CN1295312C - Method for synthesizing washing adjuvant using concave-convex rod day - Google Patents
Method for synthesizing washing adjuvant using concave-convex rod day Download PDFInfo
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- CN1295312C CN1295312C CNB2005100945929A CN200510094592A CN1295312C CN 1295312 C CN1295312 C CN 1295312C CN B2005100945929 A CNB2005100945929 A CN B2005100945929A CN 200510094592 A CN200510094592 A CN 200510094592A CN 1295312 C CN1295312 C CN 1295312C
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Abstract
The present invention relates to a method for synthesizing auxiliary washing agents by using attapulgite clay, which belongs to the technical field of auxiliary washing agents. The present invention uses attapulgite clay as raw materials and defines the technological condition for acidizing and preroasting the attapulgite clay and the technological condition for the alkali fusion, the gelification and the crystallization of auxiliary washing agent zeolite synthesized by the pretreated active attapulgite clay. The auxiliary washing agent zeolite synthesized by attapulgite clay has the advantages of low cost, good using effect, strong ion exchange capacity, etc. Therefore, using attapulgite clay to produce auxiliary washing agents (synthesized zeolite) has strong market competitive power and wide prospect.
Description
Technical field
A kind of method with the attapulgite clay synthesizing washing adjuvant belongs to the washing auxiliary detergent technical field.
Background technology
Washing auxiliary detergent is one of main ingredient of washing composition, and the exploitation of washing composition of new generation and available New-type adjuvant product have close getting in touch.The most important character of washing auxiliary detergent is: washing absorption property, ion-exchange and environmental-protecting performance.At detergent applications, auxiliary agent commonly used has tripoly phosphate sodium STPP (STPP), synthetic zeolite and laminated crystalline bisilicate SKS-6.Wherein synthetic zeolite is to be made through synthesizing by mineral.Washing auxiliary detergent is because of different with using method from different places in the washing composition, its add-on difference.Auxiliary agent market, the world is divided into North America, Europe, Japan and Korea S usually, and these regional synthetic zeolites occupy ascendancy, and tripoly phosphate sodium STPP is almost all used in other parts of the world.
Auxiliary agent in the washing composition must possess several functions, and wherein most important function reduces water hardness from the beginning exactly, promptly must remove calcium, magnesium ion preventing generating incrustation scale at fabric and heating coil from washings, thereby improve the activity of tensio-active agent.The 2nd function of auxiliary agent is to give bath water alkalescence and shock-absorbing capacity.In addition also have other functions, such as disperseing dirt ability, auxiliary agent synergistic effect and improving comprehensive scourability etc.Tripoly phosphate sodium STPP (STPP) is the optimal up to now washing auxiliary detergent of synthetic detergent, is used for detergent industry existing more than 50 year.But, it is attacked because of can making the waters eutrophication.Therefore, since the seventies in 20th century, some industrially developed country's legislations such as Europe, the United States, day or self-discipline are prohibited, are limit phosphorus, cause its consumption to decline to a great extent, and are devoted to research and develop new builder as substitute for phosphate simultaneously.The builder as substitute for phosphate of generally acknowledging has synthetic zeolite, Trisodium Citrate, NTA and lamina sodium silicate etc.
Tripoly phosphate sodium STPP, zeolite and SKS-6 have in essence difference at softening water mechanism and state in waste water.Tripoly phosphate sodium STPP plays sequestrant in washings, and depolymerization in waste water causes surface water " eutrophication "; Zeolite works by ion-exchange in washing composition, it remains in washings and the waste water with the solid form, in entering waste disposal plant, remove with mud, though zeolite has good softening water performance, but it is water insoluble, also do not possess other functions, but because its cost advantage often is subjected to the favor of washing composition manufacturer.At present the turnout of China's free phosphate detergent is very low, far can not satisfy the demands, and actual mostly be low phosphorus product, the present situation of development, exploitation and the production of real free phosphate detergent product obviously and requirement on environmental protection incompatible.The external existing precedent that adopts nonmetal clay to make washing auxiliary detergent, and also genus is blank to this exploitation in China, therefore develops the attapulgite clay washing auxiliary detergent, oneself is extremely urgent to produce real free phosphate detergent product.
The prepare zeolite method, be divided into two kinds according to the unusual of raw material and technology: a kind of is complete synthesizing process, and another kind is a semi-synthesis method.Complete synthesizing process is raw material with the chemical feedstocks all, synthesizes zeolite by certain proportioning under certain process conditions.The zeolite monocrystalline that this method synthesizes is more obvious, and the slick and sly few corner angle of crystal, better performances, and steady quality, technical maturity, but cost is higher.Semi-synthesis method mainly with natural aluminium silicate mineral rock or industrial residue as raw material, through certain removal of impurities and pre-activation treatment, add composition and regulate raw material, it is molten to carry out alkali again, adds the crystal directed agents, last crystallization goes out zeolite crystal.The most sophisticated at present technology is to produce zeolite with kaolinite and wilkinite as raw material.
Attapulgite clay is the magnesia silicate minerals of a kind of aqueous layer chain.Its basic structural unit is 2: 1 stratotypes, the octahedra component units layer of promptly two-layer silicon-oxy tetrahedron folder one deck magnesia.The tetrahedral sheet angle is pushed up at a certain distance direction and is put upside down and the form layers chain-like structure in each 2: 1 layers.At tetrahedron bar interband, form the duct parallel with the C direction of principal axis, the duct sectional area is 3.8 * 6.3 , is filled with zeolite water in the duct.Itself has big specific surface area, strong adsorptive power and ion-exchange capacity.
Attapulgite clay semi-synthesis method synthetic zeolite does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of method with the attapulgite clay synthesizing washing adjuvant, both for attapulgite clay provides a kind of new Application Areas, the production for washing composition provides new washing auxiliary detergent again.
Technical scheme of the present invention: with the attapulgite clay is raw material, the technology of, gel molten, crystallization, filtration washing, drying, abrasive dust and packing and make synthetic zeolite through peracid treatment, filtration washing, roasting, alkali, and described technology is:
(1) raw material: pulverize through selected attapulgite clay, cross 200 mesh sieves;
(2) acid treatment: the sulfuric acid of getting quantitative 20%-30% concentration joins in the reactor that has stirring, when starting stirring and being heated to 60-80 ℃, drops into attapulgite clay by liquid-solid ratio 2: 1～3: 1L/kg, and dropping into finishes picks up counting acidification reaction time 4-7h;
(3) filtration washing: after acidifying finishes, carry out mother liquor and separate, the acidifying attapulgite clay is washed;
(4) roasting: the attapulgite clay after the washing sieves in 650-850 ℃ of roasting 1-3h;
(5) alkali is molten: the caustic soda of quantitative 25%-35% concentration is joined in the reactor that has stirring, start stirring, according to NaOH: SiO
2Mol ratio is 3: 1, and constantly the attapulgite clay behind the adding calcination activation in reactor is heated to reactor 60-70 ℃, reaction times 1.5-2h simultaneously;
(6) gel: add NaAlO
2With each component mol ratio of deionized water conditioned reaction system, the mole ratio range is controlled at the Na of 2.4-3.6mol
2The Al of O:1mol
2O
3: the SiO of 1.6-2.1mol
2: the H of 77-180mol
2O promptly controls H
2O/Na
2O is 32-60, SiO
2/ Al
2O
3Be 1.6-2.1, Na
2O/SiO
2Be 1.5-1.7, gelatinization temperature is 25-30 ℃, and time 1h stirs during gel;
(7) crystallization: stop after gelatinization reaction finishes stirring, heat up then, the heating-up time is controlled in the 30min, and crystallization temperature is 70-100 ℃, and crystallization time is 3-5h;
(8) filtration washing: the crystallization material is filtered, washs dealkalize;
(9) drying, abrasive dust, packing: carry out abrasive dust after dehydrating, packing promptly gets the synthetic zeolite powder.
Through determining after the optimization Test that acid treatment is a sulfuric acid of getting quantitative 20% concentration, when temperature of reaction is 70 ℃, drop into attapulgite clay, acidification reaction time 6h by liquid-solid ratio 2: 1L/kg.The calcination process temperature is 750 ℃, roasting time 1h.Alkali is molten: with the caustic soda of 30% concentration, and the molten time 2h of alkali, 70 ℃ of alkali solubility temperatures.Gel: add NaAlO
2With each component mol ratio of deionized water conditioned reaction system, the mole ratio range is controlled at H
2O/Na
2O is 50, SiO
2/ Al
2O
3Be 2, Na
2O/SiO
2Be 1.5,28 ℃ of gel 1h.At 100 ℃ of crystallization 3h.
Beneficial effect of the present invention: zeolite is synthetic by silicate minerals, as kaolin, wilkinite etc., since not phosphorous, water body is not polluted, so zeolite is the developing direction that various countries generally acknowledge as washing auxiliary detergent.Because attapulgite clay itself has the characteristic of zeolite, zeolite with attapulgite clay production has advantages such as cost is low, result of use good, ion-exchange capacity is strong, therefore it is extremely strong to produce washing auxiliary detergent (synthetic zeolite) market competitiveness with attapulgite clay, and prospect is very wide.
The research success of attapulgite clay washing auxiliary detergent, will become the main substitute of China's washing used additives, both can fill the domestic gaps, reduce environmental pollution, improve the utility value and the utilization ratio of Xuyi County's existing resource again greatly, improved Jiangsu Province's attapulgite clay technology content and added value of products.
The product of the present invention's preparation is through scanning electron microscope, X-ray diffraction analysis, and crystallization effect is good as can be known, contains any impurity crystal hardly.The zeolite crystal formation is intact, tiny evenly.Quality product has met or exceeded the advanced index of like product.
In washing powder, replace behind the part tripoly phosphate sodium STPP its soil removal efficiency and decontamination index all than the height that does not add this zeolite, thereby to utilize attapulgite clay synthetic zeolite be a kind of good washing auxiliary detergent to proof with the attapulgite clay synthetic zeolite.
Embodiment
Determining of embodiment 1 acid treatment and roasting pretreatment technology condition
Acid treatment is to the influence of synthetic zeolite
The acid treatment process is formed by attapulgite clay and structure all exerts an influence, and is that index is controlled with whiteness and calcium ion-exchanged capacity, is auxilliary in conjunction with iron, magnesium, aluminium, calcium, titanium plasma content detection simultaneously.The acid treatment temperature is selected in 60-80 ℃, and the method when adopting low temperature long suitably guarantees certain aluminum ions content, and in conjunction with whiteness and calcium ion-exchanged capacity situation, temperature is preferably at 70 ℃.
The influence of acid treatment time, the selection acidificatoin time is 4-7h.Take all factors into consideration whiteness and calcium ion-exchanged capacity, 6 hours preferred reaction time.
Acid concentration and ratio are to the influence of synthetic zeolite, and selecting pickling agent is the sulfuric acid of 20%-30% concentration, drop into attapulgite clay by liquid-solid ratio 2: 1-3: 1L/kg.Preferably use the sulfuric acid of 20% concentration, drop into attapulgite clay by liquid-solid ratio 2: 1L/kg.By to attapulgite clay energy spectrum analysis under this condition, ferric oxide has dropped to below 0.35%, and calcium oxide has dropped to below 0.4, titanium detect substantially less than.
Embodiment 2
Maturing temperature is selected 650-850 ℃, roasting 1-3h to the influence of synthetic zeolite.750 ℃ of preferred maturing temperatures, roasting 1h.
In sum, determine that the attapulgite clay pretreatment condition is: the sulfuric acid of getting quantitative 20% concentration joins in the reactor that has stirring, when starting stirring and being heated to 70 ℃, 2: 1 (L/kg) drops into attapulgite clay by liquid-solid ratio, input finishes and picks up counting, and acidifying finishes behind the reaction 6h, carries out mother liquor then and separates, washs, be placed on 750 ℃ of following roasting 1h, sieve.
Embodiment 3
Determining of zeolite synthesis processing condition
The composition of reaction mixture adds NaAlO to the influence of synthetic zeolite
2With each component mol ratio of deionized water conditioned reaction system, the mole ratio range is controlled at the Na of 2.4-3.6mol
2The Al of O:1mol
2O
3: the SiO of 1.6-2.1mol
2: the H of 77-180mol
2O promptly controls H
2O/Na
2O is 32-60, SiO
2/ Al
2O
3Be 1.6-2.1, Na
2O/SiO
2Be 1.5-1.7.
Discover that water-sodium ratio is less to the influence of product whiteness, but bigger to the influence of product calcium ion exchange capacity.This is because water-sodium ratio is lower than at 50 o'clock, and reaction system because the water yield is less, is difficult to stir when forming gel, makes synthetic zeolite calcium ion exchange capacity reduce.Therefore, water-sodium ratio is advisable with 50-55.
When discovering that silica alumina ratio is between 1.6-2.1, the variation of silica alumina ratio is little to the quality influence of synthetic zeolite.Therefore guaranteeing that product is under the prerequisite of 4A zeolite, reducing cost that silica alumina ratio should be the bigger the better for reducing the sodium aluminate addition.
Discover that sodium-silicon-rate is advisable between 1.5-1.7, the whiteness of synthetic zeolite and calcium ion exchange capacity are all than higher.
The influence of gel process temperature
When hydrothermal synthesis reaction, the temperature when adding sodium metaaluminate formation gel generally is advisable with 25-30 ℃.The too high meeting of temperature reduces the calcium ion exchange capacity of synthetic 4A zeolite.
The influence of crystallization process temperature and time
In the crystallization process stage, improve dispersion and dissolving that crystallization temperature can promote the gel solid phase, make medium more even, increase the liquid phase component ratio of system, improve crystallization rate, shorten the crystallization phase.But along with temperature rising system force of crystallization strengthens, easily form crystal stock and glomerocryst, cause a grain size inhomogeneous, the calcium exchange capacity descends.
Discover that crystallization temperature is advisable at 70-100 ℃, it is also to be noted that the heating-up time should be controlled in the 30min, the heating-up time is long, and quality product is difficult for guaranteeing.
Crystallization time is another important factor that influences the crystallization effect.Prolongation crystallization time (insulation) can improve the purity of synthetic zeolite.But after a large amount of generations of zeolite, still too prolong crystallization time, can influence production cycle and output on the one hand, increase production cost, on the other hand because zeolite is the metastable state material on a kind of thermodynamic significance, along with the prolongation zeolite of time may transform into hydroxysodalite, cause quality product to descend.Therefore crystallization time generally is controlled at 3-5h.
The influence of stirring
One-tenth glue process with the industrial chemicals synthetic zeolite is wanted violent stirring, and the crystallization stage can stop to stir, and is allowed to condition at slowly crystallization under the stationary state.Al in the calcining attapulgite clay
2O
3And SiO
2Be evenly distributed, NaOH solution is good to the wettability of calcining attapulgite clay, so becoming glue stage stirring velocity less demanding.
But because the calcining attapulgite clay is in solid state in whole process always, batching is suspension rather than colloidal solution, so crystallisation stage also needs to stir.Stir in crystallization process, can improve the fineness of product, stirring velocity increases, and the median size of zeolite obviously descends, and small-particle content significantly increases, but little to the calcium ion exchange capacity influence of zeolite.
In sum, determine that the processing condition of attapulgite clay synthetic zeolite are: behind the molten 2h of NaOH alkali with 30% concentration under 70 ℃, add sodium aluminate and deionized water and regulate proportioning, make the reaction system proportioning consist of water-sodium ratio (H
2O/Na
2O) 50, silica alumina ratio (SiO
2/ Al
2O
3) 2, sodium-silicon-rate (Na
2O/SiO
2) 1.5,28 ℃ down with becoming glue 1h, is warming up to 100 ℃ then, after crystal synthesizes 3h, material is filtered, washs dealkalize, promptly gets zeolite powder after dehydrating.
Embodiment 4
The evaluation of synthetic zeolite
Table 1 product quality indicator
| Index name | Product of the present invention | Q/HGJ02-05-91 | U.S. P﹠G | |
| One-level | Secondary | |||
| Calcium ion-exchanged capacity (mgCaCO 3/g) | 295 | 240 | 212 | 300 |
| Granularity (%) (primary particle size＜4%) | 87 | ≥80 | ≥80 | |
| Mean particle size (μ m) | 3.10 | 4-6 | ||
| Whiteness (%) | 93.5 | ≥85 | ≥80 | |
| The pH value | 12 | 12 | 12 | 10.0-11.1 |
| Moisture (%) | 20.8 | ≤24 | ≤24 | |
Product is through scanning electron microscope, X-ray diffraction analysis, and crystallization effect is good as can be known, contains any impurity crystal hardly.The zeolite crystal formation is intact, tiny evenly.Quality product has met or exceeded the advanced index of like product.
The synthetic zeolite product replaces 50% tripoly phosphate sodium STPP with the zeolite of 1.5 times of amounts, tests its clean effect and is listed in the table below
Table 2 clean effect comparison sheet
| Standard flour | Common washing powder | The washing powder that adds the attapulgite clay synthetic zeolite | |
| Soil removal efficiency | 52.3 | 60.1 | 64.6 |
| Decontamination index | 1 | 1.15 | 1.24 |
| With common washing powder decontamination ratio | 1 | 1.07 |
In washing powder, replace behind the part tripoly phosphate sodium STPP its soil removal efficiency and decontamination index all than the height that does not add synthetic zeolite as can be seen from the table, thereby to utilize attapulgite clay synthetic zeolite be a kind of good washing auxiliary detergent to proof with synthetic zeolite.
Claims (5)
1. method with the attapulgite clay synthesizing washing adjuvant, it is characterized in that with the attapulgite clay being raw material, the technology of, gel molten, crystallization, filtration washing, drying, abrasive dust and packing and make synthetic zeolite through peracid treatment, filtration washing, roasting, alkali, described technology is:
(1) raw material: attapulgite clay is pulverized, and crosses 200 mesh sieves;
(2) acid treatment: the sulfuric acid of getting quantitative 20%-30% concentration joins in the reactor that has stirring, when starting stirring and being heated to 60-80 ℃, drops into attapulgite clay by liquid-solid ratio 2: 1～3: 1L/kg, and dropping into finishes picks up counting acidification reaction time 4-7h;
(3) filtration washing: after acidifying finishes, carry out mother liquor and separate, the acidifying attapulgite clay is washed;
(4) roasting: the attapulgite clay after the washing sieves in 650-850 ℃ of roasting 1-3h;
(5) alkali is molten: the caustic soda of quantitative 25%-35% concentration is joined in the reactor that has stirring, start stirring, according to NaOH: SiO
2Mol ratio is 3: 1, and constantly the attapulgite clay behind the adding calcination activation in reactor is heated to reactor 60-70 ℃, reaction times 1.5-2h simultaneously;
(6) gel: add NaAlO
2With each component mol ratio of deionized water conditioned reaction system, the mole ratio range is controlled at the Na of 2.4-3.6mol
2The Al of O:1mol
2O
3: the SiO of 1.6-2.1mol
2: the H of 77-180mol
2O, gelatinization temperature are 25-30 ℃, and time 1h stirs during gel;
(7) crystallization: stop after gelatinization reaction finishes stirring, heat up then, the heating-up time is controlled in the 30min, and crystallization temperature is 70-100 ℃, and crystallization time is 3-5h;
(8) filtration washing: the crystallization material is filtered, washs dealkalize;
(9) drying, abrasive dust, packing: carry out abrasive dust after dehydrating, packing promptly gets the synthetic zeolite powder.
2. the method for synthesizing washing adjuvant according to claim 1 is characterized in that acid treatment is a sulfuric acid of getting quantitative 20% concentration, and temperature of reaction is 70 ℃, drops into attapulgite clay, acidification reaction time 6h by liquid-solid ratio 2: 1L/kg.
3. the method for synthesizing washing adjuvant according to claim 1 is characterized in that the calcination process temperature is 750 ℃, roasting time 1h.
4. the method for synthesizing washing adjuvant according to claim 1 is characterized in that alkali is molten: with the caustic soda of 30% concentration, and the molten time 2h of alkali, 70 ℃ of alkali solubility temperatures.
5. the method for synthesizing washing adjuvant according to claim 1 is characterized in that gel: add NaAlO
2With each component mol ratio of deionized water conditioned reaction system, the mole ratio range is controlled at H
2O/Na
2O is 50, SiO
2/ Al
2O
3Be 2, Na
2O/SiO
2Be 1.5,28 ℃ of gel 1h; Crystallization: at 100 ℃ of crystallization 3h.
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| CN1295312C true CN1295312C (en) | 2007-01-17 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101342133B (en) * | 2008-08-25 | 2010-09-08 | 贾剑 | Concave-convex stick walnut shampoo |
| CN101342132B (en) * | 2008-08-25 | 2010-09-08 | 贾剑 | Attapulgite Chinese aloe shampoo |
| CN101342127B (en) * | 2008-08-25 | 2010-08-04 | 许庆华 | Concave-convex stick alopecia-proof anti-dandruff shampoo |
| CN101401773B (en) * | 2008-10-28 | 2010-06-23 | 郁承耀 | Attapulgite shaving gel rubber |
| CN106190643A (en) * | 2015-05-04 | 2016-12-07 | 蒋华 | A kind of method of attapulgite clay synthesizing washing adjuvant |
Citations (7)
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|---|---|---|---|---|
| EP0565364A1 (en) * | 1992-04-09 | 1993-10-13 | Crosfield Limited | Aluminosilicates |
| CN1113263A (en) * | 1995-05-17 | 1995-12-13 | 北京大学 | Method for preparation of modified zeolite assistant in detergent powder |
| CN1138630A (en) * | 1995-06-16 | 1996-12-25 | 湛江市坡头区非金属矿产公司 | Process for prodn. of phosphorus-free washing powder by utilizing 4A zeolite |
| WO1997034980A1 (en) * | 1996-03-15 | 1997-09-25 | Crosfield Limited | Modified aluminosilicate |
| CN1219505A (en) * | 1997-12-09 | 1999-06-16 | 南京大学 | Production technique for producing washing builder 4A zeolite by semi-synthesis method |
| WO2001094512A1 (en) * | 2000-06-02 | 2001-12-13 | Ineos Silicas Limited | Zeolite compositions and their use |
| WO2002004350A1 (en) * | 2000-07-12 | 2002-01-17 | Mizusawa Industrial Chemicals,Ltd. | Particulate zeolite and use thereof |
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2005
- 2005-09-26 CN CNB2005100945929A patent/CN1295312C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0565364A1 (en) * | 1992-04-09 | 1993-10-13 | Crosfield Limited | Aluminosilicates |
| CN1113263A (en) * | 1995-05-17 | 1995-12-13 | 北京大学 | Method for preparation of modified zeolite assistant in detergent powder |
| CN1138630A (en) * | 1995-06-16 | 1996-12-25 | 湛江市坡头区非金属矿产公司 | Process for prodn. of phosphorus-free washing powder by utilizing 4A zeolite |
| WO1997034980A1 (en) * | 1996-03-15 | 1997-09-25 | Crosfield Limited | Modified aluminosilicate |
| CN1219505A (en) * | 1997-12-09 | 1999-06-16 | 南京大学 | Production technique for producing washing builder 4A zeolite by semi-synthesis method |
| WO2001094512A1 (en) * | 2000-06-02 | 2001-12-13 | Ineos Silicas Limited | Zeolite compositions and their use |
| WO2002004350A1 (en) * | 2000-07-12 | 2002-01-17 | Mizusawa Industrial Chemicals,Ltd. | Particulate zeolite and use thereof |
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