KR20230102380A - ZnO impregnated biochar derived from biomass power plant for phosphate removal and its manufacturing method - Google Patents
ZnO impregnated biochar derived from biomass power plant for phosphate removal and its manufacturing method Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 239000010452 phosphate Substances 0.000 title claims abstract description 57
- 239000002028 Biomass Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000010882 bottom ash Substances 0.000 claims abstract description 54
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011787 zinc oxide Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 19
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims description 10
- 239000002956 ash Substances 0.000 claims description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 6
- 229940007718 zinc hydroxide Drugs 0.000 claims description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 6
- -1 hydroxide ions Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 235000021317 phosphate Nutrition 0.000 description 47
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- B01J20/3204—Inorganic carriers, supports or substrates
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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Abstract
본 발명은 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차에 관한 것으로, 구체적으로는 바이오매스 전소발전소로부터 배출되는 저회를 수집하는 수집단계, 상기 수집된 저회를 질산아연 용액과 혼합한 후 교반하는 혼합단계, 상기 혼합단계에서 제조된 혼합물에 알칼리 용액을 첨가하여 아연이온을 저회내에 혼입시키는 첨착단계, 상기 첨착단계에서 제조된 첨착물을 열수 반응시켜 아연이온을 활성화시키는 활성화단계, 및 상기 활성화된 첨착물에 과잉된 알칼리 성분을 세척하여 제거후 건조시켜 인산염 흡착제를 제조하는 흡착제 제조단계를 포함하는 것을 특징으로 한다.
본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차는 바이오매스 전소발전소로부터 배출되며 폐기물로 취급되는 바이오차 유사 저회를 재활용함으로써 폐기물을 저감시킬 수 있고, 표면작용기가 음하전을 띄는 바이오차 유사 저회에 산화아연을 첨착시킴으로써 인산염에 대한 친화도를 높이고 인산염의 흡착용량을 증가시키며, 수중으로 용출되는 인산염을 저감시킬 수 있는 장점이 있다.The present invention relates to a biochar derived from a ZnO-impregnated burning power plant for removing phosphate, and specifically, a collection step of collecting bottom ash discharged from a biomass burning power plant, mixing the collected bottom ash with a zinc nitrate solution and then stirring Step, an impregnation step of adding an alkali solution to the mixture prepared in the mixing step to incorporate zinc ions into the bottom ash, an activation step of activating zinc ions by hydrothermal reaction of the additive prepared in the impregnation step, and the activated additive It is characterized in that it comprises an adsorbent preparation step of preparing a phosphate adsorbent by washing and removing excess alkali components from the complex and drying them.
Biochar derived from a ZnO-doped power plant for removing phosphate according to the present invention can reduce waste by recycling biochar-like bottom ash discharged from a biomass burning power plant and treated as waste, and biochar-like bottom ash with a surface functional group having a negative charge By impregnating zinc oxide, there are advantages of increasing the affinity for phosphate, increasing the adsorption capacity of phosphate, and reducing phosphate eluted into water.
Description
본 발명은 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차와 그 제조방법에 관한 것으로, 보다 구체적으로는 바이오매스 전소발전소에서 배출되며 폐기물로 취급되는 저회에 산화아연을 첨착시켜 수중에 존재하는 인산염의 제거를 위한 흡착제로 활용할 수 있는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차와 그 제조방법에 관한 것임The present invention relates to a biochar derived from a ZnO-impregnated power plant for removing phosphate and a method for manufacturing the same, and more specifically, to a method for removing phosphate present in water by impregnating zinc oxide in bottom ash discharged from a biomass power plant and treated as waste. It is about ZnO-impregnated biochar derived from electric power plant for removing phosphate that can be used as an adsorbent for removal and its manufacturing method
최근 미세먼지 등의 환경오염 문제가 심각해지면서 국제사회를 중심으로 환경 규제가 강화되고 있다. 환경오염의 주된 원인으로는 석탄화력발전이 거론되고 있으며, 규제가 강화됨에 따라 환경설비의 단계적인 보완과 노후 설비의 조기 폐쇄가 추진 중인 상태이며, 국내의 경우 30년 이상된 노후 화력발전의 일시 가동중단 정책이 발표되었다.Recently, as environmental pollution problems such as fine dust have become serious, environmental regulations are being strengthened around the international community. Coal-fired power generation is being discussed as the main cause of environmental pollution, and as regulations are strengthened, environmental facilities are supplemented step by step and old facilities are closed early. A shutdown policy was announced.
