CN1109095C - Phosphorusfree and aluminium-free washing powder and its manufacture technology - Google Patents

Phosphorusfree and aluminium-free washing powder and its manufacture technology Download PDF

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CN1109095C
CN1109095C CN00100588A CN00100588A CN1109095C CN 1109095 C CN1109095 C CN 1109095C CN 00100588 A CN00100588 A CN 00100588A CN 00100588 A CN00100588 A CN 00100588A CN 1109095 C CN1109095 C CN 1109095C
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sodium
powder
free
ether
agent
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CN1260385A (en
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杜倩
姚宝书
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Tianjin Household Chemicals Factory
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Tianjin Household Chemicals Factory
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Abstract

The present invention relates to a manufacturing technology for non-phosphorus washing powder. The non-phosphorus washing powder is prepared from components of the following percentage by weight: 15% to 35% of composite surface active agent, 5% to 40% of composite builder, 40% to 60% of bulking agent and 0% to 2% of forming agent, wherein the composite surface active agent is prepared from an anionic surface active agent group and a nonionic surface active agent group; the composite builder is prepared from sodium polyacrylate; sodium silicate and sodium carbonate; the bulking agent is prepared from anhydrous sodium sulfate; the forming agent is prepared from dimethyl silicon oil or amino silicone oil. The present invention can dissolve in common warmed water, has great detersive power in acidic water, has no irritation to the skin, and is completely environmental protection type nontoxic washing powder.

Description

A kind of phosphate-free and aluminum-free washing powder and manufacturing process thereof
The present invention relates to a kind of manufacturing of non-phosphide detergent, particularly its phosphate-free and aluminum-free environment-friendly washing powder and method of manufacturing technology thereof of forming by complexed surfactant, compound washing assistant, weighting agent and forming agent etc.
Washing powder in the past all is the major surfaces promoting agent with the sodium alkyl benzene sulfonate, and adding a large amount of P contained compounds is that tripoly phosphate sodium STPP is to improve its function.For example, Japan special permission communique JP63-39640 discloses alkyl benzene sulphonate (ABS) sodium content 12%, and the tripolyphosphate sodium content is up to 36%.P contained compound such as contained tripoly phosphate sodium STPP in the washing powder causes river, river, the rich phosphatization in lake, makes animals and plants such as aquatic algae breed death in a large number, has polluted human drinking-water resource of depending on for existence, causes public hazards to global environment.Non-phosphide detergent is the major surfaces promoting agent with the sodium alkyl benzene sulfonate still at present, uses aluminum contained compound---zeolite replaces tripoly phosphate sodium STPP, and for example Japan speciallys permit open JP63-06098, and benzene sulfonamide phenol sodium content is 20%, and zeolite content reaches 15%.Aluminum contained compound can be accumulated and chronic poisoning in human body, and severe patient can cause dementia and renal failure.Though, prohibit phosphorus at detergent applications, limit the phosphorus tide to have swept the globe, however aluminum contained compound harm not causing as yet people's extensive attention.But the trend of people's universal demand " green " articles for washing is quite swift and violent, irresistible.
The purpose of this invention is to provide a kind of phosphate-free and aluminum-free washing powder and manufacturing process thereof.Phosphate-free and aluminum-free of the present invention is solvable Jie in normal-temperature water, and very strong detersive power is also arranged in sour water, and is non-stimulated to skin, is a kind of non-poisonous washing powder of environment-friendly type fully.
The present invention includes complexed surfactant, compound washing assistant, weighting agent and forming agent forms; Wherein complexed surfactant is by anion surfactant family and nonionogenic tenside group composition; Compound washing assistant is made up of sodium polyacrylate, water glass and yellow soda ash; Weighting agent is an anhydrous sodium sulphate; Forming agent is dimethyl silicone oil or amido silicon oil.
The weight percent of each component of the present invention is:
Complexed surfactant 15~35%
Compound washing assistant 5~40%
Weighting agent 40~60%
Forming agent 0~2%.
Anion surfactant is made up of α-sodium olefin sulfonate, sodium lauryl sulphate and sodium soap soap powder in the complexed surfactant of the present invention, and its weight percent is:
α-sodium olefin sulfonate 2~14%
Sodium lauryl sulphate 3~15%
Sodium soap soap powder 2~15%.
Nonionogenic tenside is made up of aliphatic alcohol polyethenoxy (9) ether, alkylphenol-polyethenoxy (10) ether and fatty acid alkyl amide in the complexed surfactant of the present invention, and its weight percent is:
Aliphatic alcohol polyethenoxy (9) ether 0.5~5%
Alkylphenol-polyethenoxy (10) ether 0.5~4%
Fatty acid alkyl amide 0.5~2%.
Each composition weight percent of the compound washing assistant of the present invention is:
Sodium polyacrylate 1~5%
Water glass 1~10%
Yellow soda ash 5~20%.
Manufacturing process of the present invention adopts the attached polymer molding technology, and specific operation process is: at room temperature the solid powder that separated pulverizing is good is dropped into powder by metering and give in the mixed device, mixed 3~15 minutes, powder is mixed; Liquid material is given in the mixed pot by being metered into liquid, make the logical vapour of interlayer be warmed up to 40~60 ℃, mixed 5~10 minutes, liquid material is mixed.Then with the solid powder that mixes by being metered in the Conicaldoublewormmixer, start the back duplex and carry out rotation revolution (two asymmetric screw shaft rotations in the mixing machine after 2~10 minutes, material is upwards promoted, form asymmetrical along cylinder body tube arm stud-shape streams from bottom to top, drive the spiral revolution by pivoted arm more simultaneously, along cylindrical shell wholecircle Zhou Fangwei running, reach the continual renovation diffusion of wholecircle Zhou Fangwei material.Like this, owing to rotation revolution planetary motion forms the material convection circulation.), will give mixed liquid material constant speed atomisation equably by the measuring fixed amount liquor pump, be sprinkled upon on the moving powder, carry out agglomeration, granulating and forming 3~15 minutes sprays into forming agent and essence (trace) at last, reruns shutdown, discharging 2-5 minute.Obtain even phosphate-free and aluminum-free washing powder product after making molding materials by the screening of ternary vibrating screener again.
The advantage that the present invention compared with prior art has is:
The present invention selects for use nonionogenic tensides such as anion surfactant such as α-sodium olefin sulfonate, sodium lauryl sulphate, sodium soap soap powder and aliphatic alcohol polyethenoxy (9) ether, alkylphenol-polyethenoxy (10) ether, fatty acid alkyl amide collaborative composite, has replaced sodium alkyl benzene sulfonate.α-sodium olefin sulfonate LD 50=3.26g/kg belongs to No Poison (this sodium sulfonate of alkyl LD 50=1.62g/kg), to skin non-stimulated (content is in 10% coating test-results), action temperature and, biodegradation rate is fast, the disappearance of can degrading fully in five days (sodium alkyl benzene sulfonate after month still residual 30%), and detersive power also is better than sodium alkyl benzene sulfonate, especially in hard water, when hardness equaled 100mg/kg, decontamination was higher than sodium alkyl benzene sulfonate (65%) far away still up to 83%.Excellent in importantly being that it and fatty acid sodium soap coupling can be solubilized in the water altogether, test-results is as follows:
α-olefin sulfonic acid sodium content (%) fatty acid sodium soap solubleness in water increases (%)
2 17.3
4 20.3
5 22.7
6 24.7
8 27.0
10 31.6
15 48.4
20 74.4
Therefore, α-sodium olefin sulfonate and action temperature and, be that biological degradation is nontoxic, but solubleness is little in water, the fatty acid sodium soap that easily forms soap scum in hard water is composite, will give full play to the fatty acid sodium soap advantage and significantly reduces its shortcoming, again with fully biodegradable, strong detergency, the good No Poison sodium lauryl sulphate of cold washing constitutes jointly anion surfactant family.The present invention simultaneously selects for use anti-hard water to deoil, and dirt is strong, wettability is good, but the nonionogenic tenside family that nonionogenic tenside aliphatic alcohol polyethenoxy (9) ether of cold washing, alkylphenol-polyethenoxy (10) ether and fatty acid alkyl amide are formed.Like this, the a small amount of nonionogenic tenside of adding family in anion surface activity family, anion surfactant ion head mutual expelling force is reduced, van der Waals' force between hydrophobic base key strengthens, impel capsule to be easy to form, make critical capsule concentration reduce the capsular formation of this mixing, produce best synergistic effect, thereby replaced sodium alkyl benzene sulfonate.
It is to be made of sodium polyacrylate, water glass and yellow soda ash that the present invention selects compound washing assistant for use, result of study shows, sodium polyacrylate (average molar mass: 6000~7000g/mol) just big 50~100 μ m dirt granule can be dispersed at lower concentration (20mg/L)<below the 1 μ m, 50~100 μ m calcium soap scums are dispersed into<below the 1 μ m, fine particle forms milk shape dispersion system like this, needn't precipitate, very easily rinsing.And tripoly phosphate sodium STPP can make the cohesion of dirt granule, and particle increases.It is acid that dirt generally is, the washing composition meta-alkalescence, and both neutralizations weaken washing lotion alkalescence, and the sodium polyacrylate resistance to acid is better than tripoly phosphate sodium STPP, can keep washing the system slight alkalinity, and reduce the lotion consumption.Different auxiliary agents are to the clean effect difference of different pollutents, and result of study such as table 1, table 1 are the clean effect comparisons of different auxiliary agents to different pollutents.
According to result of study, because sodium polyacrylate disperses the effect of dirt granule calcium soap scum by force, carbon black, Manganse Dioxide, kaolin are shown fine clean effect, but it is relatively poor that oily dirt is removed ability; Yellow soda ash since alkalescence show more by force Viscotrol C, removal effect that machine oil is strong; Water glass has the suspended dispersed effect because of hydrolysis in water medium can produce the silicic acid of capsule structure to dirt, and is good to the carbon black removal effect.Therefore, the present invention is with sodium polyacrylate, and yellow soda ash and water glass have carried out reasonable group of change, constitute compound washing assistant, and detersive power is improved greatly, can replace tripoly phosphate sodium STPP fully.Zeolite is made good use of carbon black, machine oil owing to its adsorption with to band coloring agent capsule dirt coagulation as can be known simultaneously, and this also is present non-phosphide detergent replaces tripoly phosphate sodium STPP with zeolite a reason.Yet zeolite is a silico-aluminate, is aluminum contained compound, and is harmful, also can get carefully sooner or later, and the present invention will not adopt.
