JP2008207169A - Manufacturing method of white chaff ash - Google Patents
Manufacturing method of white chaff ash Download PDFInfo
- Publication number
- JP2008207169A JP2008207169A JP2007279079A JP2007279079A JP2008207169A JP 2008207169 A JP2008207169 A JP 2008207169A JP 2007279079 A JP2007279079 A JP 2007279079A JP 2007279079 A JP2007279079 A JP 2007279079A JP 2008207169 A JP2008207169 A JP 2008207169A
- Authority
- JP
- Japan
- Prior art keywords
- rice husk
- white
- minutes
- pretreatment
- ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract 3
- 239000010903 husk Substances 0.000 claims description 155
- 241000209094 Oryza Species 0.000 claims description 140
- 235000007164 Oryza sativa Nutrition 0.000 claims description 140
- 235000009566 rice Nutrition 0.000 claims description 140
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 22
- 239000007844 bleaching agent Substances 0.000 claims description 19
- 238000003763 carbonization Methods 0.000 claims description 19
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910001385 heavy metal Inorganic materials 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
Description
この発明は、籾殻から白色系のもみ殻灰を製造する方法に関する。 The present invention relates to a method for producing white rice husk ash from rice husk.
稲等の脱穀の際に生じる籾殻は、農業廃棄物として毎年多量に排出され、その一部が燃料として用いられてはいるものの、その殆どが有効利用の途がなく、そのまま廃棄するか、或いは焼却して籾殻灰としてからこれを廃棄処分にしているのが現状である。近年の資源の有効活用、リサイクル利用の気運の高まりの中、このような籾殻灰についても有効利用の具体的方策をたてることが強く望まれていたところである。 Rice husks generated during threshing of rice and the like are discharged in large quantities every year as agricultural waste, and some of them are used as fuel, but most of them have no way of effective use and are discarded as they are, or The current situation is that it is incinerated and used as rice husk ash before it is disposed of. In recent years, there has been a strong demand for effective utilization of rice husk ash in the wake of increasing use of resources and recycling.
このような状況の中、籾殻を焼成して得られた籾殻灰をセメントの代替材料として利用することが提案されている（特許文献１参照）。
ところで、従来の籾殻灰は、未燃の残存炭素分により黒色や濃灰色を呈する。上記特許文献１に記載の方法で得られた籾殻灰も、未燃の炭素は少なくなっているものの依然として炭素分が残存するため、黒色又は濃灰色を呈する。 By the way, the conventional rice husk ash is black or dark gray due to unburned residual carbon. The rice husk ash obtained by the method described in Patent Document 1 also exhibits black or dark gray because carbon content still remains although unburned carbon is reduced.
しかるに、籾殻灰が有効利用される用途によってはこのような黒色や濃灰色を呈することが大きな問題となることも少なくない。例えば、籾殻灰を化粧品パウダーとして利用することを考えると、当然に白色系の色であることが要求されるし、工業用途での利用を考えた場合にも白色系の色であることが要求されるケースは多い。 However, depending on the use for which rice husk ash is effectively used, it is not uncommon for such black or dark gray to be a major problem. For example, when using rice husk ash as a cosmetic powder, it is naturally required to have a white color, and when considering use in industrial applications, a white color is also required. There are many cases.
この発明は、かかる技術的背景に鑑みてなされたものであって、籾殻から白色系のもみ殻灰を製造する方法を提供することを目的とする。 This invention is made | formed in view of this technical background, Comprising: It aims at providing the method of manufacturing white type | system | group rice husk ash from a rice husk.
前記目的を達成するために、本発明は以下の手段を提供する。 In order to achieve the above object, the present invention provides the following means.
［１］籾殻をリグニン分解剤で処理する前処理工程と、
前記前処理工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。
[1] a pretreatment step of treating rice husk with a lignin degrading agent;
A carbonization step of heating rice husks having undergone the pretreatment step at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
［２］前記リグニン分解剤として漂白剤または酸を用いる前項１に記載の白色系籾殻灰の製造方法。 [2] The method for producing white rice husk ash according to item 1, wherein a bleaching agent or an acid is used as the lignin decomposing agent.
［３］籾殻を漂白剤で処理する前処理工程と、
籾殻を酸で処理する前処理工程と、
前記２つの前処理工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。
[3] a pretreatment step of treating rice husk with a bleach;
A pretreatment step of treating rice husk with acid;
A carbonization step of heating rice husks having undergone the two pretreatment steps at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
［４］籾殻をリグニン分解剤で処理する前処理工程と、
前記前処理工程を経た籾殻を洗浄する洗浄工程と、
前記洗浄工程を経た籾殻を乾燥させる乾燥工程と、
前記乾燥工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。
[4] a pretreatment step of treating rice husk with a lignin degrading agent;
A washing step for washing rice husks that have undergone the pretreatment step;
A drying step of drying the rice husks that have undergone the washing step;
A carbonization step of heating the chaff after the drying step at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
［５］前記リグニン分解剤として漂白剤または酸を用いる前項４に記載の白色系籾殻灰の製造方法。 [5] The method for producing white rice husk ash according to item 4, wherein a bleaching agent or an acid is used as the lignin decomposing agent.
