãšæžå°ããæç¹ã§ãã©ã€ã³
ïŒïŒãéããŠã®ã¡ã¿ããŒã«ã®é液ãäžæ¢ããã After methanol removal, phenol-containing wastewater contains phenol, orthocresol, and 2,6
- Contained a total of 2.53% by weight of xylenol.
This wastewater is introduced into the fixed bed type activated carbon adsorption equipment 12 through line 11, and immediately before the phenols in the treated liquid in line 16 leak,
The liquid flowing from 1 was switched to activated carbon adsorption equipment 13 and discharged through line 16. Next, the phenol, orthocresol and 2,6
- Xylenol was desorbed through line 15.
When the concentration of desorbed methanol, that is, phenols in line 15, decreased to 6000 ppm, the flow of methanol through line 14 was stopped.
次ã«ã掻æ§çåžçèšåïŒïŒçµç±ã®ã©ã€ã³ïŒïŒäž
ã®ããšããŒã«é¡ããªãŒã¯ããçŽåã«ãåçãã掻
æ§çãå
å¡«ãããŠãã掻æ§çåžçèšåïŒïŒã«åæ
ããåè¿°ã®æäœã230åç¹°è¿ããã Next, immediately before the phenols in the line 16 via the activated carbon adsorption equipment 13 leaked, the system was switched to the activated carbon adsorption equipment 12 filled with the regenerated activated carbon, and the above operation was repeated 230 times.
以äžã®åŠçæ¹åŒã«ãããå«ããšããŒã«å»æ°Žã®åŠ
ç液ã¯ãããšããŒã«æ¿åºŠãïŒã2ppmã§ãããç¡
害åãããŠããããŸãã掻æ§çã®åççã¯ã掻æ§
çåçïŒåç®ä»¥éå¹³å89ïŒ
ã§ããã230åã®ç¹°è¿
ãã«ãããããããå
šãåççãçµæžçã«äœäžã
ãããšã¯ãªãã€ãã By the above treatment method, the treated solution of phenol-containing wastewater had a phenol concentration of 1 to 2 ppm and was rendered harmless. Furthermore, the regeneration rate of activated carbon was 89% on average after the second activated carbon regeneration, and despite 230 repetitions, the regeneration rate did not drop economically at all.
第ïŒå³ã¯å®æœäŸã®è£œé ããã»ã¹ã瀺ããããŒã·
ãŒãã§ããã
FIG. 1 is a flow sheet showing the manufacturing process of the example.
Claims (1)
ãšã¡ã¿ããŒã«ãéå±é žåç©ã®ååšäžã«æ°çžæ¥è§Šå
å¿ãè¡ãªãããªã«ãäœã¡ãã«åããšããŒã«ååç©
ã補é ããæ¹æ³ã«ãããŠã補é å·¥çšããæåºãã
ãå«ããšããŒã«ç³»å»æ°Žã掻æ§çåžçãè¡ãªãã次
ã«ãã¡ã¿ããŒã«ãçšããŠåžçç©è³ªãè±çããããš
ãç¹åŸŽãšããããšããŒã«ãŸãã¯ïŒããã³ãªã«ãäœ
ã¡ãã«åããšããŒã«ååç©ã®ååæ¹æ³ã1 In a method for producing an ortho-methylated phenolic compound by carrying out a gas phase contact reaction of phenol or/and orthocresol and methanol in the presence of a metal oxide, the phenol-containing wastewater discharged from the production process is subjected to activated carbon adsorption. A method for recovering phenol or/and ortho-methylated phenolic compounds, which comprises: desorbing the adsorbed substance using methanol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62303258A JPH01146838A (en) | 1987-12-02 | 1987-12-02 | Method for recovering phenol and phenolic compound methylated at o-position |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62303258A JPH01146838A (en) | 1987-12-02 | 1987-12-02 | Method for recovering phenol and phenolic compound methylated at o-position |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01146838A JPH01146838A (en) | 1989-06-08 |
JPH0468297B2 true JPH0468297B2 (en) | 1992-11-02 |
Family
ID=17918788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62303258A Granted JPH01146838A (en) | 1987-12-02 | 1987-12-02 | Method for recovering phenol and phenolic compound methylated at o-position |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01146838A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5151151A (en) * | 1974-10-29 | 1976-05-06 | Ube Industries | Katsuseitanno saiseiho |
JPS5154895A (en) * | 1974-10-29 | 1976-05-14 | Ube Industries | Katsuseitanno saiseihoho |
JPS5648223A (en) * | 1979-09-28 | 1981-05-01 | Mitsui Toatsu Chem Inc | Treating method of exhaust gas of alkylphenol production process |
-
1987
- 1987-12-02 JP JP62303258A patent/JPH01146838A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5151151A (en) * | 1974-10-29 | 1976-05-06 | Ube Industries | Katsuseitanno saiseiho |
JPS5154895A (en) * | 1974-10-29 | 1976-05-14 | Ube Industries | Katsuseitanno saiseihoho |
JPS5648223A (en) * | 1979-09-28 | 1981-05-01 | Mitsui Toatsu Chem Inc | Treating method of exhaust gas of alkylphenol production process |
Also Published As
Publication number | Publication date |
---|---|
JPH01146838A (en) | 1989-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH0587290B2 (en) | ||
JP2002012573A (en) | Method for recovering catalytic component from mother liquor of liquid-phase oxidation reaction | |
WO2010008055A1 (en) | Method and apparatus for treating wastewater | |
CN109516622B (en) | Treatment process of high-salt wastewater in benzyl alcohol production system | |
JP2006315931A (en) | Method and apparatus for recovering phosphoric acid from metal ion-containing mixed acid aqueous solution containing phosphoric acid and at least one kind of acid except phosphoric acid | |
CN114307523A (en) | Clean production process in chemical production field | |
CN107469862B (en) | Two-step countercurrent extraction and purification method of rhodium/diphosphonite catalyst | |
KR100381453B1 (en) | Method for treating wastewater containing acetic acid and apparatus thereof | |
EP2291330B1 (en) | Process for the treatment of the aqueous stream coming from the fischer-tropsch reaction by means of ion exchange resins | |
JP4535543B2 (en) | Isolation of glycol | |
JPH06157743A (en) | Purification of crude polyoxypropylenepolyol | |
JPH0468297B2 (en) | ||
KR100774803B1 (en) | Process for removing methanol from waste gas | |
CN100417634C (en) | Method of separating and recovering fumaric acid and phthalic acid in fumaric acid preparation wastewater | |
JPH0468298B2 (en) | ||
US3186952A (en) | Recovery of vanadium and copper values from chemical process streams by ionexchange | |
US5770777A (en) | Method reducing UV absorption in ethylene glycols, water, and mixtures | |
JP2779408B2 (en) | Recovery and reuse of phosphoric acid | |
CN109772466B (en) | Method for recovering cobalt acetate/sodium bromide catalyst in catalytic oxidation reaction | |
CN1176026C (en) | Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process | |
KR20120103633A (en) | Method for reusing waste liquid from which tetraalkylammonium ions have been removed | |
WO1997046545A1 (en) | Molybdenum epoxidation catalyst recovery | |
JPH04346954A (en) | Recovery of phenols | |
JPH04346953A (en) | Recovery of phenols | |
US6346645B1 (en) | Adsorptive removal of carbonyl impurities from oxygenated organic liquids |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081102 Year of fee payment: 16 |
|
EXPY | Cancellation because of completion of term | ||
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081102 Year of fee payment: 16 |