CN109265379B - Preparation method of free formaldehyde-free and storage-stable rongalite - Google Patents
Preparation method of free formaldehyde-free and storage-stable rongalite Download PDFInfo
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Abstract
The invention discloses a preparation method of free formaldehyde-free and storage-stable rongalite, which comprises the steps of sequentially adding sodium metabisulfite, zinc powder, a catalyst and formaldehyde into a reaction system under the condition of ultrasonic stirring to obtain a sodium formaldehyde sulfoxylate solution, adding a polyphenol compound and a drying agent into the solution to obtain a uniformly mixed stable sodium formaldehyde sulfoxylate storage solution, and finally concentrating and drying the solution to obtain the free formaldehyde-free and storage-stable rongalite. Sodium formaldehyde sulfoxylate is prepared by adopting a one-step ultrasonic method, and free formaldehyde-free and storage-stable rongalite powder is obtained by adding a polyphenol compound and silica gel. The invention realizes the one-step low-temperature method for preparing the rongalite powder which is free of free formaldehyde and stable in storage, the method reduces the reaction temperature and the reaction time required for preparing the formaldehyde sodium sulfoxylate, saves the energy consumption and the time, improves the production efficiency, reduces the production cost, and the prepared rongalite powder is free of free formaldehyde and greatly improves the storage stability.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of rongalite which is free of free formaldehyde and stable in storage.
Background
The chemical name of rongalite is sodium formaldehyde hydrosulfite dihydrate, and the printing and dyeing industry is used as a discharging agent, and the rubber industry is used as a reducing agent. Two methods are currently used in industry: zinc powder-pyrochlore-formaldehyde process (abbreviated as one-step process) and zinc powder-sulfur dioxide-formaldehyde process (abbreviated as three-step process). In recent years, the method for producing rongalite by adopting a one-step method is widely applied, but in the one-step method production process, the continuous reaction is required to be carried out for a plurality of hours at the temperature of nearly 100 ℃, so that the consumption of energy is large; the biggest problem of the current commercially available rongalite is that the rongalite contains more free formaldehyde and has poor stability in the storage process and is easy to decompose when meeting water. Aiming at the problems, a new process and a new method for reducing the synthesis reaction temperature of rongalite, improving the production efficiency, improving the storage stability of commercial rongalite and reducing the content of free formaldehyde are urgently needed in the chemical industry.
The invention patent CN 107793305A discloses a preparation method of low-free-formaldehyde and low-zinc sodium formaldehyde sulfoxylate powder, which adopts sodium pyrosulfite, zinc powder and formaldehyde solution as raw materials, inorganic acid as an activating agent, and produces sodium formaldehyde sulfoxylate (rongalite) by a one-step method, the method reduces the free formaldehyde in rongalite, and the temperature needs to be kept at the highest temperature of 95-102 ℃ for 90-120 min in the reaction process. The invention patent CN 104478682A discloses a method for improving the stability of rongalite solution, which comprises adding a buffering agent or a combination of the buffering agent, a chelating agent and a blocking agent into rongalite solution prepared in the process of rongalite production or rongalite product production, filtering the solution after fully and uniformly mixing, subpackaging the filtered solution into a clean, dark and opaque plastic container, and storing the container in a sealed way.
The synthesis and stability preparation method of the low free formaldehyde rongalite reduces the content of free formaldehyde by controlling the process conditions in the rongalite synthesis process, does not meet the requirement of no free formaldehyde, does not reduce the reaction temperature of synthesis, and mainly studies the temperature property of rongalite solution and cannot be applied to the stability of rongalite powder. At present, no low-temperature synthesis method of rongalite is available, and no report on a preparation method of rongalite powder which is free of free formaldehyde and stable in storage is available.
Disclosure of Invention
The invention aims to solve the technical problems that the reaction temperature is high in the synthesis process of the current rongalite, the commercial rongalite contains more free formaldehyde and the stability is poor in the storage process, and provides a method for reducing the reaction temperature by adding ultrasound in the synthesis process of the rongalite, and uniformly mixing a polyphenol compound and silica gel in rongalite solution to realize free formaldehyde-free and stable storage in the commercial rongalite.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of free formaldehyde-free and storage-stable rongalite is characterized by comprising the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 80-120 g of sodium metabisulfite (Na)2S2O5) Dissolving the sodium metabisulfite in 200-800 ml of ice water, stirring at the rotating speed of 500-10000 r/min under the ultrasonic condition, adding 80-120 g of zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 20-30 ℃, keeping the temperature for 5-20 min, adding 5-20 g of catalyst into the system, and finally adding 45-75 ml of 50% formaldehyde (CH)2O) solution, heating to 60-80 ℃, preserving heat for 0.5-1 h, washing and filtering a product after reaction to obtain a washing liquid, namely sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: adding 1-5 g of polyphenol compounds and 2-10 g of drying agent nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, mixing uniformly, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain a solid rongalite which is free from free formaldehyde and stable in storage; the polyphenol compound and the drying agent are added in the step (2), the polyphenol compound can effectively adsorb free formaldehyde, the silica gel can quickly absorb moisture in the air, so that the rongalite powder has no free formaldehyde and can be stably stored due to no moisture, and the polyphenol compound, the drying agent and the rongalite in the step (2) are fully mixed, so that the free formaldehyde and the moisture can be adsorbed in time.
The whole process of synthesizing the sodium formaldehyde sulfoxylate in the step (1) is carried out under the ultrasonic condition.
The catalyst in the step (1) is a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1.
In the step (1), the whole synthesis process of the sodium formaldehyde sulfoxylate is carried out under the ultrasonic condition, so the synthesis temperature is reduced to 60-80 ℃, and the synthesis time is shortened to 0.5-1 h.
The polyphenol compound in the step (2) is one or more of catechin, epicatechin, bisabolol catechin and epigallophenol catechin.
And (3) the drying agent in the step (2) is one or more of anhydrous calcium chloride, silica gel, montmorillonite, molecular sieve and attapulgite.
The invention has the beneficial effects that: the one-step ultrasonic method is adopted to prepare the formaldehyde sodium sulfoxylate, the whole synthesis process of the formaldehyde sodium sulfoxylate is carried out under the ultrasonic condition, and the synthesis temperature is reduced to 60-80 ℃ due to the action of the catalyst, the synthesis time is shortened to 0.5-1 h, the ultrasonic condition is favorable for fully mixing and refining reactants in the reaction process and maintaining the graphene oxide in the catalyst in a higher single-layer state, a compound formed by the single-layer graphene oxide and hexadecyl trimethyl ammonium bromide is easily adsorbed to the surface of the zinc powder in the reaction process, the specific surface area of the zinc powder is improved, the reaction among the zinc powder, sodium metabisulfite and formaldehyde is promoted, and compared with the traditional one-step preparation method, the reaction temperature is reduced, the reaction time is shortened, the production efficiency is improved, and the energy consumption is saved; and the polyphenol compounds and the silica gel are added into the sodium formaldehyde sulfoxylate solution, so that free formaldehyde is effectively removed, and moisture is effectively adsorbed, so that the rongalite powder has no free formaldehyde, and the rongalite is stable to store due to the absence of the moisture. The technical scheme of the invention has simple and feasible process, has no special requirements on synthetic raw materials, can realize large-scale production by utilizing conventional factory equipment, and has wide application prospect.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
The invention discloses a preparation method of rongalite without free formaldehyde and with storage stability, which is characterized by comprising the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 80-120 g of sodium metabisulfite (Na)2S2O5) Ultrasonic wave of 200-800W dissolved in 200ml of ice waterStirring at a rotating speed of 500-10000 r/min under the condition, adding 80-120 g of zinc powder (Zn) into the sodium metabisulfite ice-water bath, heating to 20-30 ℃, keeping the temperature for 5-20 min, adding 5-20 g of a catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1) into the system, and finally adding 45-75 ml of 50% formaldehyde (CH)2And O) heating the solution to 60-80 ℃, keeping the temperature for 0.5-1 h, washing and filtering a product after reaction to obtain a washing liquid, namely the sodium formaldehyde sulfoxylate solution.
(2) Preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 1-5 g of polyphenol compounds and 2-10 g of drying agent nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, uniformly mixing, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free of free formaldehyde and stable in storage.
Example 1
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 80g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml of ice water, stirring at a rotation speed of 500r/min under 200W under an ultrasonic condition, adding 100g of zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 20 ℃, keeping the temperature for 10min, adding 5g of catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1) into the system, and finally adding 55ml of 50% formaldehyde (CH)2O) solution, heating to 60-80 ℃, keeping the temperature for 0.5h, washing and filtering a product after reaction to obtain a washing liquid, namely sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 1g of polyphenol compound epicatechin and 5g of desiccant montmorillonite nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring and mixing uniformly at a high speed, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free of free formaldehyde and stable in storage.
Example 2
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 120g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml of ice water, stirring at 10000r/min under the ultrasonic condition of 800W, adding 120g of zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 30 ℃, keeping the temperature for 20min, adding 20g of catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1) into the system, and finally adding 75ml of 50% formaldehyde (CH)2O) solution, heating to 70 ℃, keeping the temperature for 1h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 2g of polyphenol compound catechin and 8g of drying agent nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, mixing uniformly, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain a solid rongalite which is free from free formaldehyde and stable in storage.
Example 3
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 100g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water, stirring at a rotation speed of 5000r/min under the ultrasonic condition of 400W, adding 90g of zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 25 ℃, keeping the temperature for 15min, adding 8g of catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1) into the system, and finally adding 65ml of 50% formaldehyde (CH)2O), heating the solution to 70 ℃, keeping the temperature for 0.8h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 5g of polyphenol compound catechin and 2g of desiccant silica gel nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, mixing uniformly, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain a solid rongalite which is free of free formaldehyde and stable in storage.
Example 4
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 110g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water, stirring at 2000r/min under ultrasonic condition of 600W, adding 100g zinc powder (Zn) into the sodium pyrosulfite ice water bath, heating to 20 deg.C, maintaining for 16min, adding 12g catalyst (mixture of graphene oxide and hexadecyl trimethyl ammonium bromide at a mass ratio of 1: 1) into the system, and adding 65ml 50% formaldehyde (CH)2O), heating the solution to 65 ℃, keeping the temperature for 0.6h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 4g of polyphenol compound catechin and 10g of desiccant montmorillonite nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring and mixing uniformly at a high speed, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain a solid rongalite which is free of free formaldehyde and stable in storage.
Example 5
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 105g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water at 700W under ultrasonic condition, stirring at 3000r/min, adding 110g zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 28 deg.C, maintaining for 12min, adding 10g catalyst (mixture of graphene oxide and hexadecyl trimethyl ammonium bromide at a mass ratio of 1: 1) into the system, and adding 70ml 50% formaldehyde (CH)2O) solution, heating to 75 ℃, keeping the temperature for 1h, washing and filtering a product after reaction to obtain a washing liquidSodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 5g of polyphenol compounds (3g of epicatechin, 2g of bisabolol catechin) and 10g of drying agents (5g of silica gel and 5g of montmorillonite) nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring and mixing uniformly at a high speed, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free from free formaldehyde and stable in storage.
Example 6
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 80g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water, stirring at 8000r/min under ultrasonic condition of 300W, adding 90g zinc powder (Zn) into the sodium pyrosulfite ice water bath, heating to 20 deg.C, maintaining for 10min, adding 15g catalyst (mixture of graphene oxide and hexadecyl trimethyl ammonium bromide at a mass ratio of 1: 1) into the system, and adding 45ml 50% formaldehyde (CH)2O), heating the solution to 60 ℃, keeping the temperature for 0.5h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: and (2) adding 3g of polyphenol compound bisabolol catechin and 6g of desiccant molecular sieve nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, uniformly mixing, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free from free formaldehyde and stable in storage.
Example 7
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 100g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water, stirring at 1500r/min under ultrasonic condition of 400W, adding 90g zinc powder (Zn) into the above sodium pyrosulfite ice water bath, heating to 20 deg.CKeeping the temperature for 10min, adding 18g of catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1) into the system, and finally adding 55ml of 50% formaldehyde (CH)2O), heating the solution to 68 ℃, keeping the temperature for 0.6h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: adding 4g of polyphenol compound epigallocatechin and 2g of desiccant attapulgite nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, mixing uniformly, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free from free formaldehyde and stable in storage.
Example 8
The preparation method of the rongalite without free formaldehyde and with storage stability of the embodiment comprises the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: 100g of sodium metabisulfite (Na)2S2O5) Dissolving in 200ml ice water, stirring at the rotating speed of 4500r/min under the ultrasonic condition of 500W, adding 110g of zinc powder (Zn) into the sodium metabisulfite ice water bath, heating to 30 ℃, keeping the temperature for 10min, adding 14g of catalyst (a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in the mass ratio of 1: 1) into the system, and finally adding 60ml of 50% formaldehyde (CH)2O), heating the solution to 75 ℃, keeping the temperature for 0.9h, washing and filtering a product after reaction to obtain a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing rongalite which is free of free formaldehyde and stable in storage: adding 4g of polyphenol compounds (2g of catechin and 2g of epigallocatechin) and 8g of drying agent (4g of anhydrous calcium chloride and 4g of attapulgite) nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, uniformly mixing, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain the solid rongalite which is free from free formaldehyde and stable in storage.
Effects of the invention
After the treatment of examples 1-8, the following tests were carried out on the fabric, and the test results are shown in Table 1.
1) Determination of free Formaldehyde
The content of free formaldehyde in rongalia is measured according to GB/T5543-2006 method for measuring the content of total formaldehyde in resin finishing agent.
2) Relative yield of rongalite
The yield of the example was calculated based on 100%.
3) Storage stability determination
After the rongalite sample is exposed and stored in the air for half a month, the effective content of the rongalite is determined by an iodometry method so as to test the storage stability of the rongalite.
Table 1 test results of the fabrics performed
Note: the traditional one-step method is synthesized according to a high-temperature synthesis one-step method adopted by the current enterprises; comparative sample 1 is a reaction system in which ultrasonic reaction is used but no catalyst is added. Comparative sample 2 was prepared by adding a catalyst to the reaction system without using ultrasonic reaction.
As can be seen from table 1, the rongalite synthesized by the traditional one-step method contains a certain amount of free formaldehyde, but the rongalite synthesized by the technical scheme provided by the invention does not contain free formaldehyde, and compared with a comparative sample 1 and a comparative sample 2, the single ultrasound and the single catalyst can not completely react at low temperature, but the embodiment simultaneously introduces the ultrasound and the single catalyst into the reaction system, so that the reaction temperature is reduced, and the conversion rate of the rongalite is also improved. Therefore, the technical scheme provided by the invention can endow the rongalite with zero free formaldehyde emission and stable storage stability.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A preparation method of free formaldehyde-free and storage-stable rongalite is characterized by comprising the following steps:
(1) synthesizing sodium formaldehyde sulfoxylate by a one-step method: dissolving 80-120 g of sodium metabisulfite in 200ml of ice water, stirring at a rotating speed of 500-10000 r/min under an ultrasonic condition of 200-800W, adding 80-120 g of zinc powder into the sodium metabisulfite ice water bath, heating to 20-30 ℃, preserving heat for 5-20 min, adding 5-20 g of catalyst into the system, finally adding 45-75 ml of 50% formaldehyde solution into the system, heating to 60-80 ℃, preserving heat for 0.5-1 h, washing and filtering a reacted product, and obtaining a washing liquid, namely a sodium formaldehyde sulfoxylate solution;
(2) preparing the rongalite which is free of free formaldehyde and stable in storage: adding 1-5 g of polyphenol compounds and 2-10 g of drying agent nanoparticles into the sodium formaldehyde sulfoxylate solution obtained in the step (1), stirring at a high speed, mixing uniformly, and then carrying out vacuum concentration and drying on the sodium formaldehyde sulfoxylate solution to obtain free formaldehyde-free and storage-stable rongalite;
the catalyst in the step (1) is a mixture of graphene oxide and hexadecyl trimethyl ammonium bromide in a mass ratio of 1: 1;
the polyphenol compound in the step (2) is one or more of catechin, epicatechin, bisabolol catechin and epigallophenol catechin.
2. The method for preparing a free formaldehyde-free and storage-stable rongalite according to claim 1, characterized in that: the whole process of synthesizing the sodium formaldehyde sulfoxylate in the step (1) is carried out under the ultrasonic condition.
3. The method for preparing a free formaldehyde-free and storage-stable rongalite according to claim 1, characterized in that: and (3) the drying agent in the step (2) is one or more of anhydrous calcium chloride, silica gel, montmorillonite, molecular sieve and attapulgite.
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