［６］前記漂白剤として次亜塩素酸ナトリウムを用いる前項２、３または５に記載の白色系籾殻灰の製造方法。 [6] The method for producing white rice husk ash according to item 2, 3 or 5, wherein sodium hypochlorite is used as the bleaching agent.
［７］前記焼成工程における焼成温度を５００〜７９５℃の範囲に設定する前項１〜６のいずれか１項に記載の白色系籾殻灰の製造方法。 [7] The method for producing white husk ash according to any one of items 1 to 6, wherein a firing temperature in the firing step is set in a range of 500 to 795 ° C.
［１］の発明では、前処理として籾殻をリグニン分解剤で処理するので、黒色系着色の主な原因であると考えられるリグニン成分を分解除去することができる。また、この前処理工程を経た籾殻を２５０〜３５０℃の低温で３０分以上加熱・炭化するので、炭素が溶融塩（Ｋ2Ｏ等）に包含されることを防止できる。更に、籾殻を４８０℃以上の温度で３０分以上焼成することによって炭化分を焼成除去することができ、これにより白色系の籾殻灰を得ることができる。本製造方法では、前処理として籾殻をリグニン分解剤で処理することでリグニン成分をこの段階で分解除去するので、後の焼成工程を経て得られる籾殻灰における残留炭素分を実質的に０％にすることが可能となる。 In the invention of [1], rice husk is treated with a lignin decomposing agent as a pretreatment, so that the lignin component considered to be the main cause of black coloring can be decomposed and removed. In addition, since the rice husk that has undergone this pretreatment step is heated and carbonized for 30 minutes or more at a low temperature of 250 to 350 ° C., it is possible to prevent carbon from being included in the molten salt (K 2 O or the like). Furthermore, by burning the rice husk at a temperature of 480 ° C. or higher for 30 minutes or more, the carbonized component can be removed by baking, whereby white husk ash can be obtained. In this production method, the rice husk is treated with a lignin decomposing agent as a pretreatment, so that the lignin component is decomposed and removed at this stage, so that the residual carbon content in the rice husk ash obtained through the subsequent firing step is substantially 0%. It becomes possible to do.
［２］の発明では、リグニン分解剤として漂白剤または酸を用いるので、黒色系着色の主原因と考えられるリグニン成分を十分に分解除去することができ、一層純白に近い白色系籾殻灰を製造できる。なお、漂白剤と酸の比較では、漂白剤で前処理した方が、より白に近い白色系籾殻灰を製造できる。また、リグニン分解剤として酸を用いた場合には、重金属を十分に除去することができる。 In the invention of [2], since a bleaching agent or an acid is used as a lignin decomposing agent, the lignin component considered to be the main cause of the black coloring can be sufficiently decomposed and removed, and a white husk ash that is closer to pure white is produced. it can. In comparison between the bleaching agent and the acid, the white rice husk ash closer to white can be produced by pretreatment with the bleaching agent. Moreover, when an acid is used as a lignin decomposing agent, heavy metals can be sufficiently removed.
［３］の発明では、前処理として籾殻をリグニン分解剤で処理する（漂白剤による前処理及び酸による前処理を行う）ので、黒色系着色の主な原因であると考えられるリグニン成分を分解除去することができる。また、この前処理工程を経た籾殻を２５０〜３５０℃の低温で３０分以上加熱・炭化するので、炭素が溶融塩（Ｋ2Ｏ等）に包含されることを防止できる。更に、籾殻を４８０℃以上の温度で３０分以上焼成することによって炭化分を焼成除去することができ、これにより白色系の籾殻灰を得ることができる。本製造方法では、前処理として籾殻をリグニン分解剤で処理することでリグニン成分をこの段階で分解除去するので、後の焼成工程を経て得られる籾殻灰における残留炭素分を実質的に０％にすることが可能となる。また、籾殻を酸で処理する工程を有するので、重金属を十分に除去することができる。なお、この［３］の発明において、漂白剤で処理する前処理工程、酸で処理する前処理工程の実施順序は、特に限定されず、いずれを先に行っても良い。 In the invention of [3], rice husk is treated with a lignin decomposing agent as a pretreatment (pretreatment with a bleaching agent and acid pretreatment is performed), so that the lignin component considered to be the main cause of black coloring is decomposed. Can be removed. In addition, since the rice husk that has undergone this pretreatment step is heated and carbonized for 30 minutes or more at a low temperature of 250 to 350 ° C., it is possible to prevent carbon from being included in the molten salt (K 2 O or the like). Furthermore, by burning the rice husk at a temperature of 480 ° C. or higher for 30 minutes or more, the carbonized component can be removed by baking, whereby white husk ash can be obtained. In this production method, the rice husk is treated with a lignin decomposing agent as a pretreatment, so that the lignin component is decomposed and removed at this stage, so that the residual carbon content in the rice husk ash obtained through the subsequent firing step is substantially 0%. It becomes possible to do. Moreover, since it has the process of processing rice husk with an acid, a heavy metal can fully be removed. In the invention [3], the order of execution of the pretreatment step for treatment with a bleaching agent and the pretreatment step for treatment with an acid is not particularly limited, and either may be carried out first.
