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Publication numberUSRE28629 E
Publication typeGrant
Publication dateNov 25, 1975
Filing dateSep 10, 1970
Priority dateDec 19, 1966
Publication numberUS RE28629 E, US RE28629E, US-E-RE28629, USRE28629 E, USRE28629E
InventorsPhilip K. Maher
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Ion exchange of crystalline zeolites
US RE28629 E
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

I E Re. 28,629

[ Reissued Nov. 25, 1975 UN ION EXCHANGE OF CRYSTALLINE ZEOLITES [75! inventors: Philip K. Maher, Baltimore; Carl V.

McDaniel, Laurel, both of Md.

[73] Assignee: W. R. Grace & Co., New York,

22 Filed: Sept. 10, 1970 211 Appl.No.:7l,283

Related U.S. Patent Documents Reissue of:

[64] Patent No.1 3,402,996

lssued: Sept. 24, [968 App]. No: 602,766 Filed: Dec. 19, 1966 US. Applications:

[63] Continuation-impart of Ser. No. 48l,669, Aug. 23, I965, Pat. No. 3,293,]92, and a continuatiomin-part of Ser. No. 553,272. May 27. I966, abandoned, and a continuation-in-part of Ser. No. 427.967, Jan. 25, I965, Pat. No. 3.375065.

[52] [1.5. CI 423/"2; 423/l l8; 252/455 Z [5i] Int. Cl. Coll) 33/23; BOlj 11/40 [58] Field of Search 252/455 Z; 423/112, 118

[56] References Cited UNITED STATES PATENTS 3,130,006 4/l964 Rabo et al 252:23/455 Z 3,173,854 3/l965 Eastwood ct ttl. 208/11] 3,236,761 2/l966 Rabo et al. 208/1 ll 3.293,l92 l2/l966 Maher et al 252/455 Z FOREIGN PATENTS ()R APPLICATlONS 612,551 7/1962 Belgium Primary Examiner-Carl F. Dees Attorney, Agent, or Firm-Kenneth E. Price; Arthur P. Savage [57] ABSTRACT Method of cation exchanging zeolites comprising a conventional ion exchange step, whereby the more easily exchangeable cations are ion exchanged, followed by a calcination step at 400 to I500 F., whereby the difficult to exchange cations are redistributed. the redistributed cations are then ion exchanged by an additional conventional ion exchange step. One or more calcinations and additional ion exchange steps may be used. This method is particularly applica ble to the ion exchange removal of sodium ions from crystalline zeolites.

9 Claims, 1 Drawing Figure Reissued Nov. 25, 1975 ION EXCHANGE OF SODIUM ION FROM 5,0 TYPE Y SODIUM ZEOLITE BY EXCHANGE WITH AMMONIUM ION.

4.0- Z LL) U [I LIJ I1 I I L LIJ 3 3.0

0 NO HEAT TREATMENT o CALCINED 2 HRSAT 400 g x CALCINED 2 HRS T IOOOOF 0 QALC|NED 2 I-IRSAT I500 F c I.O

o l I l O I 2 3 4 5 X HA E STEPS NUMBER OF ION E C NG ENTORS CARL VANCE MCDANIEL PHILIP KENERICK MAHER BY Ml ION EXCHANGE OF CRYSTALLINE ZEOLITES Matter enclosed in heavy brackets I: appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

I This application is a continuation-in-part of application Ser. No. 481,669, filed Aug. 23, 1965, now US. Patent 3,293,l92.]

This application is an application for reissue of U.S. Pat. No. 3,402,996, issued Sept. 24, 1968, filed as Ser. No. 602,766 on Dec. 19, 1966, a continuation-impart of applications: Ser. No. 48l,669,filed Aug. 23, 1965, now US. Pat. No. 3,293,192; Ser. No. 553,272,filed May 27, 1966, now abandoned; and Ser. No. 427,967, filed Jan.25,1965, now U.S. Pat. No. 3,375,065.

This invention relates to a new and unobvious method of zeolite cation exchange whereby essentially lOO percent of the mobile cations are exchanged. In particular, the method of this invention comprises an initial ion exchange step whereby the more easily exchangeable cations are ion exchanged followed by a heat treatment to provide the necessary activation energy for the redistribution of the remaining locked in cations, and a final ion exchange step whereby the redistributed cations are exchanged.

The crystalline aluminosilicate zeolites are of general interest because of their selective adsorption properties and extremely high catalytic activity for certain acidtype catalyzed reactions. It has been estimated that their catalytic activity is often of the order of 1,000 times that of conventional amorphous aluminosilicate catalysts. The use of crystalline aluminosilicate zeolites is of particular interest in the field of hydrocarbon cracking. It is further particularly important in the hydrocarbon industry that the zeolite does not contain cations such as sodium since even as little as 1% by weight sodium will prevent the zeolite catalyst from having the thermal stability required to prevent crystal collapse during normal hydrocarbon cracking and catalyst regeneration.

The catalytic behavior of the zeolites is very dependent on the nature of the cation present, the most active being those containing polyvalent ions or protons. Most of the fundamental work that has been reported has been restricted to zeolites containing monovalent cations and in particular the alkali metal cations. This is largely due to the fact that zeolites are generally synthesized in these forms. The prior art has had considerable difficulty in attempting to cation exchange these alkali metal cations completely for polyvalent cations.

Chemically the zeolites may be represented by the general formula:

M,,,O:AI,O;,:xSiO,:yH,O where M is a cation and n is its valence. wherein x is normally in the range of L0 to 15 and y is a function of the degree of dehydration.

The structure of a number of the zeolites has been shown to be based on units consisting of tetrahedra of silica and alumina, which in turn are connected to form a cubo-octahedral unit similar to that found in the natural mineral sodalite. A variation in stacking or combination of these octahedral units will lead to a variety of zeolites, one typical such structure being the zeolite faujasite. The faujasite structure consists ofa diamond type lattice of the eubo-octahedral units joined by pairs of six-membered oxygen rings. Faujasite has a well-or dered structure having all the aluminum atoms tetrahedrally coordinated with oxygen and having one excess negative charge for each aluminum atom in the lattice. This charge is electrically balanced by the presence of a cation that has a great degree of mobility. This cation may be exchanged with other cations and it is the ex change of this cation that we are primarily concerned with in this invention.

In general, the mechanism of ion exchanging zeolites is the same as for the organic exchangers and may be considered as a Donnan membrane type equilibrium. The zeolite system does, however, save some basic differences from the crosslinked organic exchangers. For example, the relatively rigid structural framework of the crystalline zeolite does not permit the large degree of osmotic type swelling encountered in the non-crystalline organic exchangers. Also, the more ordered nature of the crystalline materials results in a discrete number of types of exchange sites, whereas in the organic exchangers a continuum of site-types probably exists.

I It has been observed in many of the zeolites and particularly in the sodium Y type faujasite that only about 85 percent of the sodium ions are readily accessible for ion exchange by conventional ion exchange techniques. An exception to this is the exchange by silver ions where the silver ion is apparently small enough and selective enough to readily replace sodium and other ions even in the inaccessible sites. The problems of effeeting essentially complete cation exchange is further discussed in an article by Howard S. Sherry in the Jr. of Phys. Chem., vol. 70, No. 4, April [966, pp. 1 158-1 168.

The ion exchange technique in our invention resides in an initial exchange of the more easily removable ions, followed by a heat treatment which provides the necessary activation energy for the redistribution of the remaining locked in ions. The redistributed ions are thus made easily accessible for exchange by a second ion exchange step. The ion exchange technique of this invention is applicable to the ion exchange of any crystalline zeolite especially those having difficult to exchange cations. Examples of these zeolites include the zeolite designated by the Linde Division of Union Car bide Corporation by the letters X, Y, A, L (these zeo lites are described in US. Patents Nos. 2,882,244, 3,130,007, 2,882,243 and Belgium Patent No. 575,1 17, respectively), as well as the naturally occurring crystalline zeolites, chabazite, erionite, faujasite, mordenite, sodalite, etc. Any exchangeable cation may be used, for example, ammonium ion and cations of the rare earth metals and Groups ll-A, Ill-A and VIII of the Periodic Table.

The drawing illustrates the ion exchange removal of sodium ion from type Y sodium zeolite by the method of this invention and by conventional ion exchange.

In carrying out our process, the zeolite. normally in the sodium form, is exchanged with a salt solution of the particular cation desired to be exchanged. The concentration of the salt solution and the particular anion are not critical. Any of the soluble inorganic salts such as, for example, chloride sulfate or nitrate, etc., may be used, as as well as the organic salts, such as acetate and formate. The exchange is carried out by mixing an excess of the salt solution with the zeolite for the proper period of time, normally 5 minutes to 5 hours.

The rate of exchange can be increased by carrying out the exchange at an elevated temperature. ()bvi ously. the exchange temperature of the solution must be below the atmosphere boiling point of the solution. unless pressure equipment is used. Suitable exchange may be carried out at temperatures of from about 25 C. to 95 C. The excess salt solution is then removed from contact with the zeolite after a suitable period of time. for example. 5 minutes to 5 hours. The time of contact between the cation exchange solution and the leolite is such as to effectively replace the easily exchangeable cations in the aluminosilicate to about 3 percent calculated as the oxide of the cation. for example. Na O.

In the second step of our process. the exchanged zeolite is washed to remove any excesss salts. This washing is a conventional step and is normally carried out with deionized water.

After the washing step. the zeolite. now partially exchanged with the cation desired and having H) to percent of the original cations remaining (depending on the particular zeolite) is dried and heat treated to redistribute the locked in cations. The heat treatment is normally carried out at a temperature of 400 to l.500 F., preferably about 600 to 1.200 F. However. the temperature must be low enough so as not to cause the zeolite crystalline structure to collapse, since some of the zeolites in the low initial cations condition enter into what is known as a metastable condition. wherein the crystalline structure will collapse when subjected to thermal treatment. The duration of the heat treatment is dependent upon the temperature, e.g.. a lower heat treatment duration will require a higher temperature. Suitable results are obtained when the heat treatment is carried out at a temperature ofabout l.000 F. for peri ods of 0.10 hour to 3 hours.

ln the final step of our process. the zeolite is cooled to room temperature and a final exchange carried out to reduce the initial cation content to the desired level. The heat treatment step has unlocked the locked initial cations (normally alkali cations] and thus an almost l00 percent removal of the initial cations may be effected. This final exchange may be carried out with any suitable salt solution dependent upon the cation desired in the exchanged zeolitc. Examples of suitable salt solutions are ammonium salt solutions, rare earths and alkali earth metal salts. such as calcium. magnesium. etc. The zeolite is then given a final wash and dried. Prior to actual use. the zeolite is normally calcined to activate it by removing the water molecules. Such calcination is conventional and may. for example. be car ried out at 700 F. to l.000 F. for 3 hours.

The process is. of course. capable of modification. for example. the heating (to redistribute the locked in cations) and the ion exchange step may be carried out as a series of repeating cycles.

The following examples are merely illustrative of the ion exchange process of this invention and are not in any way intended to be limiting thereof. (All percentages are weight percentages unless otherwise indicated and in each example. a crystalline zeolite was used.)

Example I Several runs were made in which the starting material was a Z-l4HS (type Y) Na zeolite containing about l37r Na O. This material had a surface area after calci nation at 700 F. of 942 square meters per grant. The unit cell size was 24.65 Angstroms.

LII

A quantity of this material was treated with alt ammonium sulfate-water solution. The treating slurry consisted of 20 pounds of the zeolite. 30 pounds of ammo nium sulfate. and I50 pounds of water. This treatment was carried out for a period of one hour. At the end of this time. the product was removed. washed and the sodium content ofthe product determined. The Composition had a Na O content of 4.|5 weight percent. This composition was again washed with ammonium sulfate solution in the same proportions as used in the first treatment. At this point. the exchange was carried out at a temperature of l00 C. for a period of two hours. The product was filtered. washed and the sodium oxide content of the product determined. The product was found to have a M11 0 content of 2.2 weight percent.

This product was washed thoroughly to remove sulfate and calcined at l.000 F. for two hours. After the calcination. the product was cooled to room temperature and subjected to another ammonium sulfate exchange step. In this exchange. 4.17 pounds of the zeolite were mixed with l2 pounds of ammonium sulfate and 250 pounds of water. The exchange was continued at a temperature of l00 C. for a period of 3 hours. At the end of this time. the Na O content of the product had decreased to 0.55 weight percent.

The exchange treatment was repeated using the same ratio of reactants as the previous exchange. The exchange was carried out for a period of one hour at a temperature of I00" C. At the end of this time. the product was sampled and the M1 0 content determined. It was found that the Na O content ofthe product was 0.32 weight percent Na O. The product was then calcined for 3 hours at I500 F. The surface area of this material as determined by the well-known BrunaueFEmmett-Teller method (S. Brunauer. P. Emmett and E. Teller. J. Am. Chem. Soc. 60. 309 1938)). was 438 square meters per gram. The unit cell of this material was 24.29 Angstroms.

Example ll Another sample of the starting material of Example II was treated as in Example I. The treatment prior to the first calcination at l.000 F. was identical to the product of Example I. The product had a Na O content of 2.2 weight percent.

The product was washed thoroughly to remove sulfate and calcined at l.000 F. for two hours. After the calcination the product was again exchanged with am monium sulfate. In this exchange 4.17 pounds of zeolite. l2.5 pounds of ammonium sulfate and 250 pounds of water were stirred together for a period of 3 hours at a temperature of C. The exchange was repeated as in Example I using the same ratio of reactants. The second exchange was continued at I00" C. for a period of one hour.

After the second exchange. the Na- O content of the product was found to be 0.093 weight percent. The product was then calcined for 4 hours at l.500 F. The unit cell size of the product was 24.309 Angstroms.

The improved stability was demonstrated by calcining a portion of this product at a temperature of I800 F. and determining the surface area after calcination. The surface area was found to be 378 square meters per gram.

Example lll Three additional runs were made to determine whether the preliminary exchange would give a satisfactory product when the exchange was carried out for a period of one hour.

In this run, the starting material was the same starting material as in Example I. The Z-l4HS (type Y) Na composition had a Na O content of I392, 21 surface area of 700 square meters per gram and a unit cell size of 24.653 Angstroms. This material was exchanged with ammonium sulfate by mixing 20 pounds of the zeolite, 30 pounds of ammonium sulfate and 150 pounds of water at a temperature of 100 C. for a period of one hour. When the Na O content of a sample of this material was determined, it was found to be 4.25 weight percent.

This composition was subjected to a second exchange using the same quantity of reactants. The exchange was again carried out for a period of one hour at a temperature of l00 C. At the end of this treatment, a sample of the composition was analyzed and found to contain 2.56 weight percent Na O. This product was then washed thoroughly to remove sulfate and calcined for 4 hours at l000 F. The calcined product was again exchanged as in Examples l and II. Exchange was carried out by mixing 4.17 pounds of the zeolite, l2.5 pounds of ammonium sulfate and 250 pounds of water for a period of 3 hours at a temperature of 100 C. The sodium content after this third exchange is set out in the table below. This material was subjected to a fourth exchange using the same conditions and followed by calcination for a period of 4 hours at a temperature of 1,500 F.

TABLE I Run 1 2 3 Na,() content after 3rd exchange in The surface area after calcination at [,900" F. proved the extreme thermal stability of this product. Stability of this order would have been impossible without essentially complete removal of the sodium ion.

Example IV This example illustrates a conventional cation exchange of a type Y sodium zeolite with a magnesium ion.

A 20% magnesium sulfate solution was made by dissolving 1 pound of MgSO .7H O crystals into i800 ml. of deionized water. 300 grams of Z-l4HS (type Y) sodium zeolite (about 13% Na O) were slurried with 500 ml. of the magnesium sulfate solution. The slurry was heated to 100 C, in a resin kettle equipped with a condenser column to retard evaporation. This treatment was effected for approximately 1 hour with samples of the zeolite being taken after 15 minutes. :5 hour and 1 hour and analyzed for sodium ion content to insure that ion exchange equilibrium had been reached. The analysis of these samples were as follows:

15 minutes treatment 8.0 30 minutes treatment 7.9 l hour treatment 8.6 Average sodium ion content 8.2

Na o

[5 minutes treatment 6. 1/2 hour treatment 5.9 1 hour treatment 6.3 Average sodium ion content 6.2

The solution was again filtered off and the remaining zeolite was again ion exchanged with 500 ml. of the fresh magnesium sulfate solution as in the previous ion exchange steps. Samples were again taken and analysis made as with the previous ion exchanges. The results of these analyses showed:

Na O

l5 minutes treatment 5.! H2 hour treatment 5.8 l hour treatment 5.2 Average sodium ion content 5.4

Example V This example illustrates the method according to our invention of cation exchanging Z-l4HS (type Y) sodium zeolite with magnesium cation.

A 9% magnesium sulfate solution was made by dissolving 50 grams of magnesium sulfate in 500 grams of water. 50 grams of Z-l4HS sodium zeolite (about l3% by wt. Na O) was slurried into this solution and allowed to stand 16 hours at room temperature. The slurry was then filtered and the filter cake washed with deionized water, dried, and then calcined at l,000 F. for 2 hours. An analysis of this material showed a Na,() content of 5.7% by weight. 10 grams of the calcined material was then slurried with a solution of 500 ml. of water and 50 grams of MgSO,, and allowed to stand overnight. This slurry was then filtered and the filter cake washed with deionized water, dried. and then calcined at 1,000 F.

for l hour. An analysis of a sample of this material showed a Na O content of 3.8% by weight. After the second calcination, the material was then given a third ion exchange treatment by slurrying with a solution of 50 grams of MgSO and 500 ml. of water and allowing it to stand for 12 hours. The slurry was then filtered and the filter cake washed with deionized water, dried at ll C. and calcined for 2 hours at l,O00 F. An analysis showed that the sodium ion content had been reduced to [51% by weight N3 0. Thus, it may be seen that the ion exchange method of this invention is effective in removing sodium ions to a level greatly beyond the level which may be obtained by conventional ion exchange methods.

Example VI This example illustrates the method according to our invention of cation exchanging Zl4HS (type Y) sodium zeolite with rare earth metal.

A 9% rare earth chloride solution was made by dissolving 50 grams of rare earth chloride in 500 grams of water. 50 grams of Z-14HS sodium zeolite (about 13% by weight Na O) was slurried into this solution and allowed to stand 16 hours at room temperature. The slurry was then filtered and the filter cake washed with deionized water, dried, and then calcined at 1,000" F. for 2 hours. An analysis of this material showed a Na O content of 3.8% by weight. 20 grams of the calcined material was then slurried with a solution of 500 ml. of water and 50 grams of rare earth chloride and allowed to stand overnight. This slurry was then filtered and the filter cake washed with deionized water, dried, and then calcined at l,000 F. for l hour. An analysis of a sample of this material showed a Na O content of l.2% by weight. The remaining material was then given a third ion exchange treatment by slurrying with a solution of 50 grams of rare earth chloride and 500 ml. of water and allowing it to stand for 12 hours. The slurry was then filtered and the filter cake washed with deionized water. dried at 1 C. and calcined for 2 hours at 1000 F. An analysis showed that the sodium ion content had been reduced to 0.26% by weight Na o.

Example Vll This example illustrates a modified process according to our invention wherein a type X sodium zeolite (about 13 percent NA O by weight) is first cation exchanged with a rare earth cation, then calcined and cation exchanged with ammonium cation. Thus, illustrating different cations may be used in effecting our inventive method.

A slurry of about 50 percent water and 50 percent type X sodium zeolite (about [9% Na O) treated in a solution of mixed rare earth chlorides at a temperature of about 95 C. for a period of minutes. The ratio of molecular sieve to rare earth chloride to water in the mixture weight basis was 1 to 0.5:5. After the mixture had been stirred for about 15 minutes, the solution was removed by filtration and the molecular sieve portion was treated with a fresh solution of mixed rare earth chloride. The solution was heated to a temperature of 95 C. This temperature was maintained during the balance of the exchange for a period of about 15 minutes. The solution used in this second exchange contained twice as much rare earth chlorides and water so that the ratio of molecular sieve to rare earth chloride to water was 1 to 1 to lO. The solution was removed from the molecular sieve by filtration and the product was washed free of chloride ion, and calcined at a temperature of I000 C. for a period of 2 hours. The product contained 2.5% Na O at this stage. After calcination, the product was treated with an ammonium sulfate solution heated to C. for a period of 15 minutes. The ratio of molecular sieve to ammonium sulfate to water on a weight basis was I to l to 20. After this treatment, the solution was removed by filtration and the ammonium sulfate treatment repeated. After the second treatment, the product was washed free of sulfate ion and dried. The product recovered had the following properties:

Sodium content, Na O0.36%.

Example Vlll This example illustrates the comparison between conventional ion exchanging and ion exchanging by our invention.

In this example, grams of type Y sodium zeolite was slurried with an ammonium sulfate solution; the ratio of zeolite to ammonium sulfate to water used was 1:0.5220. The exchange was carried out for one hour at a temperature near (below) the boiling point of the solution. The solution was then filtered off and a sample of the zeolite taken and analyzed for Na,(). This procedure was then repeated twice more using fresh solution for each additional exchange. In order to illustrate the difference between treatment by conventional ion exchange and by our invention, the zeolite was then divided into four equal portions (A. B, C, D) and each portion treated as follows:

A. Conventional ion exchange.This portion was given two additional ion exchange treatments with fresh ammonium sulfate solution with the same ratio and in the same manner as the previous exchanges.

B. Portion B was calcined for 2 hours at 400 F. and then ion exchanged twice with fresh ammonium sulfate solutions in exactly the same manner as portion A.

C. Portion C was calcined for 2 hours at l000 F. and then ion exchanged twice with fresh ammonium sulfate solutions in exactly the same manner as portion A.

D. Portion D was calcined for 2 hours at l500 F. and then ion exchanged twice with fresh ammonium sulfate solutions in exactly the same manner as portion A.

Each portion was thus subjected to a total of five ion exchanges (three before apportionment and two after). After each exchange 1 gram zeolite samples were taken and analyzed for Na -O. The results are summarized below in Table [1.

TABLE II [on exchange Weight percent Na,0

number A B C D 0 I29 l2.9 I29 I29 I 5.6 5.6 5.6 5.6 2 3.4 3.4 3.4 3.4 3 2.7 2.7 2.7 2.7 4 2.4 2.2 1.2 1.1 5 2.l L6 0.4 0.5

9 400 F. that a considerably greater advantage will be achieved if the heat treatment is carried out at a temperature of [000 F. and further that no appreciably, if any, advantage is gained over the l000 F. heat treatment by heat treating at i500 F.

Obviously many variations and modifications may be made without departing from the essence of our invention and only such limitations as are recited in the appended claims should be applied.

What is claimed is:

l. A process of cation exchanging crystalline zeolite aluminosilicates, including exchanging locked-in cations comprising:

(a) Exchanging the zeolite with a solution of a salt of at least one desired metal cation to an original cation content of less than 3-4% by weight.

(b) Washing to remove excess salts,

(c) Drying and heating the exchanged zeolite at a temperature of 400 to 1500 F. to redistribute the locked-in cations for each exchange,

((1) Cooling the calcined zeolite and reducing the original cation content by a second ion exchange,

(e) Washing, drying and recovering the product.

2. The process of claim 1 wherein the original cation is an alkali metal cation.

3. The process of claim I wherein the redistribution heating step and cation exchange step is effected as a series of alternating calcination and cation exchange steps.

I 4. The process of claim 1 wherein different cations are used for the cation exchange step proceeding the redistribution heating step and the cation exchange step following the redistribution heating step] 5. The process of claim 1 wherein the desired cation is a polyvalent cation.

6. The process of claim 1 wherein the desired cation is bivalent.

7. The process of claim 1 wherein the zeolite is a zeolite from the group consisting of type Y, type X and type A.

8. The process of claim 1 wherein the temperature of the ion exchange solutions is from 50 to 90 C.

9. The process of claim I wherein the drying and heating temperature is between 800l 200 F.

10. The process of claim 2 wherein the desired metal cation is a rare earth metal cation.

t II IF

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3130006 *Dec 30, 1959Apr 21, 1964Union Carbide CorpDecationized molecular sieve compositions
US3173854 *Mar 8, 1961Mar 16, 1965Socony Mobil Oil Co IncCatalytic hydrocracking with a crystalline zeolite containing hydrogenation metals and a rare earth
US3236761 *Feb 7, 1962Feb 22, 1966Union Carbide CorpHydrocarbon conversion process and catalyst
US3293192 *Aug 23, 1965Dec 20, 1966Grace W R & CoZeolite z-14us and method of preparation thereof
BE612551A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5302567 *Nov 4, 1991Apr 12, 1994W. R. Grace & Co.-Conn.Zeolite octane additive
EP0158584A2 *Apr 4, 1985Oct 16, 1985Beloit CorporationHeadbox trailing element
Classifications
U.S. Classification423/112
International ClassificationB01J29/08, B01J20/18, B01J20/10, B01J29/00
Cooperative ClassificationB01J29/082, B01J20/186, B01J29/084, B01J2229/40
European ClassificationB01J20/18D, B01J29/08Y, B01J29/08W