KR102630759B1 - Method of removing phthalide derivatives contained in waste sulfuric acid solution - Google Patents
Method of removing phthalide derivatives contained in waste sulfuric acid solution Download PDFInfo
- Publication number
- KR102630759B1 KR102630759B1 KR1020210098486A KR20210098486A KR102630759B1 KR 102630759 B1 KR102630759 B1 KR 102630759B1 KR 1020210098486 A KR1020210098486 A KR 1020210098486A KR 20210098486 A KR20210098486 A KR 20210098486A KR 102630759 B1 KR102630759 B1 KR 102630759B1
- Authority
- KR
- South Korea
- Prior art keywords
- sulfuric acid
- activated carbon
- acid solution
- bar
- phthalide
- Prior art date
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 238000000034 method Methods 0.000 title claims abstract description 26
- 125000005506 phthalide group Chemical class 0.000 title claims abstract 6
- 239000002699 waste material Substances 0.000 title description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 206
- 239000000243 solution Substances 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical class C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 46
- 238000004519 manufacturing process Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000701 coagulant Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000979 synthetic dye Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000000686 lactone group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010888 waste organic solvent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
Abstract
본 발명은 폐황산 용액에서 프탈라이드 유도체 및 불순물을 간단하고 경제적인 공정을 통해 효과적으로 제거할 수 있는 방법을 제공한다. The present invention provides a method for effectively removing phthalide derivatives and impurities from a spent sulfuric acid solution through a simple and economical process.
Description
본 발명은 폐황산 용액을 정제하는 방법에 관한 것으로, 구체적으로 폐황산 용액에 포함된 프탈라이드 유도체 제거 방법에 관한 것이다.The present invention relates to a method for purifying a spent sulfuric acid solution, and specifically to a method for removing phthalide derivatives contained in the spent sulfuric acid solution.
합성염료는, 섬유공업, 합성피혁산업, 종이산업, 식품공업, 광전자화학전지, 머리염색 등의 최신기술분야에 이르기까지 다방면으로 활용되고 있고, 전세계적으로 합성염료의 생산량은 알려져 있지 않으나, 년간 약 1 만톤 정도로 추정되며, 염료의 생산 또는 염료를 사용하는 과정에서 폐수 형태로 환경에 배출되는 양은 집계하기가 매우 어려우나, 대략 약 1~10% 정도로 추정된다. 이러한 합성염료는 대량생산과 폭넓은 이용으로 인해 상당한 환경오염문제와 심각한 건강상의 요인이 될 수 있다.Synthetic dyes are used in a variety of fields, including the latest technology fields such as the textile industry, synthetic leather industry, paper industry, food industry, photoelectrochemical cells, and hair dyeing. Although the production volume of synthetic dyes worldwide is unknown, the annual production volume of synthetic dyes is unknown. It is estimated at approximately 10,000 tons, and the amount discharged into the environment in the form of wastewater during the production or use of dyes is very difficult to calculate, but is estimated to be approximately 1 to 10%. These synthetic dyes can cause significant environmental pollution problems and serious health problems due to their mass production and wide use.
여기에서 발생된 합성염료 폐수는 종래의 폐수처리기술로는 염료의 화학적 안정성 때문에 처리효과가 떨어지고 있어서 최근에는 흡착, 광촉매 분해나 산화방법, 미생물이나 효소를 이용한 분해방법 등의 폐수처리방법이 폭넓게 연구되고 있다.Conventional wastewater treatment technologies for the synthetic dye wastewater generated here are ineffective due to the chemical stability of the dye. Recently, wastewater treatment methods such as adsorption, photocatalytic decomposition or oxidation methods, and decomposition methods using microorganisms or enzymes have been widely studied. It is becoming.
그러나, 광촉매 분해나 산화방법은 과산화수소, Fe 촉매, TiO2 등을 사용함으로써 환경비용이 증가하는 단점이 있고, 미생물이나 효소를 이용한 처리방법은 매력적이나 생물학적 반응 메커니즘이 복잡하고, 강산이나 강알카리 조건에서 처리할 수 없다는 단점이 있다.However, photocatalytic decomposition or oxidation methods have the disadvantage of increasing environmental costs by using hydrogen peroxide, Fe catalyst, TiO 2 , etc., and treatment methods using microorganisms or enzymes are attractive, but the biological reaction mechanism is complex and cannot be used under strong acid or strong alkali conditions. The disadvantage is that it cannot be processed.
대한민국 등록특허 제10-0587493호 에서 황산 폐기물 내의 디메틸에테르를 질소의 상승기류 하에서 스트립퍼(stripper) 내부의 충전물층을 통과시켜 디메틸에테르의 함량을 2~3%대로 낮추는 기술이 소개되어 있으나, 디메틸에테르를 효과적으로 제거하지 못하는 단점이 있다.In Republic of Korea Patent No. 10-0587493, a technology is introduced to reduce the content of dimethyl ether to 2-3% by passing dimethyl ether in sulfuric acid waste through a packing layer inside a stripper under an updraft of nitrogen. However, dimethyl ether It has the disadvantage of not being able to remove effectively.
대한민국 공개특허 제10-2019-0115868호에서 반도체 제조공정에서 발생되는 황산폐기물을 이용하여 수처리용 약품을 제조하는 기술이 소개되어 있으나 과산화수소를 포함하고 있어 다른 용도로 사용이 불가능하다는 단점이 있다.Republic of Korea Patent Publication No. 10-2019-0115868 introduces a technology for manufacturing water treatment chemicals using sulfuric acid waste generated in the semiconductor manufacturing process, but it has the disadvantage that it cannot be used for other purposes because it contains hydrogen peroxide.
또한, 대한민국 공개특허 제10-2019-0112616호에서 인산비료 제조 공정 중 발생되는 폐황산을 이용하여 시멘트용 석고를 제조하는 기술이 소개되어 있으나 인산과 불산이 포함되어 있어 수처리제나 시멘트용으로 밖에 사용할 수 없다는 단점이 있다.In addition, Republic of Korea Patent Publication No. 10-2019-0112616 introduces a technology for manufacturing gypsum for cement using waste sulfuric acid generated during the phosphoric acid fertilizer manufacturing process, but it contains phosphoric acid and hydrofluoric acid and can only be used as a water treatment agent or cement. The downside is that it cannot be done.
그러나, 본 발명에 따른 폐황산 용액에 포함된 프탈라이드 유도체 제거 방법은 감열염료 제조과정 중 발생되는 폐기물인 황산 폐액에서 간단한 연속공정을 통해 프탈라이드 유도체를 효과적으로 제거할 수 있을 뿐 아니라, 과산화수소, 인산, 불산 등이 포함되지 않은 정제된 황산을 제공할 수 있다. However, the method for removing phthalide derivatives contained in waste sulfuric acid solution according to the present invention not only effectively removes phthalide derivatives from sulfuric acid waste, which is a waste generated during the heat-sensitive dye manufacturing process, through a simple continuous process, but also can effectively remove phthalide derivatives from sulfuric acid waste liquid generated during the heat-sensitive dye manufacturing process, as well as hydrogen peroxide and phosphoric acid. , purified sulfuric acid that does not contain hydrofluoric acid, etc. can be provided.
