GB1571535A - Crystalline zeolite powder of type - Google Patents
Crystalline zeolite powder of type Download PDFInfo
- Publication number
- GB1571535A GB1571535A GB4703277A GB4703277A GB1571535A GB 1571535 A GB1571535 A GB 1571535A GB 4703277 A GB4703277 A GB 4703277A GB 4703277 A GB4703277 A GB 4703277A GB 1571535 A GB1571535 A GB 1571535A
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- GB
- United Kingdom
- Prior art keywords
- weight
- zeolite powder
- crystalline zeolite
- alkali metal
- period
- 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.)
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Crystalline zeolite powder of type A of the composition 1.O+/-0.2M2/nO:Al2O3:1.85+/-0.5SiO2.yH2O, where M is a metal cation, n is its valency and y has a value of up to 6, with 50% by weight of particles below at most 4.8 mu m and with a particle spectrum Fraction Proportion ( mu m) (% by weight) < 3 from 10 to 18 < 5 from 55 to 70 <10 from 93 to 99 <15 from 96 to 100 This is prepared by stirring an alkali metal silicate solution of 30-80 DEG C over a period of 10-200 min into aqueous sodium hydroxide of 30-100 DEG C, containing 0.1-500 g/l of NaOH, followed by stirring in a sodium aluminate lye of 30-100 DEG C, containing 10-200 g/l of Al2O3 and 10-250 g/l of Na2O over a period of 10-200 min, and crystallisation at 20-175 DEG C over a period of at least 15 min. The grit-free, fine-grained zeolite powder obtained is particularly suitable as a phosphate substitute in detergents, rinsing agents and cleaning agents.
Description
(54) CRYSTALLINE ZEOLITE POWDER OF TYPE A
(71) We, DEUTSCHE GOLD-UND SILBER-SCHEIDEANSTALT VORMALS
VORMALS ROESSLER a body corporate organised under the laws of Germany of 9
Weissfrauenstrasse, 6 Frankfurt Main 1, Germany and HENKEL Kommanditgesellschaft auf Aktien a body corporate organised under the laws of Germany of Henkelstrasse 67, 4000 Dusseldorf, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to crystalline zeolite powder of type A.
More particularly the invention relates to a crystalline zeolite powder of type A having the composition 1.0 i 0.2 M2 : Al2O3:1.85 + 0.5 Six2. y H2O where M is an alkali metal cation, and y is an integer of up to 6, with 50% by weight of the articles below 4.8 R in size, to a process for producing the crystalline zeolite powder by the hydrothermal crystallisation of an alkali metal aluminate/silicate mixture and to the use of the crystalline zeolite powder in washing rinsing and cleaning agents.
Zeolitic molecular sieves with their special properties for ion exchange and adsorption I have long been known. Their synthesis comprises heating an aqueous synthesis mixture with the components a Na2O . b A1203 . cSiO2 to a temperature of from 50 to 300 C.
Depending upon the composition of the starting mixture, the reaction temperature and reaction time, differently structured compounds corresponding to the general formula Na.AlxSiyO2(x+y) .n H20 are obtained and are distinguishable from one another on the basis of their X-ray spectra. The sodium may be replaced by other monovalent or divalent metal cations.
For use as adsorbents, catalyst supports or ion exchangers, the molecular sieves are converted into shaped structures with a suitable binder. The production of the shaped structures involves considerable technical outlay and, at the same time, reduces the effect of the molecular sieves due to the presence of the binder. In addition, the reaction velocity is reduced to a considerable extent by the long diffusion paths which makes it difficult to dry organic liquids for example. Accordingly, it is advisable for some applications to use powder-form molecular sieve.
One factor common to conventional production processes (for example German Patent No. 1,038,017) is that, in the synthesis of the molecular sieve, crystals are obtained of which the average diameter is above about 2 Il, a considerable proportion of the crystals, normally between 3 and 12% by weight, having a limiting particle size above 45 y. This proportion is known as grit which is determined in accordance with DIN 53 580 by wet screening using the Mocker method. In one product typical of this process, it can be shown that: approximately 25% by weight of the particles have a diameter below 10eel, 50% by weight have a particle diameter of 13 (D.W. Breck, Zeolite Molecular Sieves, page 388, John
Wiley & Sons, New York - London - Sydney - Toronto, 1974).
An object of the present invention is to develop a process by which it is possible to; synthesise powder-form zeolitic molecular sieves of type A without any grit (particles < 45 ) and with relatively small particle sizes, in particular for use as ion exchangers, for example for softening water. The absence of grit and a relatively small particle size are essential to the use of these molecular sieves inter alia as a phosphate substitute in washing, rinsing and cleaning agents as proposed in accordance with the invention. This is because washing and cleaning operations, particularly in machines, require the molecular sieves to remain in suspension (through a minimal tendency towards sendimentation) in the solution in order to enable them to be completely washed out on completion of the operation.
The present invention provides a crystalline zeolite powder of type A having the composition 1.0 + 0.2 M2: Awl203: 1.85 i 0.5 SiO2 . y H2O, where M is an alkali metal cation, andy is an integer of up to 6, with 50% by weight of the particles below 4.8 U in size and with the following particle size distribution:
Fraction (\L) Proportion (% by weight)
< 3 10 to 18
< 5 55 to 70
< 10 93 to 99
< 15 96 to 10û U. K. Application Nos. 47031/77, 47033/77, 47034/77, 47035/77, and 47036/77 (Serial
Nos. 1571534 1571536 1571537 1571538 1571539) also describe and claim a crystalline zeolite powder of type A and a method for preparing the powder.
The present invention also provides a process for producing the crystalline zeolite powder according to the invention which comprises preparing an alkali metal aluminate/water/ silicate synthesis mixture containing Six2, Awl203, M2 and water, wherein M is defined above, and allowing the synthesis mixture to undergo hydrothermal crystallisation which is optionally followed by a heating stage, stirring optionally being replaced by the plication of shear forces during crystallisation and the heating stage, wherein an aqueous alkali metal hydroxide solution containing from 0.1 to 500 g of MOH per litre is introduced into a container and heated to a temperature of from 30 to 1000C followed by the addition with stirring over a period of 10 to 200 minutes of an alkali metal silicate solution having a temperature of from 30 to 800C after which an alkali metal aluminate liquor containing from 10 to 200 g/1 of Alto03 and from 10 to 250 g/1 of M2O is added with stirring over a period of from 10 to 200 minutes at a temperature of from 30 to 1000C and the synthesis mixture thus obtained is allowed to undergo hydrothermal crystallisation over a period of at least 15 minutes at a temperature of from 20 to 1750C.
In one preferred embodiment, waterglass may be used as the alkali metal silicate solution.
Instead of stirring, shear forces may be applied in the process according to the invention, for which purpose known apparatus may be used. This known measure increases the fineness of the particles, but Is not essential to the process according to the invention.
In the process according to the invention, shear forces may be allowed to act on the synthesis mixture, which may contain the individual components in molar ratios such as are used in known processes (for example German Patent No. 1,038,017 and DT-AS No.
1,095,796), during crystallisation and during the heating stage by which it may optionally be followed.
In the process according to the invention, shear forces may be allowed to act on the synthesis mixture during crystallisation and during the tempering stage by which it may optionally be followed.
In the context of the invention, the expression "shearing" applies to any size-reducing mechanical stressing of suspended, discrete particles which is predominantly based on a genuine shearing effect. The shear forces may be applied continuously or at intervals.
It is preferred to use a turbine impeller, for example an EKATO turbine impeller, for generating the shear forces. However, the shear forces may also be generated by means of toothed-disc dissolvers, disperser pumps, rotary pumps or the like.
Whereas in the present case crystallisation may be carried out for example at 930C, it has proved to be advantageous to carry out the heating stage at a temperature of from 85 to 105"C in the crystallisation mother liquor, heating times of from 0.2 to 6 hours, preferably from 0.8 to 4.0 hours, more particularly 3 hours, being favourable.
The time of the heating stage begins at the point at which crystallisation ends, as reflected in the development of maximum ion exchange capacity, the reaching of maximum X-ray line intensity and the production of approximately 22.5% water vapour adsorption. In practice, an empirical value determined by optimisation of the recipe is used as a basis.
A shearing effect acting up to the end of the crystallisation phase may be intensified to such an extent that the average particle diameter can be reduced to very small values. At the same time, the values for the limiting particle size and its percentage proportion in the product may also be reduced. However, shearing during the heating phase influences only the limiting particle size and its percentage proportion.
Finally, the invention relates to the use of the crystalline zeolite powder of type A according to the invention as an ion exchanger, for example for softening water, and in particular as a phosphate substitute in washing, rinsing and cleaning agents.
Washing agents of the type in question are combinations of interfacially active wash-active raw materials, although m general they also contain other, predominantly inorganic additives which contribute towards the success of the washing operation or are necessary for the production process and for the external quality of production. The composition of the washing agents differs according to the particular application for which they are intended. In particular, it is dependent upon the type of fibres in question, upon dyeing and upon the washing temperature and also upon whether washing is carried out by hand, for example in a copper, in a domestic washing machine or in a laundry. Most washing agents are in the form of bulk powders.However, there are also liquid or paste-like products (see Ullmann's Encyklopadie der technischen Chemie, 3rd Edition, Vol. 18,
Urban & Schwarzenberg, Munich 1967).
The advantage of the crystalline zeolite powder of type A according to the invention is that it is grit-free and contains relatively small particles during its actual production.
Accordingly where it is used as a phosphate substitute in washing and cleaning agents, it may readily be kept in suspension in the particular solutions can be completely washed out particularly easily from washing and cleaning machines and their contents.
The process according to the invention is illustrated by the following Examples.
EXAMPLE 1
560 litres of sodium hydroxide solution (Na2O = 63 g/litre) with a temperature of 70"C are initially introduced into a 2 cubic meter capacity tank. 300 litres of waterglass (Q = 1.35 kg/litre) having a temperature of 70"C and containing 8.0% of Na2O and 26.7% of SiO2 are then added over a period of 40 minutes while stirring with a three-stage MIG stirrer. The solution remains clear.
900 litres of a sodium aluminate liquor containing 147 g/l of Na2O and 103 g/1 of Al203 and heated to 70"C are then added to this solution over a period of 98 minutes after 100 litres of the same liquor have previously been added over a period of 15 minutes. The reaction mixture is heated to 85" and crystallised over a period of 3 hours. X-ray photographically pure zeolite A with the following particle size distribution is obtained:
Fraction Proportion (% by weight)
< 3 It 15
< 3 eel 62
< 10 cm 98
< 15 R 99 a proportion of 50% by weight being below 4.3 Rm in size.
The particle size is determined by Coulter Counter measurement.
EXAMPLE 2
Perborate-containing washing agent 45.0% by weight of sodium aluminium silicate obtained in accordance with Example 1 (dried for 6 hours at 900C, water content 16.8% by weight); 20.0% by weight of sodium perborate; 35.0% by weight of a washing agent powder, obtained for example by hot drying, with the composition::
21.0% by weight of ABS (dodecyl benzene sulphonate);
7.5% by weight of ethoxylated tallow alcohol (1 mole of tallow alcohol + 14 moles of
ethylene oxide);
7.2% by weight of soap (sodium salt of saturated, essentially C18-C22 fatty acids);
9.0% by weight of waterglass (Na2O . 3.3 SiO2);
4.5% by weight of magnesium sulphate;
2.0% by weight of carboxymethyl cellulose;
0.6% by weight of optical brightener;
9.0% by weight of soluble complex-former salt (for example sodium citrate, NTA,
EDTA, sodium triphosphate, POC, etc);
35.0% by weight of sodium sulphate;
rest water.
The washing agent is produced by mixing the three powder-form constituents.
EXAMPLE 3
Perborate-free washing agent
2.0% by weight of ethoxylated C1l/Cl5- oxoalcohol (1 mole of oxoalcohol + 3 moles of ethylene oxide(;*)
5.0% by weight of ethoxylated C1l/Cl5-oxoalcohol
(1 mole of oxoalcohol + 13 moles of ethylene oxide);**) 40.0% by weight of sodium aluminium silicate obtained in accordance with Example 1 (dried for 6 hours at 90"C, water content 16.8% by weight); 15.0% by weight of soda;
5.0% by weight of sodium citrate;
4.0% by weight of waterglass (Na2O . 3.3 SiO2);
1.5% by weight of carboxymethyl cellulose;
0.2% by weight of optical brightener; 23.0% by weight of sodium sulphate; rest water.
The washing agent is produced by spraying the ethoxylation products (nonionic surfactants) onto the powder particles consisting of the other constituents.
* replaceable by tallow alcohol + 5 moles of ethylene oxide.
**) replaceable by tallow alcohol + 14 moles of ethylene oxide.
WHAT WE CLAIM IS: 1. A crystalline zeolite powder of type A having the composition 1.0 + 0.2 M2 : Awl203; 1.85 + 0.5 SiO2 . y H2O, where M is an alkali metal cation, andy is an integer of up to 6, with 50% by weight of the particles below 4.8 y in size and with the following particle size distribution: Fraction ( > ) Proportion (% by weight)
< 3 10 to 18
< 5 55 to 70
< 10 93 to 99
< 15 96 to 100 2. A crystalline zeolite powder of type A substantially as described with particular reference to Example 1.
3. A process for producing the crystalline zeolite powder claimed in claim 1 which comprises preparing an alkali metal aluminate/water/silicate synthesis mixture containing
SiO2, Al203M20 and water, wherein M is defined as in claim 1, and allowing the synthesis mixture to undergo hydrothermal crystallisation which is optionally followed by a heating stage, stirring optionally being replaced by the application of shear forces during crystallisation and the heating stage, wherein an aqueous alkali metal hydroxide solution containing from 0.1 to 500 g of MOH per litre is introduced into a container and heated to a temperature of from 30 to 1000C followed by the addition with stirring over a period of 10 to 200 minutes to an alkali metal silicate solution having a temperature of from 30 to 800C after which an alkali metal aluminate liquor containing from 10 to 200 g/1 of Al203 and from 10 to 250 g/1 of M2O is added with stirring over a period of 10 to 200 minutes at a temperature of from 30 to 1000C and the synthesis mixture thus obtained is allowed to undergo hydrothermal crystallisation over a period of at least 15 minutes at a temperature of from 20 to 175"C.
4. A process for producing a crystalline zeolite powder substantially as described with particular reference to Example 1.
5. A crystalline zeolite powder when produced by a process as claimed in claim 3 or 4.
6. A washing, rinsing or cleaning agent including as a phosphate substitute a zeolite powder as claimed in claim 1, 2 or 5.
7. A washing, rinsing or cleaning agent substantially as described with particular
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (7)
1.5% by weight of carboxymethyl cellulose;
0.2% by weight of optical brightener; 23.0% by weight of sodium sulphate; rest water.
The washing agent is produced by spraying the ethoxylation products (nonionic surfactants) onto the powder particles consisting of the other constituents.
* replaceable by tallow alcohol + 5 moles of ethylene oxide.
**) replaceable by tallow alcohol + 14 moles of ethylene oxide.
WHAT WE CLAIM IS: 1. A crystalline zeolite powder of type A having the composition 1.0 + 0.2 M2 : Awl203; 1.85 + 0.5 SiO2 . y H2O, where M is an alkali metal cation, andy is an integer of up to 6, with 50% by weight of the particles below 4.8 y in size and with the following particle size distribution: Fraction ( > ) Proportion (% by weight)
< 3 10 to 18
< 5 55 to 70
< 10 93 to 99
< 15 96 to 100
2. A crystalline zeolite powder of type A substantially as described with particular reference to Example 1.
3. A process for producing the crystalline zeolite powder claimed in claim 1 which comprises preparing an alkali metal aluminate/water/silicate synthesis mixture containing
SiO2, Al203M20 and water, wherein M is defined as in claim 1, and allowing the synthesis mixture to undergo hydrothermal crystallisation which is optionally followed by a heating stage, stirring optionally being replaced by the application of shear forces during crystallisation and the heating stage, wherein an aqueous alkali metal hydroxide solution containing from 0.1 to 500 g of MOH per litre is introduced into a container and heated to a temperature of from 30 to 1000C followed by the addition with stirring over a period of 10 to 200 minutes to an alkali metal silicate solution having a temperature of from 30 to 800C after which an alkali metal aluminate liquor containing from 10 to 200 g/1 of Al203 and from 10 to 250 g/1 of M2O is added with stirring over a period of 10 to 200 minutes at a temperature of from 30 to 1000C and the synthesis mixture thus obtained is allowed to undergo hydrothermal crystallisation over a period of at least 15 minutes at a temperature of from 20 to 175"C.
4. A process for producing a crystalline zeolite powder substantially as described with particular reference to Example 1.
5. A crystalline zeolite powder when produced by a process as claimed in claim 3 or 4.
6. A washing, rinsing or cleaning agent including as a phosphate substitute a zeolite powder as claimed in claim 1, 2 or 5.
7. A washing, rinsing or cleaning agent substantially as described with particular
reference to Example 2 or 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762651445 DE2651445A1 (en) | 1976-11-11 | 1976-11-11 | TYPE A II CRYSTALLINE ZEOLITE POWDER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1571535A true GB1571535A (en) | 1980-07-16 |
Family
ID=5992899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB4703277A Expired GB1571535A (en) | 1976-11-11 | 1977-11-11 | Crystalline zeolite powder of type |
Country Status (11)
| Country | Link |
|---|---|
| JP (3) | JPS5360898A (en) |
| BE (1) | BE860755A (en) |
| BR (1) | BR7707456A (en) |
| CA (1) | CA1083553A (en) |
| CH (1) | CH631945A5 (en) |
| DE (1) | DE2651445A1 (en) |
| ES (1) | ES463994A1 (en) |
| FR (1) | FR2370693A1 (en) |
| GB (1) | GB1571535A (en) |
| IT (1) | IT1143827B (en) |
| NL (1) | NL180738C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2734296A1 (en) * | 1977-07-29 | 1979-02-08 | Degussa | PROCESS FOR THE PRODUCTION OF FINE PARTICULAR, WATER-INSOLUBLE SILICATES ENABLED FOR CATION EXCHANGE |
| FR2444005A1 (en) * | 1978-12-15 | 1980-07-11 | Ugine Kuhlmann | INDUSTRIAL PROCESS FOR THE SEMI-CONTINUOUS MANUFACTURE OF ZEOLITE A |
| DE2856278A1 (en) * | 1978-12-27 | 1980-07-10 | Degussa | METHOD FOR PRODUCING FINE-PARTICLE SODIUM ALUMINUM SILICATES |
| DE3132379A1 (en) * | 1981-08-17 | 1983-02-24 | Degussa Ag, 6000 Frankfurt | ZEOLITE GRANULES, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE3132928C1 (en) | 1981-08-20 | 1983-01-13 | Degussa Ag, 6000 Frankfurt | Process for accelerating the setting of hydraulic cement mixtures |
| DE3444311A1 (en) * | 1984-12-05 | 1986-06-05 | Degussa Ag, 6000 Frankfurt | AQUEOUS, STABLE SUSPENSION OF WATER-INSOLUBLE SILICATES CAPABLE OF CALCIUMIONS AND THE USE THEREOF FOR THE PRODUCTION OF DETERGENT AND CLEANING AGENTS |
| DE4309656A1 (en) * | 1993-03-25 | 1994-09-29 | Henkel Kgaa | Process for the production of very finely divided zeolitic alkali metal aluminum silicates |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1038017B (en) | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
| US3310373A (en) | 1963-04-03 | 1967-03-21 | Mobil Oil Corp | Method for producing crystalline aluminosilicates |
| SE419975C (en) * | 1973-04-13 | 1986-08-18 | Henkel Kgaa | DETERGENTS AND / OR BLENDS CONTAINING A CRYSTALLINE WATER-INSULATED SILICATE PROCEDURE FOR ITS PREPARATION AND USE |
| AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
| CA1037815A (en) * | 1973-06-20 | 1978-09-05 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate |
| DE2433485A1 (en) * | 1973-07-16 | 1975-02-06 | Procter & Gamble | ALUMINOSILICATE ION EXCHANGERS SUITABLE FOR USE IN DETERGENTS |
| DE2447021C3 (en) | 1974-10-02 | 1984-03-22 | Degussa Ag, 6000 Frankfurt | Type A crystalline zeolite powder and the process for its preparation |
| DE2517218B2 (en) | 1975-04-18 | 1977-05-05 | Henkel & Cie GmbH, 4000 Düsseldorf; Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, 6000 Frankfurt | TYPE A CRYSTALLINE ZEOLITE POWDER |
-
1976
- 1976-11-11 DE DE19762651445 patent/DE2651445A1/en not_active Ceased
-
1977
- 1977-08-31 NL NL7709581A patent/NL180738C/en not_active IP Right Cessation
- 1977-09-21 FR FR7728476A patent/FR2370693A1/en active Granted
- 1977-09-29 IT IT6914777A patent/IT1143827B/en active
- 1977-10-13 CA CA288,603A patent/CA1083553A/en not_active Expired
- 1977-11-07 BR BR7707456A patent/BR7707456A/en unknown
- 1977-11-10 ES ES463994A patent/ES463994A1/en not_active Expired
- 1977-11-10 BE BE6046217A patent/BE860755A/en not_active IP Right Cessation
- 1977-11-10 CH CH1374477A patent/CH631945A5/en not_active IP Right Cessation
- 1977-11-10 JP JP13520077A patent/JPS5360898A/en active Pending
- 1977-11-11 GB GB4703277A patent/GB1571535A/en not_active Expired
-
1981
- 1981-04-08 JP JP5191781A patent/JPS5727917A/en active Granted
- 1981-04-08 JP JP5191881A patent/JPS5723696A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2651445A1 (en) | 1978-05-18 |
| JPS6324926B2 (en) | 1988-05-23 |
| FR2370693A1 (en) | 1978-06-09 |
| ES463994A1 (en) | 1978-06-16 |
| NL180738C (en) | 1987-04-16 |
| NL180738B (en) | 1986-11-17 |
| JPS5360898A (en) | 1978-05-31 |
| BR7707456A (en) | 1978-08-01 |
| JPS5723696A (en) | 1982-02-06 |
| BE860755A (en) | 1978-05-10 |
| FR2370693B1 (en) | 1980-08-01 |
| JPS5727917A (en) | 1982-02-15 |
| CH631945A5 (en) | 1982-09-15 |
| NL7709581A (en) | 1978-05-16 |
| IT1143827B (en) | 1986-10-22 |
| CA1083553A (en) | 1980-08-12 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19971110 |