JPH0460957B2 - - Google Patents
Info
- Publication number
- JPH0460957B2 JPH0460957B2 JP5184685A JP5184685A JPH0460957B2 JP H0460957 B2 JPH0460957 B2 JP H0460957B2 JP 5184685 A JP5184685 A JP 5184685A JP 5184685 A JP5184685 A JP 5184685A JP H0460957 B2 JPH0460957 B2 JP H0460957B2
- Authority
- JP
- Japan
- Prior art keywords
- magnesium
- mma
- waste acid
- added
- sulfate
- 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.)
- Expired
Links
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 70
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 34
- 239000000395 magnesium oxide Substances 0.000 claims description 33
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 21
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 19
- 239000003337 fertilizer Substances 0.000 claims description 19
- 238000004898 kneading Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- PWSPYJYNHXXPRD-UHFFFAOYSA-L N.S(=O)(=O)([O-])[O-].[Mg+2] Chemical compound N.S(=O)(=O)([O-])[O-].[Mg+2] PWSPYJYNHXXPRD-UHFFFAOYSA-L 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 description 30
- 239000002253 acid Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- WQVVYEYAFFYPIX-UHFFFAOYSA-N azane;magnesium Chemical class N.[Mg] WQVVYEYAFFYPIX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulfuric acid magnesium ammonia Chemical compound 0.000 description 1
Landscapes
- Fertilizers (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は硫酸苦土アンモニア肥料の製造方法に
関し、とくにメタクリル酸メチル製造時の廃酸を
有効に利用するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a sulfuric acid magnesium ammonia fertilizer, and in particular, to effectively utilize waste acid from the production of methyl methacrylate.
［従来の技術］
従来メタクリル酸メチル製造時、副生する廃液
（いわゆるMMA廃酸）は概ね下記の組成のもの
である。[Prior Art] Conventionally, during the production of methyl methacrylate, the waste liquid produced as a by-product (so-called MMA waste acid) generally has the following composition.
（アンモニウム）
酸性硫酸アンモニア 44〜52（重量％）
硫酸 15〜20〃
水分 25〜35〃
その他有機物 数〃
このものに直接アンモニアガスを加えて従来硫
安を製造して来たが、製造コストが高く、硫安需
要の不安定さをも手伝いMMA廃酸の経済的な利
用法の検索はその量が製品の約2.5〜3.0倍（重
量）という大量に及んでいるためメタクリル酸メ
チル（MMA）製造のキーポイントにもなつてい
た。このため最近は原料の青酸の品薄の関係もあ
り、製法の転換が相次いで行われつつあるのが現
状である。しかし青酸原料の入手が安定している
場合には、この廃液の処理が有効に行なわれれば
新規のプロセスに充分対抗し得るものである。(Ammonium) Acidic ammonia sulfate 44-52 (wt%) Sulfuric acid 15-20 Moisture 25-35 Other organic substances Number Ammonium sulfate has traditionally been produced by directly adding ammonia gas to this material, but the production cost is high. Due to the instability of demand for ammonium sulfate, the search for an economical way to use MMA waste acid has led to an investigation into the production of methyl methacrylate (MMA), as the amount of MMA waste acid is approximately 2.5 to 3.0 times the product (by weight). It was also a key point. For this reason, there has been a recent shortage of prussic acid as a raw material, and the current situation is that manufacturing methods are being changed one after another. However, if the raw material for hydrocyanic acid is stably available, and the waste liquid is treated effectively, it will be sufficient to compete with the new process.
最近、水溶性のマグネシウム肥料がその速効性
の故に畑作やハウス園芸等に注目されている。そ
こでメタクリル酸のメチルの製造時に副生する
MMA廃酸を利用して硫酸苦土アンモニア肥料の
製造への新しい方向を見出そうとするものであ
る。 Recently, water-soluble magnesium fertilizers have been attracting attention for field crops and greenhouse gardening because of their quick-acting properties. Therefore, it is produced as a by-product during the production of methyl methacrylate.
This project aims to find a new direction for producing sulfated magnesium ammonia fertilizer using MMA waste acid.
［発明の目的］
本発明は上述のようにメタクリル酸メチル製造
時の副生するMMA廃酸を利用して硫酸苦土アン
モニア肥料を製造しようとするものである。[Object of the Invention] As described above, the present invention aims to produce a magnesium sulfate ammonia fertilizer by using MMA waste acid produced as a by-product during the production of methyl methacrylate.
［発明の解決しようとする問題点］
本発明は上記のMMA廃酸を利用して硫酸苦土
アンモニア肥料を粉末状として製造しようとする
もので、硫酸苦土アンモニアは（NH4）2Mg
（SO4）2・nH2Ｏ、ｎ＝０，１，４，６で示され、
アンモニア性チツソ７重量％以上を含有し、かつ
水溶性マグネシウムを10重量％以上を含んでいる
ため、肥効の上で一層有利で、かつこの肥料は配
合肥料の原料としても勿論有効に利用できるもの
であるから、本発明はこのMMA廃酸の利用と相
俟つて硫酸苦土アンモニア肥料の製造において経
済的に極めて有利である。MMA廃酸を利用して
硫酸苦土アンモニア肥料を合成する方法としては
これにマグネシウム化合物と硫安とを混合する方
法があるが、マグネシウム化合物として水酸化マ
グネシウムを用いて、硫酸苦土アンモニアを経済
的に製造する方法及び最近マグネシウム化合物と
して水酸化マグネシウムよりも安価な酸化マグネ
シウムの１種である軽焼マグネシアが輸入される
ようになつたが、これを利用できればより経済的
にMMA廃酸を用いて硫酸苦土アンモニア肥料が
製造出来ると考えられる。[Problems to be Solved by the Invention] The present invention attempts to produce a powdered magnesium sulfate ammonia fertilizer using the above-mentioned MMA waste acid, and the ammonia magnesium sulfate is (NH 4 ) 2 Mg.
(SO 4 ) 2 ·nH 2 O, represented by n=0, 1, 4, 6,
Contains 7% by weight or more of ammoniacal magnesium and 10% by weight or more of water-soluble magnesium, making it more effective as a fertilizer, and of course, this fertilizer can also be effectively used as a raw material for compound fertilizers. Therefore, the present invention, together with the utilization of this MMA waste acid, is economically extremely advantageous in the production of magnesium sulfate ammonia fertilizer. One way to synthesize magnesium sulfate ammonia fertilizer using MMA waste acid is to mix it with a magnesium compound and ammonium sulfate. Recently, light calcined magnesia, a type of magnesium oxide that is cheaper than magnesium hydroxide, has been imported as a magnesium compound, but if it could be used, it would be more economical to use MMA waste acid. It is thought that sulfate magnesium ammonia fertilizer can be produced.
［問題点を解決するための手段］
上述の近況から、水酸化マグネシウムと酸化マ
グネシウムを利用して硫酸苦土アンモニア肥料を
MMA廃酸を用いて安価に製造しようとするもの
で、その要旨とするところはMMA廃酸を15℃〜
100℃に保ちながら硫安を溶解して加え、これに
水酸化マグネシウムと酸化マグネシウムを水酸化
マグネシウム１重量部に対し酸化マグネシウム１
〜３重量部の割合で（含有MgO換算量）加えて
かきまぜ、スラリーを生成させ、これを捏和機に
流し込み一定時間捏和することにより直接粉末状
の硫酸苦土アンモニア肥料を製造するものであ
り、ドライヤーを用いないでも粉末状で得られる
ことを大きな特徴とするものである。[Means to solve the problem] Based on the recent situation mentioned above, it is possible to use magnesium sulfate ammonia fertilizer using magnesium hydroxide and magnesium oxide.
The aim is to produce it at a low cost using MMA waste acid, and the gist of it is to produce MMA waste acid at 15°C or higher.
Dissolve and add ammonium sulfate while maintaining the temperature at 100°C, and add magnesium hydroxide and magnesium oxide in a ratio of 1 part by weight of magnesium hydroxide to 1 part by weight of magnesium oxide.
This method directly produces powdered magnesium sulfate ammonia fertilizer by adding ~3 parts by weight (contained MgO equivalent) and stirring to form a slurry, which is then poured into a kneading machine and kneaded for a certain period of time. A major feature of this product is that it can be obtained in powder form without using a dryer.
［作用］
MMA廃酸に酸化マグネシウムを反応させると
激しい発熱と発泡を伴い、急激に固化し、その後
で硫安を作用させたのでは硫酸苦土アンモニアの
生成反応は充分には進行しない。そこで本願発明
者らは先ずMMA廃酸に硫安を加えて溶解し、そ
の後で酸化マグネシウムを作用させたが反応の激
しさは幾分緩和されるが数分で固化するので、未
反応の酸化マグネシウムが残存するとともに混合
反応器から捏和機への流入輸送も円滑に行われな
い。一方、MMA廃酸に硫安を加えて溶解し、そ
こに水酸化マグネシウムを加えると固化速度が極
めて遅く、生成したスラリーはパウダー状になり
難い。そこでこれらの事実から最適反応条件を求
めて各種の試験の結果本発明に到達した。[Function] When magnesium oxide is reacted with MMA waste acid, it rapidly solidifies with intense heat generation and foaming.If ammonium sulfate is then reacted with, the reaction to produce ammonia sulfate does not proceed sufficiently. Therefore, the inventors of the present application first added ammonium sulfate to MMA waste acid to dissolve it, and then applied magnesium oxide to it, but although the intensity of the reaction was somewhat alleviated, it solidified within a few minutes, so unreacted magnesium oxide remains, and the inflow and transportation from the mixing reactor to the kneading machine cannot be carried out smoothly. On the other hand, when ammonium sulfate is added to dissolve MMA waste acid and magnesium hydroxide is added thereto, the solidification rate is extremely slow and the resulting slurry is difficult to form into powder. Therefore, based on these facts, optimal reaction conditions were determined, and as a result of various tests, the present invention was arrived at.
すなわちMMA廃酸に硫安を加えて溶解し、酸
化マグネシウムの全反応量のうち、一部を水酸化
マグネシウムに置き換えて反応させたところ、反
応は比較的穏やかで、生成したスラリーの固化速
度も遅くなり、そのため混合反応器から捏和機へ
の輸送は極めて平滑に行われるとともに、捏和初
期はスラリー状を保つているため均一な混合が行
われ、またその混合スラリーは10〜20分という短
時間で粉末状に固化することが見出された。 In other words, when ammonium sulfate was added and dissolved in MMA waste acid and a portion of the total reaction amount of magnesium oxide was replaced with magnesium hydroxide, the reaction was relatively mild and the solidification rate of the resulting slurry was slow. Therefore, the transportation from the mixing reactor to the kneading machine is extremely smooth, and since the slurry remains in the initial stage of kneading, uniform mixing is achieved, and the mixed slurry can be produced in a short time of 10 to 20 minutes. It was found that it solidified into powder over time.
この水酸化マグネシウムと酸化マグネシウムの
添加量の比率は外気温度やMMA廃酸温度により
異り、それらの温度が低ければ水酸化マグネシウ
ムの添加量を少なめにし、それらの温度が高かけ
れば水酸化マグネシウムの添加量を多くすればよ
く、その比率の適正量は実用上、水酸化マグネシ
ウム１重量部に対し、酸化マグネシウム１〜３重
量部（MgO換算比）の範囲にあることも試験の
結果明らかになつた。また水酸化マグネシウムと
酸化マグネシウムの添加は同時または水酸化マグ
ネシウム次いで酸化マグネシウムの順のいずれか
でもよいことも明らかになつた。 The ratio of the amount of magnesium hydroxide and magnesium oxide added varies depending on the outside air temperature and the temperature of the MMA waste acid.If the temperature is low, the amount of magnesium hydroxide added will be small, and if the temperature is high, the amount of magnesium hydroxide added will be smaller. The test results also revealed that the appropriate ratio is practically 1 to 3 parts by weight of magnesium oxide to 1 part by weight of magnesium hydroxide (MgO conversion ratio). Summer. It has also been found that magnesium hydroxide and magnesium oxide can be added either simultaneously or in the order of magnesium hydroxide and then magnesium oxide.
この反応によりマグネシウム化合物の全反応量
のうち50％以上の酸化マグネシウムの使用が可能
になつたがMMA廃酸は100℃以上ではマグネシ
ウムとの反応が激しすぎ、15℃以下では結晶が析
出するため、15〜100℃に保つて反応させる必要
があることも判明した。この反応の製造工程とし
て考えられるものの１例を第１図に示した。１は
混合反応器でａはMMA廃酸、ｂは硫安、２は攪
拌機である。混合反応器中でMMA廃酸に硫安を
溶かしスラリー状のものｅを第２混合反応器３に
送り、この中で酸化マグネシウムｃと水酸化マグ
ネシウムｄが添加混合されスラリーe′状としたも
のと捏和機４に移送する。こゝでは反応物が固く
固化することなく粉末状となるのでこれを乾燥工
程を終ないで製品ｆとすることができる。 This reaction made it possible to use more than 50% of the total reaction amount of magnesium compounds as magnesium oxide, but MMA waste acid reacts too vigorously with magnesium at temperatures above 100℃, and crystals precipitate below 15℃. Therefore, it was found that it was necessary to maintain the temperature between 15 and 100°C for the reaction. An example of a possible manufacturing process for this reaction is shown in FIG. 1 is a mixing reactor, a is MMA waste acid, b is ammonium sulfate, and 2 is a stirrer. Ammonium sulfate is dissolved in MMA waste acid in a mixing reactor and a slurry e is sent to the second mixing reactor 3, where magnesium oxide c and magnesium hydroxide d are added and mixed to form a slurry e'. Transfer to kneading machine 4. In this case, the reactant does not harden and becomes powder, so it can be used as product f without completing the drying process.
［実施例］
本発明を更に具体的にするために実施例につい
て述べる。[Examples] Examples will be described in order to make the present invention more specific.
比較例 １
外気温度11℃で60℃のMMA廃酸を用いた。
MMA廃酸の組成は酸性硫酸アンモニア51％、硫
酸18％、水分29％のものである。このMMA廃酸
3800ｇに軽焼マグネシア715ｇを加えてかきまぜ
た。激しい発熱と発泡が起り、未反応の軽焼マグ
ネシウムがあるのにスラリーの固化が始まり、こ
れに硫安1028ｇを加えて捏和しても未反応の硫安
と軽焼マグネシアが残存しているのが観察され、
反応は充分に進行しなかつた。Comparative Example 1 MMA waste acid at 60°C was used at an outside temperature of 11°C.
The composition of MMA waste acid is 51% acidic ammonia sulfate, 18% sulfuric acid, and 29% water. This MMA waste acid
Add 715g of light roasted magnesia to 3800g and stir. Vigorous heat generation and foaming occurred, and the slurry began to solidify even though there was unreacted light-burnt magnesium. Even after adding 1028 g of ammonium sulfate and kneading, unreacted ammonium sulfate and light-burnt magnesia remained. observed,
The reaction did not proceed sufficiently.
比較例 ２
外気温度10℃で95℃のMMA廃酸（比較例１と
同じもの）3800ｇに硫安1028ｇを混合反応器にて
溶解し、これに軽焼マグネシア715ｇを加えて反
応させたところ比較例１ほどではなかつたが激し
い発熱と発泡が起り、充分に反応が進まない中に
固化が始まり、生成スラリーの捏和機への輸送は
流動性がないため困難で、また捏和機で捏和後も
未反応の軽焼マグネシアが観察され反応は充分進
行しなかつた。Comparative Example 2 1028 g of ammonium sulfate was dissolved in 3800 g of MMA waste acid (same as in Comparative Example 1) at 95°C at an outside temperature of 10°C in a mixing reactor, and 715 g of lightly calcined magnesia was added and reacted. Although it was not as strong as in step 1, intense heat generation and foaming occurred, and solidification began before the reaction progressed sufficiently, making it difficult to transport the resulting slurry to the kneading machine due to its lack of fluidity, and it was difficult to knead it in the kneading machine. Even after that, unreacted light burnt magnesia was observed, indicating that the reaction did not proceed sufficiently.
実施例 １
外気温度３℃で50℃のMMA廃酸（比較例にお
けると同じ）3800ｇに硫安1028ｇを加えて溶解
し、これに水酸化マグネシウム271ｇと軽焼マグ
ネシア511ｇを同時に添加して、かきまぜた（水
酸化マグネシウムと軽焼マグネシアとのMgO換
算比は１：2.5である）。発熱と発泡は比較例２よ
りは少なく、生成したスラリーは消泡後は５分以
上流動性を保持していたため捏和機への輸送はス
ムーズに行われ、捏和機で15分捏和後小粒を含ん
だパウダー状に固化した。このものは翌日若干固
結していたが手で簡単にほぐすことができた。こ
の生成物はアンモニア態チツソ9.1％、水溶性
MgO13.3％を含み、MgO分の99％以上が水溶性
化していた。生成物中の（NH4）2Mg（SO4）2・
6H2Ｏ含有量はＸ−線回析で定量したところ70％
含有されていた。残りは（NH4）2Mg（SO4）2０〜
4H2Ｏが大部分と推定される。なおこの生成物は
肥料取締法による公定規格の条件をすべて満たし
ていた。Example 1 1028g of ammonium sulfate was added and dissolved in 3800g of MMA waste acid (same as in the comparative example) at 50°C at an outside temperature of 3°C, and 271g of magnesium hydroxide and 511g of lightly calcined magnesia were added at the same time and stirred. (The MgO conversion ratio of magnesium hydroxide and light calcined magnesia is 1:2.5). The heat generation and foaming were lower than in Comparative Example 2, and the generated slurry maintained fluidity for more than 5 minutes after defoaming, so it was smoothly transported to the kneading machine, and after kneading for 15 minutes in the kneading machine. It solidified into a powder containing small particles. This product was a little hardened the next day, but I was able to easily loosen it by hand. This product contains 9.1% ammonia, water soluble
It contained 13.3% MgO, and more than 99% of the MgO content was water-soluble. (NH 4 ) 2 Mg(SO 4 ) 2 in the product
The 6H 2 O content was determined to be 70% by X-ray diffraction.
It was contained. The rest is (NH 4 ) 2 Mg (SO 4 ) 2 0~
It is estimated that the majority is 4H 2 O. Furthermore, this product met all the conditions of the official standards according to the Fertilizer Control Law.
実施例 ２
外気温度16℃で95℃のMMA廃酸（前出）3800
ｇに硫安1028ｇを加えて溶解し、そこへ水酸化マ
グネシウム316ｇを加え、次いで軽焼マグネシア
477ｇを加えてかきまぜた。水酸化マグネシウム
と軽焼マグネシアとの比はMgO換算で１：２、
発熱と発泡は比較例２の場合よりは少なく、生成
したスラリーは消泡後５分以上流動性を保つてい
たため捏和機への輸送はスムーズに行なわれ、捏
和機で12分捏和後、小粒混じりのパウダー状に固
化した。このパウダーは翌日若干固結していたが
手で簡単にほぐすことができた。この生成物はア
ンモニア態チツソ9.2％、水溶性MgO13.2％を含
み、MgO分の約99％は水溶性化していた。生成
物中の（NH4）2Mg（SO4）2・6H2Ｏの含有量はＸ
−線回析で定量したところ、73％含まれており、
残りは（NH4）2Mg（SO4）2０〜4H2Ｏが大部分と
推定される。なおこの生成物は肥料取締法による
公定規格の条件をすべて満たしていた。Example 2 MMA waste acid (mentioned above) 3800 at 95°C at an outside temperature of 16°C
1,028g of ammonium sulfate was added to 1,028g of ammonium sulfate and dissolved, 316g of magnesium hydroxide was added thereto, and then lightly calcined magnesia
Added 477g and stirred. The ratio of magnesium hydroxide and light calcined magnesia is 1:2 in terms of MgO.
The heat generation and foaming were lower than in Comparative Example 2, and the generated slurry maintained its fluidity for more than 5 minutes after defoaming, so it was smoothly transported to the kneading machine. It solidified into a powder containing small particles. This powder was slightly hardened the next day, but I was able to easily loosen it by hand. This product contained 9.2% of ammonia and 13.2% of water-soluble MgO, and approximately 99% of the MgO content was water-soluble. The content of (NH 4 ) 2 Mg(SO 4 ) 2・6H 2 O in the product is
-As determined by linear diffraction, it contains 73%;
The remainder is estimated to be mostly ( NH4 ) 2Mg ( SO4 ) 20-4H2O . Furthermore, this product met all the conditions of the official standards according to the Fertilizer Control Law.
［効果］
本発明は上記の構成となつているのでメタクリ
ル酸メチル製造時に副生するMMA廃酸を利用
し、これを15〜100℃に保ちながら硫安を加えて
溶解し、これに水酸化マグネシウムと酸化マグネ
シウムを含有MgO換算で１：１〜３の割合で加
えてかきまぜて反応させることにより固く固化す
ることなくスラリー状となるので、捏和機にスム
ーズに輸送でき、捏和機で粉末状の硫酸苦土アン
モニア肥料を極めて容易に製造できるもので、固
い固形化物を粉砕する手間や篩別の作業を必要と
しないで粉末状の生成物が直接製造でき、しかも
安価な軽焼マグネシアを利用するので極めて低コ
ストの硫酸苦土アンモニア肥料を製造することが
できるようになつた。[Effect] Since the present invention has the above-mentioned structure, MMA waste acid produced as a by-product during the production of methyl methacrylate is used, and ammonium sulfate is added and dissolved while maintaining it at 15 to 100°C, and magnesium hydroxide is added to this. By adding and stirring and reacting magnesium oxide and magnesium oxide at a ratio of 1:1 to 3 in terms of MgO content, it becomes a slurry without solidifying, so it can be smoothly transported to a kneading machine, and the kneading machine can turn it into a powder. It is extremely easy to produce sulfuric acid magnesia ammonia fertilizer, and the powdered product can be produced directly without the need for pulverizing hard solidified materials or sieving, and it uses inexpensive light calcined magnesia. As a result, it has become possible to produce extremely low-cost magnesium sulfate ammonia fertilizer.
第１図は本発明の硫酸苦土アンモニア肥料の製
造工程の一例を示す説明図である。
１……混合反応器、２……攪拌機、３……混合
反応機、４……捏和機、ａ……MMA廃酸、ｂ…
…硫安、ｃ……酸化マグネシウム、ｄ……水酸化
マグネシウム、ｅ，e′……スラリー、ｆ……粉末
状製品。
FIG. 1 is an explanatory diagram showing an example of the manufacturing process of the magnesium sulfate ammonia fertilizer of the present invention. 1... Mixing reactor, 2... Stirrer, 3... Mixing reactor, 4... Kneading machine, a... MMA waste acid, b...
...Ammonium sulfate, c...Magnesium oxide, d...Magnesium hydroxide, e, e'...Slurry, f...Powdered product.
Claims (1)
で排出される硫酸水素アンモニウム及び硫酸を主
成分とする廃液を15°〜100℃に保ちながら硫安を
加えて溶解し、これに水酸化マグネシウムと酸化
マグネシウムを、水酸化マグネシウム１重量部に
対し酸化マグネシウム１〜３重量部の割合（含有
MgO換算量）で加えてかきまぜ、スラリーを生
成し、これを捏和機へ流し込み、一定時間捏和す
ることにより粉末状の硫酸苦土アンモニア肥料を
製造する方法。1 Ammonium sulfate is added and dissolved while maintaining ammonium hydrogen sulfate and sulfuric acid as the main components, which are discharged in the esterification process during the production of methyl methacrylate, and magnesium hydroxide and magnesium oxide are added to this. , ratio of 1 to 3 parts by weight of magnesium oxide to 1 part by weight of magnesium hydroxide (contains
A method of producing powdered magnesium sulfate ammonia fertilizer by adding (MgO equivalent amount) and stirring to generate a slurry, pouring this into a kneading machine, and kneading for a certain period of time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5184685A JPS61215283A (en) | 1985-03-15 | 1985-03-15 | Manufacture of ammonia magnesium sulfate fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5184685A JPS61215283A (en) | 1985-03-15 | 1985-03-15 | Manufacture of ammonia magnesium sulfate fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61215283A JPS61215283A (en) | 1986-09-25 |
| JPH0460957B2 true JPH0460957B2 (en) | 1992-09-29 |
Family
ID=12898214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5184685A Granted JPS61215283A (en) | 1985-03-15 | 1985-03-15 | Manufacture of ammonia magnesium sulfate fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61215283A (en) |
-
1985
- 1985-03-15 JP JP5184685A patent/JPS61215283A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61215283A (en) | 1986-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1067363C (en) | Process for preparation of products containing phosphorus-nitrogen and prodcts obtained | |
| US4028088A (en) | Soil amendment and method | |
| AU672483B2 (en) | Metal ammonium phosphate-alkylene urea buffered fertilizer | |
| US3149956A (en) | Preparation of granular nitrogenous fertilizer | |
| JPH0460957B2 (en) | ||
| CN101624299A (en) | Agricultural magnesium sulfate fertilizer, preparation method thereof and special mixing reactor thereof | |
| JPH0520376B2 (en) | ||
| US2770539A (en) | Process for producing a mixed fertilizer | |
| US2867522A (en) | Method for producing fertilizers and bases from sludges | |
| JPH0460956B2 (en) | ||
| US4101637A (en) | Direct granulation process for triple superphosphate | |
| JPH0159239B2 (en) | ||
| US2079324A (en) | Method of producing fertilizers | |
| CN1050819C (en) | Technology for producing potassium sulfate using flue gas desulfating gypsum | |
| JP4078111B2 (en) | Phosphate fertilizer composition | |
| JPS6117795B2 (en) | ||
| WO2003018512A1 (en) | Fertiliser | |
| JP3383224B2 (en) | Manufacturing method of granular fertilizer | |
| JPS61141688A (en) | Quick modification of lime nitrogen | |
| EP2067760A1 (en) | Process for obtaining fertilizers from tio2 subproducts, and products obtained in this manner | |
| JPH0475017B2 (en) | ||
| JP2000095587A (en) | Granular magnesium sulfate fertilizer and its production | |
| SU1724654A1 (en) | Process for producing granulated fertilizer | |
| JPS5918342B2 (en) | Method for producing inorganic cured body | |
| CN1229777A (en) | Method for producing sulfonyl nitrogen-potassium compound fertilizer |