본 발명은, 폐황산 용액 내 프탈라이드 유도체를 활성탄을 이용하여 간단한 연속공정을 통해 효과적으로 제거하고, 산업적으로 재사용할 수 있도록 제공하는 것을 목적으로 한다.The purpose of the present invention is to effectively remove phthalide derivatives in a spent sulfuric acid solution through a simple continuous process using activated carbon and provide industrial reuse.
상기 과제를 해결하기 위해 본 발명은, In order to solve the above problem, the present invention,
폐황산 용액 100 중량%에 대해 활성탄 0.2 내지 5.0 중량%가 포함된, 활성탄 패드에 폐황산 용액을 여과시키는 제1 단계;A first step of filtering the spent sulfuric acid solution through an activated carbon pad containing 0.2 to 5.0% by weight of activated carbon based on 100% by weight of the spent sulfuric acid solution;
상기 폐황산 용액에 포함된 프탈라이드 유도체를 흡착시키는 제2 단계;A second step of adsorbing the phthalide derivative contained in the spent sulfuric acid solution;
상기 프탈라이드 유도체 흡착 후 활성이 떨어진 활성탄을 재활성화 시키는 제 3단계; 및A third step of reactivating activated carbon that has lost its activity after adsorption of the phthalide derivative; and
상기 재활성화된 활성탄층을 이용하여 폐황산 용액을 정제하는 제4 단계;A fourth step of purifying the spent sulfuric acid solution using the reactivated activated carbon layer;
를 포함하는 폐황산 내의 프탈라이드 유도체를 연속적으로 제거하는 방법을 제공한다.It provides a method for continuously removing phthalide derivatives in waste sulfuric acid containing.
본 발명에 따르면 폐황산 용액에 포함된 프탈라이드 유도체 및 불순물을 간단하고 경제적인 공정을 통해 효과적으로 제거할 수 있다.According to the present invention, phthalide derivatives and impurities contained in a spent sulfuric acid solution can be effectively removed through a simple and economical process.
또한, 본 발명에 따르면 황산이 포함된 폐수의 중화처리에 소요되는 환경비용을 절감하고 환경오염을 방지할 수 있을 뿐만 아니라, 폐기 처리되던 폐황산 용액을 자원으로 순환하여 환경오염을 방지함과 동시에 자원절약을 달성할 수 있는 효과가 있다.In addition, according to the present invention, it is possible to not only reduce the environmental costs required for neutralizing wastewater containing sulfuric acid and prevent environmental pollution, but also prevent environmental pollution by circulating the discarded waste sulfuric acid solution as a resource. It has the effect of achieving resource conservation.
도 1은 본 발명의 일 실시예에 따른 폐황산 용액에 포함된 프탈라이드 유도체 제거과정을 나타내는 블럭도이다.
도 2는 본 발명의 일 실시예에 따른 활성탄 패드의 단면이다.
도 3은 본 발명의 일 실시예에 따른 활성탄 패드의 단면이다.
도 4는 본 발명의 일 실시예에 따른 무기계 응집제를 나타낸다.
도 5는 본 발명의 비교예에 따른 무기계 응집제를 나타낸다.Figure 1 is a block diagram showing a process for removing phthalide derivatives contained in a spent sulfuric acid solution according to an embodiment of the present invention.
Figure 2 is a cross-section of an activated carbon pad according to an embodiment of the present invention.
Figure 3 is a cross-section of an activated carbon pad according to an embodiment of the present invention.
Figure 4 shows an inorganic coagulant according to an embodiment of the present invention.
Figure 5 shows an inorganic coagulant according to a comparative example of the present invention.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다.Since the present invention can make various changes and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description.
그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.The terms used in this application are only used to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.
본 발명에서, "폐황산 용액"은 "황산 폐용액", "황산 폐액", "황산 함유 폐수", "폐황산 함유 용액", 또는 "황산 함유 폐수"를 의미한다.In the present invention, “spent sulfuric acid solution” means “sulfuric acid waste solution”, “sulfuric acid waste liquid”, “sulfuric acid-containing wastewater”, “spent sulfuric acid-containing solution”, or “sulfuric acid-containing wastewater”.
본 발명에서, "함유한다", "포함한다", 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성 요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.In the present invention, terms such as "contains", "comprises", or "has" are intended to indicate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification. It should be understood that this does not exclude in advance the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.
본 발명은 폐황산 용액에 포함된 프탈라이드 유도체를 제거하는 방법에 관한 것이다.The present invention relates to a method for removing phthalide derivatives contained in a spent sulfuric acid solution.
본 발명은 폐수의 물리화학적 처리방법 중 하나인 담체의 흡착능력을 이용한 방법이다. 담체의 종류로는 무기질, 탄소계, 또는 유기성 담체가 있으며, 본 발명에 사용된 담체는 탄소계 흡착제인 활성탄으로, 이를 이용하여 폐황산 용액에 포함된 합성염료의 일종인 프탈라이드 유도체를 분리해 낼 수 있다. The present invention is a method using the adsorption capacity of a carrier, which is one of the physical and chemical treatment methods of wastewater. Types of carriers include inorganic, carbon-based, or organic carriers. The carrier used in the present invention is activated carbon, a carbon-based adsorbent, which is used to separate phthalide derivatives, a type of synthetic dye, contained in a spent sulfuric acid solution. I can pay it.
본 발명에서 분리·제거하고자 하는 프탈라이드 유도체는 산성조건에서 락톤 고리 (lactone ring)가 쉽게 개환 (ring opening)되는 특성을 가지고 있다. 개환된 락톤 고리의 음이온은 활성탄 표면의 양이온과 정전기적 인력이 발생하여 활성탄에 흡착하게 된다. The phthalide derivative to be separated and removed in the present invention has the characteristic of easy ring opening of the lactone ring under acidic conditions. The anion of the ring-opened lactone ring is adsorbed to the activated carbon due to electrostatic attraction with the positive ion on the surface of the activated carbon.
일반적으로 감열지에 사용되는 감열염료 제조과정은, 하기 화학식 1의 (I)로 표시되는 2-(2-히드록시-4-디알킬아미노벤조일)벤조산과 하기 화학식 1의 (II)로 표시되는 2-알킬-4-메톡시페닐아민을, 농황산 (98%이상) 조건에서 반응시켜 하기 화학식 1의 (III)으로 표시되는 프탈라이드 유도체를 합성하는 제1단계반응과; 알칼리 조건하에서 반응시켜 하기 화학식 1의 (IV)로 표시되는 플루오란계 감열염료를 합성하는 제2단계반응으로 합성한다.The manufacturing process for thermal dyes generally used in thermal paper is 2-(2-hydroxy-4-dialkylaminobenzoyl)benzoic acid represented by (I) in the following formula 1 and 2 represented by (II) in the formula 1 below. -A first step reaction of synthesizing a phthalide derivative represented by (III) of the following formula (1) by reacting alkyl-4-methoxyphenylamine under concentrated sulfuric acid (98% or more) conditions; It is synthesized in a second stage reaction to synthesize a fluorane-based thermosensitive dye represented by (IV) of the following formula (1) by reacting under alkaline conditions.
상기 화학식 1에서, R1 및 R2는 각각 독립적으로, C1∼C6의 알킬기, C1∼C6의 할로알킬기 또는 C1∼C6의 히드록시알킬기이거나, 또는 R1및 R2가 질소원자(N)와 함께 결합되어 4 내지 7원자의 헤테로고리를 형성할 수 있고;In Formula 1, R 1 and R 2 are each independently a C1-C6 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 hydroxyalkyl group, or R 1 and R 2 are a nitrogen atom (N) and may be bonded together to form a heterocycle of 4 to 7 atoms;
R3은 수소원자, 할로겐 원자 또는 C1∼C6의 알킬기이다.R 3 is a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group.
현재 산업적으로 가장 널리 사용되고 있는 화합물은 치환기 R1 및 R2가 각각 독립적으로, 에틸기, 부틸기, 또는 아이소펜틸기이고, R3은 메틸기 또는 염소 원자(Cl)인, 화합물이다.Currently, the most widely used industrially used compounds are compounds in which the substituents R 1 and R 2 are each independently an ethyl group, a butyl group, or an isopentyl group, and R 3 is a methyl group or a chlorine atom (Cl).
여기서, 화학식 (III)으로 표시되는 프탈라이드 유도체를 합성하는 공정 중에 다량의 황산 폐수가 발생된다. 이러한 화학식 (III)으로 표시되는 프탈라이드 유도체는, 제조과정 중 발생되는 폐기물인 황산용액에 대해 약 1.0 내지 3.0% 정도 함유되어 있고, 이때 황산의 농도는 약 18 내지 40%이며, 그 밖에 미량의 불순물이 포함되어 있다.Here, a large amount of sulfuric acid wastewater is generated during the process of synthesizing the phthalide derivative represented by formula (III). The phthalide derivative represented by the formula (III) contains about 1.0 to 3.0% of the sulfuric acid solution, which is a waste generated during the manufacturing process. In this case, the concentration of sulfuric acid is about 18 to 40%, and a trace amount of other sulfuric acid is present. Contains impurities.
이러한 폐황산 용액에 포함된 프탈라이드 유도체는 황산의 농도에 따라 보라색 또는 검은색 계열의 색깔을 가지며, 이러한 불순물이 포함된 폐황산 용액을 재활용할 경우 폐황산 용액 내부의 프탈라이드 유도체로 인해 보라색 또는 검은색이 포함된 제품이 생산되는 문제점이 발생한다. The phthalide derivatives contained in the spent sulfuric acid solution have a purple or black color depending on the concentration of sulfuric acid. When the spent sulfuric acid solution containing these impurities is recycled, the phthalide derivatives inside the spent sulfuric acid solution cause the color to be purple or black. A problem arises when products containing black are produced.
일반적으로 프탈라이드 유도체를 제거하는 방법은, 폐황산 용액에서 황산의 농도를 3% 미만으로 희석하여 석출된 프탈라이드 유도체를 제거하고, 다시 물을 농축하여 황산의 농도를 조절하거나, 농황산 (농도 98% 이상)을 혼합하여 농도를 조절하는 방법이 사용되고 있다. 그러나 이러한 방법은 폐황산 용액 내부에 잔류하는 프탈라이드 유도체를 효과적으로 제거하지 못하며, 황산의 농도를 농황산으로 조절할 때 잔류한 프탈라이드 유도체의 영향으로 보라색 계열의 색깔을 띄게되는데, 이의 재처리시 상당한 비용이 발생하게 된다.In general, the method of removing phthalide derivatives is to remove the precipitated phthalide derivatives by diluting the concentration of sulfuric acid in the spent sulfuric acid solution to less than 3%, and then adjusting the concentration of sulfuric acid by concentrating the water again, or using concentrated sulfuric acid (concentration 98%). A method of controlling the concentration by mixing % or more is being used. However, this method does not effectively remove the phthalide derivatives remaining in the spent sulfuric acid solution, and when the concentration of sulfuric acid is adjusted to concentrated sulfuric acid, the residual phthalide derivatives produce a purple color, which costs a considerable amount of money when reprocessing. This happens.
하지만, 본 발명의 일 실시예에 따른 방법은 황산이 포함된 폐수의 중화처리에 소요되는 환경비용을 절감하고 환경오염을 방지할 수 있을 뿐만 아니라, 폐기처리되던 황산용액을 기타 제품생산공정에 재사용하거나 별도의 제품으로 판매할 수 있어 생산비를 절감하고 자원을 효율적으로 이용할 수 있다.However, the method according to an embodiment of the present invention not only reduces the environmental costs required for neutralizing wastewater containing sulfuric acid and prevents environmental pollution, but also allows the discarded sulfuric acid solution to be reused in other product production processes. Alternatively, it can be sold as a separate product, reducing production costs and using resources efficiently.
본 발명의 목적을 실현하기 위한 수단으로서, 도 1에 도식되어 있듯이, 본 발명은 하기의 단계를 포함하는 폐황산 용액에 포함된 프탈라이드 유도체를 연속적으로 제거하는 방법을 제공한다.As a means for realizing the object of the present invention, as schematized in FIG. 1, the present invention provides a method for continuously removing phthalide derivatives contained in a spent sulfuric acid solution including the following steps.
폐황산 용액 100 중량%에 대해, 활성탄 0.2 내지 5.0 중량%가 포함된, 활성탄 패드에 폐황산 용액을 여과시키는 제1 단계;A first step of filtering the spent sulfuric acid solution through an activated carbon pad containing 0.2 to 5.0% by weight of activated carbon based on 100% by weight of the spent sulfuric acid solution;
상기 폐황산 용액에 포함된 프탈라이드 유도체를 흡착시키는 제2 단계;A second step of adsorbing the phthalide derivative contained in the spent sulfuric acid solution;
상기 프탈라이드 유도체 흡착 후 활성이 떨어진 활성탄을 재활성화 시키는 제3 단계; 및A third step of reactivating activated carbon that has lost its activity after adsorption of the phthalide derivative; and
상기 재활성화된 활성탄층을 이용하여 폐황산 용액을 정제하는 제4 단계.A fourth step of purifying the spent sulfuric acid solution using the reactivated activated carbon layer.
이하에서, 본 발명을 보다 상세하게 설명한다.Below, the present invention is described in more detail.
먼저, 상기 제1 단계인 폐황산 용액을 여과시키는 데 필요한 일 실시예에 따른 활성탄 패드 제조방법을 도 2 및 도 3을 예로 들어 설명한다.First, a method of manufacturing an activated carbon pad according to an embodiment required for filtering the waste sulfuric acid solution, which is the first step, will be described using FIGS. 2 and 3 as an example.
