CA1154738A - Aluminum deficient zeolite compositions and process for preparing same - Google Patents
Aluminum deficient zeolite compositions and process for preparing sameInfo
- Publication number
- CA1154738A CA1154738A CA000370359A CA370359A CA1154738A CA 1154738 A CA1154738 A CA 1154738A CA 000370359 A CA000370359 A CA 000370359A CA 370359 A CA370359 A CA 370359A CA 1154738 A CA1154738 A CA 1154738A
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- zeolite
- process according
- fluorine
- crystalline
- aluminosilicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- 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
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/21—Faujasite, e.g. X, Y, CZS-3, ECR-4, Z-14HS, VHP-R
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- 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
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- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241
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- 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
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- Y10S423/23—Ferrierite, e.g. SR-D ZSM-33
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/26—Mazzite, e.g. ZSM-4, omega
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- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/27—Beta, e.g. NU-2
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- 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
- Y10S423/28—LTL, e.g. BA-G, L, AG-1, AG-2, AG-4, BA-6
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- 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
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/29—MEL, e.g. ZSM-11
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- 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
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/33—MTW, e.g. ZSM-12, NU-13, CZH-5, TPZ-3
Abstract
ALUMINUM DEFICIENT ZEOLITE COMPOSITIONS
AND PROCESS FOR PREPARING SAME
ABSTRACT OF DISCLOSURE
The hydrophobicity of crystalline zeolites is enhanced and their catalytic activity altered by treatment with fluorine under controlled condi-tions which result in dealumination and structural stabilization as evidenced by changes observed in their infrared framework spectra.
S P E C I F I C A T I O N
AND PROCESS FOR PREPARING SAME
ABSTRACT OF DISCLOSURE
The hydrophobicity of crystalline zeolites is enhanced and their catalytic activity altered by treatment with fluorine under controlled condi-tions which result in dealumination and structural stabilization as evidenced by changes observed in their infrared framework spectra.
S P E C I F I C A T I O N
Description
~ 7 3 ~
The present invention relates in general to crystalline zeolite compositions which have enhanced hydrophobic character and modified cataly~ic properties.
More particularly it relates to crystalline zeolites which have been treated with fluorine to alter the framework aluminum content and the acidic sites thereof with resultant modification of both the adsorp-tive and catalytic properties.
Although there are a few notable exceptions, the vast majority of naturally-occurring and synthetic crystalline zeolites contain a substantial proportion of A104 - tetrahedra, i.e. frameworks aluminum atoms, which together with the SiO4 tetrahedra comprise the zeolite crystal framework. It is generally accepted that these aluminum-containing structural units pro-vide the so-called "acid sites" which account for the catalytic activity of zeolites in such hydrocarbon conversion reactions as catalytic cracking. These same acid sites are also responsible in one or more ways for the adsorptive preference of most zeolites for strongly polar molecules such as water, i.e., their hydrophilic ch~racter.
A number of different techniques have hereto-fore been proposed to remove framework aluminum atoms from zeolites to create aluminum-deficient la~tice structures having fewer acid sites, and consequently less hydrophilicity, and an altered catalytic activity.
In some instances the techniques employed are too rigorous to permit sufficient dealumination to significantly alter either the hydrophilicity or the catalytic ac~ivity
The present invention relates in general to crystalline zeolite compositions which have enhanced hydrophobic character and modified cataly~ic properties.
More particularly it relates to crystalline zeolites which have been treated with fluorine to alter the framework aluminum content and the acidic sites thereof with resultant modification of both the adsorp-tive and catalytic properties.
Although there are a few notable exceptions, the vast majority of naturally-occurring and synthetic crystalline zeolites contain a substantial proportion of A104 - tetrahedra, i.e. frameworks aluminum atoms, which together with the SiO4 tetrahedra comprise the zeolite crystal framework. It is generally accepted that these aluminum-containing structural units pro-vide the so-called "acid sites" which account for the catalytic activity of zeolites in such hydrocarbon conversion reactions as catalytic cracking. These same acid sites are also responsible in one or more ways for the adsorptive preference of most zeolites for strongly polar molecules such as water, i.e., their hydrophilic ch~racter.
A number of different techniques have hereto-fore been proposed to remove framework aluminum atoms from zeolites to create aluminum-deficient la~tice structures having fewer acid sites, and consequently less hydrophilicity, and an altered catalytic activity.
In some instances the techniques employed are too rigorous to permit sufficient dealumination to significantly alter either the hydrophilicity or the catalytic ac~ivity
-2-~ 3 ~
before causing the collapse of the entire cr~stal lattice. In other cases the lattice structure of the starting zeolite has sufficient integrity so that the dealumination is permitted to proceed to a degree which engenders a remarkable degree of hydrophobicity in the product zeolite and further enhances its thermal and/or hydrothermal stability.
One of the more common early techniques for dealuminizing zeolites involves contacting either the hydrogen or decationized orm of a zeolite with a known chelatin~ agent for aluminum such as ethylene diaminetetraacetic acid (EDTA) or acetylacetone and removing aluminum as an organometallic complex. A
more recent and more widely used procedure involves prolonged contact of non-metallic cation forms of zeolites with steam at elevated temperatures which can exceed 800C. Although quite effective for their intended purpose, these steaming procedures are very costly and highly energy-consuming.
It is therefore the general object of the present invention to provide an a~ternate process for enhancing the hydrophobic character and stability of zeolites by decrcasing the number of acid sites in the framework structure. This object, and others which will be apparent from the present specification is accomplished by the process which comprises;
(a) providing an activated crystalline zeolitic aluminosilicate having a SiO2/A1203 molar ratio of at least 2, preferably in the ran~e of 4 to 190 , and having at least 50 percent, preferably at least 90 percent, of the framework aluminum atoms not ~ ,3~ D-12250 associated with metal cations;
(b) contacting said activated aluminosilicate with a gas mixture comprising ~i) from 0.1 to 20 volume percent fluorine (ii) from zero to 21 volume percent oxygen (iii) and as the remainder, one or a mixture of two or more inert gases, preferably nitrogen, said contact being at a temperature of from about 50 to 400F
for a period of at least 1 minute preferably from about 5 to 60 minutes. Optionally the resulting fluorinated zeolite can be further treated by calcination at temperatures above 500C and up to the crystal destruction temperature of the zeolite, or by rehydrating same, or a combination of the two treatments in either order.
Crystalline zeolites suitably treated in accordance with the present invention include erionite, mordenite, zeolite Y, zeolite omega, zeolite be~a, zeolite ZSM-5, zeolite ZSM-ll, zeolite L, and zeolite ZSM-35. Both natural and synthetic zeolites can be used. Zeolite Y is disclosed in U.S.P. 3,130,007 (Breck); zeolite omega in U.S.P.
4,241,036 (Flanigen et al.); zeolite beta in U.S.P. 3,308,069;
zeolite ZSM-5, in U.S.P. 3,702,886 (Wadlinger et al.);
zeolite ZSM-ll in U.S.P. 3,709,979 (Chu); zeolite L in U.S.P.
before causing the collapse of the entire cr~stal lattice. In other cases the lattice structure of the starting zeolite has sufficient integrity so that the dealumination is permitted to proceed to a degree which engenders a remarkable degree of hydrophobicity in the product zeolite and further enhances its thermal and/or hydrothermal stability.
One of the more common early techniques for dealuminizing zeolites involves contacting either the hydrogen or decationized orm of a zeolite with a known chelatin~ agent for aluminum such as ethylene diaminetetraacetic acid (EDTA) or acetylacetone and removing aluminum as an organometallic complex. A
more recent and more widely used procedure involves prolonged contact of non-metallic cation forms of zeolites with steam at elevated temperatures which can exceed 800C. Although quite effective for their intended purpose, these steaming procedures are very costly and highly energy-consuming.
It is therefore the general object of the present invention to provide an a~ternate process for enhancing the hydrophobic character and stability of zeolites by decrcasing the number of acid sites in the framework structure. This object, and others which will be apparent from the present specification is accomplished by the process which comprises;
(a) providing an activated crystalline zeolitic aluminosilicate having a SiO2/A1203 molar ratio of at least 2, preferably in the ran~e of 4 to 190 , and having at least 50 percent, preferably at least 90 percent, of the framework aluminum atoms not ~ ,3~ D-12250 associated with metal cations;
(b) contacting said activated aluminosilicate with a gas mixture comprising ~i) from 0.1 to 20 volume percent fluorine (ii) from zero to 21 volume percent oxygen (iii) and as the remainder, one or a mixture of two or more inert gases, preferably nitrogen, said contact being at a temperature of from about 50 to 400F
for a period of at least 1 minute preferably from about 5 to 60 minutes. Optionally the resulting fluorinated zeolite can be further treated by calcination at temperatures above 500C and up to the crystal destruction temperature of the zeolite, or by rehydrating same, or a combination of the two treatments in either order.
Crystalline zeolites suitably treated in accordance with the present invention include erionite, mordenite, zeolite Y, zeolite omega, zeolite be~a, zeolite ZSM-5, zeolite ZSM-ll, zeolite L, and zeolite ZSM-35. Both natural and synthetic zeolites can be used. Zeolite Y is disclosed in U.S.P. 3,130,007 (Breck); zeolite omega in U.S.P.
4,241,036 (Flanigen et al.); zeolite beta in U.S.P. 3,308,069;
zeolite ZSM-5, in U.S.P. 3,702,886 (Wadlinger et al.);
zeolite ZSM-ll in U.S.P. 3,709,979 (Chu); zeolite L in U.S.P.
3,216,789 (Breck et al.); and zeolite ZSM-35 in U.S.P. 4,137,195 (Chu). Those zeolite species which in their assynthesized form contain the requisite proportion of non-metallic cations can be utilized without modification of
-4-.
~ 3 ~
their cation population. In those cases in which the zeolite contains too large a proportion of metal cations associated with ~he A104 - tetrahedra, conventional ion-exchange techniques can be resorted to in order to replace a sufficient proportion of me~al cation with non-metallic cations such as hydrogen, ammonium or quaternary ammonium species. The zeolites can, if desired, be calcined to thermally remove some or all of the non-metallic cations to produce the corres~onding decationized form.
Calcination at a temperature of about 400~C for 2 hours is usually sufficient to activate hydrated zeolites by the evolution of their water of hydration.
In contacting the zeolite starting materials with fluorine it is advantageous to utilize a reactor having means for evacuating the gases therefrom as well as means for re~ulating the temperature. A suitable procedure is to introduce the zeolite starting material into the reactor, adjust the temperature to the range of ambient to 60C, remove the bulk of the air over the zeoliteby~eans of a vacuum pump (a pressure of about torr is ade~uate), introduce the fluorine-oxygen-inert gas mixture into the reactor using fluorine to zeolite pro?ortions of from about 7 x 10 3 to 1.4 grams fluorine per gram of zeolite for a ~eriod of about l to 60 minutes, and then evacuate the reactor to remove the residual fluorine. Thereafter the fluorine treated æeolite lS
heated to a teF~erature of about ambient to 150~C under vacuum to remove adsorbed fluorine.
Although it has heretofore been proposed ~o treat silica gel with fluorine or hydrogen fluoride to increase its hydrophobicity, such procedure modi~es the l~LS~
surface only. The hydrophobicity is created by the conversion of Si-OH groups to -Si-F groups. Pro longed contact of the fluorinated product in contact with atmospheric water vapor results in the reconversion of the -Si-F groups to _Si-OH groups with the consequent loss of hydrophobicity. In marked contrast, the direct ~luorination of zeolites in accordance with the present process not only modifies the zeolite surface, but also removes framework aluminum atoms and tends to stabilize the structure. Post-fluorination calcination at tempera-tues in the range of about 500 C to 700 C creates a permanently hydrophobic zeolite product.
The following examples illustrate the present process. In evaluting the hydrophobic character of the fluorinated zeolite products, one test procedure employed was a "shake-test" in which one gram of the activated zeolite sample was introduced into lO ml. of a solution of l.O vol.-% n-butanol in water. The slurry of zeolite and solution was shaken for 90 minutes at ambient room temperature, and then the liquid phase was analyzed for residual n-butanol content. By difference the percent n-butanol adsorbed by the zeolite sample was determined, thereby providing a measure of the relative preference of the zeolite for the less polar adsorbate, i.e., its hydrophobicity. Another test procedure was a n-hexane delta loading test wherein a test sample o~ the zeolite was placed in a McBain-Bak~ balance, activated at 350C
for 16 hours under vacuun (10 5 torr), and then exposed to about 20 torr of water vapor at ambient reom tem~erature.
After the adsorbed water loading on the zeolite reached a steady state under these conditions, n-hexane at a partial pressure of 40-50 torr was introduced into the 1~4~3B
water~ont~ining atn~sphere ove~ ~he zeolite . The weight gain of the ~eol~e m~S6 due t~ adsorption of n-hexane under the~e contiS~sn~ ~the delta n-hexane l~ading) was u6ed ~s sn indication of the de~ree vf hydroph~bl~lty .- of the ~ample. The greater the weight gain due to n-hexane adsorpt~on the greater the degree ~f hydrophob~city.
Example 1 ~ a) A series of ~even 10 ~ram ~amples of ~ynthetic large-port hydrogen ~ordeni~e ha~ng a SiO2/
A1203 ~olar ra~io of 15.3 ~nd having a Na20/A1203 molar ratio of Q.06 were caleined at 600C for about 120 minutes, cooled eo 60C, and contacted wit~ fluorine-oxygen-nitrogen mixtures of various propostions for ' ~arious time periods. The treated 6amples were ~hen caleined in a~r at 600C for 120 minutes a~d thereafter testes for hydrophobicity us~ng the ~queous n-butanol ~olution ~hake test. The pertinent data ~re 6e~ for~h below ~n Table 1.
~A3LE I
S~ ST
Tre~ ~ Condlelon~ 2 n-~ucan~l r~ m~inln~ ln test ID~
~plc ~ ~ O Cont~lct _ _ _ 2 Ti~ne, ~n. l~ Sr~ }2 A S 2 10 O . 605 ID . 605 10 2 10 O. 747 D . 73B
C 10 2 5 0.~4't 0,738 10 2 10 0.747 0.~46 iO O 10 0.813 ~.~95 . ~ 10 2 10 0.747 0.~38 1010 10 0.781 ~1.76~
O O O 0.989 0.996 .
~ 3 Example 2 (a) A series of ten samples of various synthetic zeolites were contacted wi~h fluorine-oxygen-nitrogen mixtures in various proportions at either ambient room temperature (-23C) or 6QC for various time periods. The treated samples were then calcined in air at 600C for 2 hours and thereafter the infrared spectra were run for ban positions using a Fourier transform I.R. spectrometer.
The pertinent data are set forth in Table II below:
In reporting the fluorine-containing gas mixture, only the volume-% of fluorine and oxygen are specified.
In eaich case the remaining portion of the gas mixture is nitrogen. Three prominent I.R. bands are also reported.
Shifts in these bands to higher wave numbers in the fluorine-treated samples compared with the untreated starting zeolites, coupled with a degree of band sharpening are strong evidence of structureal dealumination and stablilization.
n ~ :~ j B
_'0'0 ID ~'0 ~ ~ ~ _ i & o ~ ~ D
~ ~-., ~5,t~ U ~ ~ ~ , ,'9-" ~e ~ ~;~ ~ ~
1~. D 0 ~ .--c~ IC rl K ~ v~ C) O t~ > ~ I
~ ~~n3J~ ~ ~~.
D G I r ~3 O ~ ~O ~ ~ U~ O ~ C~ o 1--n :~
~ c D ~ : : ~ n ~3 ~ ~3 o- ¦ o I o r~ _ __ _ _ _ . _ o ~ C~ o c~ O C~ C C~ ~
b C ~ ~
; ~1 ~ ~ ~I ~I _ ~ID ~ e D _ ~ ~ QD S~ OD ~ r o .
8 ' ~ D 9 F i .
e ' ~ .
3 ~
~ b) For purposes of comparison with the samples of part (a) of this Example, samples of sodium zeolite Omega, potassium zeolite L, sodium zeolite Y and sodium mordenite were each contacted at 60C for 5 minutes with a mixture of 2% fluorine, 5% oxygen and 93% nitrogen at 60C. The respective starting zeolites are characterized as follows:
1. Sodium zeolite Omega: Prepared by calcining an as-synthesized zeolite ~mega sample having a Si02/A1203 molar ratio of 7.5 at 525C for about 40 minutes. The product has a Na20/A1203 molar ratio of 0.77 2. Potassium zeolite L: Si02/A1203 molar ratio -- 6.1 and the K20/A1203 molar ratio was o.a2 3 ~dlu~ zeolite Y: Si02/A1203 molar ratio =
4.7 and the Na20/A1203 molar ratio was 0.93 4. Sodium mordenite: A commercially available material obtained from Norton Company Si02/A1203 =
10.9; Na20/A12~3 = 0-99 In each case the same characterizing I.R. bands as reported in part (a) were found to shift to higher wave numbers (indicating dealumination) but broadening of the bands rather than sharpening thereof occurred.
This indicates stabilization had not occurred.
xample 3 A decationized zeolite Y composition was prepared by steaming an ammonium-exchanged form having the composition (anhydrous) 0 9 N 0 0 8 (MH +) 0: Al 0 : 5 7 Si0 at a temperature of 600C for 0.67 hours with 1 atmosphere steam, cooling the steamed product, reduc.ing the residual LJ--L~U
~s~dilim leve~- ~D 0.07 ~e~ght-~ (anhydrous) 'by ~ sec~nt ~H4~ exch~rlge. ~e prc~duct h~d the ~mpo~ition (anhydrous).
~ .01 Na20: 0.9 ~ 320: 2 3 2 Two sale~ ~f ehe pr~duct, c~ch weigh~n~ 10 grams were cont~cted with a flu4r~n2-~xy~en-nitr~,een ~x~ure ~t 60~C for 5~n~nute~ ~nd then c~lc~ned a~c 600~C
ln ais for 2 h~ . Thes~eafter testG for hyd~ophDbic~ty usin~ the n-Butanol Shalce Te~t were carried out on ~he n~n-fluorinated ~nd the fluor~naeed ~amples. The resul~s were as follows:
S~ ~HAxE ~5 L~ ment I ~ ~ u~ I rema~rlng in t~st ~a . ~ ~ ~a~ I _ A 0 0 ___ 0 .93 0 .92 a 2 5 5 0.63 0.62 C 2 5 5 0.6~ o.ss Exas~le 4 Samples of tbe 6a~e ~teamed ~eol~te Y, ~ -m~rdenite and ~ -ZSY:5 type zeolite ~tarting ~aterials as ut~llzed ~n Example 2, ~u~ra, were trested with ~arious fluorine~oxygen-nitrogen ~ixture~ f~r Ya~ous ~e per~ods ~nd ~t ~arious temperature~. The 6a~ple~ were tbe~ cslc~ned a~ 600~C ~n ~ir ~or tw~ hour~ and there-~ft~r te~ed for bydrophcbicity us~ng ~he ~-hexane ~elta l~d~ng tes~ ~ here~nbeose described. The pert~ne~t dat~ ~re ~et for~h ~ ble IV below.
.
5A~ IV
~r~e~ne nd~ t~ _ ont~ct sll - Hex~ne ~
~ e~eol~t~ ~2 ~2 ~ in. ~e~p., C. Lo~d~n~, wt.-%
_ . _ _ _ _ _ Alrype -Y D O O ___ 0 . 2 ~ .. 5 5 5 6~ , 2.û
C .. 2 5 5 ~0 1.2 D .- 5 5 10 ~bie~t 2 . 0 E .. 2 0 5 60 1. 6 F .. 2 5 5 52 3 . 5 G lit-Morden~t ~ O ._ __ nil ~I .. 10 2 1~ 60 1.1 .- 5 2 10 52 1.~
J .. 5 2 lQ 52 1.3 R ~-ZSH-5 ~rype O O __ 2 . û
.. lD 2 10 60 6 . 0 Example 5 Samples of ~ ame erio~ite mineral, stea~ed zeoli~e Y, N -mordeni~e and ZSM-5 ~ype zeoli~e startin~
material6 as utilized ~n Example 2, ~upra, were treated with various flu~rine-oxygen-~it~ogen ~ixtures at variDus temperatures for various periods of time. ~he samples were then c~lc~ned at 6DO~C ~h alr for two h~urs and thereaf~er the sample~ ~ere loated ln a quartz-spring McBain-Bakr a?naratus to deter~ine (a) th~ir o~vpen adsorption ca~ac~tv a~ 10~ torr oxygen ~ressure and -183C
and (b) their water ~spor ad~s~t~on ca~aci~y at 4.6 eorr water v~por pr~ure and ~mbien~ room temperature. The result~ ~re set forth ~n 5~1e V below:
. . . . ....... . , .. , ,. . ,. _ .. ..... .. . .. . . .. .. . .
~'. .
. ~ ~ I l~ontact AdsDrpti~n ,wt-%
~mple Zeolllte 7.F2 ~2 ~iloe, ~in. ~emp., C 2 H20 ,_ _. _ _ _ __ : --A Typ~ lr O O 0 _ __ 24 . 6 23 . 2 ;~ .. 2 0 5 60 20.2 ~.4 ~: ~ r~en~ t ~ ~ O ___ 20. 2 16 . O
D .. 5 S 5 60 1~ . 2 3. 5 . E Z5M-5-Type O O O ___ 13 . 7 6 . 5 .. 5 5 10 65 10. 7 1.1 t: Er~o~lte O O O ___ 21. ~ 1~ . 8 1~ ~- 5 5 5 ~0 17.3 7.2 *Samples act$vated at 350C for lS hours under vacuum (10 3 torr) The very low water loadin~, ~f ~che fluorina~ed samPles when compared ~o their untreated precursors havin~
comparable crystallinity (~s lndicated by the O2-adsorption capacity) i~ a clear ~dication of the degree of hydro-phobicity ~tta ine t .
Example 6 To illustr . te the effect of flu~rina~cion on ~che catal~tic pr~per~cies of zeolites, ~a~les of both fluorinated ~nd non-fluorirlated zeolite~ as described hereinbefore in Exa~les 2-5 were tested for the cat~lytic cr~cklng of n-butane at ~00C. In each case ~` the sodiur. cc~ntent ~f the zeolite was below 0.1 wt~
The act$vitie6 of the zeolites were determined in ~che conditlon in which they exi~ted ~mmediately af~cer `. fluorination ~ith a ~lu~r~ne-oxygen-nitrogen ~ixture, a~d after po~t-fluorination ~alcination ~t 600C for . ~ .
- ~3 -:
2 h~ur~ ~ ~ir ~nd afeer po~t-fluorina~cion washin~
with water. The resule~ ~re set forth ~n Sable VI below.
~ABL~ ~
rl-but~n~ cr~ck~n~ at ~on-c. F~r~ orter r~te ~onstant Tre~ tment Condit~c)nE _ (c~ /~ec.p.~
SUDP1~ Zec~lite %F2~2 ~l~e ,M~n . T~mp ., C trellted C~lcln~d ~'ash~c _ . _ .
A ~ype-Y O O ~ _ _ ._ _ 2 3 . O __ _ B .. 2 5 5 64 28 . 0 15 . 3 17 .1 C " 5 0 15 57 2.0 O.B 11.9 D .. 2 O ~5 i~ltnt ___ 45 . 3 ___ E H-~rder~lt O O O ___ ___ 68 . 5 _ __ F .. 5 5 5 60 50. B 1. 7 72 . 3 G .- 5 O lQ hibient __ _ 172 159 .. 5 O 30 A~ent ___ 231 2 38 H-ZSM-5 O O O .. __ __.... 27 .1 ___ J .. 5 5 10 65 '22.0 0.9 ~6.1 It l~N4~- Q ~ O O O _ ,~ 156 L .- 5 5 5 65 232 _ _ 191 1. Prepared ~y ~H4~-exchan~ing zeol~e oc~e~a ynthesized. Produce had a S~02/A1203 m~ar ratio of 7 ~nd a Na20/Al203 ~olar ratio of 0.004.
A~ i~ read~ly ~pparent from the ~re~ing da~a, the n-butane crack~n~, ab~lley, ~nd thus the cidity, of a ze~l~te can be altered by the fluorine treatment ~; ps~ces~ of the pre~ent ~nventiorl.
\
.
~ 3 ~
their cation population. In those cases in which the zeolite contains too large a proportion of metal cations associated with ~he A104 - tetrahedra, conventional ion-exchange techniques can be resorted to in order to replace a sufficient proportion of me~al cation with non-metallic cations such as hydrogen, ammonium or quaternary ammonium species. The zeolites can, if desired, be calcined to thermally remove some or all of the non-metallic cations to produce the corres~onding decationized form.
Calcination at a temperature of about 400~C for 2 hours is usually sufficient to activate hydrated zeolites by the evolution of their water of hydration.
In contacting the zeolite starting materials with fluorine it is advantageous to utilize a reactor having means for evacuating the gases therefrom as well as means for re~ulating the temperature. A suitable procedure is to introduce the zeolite starting material into the reactor, adjust the temperature to the range of ambient to 60C, remove the bulk of the air over the zeoliteby~eans of a vacuum pump (a pressure of about torr is ade~uate), introduce the fluorine-oxygen-inert gas mixture into the reactor using fluorine to zeolite pro?ortions of from about 7 x 10 3 to 1.4 grams fluorine per gram of zeolite for a ~eriod of about l to 60 minutes, and then evacuate the reactor to remove the residual fluorine. Thereafter the fluorine treated æeolite lS
heated to a teF~erature of about ambient to 150~C under vacuum to remove adsorbed fluorine.
Although it has heretofore been proposed ~o treat silica gel with fluorine or hydrogen fluoride to increase its hydrophobicity, such procedure modi~es the l~LS~
surface only. The hydrophobicity is created by the conversion of Si-OH groups to -Si-F groups. Pro longed contact of the fluorinated product in contact with atmospheric water vapor results in the reconversion of the -Si-F groups to _Si-OH groups with the consequent loss of hydrophobicity. In marked contrast, the direct ~luorination of zeolites in accordance with the present process not only modifies the zeolite surface, but also removes framework aluminum atoms and tends to stabilize the structure. Post-fluorination calcination at tempera-tues in the range of about 500 C to 700 C creates a permanently hydrophobic zeolite product.
The following examples illustrate the present process. In evaluting the hydrophobic character of the fluorinated zeolite products, one test procedure employed was a "shake-test" in which one gram of the activated zeolite sample was introduced into lO ml. of a solution of l.O vol.-% n-butanol in water. The slurry of zeolite and solution was shaken for 90 minutes at ambient room temperature, and then the liquid phase was analyzed for residual n-butanol content. By difference the percent n-butanol adsorbed by the zeolite sample was determined, thereby providing a measure of the relative preference of the zeolite for the less polar adsorbate, i.e., its hydrophobicity. Another test procedure was a n-hexane delta loading test wherein a test sample o~ the zeolite was placed in a McBain-Bak~ balance, activated at 350C
for 16 hours under vacuun (10 5 torr), and then exposed to about 20 torr of water vapor at ambient reom tem~erature.
After the adsorbed water loading on the zeolite reached a steady state under these conditions, n-hexane at a partial pressure of 40-50 torr was introduced into the 1~4~3B
water~ont~ining atn~sphere ove~ ~he zeolite . The weight gain of the ~eol~e m~S6 due t~ adsorption of n-hexane under the~e contiS~sn~ ~the delta n-hexane l~ading) was u6ed ~s sn indication of the de~ree vf hydroph~bl~lty .- of the ~ample. The greater the weight gain due to n-hexane adsorpt~on the greater the degree ~f hydrophob~city.
Example 1 ~ a) A series of ~even 10 ~ram ~amples of ~ynthetic large-port hydrogen ~ordeni~e ha~ng a SiO2/
A1203 ~olar ra~io of 15.3 ~nd having a Na20/A1203 molar ratio of Q.06 were caleined at 600C for about 120 minutes, cooled eo 60C, and contacted wit~ fluorine-oxygen-nitrogen mixtures of various propostions for ' ~arious time periods. The treated 6amples were ~hen caleined in a~r at 600C for 120 minutes a~d thereafter testes for hydrophobicity us~ng the ~queous n-butanol ~olution ~hake test. The pertinent data ~re 6e~ for~h below ~n Table 1.
~A3LE I
S~ ST
Tre~ ~ Condlelon~ 2 n-~ucan~l r~ m~inln~ ln test ID~
~plc ~ ~ O Cont~lct _ _ _ 2 Ti~ne, ~n. l~ Sr~ }2 A S 2 10 O . 605 ID . 605 10 2 10 O. 747 D . 73B
C 10 2 5 0.~4't 0,738 10 2 10 0.747 0.~46 iO O 10 0.813 ~.~95 . ~ 10 2 10 0.747 0.~38 1010 10 0.781 ~1.76~
O O O 0.989 0.996 .
~ 3 Example 2 (a) A series of ten samples of various synthetic zeolites were contacted wi~h fluorine-oxygen-nitrogen mixtures in various proportions at either ambient room temperature (-23C) or 6QC for various time periods. The treated samples were then calcined in air at 600C for 2 hours and thereafter the infrared spectra were run for ban positions using a Fourier transform I.R. spectrometer.
The pertinent data are set forth in Table II below:
In reporting the fluorine-containing gas mixture, only the volume-% of fluorine and oxygen are specified.
In eaich case the remaining portion of the gas mixture is nitrogen. Three prominent I.R. bands are also reported.
Shifts in these bands to higher wave numbers in the fluorine-treated samples compared with the untreated starting zeolites, coupled with a degree of band sharpening are strong evidence of structureal dealumination and stablilization.
n ~ :~ j B
_'0'0 ID ~'0 ~ ~ ~ _ i & o ~ ~ D
~ ~-., ~5,t~ U ~ ~ ~ , ,'9-" ~e ~ ~;~ ~ ~
1~. D 0 ~ .--c~ IC rl K ~ v~ C) O t~ > ~ I
~ ~~n3J~ ~ ~~.
D G I r ~3 O ~ ~O ~ ~ U~ O ~ C~ o 1--n :~
~ c D ~ : : ~ n ~3 ~ ~3 o- ¦ o I o r~ _ __ _ _ _ . _ o ~ C~ o c~ O C~ C C~ ~
b C ~ ~
; ~1 ~ ~ ~I ~I _ ~ID ~ e D _ ~ ~ QD S~ OD ~ r o .
8 ' ~ D 9 F i .
e ' ~ .
3 ~
~ b) For purposes of comparison with the samples of part (a) of this Example, samples of sodium zeolite Omega, potassium zeolite L, sodium zeolite Y and sodium mordenite were each contacted at 60C for 5 minutes with a mixture of 2% fluorine, 5% oxygen and 93% nitrogen at 60C. The respective starting zeolites are characterized as follows:
1. Sodium zeolite Omega: Prepared by calcining an as-synthesized zeolite ~mega sample having a Si02/A1203 molar ratio of 7.5 at 525C for about 40 minutes. The product has a Na20/A1203 molar ratio of 0.77 2. Potassium zeolite L: Si02/A1203 molar ratio -- 6.1 and the K20/A1203 molar ratio was o.a2 3 ~dlu~ zeolite Y: Si02/A1203 molar ratio =
4.7 and the Na20/A1203 molar ratio was 0.93 4. Sodium mordenite: A commercially available material obtained from Norton Company Si02/A1203 =
10.9; Na20/A12~3 = 0-99 In each case the same characterizing I.R. bands as reported in part (a) were found to shift to higher wave numbers (indicating dealumination) but broadening of the bands rather than sharpening thereof occurred.
This indicates stabilization had not occurred.
xample 3 A decationized zeolite Y composition was prepared by steaming an ammonium-exchanged form having the composition (anhydrous) 0 9 N 0 0 8 (MH +) 0: Al 0 : 5 7 Si0 at a temperature of 600C for 0.67 hours with 1 atmosphere steam, cooling the steamed product, reduc.ing the residual LJ--L~U
~s~dilim leve~- ~D 0.07 ~e~ght-~ (anhydrous) 'by ~ sec~nt ~H4~ exch~rlge. ~e prc~duct h~d the ~mpo~ition (anhydrous).
~ .01 Na20: 0.9 ~ 320: 2 3 2 Two sale~ ~f ehe pr~duct, c~ch weigh~n~ 10 grams were cont~cted with a flu4r~n2-~xy~en-nitr~,een ~x~ure ~t 60~C for 5~n~nute~ ~nd then c~lc~ned a~c 600~C
ln ais for 2 h~ . Thes~eafter testG for hyd~ophDbic~ty usin~ the n-Butanol Shalce Te~t were carried out on ~he n~n-fluorinated ~nd the fluor~naeed ~amples. The resul~s were as follows:
S~ ~HAxE ~5 L~ ment I ~ ~ u~ I rema~rlng in t~st ~a . ~ ~ ~a~ I _ A 0 0 ___ 0 .93 0 .92 a 2 5 5 0.63 0.62 C 2 5 5 0.6~ o.ss Exas~le 4 Samples of tbe 6a~e ~teamed ~eol~te Y, ~ -m~rdenite and ~ -ZSY:5 type zeolite ~tarting ~aterials as ut~llzed ~n Example 2, ~u~ra, were trested with ~arious fluorine~oxygen-nitrogen ~ixture~ f~r Ya~ous ~e per~ods ~nd ~t ~arious temperature~. The 6a~ple~ were tbe~ cslc~ned a~ 600~C ~n ~ir ~or tw~ hour~ and there-~ft~r te~ed for bydrophcbicity us~ng ~he ~-hexane ~elta l~d~ng tes~ ~ here~nbeose described. The pert~ne~t dat~ ~re ~et for~h ~ ble IV below.
.
5A~ IV
~r~e~ne nd~ t~ _ ont~ct sll - Hex~ne ~
~ e~eol~t~ ~2 ~2 ~ in. ~e~p., C. Lo~d~n~, wt.-%
_ . _ _ _ _ _ Alrype -Y D O O ___ 0 . 2 ~ .. 5 5 5 6~ , 2.û
C .. 2 5 5 ~0 1.2 D .- 5 5 10 ~bie~t 2 . 0 E .. 2 0 5 60 1. 6 F .. 2 5 5 52 3 . 5 G lit-Morden~t ~ O ._ __ nil ~I .. 10 2 1~ 60 1.1 .- 5 2 10 52 1.~
J .. 5 2 lQ 52 1.3 R ~-ZSH-5 ~rype O O __ 2 . û
.. lD 2 10 60 6 . 0 Example 5 Samples of ~ ame erio~ite mineral, stea~ed zeoli~e Y, N -mordeni~e and ZSM-5 ~ype zeoli~e startin~
material6 as utilized ~n Example 2, ~upra, were treated with various flu~rine-oxygen-~it~ogen ~ixtures at variDus temperatures for various periods of time. ~he samples were then c~lc~ned at 6DO~C ~h alr for two h~urs and thereaf~er the sample~ ~ere loated ln a quartz-spring McBain-Bakr a?naratus to deter~ine (a) th~ir o~vpen adsorption ca~ac~tv a~ 10~ torr oxygen ~ressure and -183C
and (b) their water ~spor ad~s~t~on ca~aci~y at 4.6 eorr water v~por pr~ure and ~mbien~ room temperature. The result~ ~re set forth ~n 5~1e V below:
. . . . ....... . , .. , ,. . ,. _ .. ..... .. . .. . . .. .. . .
~'. .
. ~ ~ I l~ontact AdsDrpti~n ,wt-%
~mple Zeolllte 7.F2 ~2 ~iloe, ~in. ~emp., C 2 H20 ,_ _. _ _ _ __ : --A Typ~ lr O O 0 _ __ 24 . 6 23 . 2 ;~ .. 2 0 5 60 20.2 ~.4 ~: ~ r~en~ t ~ ~ O ___ 20. 2 16 . O
D .. 5 S 5 60 1~ . 2 3. 5 . E Z5M-5-Type O O O ___ 13 . 7 6 . 5 .. 5 5 10 65 10. 7 1.1 t: Er~o~lte O O O ___ 21. ~ 1~ . 8 1~ ~- 5 5 5 ~0 17.3 7.2 *Samples act$vated at 350C for lS hours under vacuum (10 3 torr) The very low water loadin~, ~f ~che fluorina~ed samPles when compared ~o their untreated precursors havin~
comparable crystallinity (~s lndicated by the O2-adsorption capacity) i~ a clear ~dication of the degree of hydro-phobicity ~tta ine t .
Example 6 To illustr . te the effect of flu~rina~cion on ~che catal~tic pr~per~cies of zeolites, ~a~les of both fluorinated ~nd non-fluorirlated zeolite~ as described hereinbefore in Exa~les 2-5 were tested for the cat~lytic cr~cklng of n-butane at ~00C. In each case ~` the sodiur. cc~ntent ~f the zeolite was below 0.1 wt~
The act$vitie6 of the zeolites were determined in ~che conditlon in which they exi~ted ~mmediately af~cer `. fluorination ~ith a ~lu~r~ne-oxygen-nitrogen ~ixture, a~d after po~t-fluorination ~alcination ~t 600C for . ~ .
- ~3 -:
2 h~ur~ ~ ~ir ~nd afeer po~t-fluorina~cion washin~
with water. The resule~ ~re set forth ~n Sable VI below.
~ABL~ ~
rl-but~n~ cr~ck~n~ at ~on-c. F~r~ orter r~te ~onstant Tre~ tment Condit~c)nE _ (c~ /~ec.p.~
SUDP1~ Zec~lite %F2~2 ~l~e ,M~n . T~mp ., C trellted C~lcln~d ~'ash~c _ . _ .
A ~ype-Y O O ~ _ _ ._ _ 2 3 . O __ _ B .. 2 5 5 64 28 . 0 15 . 3 17 .1 C " 5 0 15 57 2.0 O.B 11.9 D .. 2 O ~5 i~ltnt ___ 45 . 3 ___ E H-~rder~lt O O O ___ ___ 68 . 5 _ __ F .. 5 5 5 60 50. B 1. 7 72 . 3 G .- 5 O lQ hibient __ _ 172 159 .. 5 O 30 A~ent ___ 231 2 38 H-ZSM-5 O O O .. __ __.... 27 .1 ___ J .. 5 5 10 65 '22.0 0.9 ~6.1 It l~N4~- Q ~ O O O _ ,~ 156 L .- 5 5 5 65 232 _ _ 191 1. Prepared ~y ~H4~-exchan~ing zeol~e oc~e~a ynthesized. Produce had a S~02/A1203 m~ar ratio of 7 ~nd a Na20/Al203 ~olar ratio of 0.004.
A~ i~ read~ly ~pparent from the ~re~ing da~a, the n-butane crack~n~, ab~lley, ~nd thus the cidity, of a ze~l~te can be altered by the fluorine treatment ~; ps~ces~ of the pre~ent ~nventiorl.
\
.
Claims (10)
1. Process for enhancing the hydrophobicity of crystalline zeolites which comprises:
(a) providing an activated crystalline zeolitic aluminosilicate having a SiO2/A1203 molar ratio of at least 2, and having at least 60 percent, of the framework aluminum atoms not associated with metal cations;
(b) contacting said activated aluminosilicate with a gas mixture comprising (i) from 0.1 to 20 volume percent fluorine (ii) from zero to 21 volume percent oxygen (iii) and as the remainder, one or a mixture of two or more inert gases, said contact being at a temperature of from about 50°F to 400°F for a period of at least 1 minute.
(a) providing an activated crystalline zeolitic aluminosilicate having a SiO2/A1203 molar ratio of at least 2, and having at least 60 percent, of the framework aluminum atoms not associated with metal cations;
(b) contacting said activated aluminosilicate with a gas mixture comprising (i) from 0.1 to 20 volume percent fluorine (ii) from zero to 21 volume percent oxygen (iii) and as the remainder, one or a mixture of two or more inert gases, said contact being at a temperature of from about 50°F to 400°F for a period of at least 1 minute.
2. Process according to claim 1 wherein the starting activated crystalline aluminosilicate has a SiO2/A12O3 molar ratio of from 4 to 190.
3. Process according to claim 2 wherein at least about 90 percent of the framework aluminum atoms of the starting zeolite are not associated with metal cations.
4. Process according to claim 3 wherein the crystal-line zeolitic aluminosilicate has the zeolite Y crystal structure.
5. Process according to claim 3 wherein the crystalline zeolitic aluminosilicate has the mordenite crystal structure.
6. Process according to claim 3 wherein the crystalline zeolitic aluminosilicate has the zeolite ZSM-5 crystal structure.
7. Process according to claim 3 wherein the crystalline zeolitic aluminosilicate has the zeolite omega crystal structure.
8. Process according to claim 1 which includes the further step of calcining the fluorine-treated zeolite at a temperature of from 500°C up to the crystal destruction temperature of the zeolite.
9. Process according to claim 8 which includes the further step of rehydrating the fluorine-treated and calcined zeolite.
10. Process according to claim 1 which includes the further step of rehydrating the fluorine-treated zeolite.
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US4839025A (en) * | 1979-10-15 | 1989-06-13 | Union Oil Company Of California | Mild hydrocracking with a catalyst containing non-hydrolyzable halogen |
DE3132024C2 (en) * | 1981-08-13 | 1983-12-08 | Basf Ag, 6700 Ludwigshafen | Process for the production of olefins from methanol and / or dimethyl ether |
US4444902A (en) * | 1981-12-22 | 1984-04-24 | Mobil Oil Corporation | Activation of high silica zeolites |
CA1190206A (en) * | 1982-03-30 | 1985-07-09 | Brent M. Lok | Modification of zeolites by treatment with chlorine gas |
US4498976A (en) * | 1982-04-15 | 1985-02-12 | Mobil Oil Corporation | Suppression of light gas production in cracking processes by the addition of highly siliceous materials having high surface area and low acidity |
US4569833A (en) * | 1982-08-02 | 1986-02-11 | Union Carbide Corporation | Modification of aluminophosphate molecular sieves by treatment with a silicon tetrafluoride gas mixture |
CA1220771A (en) * | 1982-08-02 | 1987-04-21 | Frank P. Gortsema | Modification of molecular sieves by treatment with a silicon tetrafluoride gas mixture |
JPS59146925A (en) * | 1983-02-09 | 1984-08-23 | Toa Nenryo Kogyo Kk | Novel crystalline aluminosilicate and its production and converting method of organic raw material using crystalline aluminosilicate |
AU567253B2 (en) * | 1983-06-30 | 1987-11-12 | Union Carbide Corporation | Treatment process for removing fluoride impurities from zeolites |
JPS6042219A (en) * | 1983-08-15 | 1985-03-06 | モビル オイル コ−ポレ−シヨン | Modification of zeolites by ammonium fluoride |
US4678766A (en) * | 1983-10-19 | 1987-07-07 | Mobil Oil Corporation | Enhancement of shape selectivity of zeolites |
US4670614A (en) * | 1984-06-15 | 1987-06-02 | Research Association For Petroleum Alternative Development | Hydrocarbon conversion process |
US4844792A (en) * | 1984-08-07 | 1989-07-04 | Union Oil Company Of California | Hydroprocessing with a specific pore sized catalyst containing non-hydrolyzable halogen |
US4844791A (en) * | 1984-08-07 | 1989-07-04 | Union Oil Company Of California | Hydroprocessing with a catalyst containing non-hydrolyzable halogen |
US5000931A (en) * | 1984-08-29 | 1991-03-19 | Uop | Halogen modification of aluminophosphate molecular sieves |
US4684511A (en) * | 1984-08-29 | 1987-08-04 | Union Carbide Corporation | Process for the halogen modification of aluminophosphate molecular sieves and a product so produced |
US4701313A (en) * | 1984-12-19 | 1987-10-20 | Mobil Oil Corporation | Replacing boron with silicon in zeolite beta using SiCl4 |
US4695296A (en) * | 1985-05-31 | 1987-09-22 | Rockwell International Corporation | Method for the selective separation of gases |
DE3661989D1 (en) * | 1985-06-19 | 1989-03-09 | Inst Francais Du Petrole | STABILIZED AND DEALUMINATED ZEOLITE OMEGA |
DE3661990D1 (en) * | 1985-09-04 | 1989-03-09 | Inst Francais Du Petrole | Omega structure zeolite |
US4855154A (en) * | 1987-06-30 | 1989-08-08 | Uop | Process for deodorizing marine oils |
US5254337A (en) * | 1987-06-30 | 1993-10-19 | Uop | Deodorizing compositions for animal grooming |
US5139761A (en) * | 1990-12-17 | 1992-08-18 | Uop | Modified zeolite omega and processes for preparing and using same |
US5932512A (en) * | 1997-08-19 | 1999-08-03 | Exxon Chemical Patents, Inc. | Fluorination of synthesized molecular sieve catalysts for increased selectivity to ethylene during conversion of oxygenates to olefins |
CN1151964C (en) | 1999-03-03 | 2004-06-02 | Pq控股公司 | Process for preparing modified zeolite |
US7700511B2 (en) * | 2007-01-12 | 2010-04-20 | Uop Llc | Aromatic transalkylation using a modified LZ-210 zeolite |
US20080171649A1 (en) * | 2007-01-12 | 2008-07-17 | Deng-Yang Jan | Modified Y-85 and LZ-210 Zeolites |
US20080171902A1 (en) * | 2007-01-12 | 2008-07-17 | Deng-Yang Jan | Aromatic Transalkylation Using a Y-85 Zeolite |
WO2016053637A1 (en) * | 2014-09-29 | 2016-04-07 | Basf Corporation | Preparation and applications of hydrophobic materials |
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US3477965A (en) * | 1967-06-30 | 1969-11-11 | Universal Oil Prod Co | Method of catalyst manufacture |
US3839539A (en) * | 1969-02-27 | 1974-10-01 | Grace W R & Co | Synthetic fluoride containing zeolite systems |
US3594331A (en) * | 1969-02-27 | 1971-07-20 | Grace W R & Co | Method of increasing the thermal stability of crystalline zeolites |
JPS4945477B1 (en) * | 1969-03-05 | 1974-12-04 | ||
US3630965A (en) * | 1969-03-11 | 1971-12-28 | Exxon Research Engineering Co | Hydrocarbon conversion catalyst |
US3702312A (en) * | 1970-10-05 | 1972-11-07 | Shell Oil Co | Fluoride-containing crystalline alumino-silicates |
US3933983A (en) * | 1971-06-07 | 1976-01-20 | W. R. Grace & Co. | Method of increasing the thermal stability of crystalline zeolites |
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