GB2053880A - Improvements in and relating to zeolites - Google Patents
Improvements in and relating to zeolites Download PDFInfo
- Publication number
- GB2053880A GB2053880A GB8022826A GB8022826A GB2053880A GB 2053880 A GB2053880 A GB 2053880A GB 8022826 A GB8022826 A GB 8022826A GB 8022826 A GB8022826 A GB 8022826A GB 2053880 A GB2053880 A GB 2053880A
- Authority
- GB
- United Kingdom
- Prior art keywords
- zeolite
- suspensions according
- foregoing
- copolymer
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 46
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 35
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003381 stabilizer Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims abstract 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 229920002125 Sokalan® Polymers 0.000 abstract description 2
- 239000004584 polyacrylic acid Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001033 granulometry Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
By using an ethyl acrylate/methacrylic acid copolymer instead of the prior art polyacrylic acid stabilizer it is possible to obtain highly stable zeolite suspensions in water with less stabilizer and a higher concentration of zeolite. The copolymer may have a molecular weight of 10<5>-10<8> and the suspension may have a viscosity of 100-3500 centipoises. A suitable copolymer may contain about 35% by weight of methacrylic acid; the sodium salt of the copolymer may be used.
Description
SPECIFICATION
Improvements in and relating to zeolites
This invention relates to stabilized suspensions of zeolites in water.
British patent 1,529,713 discloses that, by dissolving a polymer of acrylic acid in deionized water and subsequently adding a zeolite, stable suspensions are obtained, which can be stored without sedimentation and have a viscosity sufficiently iow for transference and pumping even after long storing periods. From the same patent it can be inferred that the amount of stabilizer should range from 0.5 to 6% by weight in respect of the suspension, and that the molecular weight of the stabilizer should be relatively low; in fact a molecular weight of about 20,000 is suggested for the polyacrylic acid.
However, the stabilizer amounts indicated in the above-mentioned patent are anything but negligible.
It is an object of this invention to enable the preparation of stable suspensions of zeolites in water, having good rheological properties, by using very small amounts of stabilizer; further objects will clearly appear from the following description.
Broadly, this invention concerns stable suspensions of zeolites in water, endowed with good rheological properties, characterized by the presence of amounts of from 0.01 to 0.50%, preferably of from 0.05 to 0.20% by weight, with respect to the suspension, of a stabilizer consisting of a copolymer of ethylate with methacrylic acid, having a molecular weight ranging from 105 to 108, preferably from 500,000 to 106, and of amounts of anhydrous zeolite varying from 42 to 56% preferably from 48 to 54% by weight, with respect to the suspension.
As stabilizer it is possible to use the copolymer as such, or the product obtained by neutralizing the copolymer with caustic soda, i.e. the sodium salt.
It is remarkable that, by using the particular copolymer and quite high amounts of zeolite, the suspensions are more stable and less viscous, although the amount of stabilizer is much lower than hitherto employed.
The stable suspensions according to this invention may contain up to 70% by weight of zeolite 4A, of the general formula: Na20.AI203.2SiO2-4-5H2o corresponding to 56% by weight of anhydrous zeolite. The presence of the stabilizers according to the invention permits adjustment in a particularly simple way of the viscosity of the suspensions and therefore their rheolical characteristic during, transfer, storage, pumping and spray-drying operations.
Generally the viscosity of the suspensions according to this invention is between 100 and 3500 centipoises. Due to their high stability the suspensions according to this invention can be stored and transported by conventional tank cars, without formation of deposits which are difficult to re-disperse in the fluid part of the suspension. They can be used very advantageously for preparing products to be employed in water-softening and in particular for detergent formulations.
The stable suspensions according to the present invention can be prepared by various methods; for example it is possible first to add the stabilizer in aqueous solution and then the zeolite; or it is possible to synthesize the zeolite as an aqueous suspension, starting from aqueous soiutions of sodium aluminate and sodium silicate as described, for example, in our patent application 80/02858, and then directly to add the stabilizer to the wet zeolite discharged from the centrifuges, which would normally have been fed to a drying stage; if the amount of water is not sufficient for the desired purpose, it is merely necessary to add more. This procedure offers the great advantage of avoiding the drawbacks associated with powder handling. The alkalinity of the suspensions, generally from pH 11 to 13, does not affect the degree of stability.
The following Examples illustrate how the present invention may be carried into effect, without being however a limitation of the wider aspects thereof. In particular, although the Examples are all concerned with zeolites of type 4A, the invention is successfully applicable also to other types of zeolite and in particular to mixtures of zeolites of type 4A and of type X. The particle size of the zeolites for the suspensions according to this invention should be less than 100 ,um, preferably less than 30 ,um and, even better, less than 1 5 ,um.
EXAMPLES 1 to 5
At room temperature a stabilizer as described below was dissolved in deionized water (except in the case of comparative Example 1), whereupon a selected sample of zeolite A was added whilst stirring and at room temperature; the resulting suspension was kept stirred until homogenization was complete.
It was then allowed to stand at a temperature ranging from 20 to 250C in a vertical cylinder having a
diameter of about 3 cm and filled to a height of 1 20 mm. Finally, the stability of the suspension was
evaluated by application of the formula: (H-h)
S= x100 H
wherein S is the empirical degree of stability, H is the height of the suspension in the tank (120 mm)
and h is the height of the decanted sediment layer at the conclusion of the test; when h =0, the
maximum stability is attached (S = 100%). In the various tests different types of zeolite A were
employed, which had been obtained according to the method described in our patent application
80/02853.
The characteristics of the zeolites utilized in these Examples and in those that follow were: ZEOLlTEA/l Formula: Na2O.Al2O3.2SiO2.4.5H2O; crystallinity: 100% (determined by X-ray analysis). Exchange
power 172 mg of CaO per gram of anhydrous zeolite (determination carried out according to the
method described in our patent application 80/02853 and which comprises stirring the zeolite suspension in a CaCI2 solution for 15 minutes at 22 + 20 C).
Granulometry:
(determined in a Coulter Counter)
Size of the Particles Amounts of the particles
> 15 m 1.0%
> 10 m 2.0%
> 8 m 3.0% > 6,um 6.5%
> 4 m 35.0%
> 2 m 97.0%
ZEOLITE A/II
Formula and crystallinity: see Zeolite A/I; exchange power: 173.5 mg of CaO/g.
Granulometry:
Size of the Particles Amounts of the Particles > 15ym 1% > 10 m 2% > 8,um 3% > 6,um 5% > 4 ym 32% > ym 85% ZEOLITE Aglil Formula and crystallinity: see Zeolite A/I; exchange power: 176 mg of CaO/g.
Granulometry:
Size of the Particles Amounts of the Particles > 15y 0%
> 10 m 1.5% > 8 ym 2.5% > 6 m 10.0%
> 4 m 65.0%
> m 98.5%
As stabilizers the followina were used:
(a) a first copolymer, designated PA2, in which the ethyl acrylate/methacrylic acid ratio was 65/35 by weight, and the intrinsic viscosity of the copolymer (dissolved in dimethylformamide) was 1.1 5, corresponding to a molecular weight higher than 500,000;
(b) a second copolymer, designated PAl , obtained by neutralizing with caustic soda an aqueous 30% suspension of PA2, to a pH of 9 to 10.
In all the Examples the stabilizer was added as an aqueous 30% w/w suspension calculated as nonneutralized copolymer. Data and results are set out in Table I, together with those for the succeeding
Examples 6-10. The viscosities of the suspensions were determined by means of a BROOKFIELD
rotational viscosimeter.
TABLE 1
Initial viscosity Final stability of the Stabilizer Zeolite Delonized suspension (H-h) x 100 water (centipoise S= H Ex. Type g Type g (grams) at 25 C) Test period 1 absent - A/I 60 40 50 5 days 75% (*) 2 PA.1 0,09 " 60 40 100 1 days 98.5% 3 PA 1 0,09 " 60 40 100 7 days 96% 4 PA 1 0,24 " 60 40 720 12 " 100% 5 PA 2 0,24 " 60 40 800 12 " 100% 6 PA 2 0,10 A/II 62 38 240 4 days 99.5% 7 PA 2 0,10 " 62 38 240 12 days 97.5% 8 PA 2 0,20 " 62 38 1600 12 " 100% 9 PA 2 2(**) A/III 620 380 1480 12 " 100% 10 PA 2 2(**) " 620 380 1480 2 months 97.5% (*) The sedimentation layer appears as a consistent mass, absolutely not transferable by means of conventional pumps.
(**) = 0.20%.
EXAMPLES 6 to 10
A critical variant was introduced to the parameters of the preceding Examples: instead of adding the zeolite to the water, already mixed with the stabilizer, the zeolite was first dispersed in deionized water, whilst stirring, and then, with continued stirring, the predetermined amount of stabilizer was added. The encouraging results, set out out in Table I, suggest the possibility of directly using wet zeolite masses discharged from the zeolite production line, so avoiding drying operations: the actual realization of success in such a precedure is established by the following Examples.
EXAMPLE 11
20 kg of an aqueous dispersion of zeolite A/Ill having pH 11.5 and derived directly from a zeolite synthesis plant, without any drying step, were used as raw material.The dispersion contained about 46% by weight of water (including the crystallization water of the zeolite) and 54% by weight of an anhydrous zeolite (residue after calcination at 8000 C). 40 g of stabilizer PA2 (0.20% by weight referred to the suspension) were then added whilst stirring, the suspension was homogenized and the stability was evaluated after a long dwell; the suspension exhibited an initial viscosity of 1,560 centipoises (at 250 C) and a final stability, after 12 days, of 100%.
EXAMPLES 12 to 17
Examples 8 and 11 were repeated but subsequently causing the stabilizer-containing suspension to sediment at different temperatures and for different times, so obtaining the following results:
Final Stability (H - H) Ex. No. Temperature Test Period S= x 100 H 12 (*) 39 C 3 days 98.5% 13 (*) 39 C 12 " 98.5% 14 (**) 39 C 12 " 100% 15 (*) 8 C 3 days 98.5% 16 (*) 8 C 12 " 98.5% 17 (**) 8 C 12 " 100% (*) = repetition of Example 8
(**) = repetition of Example 11
Claims (16)
1. Stable aqueous suspensions of zeolites containing amounts of from 0.01 to 0.05% by weight, based on the suspension, of an ethyl acrylate/methacrylic acid copolymer stabilizer, and amounts of zeolite ranging from 42 to 56%, by weight, based on the suspension and calculated as the anhydrous zeolite.
2. Suspensions according to Claim 1, in which the stabilizer is added as an aqueous suspension.
3. Suspensions according to Claim 1 or 2, in which the intrinsic viscosity of the copolymer, determined in dimethyl-formamide solutions, is 1.1 to 1.2.
4. Suspensions according to Claim 1 or 2, in which the molecular weight of the copolymer ranges from 100,000 to 106
5. Suspensions according to any foregoing Claim, having a viscosity of from 100 to 3,500 centipoises.
6. Suspensions according to any foregoing Claim in which 0.05% to 0.20% by weight of the copolymer is present.
7. Suspensions according to any foregoing Claim in which 48% to 54% by weight of the zeolite is
present.
8. Suspensions according to any foregoing Claim in which the molecular weight of the copolymer is from 500,000 to 108.
9. Suspensions according to any foregoing Claim having a viscosity or 500 to 2,000 cent@poses
10. Suspensions according to any foregoing Claim having pH of 11 to 13.
11. Suspensions according to any foregoing Claim in which the zeolite is of type 4a, with a granulometric modulation index of or higher than 80.
12. Suspensions according to claim 11 in which the zeolite coarse fraction is 3% or less.
13. Suspensions according to any of Claims 1-10 in which the zeolite is a mixture of zeolites 4A and X.
14. Suspensions according to any of the foregoing Claims in which the copolymer stablizer is used in the form of a sodium salt.
15. Suspensions according to Claim 1, substantially as described in any of the foregoing Examples 2-11.
16. A method for the preparation of a suspension according to any of the foregoing Claims in which the wet zeolite masses discharged from a production line are fed directly to a vessel or vessels for the preparation of the suspension without intermediate drying and optionally after dilution with water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24372/79A IT1193481B (en) | 1979-07-16 | 1979-07-16 | STABLE SUSPENSIONS OF ZEOLITES IN WATER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2053880A true GB2053880A (en) | 1981-02-11 |
| GB2053880B GB2053880B (en) | 1983-03-16 |
Family
ID=11213301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8022826A Expired GB2053880B (en) | 1979-07-16 | 1980-07-11 | Zeolites |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE3026511A1 (en) |
| FR (1) | FR2461516A1 (en) |
| GB (1) | GB2053880B (en) |
| IT (1) | IT1193481B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2523950A1 (en) * | 1982-03-23 | 1983-09-30 | Mizusawa Industrial Chem | Zeolite suspension with static and dynamic stability - obtd. by neutralising suspension, adding organic polymer dispersant e.g. CMC and shearing |
| FR2655998A1 (en) * | 1989-12-18 | 1991-06-21 | Enimont Augusta Ind Srl | AQUEOUS STABLE SUSPENSIONS OF INORGANIC MATERIALS BASED ON SILICA AND INSOLUBLES IN WATER. |
| EP0459077A1 (en) * | 1990-06-01 | 1991-12-04 | Lion Corporation | Zeolite containing liquid detergent composition |
| EP0522365A1 (en) * | 1991-07-01 | 1993-01-13 | ENICHEM AUGUSTA INDUSTRIALE S.r.l. | Stable aqueous suspensions of zeolite which can be easily pumped |
| EP0580245A2 (en) * | 1992-07-20 | 1994-01-26 | Colgate-Palmolive Company | Stabilized built aqueous liquid softergent compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT335035B (en) * | 1974-10-10 | 1977-02-25 | Henkel & Cie Gmbh | STABLE SUSPENSIONS OF WATER-INSOLUBLE, SILICATES CAPABLE OF BINDING CALCIUMIONS AND THEIR USE FOR THE MANUFACTURE OF DETERGENTS AND DETERGENTS |
| DE2854484A1 (en) * | 1978-12-16 | 1980-06-26 | Bayer Ag | STABLE AQUEOUS ZEOLITE SUSPENSIONS |
-
1979
- 1979-07-16 IT IT24372/79A patent/IT1193481B/en active
-
1980
- 1980-07-11 FR FR8015473A patent/FR2461516A1/en active Granted
- 1980-07-11 GB GB8022826A patent/GB2053880B/en not_active Expired
- 1980-07-12 DE DE19803026511 patent/DE3026511A1/en not_active Withdrawn
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2523950A1 (en) * | 1982-03-23 | 1983-09-30 | Mizusawa Industrial Chem | Zeolite suspension with static and dynamic stability - obtd. by neutralising suspension, adding organic polymer dispersant e.g. CMC and shearing |
| FR2655998A1 (en) * | 1989-12-18 | 1991-06-21 | Enimont Augusta Ind Srl | AQUEOUS STABLE SUSPENSIONS OF INORGANIC MATERIALS BASED ON SILICA AND INSOLUBLES IN WATER. |
| GB2239236A (en) * | 1989-12-18 | 1991-06-26 | Enimont Augusta Ind | Stable aqueous suspensions of silica based, water insoluble inorganic materials |
| GR900100867A (en) * | 1989-12-18 | 1992-05-12 | Enimont Augusta Ind | Stable aqueous suspensions of inorganic materials on silica basis and insoluble in water |
| GB2239236B (en) * | 1989-12-18 | 1993-10-27 | Enimont Augusta Ind | Stable aqueous suspensionns of silica based,water insoluble inorganic materials |
| BE1006274A3 (en) * | 1989-12-18 | 1994-07-12 | Enimont Augusta Ind | Stable aqueous suspensions of contents inorganic silica based and water insoluble. |
| EP0459077A1 (en) * | 1990-06-01 | 1991-12-04 | Lion Corporation | Zeolite containing liquid detergent composition |
| US5182044A (en) * | 1990-06-01 | 1993-01-26 | Lion Corporation | Zeolite containing liquid detergent composition |
| EP0522365A1 (en) * | 1991-07-01 | 1993-01-13 | ENICHEM AUGUSTA INDUSTRIALE S.r.l. | Stable aqueous suspensions of zeolite which can be easily pumped |
| EP0580245A2 (en) * | 1992-07-20 | 1994-01-26 | Colgate-Palmolive Company | Stabilized built aqueous liquid softergent compositions |
| EP0580245A3 (en) * | 1992-07-20 | 1996-05-15 | Colgate Palmolive Co | Stabilized built aqueous liquid softergent compositions |
| TR28471A (en) * | 1992-07-20 | 1996-07-24 | Colgate Palmolive Co | Stabilized, hydrated liquid softerjan compounds. |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2461516B1 (en) | 1984-04-20 |
| DE3026511A1 (en) | 1981-02-05 |
| GB2053880B (en) | 1983-03-16 |
| FR2461516A1 (en) | 1981-02-06 |
| IT1193481B (en) | 1988-07-08 |
| IT7924372A0 (en) | 1979-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5229026A (en) | Linear viscoelastic aqueosous liquid automatic dishwasher detergent composition | |
| EP0848647B1 (en) | High solids lime as a caustic replacement | |
| US4280920A (en) | Stabilized aluminosilicate slurries | |
| EP0884312A1 (en) | Triazinylaminostilbene compounds | |
| US4529541A (en) | Stabilized zeolite A suspensions | |
| JPS60262899A (en) | Detergent composition containing builder for textile soft finish | |
| US4370171A (en) | Method for dispersing comminuted solids | |
| EP0407187A2 (en) | Aqueous thixotropic cleaning composition | |
| GB2053880A (en) | Improvements in and relating to zeolites | |
| JP3866764B2 (en) | Process for producing suspensions of cellulose ethers in water and dry mixtures suitable for use in the production of suspensions | |
| GB2048841A (en) | Suspensions of zeolites | |
| US2763633A (en) | Substantially non-caking compositions containing a normally coalescent copolymer of vinyl acetate and an ethylenically unsaturated organic carboxylic compound having at least one carboxyl group | |
| US4671887A (en) | Aqueous stable suspensions of water insoluble silicates capable of binding calcium ions and their use for the production of washing and cleaning agents | |
| WO2005028395A1 (en) | Stabilized slurry composition and method of making the same | |
| US3962115A (en) | Treatment of optical brightening agents | |
| US5034062A (en) | Use of acid-containing anionic emulsion copolymers as calcined clay slurry stabilizers | |
| US4692264A (en) | Stable, pumpable aqueous zeolite suspensions | |
| US5302314A (en) | Stable aqueous-suspensions of inorganic materials on silica basis and insoluble in water | |
| US5216100A (en) | Non-toxic stabilizing agent for aqueous suspensions of sodium silico-aluminates | |
| EP0517309A1 (en) | Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability | |
| US2507131A (en) | Method of incorporating gas into clay slurries | |
| JPS59223799A (en) | Aluminosilicate aqueous suspension for detergent | |
| JP2677100B2 (en) | Production method of chlorinated polyolefin | |
| JPH1135316A (en) | Amorphous aluminosilicate | |
| KR810000660B1 (en) | Improved process for detergent composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |