阅读说明：本技术 一种环保无磷的洗衣粉及其制备工艺 (Environment-friendly phosphorus-free washing powder and preparation process thereof ) 是由 张栋栋 郑鹏波 陆伟明 于 2020-05-26 设计创作，主要内容包括：本发明涉及一种环保无磷的洗衣粉及其制备工艺,属于洗衣粉的技术领域,包括以下重量份数比的组分：AES10-30份；小苏打20-40份；硅酸钠1-5份；马来酸-丙烯酸聚合物1-5份；元明粉20-50份；CMC-Na0-2份；过碳酸钠0-10份；JFC0-3份；添加剂0-3份；其中,所述过碳酸钠上包覆有用于提高其稳定性的稳定剂。本发明具有能够保证去污能力的前提下,更加环保的优点。(The invention relates to an environment-friendly phosphorus-free washing powder and a preparation process thereof, belonging to the technical field of washing powder and comprising the following components in parts by weight: AES10-30 parts; 20-40 parts of baking soda; 1-5 parts of sodium silicate; 1-5 parts of maleic acid-acrylic acid polymer; 20-50 parts of anhydrous sodium sulphate; CMC-Na0-2 parts; 0-10 parts of sodium percarbonate; JFC0-3 parts; 0-3 parts of an additive; wherein the sodium percarbonate is coated with a stabilizer for improving its stability. The invention has the advantage of environmental protection on the premise of ensuring the decontamination capability.)

1. An environment-friendly phosphorus-free washing powder is characterized in that: the paint comprises the following components in parts by weight:

wherein the sodium percarbonate is coated with a stabilizer for improving its stability.

2. The environment-friendly phosphorus-free washing powder according to claim 1, which is characterized in that: the additive comprises the following components in percentage by weight:

32-35% of essence;

32-35% of an enzyme preparation;

32-35% of color particles;

wherein the enzyme preparation comprises the following components in percentage by weight:

90-96% of enzyme core;

4-10% of a protective layer.

3. The environment-friendly phosphorus-free washing powder according to claim 2, which is characterized in that: wherein the enzyme core comprises the following components in percentage by weight

15-20% of amylase;

40-50% of protease;

sodium alginate 30-40%.

4. The environment-friendly phosphorus-free washing powder according to claim 3, which is characterized in that: the protective layer comprises the following components in percentage by weight:

40-60% of an inner protective layer;

40-60% of an outer protective layer;

the inner protection layer comprises hydroxyethyl cellulose ether, ethanol and water, and is composed of (1-2) by weight: (30-35): (60-65);

wherein, the outer protective layer comprises sodium sulfate, sodium chloride and water, and consists of (1-2) according to the following weight ratio: (1-2): (15-20).

5. The environment-friendly phosphorus-free washing powder according to claim 4, which is characterized in that: the outer protective layer also comprises catalase, and the weight ratio of the components of the outer protective layer is that the catalase: sodium sulfate: sodium chloride: water ═ (0.1-0.2): (1-2): (1-2): (15-20).

6. The environment-friendly phosphorus-free washing powder according to claim 5, which is characterized in that: the coating process of the protective layer specifically comprises the following process steps:

s1, dissolving, adding hydroxyethyl cellulose into ethanol according to the proportion within 15-20 minutes, keeping stirring in the adding process to obtain a mixture A, then adding the mixture A into water, keeping stirring in the adding process until all solids are dissolved to obtain a solution A; putting sodium sulfate and sodium chloride into water according to a ratio, and stirring until the solid is completely dissolved to obtain a solution B;

s2, spraying an inner protective layer, spraying the solution A on an enzyme core in a fluidized bed, wherein the spraying temperature is 60-70 ℃, and drying for 5 minutes after the spraying is finished to obtain a semi-finished enzyme preparation;

s3, spraying an outer protective layer, spraying the solution B on the semi-finished enzyme preparation obtained in the step S2 in a fluidized bed, and drying for 5 minutes after the spraying is finished to obtain the enzyme preparation.

7. The environment-friendly phosphorus-free washing powder according to any one of claims 1 to 6, wherein: the stabilizer comprises 3 wt% of polyacrylamide gel and citric acid monohydrate, and is composed of (90-100): (3-5).

8. The environment-friendly phosphorus-free washing powder according to claim 7, which is characterized in that: the coating process of the stabilizer specifically comprises the following process steps:

s1, spraying polyacrylamide gel onto sodium percarbonate in a fluidized bed, wherein the spraying temperature is 50-70 ℃, and drying for 1-2 minutes after the spraying is finished to obtain a semi-finished product A;

s2, spraying solid citric acid monohydrate powder into the fluidized bed with the semi-finished product A to enable the citric acid monohydrate to be adhered to polyacrylamide gel, and continuing to dry for 10 minutes to coat the stabilizer on the sodium percarbonate.

9. The process for preparing the environment-friendly phosphorus-free washing powder according to claims 1 to 8, wherein the process comprises the following steps: the method comprises the following process steps:

s1, stirring and mixing the AES, the baking soda and the anhydrous sodium sulphate according to the proportion, so that the baking soda and the anhydrous sodium sulphate uniformly disperse the AES to obtain primary powder;

s2, adding CMC-Na, maleic acid-acrylic acid polymer and sodium silicate into the primary powder obtained in the step S1, and continuously stirring and mixing, wherein the mixture is a wet sticky material;

s3, granulating the wet sticky material obtained in the step S2 to obtain AES particles;

s4, drying the AES particles obtained in the step S3 at the drying temperature of 145-175 ℃ for 30 minutes to obtain dried particles;

s5, mixing the dried particles obtained in the step S4 with the rest components, and uniformly stirring to obtain the washing powder containing AES particles.

Technical Field

The invention relates to the technical field of washing powder, in particular to environment-friendly phosphorus-free washing powder and a preparation process thereof.

Background

The Washing powder is Washing powder, and the synthetic detergent is prepared with surfactant as main component and proper amount of detergency promoter. The washing powder is a powdery (granular) synthetic detergent.

For example, the Chinese patent application publication No. CN103571641A discloses a washing powder, which comprises the following components in parts by weight: sodium linear alkyl benzene sulfonate 25; sodium tripolyphosphate 15; a zeolite 15; triethanolamine salts of alkylbenzenesulfonic acid 8; 5, fatty alcohol-polyoxyethylene ether; sodium hexametaphosphate 15; 10 parts of sodium silicate; sodium carboxymethylcellulose 2; 0.05 parts of essence; 50 parts of sodium sulfate; 5 parts of asparagus extract; 7 of ginseng extract; the washing powder is prepared by the following steps: mixing the above components except essence, pulping, filtering, homogenizing, spray drying to obtain hollow granule, cooling, aging, sieving, and adding essence.

The above prior art solutions have the following drawbacks: the sodium linear alkylbenzene sulfonate is used as a main surfactant, and although the sodium linear alkylbenzene sulfonate has strong detergency, the sodium linear alkylbenzene sulfonate has a great disadvantage of not resisting hard water. In order to improve the hard water resistance of the washing powder, a large amount of chelating agents, such as sodium tripolyphosphate and zeolite added in the above technical scheme, must be added into the formula of the washing powder, but the use of sodium tripolyphosphate as a phosphorus-containing additive is forbidden at present, and the zeolite is insoluble in water and is easy to deposit on fabrics to form ash, so that the fabrics are damaged. Therefore, the washing powder which is more environment-friendly on the premise of ensuring the decontamination capability is needed.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the environment-friendly phosphorus-free washing powder which has the advantage of being more environment-friendly on the premise of ensuring the decontamination capability.

The invention also aims to provide a preparation process of the environment-friendly phosphorus-free washing powder, which has the effect of reducing the possibility of reduction of the washing effect of the washing powder in the production process.

The above object of the present invention is achieved by the following technical solutions:

the environment-friendly phosphorus-free washing powder comprises the following components in parts by weight:

wherein the sodium percarbonate is coated with a stabilizer for improving its stability.

By adopting the technical scheme, the method has the advantages that,

firstly, AES is a hard water-resistant anionic surfactant, and the washing powder does not need to be compounded with sodium tripolyphosphate and 4A zeolite as chelating builders, so that the washing powder is environment-friendly and economical. However, AES cannot be sprayed at high temperature under alkaline slurry, because AES is decomposed under the condition of high-temperature and high-alkaline slurry, and thus the effect is lost. Therefore, the washing powder is not added with a strong alkaline auxiliary agent, but is added with mild baking soda, so that the irritation is reduced, the hands are not hurt really, and the washing powder is suitable for people with sensitive skin. More importantly, the formula does not need to be prepared into slurry, so that the risk of AES decomposition is avoided. And JFC as a penetrant can improve the permeability of AES, so that the detergency of the washing powder is improved.

CMC-Na is used as a coagent, has strong performance of emulsifying and protecting colloid, and can enable the surface of clothes to have negative charge in the washing process, thereby enabling dirt particles to have phase separation property in a water phase and have repellency with the surface of solid-phase washed objects, and preventing the dirt from being deposited on the washed objects again.

The sodium silicate is an adhesive and a framework support, can bond various inorganic washing aids together, and can support particles from being damaged after being dried.

The maleic acid-acrylic acid polymer is an anti-redeposition agent for adhesives and washing powder.

The sodium percarbonate can release active oxygen in water, has bleaching and sterilizing properties, and can effectively remove coffee stains, fruit juice, blood stains and the like. Sodium percarbonate is susceptible to deterioration due to moisture and to the problem of swelling of the sodium percarbonate, and therefore, it is necessary to coat a stabilizer on the sodium percarbonate.

As the whole formula is not added with strong alkaline components and phosphorus-containing components, the whole formula is very environment-friendly, and the synergy of AES and CMC-Na is matched with the rest materials, so that a good washing effect can be achieved, and the environment-friendly washing effect and the washing effect are both achieved.

The present invention in a preferred example may be further configured to: the additive comprises the following components in percentage by weight:

32-35% of essence;

32-35% of an enzyme preparation;

32-35% of color particles;

wherein the enzyme preparation comprises the following components in percentage by weight:

90-96% of enzyme core;

4-10% of a protective layer.

By adopting the technical scheme, the enzyme preparation can obviously improve the washing effect of the washing powder under a proper condition, and the baking soda added in the washing powder is weaker in alkalinity and has smaller influence on the activity of the enzyme preparation, which is different from the existing general washing powder added with strong alkali substances.

However, sodium percarbonate is added into the washing powder, and the sodium percarbonate has strong oxidative bleaching capacity, so that the oxidative failure of an enzyme preparation is easily caused, and the washing effect of the washing powder is influenced. The protective layer is then able to form a protection outside the enzyme preparation, thereby delaying the dissolution of the various enzymes within the enzyme core. Therefore, after the washing powder is added into water, the sodium percarbonate firstly releases active oxygen to bleach and disinfect clothes, and the sodium percarbonate is gradually and completely decomposed with the time. At this time, various enzymes in the enzyme core are gradually released to further clean the laundry. By staggering the effective time of the sodium percarbonate and the enzyme preparation, the influence of the sodium percarbonate on the enzyme preparation is greatly reduced.

The present invention in a preferred example may be further configured to: the enzyme core comprises the following components in percentage by weight

15-20% of amylase;

40-50% of protease;

sodium alginate 30-40%.

By adopting the technical scheme, the sodium alginate used as the adhesive can bond the amylase and the protease together, and the dissolution of the sodium alginate needs time, so that the release time of the amylase and the protease is prolonged, and the effective time of the amylase and the protease with sodium percarbonate is further staggered. In addition, the surface of the clothes is charged with negative charges due to the added CMC-Na, and the sodium alginate has certain polyanion behavior in water, which means that the enzyme preparation can be well adhered to the surface of the clothes, so that the released amylase and protease can be released in a targeted manner and can decompose stains on the clothes.

The present invention in a preferred example may be further configured to: the protective layer comprises the following components in percentage by weight:

40-60% of an inner protective layer;

40-60% of an outer protective layer;

the inner protection layer comprises hydroxyethyl cellulose ether, ethanol and water, and is composed of (1-2) by weight:

(30-35)：(60-65)；

wherein, the outer protective layer comprises sodium sulfate, sodium chloride and water, and consists of (1-2) according to the following weight ratio: (1-

2)：(15-20)。

By adopting the technical scheme, the method has the advantages that,

firstly, hydroxyethyl cellulose ether is a water-soluble compound, has good film-forming properties, and is a good coating material. In addition, the hydroxyethyl cellulose ether has good dispersion, suspension and emulsification effects after being dissolved in water, so that the hydroxyethyl cellulose ether is matched with CMC-Na to uniformly disperse and suspend the washed dirt, thereby reducing the possibility of redeposition of the dirt on clothes. The emulsifying capacity of the hydroxyethyl cellulose ether can further improve the dirt-removing capacity of the washing powder.

When hydroxyethyl cellulose ether is coated on the outer layer of the enzyme preparation, the hydroxyethyl cellulose ether needs to be dissolved into a viscous colloid by water so as to be coated. In the current common method, hydroxyethyl cellulose ether is directly added into water for dissolution, but in practical operation, we find that the hydroxyethyl cellulose ether is directly added into water for dissolution, and is always in a relatively turbid state for a long time. The hydroxyethyl cellulose ether powder is observed to be agglomerated. In order to solve this problem, ethanol is added to the system, and we have found that the use of ethanol and water as the dispersion medium can significantly improve the dispersion properties of hydroxyethyl cellulose ether, as compared to the use of water alone as the dispersion medium.

This is because hydroxyethyl cellulose ether is involved in surface tension, wettability, polarity, and the like between dispersion media. And strong hydrogen bonds between water molecules, which have a strong affinity for hydroxyethyl cellulose ether. Ethanol is less polar than water and, therefore, hydroxyethyl cellulose ether has less wettability in ethanol than in water. Furthermore, the ethanol surface tension is smaller, which also reduces the agglomeration of the hydroxyethyl cellulose ether. In combination, the combination of ethanol and water can improve the effect of the surface tension and wettability, thereby reducing the possibility of agglomeration of the hydroxyethyl cellulose ether.

However, hydroxyethyl cellulose ether has strong moisture absorption, sodium sulfate and sodium chloride can form a pane type intercalation compound, and after moisture enters the crystal lattice of the hydroxyethyl cellulose ether, the bonding force is stronger than that of common crystal water, so that the possibility of moisture absorption of the enzyme preparation can be reduced by coating the sodium sulfate and the sodium chloride outside the hydroxyethyl cellulose ether, and the whole enzyme preparation has good stability. In addition, the release of the enzyme can be greatly delayed by the matching of the multilayer coating and the sodium alginate in the enzyme core, so that the effective period of the enzyme preparation is effectively staggered with that of sodium percarbonate. And after the sodium sulfate is dissolved in water, a crystal-shaped structure is formed, and the existence of the structure plays a role in compressing the double electric layers of the surfactant, thereby being beneficial to promoting the surfactant to be adsorbed on the surface of clothes and improving the adsorption effect of the surfactant.

The present invention in a preferred example may be further configured to: the outer protective layer also comprises catalase, and the weight ratio of the components of the outer protective layer is that the catalase: sodium sulfate: sodium chloride: water ═ (0.1-0.2): (1-2): (1-2): (15-20).

By adopting the technical scheme, the mechanism of oxygen release of the sodium percarbonate is determined, the sodium percarbonate can be firstly decomposed to generate hydrogen peroxide, and the hydrogen peroxide can release oxygen. The catalase is added into the outer protective layer to catalyze the hydrogen peroxide to be rapidly decomposed, so that oxygen stored in the sodium percarbonate is rapidly released, and the concentration of the hydrogen peroxide in water is reduced. When the amylase and the protease are released, the content of hydrogen peroxide in water is low, the influence on the activity of the enzyme is small, the activity of the enzyme is high, and the decontamination effect of the washing powder is better.

The present invention in a preferred example may be further configured to: the coating process of the protective layer specifically comprises the following process steps:

s1, dissolving, adding hydroxyethyl cellulose into ethanol according to the proportion within 15-20 minutes, keeping stirring in the adding process to obtain a mixture A, then adding the mixture A into water, keeping stirring in the adding process until all solids are dissolved to obtain a solution A; putting sodium sulfate and sodium chloride into water according to a ratio, and stirring until the solid is completely dissolved to obtain a solution B;

s2, spraying an inner protective layer, spraying the solution A on an enzyme core in a fluidized bed, wherein the spraying temperature is 60-70 ℃, and drying for 5 minutes after the spraying is finished to obtain a semi-finished enzyme preparation;

s3, spraying an outer protective layer, spraying the solution B on the semi-finished enzyme preparation obtained in the step S2 in a fluidized bed, and drying for 5 minutes after the spraying is finished to obtain the enzyme preparation.

By adopting the technical scheme, the hydroxyethyl cellulose with good film-forming property forms a layer of coating film outside the enzyme core, and the dried sodium sulfate and sodium chloride form a pane type intercalation. The reason for controlling the spraying temperature to 60-70 ℃ is that when the temperature is too high, the enzyme is easy to deform and deactivate, and when the temperature is too low, the water volatilization is too slow, so that the coating of the protective layer is easy to be uneven, even the particles are adhered, and the protective effect of the protective layer is reduced.

The present invention in a preferred example may be further configured to: the stabilizer comprises 3 wt% of polyacrylamide gel and citric acid monohydrate, and is composed of (90-100): (3-5).

By adopting the technical scheme, the method has the advantages that,

firstly, the polyacrylamide gel can well coat the sodium percarbonate, and the polyacrylamide is a water-soluble linear high molecular polymer, so that the polyacrylamide coating the sodium percarbonate maintains the solubility of the sodium percarbonate, improves the stability of the sodium percarbonate, and is not easy to cause the decomposition of the sodium percarbonate.

In addition, the polyacrylamide has good anti-blocking effect, and can greatly increase the dryness of the washing powder aqueous solution, thereby reducing the abrasion to hands in the washing process and playing a role in protecting hands. In addition, polyacrylamide acts as a flocculant, which, in conjunction with CMC-Na, further improves the phase separation of the soil particles in water.

However, polyacrylamide has certain moisture absorption, and the washing powder is easy to agglomerate after absorbing moisture, which greatly affects subsequent use. Therefore, citric acid monohydrate is required to be coated on the outer layer of the polyacrylamide, and because the citric acid monohydrate has crystallization water and is not easy to absorb moisture unlike the common anhydrous citric acid, the possibility of losing moisture absorption of the sodium percarbonate is reduced.

And when the citric acid monohydrate is in a solid state, the citric acid monohydrate does not react with the baking soda in the washing powder because the citric acid monohydrate is not ionized. When the washing powder is put into water, the citric acid directly reacts with the baking soda dissolved in the water to generate more carbon dioxide, so that the washing powder added into the water is stirred, and the dispersibility and uniformity of the washing powder, particularly the sodium percarbonate, are improved. The function greatly reduces the possibility that the washing powder is locally agglomerated and deposited on clothes; after the stabilizer is dissolved, the sodium percarbonate can uniformly bleach, disinfect and wash clothes, so that the problem of unclean washing caused by non-uniform dispersion of washing powder is solved.

In addition, sodium citrate produced by the reaction of citric acid and baking soda has a chelating effect, which can soften hard water, and CMC-Na in the washing powder component is sensitive to water hardness, and the detergency thereof is easily affected by the hardness of water. While AES has better detergency in hard water, it has significantly stronger detergency in soft water. Namely, the sodium citrate monohydrate has the property of difficult moisture absorption, can well protect sodium percarbonate, can generate an effervescence effect with sodium bicarbonate after being added into water, and the reaction product sodium citrate has a chelation effect, so that the synergistic effect with CMC-Na and AES is formed.

The present invention in a preferred example may be further configured to: the coating process of the stabilizer specifically comprises the following process steps:

s1, spraying polyacrylamide gel onto sodium percarbonate in a fluidized bed, wherein the spraying temperature is 50-70 ℃, and drying for 1-2 minutes after the spraying is finished to obtain a semi-finished product A;

s2, spraying solid citric acid monohydrate into the fluidized bed with the semi-finished product A to enable the citric acid monohydrate to be adhered to polyacrylamide gel, and continuing drying for 10 minutes to coat the stabilizer on the sodium percarbonate.

By adopting the technical scheme, under the process condition, the drying time of the polyacrylamide gel is about 10 minutes, so that the viscosity of the polyacrylamide is high after drying for 1-2 minutes, but the polyacrylamide is not solidified. At the moment, the citric acid monohydrate solid is directly sprayed into the fluidized bed, and then is fully collided with the polyacrylamide under the driving of the air flow, so that the citric acid monohydrate solid is adhered to and embedded in the polyacrylamide. After the drying is finished, the sodium percarbonate can be coated with the polyacrylamide protective layer, and the citric acid monohydrate is uniformly coated and inlaid on the polyacrylamide protective layer.

The process is selected because the citric acid monohydrate generally adopts a cooling crystallization process, and if the citric acid monohydrate is recrystallized to the polyacrylamide by adopting the cooling crystallization process, the polyacrylamide protective layer is damaged on one hand, and the process is very responsible for large energy consumption. Therefore, the coating process of the stabilizer is more sophisticated, and according to the research of the applicant for many years, the process steps are obtained, so that the citric acid monohydrate is coated on the acrylamide protective layer in a low-energy consumption mode on the premise of not influencing the polyacrylamide protective layer.

The second aim of the invention is realized by the following technical scheme: a preparation process of environment-friendly phosphorus-free washing powder comprises the following process steps:

s1, stirring and mixing the AES, the baking soda and the anhydrous sodium sulphate according to the proportion, so that the baking soda and the anhydrous sodium sulphate uniformly disperse the AES to obtain primary powder;

s2, adding CMC-Na, maleic acid-acrylic acid polymer and sodium silicate into the primary powder obtained in the step S1, and continuously stirring and mixing, wherein the mixture is a wet sticky material;

s3, granulating the wet sticky material obtained in the step S2 to obtain AES particles;

s4, drying the AES particles obtained in the step S3 at the drying temperature of 145-175 ℃ for 30 minutes to obtain dried particles;

s5, mixing the dried particles obtained in the step S4 with the rest components, and uniformly stirring to obtain the washing powder containing AES particles.

By adopting the technical scheme, the enzyme preparation and the sodium percarbonate are added in the step S5 instead of being added before, so that the water in the step S2 does not influence the protective layer outside the enzyme preparation and the stabilizer outside the sodium percarbonate; the granulation process in step S4 does not cause the falling off of the protective layer outside the enzyme preparation and the stabilizer outside the sodium percarbonate and the pulverization of the granules; and the high-temperature drying process in the step S4 can not cause the decomposition of sodium percarbonate and the denaturation and inactivation of the enzyme preparation.

In summary, the invention includes at least one of the following beneficial technical effects:

1. through the synergy of substances such as AES, CMC-Na, sodium percarbonate and the like, a good washing effect can be obtained without adding phosphorus-containing substances, so that the environmental protection and the washing effect are achieved;

2. by adding the enzyme preparation and coating the protective layer outside the enzyme core, the effective time of the enzyme and the effective time of the sodium percarbonate are staggered, so that the influence of the sodium percarbonate on the enzyme preparation is reduced;

3. sodium alginate is added into the enzyme core, and a plurality of protective layers are coated outside the enzyme core, so that the release and action time of the enzyme is delayed, and the cleaning effect of the washing powder is closer to a theoretical value; by limiting the components of the inner protective layer and the outer protective layer, the hydroxyethyl cellulose ether and the outer protective layer can reduce the possibility of soil redeposition synergistically, and the outer protective layer can greatly reduce the possibility of moisture absorption of the enzyme preparation;

4. the stabilizer is coated outside the sodium percarbonate, so that the possibility of sodium percarbonate decomposition in the washing powder storage process can be greatly reduced, the polyacrylamide serving as the stabilizer component also has the effect of protecting hands, and can be used for improving the phase separation property of dirt particles by cooperating with CMC-Na;

5. by limiting the coating process of the stabilizer, the complexity of the process can be reduced, and the production cost can be reduced;

6. by the production process of the washing powder, the possibility that the effect of each material of the washing powder is damaged in the production process is reduced, so that the washing effect of the washing powder is improved.

Detailed Description