특히, 2017년 탈석탄, 탈원전 정책이 등장함에 따라 발전분야는 2016년 기준 40% 수준인 석탄 화력과 30%인 원자력을 2030년까지 각각 23.7%, 17.9%로 축소하고 LNG 비율 38.4%, 태양광 및 풍력 중심의 신재생 비율의 20% 증가를 목표로 하고 있다.In particular, with the advent of coal-fired and nuclear power plant policies in 2017, the power generation sector will reduce the 40% of coal-fired power and 30% of nuclear power from 2016 to 23.7% and 17.9%, respectively, by 2030, and the LNG ratio of 38.4% and solar power. It is targeting a 20% increase in the share of renewables centered on light and wind.
최근 2050 탄소중립 시나리오에 의해 2050년까지 화력발전소를 폐쇄해야 하며, 이에 따라 화력발전소는 노후석탄화력중 일부를 우드펠릿 연료로 전환하여 바이오매스 전소발전소를 운영하고 있으며, 남동발전의 영동 1호기의 경우 우드펠릿의 사용 증가에 인해 발생되는 발생회인 비회와 저회의 1일 발생량은 각각 14톤 및 19톤 정도로 꾸준히 발생할 것으로 전망된다.Recently, thermal power plants have to be closed by 2050 according to the 2050 carbon-neutral scenario, and accordingly, thermal power plants convert some of the old coal-fired power to wood pellet fuel to operate biomass power plants, and South-East Power's Yeongdong Unit 1 In this case, the daily production of fly ash and bottom ash, which are generated due to the increased use of wood pellets, is expected to steadily occur at about 14 tons and 19 tons, respectively.
그러나, 발전시설로부터 발생된 회(재)는 재활용되는 부분을 제외하고는 대부분 매립하는 방식으로 처리되고 있으며, 매립지 및 회처리장의 만지(滿地)로 인하여 매립방식의 처리를 지속할 수 없을 뿐 아니라 매립부지의 확보가 어렵고, 회 매립으로부터 야기되는 환경 문제 또한 우려되고 있는 실정이다.However, most of the ash (ash) generated from power generation facilities is disposed of in a landfill, except for the recycled part, and landfill treatment cannot be continued due to the landfill and ash treatment plant. In addition, it is difficult to secure a landfill site, and environmental problems caused by ash landfill are also a concern.
한편, 최근 바이오매스 전소발전소로부터 배출된 저회의 구조와 이화학적 특성은 기존 토양개량제, 지구온난화 및 환경정화용 제재로서 각광받고 있는 Biochar와 유사한 것으로 보고되었다. Biochar는 농업 및 산림 부산물을 무산소 조건하에 열분해하여 제조되고 있으며, 최근 연구에 의해 토양개량효과, 작물생육 증진효과, 온실가스 저감효과, 탄소격리 효과 및 환경정화 효과 등으로 주목받고 있는 탄소기반 소재이다.On the other hand, it has been reported that the structure and physicochemical properties of bottom ash discharged from biomass power plants are similar to biochar, which is in the spotlight as an existing soil conditioner, global warming and environmental purification agent. Biochar is manufactured by pyrolysis of agricultural and forest by-products under anoxic conditions, and is a carbon-based material that has attracted attention in recent studies for its soil improvement effect, crop growth enhancement effect, greenhouse gas reduction effect, carbon sequestration effect, and environmental purification effect. .
일반적인 바이오차의 경우 표면 작용기의 특성으로 인하여 대부분 음하전을 띄게 되고, 이러한 영향으로 인하여 음하전을 띄는 인산염에 대해 상대적으로 낮은 처리효율을 보이거나 Biochar 내에 존재하는 인산염의 용출로 인하여 초기 주입된 인산염의 농도보다 더 증가된 값을 나타내기도 한다.In the case of general biochar, most of them are negatively charged due to the characteristics of surface functional groups, and due to this effect, relatively low treatment efficiency for negatively charged phosphates or the concentration of initially injected phosphates due to the elution of phosphates present in biochar It may also indicate a higher value.
한편, 친환경 소재인 산화아연(ZnO)은 다양한 용도로 사용되어 왔으며, 연간 150만톤이 생산되고 있다. 또한, 산화아연은 인산염에 효과적인 물질로 알려져 있으나, 자연적으로 존재하는 산화아연의 경우 입자가 작고 자체응집에 의하여 수처리제로 활용시 공급폐쇄 현상이 발생하여 그 자체를 수질여과제로 활용하기에는 제한적인 것으로 알려져 있다.Meanwhile, zinc oxide (ZnO), an eco-friendly material, has been used for various purposes, and 1.5 million tons are produced annually. In addition, zinc oxide is known to be an effective material for phosphate, but in the case of naturally occurring zinc oxide, the particle size is small and self-aggregation causes a supply closure phenomenon when used as a water treatment agent. there is.