［４］の発明では、前処理として籾殻をリグニン分解剤で処理するので、黒色系着色の主な原因であると考えられるリグニン成分を分解除去することができる。また、この前処理工程を経た籾殻を２５０〜３５０℃の低温で３０分以上加熱・炭化するので、炭素が溶融塩（Ｋ2Ｏ等）に包含されることを防止できる。更に、籾殻を４８０℃以上の温度で３０分以上焼成することによって炭化分を焼成除去することができ、これにより白色系の籾殻灰を得ることができる。本製造方法では、前処理として籾殻をリグニン分解剤で処理することでリグニン成分をこの段階で分解除去するので、後の焼成工程を経て得られる籾殻灰における残留炭素分を実質的に０％にすることが可能となる。加えて、この製法では、前処理工程を経た籾殻を洗浄するので、前処理で用いたリグニン分解剤を十分に洗浄除去することができる。 In the invention of [4], rice husk is treated with a lignin decomposing agent as a pretreatment, so that the lignin component considered to be the main cause of black coloring can be decomposed and removed. In addition, since the rice husk that has undergone this pretreatment step is heated and carbonized for 30 minutes or more at a low temperature of 250 to 350 ° C., it is possible to prevent carbon from being included in the molten salt (K 2 O or the like). Furthermore, by burning the rice husk at a temperature of 480 ° C. or higher for 30 minutes or more, the carbonized component can be removed by baking, whereby white husk ash can be obtained. In this production method, the rice husk is treated with a lignin decomposing agent as a pretreatment, so that the lignin component is decomposed and removed at this stage, so that the residual carbon content in the rice husk ash obtained through the subsequent firing step is substantially 0%. It becomes possible to do. In addition, in this production method, the rice husks that have undergone the pretreatment process are washed, so that the lignin decomposing agent used in the pretreatment can be sufficiently washed away.
［５］の発明では、リグニン分解剤として漂白剤または酸を用いるので、黒色系着色の主原因と考えられるリグニン成分を十分に分解除去することができ、一層純白に近い白色系籾殻灰を製造できる。なお、漂白剤と酸の比較では、漂白剤で前処理した方が、より白に近い白色系籾殻灰を製造できる。また、リグニン分解剤として酸を用いた場合には、重金属を十分に除去することができる。 In the invention of [5], since a bleaching agent or an acid is used as a lignin decomposing agent, the lignin component considered to be the main cause of the black coloring can be sufficiently decomposed and removed, and a white husk ash that is closer to pure white is produced. it can. In comparison between the bleaching agent and the acid, the white rice husk ash closer to white can be produced by pretreatment with the bleaching agent. Moreover, when an acid is used as a lignin decomposing agent, heavy metals can be sufficiently removed.
［６］の発明では、上記漂白剤として次亜塩素酸ナトリウムを用いるので、より一層純白に近い白色系籾殻灰を製造できる。 In the invention of [6], since sodium hypochlorite is used as the bleaching agent, white husk ash that is closer to pure white can be produced.
［７］の発明では、焼成工程における焼成温度を５００〜７９５℃の範囲に設定するので、非晶質の白色系籾殻灰を製造することができる。 In the invention of [7], since the firing temperature in the firing step is set in a range of 500 to 795 ° C., amorphous white rice husk ash can be produced.
この発明に係る白色系籾殻灰の製造方法について説明する。まず、籾殻をリグニン分解剤で処理する（前処理工程）。 A method for producing white rice husk ash according to the present invention will be described. First, rice husk is treated with a lignin decomposing agent (pretreatment step).
製造原料である籾殻としては、特に限定されるものではないが、例えば精米脱穀等によって得られた籾殻などが挙げられる。 The rice husk as a raw material for production is not particularly limited, and examples thereof include rice husks obtained by threshing of polished rice.
