JPS61151086A - Solidification prevention for substance for hygroscopic fertilizer - Google Patents
Solidification prevention for substance for hygroscopic fertilizerInfo
- Publication number
- JPS61151086A JPS61151086A JP59271971A JP27197184A JPS61151086A JP S61151086 A JPS61151086 A JP S61151086A JP 59271971 A JP59271971 A JP 59271971A JP 27197184 A JP27197184 A JP 27197184A JP S61151086 A JPS61151086 A JP S61151086A
- Authority
- JP
- Japan
- Prior art keywords
- urea
- formaldehyde
- aqueous solution
- particulate
- condensation product
- 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.)
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(産業上の利用分野)
この発明1は、バルクブレンド等に利用される吸湿性肥
料用物質の固結防止に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention 1 relates to prevention of caking of hygroscopic fertilizer substances used in bulk blends and the like.
詳しくは、特定の尿素とホルムアルデヒドの縮合生成物
水溶液に硬化剤を添加した水溶液で処理することからな
る吸湿性肥料用物質の固結防止方法に関する。Specifically, the present invention relates to a method for preventing caking of hygroscopic fertilizer substances, which comprises treating an aqueous solution of a specific condensation product of urea and formaldehyde with a hardening agent added thereto.
(従来の技術)
吸湿性肥料用物質、例えば粒子径が2ミリ以上(通常は
2〜5ミリ)の大粒尿素はバルクブレンド肥料の高成分
比及び製造コストの低減など需要家の要望によりその需
要が増大している。(Prior art) Hygroscopic fertilizer substances, such as large-grain urea with a particle size of 2 mm or more (usually 2 to 5 mm), are in demand due to customer demands such as high component ratio of bulk blend fertilizer and reduction in manufacturing cost. is increasing.
しかしながら、粒子状の尿素は貯蔵の際に経時的に固結
してしまう問題があり、それに対しては古くから多くの
固結防止方法が提案されている。However, particulate urea has the problem of caking over time during storage, and many methods for preventing caking have been proposed for a long time.
水分を少なくしたり、粒子形状を整えたり、粒子表面の
結晶ブリッジを減らすなど固結性物質の物性をかえる方
法や、珪藻土、シリカゲル、タルク、硫酸カルシウム、
粘度等を用いる方法がある。Methods of changing the physical properties of caking substances, such as reducing moisture content, adjusting particle shape, and reducing crystal bridges on particle surfaces; diatomaceous earth, silica gel, talc, calcium sulfate,
There is a method using viscosity, etc.
これらの添加剤は、多量に添加する必要があり、この事
は吸湿性を高める結果となり、又、粉立ちの原因ともな
り小袋ならびにフレコンバンクからの排出時に著しく粉
立ちかみもれ作業環境上好ましくなく、又フルイの目詰
り、装置内への付着等大きな問題を引起す。又、防結性
効果としても不十分である。These additives need to be added in large quantities, which increases hygroscopicity and also causes dust to form, which is undesirable in terms of the working environment as it causes significant dust to form and leak when discharging from sachets or flexible container banks. Otherwise, it can cause major problems such as clogging of the sieve and adhesion inside the equipment. Also, the anti-caking effect is insufficient.
更に、界面活性剤(スルホネート又はアミンの如き)で
処理する方法も提案されているが、効果が全(ないか不
十分である。Additionally, methods of treatment with surfactants (such as sulfonates or amines) have been proposed, but they are not at all (or insufficiently) effective.
これに対して、ホルムアルデヒドもしくは尿累−ホルム
アルデヒド縮合物で処理する方法も知られており、例え
ば英国特許第875,730号ではホルムアルデヒドを
含有する水溶液を均一に分布させる方法が、又特公昭5
0−34536号では尿素−ホルムアルデヒド縮合生成
物水溶液で処理する方法が提案されている。On the other hand, a method of treating with formaldehyde or a urine-formaldehyde condensate is also known; for example, British Patent No. 875,730 describes a method of uniformly distributing an aqueous solution containing formaldehyde;
No. 0-34536 proposes a method of treatment with an aqueous solution of a urea-formaldehyde condensation product.
(発明が解決しようとする問題点)
上記後者の2つの方法は固結防止効果の大きい優れた方
法である。しかし英国特許W、 875,730号の方
法では、ホルムアルデヒドと尿素とを反応させるために
一定時間反応せしめるか、長時間の処理時間と乾燥工程
ならびに排気ガスの洗滌処理設備が必要となり、多額の
設備費を要する問題がある。又、特公昭50−3453
6号の方法では、尿素のモルあたり2〜5モルの結合し
たおよび遊離ホルムアルデヒドを含有しており、ホルム
アルデヒドの過剰率が高いため遊離ホルムアルデヒドあ
るいはメチロール基が加水分解して生成するホルムアル
デヒドが排気ガスとして発生し環境汚染を起すため排気
ガス処理設備を必要とし、又混合処理時間が長いため、
例えば、混合のための回転ドラムが大型化する。更には
、処理後35“Cよりも高くない温度に冷却する必要か
ある等、工業的には多くの問題がある。(Problems to be Solved by the Invention) The latter two methods are excellent methods that have a large caking prevention effect. However, in the method of British Patent W, 875,730, formaldehyde and urea are reacted for a certain period of time, or long processing times, drying steps, and exhaust gas cleaning equipment are required, requiring a large amount of equipment. There are costly problems. Also, special public service Sho 50-3453
Method No. 6 contains 2 to 5 moles of bound and free formaldehyde per mole of urea, and because the excess of formaldehyde is high, free formaldehyde or formaldehyde produced by hydrolysis of methylol groups is used as exhaust gas. Because the gas is generated and causes environmental pollution, exhaust gas treatment equipment is required, and the mixing process takes a long time.
For example, the rotating drum for mixing becomes larger. Furthermore, there are many industrial problems, such as the need for cooling to a temperature no higher than 35"C after treatment.
(問題点を解決するだめの手段)
すなわち、本発明は、粒子状尿素等の吸湿性肥料用物質
を尿素1モル当り1.2〜6モルのホルムアルデヒドを
含有する尿素とホルムアルデヒドの縮合生成物水溶液に
硬化剤を添加した水溶液で処理することを特徴とする吸
湿性肥料用物質の固結防止方法である。(Another Means to Solve the Problems) That is, the present invention provides a method for converting a hygroscopic fertilizer substance such as particulate urea into an aqueous solution of a condensation product of urea and formaldehyde containing 1.2 to 6 moles of formaldehyde per mole of urea. This is a method for preventing caking of hygroscopic fertilizer substances, which is characterized by treating with an aqueous solution containing a hardening agent.
本発明において、処理される粒子状尿素等の吸質性肥料
用物質の製造法としては、特に制限はなく、例えば溶融
した尿素を造粒塔で造粒する方法(特開昭50− n′
43so )、或は、尿素小塊及びグリル尿素を流動状
態で溶融尿素をスプレー造粒したもの(特開昭56−7
6236 )、もしくは、皿型造粒機で造粒して得られ
る粒子径が2〜5朋のものが好ましく用いられる。In the present invention, there are no particular restrictions on the method for producing the absorbent fertilizer substance such as particulate urea, and for example, the method of granulating molten urea in a granulation tower (JP-A-50-N'
43so), or spray granulation of molten urea in a fluidized state using small urea lumps and grilled urea (Japanese Patent Laid-Open No. 56-7
6236) or particles having a particle diameter of 2 to 5 mm obtained by granulation with a dish-type granulator are preferably used.
本発明の方法は、粒子状尿素等の温度が40〜80℃、
好ましくは、60〜70℃で処理される。In the method of the present invention, the temperature of particulate urea etc. is 40 to 80 °C,
Preferably, the treatment is performed at 60-70°C.
もし粒子状尿素等の粒子温度が所定の温度より低い場合
は、被覆装置に熱風を送り込み粒子を加熱しながら処理
しても良い。If the temperature of particles such as particulate urea is lower than a predetermined temperature, hot air may be fed into the coating device to heat the particles while processing.
処理時間は、粒子温度で異なるが3〜11分、好ましく
は5〜8分で均一な被覆状態で反応は完了する。Although the treatment time varies depending on the particle temperature, the reaction is completed in 3 to 11 minutes, preferably 5 to 8 minutes, with uniform coating.
尿素−ホルムアルデヒド縮合生成物の水溶液に硬化剤を
添加した処理液の粒子状尿素等への添加量は、吸湿性肥
料用物質により異なるが、粒子状尿素の場合には処理さ
れるべき、粒子状尿素あたり、005〜0.4重量%、
好ましくは約0.1〜0.2重量%で十分である。The amount of the treatment liquid obtained by adding a curing agent to an aqueous solution of urea-formaldehyde condensation product to particulate urea, etc. varies depending on the hygroscopic fertilizer substance, but in the case of particulate urea, the amount of particulate urea to be treated is 005-0.4% by weight per urea,
Preferably about 0.1-0.2% by weight is sufficient.
添加量を増加するのは何か特別の事でもない限り得策で
はない、それは処理液から持込まれる水分が尿素粒子に
残り好ましくな(・、これは粒子状尿素の硬度低下もし
くは処理された製品の品質を経時的に変化させる原因と
もなる。Increasing the amount added is not a good idea unless there is something special about it; this is because moisture brought in from the processing solution remains in the urea particles (・, this may cause a decrease in the hardness of the particulate urea or a decrease in the hardness of the processed product). It also causes quality to change over time.
本発明の方法に用いられる尿素−ホルムアルデヒド縮合
生成物の水溶液は、尿素1モルあたりホルムアルデヒド
1.2〜6モルであるものが用いられ、例えばプラスチ
ック材料講座11ユリア・メラミン樹脂”P−318に
記載の方法により簡単に製造できる。又、ホルムアルデ
ヒド水溶液に希薄な水酸化アルカリ水溶液を加えて弱ア
ルカリ性で尿素の1部を加えて反応、次−・で弱酸性と
し、更に、尿素を1部添加゛して反応させ、次いで水酸
化アルカリ水溶液で中和し、残りの尿素を添加して反応
させ、最後にpH緩衡剤を添加して製造したものでもよ
い。反応温度は約50〜70℃である。この様にして製
造された尿素−ホルムアルデヒド縮合生成物の尿素モル
あたり全ホルムアルデヒドのモル比は1.2〜6になる
様に尿素添加量を調整される。The aqueous solution of the urea-formaldehyde condensation product used in the method of the present invention is one containing 1.2 to 6 moles of formaldehyde per mole of urea, and is described, for example, in Plastic Materials Course 11 "Urea Melamine Resin" P-318. It can be easily produced by the following method.Additionally, a dilute aqueous alkali hydroxide solution is added to a formaldehyde aqueous solution to make it weakly alkaline, and then react by adding 1 part of urea. It may also be produced by reacting with an aqueous alkali hydroxide solution, adding the remaining urea and reacting, and finally adding a pH buffer.The reaction temperature is about 50 to 70°C. The amount of urea added is adjusted so that the molar ratio of total formaldehyde per mole of urea in the urea-formaldehyde condensation product produced in this manner is 1.2 to 6.
本発明にオ6いて、尿素−ホルムアルデヒド縮合生成物
の水溶液における尿素1モルあたりホルムアルデヒドの
モル数は1゜2〜6が使用出来るがホルムアルデヒドの
モル数が大きくなると遊離ホルマリン濃度が高くなり、
且つ硬化速度も早くなる等不都合な而があるので1,2
5〜2モル比迄の水溶液を使用するのが好ましい。又、
本水溶液の固形物割合ははM40〜80重量シbである
のか一般的である。In the present invention, the number of moles of formaldehyde per mole of urea in the aqueous solution of the urea-formaldehyde condensation product can be 1°2 to 6, but as the number of moles of formaldehyde increases, the concentration of free formalin increases.
In addition, there are disadvantages such as faster curing speed, so 1, 2
Preference is given to using aqueous solutions of up to 5 to 2 molar ratios. or,
The solid content of this aqueous solution is generally 40 to 80% by weight.
本発明における尿素−ホルムアルデヒド縮合生成物の水
溶液に添加される硬化剤としては、塙酸、蟻酸、塩化ア
ンモニウム、硫安、りん酸アンモン、酢酸アンモン等が
使用出来るが、塩化アンモニウムが好ましい。その添加
量は、1〜2重量%が適当であり、その添加方法は、あ
らかじめ水に溶解して20重量%水溶液として用℃・ら
れるが、尿素−ホルムアルデヒド縮合生成物の水溶液と
使用直前に添加するのが好まし℃・、具体的には例えば
、別々の貯槽から供給して配管内で混合する方法が挙げ
られる。As the curing agent added to the aqueous solution of the urea-formaldehyde condensation product in the present invention, silanic acid, formic acid, ammonium chloride, ammonium sulfate, ammonium phosphate, ammonium acetate, etc. can be used, but ammonium chloride is preferred. The appropriate amount to add is 1 to 2% by weight, and the method for adding it is to dissolve it in water in advance and use it as a 20% by weight aqueous solution. It is preferable to supply the components from separate storage tanks and mix them in a pipe.
粒子状尿素の被覆処理を行うための装置としては、粒子
表面えの被覆が均一に出来れば良く、例えば回転ドラム
型、皿型転動装置が好ましく、連続的に粒子状尿素等の
被覆処理が可能である。As a device for coating particulate urea, it is sufficient as long as the particle surface can be coated uniformly, for example, a rotating drum type or a plate type rolling device is preferable, and the device can continuously coat particulate urea, etc. It is possible.
被覆処理装置には、被覆処理液から持込まれる水分が蒸
発してくるものを速やかに系外に取除ける様に送風する
のか好ましく良い結果か得られる。Preferably, good results can be obtained by blowing air into the coating processing apparatus so that the moisture brought in from the coating solution and evaporated can be quickly removed from the system.
この場合の風量は僅かで良くその排気中にはホルムアル
デヒドは実質的に含まれておらすそのまま放出が可能で
ある。In this case, the amount of airflow may be small and formaldehyde is substantially contained in the exhaust gas and can be discharged as is.
(作用)
本発明の方法を例えば粒子状尿素に適用した場合につい
て(・えば、粒子状尿素を尿素とホルムアルデヒド縮合
生成物の水溶液で被覆する事により粒子表面の結晶ブリ
ッジを減らし平滑さを付与し表面積を減少する事により
、結果として尿素の水分に対する敏感さを少なくすると
共に粒子状尿素のケーキ形成を防止すること、粒子状尿
素の硬度が高められることから粒子状尿素の固結が防止
できるものと推定される。(Function) When the method of the present invention is applied to particulate urea, for example, by coating particulate urea with an aqueous solution of a condensation product of urea and formaldehyde, crystal bridges on the particle surface are reduced and smoothness is imparted. By reducing the surface area, the sensitivity of urea to moisture can be reduced and cake formation of particulate urea can be prevented, and the hardness of particulate urea can be increased to prevent caking of particulate urea. It is estimated to be.
(実施例) ′ 以下、本発明を実施例により具体的に説明する。(Example) ' Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例1〜11
容量51の回転混合ドラムを用℃・て回分式で温度40
〜80℃の大粒尿素に処理液3種類を用い各々所定の添
加量を噴霧しドラム中における処理時間を約3分〜11
分の間で処理した。Examples 1 to 11 Using a rotating mixing drum with a capacity of 51 °C, the temperature was 40 °C in batch mode.
Three types of treatment liquids were used to spray large particles of urea at ~80°C, each in a predetermined amount, and the treatment time in the drum was approximately 3 minutes to 11 minutes.
Processed within minutes.
この時、ドラム内で混合する間、ドラムは密封して行な
い、処理後直ちに気相中のホルムアルデヒド濃度を測定
した。At this time, the drum was sealed while mixing in the drum, and the formaldehyde concentration in the gas phase was measured immediately after the treatment.
この様に処理した大粒尿素について固結性をテストした
。The caking properties of the large urea particles treated in this manner were tested.
尚、ホルムアルデヒドは北側式検知管で測定した。In addition, formaldehyde was measured using the north type detection tube.
一方、固結テストはシリンダー型10CrrLφのSU
S製容器に試料3509−を装入し室温40°C1湿度
RH40%の條件下荷重0.55 kg/、fflで2
日間保存した。On the other hand, the consolidation test was conducted using a cylinder type 10CrrLφ SU.
Sample 3509- was charged into a container made of S, and the load was 0.55 kg/, ffl under the conditions of room temperature 40°C and humidity 40%.
Stored for days.
荷重を取り徐き山中式土壌硬度計で固結硬度を測定した
。対比のため縮合生成物水溶液を添加しない例を1〜1
1に示す。結果を表−1に示す。The load was removed and the consolidation hardness was measured using a Yamanaka soil hardness meter. For comparison, examples 1 to 1 are shown in which no aqueous condensation product solution is added.
Shown in 1. The results are shown in Table-1.
比較例1〜4
本発明の硬化剤を添加することの効果をみるために硬化
剤を使用しないほかは、実施例1と同様のテストを行っ
た。結果を表−1に示す。Comparative Examples 1 to 4 In order to examine the effect of adding the curing agent of the present invention, tests similar to those in Example 1 were conducted except that no curing agent was used. The results are shown in Table-1.
以上の結果から明らかな如く、実施例に較べて比較例2
における回転混合ドラム内、気相中のホルムアルデヒド
濃度は著しく高く又、処理後の製品は粒子表面が粘着性
を帯びており、固結テストにおいてシリンダー内壁えの
付着が掻く認められ、且つ固結強度も高く劣る。As is clear from the above results, Comparative Example 2
The concentration of formaldehyde in the gas phase inside the rotating mixing drum is extremely high, and the particle surface of the treated product is sticky, and in the consolidation test, it was observed that there was some adhesion to the inner wall of the cylinder, and the consolidation strength was low. It is also high and inferior.
実施例12〜18
流動床方式にお(・て造粒された大粒尿素を篩分機で製
品サイズの粒度とした。このものは粒子温度70℃を有
しており連続的に回転混合ドラムに供給され尿素−ホル
ムアルデヒド縮合生成物の水溶液II CI+に硬化剤
としてNH4Clを1重量%添加混合したものを噴霧し
転動させながら約5分間処理した。Examples 12 to 18 Large urea particles granulated using a fluidized bed method were sized to the product size using a sieve machine. This material had a particle temperature of 70°C and was continuously fed to a rotating mixing drum. An aqueous solution II CI+ of the urea-formaldehyde condensation product mixed with 1% by weight of NH4Cl as a curing agent was sprayed and treated for about 5 minutes while rolling.
この際、ドラム内は僅少の空気を送り込み蒸発水分を系
外に取り出した。この時気相中のホルムアルデヒドは不
検出(2ppm以下)であった。At this time, a small amount of air was pumped into the drum to remove evaporated moisture from the system. At this time, formaldehyde in the gas phase was not detected (2 ppm or less).
この様に処理された製品につ(・て固結試験を実施した
。結果を表−2に示す。Consolidation tests were conducted on the products treated in this way. The results are shown in Table 2.
比較例5〜8
実施例13〜18と同様操作した、但し尿素−ホルムア
ルデヒド縮合生成物の水溶液には硬化剤は添加しないで
噴霧した。Comparative Examples 5-8 The procedure was the same as in Examples 13-18, except that the aqueous solution of the urea-formaldehyde condensation product was sprayed without adding a curing agent.
その結果、ドラム排気中のホルムアルデヒド濃度は6
ppmと高(実施例より損失が太きい。As a result, the formaldehyde concentration in the drum exhaust was 6.
ppm and high (loss is greater than in the example).
結果を表−2に示す。The results are shown in Table-2.
以上の結果、本発明の方法は、混合処理ドラム排気中の
ホルムアルデヒド濃度も低く、優れた方法である事が判
る。硬化剤を使用しないと固結性に関しても特にI T
F/132段積では経時変化も大きく、排出に何らか
のハンドリングが必要である。The above results show that the method of the present invention has a low formaldehyde concentration in the exhaust gas from the mixing drum, and is an excellent method. Especially with regard to caking properties, IT
In the F/132 stack, there is a large change over time, and some sort of handling is required for ejection.
表−2
庄)fl120kgポリ袋堆積テスト方法條注、ノービ
ンポリエチレン袋、荷重4T/m′堆積テスト後1 m
の高さから床上に水平に落下し、開袋後、篩分し10
m/’m以上の塊りの重量を秤量しこれを固塊率とする
。Table 2) FL120kg polyethylene bag deposition test method Note: No-bin polyethylene bag, load 4T/m' after 1m deposition test
After opening the bag, it was sieved for 10 minutes.
The weight of the lumps of m/'m or more is weighed and this is taken as the solid lump ratio.
固結強度は、山中式土壌硬度計で塊りの強度を測定した
。Consolidation strength was determined by measuring the strength of the lumps using a Yamanaka soil hardness meter.
(2) I T Fl 2段積堆積テストは(1トン入
りのフレコンバックを2段重ね)、下段の排出状況を確
認し排出される固塊物の固結強度を上記同様測定した。(2) In the I T Fl two-tier stacking test (two tiers of 1-ton flexible container bags were stacked), the discharge status of the lower tier was checked, and the consolidation strength of the discharged solids was measured in the same manner as above.
(発明の効果)
本発明によれば、粒子状尿素等の吸湿性肥料用物質を尿
素−ホルムアルデヒド縮合生成物の水溶液に硬化剤を添
加して被覆処理する事により粒子状尿素等と処理剤との
処理時間が短時間で良く、特に、加熱乾燥設備は必要と
せず、排気中のホルムアルデヒド濃度も従来公知の方法
に較べて著しく低濃度であり、従ってホルムアルデヒド
の損失も少な(有効に利用する事が可能となる。(Effects of the Invention) According to the present invention, by coating a hygroscopic fertilizer substance such as particulate urea with a hardening agent added to an aqueous solution of a urea-formaldehyde condensation product, the particulate urea and the processing agent are combined. The processing time is short, in particular, no heating drying equipment is required, and the concentration of formaldehyde in the exhaust gas is significantly lower than that of conventionally known methods. becomes possible.
本発明の方法で処理された、粒子状尿素等は、固結性か
犬「1〕に改良されると共に機械的強度の面でも改善さ
れる等多くの特長を有し、製品は長期にわたって自由流
動性を示し、倉庫における貯蔵、移動、フレコンバック
、プラスチック袋での輸送堆積貯蔵もげ能となり、更に
、非常に変動する気候状態の地域におし・でも何らの困
難も伴わず輸送貯蔵かり能となる。Particulate urea, etc. treated by the method of the present invention has many features such as improved caking property and improved mechanical strength, and the product remains free for a long time. It exhibits fluidity, has the ability to be stored in warehouses, moved, transported in flexible container bags and plastic bags, and can be transported and stored without any difficulty even in areas with highly variable climatic conditions. becomes.
Claims (1)
のホルムアルデヒドを含有する尿素とホルムアルデヒド
の縮合生成物水溶液に硬化剤を添加した水溶液で処理す
る事を特徴とする吸湿性肥料用物質の固結防止方法。1) A hygroscopic fertilizer product characterized in that a hygroscopic fertilizer material is treated with an aqueous solution of a condensation product of urea and formaldehyde containing 1.2 to 6 moles of formaldehyde per 1 mole of urea and a hardening agent added thereto. Method of preventing caking of substances.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59271971A JPS61151086A (en) | 1984-12-25 | 1984-12-25 | Solidification prevention for substance for hygroscopic fertilizer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59271971A JPS61151086A (en) | 1984-12-25 | 1984-12-25 | Solidification prevention for substance for hygroscopic fertilizer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61151086A true JPS61151086A (en) | 1986-07-09 |
Family
ID=17507354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59271971A Pending JPS61151086A (en) | 1984-12-25 | 1984-12-25 | Solidification prevention for substance for hygroscopic fertilizer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61151086A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015010029A (en) * | 2013-07-02 | 2015-01-19 | セントラル硝子株式会社 | Compound fertilizer |
-
1984
- 1984-12-25 JP JP59271971A patent/JPS61151086A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015010029A (en) * | 2013-07-02 | 2015-01-19 | セントラル硝子株式会社 | Compound fertilizer |
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