본 발명의 일 실시예에 따르면, 도 2에 도식되어 있듯이, 첫번째 셀라이트층을 충진하고, 상기 셀라이트층 위로 활성탄을 충진하며, 상기 활성탄층 위로 모래를 충진하여 1단의 패드를 제작할 수 있다.According to one embodiment of the present invention, as shown in Figure 2, a one-stage pad can be manufactured by filling the first celite layer, filling the celite layer with activated carbon, and filling the activated carbon layer with sand. .
본 발명의 다른 일 실시예에 따르면, 도 3에 도식되어 있듯이, 첫번째 제1 셀라이트층을 충진하고, 상기 제1 셀라이트층 위로 제1 활성탄을 충진하고, 다시 상기 제1 활성탄층 위에 제2 셀라이트를 충진하고, 상기 제2 셀라이트층 위에 제2 활성탄을 다시 충진하며, 마지막에 모래층을 충진하여 2단의 활성탄 패드를 제작할 수 있다. According to another embodiment of the present invention, as schematized in FIG. 3, the first celite layer is filled, the first activated carbon is filled on the first celite layer, and the second activated carbon is again placed on the first activated carbon layer. A two-stage activated carbon pad can be manufactured by filling Celite, filling the second activated carbon again on top of the second Celite layer, and finally filling the sand layer.
상기 셀라이트층은 패드형태로 충진된 활성탄층이 여과액으로 통과하지 못하게 방지해 주며, 마지막의 모래층은 폐황산 용액을 통과시킬 때 활성탄 패드의 파손을 방지하는 역할을 한다. The celite layer prevents the activated carbon layer filled in the form of a pad from passing through the filtrate, and the final sand layer serves to prevent damage to the activated carbon pad when passing the spent sulfuric acid solution.
상기 활성탄 패드에 충진되는 활성탄층의 단수는 3단에서 10단까지 충진할 수 있고, 예를 들어, 1.5단을 더 포함할 수 있다.The number of stages of activated carbon layers filled in the activated carbon pad may range from 3 to 10 stages, and, for example, may further include 1.5 stages.
상기 활성탄 패드 하나의 층에 충진되는 셀라이트의 양은, 여과되는 폐황산 용액 100 중량%에 대해 0.1 내지 10.0 중량% 일 수 있고, 바람직하게는 0.5 내지 1.0 중량% 일 수 있다.The amount of Celite filled in one layer of the activated carbon pad may be 0.1 to 10.0% by weight, preferably 0.5 to 1.0% by weight, based on 100% by weight of the filtered waste sulfuric acid solution.
상기 활성탄 패드 하나의 층에 충진되는 활성탄의 양은 폐황산 용액 100 중량%에 대해 0.2 내지 5.0 중량%일 수 있고, 바람직하게는 0.3 내지 1.0 중량% 일 수 있다.The amount of activated carbon filled in one layer of the activated carbon pad may be 0.2 to 5.0% by weight, preferably 0.3 to 1.0% by weight, based on 100% by weight of the spent sulfuric acid solution.
상기 활성탄 패드에 충진되는 모래의 양은 폐황산 용액 100 중량%에 대해 0.5 내지 10.0 중량% 일 수 있고, 바람직하게는 1.0 내지 3.0 중량%일 수 있다.The amount of sand filled in the activated carbon pad may be 0.5 to 10.0% by weight, preferably 1.0 to 3.0% by weight, based on 100% by weight of the spent sulfuric acid solution.
상기 활성탄 패드에 충진되는 활성탄은 형상에 따라 입상활성탄 (Granular Activated Carbon), 분말 활성탄 (Powdered Activated Carbon), 조립 활성탄 (Constructed Carbon)을 각각 혹은 혼합하여 사용할 수 있고, 바람직하게는 분말 활성탄을 사용할 수 있다.Activated carbon filled in the activated carbon pad can be used individually or in a mixture of granular activated carbon, powdered activated carbon, and constructed activated carbon depending on the shape, preferably powdered activated carbon. there is.
상기 활성탄 패드에 충진되는 활성탄은 종류에 따라 야자각, 석탄계, 페놀 수지계, Pitch계 등을 각각 혹은 혼합하여 사용할 수 있고, 바람직하게는 야자각 활성탄을 사용할 수 있다.Depending on the type of activated carbon filled in the activated carbon pad, coconut shell, coal-based, phenolic resin-based, pitch-based, etc. can be used individually or in combination, and coconut shell activated carbon is preferably used.
상기 활성탄 패드에 충진되는 활성탄은 pH가 산성 또는 중성인 활성탄을 각각 혹은 혼합하여 사용할 수 있고, 바람직하게는 중성활성탄일 수 있다.The activated carbon filled in the activated carbon pad may be activated carbon having an acidic or neutral pH, or may be used in combination, and is preferably neutral activated carbon.
상기 제1 단계에서, 폐황산 용액이 상기 활성탄 패드에 의해 여과될 때의 내부압력은 0.1 내지 10.0 bar 일 수 있고, 바람직하게는 0.1 내지 3.0 bar 일 수 있으며, 보다 바람직하게는 0.3 내지 2.0 bar 일 수 있다. 여과 시 내부압력이 0.1 bar 미만으로 가압할 경우, 폐황산 용액이 활성탄 패드를 통과하는 시간이 수시간에서 수십시간의 범위로 증가하여 경제적으로 바람직하지 않으며, 10.0 bar 초과 압력으로 가압할 경우, 폐황산 용액 내의 프탈라이드 유도체가 활성탄에 흡착되지 않을 수 있다.In the first step, the internal pressure when the spent sulfuric acid solution is filtered by the activated carbon pad may be 0.1 to 10.0 bar, preferably 0.1 to 3.0 bar, and more preferably 0.3 to 2.0 bar. You can. If the internal pressure during filtration is pressurized to less than 0.1 bar, the time for the spent sulfuric acid solution to pass through the activated carbon pad increases to a range of several hours to tens of hours, which is economically undesirable, and if pressurized to a pressure exceeding 10.0 bar, the waste sulfuric acid solution passes through the activated carbon pad. Phthalide derivatives in sulfuric acid solution may not be adsorbed to activated carbon.
또한, 상기 제1 단계에서 가압시 주입되는 기체는 압축공기, 질소, 헬륨, 아르곤 등을 사용할 수 있으며, 바람직하게는 압축공기를 사용할 수 있다.Additionally, the gas injected during pressurization in the first step may be compressed air, nitrogen, helium, argon, etc., and compressed air may be preferably used.
상기 제2 단계는 상기 제1 단계에 의한 여과로 폐황산 용액에 포함된 프탈라이드 유도체가 흡착되어 제거되는 단계이다.The second step is a step in which the phthalide derivative contained in the spent sulfuric acid solution is adsorbed and removed through filtration in the first step.
상기 제3 단계는 상기 제2 단계에서 프탈라이드 유도체 흡착 후의 활성탄을 재활성화 시키는 단계로, 상기 제2 단계 후 폐황산 용액 내에 프탈라이드 유도체 내지 불순물이 목적하는 바대로 제거되지 않은 경우, 상기 제3 단계를 거쳐 활성이 떨어진 활성탄을 재활성화시킬 수 있다. 구체적으로, 활성이 떨어진 활성탄 패드에, 증류수를 통과시켜 활성탄 내부의 산도를 제거하고, 알칼리 수용액, 및 유기 용매를 순차적으로 통과시켜 프탈라이드 유도체를 활성탄에서 제거하고, 다시 증류수를 통과시켜 활성탄 내부의 유기 용매를 제거하여 활성이 떨어진 활성탄을 재활성화 시킨다. The third step is a step of reactivating the activated carbon after adsorption of the phthalide derivative in the second step. If the phthalide derivative or impurities are not removed as desired in the spent sulfuric acid solution after the second step, the third step Activated carbon that has lost its activity can be reactivated through steps. Specifically, distilled water is passed through a deactivated activated carbon pad to remove the acidity inside the activated carbon, an aqueous alkaline solution and an organic solvent are sequentially passed through the activated carbon to remove phthalide derivatives, and then distilled water is passed again to remove the acidity inside the activated carbon. Reactivate activated carbon that has lost its activity by removing the organic solvent.
상기 제3 단계에서의 알칼리 수용액은 수산화소듐, 수산화포타슘, 탄산수소소듐, 탄산소듐, 또는 탄산포타슘 수용액 일 수 있고, 바람직하게는 수산화소듐 수용액일 수 있다.The aqueous alkaline solution in the third step may be an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or potassium carbonate, and preferably an aqueous solution of sodium hydroxide.
상기 제3 단계에서의 유기용매는 아세톤, 메탄올, 에탄올, 부탄올, 이소프로필알코올, 아세토나이트릴, 또는 테트라하이드로푸란일 수 있고, 바람직하게는 아세톤일 수 있다. 또한, 사용한 용매는 필요에 따라 증류정제하여 사용할 수 있다.The organic solvent in the third step may be acetone, methanol, ethanol, butanol, isopropyl alcohol, acetonitrile, or tetrahydrofuran, and is preferably acetone. Additionally, the solvent used can be distilled and purified as needed.
상기 제3 단계에서 주입하는 증류수의 양은 폐황산 용액 100 중량%에 대해 1.0 내지 50.0 중량%일 수 있고, 바람직하게는 5.0 내지 10.0 중량% 일 수 있다. 주입하는 증류수 양이 1.0 중량 %미만으로 사용할 경우, 활성탄 내부의 황산의 농도가 증가하여 이후 알칼리 수용액 주입 시 활성탄 내부의 프탈라이드 유도체가 완전히 제거되지 않을 수 있고, 50.0 중량% 초과 주입할 경우, 폐수 발생량이 증가하여 경제적으로 바람직하지 않다. The amount of distilled water injected in the third step may be 1.0 to 50.0% by weight, preferably 5.0 to 10.0% by weight, based on 100% by weight of the spent sulfuric acid solution. If the amount of distilled water injected is less than 1.0% by weight, the concentration of sulfuric acid inside the activated carbon increases, so the phthalide derivatives inside the activated carbon may not be completely removed when the alkaline aqueous solution is subsequently injected. If the amount of distilled water injected exceeds 50.0% by weight, wastewater may not be completely removed. The amount generated increases, making it economically undesirable.
상기 제3 단계에서 주입하는 알칼리 수용액의 양은 폐황산 용액 100 중량%에 대해 10.0 내지 100.0 중량% 일 수 있고, 바람직하게는 10.0 내지 20.0 중량% 일 수 있다. 주입하는 알칼리 수용액 양이 10.0 중량 %미만인 경우, 활성탄 내부의 pH가 산성상태로 유지되어 프탈라이드 유도체가 완전히 제거되지 않을 수 있고, 100.0 중량% 초과 사용할 경우 폐수 발생량이 증가하여 경제적으로 바람직하지 않다.The amount of the aqueous alkaline solution injected in the third step may be 10.0 to 100.0% by weight, preferably 10.0 to 20.0% by weight, based on 100% by weight of the spent sulfuric acid solution. If the amount of aqueous alkaline solution injected is less than 10.0% by weight, the pH inside the activated carbon may remain acidic and the phthalide derivative may not be completely removed, and if used in excess of 100.0% by weight, the amount of wastewater generated increases, making it economically undesirable.
상기 알칼리 수용액의 농도는 폐황산 용액 100 중량%에 대해 0.1 내지 45.0 중량%일 수 있고, 바람직하게는 4.0 내지 8.0 중량% 일수 있다. 주입하는 알칼리 수용액의 농도가 0.1 중량% 미만인 경우, 활성탄 내부의 pH가 산성상태로 유지되어 프탈라이드 유도체가 완전히 제거되지 않을 수 있고, 45.0 중량% 초과일 경우, 폐수 발생량이 증가하여 경제적으로 바람직하지 않다.The concentration of the aqueous alkaline solution may be 0.1 to 45.0% by weight, preferably 4.0 to 8.0% by weight, based on 100% by weight of the spent sulfuric acid solution. If the concentration of the injected aqueous alkaline solution is less than 0.1% by weight, the pH inside the activated carbon may remain acidic and the phthalide derivative may not be completely removed, and if it is more than 45.0% by weight, the amount of wastewater generated increases, making it economically undesirable. not.
상기 제3 단계에서 주입하는 유기 용매의 양은 폐황산 용액 100 중량%에 대해 1.0 내지 100.0 중량%일 수 있고, 바람직하게는 5.0 내지 10.0 중량% 일 수 있다. 주입하는 유기 용매의 양이 1.0 중량% 미만으로 사용할 경우, 활성탄 내부에 잔류한 유기물 및 프탈라이드 유도체가 완전히 제거되지 않을 수 있고, 100.0 중량% 초과 사용할 경우, 폐유기용재의 발생량이 증가하여 경제적으로 바람직하지 않다.The amount of organic solvent injected in the third step may be 1.0 to 100.0% by weight, preferably 5.0 to 10.0% by weight, based on 100% by weight of the spent sulfuric acid solution. If the amount of organic solvent injected is less than 1.0% by weight, the organic substances and phthalide derivatives remaining inside the activated carbon may not be completely removed, and if it is used in excess of 100.0% by weight, the amount of waste organic solvent generated increases, making it economically undesirable. don't do it
상기 제3 단계에서, 활성탄을 재활성화 시킬 때의 내부압력은 0.1 내지 10.0 bar 일 수 있고, 바람직하게는 0.1 내지 3.0 bar일 수 있으며, 보다 바람직하게는 0.3 내지 2.0 bar 일 수 있다. 활성탄 재활성화 시 내부압력이 0.1 bar 미만으로 가압할 경우, 활성탄 재활성화 시간이 수시간에서 수십 시간의 범위로 증가하여 경제적으로 바람직하지 않으며, 10.0 bar 초과 압력으로 가압할 경우, 활성탄 내부의 프탈라이드 유도체가 완전히 제거되지 않을 수 있다.In the third step, the internal pressure when reactivating the activated carbon may be 0.1 to 10.0 bar, preferably 0.1 to 3.0 bar, and more preferably 0.3 to 2.0 bar. When reactivating activated carbon, if the internal pressure is pressurized below 0.1 bar, the activated carbon reactivation time increases from several hours to tens of hours, which is economically undesirable, and when pressurized at a pressure exceeding 10.0 bar, phthalide inside the activated carbon Derivatives may not be completely removed.