前記リグニン分解剤としては、籾殻に含まれるリグニンを分解し得るものであれば特に限定されず、どのようなものでも使用できる。中でも、リグニン分解剤としては、漂白剤、酸が好適に用いられる。前記漂白剤としては、特に限定されるものではないが、例えば次亜塩素酸ナトリウム、次亜硫酸ナトリウム、過酸化水素、オゾン等が挙げられる。これらの中でも、次亜塩素酸ナトリウムが特に好適である。また、前記酸としては、特に限定されるものではないが、例えば塩酸、酢酸、硝酸、ギ酸等が挙げられる。 The lignin decomposing agent is not particularly limited as long as it can decompose lignin contained in rice husks, and any lignin decomposing agent can be used. Of these, bleaching agents and acids are preferably used as the lignin decomposing agent. The bleaching agent is not particularly limited, and examples thereof include sodium hypochlorite, sodium hyposulfite, hydrogen peroxide, ozone and the like. Among these, sodium hypochlorite is particularly suitable. The acid is not particularly limited, and examples thereof include hydrochloric acid, acetic acid, nitric acid, formic acid and the like.
なお、リグニン分解剤として酸を用いて前処理した場合には、重金属成分の含有率を顕著に低減させることができるので、得られた白色系籾殻灰は、化粧品パウダーとして特に好適である。 In addition, since the content rate of a heavy metal component can be reduced significantly when pre-processing using an acid as a lignin decomposing agent, the obtained white rice husk ash is particularly suitable as a cosmetic powder.
前記処理の方法としては、特に限定されるものではないが、例えば籾殻をリグニン分解剤の水溶液に浸漬する方法等が挙げられる。前記リグニン分解剤の水溶液の濃度としては０．１〜１２質量％の範囲が好ましい。 The method for the treatment is not particularly limited, and examples thereof include a method of immersing rice husks in an aqueous solution of a lignin decomposing agent. The concentration of the aqueous solution of lignin decomposing agent is preferably in the range of 0.1 to 12% by mass.
前記前処理工程を経た籾殻は、水等による洗浄処理を施した後、乾燥処理を行うのが好ましい。洗浄することで、前処理で用いたリグニン分解剤を十分に洗浄除去することができる。 The rice husks that have undergone the pretreatment step are preferably subjected to a drying treatment after being washed with water or the like. By washing, the lignin decomposing agent used in the pretreatment can be sufficiently washed away.
前記乾燥処理は、自然乾燥であっても良いし、加熱乾燥であっても良く、その方法は特に限定されない。 The drying treatment may be natural drying or heat drying, and the method is not particularly limited.
次に、籾殻を２５０〜３５０℃で３０分以上加熱する（炭化工程）。中でも、籾殻を２６０〜３４０℃で３０分以上加熱するのが好ましく、特に好ましい温度範囲は２８０〜３２０℃である。 Next, the rice husk is heated at 250 to 350 ° C. for 30 minutes or more (carbonization step). Especially, it is preferable to heat a rice husk at 260-340 degreeC for 30 minutes or more, and a especially preferable temperature range is 280-320 degreeC.
このように籾殻を２５０〜３５０℃の低温で３０分以上加熱することによって、炭素（炭化物）が溶融塩（Ｋ2Ｏ等）に包含されてしまうことを十分に防止できる。即ち、このような２５０〜３５０℃で３０分以上加熱する炭化工程を経ることなく、焼成工程を行うと、炭素が溶融塩（Ｋ2Ｏ等）に包含されてしまって外に出られず、その結果、黒色や濃灰色の籾殻灰が得られるものとなる。従って、籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程を実施することは、白色系籾殻灰を得る上で重要である。 Thus, by heating the rice husk at a low temperature of 250 to 350 ° C. for 30 minutes or more, it is possible to sufficiently prevent carbon (carbide) from being included in the molten salt (K 2 O or the like). That is, without performing the carbonization step of heating at 250 to 350 ° C. for 30 minutes or more, when the baking step is performed, the carbon is included in the molten salt (K 2 O or the like) and cannot go out, As a result, black or dark gray rice husk ash is obtained. Therefore, it is important to carry out the carbonization step of heating rice husks at 250 to 350 ° C. for 30 minutes or more in order to obtain white husk ash.
前記炭化工程は、閉鎖系空気雰囲気中で行うのが好ましく、この場合には均一に炭化できる利点がある。また、前記炭化工程は、通常、燃焼炉内で行う。 The carbonization step is preferably performed in a closed air atmosphere. In this case, there is an advantage that carbonization can be performed uniformly. Moreover, the said carbonization process is normally performed within a combustion furnace.
次に、前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する（焼成工程）。中でも、５００〜７９５℃で３０分以上焼成するのが好ましく、この場合には非晶質の白色系籾殻灰が得られる。一方、８００℃以上の温度で３０分以上焼成した場合には結晶質の白色系籾殻灰が得られる。 Next, the rice husks that have undergone the carbonization step are baked at a temperature of 480 ° C. or higher for 30 minutes or longer (baking step). Among these, baking at 500 to 795 ° C. for 30 minutes or more is preferable. In this case, amorphous white rice husk ash is obtained. On the other hand, when baked at a temperature of 800 ° C. or higher for 30 minutes or longer, crystalline white rice husk ash is obtained.