본 발명은 상술한 바와 같은 문제점을 해결하기 위한 것으로, 본 발명의 목적은 기존 바이오매스 전소발전소에서 배출되는 발생회에 ZnO를 첨착한 바이오차를 인산염 흡착제로 활용하는 것이다.The present invention is to solve the above-described problems, and an object of the present invention is to utilize biochar impregnated with ZnO as a phosphate adsorbent in ash discharged from an existing biomass burning power plant.
또한, 본 발명의 다른 목적은 기존 바이오매스 전소발전소 저회의 경우 표면작용기가 대부분 음하전을 띄어 인산염 제거가 어려운 문제를 전소발전소 유래 바이오차에 산화아연을 첨착시킴으로써 인산염의 흡착능력을 향상시킨 ZnO 첨착 바이오차를 흡착제로 제공하는 것이다.In addition, another object of the present invention is to improve the adsorption capacity of phosphate by impregnating zinc oxide to biochar derived from a power plant to solve the problem of difficult phosphate removal because most of the surface functional groups are negatively charged in the case of bottom ash of existing biomass power plants. ZnO impregnated bio to serve tea as an adsorbent.
상기와 같은 목적을 달성하기 위한 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 저회 바이오차의 제조방법은 바이오매스 전소발전소로부터 배출되는 저회를 수집하는 수집단계, 상기 수집된 저회를 질산아연 용액과 혼합한 후 교반하는 혼합단계, 상기 혼합단계에서 제조된 혼합물에 알칼리 용액을 첨가하여 아연이온을 저회내에 혼입시키는 첨착단계, 상기 첨착단계에서 제조된 첨착물을 열수 반응시켜 아연이온을 활성화시키는 활성화단계, 및 상기 활성화된 첨착물에 과잉된 알칼리 성분을 세척하여 제거후 건조시켜 인산염 흡착제를 제조하는 흡착제 제조단계를 포함하는 것을 특징으로 한다.In order to achieve the above object, the method for manufacturing ZnO-impregnated bottom ash biochar for removing phosphate according to the present invention includes a collection step of collecting bottom ash discharged from a biomass burning power plant, mixing the collected bottom ash with a zinc nitrate solution A mixing step of post-stirring, an impregnation step of incorporating zinc ions into the bottom ash by adding an alkali solution to the mixture prepared in the mixing step, an activation step of activating zinc ions by hydrothermal reaction of the additive prepared in the impregnation step, and It is characterized in that it comprises an adsorbent preparation step of preparing a phosphate adsorbent by washing and removing an excess alkali component from the activated additive and drying it.
또한, 상기 혼합단계는 40mM의 Zn(NO3)2·4H2O 용액 1L 당 상기 저회 5 내지 10g을 혼합후 1 내지 2시간 동안 교반하여 혼합물을 제조하는 것을 특징으로 한다.In the mixing step, 5 to 10 g of the bottom ash per 1 L of a 40 mM Zn(NO 3 ) 2 .4H 2 O solution is mixed and then stirred for 1 to 2 hours to prepare a mixture.
또한, 상기 첨착단계는 상기 혼합물에 20 내지 30% NH4OH를 주입하여 pH를 10 내지 11까지 증가시키고 용해된 아연이온을 수산화이온 형태로 상기 저회내에 혼입시켜 첨착물을 제조하는 것을 특징으로 한다.In addition, the impregnation step is characterized by preparing an admixture by injecting 20 to 30% NH 4 OH into the mixture to increase the pH to 10 to 11 and incorporating dissolved zinc ions into the bottom ash in the form of hydroxide ions. .
또한, 상기 활성화단계는 상기 첨착물을 오토클레이브 내에서 90 내지 100℃로 1 내지 2시간 동안 반응시켜 상기 저회내에 수산화아연을 산화아연으로 활성화시키는 것을 특징으로 한다.In addition, the activation step is characterized in that the zinc hydroxide in the bottom ash is activated into zinc oxide by reacting the additive in an autoclave at 90 to 100 ° C. for 1 to 2 hours.
또한, 상기 흡착제 제조단계는 상기 활성화된 첨착물 용액 및 상기 저회 표면에 잔존하는 알칼리 성분을 제거하여 pH가 중성이 될때까지 세척하는 세척단계와, 상기 세척된 첨착물을 80 내지 120℃ 온도하에 24시간 건조하는 건조단계를 포함하는 것을 특징으로 한다.In addition, the adsorbent preparation step includes a washing step of washing until the pH becomes neutral by removing the activated additive solution and the alkaline component remaining on the surface of the bottom ash, and the washed additive at a temperature of 80 to 120
또한, 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 저회 바이오차는 상기 제조방법에 의해 제조되는 것을 특징으로 한다.In addition, the low-ash biochar impregnated with ZnO for phosphate removal according to the present invention is characterized in that it is produced by the above manufacturing method.