또한 상기 제3 단계에서 가압시 주입되는 기체는 압축공기, 질소, 헬륨, 아르곤 등을 사용할 수 있으며, 바람직하게는 압축공기를 사용할 수 있다.In addition, the gas injected during pressurization in the third step can be compressed air, nitrogen, helium, argon, etc., and compressed air can be preferably used.
상기 제4 단계는 상기 제3 단계에 의해 재활성화된 활성탄층을 이용하여 연속적으로 폐황산 용액을 재정제하는 단계이다.The fourth step is a step of continuously repurifying the spent sulfuric acid solution using the activated carbon layer reactivated in the third step.
이하, 본 발명을 제조예 및 실시예에 의해 보다 상세히 설명한다. 단, 하기 제조예 및 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 제조예 및 실시예에 한정되는 것은 아니다Hereinafter, the present invention will be described in more detail through preparation examples and examples. However, the following preparation examples and examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following preparation examples and examples.
<제조예><Manufacturing example>
[제조예 1] 1단의 활성탄 패드 제조[Preparation Example 1] Preparation of 1-stage activated carbon pad
지름이 2.5 cm이고 높이가 60 cm인 컬럼용 유리관에 셀라이트 5.0 g을 투입하고, 셀라이트내부가 갈라짐이 없도록 충진하였다. 충진된 셀라이트 위에 분말상태의 중성 활성탄 5.0 g을 투입하고, 활성탄 내부가 갈라짐이 없도록 충진하였다. 그리고, 충진된 활성탄 위에 다시 모래 10.0 g을 충진하였다. 이때, 활성탄 패드의 전체 높이는 약 2.5 내지 3.0 cm가 되었다. 충진된 활성탄패드에 증류수 50 mL를 첨가하고, 내부압력 0.5 내지 1.0 bar범위에서 가압하여 활성탄 패드를 세척하였다. 5.0 g of Celite was put into a glass tube for a column with a diameter of 2.5 cm and a height of 60 cm, and the Celite was filled so that the inside of the Celite was not cracked. 5.0 g of neutral activated carbon in powder form was added onto the filled Celite, and the activated carbon was filled so that the inside of the activated carbon was not cracked. Then, 10.0 g of sand was again filled on the filled activated carbon. At this time, the total height of the activated carbon pad was about 2.5 to 3.0 cm. 50 mL of distilled water was added to the filled activated carbon pad, and the activated carbon pad was washed by pressurizing the internal pressure in the range of 0.5 to 1.0 bar.
[제조예 2] 2단의 활성탄 패드 제조[Preparation Example 2] Preparation of two-stage activated carbon pad
실시예 1과 동일한 방법으로 셀라이트, 활성탄, 셀라이트, 활성탄, 모래의 순서로 2단의 활성탄패드를 제작하였다. 이때, 활성탄 패드의 전체 높이는 약 4.5 내지 5.0 cm가 되었다. 충진된 활성탄패드에 증류수 100 mL를 첨가하고 내부압력 0.5 내지 1.0 bar범위에서 가압하여 활성탄 패드를 세척하였다.In the same manner as in Example 1, a two-stage activated carbon pad was manufactured in the order of Celite, activated carbon, Celite, activated carbon, and sand. At this time, the total height of the activated carbon pad was about 4.5 to 5.0 cm. 100 mL of distilled water was added to the filled activated carbon pad, and the activated carbon pad was washed by pressurizing it at an internal pressure of 0.5 to 1.0 bar.
<실시예><Example>
[활성탄의 재활성화][Reactivation of activated carbon]
활성이 떨어진 활성탄 패드에 증류수 약 50 내지 60 g을 통과시켜 활성탄 내부의 산도를 일부 제거하고, 5% NaOH 수용액 100 g을 1시간 동안 통과시켜 활성탄 내부의 pH를 알칼리 상태를 유지해 주었다. 다시 활성탄 패드에 아세톤 50 g을 30분 동안 통과시켜 활성탄 내부에 잔류하는 불순물을 제거하였다. 불순물이 제거된 활성탄 패드에 증류수 약 50 내지 60 g을 통과시켜 활성탄 내부의 유기용매를 제거하였다.About 50 to 60 g of distilled water was passed through the deactivated activated carbon pad to remove some of the acidity inside the activated carbon, and 100 g of a 5% NaOH aqueous solution was passed for 1 hour to maintain the pH inside the activated carbon in an alkaline state. Again, 50 g of acetone was passed through the activated carbon pad for 30 minutes to remove impurities remaining inside the activated carbon. About 50 to 60 g of distilled water was passed through the activated carbon pad from which impurities were removed to remove the organic solvent inside the activated carbon.
[실시예 1] [Example 1]
상기 제조예 1에서 제조된 활성탄 패드에, 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 1,000 g을 투입하고, 질소를 이용하여 내부압력 0.3 내지 1.0 bar를 유지하면서 1시간 동안 여과시켰다.1,000 g of waste sulfuric acid containing a sulfuric acid concentration of 22 to 28% and a phthalide derivative of 2.0 wt% was added to the activated carbon pad prepared in Preparation Example 1, and the internal pressure was maintained at 0.3 to 1.0 bar using nitrogen. It was filtered for 1 hour.
[실시예 2][Example 2]
상기 활성탄의 재활성 공정에 의해 재활성화된 활성탄 패드에, 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 1,000 g을 투입하고, 질소를 이용하여 내부압력을 0.3 내지 1.0 bar를 유지하면서 1시간 동안 여과시켰다.1,000 g of waste sulfuric acid containing a sulfuric acid concentration of 22 to 28% and a phthalide derivative of 2.0% by weight was added to the activated carbon pad reactivated by the activated carbon reactivation process, and the internal pressure was adjusted to 0.3 using nitrogen. It was filtered for 1 hour while maintaining 1.0 bar.
[실시예 3 및 3-1][Example 3 and 3-1]
제조일이 서로 다른 폐황산을 이용하여 여과 공정을 2회 더 진행한 것 외에는 상기 실시예 2와 동일한 방법으로 폐황산을 여과시켰다. Waste sulfuric acid was filtered in the same manner as in Example 2, except that the filtration process was performed two more times using waste sulfuric acid of different production dates.
[실시예 4][Example 4]
상기 제조예 2에서 제조된 활성탄 패드에 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 2,000 g을 투입하고 질소를 이용하여 내부압력을 1.0 내지 2.0 bar를 유지하며 1시간 동안 여과시킨 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 폐황산을 여과시켰다. 2,000 g of waste sulfuric acid containing a sulfuric acid concentration of 22 to 28% and a phthalide derivative of 2.0% by weight was added to the activated carbon pad prepared in Preparation Example 2, and the internal pressure was maintained at 1.0 to 2.0 bar using nitrogen. Waste sulfuric acid was filtered in the same manner as Example 2, except that it was filtered for 1 hour.