前記焼成工程は、開放系空気雰囲気中で行うのが好ましく、この場合には均一に白色化できる利点がある。また、前記焼成工程は、通常、燃焼炉内で行う。 The firing step is preferably performed in an open air atmosphere. In this case, there is an advantage that the whitening can be performed uniformly. Moreover, the said baking process is normally performed within a combustion furnace.
前記焼成工程を経て得られた籾殻灰は、そのまま使用することもできるし、必要に応じて粉砕処理を行って所望の粒径の粉末にしても良い。 The rice husk ash obtained through the baking step can be used as it is, or may be pulverized as necessary to obtain a powder having a desired particle size.
前記焼成工程を経て得られた籾殻灰は、炭素を含有しないものであり、白色系の色を呈するので、例えば、化粧品パウダー等として利用できる。また、得られた籾殻灰は、ナノサイズの超微細孔が多数形成されたものとなり（図３参照）、これにより水分や脂肪質等の吸着作用、保湿効果が得られるので、この観点からも化粧品パウダーとして特に好適に用いられる。また、得られた籾殻灰は、ナノサイズの超微細孔が多数形成されていることで、香料等の成分の徐放性向上効果も得られるので、様々な用途に利用できるものである。 The rice husk ash obtained through the baking step does not contain carbon and exhibits a white color, so that it can be used, for example, as a cosmetic powder. In addition, the obtained rice husk ash has a large number of nano-sized ultrafine pores formed (see FIG. 3), and this can provide an adsorption action and moisture retention effect on moisture and fat. It is particularly preferably used as a cosmetic powder. Moreover, since the obtained rice husk ash has a large number of nano-sized ultrafine pores, the effect of improving the sustained release of components such as fragrances can also be obtained, so that it can be used for various purposes.
次に、この発明の具体的実施例について説明するが、本発明はこれら実施例のものに特に限定されるものではない。 Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.
＜実施例１＞
容器内に籾殻（精米脱穀によって得られた籾殻）を入れた後、さらに次亜塩素酸ナトリウム水溶液（濃度２質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。しかる後、籾殻を通気乾燥させ、次いでこの乾燥した籾殻を燃焼炉内で閉鎖系空気雰囲気中で３００℃で２時間加熱した後、そのまま１時間かけて昇温速度５０℃／１０分で６００℃まで昇温し、燃焼炉内で開放系空気雰囲気中で６００℃で２時間焼成することによって、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 1>
After putting rice husk (rice husk obtained by rice threshing) in the container, an aqueous sodium hypochlorite solution (concentration 2% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Thereafter, the rice husk is dried by ventilation, and then the dried rice husk is heated in a closed air atmosphere at 300 ° C. for 2 hours in a combustion furnace, and then is directly heated to 600 ° C. at a temperature rising rate of 50 ° C./10 minutes. The mixture was baked at 600 ° C. for 2 hours in an open air atmosphere in a combustion furnace to obtain white husk ash (powder). This white rice husk ash was a white color close to pure white.
この実施例１で得られた白色系籾殻灰の電子顕微鏡写真を図３に示す。これより、この白色系籾殻灰には、ナノサイズの超微細孔が多数形成されていることがわかる。 An electron micrograph of the white husk ash obtained in Example 1 is shown in FIG. From this, it can be seen that a number of nano-sized ultrafine pores are formed in the white husk ash.
また、得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。 Table 1 shows the composition analysis result of the obtained white chaff ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash.
＜実施例２＞
容器内に籾殻（精米脱穀によって得られた籾殻）を入れた後、さらに次亜塩素酸ナトリウム水溶液（濃度２質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。しかる後、籾殻を通気乾燥させ、次いでこの乾燥した籾殻を燃焼炉内で閉鎖系空気雰囲気中で３００℃で２時間加熱した後、そのまま１時間かけて昇温速度５０℃／１０分で８００℃まで昇温し、燃焼炉内で開放系空気雰囲気中で８００℃で２時間焼成することによって、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 2>
After putting rice husk (rice husk obtained by rice threshing) in the container, an aqueous sodium hypochlorite solution (concentration 2% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Thereafter, the rice husk is dried by ventilation, and then the dried rice husk is heated in a closed air atmosphere at 300 ° C. for 2 hours in a combustion furnace, and then heated at a heating rate of 50 ° C./10 minutes at 800 ° C. over 1 hour. The mixture was baked at 800 ° C. for 2 hours in an open air atmosphere in a combustion furnace to obtain white husk ash (powder). This white rice husk ash was a white color close to pure white.