본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차는 바이오매스 전소발전소로부터 배출되며 폐기물로 취급되는 바이오차 유사 저회를 재활용함으로써 폐기물을 저감시킬 수 있는 효과가 얻어진다.According to the present invention, biochar derived from a ZnO-impregnated burning power plant for removing phosphate can reduce waste by recycling biochar-like bottom ash discharged from a biomass burning power plant and treated as waste.
또한, 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차는 표면작용기가 음하전을 띄는 바이오차 유사 저회에 산화아연을 첨착시킴으로써 인산염에 대한 친화도를 높이고 인산염의 흡착용량을 증가시키며, 수중으로 용출되는 인산염을 저감시킬 수 있는 효과가 얻어진다.In addition, the ZnO-impregnated biochar for removing phosphate according to the present invention, by impregnating zinc oxide to biochar-like bottom ash having a negatively charged surface functional group, increases the affinity for phosphate and increases the adsorption capacity of phosphate. The effect of reducing the eluted phosphate is obtained.
도 1은 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법을 나타내는 순서도,
도 2는 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법을 개략적으로 나타내는 도면,
도 3은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 표면구조특성과 구성원소를 나타내는 도면,
도 4는 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 산화아연 결정의 분포를 나타내는 도면,
도 5는 일반적인 바이오애쉬와 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 인산염 흡수량을 나타내는 도면,
도 6은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 수중 인산염 농도에 따른 인산염 흡착량을 나타내는 도면, 및
도 7은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 접촉시간별 인산염 흡착량을 나타내는 도면이다.1 is a flow chart showing a method for manufacturing biochar derived from a ZnO-impregnated electric power plant for removing phosphate according to the present invention;
2 is a view schematically showing a method for manufacturing biochar derived from a ZnO-impregnated electric power plant for removing phosphate according to the present invention;
3 is a view showing the surface structure characteristics and constituent elements of ZnO-impregnated electric power plant-derived biochar according to the present invention;
4 is a view showing the distribution of zinc oxide crystals of biochar derived from a ZnO-impregnated power plant according to the present invention;
5 is a view showing the amount of phosphate absorption of general bioash and biochar derived from a ZnO-impregnated power plant according to the present invention;
6 is a view showing the amount of phosphate adsorption according to the concentration of phosphate in water of biochar derived from a ZnO-impregnated power plant according to the present invention, and
7 is a diagram showing the amount of phosphate adsorption by contact time of biochar derived from a ZnO-impregnated power plant according to the present invention.
이하에서는, 본 발명의 바람직한 실시예를 첨부한 도면을 이용하여 구체적으로 설명하기로 한다. 다만, 하기의 실시예는 본 발명의 예시에 불과하므로 본 발명의 범위가 하기의 실시예들에 의하여 제한되지는 않는다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, since the following examples are merely examples of the present invention, the scope of the present invention is not limited by the following examples.
도 1은 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법을 나타내는 순서도이고, 도 2는 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법을 개략적으로 나타내는 도면이다.1 is a flow chart showing a method for manufacturing biochar derived from a ZnO-impregnated power plant for removing phosphate according to the present invention, and FIG. 2 schematically shows a method for manufacturing biochar derived from a ZnO-impregnated power plant for removing phosphate according to the present invention. It is a drawing that represents
본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차는 바이오매스 전소발전소에서 발생하며 폐기물로 취급되는 저회를 재활용하기 위한 것이며, 특히 인산염과 친화력이 있는 산화아연을 바이오매스 저회에 첨착시킴으로써 인산염 흡착제로 활용하는 것을 특징으로 한다.The biochar derived from ZnO-impregnated burning power plants for removing phosphate according to the present invention is for recycling bottom ash generated in biomass burning power plants and treated as waste. It is characterized by the use of
본 실시예에서는 ZnO 첨착 전소발전소 유래 바이오차는 수중에서 인산염을 제거하기 위한 산화아연이 결정형태로 바이오차에 첨착되며, 이때 바이오차는 산화아연 및 인산염이 수중으로 용출되는 것을 방지하는 고체지지체의 역할을 한다.In this embodiment, ZnO-impregnated biochar from a power plant is impregnated with zinc oxide in the form of crystals to remove phosphate from water. do.