[실시예 5][Example 5]
상기 제조예 2에서 제조된 활성탄 패드에 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 3,000 g을 투입하고 질소를 이용하여 내부압력을 1.0 내지 2.0 bar를 유지하며 1시간 동안 여과시킨 것을 제외하고는, 상기 실시예 2와 동일한 방법으로 폐황산을 여과시켰다. 3,000 g of waste sulfuric acid having a sulfuric acid concentration of 22 to 28% and 2.0 wt% of phthalide derivatives was added to the activated carbon pad prepared in Preparation Example 2, and the internal pressure was maintained at 1.0 to 2.0 bar using nitrogen. Waste sulfuric acid was filtered in the same manner as Example 2, except that it was filtered for 1 hour.
[실시예 6][Example 6]
상기 제조예 1에서 분말상태의 중성 활성탄 50.0 g을 투입하여 제조된 활성탄 패드에 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 1,000 g을 투입하고, 질소를 이용하여 내부압력을 1.0 내지 2.0 bar를 유지하며 1시간 동안 여과시킨 것을 제외하고는, 상기 실시예 1와 동일한 방법으로 폐황산을 여과시켰다. In Preparation Example 1, 1,000 g of waste sulfuric acid having a sulfuric acid concentration of 22 to 28% and 2.0 wt% of a phthalide derivative was added to the activated carbon pad prepared by adding 50.0 g of powdered neutral activated carbon, and nitrogen was used. Waste sulfuric acid was filtered in the same manner as in Example 1, except that the internal pressure was maintained at 1.0 to 2.0 bar and filtered for 1 hour.
[비교예 1][Comparative Example 1]
상기 제조예 1에서 제조된 활성탄 패드에, 황산의 농도가 22 내지 28%이고, 프탈라이드 유도체가 2.0 중량% 함유된 폐황산 3,000 g을 투입하고 질소를 이용하여 내부압력을 0.3 내지 1.0 bar를 유지하며 3시간 동안 여과시킨 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 폐황산을 여과시켰다. 3,000 g of waste sulfuric acid containing a sulfuric acid concentration of 22 to 28% and a phthalide derivative of 2.0% by weight was added to the activated carbon pad prepared in Preparation Example 1, and the internal pressure was maintained at 0.3 to 1.0 bar using nitrogen. Waste sulfuric acid was filtered in the same manner as in Example 1, except that it was filtered for 3 hours.
<평가><Evaluation>
[평가예 1] 프탈라이드 유도체 및 불순물 잔류량 평가[Evaluation Example 1] Evaluation of residual amounts of phthalide derivatives and impurities
상기 실시예 1 내지 6 및 3-1과 비교예 1의 구체적인 실험 조건을 하기 표 1에 나타내었다.The specific experimental conditions of Examples 1 to 6 and 3-1 and Comparative Example 1 are shown in Table 1 below.
상기 실시예 1 내지 6과 3-1 및 비교예 1에 따라 실시하여 정제황산 내의 프탈라이드 유도체 및 불순물 잔류량을 HPLC 분석방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다.The residual amounts of phthalide derivatives and impurities in purified sulfuric acid were measured using HPLC analysis using Examples 1 to 6, 3-1, and Comparative Example 1, and the results are shown in Table 2 below.
상기 표 1 및 표 2를 참고하면, 활성탄 패드의 층수가 증가되거나 여과 내부압력이 2.0 bar 미만인 경우, 정제황산 내 프탈라이드 유도체가 효과적으로 제거되는 것을 확인할 수 있다. 또한, 활성탄 패드에 충진되는 활성탄의 양이 투입되는 폐황산 용액 대비 0.2 중량% 미만으로 사용된 비교예 1과 대비하여 실시예는 정제황산 내에 프탈라이드 유도체가 효과적으로 제거되어 검출되지 않는 것을 확인할 수 있다.Referring to Tables 1 and 2 above, it can be seen that when the number of layers of the activated carbon pad is increased or the filtration internal pressure is less than 2.0 bar, phthalide derivatives in purified sulfuric acid are effectively removed. In addition, compared to Comparative Example 1, in which the amount of activated carbon filled in the activated carbon pad was less than 0.2% by weight compared to the injected waste sulfuric acid solution, it can be confirmed that the phthalide derivatives in the example are effectively removed and not detected in purified sulfuric acid. .
[평가예 2] 무기계 응집제 제조 [Evaluation Example 2] Production of inorganic coagulant
상기 실시예 1에 의해 여과된 정제황산 (농도 22%) 252 g과 알루미늄 하이드록사이드 30 g을 상온에서 반응기에 투입하고, 내부온도 100 내지 110℃에서 2시간 동안 상압 증류하였다. 이때 증류된 물의 양은 100 g이었고 반응완료 후 물 80 g을 다시 반응기로 재투입하였다. 252 g of purified sulfuric acid (concentration 22%) filtered in Example 1 and 30 g of aluminum hydroxide were added to the reactor at room temperature, and distilled under normal pressure for 2 hours at an internal temperature of 100 to 110°C. At this time, the amount of distilled water was 100 g, and after completion of the reaction, 80 g of water was reintroduced into the reactor.
이렇게 얻어진 생성물을 여과하여 Al2O3의 농도가 7%인 최종 무기계 응집제를 얻었다. 최종 무기계 응집제의 색깔은 도 4와 같이 무색인 것을 확인할 수 있다.The product thus obtained was filtered to obtain a final inorganic coagulant with an Al 2 O 3 concentration of 7%. The color of the final inorganic coagulant can be confirmed to be colorless as shown in Figure 4.
[평가예 3] 무기계 응집제 제조 [Evaluation Example 3] Production of inorganic coagulant
활성탄 처리를 하지 않은 폐황산 용액을 사용하여 상기 평가예 2에서와 동일한 방법으로 공정을 진행하였다. The process was carried out in the same manner as in Evaluation Example 2 using a waste sulfuric acid solution without activated carbon treatment.
이렇게 얻어진 생성물을 여과하여 Al2O3의 농도가 7%인 최종 무기계 응집제를 얻었다. 최종 무기계 응집제의 색깔은 도 5와 같이 보라색인 것을 확인할 수 있다.The product thus obtained was filtered to obtain a final inorganic coagulant with an Al 2 O 3 concentration of 7%. It can be seen that the color of the final inorganic coagulant is purple as shown in Figure 5.
상기 평가예 2 및 3으로부터, 본 발명의 일 실시예에 따른 방법으로 폐기처리되던 폐황산 용액을 기타 제품생산공정에 재사용하거나 별도의 제품으로 재판매가 가능할 것으로 예상되어 생산비 절감 및 효율적인 자원 활용이 가능할 것임을 확인하였다.From the above Evaluation Examples 2 and 3, it is expected that the waste sulfuric acid solution that was disposed of by the method according to an embodiment of the present invention can be reused in other product production processes or resold as a separate product, thereby enabling reduction of production costs and efficient use of resources. It was confirmed that it was.
Claims (6)
상기 폐황산 용액에 포함된 프탈라이드 유도체를 흡착시키는 제2 단계;
상기 프탈라이드 유도체 흡착 후 활성이 떨어진 활성탄을 재활성화 시키는 제3 단계; 및
상기 재활성화된 활성탄층을 이용하여 폐황산 용액을 정제하는 제4 단계;
를 포함하고,
상기 프탈라이드 유도체는 하기 화학식 1의 (III)으로 표시되는, 폐황산 용액에 포함된 프탈라이드 유도체 제거 방법:
[화학식 1]
상기 화학식 1의 (III)에서,
R1 및 R2는 각각 독립적으로, 에틸기, 부틸기, 또는 아이소펜틸기이고,
R3은 메틸기 또는 염소 원자(Cl) 이다.A first step of filtering the spent sulfuric acid solution through an activated carbon pad containing 0.2 to 5.0% by weight of activated carbon based on 100% by weight of the spent sulfuric acid solution;
A second step of adsorbing the phthalide derivative contained in the spent sulfuric acid solution;
A third step of reactivating activated carbon that has lost its activity after adsorption of the phthalide derivative; and
A fourth step of purifying the spent sulfuric acid solution using the reactivated activated carbon layer;
Including,
The phthalide derivative is represented by (III) of the following formula (1): Method for removing the phthalide derivative contained in the spent sulfuric acid solution:
[Formula 1]
In (III) of Formula 1,
R 1 and R 2 are each independently an ethyl group, butyl group, or isopentyl group,
R 3 is a methyl group or a chlorine atom (Cl).
상기 활성탄 패드는 적어도 한 층의 셀라이트층, 적어도 한 층의 활성탄층, 및 모래층을 포함하는, 프탈라이드 유도체 제거 방법.According to paragraph 1,
The activated carbon pad includes at least one layer of celite, at least one layer of activated carbon, and a sand layer.
상기 제1 단계에서의 여과 압력은 0.1 내지 10.0 bar, 또는 0.1 내지 3.0 bar, 또는 0.3 내지 2.0 bar 인, 프탈라이드 유도체 제거 방법.According to paragraph 1,
The filtration pressure in the first step is 0.1 to 10.0 bar, or 0.1 to 3.0 bar, or 0.3 to 2.0 bar.
상기 제3 단계는 증류수, 알칼리 수용액, 유기 용매, 및 증류수를 순차적으로 통과시키는 단계를 더 포함하는, 프탈라이드 유도체 제거 방법.According to paragraph 1,
The third step further includes sequentially passing distilled water, an aqueous alkaline solution, an organic solvent, and distilled water.
상기 제3 단계에서의 여과 압력은 0.1 내지 5.0 bar, 또는 0.1 내지 3.0 bar, 또는 0.3 내지 2.0 bar 인, 프탈라이드 유도체 제거 방법.According to paragraph 1,
The filtration pressure in the third step is 0.1 to 5.0 bar, or 0.1 to 3.0 bar, or 0.3 to 2.0 bar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210098486A KR102630759B1 (en) | 2021-07-27 | 2021-07-27 | Method of removing phthalide derivatives contained in waste sulfuric acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020210098486A KR102630759B1 (en) | 2021-07-27 | 2021-07-27 | Method of removing phthalide derivatives contained in waste sulfuric acid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20230016916A KR20230016916A (en) | 2023-02-03 |
| KR102630759B1 true KR102630759B1 (en) | 2024-01-30 |
Family
ID=85226132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020210098486A KR102630759B1 (en) | 2021-07-27 | 2021-07-27 | Method of removing phthalide derivatives contained in waste sulfuric acid solution |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102630759B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100439903B1 (en) * | 2003-06-11 | 2004-07-12 | 홍성수 | The method and equipment of wastewater treatment contained organic compound of high concentration |
| KR102047212B1 (en) | 2019-07-03 | 2019-11-20 | 정영남 | Active carbon catalyst decomposition method for elimination of hydrogen peroxide in waste sulfuric acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH072212B2 (en) * | 1986-11-15 | 1995-01-18 | 東邦レーヨン株式会社 | Method for decolorizing melanoidin pigment-containing liquid |
| JPH10165938A (en) * | 1996-12-10 | 1998-06-23 | Jiro Sasaoka | Method and apparatus for fluid-cleaning and porous adsorbent |
-
2021
- 2021-07-27 KR KR1020210098486A patent/KR102630759B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100439903B1 (en) * | 2003-06-11 | 2004-07-12 | 홍성수 | The method and equipment of wastewater treatment contained organic compound of high concentration |
| KR102047212B1 (en) | 2019-07-03 | 2019-11-20 | 정영남 | Active carbon catalyst decomposition method for elimination of hydrogen peroxide in waste sulfuric acid |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230016916A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE60102165T2 (en) | INTEGRATED METHOD FOR PRODUCING AN EPOXY | |
| KR100753070B1 (en) | Titanosilicate, process for its production, and its use in producing oxidized compound | |
| EP1160196B1 (en) | Catalyst and process for the direct synthesis of hydrogen peroxide | |
| Song et al. | Highly selective synthesis of methyl ethyl ketone oxime through ammoximation over Ti-MWW | |
| CN104448381B (en) | The preparation and its application of imidazoles functionalized ordered mesoporous phenolic resin material | |
| CN108097323B (en) | Method for preparing imine by primary amine oxidative coupling at room temperature | |
| Dapurkar et al. | Solvent-free allylic oxidation of cycloolefins over mesoporous CrMCM-41 molecular sieve catalyst at 1 atm dioxygen | |
| CN103055883A (en) | Supported nickel-based catalyst and its preparation method and use | |
| KR102630759B1 (en) | Method of removing phthalide derivatives contained in waste sulfuric acid solution | |
| CN103570591B (en) | Method for removing residues out of dimethyl sulfate | |
| CN105524016B (en) | The synthetic method and application of phenthazine and/or its derivative | |
| CN109985611B (en) | Catalyst and preparation method thereof, and preparation method of N-alkyl imidazole compound | |
| US5906954A (en) | Removal of titanium atoms from titanium silicate molecular sieves | |
| CN105085462B (en) | A kind of method of oxidizing cyclohexanone | |
| CN109746004B (en) | Catalyst and application thereof in preparation of 2,2,6, 6-tetramethyl-4-piperidone | |
| CN105523894A (en) | Cyclohexene oxidation method | |
| JP3862883B2 (en) | Nuclear hydrogenation process for aromatic epoxy compounds | |
| CN102850205A (en) | Method for producing 1,2-cyclohexanediol and adipic acid | |
| CN106542979A (en) | A kind of high-selectivity synthesis method of 1,1,3 trichloroacetone | |
| CN113620809A (en) | Recycling treatment method for industrial wastewater generated in production of 5-chloro-2-nitrobenzotrifluoride | |
| US4185022A (en) | Furfuryl alcohol production process | |
| WO2016068061A1 (en) | Method for producing acetonitrile | |
| JP2007182428A (en) | Method for producing cyclohexanone oxime | |
| JP4035611B2 (en) | Process for producing cyclooctene oxide | |
| CN110124744B (en) | Catalyst for catalytic synthesis of chalcone compounds and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |