CA1162523A - Method for preparing aluminum-silicate having a zeolite-like structure - Google Patents
Method for preparing aluminum-silicate having a zeolite-like structureInfo
- Publication number
- CA1162523A CA1162523A CA000372186A CA372186A CA1162523A CA 1162523 A CA1162523 A CA 1162523A CA 000372186 A CA000372186 A CA 000372186A CA 372186 A CA372186 A CA 372186A CA 1162523 A CA1162523 A CA 1162523A
- Authority
- CA
- Canada
- Prior art keywords
- alkali metal
- zeolite
- organic substance
- silica
- source
- 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
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
-
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
- C01B39/445—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 using at least one organic template directing agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/25—Mordenite, e.g. NA-D, pttilolite, zeolon
Abstract
A B S T R A C T O F T H E D I S C L O S U R E
An improved process is disclosed for producing alumino--silicates having a porous structure, of the zeolite class, the process essentially comprising the step of preparing a homogeneous aqueous mixture containging a source of alu-mina, a source of silica and alkali metal bases and/or alkaline earth metal bases, the improvement consisting in adding to said mixture at least one substance which contains at least a hydroxyl group in its molecule.
The advantages are that the use of nitrogenous organic substances, universally used heretofore for the preparation of certain zeolites, can be dispensed with inasmuch as the alkali metal ion is capable, alone, of displaying the counter-ion function.-
An improved process is disclosed for producing alumino--silicates having a porous structure, of the zeolite class, the process essentially comprising the step of preparing a homogeneous aqueous mixture containging a source of alu-mina, a source of silica and alkali metal bases and/or alkaline earth metal bases, the improvement consisting in adding to said mixture at least one substance which contains at least a hydroxyl group in its molecule.
The advantages are that the use of nitrogenous organic substances, universally used heretofore for the preparation of certain zeolites, can be dispensed with inasmuch as the alkali metal ion is capable, alone, of displaying the counter-ion function.-
Description
1~62$23 ~ ,r~ q M~,T~Ol~l'0.~ "}~.r~ RT-~ T~U~i.T.;.~ Sl.LI~AT
HhVI~G h Z.l`~LIl!E-LIl'~ Sr~,J't'I~
This illvefltion relat~s to a metho~ fvr the preparation of aluminum--sili.cates h~Ying a zeolite--like structure.
Qlkyl&mmonium~ or nitrogenous, zeolites are kno~n ( B~eck,D.W.,"Zeol~te Molecular Sieves", John Wiley & SollS ,N .~ ., 197~7 pages 304-312 ): these are obtained by hydrothermal ci-ysta~lization of a mixture of silica and all.lmina hydrogels in the presence of a nitrogenous org~anic ba.se., such as al.lyl~mnonium com-polmds, or their precursors : also alkali metal ions may be present in such a system.
The ni.trogenous or~anlc compounds fulfil tY/o important requirements,viz.:
-primi.ng the formation of the zeolite cavities ( template action ) and .~ctlng in a sort of sca.ffolding action to provi.de a skeleton about which the Si ~ and Al04 tetrahedra take an orderly spatial arrangemer.t,and -acting as a co~ ter-ion,by balacing the nega-tive charge whi.ch is originated due to the Al-Si ~ubsti--2Q tutiv~, possibility.
Among the zeolites of the kind rQferred.to abo-re, which are characterized, a3 a rule, by high Si:Al ratios, those desi~lated by the s~-mbol Z~q can be quoted.
On account of their quite particular structure ar~porosity, such zeolites exhibit specific cat~l~ytic ac-tiviti.es for che~ical reac'~ions of outstanding industrlal importance, such as alkylations, isomeri~ations, and the production of synthetic fuels~
The zeolita c~llad 7~ 5 ~ TJS PataIlt Specn.
3,702,88~ ) is ~nown, which ls obtalned by using tetra-~25~3 ~w, .
prop~la~mon;.u~ d~riYati~!~L~. Oth~r ~eolites are likewise l~own, with nit~c~cnous crgænic bas~s, ~l1ong which :
Zeolite ~S~ 11 ( US Pate~t C'recn. 3,70~, 97~ ) Z,eolite ZS~ 12 ( IJS Patent S~ecn~ 3.~32, 449 ) Zeolile Z~ 35 ( US Pat~ S~ecn. 4,016, 245 ) Zeolite "beta" ( US Paten-t Specn. 3,308, 069 ~
When, conversely, the zeolites are prepared without ar,y orgailic base hc-)i.ng present, that is to say,in the presence o. inorgaL.~:.o catiorls only, it is not possihle 'GO obtain zeol L it.s having the properti.es c~
those referred to a~ove.
The zeolites pre-~-,ared with inorganic cations only are materials of the types ~inde A, Faujasite X and.
Y, Mordenite and the lihe~ ~rhich are characterized by an Si : Al ratio comprised ~etween 1 and 5. Such zeolites e~hibit vexy different properties ~rom e~ch other and are used for dehydration, cation-exchange and catalytic cracking reactions.
It has now been :~o~uld, quite surprisingly, that ~0 it is possible to obtain a.l.kyla~onium-type zeolites by hydrothermal crystallizati.on of hydrogels of silica and alumina which contai.n inorg~.ic bases only, by having recourse to organic substc~ ces ~i-hich contain hydroxyl functions, such as alcohol~ and phenols, and more parti--cularly glycols, polyglycols (mol wt ovcr 400), and poly hydro~rl substances, or substances which evolve hydro~yl or polyhydroxyl compour.ds.
~he meaning OI this fact is that, contrary to the teachings of the prior alld conte~porary a-t, it is no longer necessary, for prearing such zeolites, to resort l 162~23 to nitrogenous organic subs-tances having a basic charac-ter (organic cations or precursors thereof) to which there had been exclusively attrihuted heret.ofore the privilege oE promoting the formation of the zeoli-te cavities, In particular, the present invention provides a process for producing aluminosilicates having a porous structure, oE the -type of ZSM-5 or ZSM-35 zeolites, with a molar ratio of silica to alumina of from 5 to 500, by hydrothermally treating a homogeneous aqueous mixture free from nitrogenous bases and consisting of a source of silica, a source of alumina and alkali me-tal and/or alkaline earth metal ions, in a -temperature range of from 100C to 200C for a time of from 2 days to 6 weeks, eharacterized by adding to said mixture in organic sub-stance having an hydroxyl functi.on adapted -to form zeolite eavities, said organic substance being se].ected from -the class consisting of phenols and po].yphenols, the alkali metal and/or alkaline earth metal ions acting as counter-ions only, the atomie ratio o:E the alkali metal to the aluminum being at least close to and not more than 1, and the atomic ratio of alkaline earth me-tal being at least close to and not more than 0.5.
When operating in accordance with the teachings of this inven-tion, the counter-ion .Eunction is EulEilled, quite in a surprising way, by the alkali metal ion only and exclusively. Matter-of-factly, the experiences which have been made have shown that, in the end product, the alkali metal cation : Al ratio is close to 1.
Alkaline earth metal ions can likewise be ex-ploited; in such a case, the ratio of the alkaline earth metal cation to aluminum is near 0.5.
The adoption of substances which contain -the hydroxyl function is a considerable advance in the pro-eess for manufacturing these zeolites, due to the low 1 ~2~23 cos-t, -the absence or toxicity and the lesser pollution hazards as possessed by the product which contain the hydroxyl functions as compared with the nitrogenous or-ganic bases.
Another advantage stemming from the use of a material possessing the hydroxyl function is the impro-ved ease of removal. of the fraction of organic product which, upon crystallization with the hydrothermal proce-dure, is left occludcd in thc zcol.ite challnels: this i5 a definite improvement over -the methods using nitrogenous organic bases. With these latter, in fact, carbonization is necessary and the complete removal of the organic phases is achieved only after firing in air during many hours, ./ _ - 3a -~ S~3 '-- ~L --' such as 16 llour~ or more, at 450C-5~0C.
With the organic h~rdro~ylated products used according to -the present i-n~ention, the removal, even taking place in dependellce of the molecular weight of the substance concer~ed an be started fxom 120C and takes place without any ~compositionsS so tha-t ihe substance can be recovere~ arld recycled.
The method accordillg to the present invention for producing zeolltes cor!templates the preparation OI
a homogeneous aqueous ml~ re consisting of a silica source ~nd an alun~ina source and all~ali metal bases, or alkaline earth meta] ba~es9 to which at least one organic s~1bstance is added, which contains at least one hydrogyl ~unc-tion.
The atomic ratio aluminum : alkali m~tal must not be less than 1.
The mixture in ~ue3tion is ~ubjected to a a hydrothermal pxocessing ~n at autogenous, i.e. sel~
generated, pressure, at a temperature comprised be-~Q tween 100C and 200C and Eor a time variable from 2 days to 6 weeks.
On completion of such a treatment, a crystal-line product is obtained, ~hich is withdra~m from the liquid phase, carefully ~e~ched with water and dried.
The dried product can be fired as such at the temperature of 250C, or, as an alte~nativet it can be subjected to cation-exchange with a_monlum acetate (or N~4~nitrate), according to the conventional routine. During progress of this operation, the hydrozylated product passes into the aqueous phase, wherefrom it can ~Qe recovered.
l1~2~
~ ~ ....
On completicrl of ~his v~ep, the zeoli+e ~ontains th~
ammonil~ cation ~nd can be converted, by firing, into the protonic form.
By wayr of mere r~:rientation ~.d without any limitation to the exempla.~ ranges, the preferred mo-lar ~atios for the react~ ls are :
W i d e P r e f e r r e d ~ a n g e R a n g e Si2 A123 5 ~ 500 15 - 80 ~ o~r :sio2 o- 0.6 0.01 - 0.4 ~.O~:SiOz 0.02 - 5 0.~ 2 Me+:Si.02 0.01 - 2 0.1 ~ 0.9 wherein:
-` 15 OH- are the hydroxyls of tl1e alkali metal hydroxide, R.OH indicates the hydro~ylats~d or~anic subst~nce;
Me~ stands for the ~lkali met~l cation ( or al~aline earth metal cation.
. For the reason~ set forth above of economy and~
or lo~v toxicity, ~mong the substances having the hydroxyl function, the preferred ones are, alone or in ad~ix~l-e, et~ylene glycol, propanedio.l3~ butanediols, pentanediols, hexanediols, diethylene glycol, t~iethyleneglycol, poly~
ethylene ~lycols, polypropylene glycols, glycerol, inositol, phenolmarnitol and polyphenols, such as hydroquinone.
A few e~amples will now be given hereinafter to illustrate the invention without limitation.
E x a m p 1 e This example illustrates the synthesis of a zeolite having a high Si:Al ratio, by uvlng glycerol ~ 25~3 ( l,2,3-proparletriol) as thc agent i~or promoting the ~o~mation of the zeolite cavities.
In ~ Pyzex-glass vessfl equipped with a stirrer and placed in an atmosphere devoid of carbon diov.id*, there are placed 24 g (grarnS) OI Al(N03)3~9H20, dissol-ved in 200 g of anh.e-than-Jl, ~rhereafter there are added9 with stirring, 240 g of tetraethylorthosilicate. ~s the solution becomes clear. i~,at which t~kes 30 mins~approx., there are added ~5 g o~ glycerol and, immediately there-after, 1,500 g of distilled wa-ter. There is added now, with vigorous stirring, a solution of 23 g o~ NaOH in 500 g of water : a homogeneous ~el is fo~med shortly thereafter, Heat is then a~Linistered, -the temperature being gradually raised fro~ the ambient value up -to 90 G
durin~ a period of 24 hours~ ~ith constant stirring.
At this stage, the reactloil L~i~ture~ which has a pH ll.~ , is txansferred into a stainless steel ~utoclave equipped with a stirring mechanism and the hydrothermal run is started: it is efected by majntairling the temperature at 175 C for eight(8) dæys, with stirring and ~der the self-generated or autogenous pressure. On co~pletion of this treatment, the mi~ture is cooled to room temperature and the crystalline product, thu~ obtained is collected on a filter, ~ashed ma~y a time with dist.water at about 80C ard is eventually ~r-ied at 120 C.
The chemical composition of the thusly obtained product denounces the presence of org~nic substances and water, which are driven off b~ firing in air at 350 C
during 12 hours.
The product as obtained on completion of firing l~2~2 analyzes :
Al203 : ~ on a ~qel~ht basis Na~0 : 2.~o do. do. do.
The product is co~ erted iIltO l;he protoni.c form by the corlventional ro~lti~e clf repeated eY~changes in hot conditions (9~)~) with a~ oni~m acet~te ( or nitrate ) and subsequent ~irin~ ~t 550~C for 6 hou~
The testing of ~he zeoli.te in i1;s protonie form has given the .followin~ rerllllts:
Chemical ~nalysis : L120~ by wt -- Na~0 - 0~2~/o b-r w-t Superficial area:(BcE.T. Method, with N2) -- 380 m2/g (squax~
metres ~)er gram) Volwme. of the pores : (dete~.with 2) ~ 0.17 cm3/g (cubic centimetres per gr~) The X-ray diffraction s~sctLI~m is identical with that re-portçd for zeolites conventionall~ i.ndicated as ZSl~-5 as shown in ~able 1 of US Pa-te~t Specn. 3,702~886).
~ x a m ~ 2 _ ..~..~
Thls example is .illustratiYe of th~ possibilit~-~
of obtaining dif~erent 2eo1ite structures by exploitin~
the sa~e hydroxylated subst~nce which originates the for mation of the zeolite caYit-ies, but appropriately varying the compositions of the reaGtants and/or tke operative conditions.
In point of IaCt, in tke instant ex?~ple a zeolite is cbtained, which is conventionally designated as Z~ 35, by using glycero]. as in Ex~mple 1 hereof.
With the same procedure as detailed in the previous example, a solution of 4 g of NaOH and 109 g of N?~lO2(42~o by wt of Al203 , 31% by wt Na20 , and .
~1625~3 27% by wt H20) in 80~ g Oî water, is supple~cnt~d ~!ith 736 g o~ glycel~o]. ~l coml)letion of the dlssolutio~, there are added 1200 g o~ ~udox*A.S.40~0 colloidal si-lica and the ~nixture i~ heated, ~ith stirring, to 80C
for 6 hours.
The reaction mixture (pH 12.0) iS no~ transfer-ed into a stainless-steel autoclave e~lipped with a stixrer for the hydrother~al ~un a~ C for a ~uration o:E 6 days.
On co~pletion ar this stage, the mixture is allowed to cool, and the æs formed crystalline product is collected on a filter, washe~ and dried.
The chemical analy-r;is of the ~roduct ~hich has been obtalned has given -the following results:
Al203 = 9~15~o by wt and Na20 = 5.87~ by wt The X-ray dif~raction pattern corresponds to that reported for the ~eolite ZSM-35 (US Pate~t Specn.
4 , 107 , 195, Table 1).
q'he product, converted into its protonic io~.
with the routine described in Example 1 hereof, but omit-2Q ting the pre~ious :~iring, tha-t is, upon drying at 120C, analyzed, upon calcinatiorl :
Al203 - 9.84 by wt - Na~0 _ 0.13~ by wt E ~ a ~
This example illustrates the use, as the ~ub-stance which encourages the f~r~ation of the zeolitecaviti~s, of a bivalent alcohol, that is, 1~2-pro~anediol.
With the same proced~res,reactants and amounts of the latter as described in E~a~ple 1 hereof, but with the only difference of replaoing the 45 g of glycerol by 45 g of 1,2 propanediol, a crystalline product has been .
* Trade Mark 1 162~23 obtained, which had the same structure as ZSM-5.
The product analyzes:
Product, as such: A12O3-4.7~ by wt and Na2O-2.6~ b~ wt Product, in H+form: Al2O3 = 4.7~ by wt - Na2O = 0-05% by wt Example 4 This example illustrates the synthesis of zeolites by means of polyglycols: in the case in point, the substance which is used for causing the ~ormation of the zeolite cavities is triethylene ylycol.
With the same procedures as in Example l hereof, 24 g of Al(NO3)3.9H2O, dissolved in 200 g of ethanol, are reacted with 240 g of tetraethylorthosilicate, whereafter 90 g of triethylene glycol, 1,500 g of distilled water and eventually 23 g of NaOH are added thereto. The reaction mixture (pH 11.1) is now subjected to the subsequent treatments as outlined in Example 1 hereof.
The crystalline product which is thus obtained, when examined for its X-ray pattern, shows that it is the zeolite designated as ZSM-5, the X-ray diffraction pattern of which is reported on Table 1 of the US Pat.Specn. 3,702,886.
The chemical analysis has given the following data:
Product, as such: A12O3=5.5% by wt-Na2O-3.0% by wt Product, in H+ form: A12O3=6.1% by wt - Na2O=0-01% by wt Example 5 This example is illustrative of the synthesis of a zeolite by using, as the substance which originates the forma-tion of the zeolite cavities, a naphthenic hydroxylated derivative, that is to say, 1,4-dimethoxycyclohexane (1,4-cyclohexanedimethanol), having the following formula-~! _ 9 _ 1 1~2523 ICI-120~
jH2 ~ 2 ~H 2 \
Cll With the same procedure as in Example 4 hereof, a solution of 12 g of NaOII and 1~ g of NaAlO2 (42% by wt of A12O3, 31% by wt of Na2O and 27% by wt of H2O) in 250 g of water is supplemented with 140 g of 1,4-cyclohexanedimethanol.
Upon dissolution, there are added 300 g of Ludox AS 40~
colloidal silica and heat is admini.stered with stirring at 90C for six (6) hours.
The reaction mixture, which has a pH 12.8, is transferred into an autoclave for the hydrothermal run at 145C
for a time of nine (9) days.
The thusly obtained product thus obtained, after the further steps as described in the previous examples is subjected to X-ray analysis and proved to be a ZSM-5 zeolite with traces of Mordenite.
~ xample 6 sy using the same procedures and reactants as in the previous examples hereof and replacing the 140 g of cyclo-hexanedimethanol by 140 g of inositol and carrying out the hydrothermal run at 180C for a time of ten (10) dàys, there has been obtained, on completion of the operations described herein, the zeolite designated as ZMS-5 in admixture with scanty quantities of Mordenite.
l 16252~
Example 7 This example illustrates the synthesis of a zeolite by using as the substance which determines the formation of the zeolite cavities a hydroxylated derivative having the phenolic function, and exactly hydroquinone.
With the same routine as in Example l hereof, there are dissolved 24 g of Al(NO3)3.9H2O in 200 g of anh.ethanol, whereafter there are added 240 g of tetraethylorthosilicate.
As the solution becomes clear, there are added thereto 60 g of hydroquinone and immediately afterwards 42 g of NaOH dissolved in 200 g of water.
The final mixture, having a pH 10.5, is transferred into an autoclave and maintained therein at 180C for twelve (12) days. ~he product which has been obtained after the steps described herein has been analyzed for its X-ray diffraction pattern and has proved -to be a ZSM-5 zeolite.
From the examples reported in the foregoing, it is extremely interesting the fact that the exchange operation for ohtaining the protonic formation is now feasible, accordiny to the invention, without any previous firing, contrary to what is conversely required when the organic phases suggested by the prior art are used.
This fact is a clear indication of the circumstance that the bonds with the inorganic matrix are different in the case in which the organic bases according to the prior art are used and in the case in which the organic compounds having hydroxyl functions are conversely used accoxding to the teachings of this invention.
HhVI~G h Z.l`~LIl!E-LIl'~ Sr~,J't'I~
This illvefltion relat~s to a metho~ fvr the preparation of aluminum--sili.cates h~Ying a zeolite--like structure.
Qlkyl&mmonium~ or nitrogenous, zeolites are kno~n ( B~eck,D.W.,"Zeol~te Molecular Sieves", John Wiley & SollS ,N .~ ., 197~7 pages 304-312 ): these are obtained by hydrothermal ci-ysta~lization of a mixture of silica and all.lmina hydrogels in the presence of a nitrogenous org~anic ba.se., such as al.lyl~mnonium com-polmds, or their precursors : also alkali metal ions may be present in such a system.
The ni.trogenous or~anlc compounds fulfil tY/o important requirements,viz.:
-primi.ng the formation of the zeolite cavities ( template action ) and .~ctlng in a sort of sca.ffolding action to provi.de a skeleton about which the Si ~ and Al04 tetrahedra take an orderly spatial arrangemer.t,and -acting as a co~ ter-ion,by balacing the nega-tive charge whi.ch is originated due to the Al-Si ~ubsti--2Q tutiv~, possibility.
Among the zeolites of the kind rQferred.to abo-re, which are characterized, a3 a rule, by high Si:Al ratios, those desi~lated by the s~-mbol Z~q can be quoted.
On account of their quite particular structure ar~porosity, such zeolites exhibit specific cat~l~ytic ac-tiviti.es for che~ical reac'~ions of outstanding industrlal importance, such as alkylations, isomeri~ations, and the production of synthetic fuels~
The zeolita c~llad 7~ 5 ~ TJS PataIlt Specn.
3,702,88~ ) is ~nown, which ls obtalned by using tetra-~25~3 ~w, .
prop~la~mon;.u~ d~riYati~!~L~. Oth~r ~eolites are likewise l~own, with nit~c~cnous crgænic bas~s, ~l1ong which :
Zeolite ~S~ 11 ( US Pate~t C'recn. 3,70~, 97~ ) Z,eolite ZS~ 12 ( IJS Patent S~ecn~ 3.~32, 449 ) Zeolile Z~ 35 ( US Pat~ S~ecn. 4,016, 245 ) Zeolite "beta" ( US Paten-t Specn. 3,308, 069 ~
When, conversely, the zeolites are prepared without ar,y orgailic base hc-)i.ng present, that is to say,in the presence o. inorgaL.~:.o catiorls only, it is not possihle 'GO obtain zeol L it.s having the properti.es c~
those referred to a~ove.
The zeolites pre-~-,ared with inorganic cations only are materials of the types ~inde A, Faujasite X and.
Y, Mordenite and the lihe~ ~rhich are characterized by an Si : Al ratio comprised ~etween 1 and 5. Such zeolites e~hibit vexy different properties ~rom e~ch other and are used for dehydration, cation-exchange and catalytic cracking reactions.
It has now been :~o~uld, quite surprisingly, that ~0 it is possible to obtain a.l.kyla~onium-type zeolites by hydrothermal crystallizati.on of hydrogels of silica and alumina which contai.n inorg~.ic bases only, by having recourse to organic substc~ ces ~i-hich contain hydroxyl functions, such as alcohol~ and phenols, and more parti--cularly glycols, polyglycols (mol wt ovcr 400), and poly hydro~rl substances, or substances which evolve hydro~yl or polyhydroxyl compour.ds.
~he meaning OI this fact is that, contrary to the teachings of the prior alld conte~porary a-t, it is no longer necessary, for prearing such zeolites, to resort l 162~23 to nitrogenous organic subs-tances having a basic charac-ter (organic cations or precursors thereof) to which there had been exclusively attrihuted heret.ofore the privilege oE promoting the formation of the zeoli-te cavities, In particular, the present invention provides a process for producing aluminosilicates having a porous structure, oE the -type of ZSM-5 or ZSM-35 zeolites, with a molar ratio of silica to alumina of from 5 to 500, by hydrothermally treating a homogeneous aqueous mixture free from nitrogenous bases and consisting of a source of silica, a source of alumina and alkali me-tal and/or alkaline earth metal ions, in a -temperature range of from 100C to 200C for a time of from 2 days to 6 weeks, eharacterized by adding to said mixture in organic sub-stance having an hydroxyl functi.on adapted -to form zeolite eavities, said organic substance being se].ected from -the class consisting of phenols and po].yphenols, the alkali metal and/or alkaline earth metal ions acting as counter-ions only, the atomie ratio o:E the alkali metal to the aluminum being at least close to and not more than 1, and the atomic ratio of alkaline earth me-tal being at least close to and not more than 0.5.
When operating in accordance with the teachings of this inven-tion, the counter-ion .Eunction is EulEilled, quite in a surprising way, by the alkali metal ion only and exclusively. Matter-of-factly, the experiences which have been made have shown that, in the end product, the alkali metal cation : Al ratio is close to 1.
Alkaline earth metal ions can likewise be ex-ploited; in such a case, the ratio of the alkaline earth metal cation to aluminum is near 0.5.
The adoption of substances which contain -the hydroxyl function is a considerable advance in the pro-eess for manufacturing these zeolites, due to the low 1 ~2~23 cos-t, -the absence or toxicity and the lesser pollution hazards as possessed by the product which contain the hydroxyl functions as compared with the nitrogenous or-ganic bases.
Another advantage stemming from the use of a material possessing the hydroxyl function is the impro-ved ease of removal. of the fraction of organic product which, upon crystallization with the hydrothermal proce-dure, is left occludcd in thc zcol.ite challnels: this i5 a definite improvement over -the methods using nitrogenous organic bases. With these latter, in fact, carbonization is necessary and the complete removal of the organic phases is achieved only after firing in air during many hours, ./ _ - 3a -~ S~3 '-- ~L --' such as 16 llour~ or more, at 450C-5~0C.
With the organic h~rdro~ylated products used according to -the present i-n~ention, the removal, even taking place in dependellce of the molecular weight of the substance concer~ed an be started fxom 120C and takes place without any ~compositionsS so tha-t ihe substance can be recovere~ arld recycled.
The method accordillg to the present invention for producing zeolltes cor!templates the preparation OI
a homogeneous aqueous ml~ re consisting of a silica source ~nd an alun~ina source and all~ali metal bases, or alkaline earth meta] ba~es9 to which at least one organic s~1bstance is added, which contains at least one hydrogyl ~unc-tion.
The atomic ratio aluminum : alkali m~tal must not be less than 1.
The mixture in ~ue3tion is ~ubjected to a a hydrothermal pxocessing ~n at autogenous, i.e. sel~
generated, pressure, at a temperature comprised be-~Q tween 100C and 200C and Eor a time variable from 2 days to 6 weeks.
On completion of such a treatment, a crystal-line product is obtained, ~hich is withdra~m from the liquid phase, carefully ~e~ched with water and dried.
The dried product can be fired as such at the temperature of 250C, or, as an alte~nativet it can be subjected to cation-exchange with a_monlum acetate (or N~4~nitrate), according to the conventional routine. During progress of this operation, the hydrozylated product passes into the aqueous phase, wherefrom it can ~Qe recovered.
l1~2~
~ ~ ....
On completicrl of ~his v~ep, the zeoli+e ~ontains th~
ammonil~ cation ~nd can be converted, by firing, into the protonic form.
By wayr of mere r~:rientation ~.d without any limitation to the exempla.~ ranges, the preferred mo-lar ~atios for the react~ ls are :
W i d e P r e f e r r e d ~ a n g e R a n g e Si2 A123 5 ~ 500 15 - 80 ~ o~r :sio2 o- 0.6 0.01 - 0.4 ~.O~:SiOz 0.02 - 5 0.~ 2 Me+:Si.02 0.01 - 2 0.1 ~ 0.9 wherein:
-` 15 OH- are the hydroxyls of tl1e alkali metal hydroxide, R.OH indicates the hydro~ylats~d or~anic subst~nce;
Me~ stands for the ~lkali met~l cation ( or al~aline earth metal cation.
. For the reason~ set forth above of economy and~
or lo~v toxicity, ~mong the substances having the hydroxyl function, the preferred ones are, alone or in ad~ix~l-e, et~ylene glycol, propanedio.l3~ butanediols, pentanediols, hexanediols, diethylene glycol, t~iethyleneglycol, poly~
ethylene ~lycols, polypropylene glycols, glycerol, inositol, phenolmarnitol and polyphenols, such as hydroquinone.
A few e~amples will now be given hereinafter to illustrate the invention without limitation.
E x a m p 1 e This example illustrates the synthesis of a zeolite having a high Si:Al ratio, by uvlng glycerol ~ 25~3 ( l,2,3-proparletriol) as thc agent i~or promoting the ~o~mation of the zeolite cavities.
In ~ Pyzex-glass vessfl equipped with a stirrer and placed in an atmosphere devoid of carbon diov.id*, there are placed 24 g (grarnS) OI Al(N03)3~9H20, dissol-ved in 200 g of anh.e-than-Jl, ~rhereafter there are added9 with stirring, 240 g of tetraethylorthosilicate. ~s the solution becomes clear. i~,at which t~kes 30 mins~approx., there are added ~5 g o~ glycerol and, immediately there-after, 1,500 g of distilled wa-ter. There is added now, with vigorous stirring, a solution of 23 g o~ NaOH in 500 g of water : a homogeneous ~el is fo~med shortly thereafter, Heat is then a~Linistered, -the temperature being gradually raised fro~ the ambient value up -to 90 G
durin~ a period of 24 hours~ ~ith constant stirring.
At this stage, the reactloil L~i~ture~ which has a pH ll.~ , is txansferred into a stainless steel ~utoclave equipped with a stirring mechanism and the hydrothermal run is started: it is efected by majntairling the temperature at 175 C for eight(8) dæys, with stirring and ~der the self-generated or autogenous pressure. On co~pletion of this treatment, the mi~ture is cooled to room temperature and the crystalline product, thu~ obtained is collected on a filter, ~ashed ma~y a time with dist.water at about 80C ard is eventually ~r-ied at 120 C.
The chemical composition of the thusly obtained product denounces the presence of org~nic substances and water, which are driven off b~ firing in air at 350 C
during 12 hours.
The product as obtained on completion of firing l~2~2 analyzes :
Al203 : ~ on a ~qel~ht basis Na~0 : 2.~o do. do. do.
The product is co~ erted iIltO l;he protoni.c form by the corlventional ro~lti~e clf repeated eY~changes in hot conditions (9~)~) with a~ oni~m acet~te ( or nitrate ) and subsequent ~irin~ ~t 550~C for 6 hou~
The testing of ~he zeoli.te in i1;s protonie form has given the .followin~ rerllllts:
Chemical ~nalysis : L120~ by wt -- Na~0 - 0~2~/o b-r w-t Superficial area:(BcE.T. Method, with N2) -- 380 m2/g (squax~
metres ~)er gram) Volwme. of the pores : (dete~.with 2) ~ 0.17 cm3/g (cubic centimetres per gr~) The X-ray diffraction s~sctLI~m is identical with that re-portçd for zeolites conventionall~ i.ndicated as ZSl~-5 as shown in ~able 1 of US Pa-te~t Specn. 3,702~886).
~ x a m ~ 2 _ ..~..~
Thls example is .illustratiYe of th~ possibilit~-~
of obtaining dif~erent 2eo1ite structures by exploitin~
the sa~e hydroxylated subst~nce which originates the for mation of the zeolite caYit-ies, but appropriately varying the compositions of the reaGtants and/or tke operative conditions.
In point of IaCt, in tke instant ex?~ple a zeolite is cbtained, which is conventionally designated as Z~ 35, by using glycero]. as in Ex~mple 1 hereof.
With the same procedure as detailed in the previous example, a solution of 4 g of NaOH and 109 g of N?~lO2(42~o by wt of Al203 , 31% by wt Na20 , and .
~1625~3 27% by wt H20) in 80~ g Oî water, is supple~cnt~d ~!ith 736 g o~ glycel~o]. ~l coml)letion of the dlssolutio~, there are added 1200 g o~ ~udox*A.S.40~0 colloidal si-lica and the ~nixture i~ heated, ~ith stirring, to 80C
for 6 hours.
The reaction mixture (pH 12.0) iS no~ transfer-ed into a stainless-steel autoclave e~lipped with a stixrer for the hydrother~al ~un a~ C for a ~uration o:E 6 days.
On co~pletion ar this stage, the mixture is allowed to cool, and the æs formed crystalline product is collected on a filter, washe~ and dried.
The chemical analy-r;is of the ~roduct ~hich has been obtalned has given -the following results:
Al203 = 9~15~o by wt and Na20 = 5.87~ by wt The X-ray dif~raction pattern corresponds to that reported for the ~eolite ZSM-35 (US Pate~t Specn.
4 , 107 , 195, Table 1).
q'he product, converted into its protonic io~.
with the routine described in Example 1 hereof, but omit-2Q ting the pre~ious :~iring, tha-t is, upon drying at 120C, analyzed, upon calcinatiorl :
Al203 - 9.84 by wt - Na~0 _ 0.13~ by wt E ~ a ~
This example illustrates the use, as the ~ub-stance which encourages the f~r~ation of the zeolitecaviti~s, of a bivalent alcohol, that is, 1~2-pro~anediol.
With the same proced~res,reactants and amounts of the latter as described in E~a~ple 1 hereof, but with the only difference of replaoing the 45 g of glycerol by 45 g of 1,2 propanediol, a crystalline product has been .
* Trade Mark 1 162~23 obtained, which had the same structure as ZSM-5.
The product analyzes:
Product, as such: A12O3-4.7~ by wt and Na2O-2.6~ b~ wt Product, in H+form: Al2O3 = 4.7~ by wt - Na2O = 0-05% by wt Example 4 This example illustrates the synthesis of zeolites by means of polyglycols: in the case in point, the substance which is used for causing the ~ormation of the zeolite cavities is triethylene ylycol.
With the same procedures as in Example l hereof, 24 g of Al(NO3)3.9H2O, dissolved in 200 g of ethanol, are reacted with 240 g of tetraethylorthosilicate, whereafter 90 g of triethylene glycol, 1,500 g of distilled water and eventually 23 g of NaOH are added thereto. The reaction mixture (pH 11.1) is now subjected to the subsequent treatments as outlined in Example 1 hereof.
The crystalline product which is thus obtained, when examined for its X-ray pattern, shows that it is the zeolite designated as ZSM-5, the X-ray diffraction pattern of which is reported on Table 1 of the US Pat.Specn. 3,702,886.
The chemical analysis has given the following data:
Product, as such: A12O3=5.5% by wt-Na2O-3.0% by wt Product, in H+ form: A12O3=6.1% by wt - Na2O=0-01% by wt Example 5 This example is illustrative of the synthesis of a zeolite by using, as the substance which originates the forma-tion of the zeolite cavities, a naphthenic hydroxylated derivative, that is to say, 1,4-dimethoxycyclohexane (1,4-cyclohexanedimethanol), having the following formula-~! _ 9 _ 1 1~2523 ICI-120~
jH2 ~ 2 ~H 2 \
Cll With the same procedure as in Example 4 hereof, a solution of 12 g of NaOII and 1~ g of NaAlO2 (42% by wt of A12O3, 31% by wt of Na2O and 27% by wt of H2O) in 250 g of water is supplemented with 140 g of 1,4-cyclohexanedimethanol.
Upon dissolution, there are added 300 g of Ludox AS 40~
colloidal silica and heat is admini.stered with stirring at 90C for six (6) hours.
The reaction mixture, which has a pH 12.8, is transferred into an autoclave for the hydrothermal run at 145C
for a time of nine (9) days.
The thusly obtained product thus obtained, after the further steps as described in the previous examples is subjected to X-ray analysis and proved to be a ZSM-5 zeolite with traces of Mordenite.
~ xample 6 sy using the same procedures and reactants as in the previous examples hereof and replacing the 140 g of cyclo-hexanedimethanol by 140 g of inositol and carrying out the hydrothermal run at 180C for a time of ten (10) dàys, there has been obtained, on completion of the operations described herein, the zeolite designated as ZMS-5 in admixture with scanty quantities of Mordenite.
l 16252~
Example 7 This example illustrates the synthesis of a zeolite by using as the substance which determines the formation of the zeolite cavities a hydroxylated derivative having the phenolic function, and exactly hydroquinone.
With the same routine as in Example l hereof, there are dissolved 24 g of Al(NO3)3.9H2O in 200 g of anh.ethanol, whereafter there are added 240 g of tetraethylorthosilicate.
As the solution becomes clear, there are added thereto 60 g of hydroquinone and immediately afterwards 42 g of NaOH dissolved in 200 g of water.
The final mixture, having a pH 10.5, is transferred into an autoclave and maintained therein at 180C for twelve (12) days. ~he product which has been obtained after the steps described herein has been analyzed for its X-ray diffraction pattern and has proved -to be a ZSM-5 zeolite.
From the examples reported in the foregoing, it is extremely interesting the fact that the exchange operation for ohtaining the protonic formation is now feasible, accordiny to the invention, without any previous firing, contrary to what is conversely required when the organic phases suggested by the prior art are used.
This fact is a clear indication of the circumstance that the bonds with the inorganic matrix are different in the case in which the organic bases according to the prior art are used and in the case in which the organic compounds having hydroxyl functions are conversely used accoxding to the teachings of this invention.
Claims (6)
1. A process for producing aluminosilicates having a porous structure, o-E the type of ZSM-5 or ZSM-35 zeolites, with a molar ratio of silica to alumina of from 5 to 500, by hydrothermally treating a homogeneous aqueous mixture free from nitrogenous bases and consisting of a source of silica, a source of alumina and alkali metal and/or alkaline earth metal ions, in a temperature range of from 100°C to 200°C for a time of from 2 days to 6 weeks, characterized by adding to said mixture an organic substance having an hydroxyl function adapted to form zeolite cavities, said organic substance being selec-ted from the class consisting of phenols and polyphenols the alkali metal and/or alkaline earth metal ions acting as counter-ions only, the atomic ratio of the alkali metal to the aluminum being at least close to and not more than 1, and the atomic ratio of alkaline earth metal being at least close to and not more than 0.5.
2. Process according to claim 1, wherein said organic substance is hydroquinone.
3. Process for the production of alumino-silicates having a porous structure of the zeolite class, according to claim 1, wherein the alumino-silicate recovered from said hydrothermal treatment is subjected to cation-exchange directly on completion of said hydrothermal treatment.
4. A process for producing aluminosilicates having a porous structure, of the type of ZSM-5 or ZSM-35 zeolites, with a molar ratio of silica to alumina of from 5 to 500, by hydrothermally treating a homogeneous aqueous mixture free from nitrogenous bases and consist-ing of a source of silica, a source of alumina and alkali metal ions, in a temperature range of from 100°C
to 200°C for a time of from 2 days to 6 weeks, charac-terized by adding to said mixture an organic substance having an hydroxyl function adapted to form zeolite cavities, said organic substance being selected from the class consisting of phenols and polyphenols, the alkali metal ions acting as counter-ions only, and the atomic ratio of the alkali metal to the aluminum being at least close to and not more than 1.
to 200°C for a time of from 2 days to 6 weeks, charac-terized by adding to said mixture an organic substance having an hydroxyl function adapted to form zeolite cavities, said organic substance being selected from the class consisting of phenols and polyphenols, the alkali metal ions acting as counter-ions only, and the atomic ratio of the alkali metal to the aluminum being at least close to and not more than 1.
5. Process according to claim 4, wherein said organic substance is hydroquinone.
6. Process for the production of alumino-silicates having a porous structure of the zeolite class, according to claim 4, wherein the alumino-silicate recovered from said hydrothermal treatment is subjected to cation-exchange directly on completion of said hydro-thermal treatment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20557/80A IT1140784B (en) | 1980-03-13 | 1980-03-13 | METHOD FOR THE PRODUCTION OF ZEOLITHIC STRUCTURE ALUMINUM SILICATES |
| IT20557A/80 | 1980-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162523A true CA1162523A (en) | 1984-02-21 |
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ID=11168737
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372186A Expired CA1162523A (en) | 1980-03-13 | 1981-03-03 | Method for preparing aluminum-silicate having a zeolite-like structure |
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|---|---|
| US (1) | US4431621A (en) |
| JP (1) | JPS56134517A (en) |
| AR (1) | AR226348A1 (en) |
| AU (1) | AU6769181A (en) |
| BE (1) | BE887897A (en) |
| BG (1) | BG40649A3 (en) |
| BR (1) | BR8101472A (en) |
| CA (1) | CA1162523A (en) |
| CH (1) | CH646122A5 (en) |
| CS (1) | CS225829B2 (en) |
| DD (1) | DD156801A5 (en) |
| DE (1) | DE3109055C2 (en) |
| DK (1) | DK86881A (en) |
| ES (1) | ES8206214A1 (en) |
| FR (1) | FR2478063B1 (en) |
| GB (1) | GB2071632B (en) |
| GR (1) | GR74452B (en) |
| HU (1) | HU188001B (en) |
| IL (1) | IL62261A (en) |
| IN (1) | IN154581B (en) |
| IT (1) | IT1140784B (en) |
| LU (1) | LU83204A1 (en) |
| MW (1) | MW981A1 (en) |
| NL (1) | NL8101216A (en) |
| NO (1) | NO810823L (en) |
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| PT (1) | PT72656B (en) |
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| ZA (1) | ZA811244B (en) |
| ZW (1) | ZW4781A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0042225B1 (en) * | 1980-06-12 | 1984-02-01 | Imperial Chemical Industries Plc | Zeolite synthesis |
| DE3140895A1 (en) * | 1981-10-15 | 1983-04-28 | Basf Ag, 6700 Ludwigshafen | BOROSILIKATZEOLITHE- ZBH AND METHOD FOR PRODUCING CRYSTALLINE BOROSILIKATZEOLITHE (ZHB) AND USE AS A CATALYST |
| NZ202099A (en) * | 1981-10-21 | 1986-07-11 | Ici Plc | Preparation of zeolite nu-10 |
| JPS5926924A (en) * | 1982-07-30 | 1984-02-13 | Res Assoc Petroleum Alternat Dev<Rapad> | Crystalline silicate and its preparation |
| EP0107908B1 (en) * | 1982-10-01 | 1986-03-26 | Imperial Chemical Industries Plc | Zeolites |
| JPS5973427A (en) * | 1982-10-16 | 1984-04-25 | Res Assoc Petroleum Alternat Dev<Rapad> | Novel zeolite and preparation thereof |
| GB2132993B (en) * | 1983-01-11 | 1986-03-19 | Coal Ind | Improvements in catalyst production |
| JPS59162124A (en) * | 1983-03-07 | 1984-09-13 | Res Assoc Petroleum Alternat Dev<Rapad> | Crystalline aluminosilicate and its production |
| DK84884A (en) * | 1983-03-07 | 1984-09-08 | Res Ass Petroleum Alternat Dev | CRYSTALLINIC ALUMINUM SILICATE AND PROCEDURES FOR PRODUCING THEREOF |
| US4900529A (en) * | 1984-09-04 | 1990-02-13 | W. R. Grace & Co.-Conn. | Process for making crystalline siliceous materials |
| EP0202797B1 (en) * | 1985-05-14 | 1993-01-27 | Mobil Oil Corporation | A method for the synthesis of zeolites |
| US4721607A (en) * | 1986-01-31 | 1988-01-26 | Amoco Corporation | Process for the production of boronaaronate molecular sieve using ethylenediamine and quinoline or isoquinoline |
| US5066630A (en) * | 1989-06-30 | 1991-11-19 | Sumitomo Chemical Company, Limited | Method for removing nitrogen-containing organic compounds from crystalline metallosilicate |
| FR2683519B1 (en) * | 1991-11-08 | 1994-03-04 | Elf Aquitaine Ste Nale | PROCESS FOR SYNTHESIS OF AN MTT TYPE ZEOLITH, PRODUCTS OBTAINED AND THEIR APPLICATION IN ADSORPTION AND CATALYSIS. |
| US6368571B1 (en) * | 2000-01-28 | 2002-04-09 | Chk Group, Inc. | ZSM-5 made from siliceous ash |
| CN1307099C (en) * | 2000-12-28 | 2007-03-28 | 花王株式会社 | Fine zeolite particle |
| US6884743B2 (en) * | 2002-09-16 | 2005-04-26 | Basf Aktiengesellschaft | Catalyst for epoxidation reactions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3313594A (en) * | 1963-07-05 | 1967-04-11 | Mobil Oil Corp | Method for producing crystalline aluminosilicate zeolitic particles of uniform size |
| US3516786A (en) * | 1968-02-23 | 1970-06-23 | Grace W R & Co | Method of preparing microcrystalline faujasite-type zeolite |
| US3702886A (en) * | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US3676063A (en) * | 1971-03-11 | 1972-07-11 | Nalco Chemical Co | Process for preparing synthetic crystalline zeolitic sodium aluminosilicate |
| US4175114A (en) * | 1973-12-13 | 1979-11-20 | Mobil Oil Corporation | Method for producing zeolites |
| ZA756745B (en) * | 1974-10-30 | 1976-10-27 | Ici Ltd | Improvements in and relating to zeolites |
| GB1553209A (en) * | 1975-09-29 | 1979-09-26 | Ici Ltd | Zeolites |
| US4069210A (en) * | 1976-09-30 | 1978-01-17 | Ppg Industries, Inc. | Polymeric products |
| DE2862205D1 (en) * | 1977-12-23 | 1983-04-21 | British Petroleum Co Plc | Method for preparing aluminosilicates and their use as catalyst supports and catalysts |
| NL7803662A (en) * | 1978-04-06 | 1979-10-09 | Shell Int Research | PROCESS FOR THE PREPARATION OF ZEOLITES. |
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1980
- 1980-03-13 IT IT20557/80A patent/IT1140784B/en active
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1981
- 1981-02-23 GR GR64216A patent/GR74452B/el unknown
- 1981-02-24 ZA ZA00811244A patent/ZA811244B/en unknown
- 1981-02-26 DK DK86881A patent/DK86881A/en not_active Application Discontinuation
- 1981-02-26 AU AU67691/81A patent/AU6769181A/en not_active Abandoned
- 1981-03-03 PH PH25304A patent/PH17851A/en unknown
- 1981-03-03 ZW ZW47/81A patent/ZW4781A1/en unknown
- 1981-03-03 CA CA000372186A patent/CA1162523A/en not_active Expired
- 1981-03-03 IL IL62261A patent/IL62261A/en unknown
- 1981-03-05 GB GB8106922A patent/GB2071632B/en not_active Expired
- 1981-03-06 BG BG8151122A patent/BG40649A3/en unknown
- 1981-03-06 ES ES500956A patent/ES8206214A1/en not_active Expired
- 1981-03-09 SE SE8101473A patent/SE8101473L/en not_active Application Discontinuation
- 1981-03-09 CS CS811707A patent/CS225829B2/en unknown
- 1981-03-10 DE DE3109055A patent/DE3109055C2/en not_active Expired
- 1981-03-10 TR TR21310A patent/TR21310A/en unknown
- 1981-03-10 LU LU83204A patent/LU83204A1/en unknown
- 1981-03-11 NO NO810823A patent/NO810823L/en unknown
- 1981-03-11 RO RO81103644A patent/RO82107A/en unknown
- 1981-03-11 BR BR8101472A patent/BR8101472A/en unknown
- 1981-03-11 BE BE0/203350A patent/BE887897A/en not_active IP Right Cessation
- 1981-03-12 CH CH169881A patent/CH646122A5/en not_active IP Right Cessation
- 1981-03-12 MW MW9/81A patent/MW981A1/en unknown
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- 1981-03-12 FR FR8105003A patent/FR2478063B1/en not_active Expired
- 1981-03-12 DD DD81228246A patent/DD156801A5/en unknown
- 1981-03-12 JP JP3468981A patent/JPS56134517A/en active Pending
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