Substrate is dipped in the medium because washing composition exists, make dirt and substrate surface bonding become dirt and combine with lotion, thereby dirt is broken away from and substrate surperficial and be suspended in the medium.Yet washing process is a reversing process, and the dirt that is suspended in the medium also might be redeposited in the substrate surface from medium, i.e. the redeposition process.The present invention complexed surfactant and compound washing assistant, under the prerequisite of phosphate-free and aluminum-free, reached the bonding force that has both reduced dirt and substrate surface, impel dirt to break away from the substrate surface, prevent to have washed off soil redeposition substrate surface simultaneously, made soil dispersion become milk shape dispersion, not only be difficult to deposition, and very easily rinsing, acquire strong detersive power (the decontamination ratio can reach more than 1.3~1.8 relatively).Also, in normal-temperature water, can dissolve fully because the outstanding combination of tensio-active agent of the present invention reduces best wash temperature.Washing powder concentration 2.5% pH value of solution value of the present invention is 7.5 ± 0.3, it is nearly neutral environment washing, and select for use tensio-active agent all to belong to low to stimulate non-stimulated product, thereby product of the present invention after measured to rabbit skin irritant reaction average integral in 0~0.31 scope, belong to the nonirritant product.Because this product selects for use raw material to be No Poison, through toxicity check, product LD of the present invention 50=9.26g/kg ± 0.20 (male mice), LD 50=7.94g/kg ± 0.20 (female mice), so product of the present invention is nontoxic product.
Manufacturing process of the present invention is easy, and is easy to control easy to operate, do not have the waste water and gas waste sludge discharge in manufacturing processed, thereby not only product is " green ", and to make production process also be green, is a cleaning project.After the present invention's product is used for laundry, discharging raffinate phosphate-free and aluminum-free, biological degradation has no adverse effects to environment rapidly and fully, is environmentally friendly machine.
The invention will be further described to quote embodiment below:
Embodiment 1
At room temperature with α-sodium olefin sulfonate 12kg, sodium lauryl sulphate 10kg, sodium soap soap powder 15kg, yellow soda ash 15kg, water glass 8kg, anhydrous sodium sulphate 93kg drop into powder and give in the mixed device, start and stir after 10 minutes, stop to stir, drop in the Conicaldoublewormmixer and start and stir.Meanwhile with aliphatic alcohol polyethenoxy (9) ether 4kg, alkylphenol-polyethenoxy (10) ether 3kg, fatty acid alkyl amide 2kg and sodium polyacrylate 2kg drop into liquid and give in the mixed device, start and stir and make the interlayer intensification, when the liquid material temperature reaches 50 ℃, after keeping 10 minutes under stirring, by microprocessor pump drive with uniform acceleration, by shower nozzle motion powder sprinkling in Conicaldoublewormmixer, after finishing, sprinkling continued the agglomeration granulating and forming again 5 minutes, and then spraying into dimethyl silicone oil 0.6kg, essence 0.4kg continues moulding shutdown in 2 minutes discharging.Shaped granule is dropped into the screening of ternary vibrating screener, promptly obtain the phosphate-free and aluminum-free washing powder product.2.5% aqueous solution pH7.5 by analysis, the decontamination ratio reaches 1.8 (GB/T13174-91) LD relatively 50=9.26g/kg (male mice), LD 50=7.94g/kg (female mice) is to rabbit skin irritant reaction average integral 0.25.
Embodiment 2
Operation steps is with embodiment 1, but used component raw material and proportioning are as follows:
α-sodium olefin sulfonate 8kg
Sodium lauryl sulphate 7kg
Sodium soap soap powder 4kg
Water glass 10kg
Yellow soda ash 5kg
Anhydrous sodium sulphate 60kg
Aliphatic alcohol polyethenoxy (9) ether 3kg
Alkylphenol-polyethenoxy (10) ether 1kg
Fatty acid alkyl amide 0.5kg
Sodium polyacrylate 1kg
Dimethyl silicone oil 0.4kg
Essence 0.4kg
By analysis, 2.5% aqueous solution pH7.3, relative decontamination ratio 1.75 (GB/T13174-91), LD 50=9.10g/kg (male mice), LD 50=8.00g/kg (female mice) is to rabbit skin irritation and should average 0.30.
Embodiment 3
Operation steps is with embodiment 1, but used constitutive material proportioning is as follows:
α-sodium olefin sulfonate 5kg
Sodium lauryl sulphate 4kg
Sodium soap soap powder 4kg
Water glass 10kg
Yellow soda ash 22kg
Anhydrous sodium sulphate 70kg
Aliphatic alcohol polyethenoxy (9) ether 2.5kg
Alkylphenol-polyethenoxy (10) ether 2kg
Fatty acid alkyl amide 1.5kg
Sodium polyacrylate 3kg
Amido silicon oil 0.3kg
Essence 0.2kg
By analysis, 2.5% aqueous solution pH7.8, relative decontamination ratio 1.4 (GB/T13174-91), LD 50=9.18g/kg (male mice), LD 50=8.10g/kg (female mice) is to rabbit skin irritant reaction average integral 0.31.
Embodiment 4
Operation is with embodiment 1, but used constitutive material proportioning is as follows:
α-sodium olefin sulfonate 4kg
Sodium lauryl sulphate 5kg
Sodium soap soap powder 10kg
Water glass 12kg
Yellow soda ash 20kg
Anhydrous sodium sulphate 70kg
Aliphatic alcohol polyethenoxy (9) ether 0.5kg
Alkylphenol-polyethenoxy (10) ether 1.0kg
Fatty acid alkyl amide 0.5kg
Sodium polyacrylate 4kg
By analysis: 2.5% aqueous solution pH7.7, relative decontamination ratio 1.3 (GB/T13174-91), LD 50=8.95 (male mices), LD 50=7.89 (female mices) are to rabbit skin irritant reaction average integral 0.31.
Table 1
Auxiliary agent Detersive power (%)
Tap water Viscotrol C Kaolin Carbon black Machine oil Titanium dioxide is violent
Blank * 13.8 38.5 20.8 42.33 33.4 22.5
Tripoly phosphate sodium STPP 32.2 39.5 28.3 44.38 44.6 24.9
Na 2CO 3 24.7 47.9 64.4 37.81 43.6 21.2
Na 2SiO 3 21.9 34.9 24.9 52.47 38.2 25.9
Sodium polyacrylate 30.9 24.1 34.4 58.22 30.4 67.3
Trisodium Citrate 13.7 28.6 30.7 54.79 37.4 31.9
Xylo-Mucine 16.2 30.8 27.4 41.29 32.8 20.3
Zeolite (4A) 22.9 40.9 21.5 47.12 49.8 25.3

Claims (3)

1. phosphate-free and aluminum-free washing powder is characterized in that it is made up of complexed surfactant, compound washing assistant, weighting agent and optional forming agent; Said complexed surfactant is made up of anion surfactant family and nonionogenic tenside; Said compound washing assistant is made up of sodium polyacrylate, water glass and yellow soda ash; Said weighting agent is an anhydrous sodium sulphate; Said forming agent is dimethyl silicone oil or amido silicon oil; The weight percent of above-mentioned each component is:
Complexed surfactant 15~35%
Compound washing assistant 5~40%
Weighting agent 40~60%
Forming agent 0~2%
The essence trace;
Anion surfactant is α-sodium olefin sulfonate, sodium lauryl sulphate and sodium soap soap powder in the said complexed surfactant, and its weight percent is:
α-sodium olefin sulfonate 2~14%
Sodium lauryl sulphate 3~15%
Sodium soap soap powder 2~15%;
Nonionogenic tenside is aliphatic alcohol polyethenoxy (9) ether, alkylphenol-polyethenoxy (10) ether and fatty acid alkyl amide in the said complexed surfactant, and its weight percent is:
Aliphatic alcohol polyethenoxy (9) ether 0.5~5%
Alkylphenol-polyethenoxy (10) ether 0.5~4%
Fatty acid alkyl amide 0.5~2%.
2. according to the said phosphate-free and aluminum-free washing powder of claim 1, it is characterized in that said compound washing assistant is sodium polyacrylate, water glass and yellow soda ash, its weight percent is:
Sodium polyacrylate 1~5%
Water glass 1~10%
Yellow soda ash 5~20%.
3. the method for manufacturing of the said phosphate-free and aluminum-free washing powder of claim 1 is characterized in that it is through step:
At room temperature component pressed powder material is given in the mixed device by being metered into powder, start 3~15 minutes and make mixing of materials even; Liquid material is given in the mixed pot by the liquid that is metered into the strap clamp layer, be warmed up to 40~60 ℃, make the liquid material thorough mixing even, need 5-10 minute approximately; Be added in the Conicaldoublewormmixer by metering giving mixed powder material, start the back duplex and carry out the rotation revolution after 2-10 minute, to give the even liquid material that is mixed by measuring by volume pump, import by swivel joint, shower nozzle nebulizes and is sprayed at equably in the powder of motion by the road, carries out the agglomeration granulating and forming 3~15 minutes, sprays into forming agent and essence at last, continue operation 2~5 minutes again, shutdown, discharging; With molded material,, promptly get the phosphate-free and aluminum-free washing powder product by the screening of ternary vibrating screener.
CN00100588A 2000-01-28 2000-01-28 Phosphorusfree and aluminium-free washing powder and its manufacture technology Expired - Fee Related CN1109095C (en)

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CN1109095C true CN1109095C (en) 2003-05-21

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106669536A (en) * 2015-11-05 2017-05-17 南通恒成化工有限公司 Composite surfactant
CN106753831B (en) * 2016-12-29 2020-04-28 上海和黄白猫有限公司 Washing powder slurry with high fluidity and preparation method thereof
CN108060037B (en) * 2017-12-25 2020-09-04 上海和黄白猫有限公司 Soap powder composition of sodium oleate and its preparation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1214362A (en) * 1997-10-14 1999-04-21 成都市瑞泰技术研究所 Phosphate-free disinfecting washing powder
CN1220307A (en) * 1997-07-21 1999-06-23 杜正涛 Method for preparation of non-phosphate high bulked washing powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1220307A (en) * 1997-07-21 1999-06-23 杜正涛 Method for preparation of non-phosphate high bulked washing powder
CN1214362A (en) * 1997-10-14 1999-04-21 成都市瑞泰技术研究所 Phosphate-free disinfecting washing powder

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