実施例２で得られた白色系籾殻灰のＸ線回折測定結果を図２に示す。この図２に示すＸ線回折測定グラフでは、回折角約２２度の位置に結晶質シリカの回折ピークが強く出ていることから、実施例２で得られた白色系籾殻灰は結晶質であることがわかる。 The X-ray diffraction measurement result of the white husk ash obtained in Example 2 is shown in FIG. In the X-ray diffraction measurement graph shown in FIG. 2, since the diffraction peak of crystalline silica is strong at a diffraction angle of about 22 degrees, the white rice husk ash obtained in Example 2 is crystalline. I understand that.
一方、実施例１で得られた白色系籾殻灰のＸ線回折測定結果を図１に示す。この図１に示すＸ線回折測定グラフでは、回折角約２２度の位置の結晶質シリカに基づく回折ピークが殆ど認められない（縦軸の強度のスケールを大きく拡大しても回折ピークが殆ど認められない）ことから、実施例１で得られた白色系籾殻灰は非晶質であることがわかる。 On the other hand, the X-ray diffraction measurement result of the white husk ash obtained in Example 1 is shown in FIG. In the X-ray diffraction measurement graph shown in FIG. 1, almost no diffraction peak based on crystalline silica at a diffraction angle of about 22 degrees is recognized (even if the intensity scale on the vertical axis is greatly enlarged, almost no diffraction peak is recognized). From this, it can be seen that the white rice husk ash obtained in Example 1 is amorphous.
＜実施例３＞
リグニン分解剤として、次亜塩素酸ナトリウム水溶液（濃度２質量％）に代えて、塩酸水溶液（濃度３．２質量％）を用いた以外は、実施例１と同様にして、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 3>
As a lignin decomposing agent, white chaff ash (as shown in Example 1) was used except that a hydrochloric acid aqueous solution (concentration 3.2% by mass) was used instead of a sodium hypochlorite aqueous solution (concentration 2% by mass). Powder). This white rice husk ash was a white color close to pure white.
得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。また、得られた白色系籾殻灰は、Ｍｎ等の重金属成分の含有率が、実施例１と比較して格段に小さくなっていた。即ち、リグニン分解剤として酸を用いて前処理したので、重金属成分を十分に除去することができた。 Table 1 shows the composition analysis results of the obtained white husk ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash. In addition, the obtained white rice husk ash had a significantly lower content of heavy metal components such as Mn than Example 1. That is, since the pretreatment was performed using an acid as the lignin decomposing agent, the heavy metal component could be sufficiently removed.
＜実施例４＞
容器内に籾殻（精米脱穀によって得られた籾殻）を入れた後、さらに次亜塩素酸ナトリウム水溶液（濃度２質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。次に、前記洗浄後の籾殻を容器内に入れた後、さらに塩酸水溶液（濃度３．２質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。しかる後、籾殻を通気乾燥させ、次いでこの乾燥した籾殻を燃焼炉内で閉鎖系空気雰囲気中で３００℃で２時間加熱した後、そのまま１時間かけて昇温速度５０℃／１０分で６００℃まで昇温し、燃焼炉内で開放系空気雰囲気中で６００℃で２時間焼成することによって、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 4>
After putting rice husk (rice husk obtained by rice threshing) in the container, an aqueous sodium hypochlorite solution (concentration 2% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Next, after the washed rice husk was placed in a container, an aqueous hydrochloric acid solution (concentration: 3.2% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Thereafter, the rice husk is dried by ventilation, and then the dried rice husk is heated in a closed air atmosphere at 300 ° C. for 2 hours in a combustion furnace, and then is directly heated to 600 ° C. at a temperature rising rate of 50 ° C./10 minutes. The mixture was baked at 600 ° C. for 2 hours in an open air atmosphere in a combustion furnace to obtain white husk ash (powder). This white rice husk ash was a white color close to pure white.
得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。また、得られた白色系籾殻灰は、Ｍｎ等の重金属成分の含有率が、実施例１と比較して格段に小さくなっていた。即ち、酸を用いて前処理する工程を有しているので、重金属成分を十分に除去することができた。 Table 1 shows the composition analysis results of the obtained white husk ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash. In addition, the obtained white rice husk ash had a significantly lower content of heavy metal components such as Mn than Example 1. That is, since it has the process of pre-processing using an acid, the heavy metal component was fully removable.
＜実施例５＞
リグニン分解剤として、次亜塩素酸ナトリウム水溶液（濃度２質量％）に代えて、酢酸水溶液（濃度４質量％）を用いた以外は、実施例１と同様にして、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 5>
A white rice husk ash (powder) was used in the same manner as in Example 1 except that an aqueous acetic acid solution (concentration 4% by mass) was used in place of the sodium hypochlorite aqueous solution (concentration 2% by mass) as the lignin decomposing agent. ) This white rice husk ash was a white color close to pure white.
得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。また、得られた白色系籾殻灰は、Ｍｎ等の重金属成分の含有率が、実施例１と比較して格段に小さくなっていた。即ち、リグニン分解剤として酸を用いて前処理したので、重金属成分を十分に除去することができた。 Table 1 shows the composition analysis results of the obtained white husk ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash. In addition, the obtained white rice husk ash had a significantly lower content of heavy metal components such as Mn than Example 1. That is, since the pretreatment was performed using an acid as the lignin decomposing agent, the heavy metal component could be sufficiently removed.
