JP2001515831A - Stable supersaturated solution of sodium perborate and its use in producing stabilized particles of sodium percarbonate - Google Patents
Stable supersaturated solution of sodium perborate and its use in producing stabilized particles of sodium percarbonateInfo
- Publication number
- JP2001515831A JP2001515831A JP2000510668A JP2000510668A JP2001515831A JP 2001515831 A JP2001515831 A JP 2001515831A JP 2000510668 A JP2000510668 A JP 2000510668A JP 2000510668 A JP2000510668 A JP 2000510668A JP 2001515831 A JP2001515831 A JP 2001515831A
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- particles
- weight
- supersaturated solution
- sodium percarbonate
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 41
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 229940045872 sodium percarbonate Drugs 0.000 title claims abstract description 38
- 229960001922 sodium perborate Drugs 0.000 title claims abstract description 23
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 239000004115 Sodium Silicate Substances 0.000 claims description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000012418 sodium perborate tetrahydrate Substances 0.000 claims description 8
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 18
- 230000000087 stabilizing effect Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- CPZRYQJPVUJHOS-UHFFFAOYSA-N [2-(2-phenylethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CCC1=CC=CC=C1 CPZRYQJPVUJHOS-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VSEWZMQQQHLHQT-UHFFFAOYSA-N manganese;sulfuric acid;hydrate Chemical compound O.[Mn].OS(O)(=O)=O VSEWZMQQQHLHQT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
- C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/12—Peroxyhydrates; Peroxyacids or salts thereof containing boron
- C01B15/123—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
(57)【要約】 本発明は、過ホウ酸ナトリウムの安定な過飽和水溶液及び、過炭酸ナトリウム粒子の安定化でのその使用に関する。 (57) [Summary] The present invention relates to a stable supersaturated aqueous solution of sodium perborate and its use in stabilizing sodium percarbonate particles.
Description
【０００１】[0001]
本発明は、過ホウ酸ナトリウムの安定な過飽和水溶液及び過炭酸ナトリウム粒
子の安定化におけるその使用に関する。The present invention relates to a stable supersaturated aqueous solution of sodium perborate and its use in stabilizing sodium percarbonate particles.
過炭酸ナトリウム（２Na2CO3・３H2O2）粒子は、洗剤、漂白剤及び界面活性剤
における活性酸素化合物として使用される。周囲が暖かく湿った場所及び洗剤及
び界面活性剤の様々な成分の存在下での貯蔵中でのこれらの粒子の不適当な安定
性の故に、過炭酸ナトリウム粒子は安定化されなければならない。過炭酸ナトリ
ウムを安定化する為に通常採用される方法は、それらを安定化する作用を持つ成
分のカバーで被覆する事から成る。 過ホウ酸ナトリウムをベースとした安定化作用を持つ成分のカバーの使用は、
多くの研究の対象を形成した。この様に、WO９４２０４１３は、過炭酸ナトリウ
ム粒子を、１５〜４５０ｇ／ｌの割合の過ホウ酸ナトリウム水和物から成る水溶
液又は懸濁液と一緒に噴霧する事による過炭酸ナトリウム粒子の安定化方法を開
示している。然しながら、この方法は、水中におけるその安定性よりも多い過ホ
ウ酸ナトリウム水和物含有量に対して欠点を示す。これは、過炭酸ナトリウム粒
子の均一且つ有効な被覆が過ホウ酸ナトリウム懸濁液では達成できない為である
。Sodium percarbonate (2Na 2 CO 3 .3H 2 O 2 ) particles are used as active oxygen compounds in detergents, bleaches and surfactants. Due to the improper stability of these particles in a warm and moist environment and in the presence of various components of detergents and surfactants, the sodium percarbonate particles must be stabilized. A commonly employed method for stabilizing sodium percarbonate consists of coating it with a cover of a component which acts to stabilize them. The use of a cover of ingredients with a stabilizing action based on sodium perborate,
Formed the subject of many studies. Thus, WO 9420413 describes a method for stabilizing sodium percarbonate particles by spraying sodium percarbonate particles together with an aqueous solution or suspension consisting of sodium perborate hydrate at a rate of 15 to 450 g / l. Is disclosed. However, this method shows disadvantages for sodium perborate hydrate content which is higher than its stability in water. This is because uniform and effective coating of sodium percarbonate particles cannot be achieved with a sodium perborate suspension.
【０００２】 更に、FR２，４１９、２５２は、過炭酸ナトリウム粒子を、数工程で、過ホウ
酸ナトリウムの希釈水溶液及び珪酸ナトリウム溶液と一緒に噴霧する事による過
炭酸ナトリウムの安定化粒子の製造方法を開示する。この方法は、幾つかの中間
噴霧と乾燥工程を必要とする欠点を示す。更に、この様に安定化された過炭酸ナ
トリウムの粒子は、極めて不満足な安定性を有し、望ましくない不溶解成分の割
合をもたらす。Further, FR 2,419,252 discloses a method for producing stabilized sodium percarbonate particles by spraying sodium percarbonate particles in several steps together with a dilute aqueous solution of sodium perborate and a sodium silicate solution. Is disclosed. This method has the disadvantage of requiring several intermediate spraying and drying steps. Furthermore, the particles of sodium percarbonate stabilized in this way have a very unsatisfactory stability, leading to a proportion of undesired insoluble components.
【０００３】[0003]
【発明が解決しようとする課題】 過ホウ酸ナトリウムの安定な過飽和溶液の発見のお陰で、本願出願人は、上記
の欠点を示す事のない過炭酸ナトリウムの安定化された粒子の製造方法を見出し
た。SUMMARY OF THE INVENTION Thanks to the discovery of a stable supersaturated solution of sodium perborate, Applicants have developed a process for producing stabilized particles of sodium percarbonate that does not exhibit the above disadvantages. I found it.
【０００４】[0004]
メタホウ酸ナトリウム、過酸化水素及び珪酸ナトリウムから調製される本発明
の過ホウ酸ナトリウムの安定な過飽和水溶液は、４〜４９質量％、好ましくは９
〜４９質量％の過ホウ酸ナトリウム４水和物及び、含まれるメタホウ酸ナトリウ
ム／珪酸ナトリウムの質量比が０．６〜７．３、好ましくは０．９〜３である量
の珪酸ナトリウムとから成る。The stable supersaturated aqueous solution of sodium perborate of the present invention prepared from sodium metaborate, hydrogen peroxide and sodium silicate is 4-49% by weight, preferably 9% by weight.
From about 49% by weight of sodium perborate tetrahydrate and an amount of sodium silicate in which the weight ratio of sodium metaborate / sodium silicate is 0.6 to 7.3, preferably 0.9 to 3; Become.
その様な溶液は、メタホウ酸ナトリウム、珪酸ナトリウム及び過酸化水素水溶
液を、約１：１のメタホウ酸ナトリウム：過酸化水素のモル比で混合する事によ
って得る事が出来る。 その様な溶液は、珪酸ナトリウムを含有するメタホウ酸ナトリウム水溶液を過
酸化水素水溶液と接触させる事によって調製する事が好ましい。有利に使用され
る水溶液は、メタホウ酸ナトリウムのモル濃度と同じ過酸化水素のモル濃度を有
するものである。Such a solution can be obtained by mixing sodium metaborate, sodium silicate and aqueous hydrogen peroxide in a molar ratio of sodium metaborate: hydrogen peroxide of about 1: 1. Such a solution is preferably prepared by contacting an aqueous solution of sodium metaborate containing sodium silicate with an aqueous solution of hydrogen peroxide. The aqueous solution advantageously used is one having a molar concentration of hydrogen peroxide which is the same as the molar concentration of sodium metaborate.
【０００５】 様々な成分が、反応器又は混合機（攪拌バッチ反応器、スタティックミキサー
）で混合する事が出来る。 この過飽和水溶液は、広範囲の温度内で、一般的には１５〜５０℃、好ましく
は、２０〜４０℃で安定である。 与えられる溶媒中での固体化合物の溶解度は、与えられた温度で、一定容量の
溶媒に溶解する事の出来るこの固体の最大量（質量又はモル）で表される。 溶質の濃度が、同じ温度での溶解度に相当する濃度の値よりも大きい時、その
溶液は過飽和に成ったと言う。その様な溶液は、溶質の濃度がその溶解度に達す
るまで、過剰の溶質を固体形態で放出しながら変化する。次いで、結晶化又は沈
殿が生起する。 過飽和は、溶解度からの分岐を表し、溶質の濃度対溶解度での濃度の比として
定義する事が出来る。 過飽和溶液は、固体形態での過剰溶質の放出に対して遅れ時間を示す事が出来
る。この遅れ時間は、潜在期間又は誘導期間である。 従って、本願出願人は、珪酸ナトリウムが、上記で示した割合で存在すると、
過ホウ酸ナトリウムの過飽和水溶液の潜在期間を大いに増加する事が出来、従っ
て、過ホウ酸ナトリウムの過飽和溶液を安定化し、様々な用途、例えば、特に、
過炭酸ナトリウムの安定化粒子の製造でのその処理を促進させる事が出来る事を
見出した。[0005] The various components can be mixed in a reactor or a mixer (stirred batch reactor, static mixer). This supersaturated aqueous solution is stable within a wide range of temperatures, generally at 15 to 50C, preferably at 20 to 40C. The solubility of a solid compound in a given solvent is expressed as the maximum amount (mass or mole) of this solid that can be dissolved in a given volume of solvent at a given temperature. When the concentration of the solute is greater than the value of the concentration corresponding to the solubility at the same temperature, the solution is said to have become supersaturated. Such solutions change releasing excess solute in solid form until the solute concentration reaches its solubility. Then crystallization or precipitation occurs. Supersaturation represents a branch from solubility and can be defined as the ratio of solute concentration to concentration in solubility. Supersaturated solutions can exhibit a lag time for the release of excess solute in solid form. This delay time is the latency period or the induction period. Therefore, the applicant of the present application, when sodium silicate is present in the proportions shown above,
The latency period of a supersaturated aqueous solution of sodium perborate can be greatly increased, thus stabilizing the supersaturated solution of sodium perborate, for various applications, for example,
It has been found that the treatment in the production of stabilized particles of sodium percarbonate can be accelerated.
【０００６】 本発明のその他の目的は、過炭酸ナトリウムで造られた芯と、過ホウ酸ナトリ
ウム４水和物と珪酸ナトリウムとから成るカバーとから成る過炭酸ナトリウムの
安定化粒子の製造方法である。この方法は、製造された直後の過炭酸ナトリウム
の湿潤粒子が、或いは、任意に、その後の乾燥工程によって製造された過炭酸ナ
トリウムの粒子が、上記の過ホウ酸ナトリウムの安定な過飽和水溶液と一緒に噴
霧される事を特徴とする。 過炭酸ナトリウムの安定化粒子の製造方法にとって極めて適した本発明の過ホ
ウ酸ナトリウムの安定な過飽和水溶液は、被覆を行うのに必要とされる時間より
も長い潜在期間を有する。１５分より長い潜在期間が好ましい。２０分より長い
潜在期間は、特に好ましい。 過ホウ酸ナトリウムの過飽和溶液の使用は、過炭酸ナトリウム粒子を均一に湿
潤させる事が出来るが、懸濁液は、それらの粒子の表面での拡散を一層困難なも
のとする。更に、高度に過飽和な溶液は、被覆中の水の量の導入を少なくし、従
って、局所的固化又はケーキング、溶解又は再結晶化の問題を避ける事が出来る
利点を示す。 更に、過ホウ酸ナトリウムの高度に過飽和な溶液によって導入されるこの少量
の水は、製造後直ちに得られる過炭酸ナトリウムの湿潤粒子に存在する水を相殺
する事が出来る。この様に、０〜１０質量％、好ましくは０〜７質量％の水分含
有量を有する過炭酸ナトリウム粒子を安定化する事が出来る。 過炭酸ナトリウムの乾燥粒子の１００ｇ当りに導入される水の量は、一般に、
３〜１５ｇ、好ましくは３〜１２ｇである。Another object of the present invention is a method for producing stabilized sodium percarbonate particles comprising a core made of sodium percarbonate and a cover comprising sodium perborate tetrahydrate and sodium silicate. is there. This method involves combining wet particles of sodium percarbonate immediately after manufacture, or, optionally, particles of sodium percarbonate produced by a subsequent drying step, with the stable supersaturated aqueous solution of sodium perborate described above. It is characterized by being sprayed. The stable supersaturated aqueous solution of sodium perborate of the present invention, which is highly suitable for the method of producing stabilized particles of sodium percarbonate, has a longer life time than the time required to perform the coating. A latency period of more than 15 minutes is preferred. A latency period of more than 20 minutes is particularly preferred. The use of a supersaturated solution of sodium perborate can uniformly wet the sodium percarbonate particles, but the suspension makes the diffusion of those particles at the surface more difficult. In addition, highly supersaturated solutions offer the advantage that less water is introduced into the coating, thus avoiding the problem of local solidification or caking, dissolution or recrystallization. Furthermore, this small amount of water introduced by the highly supersaturated solution of sodium perborate can offset the water present in the wet particles of sodium percarbonate obtained immediately after production. Thus, sodium percarbonate particles having a water content of 0 to 10% by mass, preferably 0 to 7% by mass can be stabilized. The amount of water introduced per 100 g of dry particles of sodium percarbonate is generally
It is 3 to 15 g, preferably 3 to 12 g.
【０００７】 安定化されるべき過炭酸ナトリウムは、乾燥経路又は湿潤経路の何れかで炭酸
ナトリウムと過酸化水素水溶液から調製される。湿潤経路が有利に選択される。 過ホウ酸ナトリウムの過飽和溶液での過炭酸ナトリウム粒子の被覆は、機械的
又は遠心分離混合機又は濾過装置で行う事が出来る。過炭酸ナトリウム粒子を安
定化する為に使用される過ホウ酸ナトリウムの過飽和溶液の量は、広範囲に変え
る事が出来る。一般的には、過炭酸ナトリウムの乾燥粒子の１ｋｇ当り２５〜６
００ｇ、好ましくは５０〜３００ｇである。 この様に安定化された過炭酸ナトリウムの粒子は、次いで、流動床乾燥機で、
３０〜８０℃、好ましくは５０〜７０℃で乾燥される。 本発明の範囲は、乾燥が噴霧工程と共に同時に行われる場合を超えるものでは
ない。 この様にして得られた過炭酸ナトリウムの粒子の安定性は、３０℃で、相対湿
度８０％のオーブン中に一週間置いたサンプルの活性酸素の損失を決定する事に
よって評価される。 この様にして安定化されたこれらの粒子の溶解速度は、１５℃の水１リットル
中に導入された過炭酸ナトリウム粒子２ｇの９０％の溶解が得られるのに必要と
される時間によって決定される。[0007] The sodium percarbonate to be stabilized is prepared from sodium carbonate and an aqueous hydrogen peroxide solution by either a dry or wet route. The wetting route is advantageously chosen. Coating of the sodium percarbonate particles with a supersaturated solution of sodium perborate can be performed mechanically or with a centrifugal mixer or filtration device. The amount of supersaturated solution of sodium perborate used to stabilize the sodium percarbonate particles can vary widely. Generally, 25-6 per kg of dry particles of sodium percarbonate
00 g, preferably 50 to 300 g. The sodium percarbonate particles thus stabilized are then passed through a fluid bed dryer.
It is dried at 30 to 80C, preferably at 50 to 70C. The scope of the present invention does not extend beyond when drying is performed simultaneously with the spraying step. The stability of the sodium percarbonate particles obtained in this way is evaluated by determining the loss of active oxygen of the samples placed in an oven at 30 ° C. and 80% relative humidity for one week. The dissolution rate of these particles stabilized in this way is determined by the time required to obtain a 90% dissolution of 2 g of sodium percarbonate particles introduced in one liter of water at 15 ° C. You.
【０００８】[0008]
〔実施例１−９〕特に指示しない限り、過酸化水素水溶液は７０質量％の過酸化
水素を含む。 使用された珪酸ナトリウムは、ローンプーラン社製の７N34タイプのもので、 固形分含有量が３４％（SiO226.2質量%、及びNa2O７．８質量％）である。 水溶液Aは、３３％メタホウ酸ナトリウム溶液、７N34珪酸ナトリウム及び水か
ら調製した。又、水溶液Bが調製され、これは、溶液Aのメタホウ酸ナトリウムの
濃度に対して同じ過酸化水素のモル濃度を有した。水溶液Aを、次いで水溶液Bを
、２３℃にサーモスタット制御された攪拌されている２５ｃｍ3の反応器に導入 した。水溶液Ｂの導入の最後をゼロ時間として、過ホウ酸ナトリウム４水和物の
最初の結晶が現れるのに必要とされた時間（又は潜在期間）を視覚的に測定した
。[Example 1-9] Unless otherwise indicated, the aqueous hydrogen peroxide solution contains 70% by mass of hydrogen peroxide. The sodium silicate used is a 7N34 type manufactured by Lawn Poulin with a solid content of 34% (26.2% by mass of SiO 2 and 7.8% by mass of Na 2 O). Aqueous solution A was prepared from a 33% sodium metaborate solution, 7N34 sodium silicate and water. Aqueous solution B was also prepared, which had the same molar concentration of hydrogen peroxide as the concentration of sodium metaborate in solution A. Aqueous solution A and then aqueous solution B were introduced into a stirred 25 cm 3 reactor thermostat controlled at 23 ° C. The time (or latency) required for the first crystals of sodium perborate tetrahydrate to appear was determined visually, with the end of introduction of aqueous solution B as zero hour.
【０００９】[0009]
【表１】 表１ [Table 1] Table 1
【００１０】 活性酸素の定量的決定 使用された試薬：Ｎ／１０過マンガン酸カリウム（Ｋ） ：硫酸（ＮＦＴ規準７３．７０３） ５０ｇの硫酸アルミニウム、５ｇの硝酸ビスマス５水和物及び５ｇの硫酸マン
ガン１水和物を５Ｎ硫酸１リットル中に溶解して調製した。 方法：２ｇの生成物を容量フラスコで正確に計量し、次いで、１００ｍｌの脱
塩水をそれに添加し、続いて、２５ｍｌの硫酸（ＮＦＴ規準７３．７０３）を添
加した。この溶液を、引き続き、持続的なピンク色が得られるまで過マンガン酸
カリウムで滴定した。 テストサンプル質量をＰｇ、使用された過マンガン酸カリウムの容量をｎｍｌ
とした場合、活性酸素の割合は次式で与えられる： 活性酸素（％）＝０．８×（（Ｋ×ｎ）／Ｐ） Ｋ＝０．１Ｎとして、活性酸素（％）＝０．０８ｎ／Ｐ 活性酸素の損失は、２ｇに関する初期活性酸素と、最終質量に関する最終活性
酸素との間の差として定義され、初期含有量の割合として表された。 〔実施例１０〕 以下の性質を有する過炭酸ナトリウムの乾燥粒子９００ｇを、５リットルのス
テンレススチールの機械的混合機（Controlab社製、ＥＮ規準１９６１）に導入 した： Ｈ2Ｏ2（質量％）＝３１ Ｎａ2ＣＯ3（質量％）＝６５．４ 見掛け嵩比重＝０．８９ｇ／ｃｍ3 溶解速度＝６４秒 平均粒径＝８００μｍ １０．６ｇのメタホウ酸ナトリウム、７．８ｇの過酸化水素水溶液、１６．９
ｇの珪酸ナトリウム７Ｎ３４及び６７．５ｇの脱塩水から調製した過ホウ酸ナト
リウムの過飽和水溶液を、次いで、１６分掛けて、約１４０回転／分で攪拌しな
がら導入した。この様に被覆された過炭酸ナトリウム粒子を、引続いて、約５５
℃の流動床で乾燥した。乾燥工程の終りで、回収された過炭酸ナトリウム粒子の
量は９２２ｇであり、この粒子は次の性質を示した： Ｈ2Ｏ2（質量％）＝３１．１ Ｎａ2ＣＯ3（質量％）＝６４ 見掛け嵩比重＝０．９５ｇ／ｃｍ3 溶解速度＝７６秒 平均粒径＝７５０μｍ 活性酸素損失＝０．６％ Quantitative determination of active oxygen Reagents used: N / 10 potassium permanganate (K): sulfuric acid (NFT standard 73.703) 50 g of aluminum sulfate, 5 g of bismuth nitrate pentahydrate and 5 g of sulfuric acid Manganese monohydrate was prepared by dissolving in 1 liter of 5N sulfuric acid. Method : 2 g of product were accurately weighed in a volumetric flask, then 100 ml of demineralized water were added to it, followed by 25 ml of sulfuric acid (NFT standard 73.703). The solution was subsequently titrated with potassium permanganate until a persistent pink color was obtained. Test sample mass is Pg, volume of potassium permanganate used is nml
, The ratio of active oxygen is given by the following formula: active oxygen (%) = 0.8 × ((K × n) / P) Assuming K = 0.1N, active oxygen (%) = 0.08 / P Reactive oxygen loss was defined as the difference between the initial active oxygen for 2 g and the final active oxygen for the final mass, expressed as a percentage of the initial content. Example 10 900 g of dry particles of sodium percarbonate having the following properties were introduced into a 5 liter stainless steel mechanical mixer (manufactured by Controlab, EN standard 1961): H 2 O 2 (% by weight) = 31 Na 2 CO 3 (mass%) = 65.4 Apparent bulk specific gravity = 0.89 g / cm 3 Dissolution rate = 64 seconds Average particle size = 800 μm 10.6 g sodium metaborate, 7.8 g aqueous hydrogen peroxide , 16.9
g of sodium silicate 7N34 and a supersaturated aqueous solution of sodium perborate prepared from 67.5 g of demineralized water were then introduced over 16 minutes with stirring at about 140 rpm. The sodium percarbonate particles coated in this way are subsequently treated for about 55
Dried in a fluidized bed at ° C. At the end of the drying step, the amount of sodium percarbonate particles recovered was 922 g, which exhibited the following properties: H 2 O 2 (% by weight) = 31.1 Na 2 CO 3 (% by weight) = 64 Apparent bulk specific gravity = 0.95 g / cm 3 Dissolution rate = 76 seconds Average particle size = 750 μm Active oxygen loss = 0.6%
【００１１】 〔実施例１１〕（本発明の実施ではない） ５０μｍ以下の粒径を有する過ホウ酸ナトリウムの微粒子２１．６２ｇ、メタ
ホウ酸ナトリウム１．３２ｇ、１６．９ｇの珪酸ナトリウム７Ｎ３４、１．１４
ｇの過酸化水素水溶液及び６１．９４ｇの脱塩水で調製した以外は、実施例１０
と同様に行った。この様にして安定化された過炭酸ナトリウムの粒子は、次の通
りであった： Ｈ2Ｏ2（質量％）＝３１．１ Ｎａ2ＣＯ3（質量％）＝６３．９ 見掛け嵩比重＝０．９３ｇ／ｃｍ3 溶解速度＝８０秒 活性酸素損失＝１％Example 11 (Not to practice the present invention) 21.62 g of sodium perborate fine particles having a particle size of 50 μm or less, 1.32 g of sodium metaborate, 16.9 g of sodium silicate 7N34, 14
Example 10 except that it was prepared with 1 g of an aqueous hydrogen peroxide solution and 61.94 g of demineralized water.
The same was done. The sodium percarbonate particles stabilized in this way were as follows: H 2 O 2 (% by weight) = 31.1 Na 2 CO 3 (% by weight) = 63.9 Apparent bulk specific gravity = 0.93 g / cm 3 dissolution rate = 80 seconds Active oxygen loss = 1%
【００１２】 〔実施例１２〕 過ホウ酸ナトリウムの過飽和溶液の導入時間を４３分とし、この混合物を引続
いて更に３分間攪拌した以外は、実施例１０と同様に行った。Example 12 The procedure was as in Example 10, except that the introduction time of the supersaturated solution of sodium perborate was 43 minutes and the mixture was subsequently stirred for a further 3 minutes.
【表２】 表２ 〔実施例１３〕 被覆されるべき過炭酸ナトリウムが５％の水分含有量を有し、過ホウ酸ナトリ
ウムの過飽和溶液が、４３質量％の過ホウ酸ナトリムと、含まれるメタホウ酸ナ
トリウム／珪酸ナトリウムの質量比が実施例１０と同じである量の珪酸ナトリウ
ムを含む事以外は、実施例１０と同様に行った。 この様にして安定化された過炭酸ナトリウムの粒子は、実施例１０で得られた
ものと同じ性質を有していた。[Table 2] Table 2 Example 13 Sodium percarbonate to be coated has a water content of 5% and a supersaturated solution of sodium perborate contains 43% by weight of sodium perborate and contained sodium metaborate / sodium silicate Was performed in the same manner as in Example 10 except that the same mass ratio of sodium silicate was used as in Example 10. The sodium percarbonate particles thus stabilized had the same properties as those obtained in Example 10.
Claims (5)
調製される過ホウ酸ナトリウムの過飽和溶液であって、４〜４９質量％の過ホウ
酸ナトリウム４水和物と、含まれる該メタホウ酸ナトリウム／珪酸ナトリウムの
質量比が０．６〜７．３である量の珪酸ナトリウムとを含む事を特徴とする過飽
和溶液。1. A supersaturated solution of sodium perborate prepared from sodium metaborate, hydrogen peroxide and sodium silicate, comprising 4 to 49% by weight of sodium perborate tetrahydrate; A supersaturated solution comprising an amount of sodium silicate / sodium silicate having a mass ratio of 0.6 to 7.3.
該メタホウ酸ナトリウム／珪酸ナトリウムの質量比が０．６〜７．３である量の
珪酸ナトリウムとを含む、請求項１に記載の過飽和溶液。2. It comprises from 9 to 49% by weight of sodium perborate tetrahydrate and an amount of sodium silicate contained by weight of said sodium metaborate / sodium silicate of from 0.6 to 7.3. A supersaturated solution according to claim 1.
該メタホウ酸ナトリウム／珪酸ナトリウムの質量比が０．９〜３である量の珪酸
ナトリウムとを含む、請求項１に記載の過飽和溶液。3. The composition according to claim 1, comprising 9 to 49% by weight of sodium perborate tetrahydrate and sodium silicate in an amount by weight of from 0.9 to 3 of said sodium metaborate / sodium silicate. Item 4. A supersaturated solution according to Item 1.
該メタホウ酸ナトリウム／珪酸ナトリウムの質量比が０．９〜３である量の珪酸
ナトリウムとを含む、請求項１に記載の過飽和溶液。4. A composition comprising 4 to 49% by weight of sodium perborate tetrahydrate and sodium silicate in an amount by weight of from 0.9 to 3 of said sodium metaborate / sodium silicate. Item 4. A supersaturated solution according to Item 1.
物及び珪酸ナトリウムから成るカバーとから成る過炭酸ナトリウムの安定化粒子
の製造方法であって、製造された直後の過炭酸ナトリウムの湿潤粒子、或いは、
乾燥段階後に得られたそれらの粒子が、請求項１〜４の何れか一項に記載の過ホ
ウ酸ナトリウムの安定な過飽和溶液と一緒に噴霧される事を特徴とする方法。5. A method for producing stabilized sodium percarbonate particles comprising a core made of sodium percarbonate and a cover made of sodium perborate tetrahydrate and sodium silicate, comprising the steps of: Wet particles of sodium carbonate, or
A method characterized in that the particles obtained after the drying step are sprayed together with a stable supersaturated solution of sodium perborate according to any of the preceding claims.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR97/11094 | 1997-09-05 | ||
| FR9711094A FR2768140B1 (en) | 1997-09-05 | 1997-09-05 | STABLE SUPERSATURATED SODIUM PERBORATE SOLUTION AND ITS APPLICATION IN THE MANUFACTURE OF STABILIZED SODIUM PERCARBONATE PARTICLES |
| PCT/FR1998/001741 WO1999012848A1 (en) | 1997-09-05 | 1998-08-05 | Stable supersaturated sodium perborate solution and its use for making stabilised sodium percarbonate particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001515831A true JP2001515831A (en) | 2001-09-25 |
Family
ID=9510825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000510668A Pending JP2001515831A (en) | 1997-09-05 | 1998-08-05 | Stable supersaturated solution of sodium perborate and its use in producing stabilized particles of sodium percarbonate |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1023239A1 (en) |
| JP (1) | JP2001515831A (en) |
| KR (1) | KR100527255B1 (en) |
| CN (1) | CN1134374C (en) |
| AU (1) | AU747168B2 (en) |
| FR (1) | FR2768140B1 (en) |
| WO (1) | WO1999012848A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA06001401A (en) * | 2003-08-06 | 2006-05-19 | Nirmal Mulye | Pharmaceutical composition containing water soluble drug. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL265028A (en) * | 1961-05-19 | 1964-06-25 | ||
| US3984342A (en) * | 1973-11-23 | 1976-10-05 | Fmc Corporation | Process for agglomerating sodium carbonate peroxide |
| DE2810379C3 (en) * | 1978-03-10 | 1980-12-11 | Degussa Ag, 6000 Frankfurt | Process for the production of stabilized sodium percarbonate |
| US5328721A (en) * | 1992-07-30 | 1994-07-12 | Fmc Corporation | Process for manufacturing sodium carbonate perhydrate particles and coating them with sodium borosilicate |
| DE4311944A1 (en) * | 1993-04-10 | 1994-10-13 | Degussa | Coated sodium percarbonate particles, process for their preparation and detergent, cleaning and bleaching compositions containing them |
-
1997
- 1997-09-05 FR FR9711094A patent/FR2768140B1/en not_active Expired - Fee Related
-
1998
- 1998-08-05 WO PCT/FR1998/001741 patent/WO1999012848A1/en not_active Application Discontinuation
- 1998-08-05 JP JP2000510668A patent/JP2001515831A/en active Pending
- 1998-08-05 CN CNB988105403A patent/CN1134374C/en not_active Expired - Fee Related
- 1998-08-05 EP EP98941541A patent/EP1023239A1/en not_active Withdrawn
- 1998-08-05 AU AU89881/98A patent/AU747168B2/en not_active Ceased
- 1998-08-05 KR KR10-2000-7002365A patent/KR100527255B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2768140A1 (en) | 1999-03-12 |
| AU8988198A (en) | 1999-03-29 |
| KR100527255B1 (en) | 2005-11-09 |
| AU747168B2 (en) | 2002-05-09 |
| KR20010023711A (en) | 2001-03-26 |
| FR2768140B1 (en) | 1999-10-08 |
| CN1134374C (en) | 2004-01-14 |
| CN1277593A (en) | 2000-12-20 |
| EP1023239A1 (en) | 2000-08-02 |
| WO1999012848A1 (en) | 1999-03-18 |
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