도 1을 참고하여, 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법은 바이오매스 전소발전소로부터 배출되는 저회를 수집하는 수집단계(S10), 수집된 저회를 질산아연 용액과 혼합한 후 교반하는 혼합단계(S20), 혼합단계에서 제조된 혼합물에 알칼리 용액을 첨가하여 아연이온을 저회내에 혼입시키는 첨착단계(S30), 첨착단계에서 제조된 첨착물을 열수 반응시켜 아연이온을 활성화시키는 활성화단계(S40), 및 활성화된 첨착물에 과잉된 알칼리 성분을 세척하여 제거후 건조시켜 인산염 흡착제를 제조하는 흡착제 제조단계(S50)를 포함할 수 있다.Referring to FIG. 1, the method of manufacturing biochar derived from a ZnO-impregnated burnt-down power plant for removing phosphate according to the present invention includes a collection step (S10) of collecting bottom ash discharged from a biomass burned-out power plant, and the collected bottom ash with a zinc nitrate solution Mixing step of stirring after mixing (S20), addition step of adding an alkali solution to the mixture prepared in the mixing step to incorporate zinc ions into bottom ash (S30), hydrothermal reaction of the additive prepared in the impregnation step to obtain zinc ions It may include an activation step of activating (S40), and an adsorbent preparation step (S50) of preparing a phosphate adsorbent by washing and removing excess alkali components from the activated additive and then drying the adsorbent.
수집단계(S10)는 바이오매스 전소발전소로부터 배출되는 바이오매스 저회를 수집하는 단계이며, 바이오매스는 주로 식물체를 전소시켜 발생되는 저회를 이용할 수 있으나, 바람직하게는 나무껍질, 톱밥, 나무 조각 등의 목재 폐기물을 펠릿형태로 압축한 우드펠릿을 전소시켜 발생하는 저회를 이용할 수 있다.The collecting step (S10) is a step of collecting the biomass bottom ash discharged from the biomass burning power plant, and biomass can mainly use bottom ash generated by burning plants, but preferably tree bark, sawdust, wood chips, etc. Bottom ash generated by burning wood pellets compressed in the form of wood waste into pellets can be used.
혼합단계(S20)는 수집된 바이오매스 저회를 질산아연 용액과 혼합한 후 교반하여 혼합물을 제조하는 단계로, 저회에 첨착시킬 아연이온을 포함하는 용액에 저회를 혼합하여 아연이온을 저회에 첨착시키는 단계이다.In the mixing step (S20), the collected biomass bottom ash is mixed with a zinc nitrate solution and then stirred to prepare a mixture. The bottom ash is mixed with a solution containing zinc ions to be attached to the bottom ash to attach zinc ions to the bottom ash It is a step.
이때, 사용되는 질산아연 용액은 바람직하게 Zn(NO3)2·4H2O 용액이 사용될 수 있으나, 이에 한정하는 것은 아니고 질산아연의 6수화물, 또는 7수화물, 또는 10수화물을 이용할 수도 있다.At this time, the zinc nitrate solution used may preferably be a Zn(NO 3 ) 2 .4H 2 O solution, but is not limited thereto, and hexahydrate, heptahydrate, or decahydrate of zinc nitrate may be used.
또한, 혼합단계에서 혼합물은 40mM의 ZnSO4·4H2O 용액 1L 당 바이오매스 저회 5 내지 10g을 혼합한 후 1시간 내지 2시간 동안 교반하여 제조될 수 있다.In addition, in the mixing step, the mixture may be prepared by mixing 5 to 10 g of biomass bottom ash per 1 L of a 40 mM ZnSO 4 .4H 2 O solution and then stirring for 1 hour to 2 hours.
다음으로, 첨착단계(S30)는 상기 혼합단계(S20)에서 제조된 혼합물에 알칼리를 주입하여 혼합물에 용해된 아연이온을 수산화아연(Zn(OH)2) 형태로 저회내에 혼입시켜 첨착물을 제조하는 단계로, 혼합물에 알칼리를 주입하여 용액의 pH를 10 내지 11까지 증가시키면 용액내 아연이온이 수산화이온 형태로 저회내에 혼입된다.Next, in the impregnating step (S30), alkali is injected into the mixture prepared in the mixing step (S20) to incorporate zinc ions dissolved in the mixture into the bottom ash in the form of zinc hydroxide (Zn(OH) 2 ) to prepare an additive. In the step of injecting alkali into the mixture to increase the pH of the solution to 10 to 11, zinc ions in the solution are incorporated into the bottom ash in the form of hydroxide ions.
이때, 알칼리는 20 내지 30% NH4OH가 사용될 수 있으나, 이에 한정하는 것은 아니고, 다른 알칼리 또는 알칼리 토금속의 수용성 수산화물을 이용할 수 있다.At this time, 20 to 30% NH 4 OH may be used as the alkali, but is not limited thereto, and water-soluble hydroxides of other alkali or alkaline earth metals may be used.