＜実施例６＞
容器内に籾殻（精米脱穀によって得られた籾殻）を入れた後、さらに次亜塩素酸ナトリウム水溶液（濃度２質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。次に、前記洗浄後の籾殻を容器内に入れた後、さらに酢酸水溶液（濃度４質量％）を籾殻の全体が浸漬されるように容器内に投入した。この浸漬状態を常温で２時間継続した後、籾殻を取り出し、この籾殻を水で３回洗浄した。しかる後、籾殻を通気乾燥させ、次いでこの乾燥した籾殻を燃焼炉内で閉鎖系空気雰囲気中で３００℃で２時間加熱した後、そのまま１時間かけて昇温速度５０℃／１０分で６００℃まで昇温し、燃焼炉内で開放系空気雰囲気中で６００℃で２時間焼成することによって、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 6>
After putting rice husk (rice husk obtained by rice threshing) in the container, an aqueous sodium hypochlorite solution (concentration 2% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Next, after the washed rice husk was placed in a container, an aqueous acetic acid solution (concentration: 4% by mass) was further introduced into the container so that the entire rice husk was immersed. After this immersion state was continued for 2 hours at room temperature, the rice husk was taken out and the rice husk was washed three times with water. Thereafter, the rice husk is dried by ventilation, and then the dried rice husk is heated in a closed air atmosphere at 300 ° C. for 2 hours in a combustion furnace, and then is directly heated to 600 ° C. at a heating rate of 50 ° C./10 minutes. The mixture was baked at 600 ° C. for 2 hours in an open air atmosphere in a combustion furnace to obtain white husk ash (powder). This white rice husk ash was a white color close to pure white.
得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。また、得られた白色系籾殻灰は、Ｍｎ等の重金属成分の含有率が、実施例１と比較して格段に小さくなっていた。即ち、酸を用いて前処理する工程を有しているので、重金属成分を十分に除去することができた。 Table 1 shows the composition analysis results of the obtained white husk ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash. In addition, the obtained white rice husk ash had a significantly lower content of heavy metal components such as Mn than Example 1. That is, since it has the process of pre-processing using an acid, the heavy metal component was fully removable.
＜実施例７＞
リグニン分解剤として、次亜塩素酸ナトリウム水溶液（濃度２質量％）に代えて、過酸化水素水（濃度２０％）を用いた以外は、実施例１と同様にして、白色系籾殻灰（粉体）を得た。この白色系籾殻灰は、純白に近い白色であった。
<Example 7>
A white rice husk ash (powder) was used in the same manner as in Example 1 except that hydrogen peroxide water (concentration 20%) was used in place of the sodium hypochlorite aqueous solution (concentration 2 mass%) as the lignin decomposing agent. Body). This white rice husk ash was a white color close to pure white.
得られた白色系籾殻灰のＸ線回折分析による組成分析結果を表１に示す。この表１から明らかなように、得られた白色系籾殻灰には残留炭素分が全く認められなかった。 Table 1 shows the composition analysis results of the obtained white husk ash by X-ray diffraction analysis. As apparent from Table 1, no carbon residue was observed in the obtained white rice husk ash.
この発明の製造方法で得られた白色系籾殻灰は、例えば、化粧品パウダー、廃ガス浄化用触媒担体、吸着材、消臭材、浄水材等として利用できるが、特にこれらの用途に限定されるものではない。 The white rice husk ash obtained by the production method of the present invention can be used, for example, as cosmetic powder, waste gas purification catalyst carrier, adsorbent, deodorant, water purification material, etc., but is particularly limited to these uses. It is not a thing.
Claims (7)
前記前処理工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。 A pretreatment step of treating rice husk with a lignin degrading agent;
A carbonization step of heating rice husks having undergone the pretreatment step at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
籾殻を酸で処理する前処理工程と、
前記２つの前処理工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。 A pretreatment step of treating rice husk with bleach;
A pretreatment step of treating rice husk with acid;
A carbonization step of heating rice husks having undergone the two pretreatment steps at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
前記前処理工程を経た籾殻を洗浄する洗浄工程と、
前記洗浄工程を経た籾殻を乾燥させる乾燥工程と、
前記乾燥工程を経た籾殻を２５０〜３５０℃で３０分以上加熱する炭化工程と、
前記炭化工程を経た籾殻を４８０℃以上の温度で３０分以上焼成する焼成工程と、を包含することを特徴とする白色系籾殻灰の製造方法。 A pretreatment step of treating rice husk with a lignin degrading agent;
A washing step for washing rice husks that have undergone the pretreatment step;
A drying step of drying the rice husks that have undergone the washing step;
A carbonization step of heating the chaff after the drying step at 250 to 350 ° C. for 30 minutes or more;
A baking step of baking the chaff after the carbonization step at a temperature of 480 ° C. or more for 30 minutes or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007279079A JP5112816B2 (en) | 2007-01-31 | 2007-10-26 | Method for producing white rice husk ash |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007021269 | 2007-01-31 | ||
| JP2007021269 | 2007-01-31 | ||
| JP2007279079A JP5112816B2 (en) | 2007-01-31 | 2007-10-26 | Method for producing white rice husk ash |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008207169A true JP2008207169A (en) | 2008-09-11 |
| JP5112816B2 JP5112816B2 (en) | 2013-01-09 |
Family
ID=39783936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007279079A Active JP5112816B2 (en) | 2007-01-31 | 2007-10-26 | Method for producing white rice husk ash |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5112816B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190073010A (en) * | 2017-12-18 | 2019-06-26 | 충남대학교산학협력단 | Method of preparation silica from rice husk using rice husk pretreatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249622A (en) * | 1988-03-30 | 1989-10-04 | Ikeda Bussan Co Ltd | Production of porous activated silica |
| JPH08104513A (en) * | 1994-10-04 | 1996-04-23 | Takeko Suda | Method of recovering silica contained in rice husks from treating solution treated by immersing rice husks |
| JP2004527445A (en) * | 2001-03-26 | 2004-09-09 | プロセス マネジメント， インコーポレイテッド | Method for producing high-purity amorphous silica from biogenic materials |
-
2007
- 2007-10-26 JP JP2007279079A patent/JP5112816B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249622A (en) * | 1988-03-30 | 1989-10-04 | Ikeda Bussan Co Ltd | Production of porous activated silica |
| JPH08104513A (en) * | 1994-10-04 | 1996-04-23 | Takeko Suda | Method of recovering silica contained in rice husks from treating solution treated by immersing rice husks |
| JP2004527445A (en) * | 2001-03-26 | 2004-09-09 | プロセス マネジメント， インコーポレイテッド | Method for producing high-purity amorphous silica from biogenic materials |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190073010A (en) * | 2017-12-18 | 2019-06-26 | 충남대학교산학협력단 | Method of preparation silica from rice husk using rice husk pretreatment |
| KR102029261B1 (en) * | 2017-12-18 | 2019-10-07 | 충남대학교산학협력단 | Method of preparation silica from rice husk using rice husk pretreatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5112816B2 (en) | 2013-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4174795B2 (en) | Method for producing high-purity amorphous silica from biogenic material | |
| KR101048410B1 (en) | Preparation of superfine purified silica, and fibers simultaneously | |
| JP4233601B1 (en) | Method for producing rice cake powder | |
| CN108722356A (en) | A kind of nano zero valence iron loads the preparation method of hydrophilic porous biological carbon composite | |
| CN107814385B (en) | Method for treating industrial wastewater and preparing graphite type porous carbon material by using biomass coke | |
| CN108579673B (en) | Silkworm excrement biochar and preparation method and application thereof | |
| CN105833835A (en) | Manganese-loaded sludge activated carbon material and preparation method thereof | |
| CN112844311A (en) | Iris pseudacorus attapulgite composite powder modified heavy metal adsorbent | |
| JP5112816B2 (en) | Method for producing white rice husk ash | |
| JP4882061B2 (en) | Processing system and processing method for effectively using biomass resources | |
| CN113244886A (en) | Biochar composite loaded with nano magnesium oxide and preparation method and application thereof | |
| CN106348360A (en) | Wastewater cleaning agent based on photocatalysis | |
| JP2005263547A (en) | Composite activated carbonized material and method for manufacturing the same | |
| CN111804277A (en) | Method for preparing charcoal activated carbon combustible gas bio-oil from crop straws | |
| CN114471546B (en) | Nano silver/biochar photocatalytic material and preparation method and application thereof | |
| JP5281926B2 (en) | Volatile organic compound adsorbent, method for producing the same, and method for using bark or molded article thereof | |
| JP4153973B1 (en) | Asbestos treatment method | |
| WO2016035669A1 (en) | Method for purifying plant-derived carbon precursor | |
| Kurama et al. | The effect of chemical treatment on the production of active silica from rice husk | |
| JP2006231137A (en) | Negatively ionized water | |
| JP5843568B2 (en) | Method and apparatus for treating incineration ash | |
| KR20180058239A (en) | Method for producing activated carbon for filter using biomass | |
| RU2534801C1 (en) | Method of obtaining activated coal | |
| JP2007167772A (en) | Method of manufacturing catalyst | |
| JP2007196205A (en) | Water cleaning agent yielded by improving carbide of fish bone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100810 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110720 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110802 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110824 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20110824 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120509 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120622 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120918 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121011 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151019 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5112816 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D02 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151019 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |