CN100441499C

CN100441499C - Method of preparing stable chloride dioxide

Info

Publication number: CN100441499C
Application number: CNB031177573A
Authority: CN
Inventors: 谢承卫; 高弦
Original assignee: Guizhou University
Current assignee: Guizhou University
Priority date: 2003-04-22
Filing date: 2003-04-22
Publication date: 2008-12-10
Anticipated expiration: 2023-04-22
Also published as: CN1454837A

Abstract

The present invention relates to a method for producing stable chlorine dioxide, which provides a new method for preparing stable chlorine dioxide. The method overcomes the defects of the existing method of short storage time and easy decomposition failure. The method causes chlorine dioxide gas to be prepared into the stable chlorine dioxide solution with high stability and long storage term and can simultaneously prepare a stable chlorite solution system. When the method is used, an acid activating agent is added into a stabilizing system, and the chlorine dioxide gas can be generated. The present invention adopts sodium carbonate and hydrogen peroxide as stable basic components of the chlorine dioxide, a series of stabilizing agents are added, the chlorine dioxide is adsorbed, the stable chlorine dioxide solution is prepared, or the sodium carbonate is used for regulating the pH value of the solution to 7 to 8 in the chlorite solution, the hydrogen peroxide and a stabilizing agent are added to prepare the stable chlorite solution, and the stabilizing agent is composed of a metallic ion compounding agent, a medium regulating and buffering agent and other modifying agents. The present invention can be widely used for the sterilization, the disinfection and the preservation of every industry or trade.

Description

A kind of method for preparing stabilized chlorine dioxide

Technical field

The present invention relates to a kind of stable sterilization, sterilization, preservation agent production method, particularly relate to the production method of stability chlorine dioxide.

Background technology

Stability chlorine dioxide is the excellent property of generally acknowledging in the world, disinfection sanitizer, deodorizing mould inhibitor, food preservative, water quality cleansing agent and the efficient SYNTHETIC OPTICAL WHITNER of highly effective and safe.The stability problem of stable ClO 2 solution is one of key issue of widening its use range and result of use.The preparation of stable ClO 2 solution, normally make with the stabilizing solution absorption dioxide peroxide of SPC-D, Sodium peroxoborate, yellow soda ash and hydrogen peroxide preparation, adopt the stable ClO 2 solution of above absorption liquid preparation, in the Japanese Patent JP58129256 that is in the patent No., point out in the patent of the quantitative analysis method of the stability chlorine dioxide of Japan Tokuyama soda company, adopted alkaline peroxide such as SPC-D as stablizer.But this method storage time is shorter, easily decomposition failure.Patent of invention GB1143604 has proposed a kind of new method, and it is oxygenant with the oxymuriate, in acidic medium, with methanol aqueous solution is that reductive agent reacts, temperature of reaction is lower than 50 ℃, and the operation feed way is to drip continuously, and reaction medium acidity is 20-25%.After chlorine dioxide took place, the method that adopts the stopping composition physical adsorption and utilize a part of stoste chemical purification to combine was carried out gas sweetening, adopted sheet alkali, boric acid, hydrogen peroxide mixing that the chlorine dioxide after purifying is stablized and absorbed again and got final product.This invention material reasonable ratio, the raw material availability height, reacting balance carries out under normal pressure.

Summary of the invention

The invention provides a kind of new preparation stabilized chlorine dioxide novel method, chlorine dioxide can be prepared into the stable ClO 2 solution that has good stability, can standing storage; The present invention can also prepare long-time stable chlorite solution's system.Stable ClO 2 solution or stable chlorite solution's system with the present invention's preparation, has good stability, can preserve for a long time, in use, in stabilising system, add the acids activator, chlorine dioxide can be produced, sterilization, the sterilization, fresh-keeping of all trades and professions can be widely used for.

Usually stability chlorine dioxide is to make with Rong Ye E Annex II chlorine monoxide such as SPC-D or Sodium peroxoborate or yellow soda ash and hydrogen peroxide, and stationary phase is shorter, easy decomposition failure.

The present invention be with yellow soda ash and hydrogen peroxide as the stable basal component of dioxide peroxide, make hydrogen peroxide excessive simultaneously, and add a series of stabilizer of hydrogen peroxide and make.Hydrogen peroxide plays keying action to the stability of stability chlorine dioxide.Peroxidation Hydrogen Energy and dioxide peroxide form title complex effectively or form supramolecular aggregation by hydrogen bond, intermolecular forces in the aqueous solution, the energy of whole system is reduced, excessive peroxidation Hydrogen Energy maintenance system is in a higher well-oxygenated environment simultaneously, thereby the strong oxidizing property of dioxide peroxide has been evened up, that is to say that dioxide peroxide is stabilized in this environment.Stable peroxide hydrogen becomes the key of stablizing whole dioxide peroxide system.As long as stable peroxide hydrogen just can be stablized whole system effectively.

The hydrogen peroxide instability is subjected to the influence of transition metal ion in light, heat, medium potential of hydrogen, the medium, is easy to decompose.At the influence factor of these several aspects, the present invention adopts the method for adding following stablizer to come stable peroxide hydrogen, thus stabilizing chlorine dioxide, chlorite solution's system.

The stabilizer type of using always has:

Metal ion Synergist S-421 95: EDTA, EDTA ^4-, polyacrylamide, oxalate, tartrate etc.

Medium is adjusted buffer reagent: silicate, hexametaphosphate, pyrophosphate salt, hydrophosphate, dihydrogen phosphate, borate etc.

Other adjusts agent: glycerol, trolamine, oxine, carboxymethyl cellulose etc.

Decapacitation of the present invention outside the stabilizing chlorine dioxide, also can be stablized chlorite solution's system well well, obtains long-time stable chlorite solution.Preparing stable chlorite solution is to realize by following steps:

In certain density chlorite solution, adjust solution pH value to 7～8 with yellow soda ash, add hydrogen peroxide and stablizer, stablizer carries out compatibility as required from mentioned reagent, amount of hydrogen peroxide is 5%～10% of stability chlorine dioxide or a chlorite amount weight percent among this chlorite solution, the hydrogen peroxide weight percent concentration is 30%, and the usage quantity of stabilizer of hydrogen peroxide is 0.5%～5% of an amount of hydrogen peroxide weight percent.

When use need be emitted dioxide peroxide, adjust solution to acidity with acids and can produce chlorine dioxide.

Concentration expressed in percentage by weight with the present invention's preparation is that 2%～5% stable ClO 2 solution or concentration expressed in percentage by weight are 2%～30% stable chlorite solution's system, has good stability, can preserve for a long time, in use, in stabilising system, add the acids activator, chlorine dioxide can be produced, sterilization, the sterilization, fresh-keeping of every profession and trade can be widely used for.

Embodiment

1, in the saturated aqueous solution that 100 gram yellow soda ash are made, adding the 55ml concentration expressed in percentage by weight is 30% hydrogen peroxide, (this stablizer weight percent consists of 5 gram stabilizer of hydrogen peroxide: water glass 40%, trisodium phosphate 30%, Sodium hexametaphosphate 99 5%, trolamine 5%, EDTA 10%, oxine 10%), stirring action is after 30 minutes, be diluted to 500ml and absorb dioxide peroxide, prepare concentration and be 5% stable ClO 2 solution as absorption liquid.Prepared stable ClO 2 solution good stability can be preserved for a long time, activates with acidic activator during use, can produce chlorine dioxide.2,8% stable chlorite water solution system: in the chlorite solution of 500ml8%, the aqueous hydrogen peroxide solution 4ml of adding 30%, add glycerol (polyvalent alcohol) 1 gram, add 0.5 gram stablizer, the stablizer weight percent consists of: water glass 50%, Sodium hexametaphosphate 99 20%, Sodium Tetraborate 10%, EDTA5%, trolamine 5%, oxine 10%.Adjust medium PH to 7～8 with yellow soda ash, make stable chlorite solution's system of 8%.Gained chlorite solution good stability can be preserved for a long time, activates with acidic activator during use, can produce chlorine dioxide.

The analytical procedure of dioxide peroxide adopts iodimetry,iodometry to carry out in the stabilizing solution dioxide peroxide, we have carried out 30 days stability and 12 months stability mensuration to the stable ClO 2 solution of preparation, stable ClO 2 solution with this method preparation, stability better, naturally after depositing 1 year, the effective concentration of its dioxide peroxide still can reach about 70% of original content.Its 30 days stability and 12 months stability are measured the stability test data plot and are seen Figure of description.

Description of drawings

Fig. 1 is 30 days stability test figure of Chlorine Dioxide Steady Liquor

Fig. 2 is 12 months stability test figure of Chlorine Dioxide Steady Liquor

Claims

1, a kind of method for preparing stabilized chlorine dioxide, it is the stable basal component of dioxide peroxide that this method adopts with yellow soda ash and hydrogen peroxide, and adding stablizer, absorb chlorine dioxide and make stable ClO 2 solution, or in the chlorite solution, adjust the solution pH value to 7-8 with yellow soda ash, add hydrogen peroxide and stablizer and make stable chlorite solution, it is characterized in that in the formed solution, amount of hydrogen peroxide is the 5%-10% of stability chlorine dioxide or chlorite solution's weight percent, the stablizer usage quantity is the 0.5%-5% of hydrogen peroxide weight percent, and stablizer is made up of following substances in percentage by weight:

Silicate 40%-50%;

One or more 20%-30% in hexametaphosphate, pyrophosphate salt, hydrophosphate, dihydrogen phosphate, the borate;

Sodium Tetraborate 5%-10%;

EDTA, EDTA ^4-Or polyacrylamide 5%-10%;

Trolamine 5%-10%;

Oxine or carboxymethyl cellulose 5%-15%.

2, the described method of claim 1 is characterized in that the stablizer in this method is made up of by following weight percent following material:

Water glass 50%;

Sodium hexametaphosphate 99 20%;

Sodium Tetraborate 10%;

EDTA?5％；

Trolamine 5%;

Oxine 10%.

3, the described method of claim 1 is characterized in that stablizer is made up of following substances in percentage by weight in this method:

Water glass 40%;

Trisodium phosphate 30%;

Sodium hexametaphosphate 99 5%;

EDTA10％；

Trolamine 5%;

Oxine 10%.