활성화단계(S40)는 상기 첨착단계(S30)에서 제조된 첨착물을 열수 반응시켜 수산화아연 형태로 저회에 혼입된 아연이온을 활성화시키는 단계이다. 활성화단계는 예시로, 오토클레이브 용기 내에서 첨착물을 90 내지 100℃로 1 내지 2시간 동안 반응시켜 저회내의 수산화아연(Zn(OH)2)을 산화아연(ZnO)으로 활성화시킨다.The activation step (S40) is a step of reacting the additive prepared in the impregnation step (S30) with hot water to activate zinc ions incorporated in the bottom ash in the form of zinc hydroxide. In the activation step, for example, zinc hydroxide (Zn(OH) 2 ) in the bottom ash is activated into zinc oxide (ZnO) by reacting the additive at 90 to 100° C. for 1 to 2 hours in an autoclave container.
흡착제 제조단계(S50)는 상기 활성화단계(S40)에서 활성화된 첨착물을 세척 및 건조하여 흡착제를 제조하는 단계로, 활성화된 첨착물 용액 및 저회 표면에 잔존하는 알칼리 성분을 제거하여 pH가 중성이 될때까지 세척하는 세척단계와, 세척단계에서 세척된 첨착물을 80 내지 120℃ 온도하에 24시간 건조하는 건조단계를 더 포함할 수 있다.The adsorbent preparation step (S50) is a step of preparing an adsorbent by washing and drying the adsorbent activated in the activation step (S40), the pH is neutral by removing the activated admixture solution and the alkali component remaining on the bottom ash surface It may further include a washing step of washing until the washing step and a drying step of drying the additive washed in the washing step for 24 hours at a temperature of 80 to 120 ° C.
이와 같이 제조되는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차는 바이오매스 전소발전소로부터 배출되며 폐기물로 취급되는 바이오매스 저회를 재활용함으로써 폐기물을 저감시킬 수 있고, 기존 바이오매스 저회의 표면작용기가 음하전을 띄어 인산염 제거에 적합하지 않던 문제를 바이오매스 저회에 산화아연을 첨착시킴으로써 인산염에 대한 친화도를 높일 수 있다.Biochar derived from a burning power plant impregnated with ZnO for removing phosphate produced in this way can reduce waste by recycling biomass bottom ash discharged from a biomass burning power plant and treated as waste, and the surface functional group of the existing biomass bottom has a negative charge. Affinity to phosphate can be increased by impregnating zinc oxide to biomass bottom ash, which is not suitable for phosphate removal.
[실시예][Example]
이하에서는 본 발명에 따른 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 구체적인 실시예를 설명한다. 그러나 하기 실시예는 본 발명의 예시일 뿐이며, 본 발명은 하기 실시예에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있음은 물론이다.Hereinafter, a specific embodiment of the ZnO-impregnated biochar from a power plant for phosphate removal according to the present invention will be described. However, the following examples are only examples of the present invention, and the present invention is not limited by the following examples and can be modified and changed in various ways, of course.
바이오매스 전소발전소로부터 배출되는 바이오매스 저회를 수집한 후, 바이오매스 저회 7g을 20mM의 Zn(NO3)2·4H2O 용액 500ml에 주입하고 2시간 동안 교반하여 혼합물을 제조하였다.After collecting biomass bottom ash discharged from a biomass burning power plant, 7 g of biomass bottom ash was injected into 500 ml of a 20 mM Zn(NO 3 ) 2 .4H 2 O solution and stirred for 2 hours to prepare a mixture.
이어서, 제조된 혼합물에 27% NH4OH를 주입하여 용액의 pH를 11까지 증가시켜 혼합물에 용해된 아연이온을 수산화이온 형태로 저회내에 첨착시켜 첨착물을 제조한다.Then, by injecting 27% NH 4 OH into the prepared mixture to increase the pH of the solution to 11, zinc ions dissolved in the mixture are impregnated in the bottom ash in the form of hydroxide ions to prepare an additive.
제조된 첨착물을 오토클레이버용 용기에 넣고 90℃의 온도하에 2시간 동안 반응시켜 저회내의 수산화아연(Zn(OH)2)를 산화아연(ZnO)로 활성화시킨다.The prepared additive was placed in a container for an autoclave and reacted for 2 hours at a temperature of 90° C. to activate zinc hydroxide (Zn(OH) 2 ) in the bottom ash into zinc oxide (ZnO).
활성화를 마친 첨착물에 잔존하는 알칼리 성분을 중성이 될 때까지 세척하고, 80 내지 120℃ 범위의 온도하에 24시간 건조하여 인산염 흡착제를 제조한다.The alkaline component remaining in the activated additive is washed until it becomes neutral, and dried for 24 hours at a temperature in the range of 80 to 120 ° C. to prepare a phosphate adsorbent.
[시험예][Test Example]
도 3은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 표면구조특성과 구성원소를 나타내는 도면이고, 도 4는 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 산화아연 결정의 분포를 나타내는 도면, 도 5는 일반적인 바이오애쉬와 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 인산염 흡수량을 나타내는 도면, 도 6은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 수중 인산염 농도에 따른 인산염 흡착량을 나타내는 도면, 도 7은 본 발명에 따른 ZnO 첨착 전소발전소 유래 바이오차의 접촉시간별 인산염 흡착량을 나타내는 도면이다.3 is a view showing the surface structure characteristics and constituent elements of ZnO-impregnated biochar derived from a pre-fired power plant according to the present invention, and FIG. 4 is a view showing the distribution of zinc oxide crystals of biochar derived from a ZnO-impregnated pre-fired power plant according to the present invention. 5 is a view showing the amount of phosphate absorption of general bioash and biochar derived from ZnO-impregnated power plant according to the present invention, and FIG. 6 shows the amount of phosphate adsorption according to the concentration of phosphate in water of biochar derived from ZnO-impregnated power plant according to the present invention. 7 is a diagram showing the amount of phosphate adsorption by contact time of biochar derived from a ZnO-impregnated power plant according to the present invention.
도 3에 도시한 바와 같이, 본 발명에 따라 제조된 ZnO 첨착 전소발전소 유래 바이오차를 전자주사현미경(SEM)을 통해 관찰한 결과, 탄소로 구성된 저회 지지체에 아연결정이 첨착된 것을 확인할 수 있었고, 구성원소의 분석결과 아연이 약 12%로 상당량이 저회에 잘 첨착된 것을 확인할 수 있었다.As shown in FIG. 3, as a result of observing the ZnO-impregnated biochar derived from a power plant impregnated with ZnO through a scanning electron microscope (SEM), it was confirmed that zinc crystals were attached to the bottom ash support composed of carbon, As a result of the analysis of the constituent elements, it was confirmed that a considerable amount of zinc, about 12%, was well attached to the bottom ash.
도 4에 도시한 바와 같이, 본 발명에 따라 제조된 ZnO 첨착 전소발전소 유래 바이오차는 저회내에 아연이 다수 첨착되었으며, 이들 대부분은 산화아연 결정형으로 구성되어있음이 확인되어 저회내에 아연이온의 활성화가 잘 이루어졌음을 확인할 수 있었다.As shown in FIG. 4, the ZnO-impregnated electric power plant-derived biochar prepared according to the present invention had a large number of zinc impregnated in the bottom ash, and it was confirmed that most of them were composed of zinc oxide crystal form, and the activation of zinc ions in the bottom ash was well I was able to confirm that it was done.
도 5에 도시한 바와 같이, 기존의 일반적인 바이오매스 저회(Bioash)의 경우 수중에서 인산염의 용출이 발생하였으나, 본 발명에 따라 제조된 ZnO 첨착 전소발전소 유래 바이오차의 경우 수중에서 인산염의 흡수율이 우수하여 ZnO 첨착 전소발전소 유래 바이오차는 인산염에 대해 높은 친화도를 나타내는 것을 확인할 수 있었다.As shown in FIG. 5, in the case of conventional biomass bottom ash (Bioash), phosphate elution occurred in water, but in the case of ZnO-impregnated biochar from a power plant impregnated with ZnO prepared according to the present invention, the absorption rate of phosphate in water was excellent As a result, it was confirmed that biochar derived from a power plant impregnated with ZnO exhibits high affinity for phosphate.
도 6에 도시한 바와 같이, 본 발명에 따라 제조된 ZnO 첨착 전소발전소 유래 바이오차를 Langmuir 등온흡착모델로부터 인산염 흡착용량을 도출한 결과, 최대 인산염 흡착용량은 약 105mg/g으로 이는 기존에 보고된 다른 인산염 흡착제들보다 높은 흡착량을 나타내고 있음을 확인할 수 있었다.As shown in FIG. 6, as a result of deriving the phosphate adsorption capacity from the Langmuir isothermal adsorption model for the ZnO-impregnated biochar derived from the electric power plant prepared according to the present invention, the maximum phosphate adsorption capacity is about 105 mg/g, which is previously reported. It was confirmed that the adsorption amount was higher than that of other phosphate adsorbents.
또한, 도 7에 도시한 바와 같이 본 발명에 따라 제조된 ZnO 첨착 전소발전소 유래 바이오차의 접촉시간별 인산염 흡착량을 확인결과, 12시간 이후부터 흡착량이 일정하게 유지되어 가장 인산염을 효과적으로 흡착하기 위한 ZnO 첨착 전소발전소 유래 바이오차의 효율적인 접촉시간은 약 12시간임을 확인할 수 있었다.In addition, as shown in FIG. 7, as a result of confirming the amount of phosphate adsorption for each contact time of the biochar derived from the ZnO-impregnated power plant prepared according to the present invention, the adsorption amount was maintained constant from 12 hours onward, resulting in ZnO for adsorbing phosphate most effectively It was confirmed that the effective contact time of the biochar derived from the impregnated power plant was about 12 hours.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다.The above description of the present invention is for illustrative purposes, and those skilled in the art can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be.
Claims (6)
상기 수집된 저회를 질산아연 용액과 혼합한 후 교반하는 혼합단계;
상기 혼합단계에서 제조된 혼합물에 알칼리 용액을 첨가하여 아연이온을 저회내에 혼입시키는 첨착단계;
상기 첨착단계에서 제조된 첨착물을 열수 반응시켜 아연이온을 활성화시키는 활성화단계; 및
상기 활성화된 첨착물에 과잉된 알칼리 성분을 세척하여 제거후 건조시켜 인산염 흡착제를 제조하는 흡착제 제조단계를 포함하는 것을 특징으로 하는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법.A collection step of collecting bottom ash discharged from a biomass burning power plant;
A mixing step of mixing the collected bottom ash with a zinc nitrate solution and then stirring;
An impregnation step of adding an alkali solution to the mixture prepared in the mixing step to incorporate zinc ions into the bottom ash;
An activation step of activating zinc ions by hydrothermal reaction of the additive prepared in the impregnation step; and
A method for producing a ZnO-impregnated electric power plant-derived biochar for removing phosphate, characterized in that it comprises an adsorbent manufacturing step of washing and removing excess alkali components from the activated additive and then drying to prepare a phosphate adsorbent.
상기 혼합단계는 40mM의 Zn(NO3)2·4H2O 용액 1L 당 상기 저회 5 내지 10g을 혼합후 1 내지 2시간 동안 교반하여 혼합물을 제조하는 것을 특징으로 하는 인산염 제거를 위한 ZnO 첨착 저회 바이오차의 제조방법.According to claim 1,
In the mixing step, 5 to 10 g of the bottom ash per 1 L of a 40 mM Zn(NO 3 ) 2 4H 2 O solution is mixed and stirred for 1 to 2 hours to prepare a mixture. ZnO impregnated low ash bio How to make tea.
상기 첨착단계는 상기 혼합물에 20 내지 30% NH4OH를 주입하여 pH를 10 내지 11까지 증가시키고 용해된 아연이온을 수산화이온 형태로 상기 저회내에 혼입시켜 첨착물을 제조하는 것을 특징으로 하는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법.According to claim 2,
The impregnation step is performed by injecting 20 to 30% NH 4 OH to the mixture to increase the pH to 10 to 11 and incorporating dissolved zinc ions into the bottom ash in the form of hydroxide ions to prepare an admixture. Phosphate removal, characterized in that Manufacturing method of ZnO impregnated electric power plant-derived biochar for
상기 활성화단계는 상기 첨착물을 오토클레이브 내에서 90 내지 100℃로 1 내지 2시간 동안 반응시켜 상기 저회내에 수산화아연을 산화아연으로 활성화시키는 것을 특징으로 하는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법.According to claim 3,
The activation step is a ZnO impregnated electric power plant-derived biochar for removing phosphate, characterized in that by reacting the additive in an autoclave at 90 to 100 ° C. for 1 to 2 hours to activate zinc hydroxide in the bottom ash to zinc oxide Manufacturing method of.
상기 흡착제 제조단계는 상기 활성화된 첨착물 용액 및 상기 저회 표면에 잔존하는 알칼리 성분을 제거하여 pH가 중성이 될때까지 세척하는 세척단계와,
상기 세척된 첨착물을 80 내지 120℃ 온도하에 24시간 건조하는 건조단계를 포함하는 것을 특징으로 하는 인산염 제거를 위한 ZnO 첨착 전소발전소 유래 바이오차의 제조방법.According to claim 4,
The adsorbent preparation step includes a washing step of washing until the pH becomes neutral by removing the activated additive solution and the alkali component remaining on the surface of the bottom ash;
A method for producing biochar derived from a ZnO-impregnated electric power plant for removing phosphate, characterized in that it comprises a drying step of drying the washed additive at a temperature of 80 to 120 ° C. for 24 hours.
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