JP7048143B1 - 撥水性多孔質膜を備えた植物用栄養分補給装置 - Google Patents
撥水性多孔質膜を備えた植物用栄養分補給装置 Download PDFInfo
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- JP7048143B1 JP7048143B1 JP2022015663A JP2022015663A JP7048143B1 JP 7048143 B1 JP7048143 B1 JP 7048143B1 JP 2022015663 A JP2022015663 A JP 2022015663A JP 2022015663 A JP2022015663 A JP 2022015663A JP 7048143 B1 JP7048143 B1 JP 7048143B1
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- water
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- repellent porous
- negative electrode
- aqueous solution
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- 239000005871 repellent Substances 0.000 title claims abstract description 319
- 235000015097 nutrients Nutrition 0.000 title claims abstract description 17
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- 239000003337 fertilizer Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 239
- 238000002955 isolation Methods 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 39
- 201000002451 Overnutrition Diseases 0.000 claims description 2
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- 238000010586 diagram Methods 0.000 abstract description 41
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
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- 239000011701 zinc Substances 0.000 description 12
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
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- 150000004678 hydrides Chemical class 0.000 description 10
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
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- 206010028980 Neoplasm Diseases 0.000 description 5
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- A61F7/03—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction
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Abstract
Description
周期表第1族、第2族および第13族に属する卑金属元素は、水に触れると、イオン化し、即座に自己放電を起こし、水素を発生する。このため、これら金属にとって水との接触は厳禁で、これらの金属を析出させる電解精製として溶融塩電気分解以外製造方法は無い。実用電池においても、水との反応が著しい周期表第1族元素および第2族のCa、Ba、Srについては、電解質水溶液を用いた一次および二次電池は存在しない。また、周期表第2族元素のうちのBeおよびMgあるいは第13族元素であるAlについては、一次電池はあるが、二次電池はない。二次電池としては、第1族元素を用いたリチウムイオン電池やナトリウムイオン電池には非水電解質溶液(有機電解質)や固体電解質が開発され、さらに第1族元素であるナトリウムを用いる電池には、それを溶融塩電解質として用いた、300℃以上の高温で動作するナトリウム硫黄電池(NS電池)が開発されている。
従来、水溶液電気化学反応では電解質水溶液の中に正負電極を設置していた。このため電気化学反応時には、電解質水溶液と電極との境界面で発生するガスによる絶縁現象を回避することが難しかった。そこで本発明では電解質水溶液に挟まれた正極および負極をそれぞれ撥水性多孔質膜で電気的に絶縁隔離し、電気化学反応を起こさせる時のみ電解質水溶液を加圧して、撥水性多孔質膜内部の細孔に電解質水溶液を充填させ、その加圧時のみ、絶縁体である隔離膜を導電体に変化させる電気回路のスイッチとしての役割を持たせることができる。とくに実用電池においては電解質水溶液を撥水性多孔質膜製袋に密閉し、該撥水性多孔質膜製袋を加圧しているときに充放電を行い、蓄電時は加圧を解除する。この加圧解除により、電極と電解質は絶縁され、自己放電や内部抵抗の増大は回避される。また電気分解(電解精製)においても電極全体が電解質水溶液と接触していないため、夫々の電極での生成物が再度電解質に溶け出す確率は少なく、かつ電極生成ガスが電極と電解質水溶液との間で起こす絶縁現象を回避することができる。また、撥水性多孔質膜によって隔離された電解質水溶液と油との境界面に網状の負電極を備え、電解質水溶液を加圧した状態で電解質水溶液を電気分解すれば、網電極の背面の油の中に負極生成物が析出する。ここで電解質に卑金属塩水溶液を用いれば、嫌水金属(水と激しく反応する周期表第1族および第2族元素)である卑金属元素を油の中で析出でき、しかも重液選別(比重選鉱)することができる。
これに対し、図2(B)に示すように電解質水溶液14に圧力印加具6により圧力をかけると撥水性多孔質膜11の細孔内に電解質水溶液が入り電圧計VMがプラス側に振れて起電力を示す。
わちPlb-Pg ≧Plba+ Plagを満足させるためには、低濃度電解質水溶液14に加え
る水圧Plbを高く(陽圧)設定するか、あるいは該気体透過電極室内の圧力(Pg)を維持するために、圧力調整弁93を介して真空ポンプで吸引して、該気体透過電極室内の圧力(Pg)を陰圧にすることにより、複数枚の撥水性多孔質膜の夫々の耐水圧の累計が反応系の最初にかかる水圧Plbと最後にかかるガス圧Pgとを調整して水の電気分解による水素と酸素または塩素を製造することができる。実用的には、撥水性多孔質膜a(11)、b(27)を同一な撥水性多孔質膜を用い、低濃度電解質水溶液14に加える水圧Plbに陽圧を加えるか、或いは気体透過電極室内の圧力Pgを陰圧にする簡便な操作を行いながら電気分解を施し、海水中や湖中で直接水素を製造できる。すなわち希硫酸や希アルカリなどの高濃度電解質水溶液が封入された密閉容器1を低濃度電解質水溶液が存在する海や湖である開放容器2の中に挿入し、該密閉容器1を圧力水頭位置まで降下させた状態で電気分解を連続的に行う。
図22(A)は単層電池の概念図、図22(B)は積層電池の概念図である。
dCl2 > LiCl > BeCl2 > CaCl2 > MnCl2 > NiCl2 > FeCl2 > CoCl2 > MgCl2 > AlCl3 > BaCl2 > KCl> NaClであり、放電容量は図1に示したように、多い順に並べると、BeCl2 > LiCl >AlCl3 >MgCl2 > CaCl2 > NaCl > KCl > SrCl2 > ZnCl2 > BaCl2である。そこで本発明では空気中で使える負極板としてZn、Mg、Al、Ni、Pbを推奨するが、第1族金属および第2族金属も使える。この場合は負極が1,2族元素の中実電極あるいは炭素製空隙電極板内部や表面の空隙に第1,2族元素を負極生成物として吸着させた電極であり、かつ該負電極の周囲を樹脂フィルムで包囲するか、あるいは該負電極内部に油を含ませた状態にすることにより外界と遮蔽することが必要である。
さらに海水や塩湖水などの電解質水溶液中で高い電気絶縁性を呈する多孔質フッ素樹脂膜に耐水圧またはそれ以上の水圧をかけると多孔質フッ素樹脂膜の細孔内部に電解質水溶液および/またはイオンが通過し、その水圧に応じて撥水性多孔質膜を透過できる水溶液やイオンの量をアナログ的に制御するスイッチの役割を担わすことができる。この撥水性多孔質膜を電解質水溶液と正負極電極室との隔離膜として用い、電解質水溶液に圧力を加えた状態で水溶液電気分解を行い、正負夫々の電極室で生成する電極生成物を電解質水溶液から分離回収させる。これにより海水や塩湖水などの電解質水溶液から直接、水素、苛性ソーダ、卑金属元素などを取り出すことができる。この技術は電解精製に留まらず、実用電池や大容量キャパシタにも利用でき、従来大電力を用い、高温下で溶融塩電気分解する方法しか無かったが、本発明によれば、常温で、しかも水溶液電気分解でできるため経済効果大である。とくに海水から得られる金属ナトリウムは石油の代替エネルギーとして、枯渇の心配もなく、地域偏存も無いエネルギー資源として、資源戦争の無い世界の創生に貢献する。さらに電解質を水溶液のまま使えるリチウムやナトリウム、カルシウムなどを原料とする卑金属元素/空気電池や卑金属元素/ハロゲン電池は、天候に左右される再生可能エネルギーの貯蔵バッテリーとしてまたは軽量で高効率のバッテリーとして電気自動車の発展に寄与し、二酸化炭素も放射線も出さない水素社会の進展に寄与すると考える。
四角柱型密閉容器87の中には2.5規定の硫酸と2.5規定の苛性ソーダを封入した場合の2回に分け、水素製造装置86を深さ3mのプールに沈め、負極電極室52および正極電極室53のガス圧を夫々200~400mmHgに保持できるように圧力調整弁93を介して真空排気を行いながら、水素の生成効率を測定した。高濃度電解質水溶液79に入れる硫酸の導電率は0.8S/cmであった。比較のため2.5規定の苛性ソーダの導電率は0.3S/cmであった。そこで水素製造装置86の両電極間に1.5Vを与えたところ、高濃度電解質水溶液が硫酸の場合には水素1m3、酸素0.5m3当たりの所要電力は2.3kWh、苛性ソーダでは5.2kWhであった。
この封筒型密閉容器55は電池の電解質水溶液貯留容器としての用途が非常に多い。そこで、この封筒型密閉容器55に電解質水溶液14,102を抑留するのが電解質水溶液抑留装置98である。封筒型密閉容器55の両面には図39(A),(B)に示すように、撥水性多孔質フッ素樹脂膜100および撥水性多孔質フッ素樹脂膜101を有している。
これら撥水性多孔質フッ素樹脂膜100,101の耐水圧は図28に示すように電解質水溶液の塩濃度により異なる。ここで図39(B)に示すように、圧力印加具6で加圧する抑留用電解質水溶液102の水圧を(WP102)、封筒型密閉容器55内の電解質水溶液の水圧を(WP55)とし、抑留用電解質水溶液102側の撥水性多孔質フッ素樹脂膜100の耐水圧を(WP100)、吸引口99側の撥水性多孔質フッ素樹脂膜101の耐水圧を(WP101)、吸引口99の空気圧を(P99)とすると、抑留用電解質水溶液102を撥水性多孔質フッ素樹脂膜100の細孔を通過させて封筒型密閉容器55内部に封入する条件は、WP102≧WP55+WP100であり、封筒型密閉容器55内の電解質水溶液を抑留させるための吸引口99で吸引する負圧条件はWP101≧P99≧-WP101である。ここで2面に用いる撥水性多孔質フッ素樹脂膜100,101を同一材質とすれば、WP100=WP101である。したがって、先ず図39(B)に示す電解質水溶液抑留装置98の吸引口99側で、撥水性多孔質フッ素樹脂膜101の耐水圧(-WP101)以上の負圧を維持した状態で、圧力印加具6により抑留用電解質水溶液102の加圧を開始し、同時に吸引口99の圧力を(+WP101)に変換して、封筒型密閉容器55に抑留用電解質水溶液102を封入する装置である。
苛性ソーダ水溶液は図18に示すように水との溶解度が高く、室温で50%である。先ず撥水性多孔質フッ素樹脂膜11からなる封筒型密閉容器55の内部に50%の苛性ソーダ水溶液を封入し、負極電極室52,57は周囲を樹脂フィルム61で包囲し、かつ油を含芯させた炭素製空隙電極からなる外気遮蔽型負極電極室57であり、正極は周囲を樹脂フィルム61で包囲し、かつ空気が出入りする空気取り入れ口105が備えられた活性炭による炭素製該空隙板電極58であり、かつ撥水性多孔質膜11と活性炭による炭素製該空隙板電極58との間に網状の充電用補助正電極56を備えた正極電極室53であり、
これら該外気遮蔽型負極電極室57と該正極電極室53は、撥水性多孔質フッ素樹脂膜11からなる封筒型密閉容器55に挟まれている構造を有している。ここで先ず予備実験として苛性ソーダ電池106上部に撥水性多孔質フッ素樹脂膜11の耐水圧に匹敵する錘104で加圧し、この状態で充電用補助正電極56と外気遮蔽型負極電極室57内の炭素製該空隙板電極との間に10Aで60分の充電を行った後、錘104を取り除き、充電を終えた。この時点での封筒型密閉容器55内部の苛性ソーダ水溶液の濃度は43%であり、原理的には10%まで充電可能である。ここで外気遮蔽型負極電極室57内の炭素製該空隙板電極と銅板からなる集電極板64との間に電気的負荷をかけ、再度錘104で加重すると、放電が始まり起電力は3Vであった。ここで錘104を取り除いたまま放置して、1ヵ月後、再度錘104で加圧すると、3Vの起電力を示し、錘104を取り除くと電圧値は0Vを示した。この錘104の付加と解除を繰り返しても、封筒型密閉容器55内部の苛性ソーダ水溶液の濃度の変化は無く、内部で自己放電が起こらないことが実証できた。
この撥水性多孔質膜11の等価回路が42(B)の低誘電率キャパシタ(C2)とスイッチ(S)である。とくに本発明では封筒型密閉容器55の内部は炭素繊維や金属繊維などからなる含空隙導電材料78が充填され、さらにその空隙を電気化学キャパシタ用電解質水溶液(希硫酸)79が含浸している。ここで圧力印加具6により耐水圧に等しい水圧をかけると撥水性多孔質膜11の細孔に希硫酸79が浸入して電気回路的にはスイッチ(S)がONになり、正極室と負極室は封筒型密閉容器55の内部の炭素繊維や金属繊維などからなる含空隙導電体78で短絡され、2個の高誘電率キャパシタ(C1)が直列の状態で充放電が行われ、電解質水溶液14の加圧が解除されると2個の低誘電率キャパシタ(C2)と2個の高誘電率キャパシタ(C1)が直列となり蓄電を保つ。電解質水溶液14が未加圧の時は撥水性多孔質膜11の細孔に電解質水溶液14が浸入しないため低誘電率キャパシタ(C2)であるが、電解質水溶液14が加圧されれば撥水性多孔質膜11の細孔に電解質水溶液が浸入して電気回路的にはスイッチ(S)がONになり、正極室と負極室は撥水性多孔質膜製密閉容器(封筒型)55を介して短絡されて、2個の高誘電率キャパシタ(C1)が直列の状態で充放電が行われ、電解質水溶液14の加圧が解除されると2個の低誘電率キャパシタ(C2)と2個の高誘電率キャパシタ(C1)が直列となり蓄電を保つ。ここではレドックスキャパシタ用金属板108にアルミニウム(Al)、レドックスキャパシタ用金属酸化皮膜109に酸化アルミニウム(Al2O3)を用いたレドックスキャパシタ装置である。
そこで洋上に洋上工場110を浮かべ、真下の海水を原料として使い、その処理の電力は洋上風力発電や太陽光発電、あるいは、特許文献19,20で本願発明者が開示している浮力重力発電装置113を海底と海面の間を往復させて風力の約1000倍の発電量が得られる浮力重力発をなどの自然エネルギーを用い、図31に示す水素製造装置86を海面下の水圧を利用して水素を製造し、図33あるいは図34に示す苛性ソーダ製造装置90,91で苛性ソーダおよび塩酸または塩素を製造する。電力は自然エネルギー発電のほか、臨海火力発電所や原子力発電所などの余剰電力や深夜電力を使って臨海工場111においても水素や苛性ソーダが作られる。この苛性ソーダは図16で示すように融点が318℃と低いため、水素化卑金属製造装置97でヒータ加熱された苛性ソーダ溶融に正負電極を備え、かつ水素ガスに逆電圧を与え、生成された水素の負イオンとナトリウムの正でイオンとを反応させて水素化ナトリウム49を製造する。しかも、水素化ナトリウムをイオン反応で製造するため電力消費が少なく、しかも図16に示すように水素化ナトリウムの比重は0.92と苛性ソーダ溶融塩の比重の2.13より小さく、かつ水素化ナトリウムの融点は800℃と苛性ソーダの融点318℃より高いため水素化ナトリウムを上滓として浮上させて簡単に比重選別できる。ここで製造した水素化ナトリウム49を水素発生装置112に挿入して水を注ぐと金属ナトリウムによる加水分解反応よりも2倍の水素を生成する。ここで製造した水素は火力発電所や水素ステーションにパイプラインで送られる。一方水素発生装置112でできた廃棄物(副産物)の苛性ソーダ31は水素化卑金属製造装置97の原料として使われ、再度水素化ナトリウム49が作られる。これは正に核燃料サイクルでは無く苛性ソーダ燃料サイクルに他ならない。一方苛性ソーダ製造装置90,91で作られた苛性ソーダの一部は図41で示した積層型苛性ソーダ電池として車載バッテリーや電力貯蔵用バッテリーとして使われる。また水素化ナトリウムを油に浸し水素発生装置112の小型装置を車載すれば、水素ボンベを積載しない水素自動車ができるなど、化石燃料に頼らない水素社会を構築するための苛性ソーダ燃料サイクルシステムである。
2…開放容器
3…負極電極室
4…正極電極室
5…連通管
6…圧力印加具(シリンダ)
7…スポイトゴム、ピペター
8…ラチェット付電動加圧装置
9…貯水槽
10…位置水頭(h)
11…撥液(水)性多孔質膜(隔離膜、)
12…生成ガス回収ホース
13…アルコール
14…電解質水溶液
15…溶質(薬品)
16…油充填電極室、
17…正極板(油槽内)
18…中間電極板(油槽内)
19…仮想負電極面(油と電解質の界面)
20…電荷(電圧)
21…電解質内の正極板
22…油
23…油(比重1以下)
24…油(比重1以上)
25…酸(塩化物の場合は塩酸)
26…陰極生成物回収口
27…撥液水性多孔質膜(淡水浸透用)
28…水道(水圧の利用)
29 大型密閉容、
30…水素製造装置
31…卑金属水酸化物(苛性ソーダ)
32…卑金属塩化物水溶液(塩化ナトリウム水溶液)
33…濃酸(塩酸)
34…水供給口
35…負極生成物回収口
36…負電極板
37…正電極(炭素繊維、炭素粒、多孔質炭素)
38…正電極板
39…卑金属塩水溶液供給槽
40…水充填電極室
41…気体透過電極室
42…正極生成物回収口(濃酸取り出し口)
43…網状負電極(炭素繊維、金属網)
44…多孔質炭素負極板兼隔離膜
45…水素ガス
46…卑金属水酸化物溶融塩(苛性ソーダ)
47…水素ガス圧入口
48…溶融塩加熱ヒータ
49…水素化卑金属(水素化ナトリウム)
50…水素マイナスイオン
51…水素化卑金属回収口
52…負極電極室(電池用、キャパシタ用)
53…正極電極室(電池用、キャパシタ用)
55…封筒型密閉容器
56…充電用補助正電極(網状金属)
57…外気遮蔽型負極電極室
58…炭素製空隙板電極(活性炭)
59…金属酸化膜(電池正極用)(CuO,AlO3,ZnO2)
60…金属板(電池用)(Cu,Al)
61…樹脂フィルム
62…負電極板(電池用)(Al,Mg,Ca,Zn,Ni,Pb)
63…金属塩化物膜(電池正極用)(ZnCl2)
64…集電極板(電池用)(Cu,Al)
65…負極電極板(Al,Mg,Zn)
66…正極(負極で用いた金属の塩化物)
67…活性炭粒または炭素繊維
68…臭素液
69…沃素粒
70…グラファイト板
71…アルミニウム(Al)負極電極板
72…誘電性溶液(油系、水系)
73…板電極(キャパシタ)
74…電気二重層電極(キャパシタ)
75…レドックスキャパシタ電極
76…ハイブリッドキャパシタ電極
77…包囲点線部
78…含空隙導電材料(金属繊維、炭素繊維、活性炭)
79…電気化学キャパシタ用電解質水溶液(希硫酸)
80…希苛性ソーダ(電気化学キャパシタ用電解質水溶液)
81…ステンレス繊維
82…炭素繊維
83…電極間距離(d)
84…海面下水素製造装置
85…多段型海面下水素製造装置
86…湖面下(海面下)水素製造装置
87…四角柱型密閉容器
88…淡水(水)
89…水道圧利用簡易水素製造装置
90…塩化ナトリウム水溶液から苛性ソーダと塩素ガスを直接製造する装置
91…塩化ナトリウム水溶液から苛性ソーダと塩酸を直接製造する装置
92…卑金属製造装置
93…1次圧力調整弁(気体透過用電極室)
94…吸引口(真空ポンプで耐水圧以下まで)
95…卑金属元素と塩酸を直接製造する装置
96…仮想負電極を利用した卑金属製造装置
97…水素化卑金属製造装置
98…電解質水溶液抑留装置
99…吸引口(真空ポンプ)
100…撥水性多孔質膜(11a)
101…撥水性多孔質膜(11b)
102…抑留用電解質水溶液
103…電解質加圧型二次電池
104…錘
105…空気取り入れ口
106…積層型苛性ソーダ電池
107…レドックスキャパシタ
108…レドックスキャパシタ用金属板
109…レドックスキャパシタ用金属酸化被膜
110…洋上工場
111…臨海工場(臨海発電所)
112…水素発生装置
113…浮力重力発電装置
114…加水分解反応制御装置
115…撥水性多孔質フッ素樹脂密閉袋
116…薬品
117…気体
118…水溶液補給用パイプ(ホース)
119…植物(野菜、果樹)
120…薬品散布ジョウロ(撥水性多孔質樹脂製袋やチューブ)
121…補給用栄養分(野菜工場)
122…制御室
123…カテーテル(管)
124…発熱剤(CaO)
125…カプセル
Claims (1)
- 植物の根部に水分や肥料から成る薬品水溶液を供給する供給口に、水溶液の窓として隔離膜機能を有する撥水性多孔質フッ素樹脂膜を、圧力スイッチとして用いた密閉容器を備えた植物用栄養分補給装置であって、
植物の根部に撥水性多孔質フッ素樹脂膜で作られたチューブまたは袋からなる該密閉容器を備え、該密閉容器を水圧によって人為的に開閉するために制御室から該密閉容器までの間をパイプで繋ぎ、該薬品水溶液を該制御室の圧力印加具で該撥水性多孔質フッ素樹脂膜の耐水圧以上の陽圧を連続または間欠的に加え、前記植物の根部に該薬品水溶液を効率よく与え、水の与え過ぎによる根腐れや栄養過多を抑えることを特徴とする植物用栄養分補給装置。
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