JPH0139962B2 - - Google Patents
Info
- Publication number
- JPH0139962B2 JPH0139962B2 JP56170311A JP17031181A JPH0139962B2 JP H0139962 B2 JPH0139962 B2 JP H0139962B2 JP 56170311 A JP56170311 A JP 56170311A JP 17031181 A JP17031181 A JP 17031181A JP H0139962 B2 JPH0139962 B2 JP H0139962B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- percarbonate
- silicate
- sodium
- soda
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 18
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 16
- 229940045872 sodium percarbonate Drugs 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- -1 alkaline earth metal salt Chemical class 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229960001922 sodium perborate Drugs 0.000 description 3
- 239000011643 sodium salts of orthophosphoric acid Substances 0.000 description 3
- 235000019857 sodium salts of orthophosphoric acid Nutrition 0.000 description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005550 wet granulation Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Glanulating (AREA)
Description
【発明の詳細な説明】
本発明は過炭酸ソーダの製造法に関し、保存安
定性を有し、水に対して極めて迅速に溶解する過
炭酸ソーダの製造法に関する。
過炭酸ソーダは過ホウ酸ソーダとならび代表的
な酸素系漂白剤である。過ホウ酸ソーダは常温程
度では溶解性が低く十分に漂白効果を発揮しな
い。このため温水で洗濯する習慣のない我国にお
いては、業務用以外には余り利用されていない。
また、塩素系漂白剤も一般に使用されているが、
これは刺激臭が強く、染色した衣料を脱色するな
どの欠点がある。
近年、塩素系漂白剤にみられる欠点を有せず、
常温程度の低温に対する溶解性が高い過炭酸ソー
ダの需要が伸長して来ている。
過炭酸ソーダの製造法としては、炭酸ソーダと
過酸化水素とを反応させて、反応晶出法により過
炭酸ソーダ結晶粉末を得、ついで湿式造粒を行な
い乾燥し製品となすのが一般的である。過炭酸ソ
ーダは一般に空気中に放置すると、吸湿して過炭
酸ソーダの活性酸素濃度の低下をきたし、使用に
際して十分なる漂白効果を発揮しなくなる。この
ために水ガラス、リン酸塩、ケイ酸塩、マグネシ
ウム塩などの無機質化合物を反応生成物に添加す
ること、あるいはポリエチレングリコール、澱
粉、CMCなどの有機質化合物を添加すること、
または造粒物に上記のごとき無機質化合物を噴
霧、被覆することなどが知られている。しかしな
がら、この様な方法によつて得られた粒状の過炭
酸ソーダは、勿論過ホウ酸ソーダにくらべて溶解
性は優れているものの常温における溶解性はそれ
程大きくなく通常の家庭で使用する場合には溶解
させるのに多大な時間を要し、そのために十分な
る漂白効果を発揮し得ない欠点があつた。
過炭酸ソーダのこの様な欠点を改良する試みと
しては造粒乾燥された過炭酸ソーダを再び75〜
135℃の温度範囲で特定時間加熱し速溶性を付与
する方法がある。この方法によれば確かに比較的
良好な溶解性を有する過炭酸ソーダを得る事がで
きるが、満足し得る速溶性の製品を得るには比較
的高温下長時間の加熱を要する。しかしながら、
この様な条件下で処理することは過炭酸ソーダの
保有する活性酸素が分解により失なわれ、速溶性
を有する様になるものの得られた製品の活性酸素
含有率が低いという致命的な欠陥を有する。又工
業的には乾燥機以外の加熱装置を必要とし大きな
不利となる。
本発明者らは、上記の如き諸点に鑑み、種々検
討の結果、本発明者らは従来安定化剤として用い
られている無機質化合物、たとえば水ガラス、ケ
イ酸塩を添加した場合の水に対する溶解性に関し
て検討した結果、上記の無機質化合物を水溶液な
いし水分散体として過炭酸ソーダに添加して湿式
造粒する際、その造粒過程において、添加された
無機質化合物はゲル化し、粒子に沈着されるが、
このゲル化の速度の大小が造粒乾燥された顆粒状
過炭酸ソーダの水に対する溶解性の大小に極めて
重大な関連があることを見出すと共に、添加剤の
種類及び組合せが極めて重要であることが判明
し、これに基づき本発明を完成した。
本発明の目的は、水に対する溶解性にすぐれ、
かつ安定性を有する顆粒状の過炭酸ソーダを提供
するにある。
本発明は、粉末状の過炭酸ソーダを造粒するに
際して、過炭酸ソーダにケイ酸ヒドロゾルもしく
はケイ酸のアルカリまたはアルカリ土類金属塩ま
たは含水酸化アルミニウムヒドロゾルから選ばれ
た少なくとも一種と、オルトリン酸、オルトまた
はメタ、硼酸またはクエン酸、コハク酸、酒石酸
から選ばれる有機多価カルボン酸のそれぞれのナ
トリウム塩から選ばれた少なくとも一種とを同時
に添加し造粒することを特徴とする過炭酸ソーダ
の製造法に関する。
本発明において使用されるケイ酸ヒドロゾルも
しくはケイ酸のアルカリまたはアルカリ土類金属
塩または含水酸化アルミニウムヒドロゾル及びオ
ルトリン酸、オルトまたはメタ硼酸、クエン酸、
コハク酸、酒石酸から選ばれる有機多価カルボン
酸のそれぞれのナトリウム塩を以下、添加剤と呼
ぶことがあり、「ケイ酸ヒドロゾルもしくはケイ
酸塩または含水酸化アルミニウムヒドロゾル」を
第１群の添加剤、「オルトリン酸、オルトまたは
メタ硼酸またはクエン酸、コハク酸、酒石酸から
選ばれる有機多価カルボン酸のそれぞれのナトリ
ウム塩」を第２群の添加剤と呼ぶ。
本発明に用いられる第１群の添加剤であるケイ
酸のアルカリまたはアルカリ土類金属塩は、市販
の１号〜３号水ガラス、ケイ酸カリウム、ケイ酸
リチウム、ケイ酸マグネシウム、粉末ケイ酸ナト
リウムから選ばれる。また、ケイ酸ヒドロゾルは
コロイダルシリカあるいはシリカゾルとも呼ば
れ、それ自体は公知であり、粒径10〜100mμの酸
化ケイ素の水分散体である（市販品としてはたと
えば商品名スノーテツクス（日産化学工業株式会
社製）がある）。含水酸化アルミニウムヒドロゾ
ルはコロイダルアルミナあるいはアルミナゾルと
も呼ばれるもので、無定形の酸化アルミニウムの
ヒドロゾルである（市販品としてはたとえばアル
ミナゾルがある）。該ケイ酸ヒドロゾル、または
含水酸化アルミニウムヒドロゾルは通常１〜30％
濃度のものが使用され、過炭酸ソーダに対し、
SiO2またはAl2O3として0.01〜0.5重量％の範囲で
添加される。また上記のケイ酸塩のうち、市販の
１号〜３号水ガラスは１〜25％濃度のものが使用
され、その他のケイ酸カリウム、ケイ酸リチウ
ム、ケイ酸マグネシウム、粉末状ケイ酸ナトリウ
ムは１〜20％濃度のものが使用され、過炭酸ソー
ダに対しSiO2として0.01〜0.5重量％の範囲で添
加される。上記ケイ酸マグネシウムは0.1〜0.3％
が好適である。本発明において上記のケイ酸ヒド
ロゾルもしくはケイ酸のアルカリまたはアルカリ
土類金属塩または含水酸化アルミニウムヒドロゾ
ルの添加量が、上記した量よりも多い場合は溶解
性が悪くなり好ましくなく、本発明の目的を十分
に達成し顕著な効果を発揮させるにはSiO2また
はAl2O3として0.01〜0.3重量％の範囲で添加する
ことが好適である。
本発明において、造粒時に添加される第１群の
添加剤と第２群の添加剤とは、造粒時に両者を同
時に添加することが大切である。第１群の添加剤
と第２群の添加剤とを経時的に個別に添加した場
合には溶解性が著しく損なわれ好ましくない。第
１群添加剤ではケイ酸ヒドロゾル、含水酸化アル
ミニウムヒドロゾル及びケイ酸塩のうち、ケイ酸
リチウム、１号〜３号水ガラスが特に好適であ
る。
本発明において使用される第２群の添加剤であ
るオルトリン酸のナトリウム塩は、第一リン酸ソ
ーダ、第二リン酸ソーダ、第三リン酸ソーダ、で
ある。また、有機多価カルボン酸のナトリウム塩
は、クエン酸、コハク酸、酒石酸である。これら
本発明における第２群の添加剤は混練、〓和中に
第１群の添加剤のPHを調製し、第１群の添加剤の
ゲル化を促進させる作用をする。
本発明において、上記第２群の添加剤としての
オルトリン酸のナトリウム塩は通常、濃度５〜30
％のものが、またオルトまたはメタ硼酸のナトリ
ウム塩、有機多価カルボン酸のナトリウム塩は通
常、濃度１〜10％のものが使用され、第２群の添
加剤の作用を十分に発揮させるために通常、過炭
酸ソーダに対し0.01〜0.5％（重量）の範囲で使
用される。
本発明において、過炭酸ソーダの造粒には湿式
造粒法が適用され、造粒に際して使用される造粒
機は湿式法に用いられるいかなる形式のものも使
用し得るが、混練、〓和が十分に行なわれる造粒
機が好適である。造粒に際しては、過炭酸ソーダ
の含水率が10〜15％程度となる様に所望に応じ水
を添加して混練、〓和される。造粒に使用される
造粒機の例としては、スクリユー押出型の混練機
の先端に孔径0.7〜1.5mmのスクリーンを設置した
型式のもの、あるいは出願人が先に出願した押出
型混練、〓和型の造粒機が使用される。
本発明により得られた製品は保存安定性にすぐ
れており、かつ冷水に対し良好な溶解性を有して
いると共に溶解時に発泡性を有する。本発明によ
り得られた顆粒状の過炭酸ソーダは酸素系漂白剤
として洗剤等に配合することができる。
本発明に使用される粉末状過炭酸ソーダは、炭
酸ソーダ水溶液に過酸化水素を作用させて水溶液
から結晶を晶出する方法（晶出法）、不活性溶媒
中でスラリー状にして反応させる溶液法、あるい
は粉末状炭酸ソーダに過酸化水素水溶液を添加す
るドライ法などいずれの方法によつて得られるも
のも使用できるが、一般には晶出法によつて得ら
れた湿潤な過炭酸ソーダが好適である。
参考例
（過炭酸ソーダの製造例）
撹拌機、温度計、冷却用の外套を備えたステン
レス製の反応機にH2O22％、Na2CO312％を含む
反応母液30を調製する。該母液を15〜20℃の温
度に保持しながら撹拌下に60％H2O22.5Kg、
Na2CO33.0Kgを同時に約１時間を要して徐々に添
加し、添加後上記温度に保ちながら１時間撹拌し
た。得られたスラリーを遠心分離機により過炭酸
ソーダ結晶と液に分離し、湿潤な過炭酸ソーダ
約3.5Kgを得た。
次に本発明の実施例を示す。
実施例
参考例の方法で得た湿潤な過炭酸ソーダ粉体を
ニーダーに供給し、これに表に示す本発明におけ
る第１群の添加剤及び第２群の添加剤を所望の濃
度でそれぞれ所定量添加し、さらに含水率が10〜
15％になる様に所望量の水を添加し、約30分間混
練した。次いで混練した湿潤塊は二軸押出式ペレ
ツター（不二電機工業株式会社製）により造粒
し、該造粒物を流動乾燥器により乾燥し製品を得
た。この製品につき溶解速度を測定した。
溶解速度の測定は、１のビーカーに25℃の純
水１を入れ、高さ40mm、巾25mmの撹拌羽根を有
する撹拌棒を250rpmで回し、５ｇの試料を投入
し粒子が完全に消失した時間を測定して行なつ
た。
また、得られた製品50ｇを100mlのビーカーに
入れ開放状態で35℃、80％RHの条件下30日間放
置し、試験前後の有効酸素量を求め、次式に従つ
て有効酸素低下率を求め、保存安定性を測定し
た。
（有効酸素低下率）＝（初期有効酸素）−（30日
後有効酸素）／（初期有効酸素）×100（％）
有効酸素低下率は第一表に示した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing soda percarbonate, which has storage stability and dissolves very quickly in water. Sodium percarbonate is a typical oxygen bleaching agent along with sodium perborate. Sodium perborate has low solubility at room temperature and does not exhibit sufficient bleaching effects. For this reason, in Japan, where there is no custom of washing clothes with hot water, they are not used for anything other than business purposes.
Chlorine bleach is also commonly used, but
This has drawbacks such as a strong pungent odor and bleaching of dyed clothing. In recent years, it does not have the drawbacks seen in chlorine bleach,
Demand for soda percarbonate, which has high solubility at low temperatures around room temperature, is increasing. The general method for producing soda percarbonate is to react sodium carbonate and hydrogen peroxide to obtain sodium percarbonate crystal powder using a reactive crystallization method, and then perform wet granulation and drying to form a product. be. Generally, when soda percarbonate is left in the air, it absorbs moisture and the active oxygen concentration of the sodium percarbonate decreases, so that it no longer exhibits a sufficient bleaching effect when used. For this purpose, inorganic compounds such as water glass, phosphates, silicates, magnesium salts are added to the reaction product, or organic compounds such as polyethylene glycol, starch, CMC, etc.
Alternatively, it is known to spray or coat the granules with the above-mentioned inorganic compounds. However, although the granular soda percarbonate obtained by such a method has superior solubility compared to sodium perborate, its solubility at room temperature is not so great and it cannot be used in normal household use. It takes a long time to dissolve, and therefore, it has the disadvantage that it cannot exhibit sufficient bleaching effect. In an attempt to improve these drawbacks of soda percarbonate, granulated and dried soda percarbonate was reused at 75~
There is a method of imparting quick solubility by heating in a temperature range of 135°C for a specific period of time. Although it is possible to obtain sodium percarbonate having relatively good solubility according to this method, heating for a long time at a relatively high temperature is required to obtain a product with satisfactory rapid dissolution. however,
Processing under such conditions causes the active oxygen possessed by sodium percarbonate to be lost through decomposition, resulting in a fatal defect in that the active oxygen content of the resulting product is low, although it becomes quickly soluble. have In addition, from an industrial perspective, a heating device other than a dryer is required, which is a big disadvantage. In view of the above points, and as a result of various studies, the present inventors have found that inorganic compounds conventionally used as stabilizers, such as water glass and silicates, can be dissolved in water. As a result of studying the properties, we found that when the above inorganic compound is added to sodium percarbonate as an aqueous solution or dispersion and wet granulated, the added inorganic compound gels and is deposited on the particles during the granulation process. but,
It was discovered that the gelation rate has a very important relationship with the water solubility of the granulated and dried granulated sodium percarbonate, and also that the type and combination of additives are extremely important. Based on this finding, the present invention was completed. The object of the present invention is to have excellent solubility in water;
The object of the present invention is to provide a granular soda percarbonate having stability. In the present invention, when powdered soda percarbonate is granulated, at least one selected from silicate hydrosol, an alkali or alkaline earth metal salt of silicic acid, or hydrated aluminum oxide hydrosol and orthophosphoric acid are added to the sodium percarbonate. , ortho- or meta-, boric acid, or at least one selected from sodium salts of organic polycarboxylic acids selected from citric acid, succinic acid, and tartaric acid. Regarding manufacturing methods. Silicic acid hydrosol or alkali or alkaline earth metal salt of silicic acid or hydrated aluminum oxide hydrosol used in the present invention and orthophosphoric acid, ortho or metaboric acid, citric acid,
Each sodium salt of an organic polycarboxylic acid selected from succinic acid and tartaric acid may be hereinafter referred to as an additive, and "silicic acid hydrosol or silicate or hydrated aluminum oxide hydrosol" is the first group of additives. , "respective sodium salts of orthophosphoric acid, ortho- or metaboric acid, or organic polyhydric carboxylic acids selected from citric acid, succinic acid, and tartaric acid" are referred to as the second group of additives. The first group of additives used in the present invention, alkali or alkaline earth metal salts of silicic acid, include commercially available No. 1 to No. 3 water glass, potassium silicate, lithium silicate, magnesium silicate, and powdered silicate. selected from sodium. Silicate hydrosol is also known as colloidal silica or silica sol, and is a water dispersion of silicon oxide with a particle size of 10 to 100 mμ. (manufactured by). Hydrous aluminum oxide hydrosol is also called colloidal alumina or alumina sol, and is an amorphous aluminum oxide hydrosol (commercially available products include, for example, alumina sol). The silicate hydrosol or hydrated aluminum oxide hydrosol usually has a content of 1 to 30%.
Concentrations are used, and compared to soda percarbonate,
It is added as SiO 2 or Al 2 O 3 in a range of 0.01 to 0.5% by weight. Among the above silicates, commercially available No. 1 to No. 3 water glasses are used in concentrations of 1 to 25%, and other potassium silicate, lithium silicate, magnesium silicate, and powdered sodium silicate are used. A concentration of 1 to 20% is used, and SiO 2 is added in a range of 0.01 to 0.5% by weight based on sodium percarbonate. The above magnesium silicate is 0.1-0.3%
is suitable. In the present invention, if the amount of the silicic acid hydrosol, alkali or alkaline earth metal salt of silicic acid, or hydrated aluminum oxide hydrosol added is greater than the above-mentioned amount, the solubility deteriorates, which is not preferable, and the purpose of the present invention is In order to fully achieve this and exhibit remarkable effects, it is preferable to add SiO 2 or Al 2 O 3 in an amount of 0.01 to 0.3% by weight. In the present invention, it is important that the first group of additives and the second group of additives are added at the same time during granulation. If the additives of the first group and the additives of the second group are added separately over time, the solubility will be significantly impaired, which is not preferable. Among the first group additives, lithium silicate and No. 1 to No. 3 water glass are particularly suitable among silicate hydrosol, hydrous aluminum oxide hydrosol, and silicate. The second group of additives used in the present invention, sodium salts of orthophosphoric acid, are monobasic sodium phosphate, dibasic sodium phosphate, and tribasic sodium phosphate. In addition, the sodium salts of organic polyhydric carboxylic acids are citric acid, succinic acid, and tartaric acid. These second group additives in the present invention function to adjust the pH of the first group additives during kneading and mixing, and to promote gelation of the first group additives. In the present invention, the sodium salt of orthophosphoric acid as the additive of the second group is usually used at a concentration of 5 to 30
%, and sodium salts of ortho or metaboric acid and sodium salts of organic polycarboxylic acids are usually used at concentrations of 1 to 10%, in order to fully exert the action of the second group of additives. It is usually used in a range of 0.01 to 0.5% (by weight) based on soda percarbonate. In the present invention, a wet granulation method is applied to granulate the sodium percarbonate, and any type of granulator used in the wet method can be used for the granulation, but the A well-performing granulator is preferred. During granulation, water is added as desired and kneaded and sludged so that the water content of the sodium percarbonate is approximately 10 to 15%. Examples of granulators used for granulation include a screw-extrusion type kneader with a screen with a hole diameter of 0.7 to 1.5 mm installed at the tip, or an extrusion type kneader that the applicant previously applied for. A Japanese-style granulator is used. The product obtained according to the present invention has excellent storage stability, good solubility in cold water, and foaming property when dissolved. The granular sodium percarbonate obtained according to the present invention can be incorporated into detergents and the like as an oxygen bleaching agent. The powdered soda percarbonate used in the present invention can be obtained by a method in which hydrogen peroxide is applied to an aqueous solution of sodium carbonate to crystallize crystals from the aqueous solution (crystallization method), or a solution in which a slurry is formed in an inert solvent and reacted. Although it is possible to use any method such as a dry method in which an aqueous hydrogen peroxide solution is added to powdered sodium carbonate, wet sodium percarbonate obtained by a crystallization method is generally preferred. It is. Reference example (Example of manufacturing soda percarbonate) Prepare a reaction mother liquor 30 containing 2% H 2 O 2 and 12% Na 2 CO 3 in a stainless steel reactor equipped with a stirrer, thermometer, and cooling jacket. . 2.5Kg of 60% H2O2 under stirring while keeping the mother liquor at a temperature of 15-20℃,
At the same time, 3.0 kg of Na 2 CO 3 was gradually added over about 1 hour, and after the addition, the mixture was stirred for 1 hour while maintaining the above temperature. The resulting slurry was separated into sodium percarbonate crystals and liquid using a centrifuge to obtain about 3.5 kg of wet sodium percarbonate. Next, examples of the present invention will be shown. Example The wet soda percarbonate powder obtained by the method of the reference example was fed to a kneader, and the additives of the first group and the second group of the present invention shown in the table were added at desired concentrations. Add a fixed amount and further increase the moisture content to 10~
A desired amount of water was added to give a concentration of 15%, and the mixture was kneaded for about 30 minutes. Next, the kneaded wet mass was granulated using a twin-screw extrusion type pelletizer (manufactured by Fuji Electric Industries, Ltd.), and the granulated product was dried using a fluidized fluidized dryer to obtain a product. The dissolution rate was measured for this product. To measure the dissolution rate, put pure water 1 at 25℃ in a beaker, turn a stirring bar with stirring blades of 40 mm in height and 25 mm in width at 250 rpm, add 5 g of sample, and measure the time until the particles completely disappear. This was done by measuring. In addition, 50 g of the obtained product was placed in a 100 ml beaker and left open for 30 days at 35°C and 80% RH, the amount of effective oxygen before and after the test was determined, and the effective oxygen reduction rate was determined according to the following formula. , storage stability was measured. (Available oxygen reduction rate) = (Initial effective oxygen) - (Available oxygen after 30 days) / (Initial effective oxygen) x 100 (%) The effective oxygen reduction rate is shown in Table 1. 【table】
Claims (1)
またはアルカリ土類金属塩または含水酸化アル
ミニウムヒドロゾルから選ばれた少なくとも一
種を過炭酸ソーダに対してSiO2またはAl2O3と
して0.01〜0.5％（重量）の量と、 (b) オルトリン酸、オルトまたはメタ硼酸または
クエン酸、コハク酸、酒石酸から選ばれる有機
多価カルボン酸のそれぞれのナトリウム塩から
選ばれた少なくとも一種を過炭酸ソーダに対し
て0.01〜0.5％（重量）の量とを 同時に過炭酸ソーダに添加し造粒することを特徴
とする過炭酸ソーダの製法。 ２ ケイ酸のアルカリまたはアルカリ土類金属塩
は１乃至３号水ガラス、ケイ酸カリウム、ケイ酸
リチウム、粉末ケイ酸ナトリウム、ケイ酸マグネ
シウムから選ばれる特許請求の範囲第１項記載の
方法。[Claims] 1. When granulating powdered soda percarbonate, (a) at least one selected from silicate hydrosol, alkali or alkaline earth metal salt of silicic acid, or hydrated aluminum oxide hydrosol is mixed with percarbonate. an amount of 0.01 to 0.5% (by weight) as SiO 2 or Al 2 O 3 relative to soda; and (b) an organic polycarboxylic acid selected from orthophosphoric acid, ortho or metaboric acid, or citric acid, succinic acid, tartaric acid. A method for producing soda percarbonate, which comprises simultaneously adding at least one selected from the respective sodium salts to soda percarbonate in an amount of 0.01 to 0.5% (by weight) based on the sodium percarbonate, and granulating the mixture. 2. The method according to claim 1, wherein the alkali or alkaline earth metal salt of silicic acid is selected from No. 1 to 3 water glass, potassium silicate, lithium silicate, powdered sodium silicate, and magnesium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17031181A JPS5874508A (en) | 1981-10-24 | 1981-10-24 | Manufacture of sodium percarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17031181A JPS5874508A (en) | 1981-10-24 | 1981-10-24 | Manufacture of sodium percarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5874508A JPS5874508A (en) | 1983-05-06 |
| JPH0139962B2 true JPH0139962B2 (en) | 1989-08-24 |
Family
ID=15902613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17031181A Granted JPS5874508A (en) | 1981-10-24 | 1981-10-24 | Manufacture of sodium percarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5874508A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1000328A5 (en) * | 1987-02-19 | 1988-10-25 | Interox Sa | PARTICLE STABILIZED peroxygen compounds, METHOD OF MAKING, AND COMPOSITION CONTAINING. |
| GB9226797D0 (en) * | 1992-12-23 | 1993-02-17 | Solvay Interox Ltd | Process for stabilisng alkali percarbonate particles,particles obtained thereby and washing and/or bleaching compositions containing them |
| GB9226796D0 (en) * | 1992-12-23 | 1993-02-17 | Solvay Interox Ltd | Process for stabilising alkali percarbonate particles,particles obtained thereby and washing and/or bleaching compositions containing them |
| DE69326833D1 (en) * | 1993-07-14 | 1999-11-25 | Procter & Gamble | Stabilized detergent compositions |
| SE9400653D0 (en) * | 1994-02-25 | 1994-02-25 | Eka Nobel Ab | Bleach |
| EP0745664B1 (en) * | 1994-02-25 | 1998-05-13 | Eka Chemicals AB | Bleaching agent |
| WO1996011252A1 (en) * | 1994-10-07 | 1996-04-18 | Eka Chemicals Ab | Bleaching agent |
| JP4506962B2 (en) * | 2004-11-05 | 2010-07-21 | 三菱瓦斯化学株式会社 | Sodium percarbonate particles with excellent foam solubility |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4969581A (en) * | 1972-08-31 | 1974-07-05 | ||
| US4179394A (en) * | 1977-01-11 | 1979-12-18 | Peroxid-Chemie Gmbh | Process for improving the storage stability of alkali persalts |
-
1981
- 1981-10-24 JP JP17031181A patent/JPS5874508A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4969581A (en) * | 1972-08-31 | 1974-07-05 | ||
| US4179394A (en) * | 1977-01-11 | 1979-12-18 | Peroxid-Chemie Gmbh | Process for improving the storage stability of alkali persalts |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5874508A (en) | 1983-05-06 |
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