CA1071611A - Resid fluid cracking catalyst - Google Patents
Resid fluid cracking catalystInfo
- Publication number
- CA1071611A CA1071611A CA243,970A CA243970A CA1071611A CA 1071611 A CA1071611 A CA 1071611A CA 243970 A CA243970 A CA 243970A CA 1071611 A CA1071611 A CA 1071611A
- Authority
- CA
- Canada
- Prior art keywords
- rare earth
- clay
- hours
- catalyst
- product
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2838—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of faujasite type, or type X or Y (UNION CARBIDE trade names; correspond to GRACE's types Z-14 and Z-14HS, respectively)
Abstract
FLUID CRACKING CATALYST
Abstract of the Disclosure A process for preparing a fluid cracking catalyst by mixing clay with an inorganic binder, such as sodium silicate, spray drying the resulting mixture, water washing to remove excess sodium, calcining at a temperature of 1800 to 1900°F., adding water, sodium hydroxide, meta-koalin and nucleation centers to the resulting mass, hot aging the resulting mass for a period of 14 to 16 hours at 150 to 212°F. to insure zeolite formation, filtering to remove the mother liquor, washing, rare earth exchang-ing the washed product, flash drying and recovering the finished product.
Abstract of the Disclosure A process for preparing a fluid cracking catalyst by mixing clay with an inorganic binder, such as sodium silicate, spray drying the resulting mixture, water washing to remove excess sodium, calcining at a temperature of 1800 to 1900°F., adding water, sodium hydroxide, meta-koalin and nucleation centers to the resulting mass, hot aging the resulting mass for a period of 14 to 16 hours at 150 to 212°F. to insure zeolite formation, filtering to remove the mother liquor, washing, rare earth exchang-ing the washed product, flash drying and recovering the finished product.
Description
sackground of the Invention There has been a concerted effort over the past few years to improve zeolite containing ca~alyst that include clay as an essential par-t of the base by making ~hese catalyst more dense and more attrition resistant.
One of the problems encountered in the operation of a fluid catalytic cracking unit is a loss of a portion of the catalyst in the regeneration cycle. A catalyst that does not have a suitable attrition resistance naturally tends to be abraded and to produce particles thal are lost to the stack gases in the regeneration cycle. If the density of the catalyst is not high enough, this tendency is, of course, increased. One of the methods suggested for improving the hardness of these catalyst is disclosed in the patents to Hayden et al. that issued in 1970 and 1972. These patents suggest the calcination of the clay at temperatures high enough so that the kaolin clay goes through the characteristic kaolin exotherm. This calcination is carried out on the spray dried particles so that the particles are in the size range desired for the catalyst product. Subsequent to the cal-cination, the catalysts are partially converted to zeolite, thus preparing a clay containing zeolitic cracking catalyst, consisting of particles in the fluidizable size range.
Thus, in accordance with the present teachings, a process is provided for preparing a zeolitic cracking ; catalyst. The process comprises mixing clay with about
One of the problems encountered in the operation of a fluid catalytic cracking unit is a loss of a portion of the catalyst in the regeneration cycle. A catalyst that does not have a suitable attrition resistance naturally tends to be abraded and to produce particles thal are lost to the stack gases in the regeneration cycle. If the density of the catalyst is not high enough, this tendency is, of course, increased. One of the methods suggested for improving the hardness of these catalyst is disclosed in the patents to Hayden et al. that issued in 1970 and 1972. These patents suggest the calcination of the clay at temperatures high enough so that the kaolin clay goes through the characteristic kaolin exotherm. This calcination is carried out on the spray dried particles so that the particles are in the size range desired for the catalyst product. Subsequent to the cal-cination, the catalysts are partially converted to zeolite, thus preparing a clay containing zeolitic cracking catalyst, consisting of particles in the fluidizable size range.
Thus, in accordance with the present teachings, a process is provided for preparing a zeolitic cracking ; catalyst. The process comprises mixing clay with about
2 to 10 weight percent o~ sodium silicate binder and spray drying, calcining the spray dried material to a temperature of 1800 to 1900F for about 2 to 4 hours, preparing a reactant solution which contains sodium hydroxide, meta-kaolin and nucleation centers and add the calcined clay : ~
~ 2 - ~
~L~7~
thereto, the mixture is heated to a temperature of 150 to 212F
for about 14 to 16 hours to convert from abou~ 10% to 50%
of the clay to faujasite zeolite and rare earth exchanging the product obtained to impart a rare earkh oxide conten-t of about 2 to 10% by weight, drying and recovering the product.
We have found that a catalyst having improved properties over the catalyst described in the Hayden Patents can be prepared by mixing sodium silicate with clay, spray drying the mixture, water washing the effluent to remove a large . .
.
- 2a -`:`
J~ ~3 b '~
portion of the sodium silicate and calcining at 1800 to 1900F., preferably 1850F. This product is mixed with water, sodium hydroxide and metakoalin. We have found that the process of ~ayden et al. is greatly improved if nucle-ation centers are added to the reactant mixture. If the reaction mixture is then hot aged at a temperature of 150 to 212F. at preferably 180F. for a period of 14 to 16 hours to complete zeolitization. Under these conditions approximately 10 to 50% of the clay is converted to the zeolite. The product is then filtered, water washed and the sodium content of the product reduced by exchanging with a mixed rare earth salt solution. The rare earth exchanged product is flash dried and the catalyst recovered.
Detailed Description of the In_ention The first step of the process is preparation of the spray dryer feed. In our process we mix raw clay with an inorganic oxide binder, such as sodium silicate, for example. Since calcined koalin is the clay that is most easily converted to ~eolite, we prefer to use koalin clay.
The clay is ground ~o a relatively fine powder prior to mixing with the binder. ~her commercially available fine sized clays,such as halloysite, for example, give satisfactory results. The sodium silicate binder is added as about 2 to 10% of the weight of the clay to a~sure that the product recovered from the spray dryer consists of particles in the fluidizable size range. The effluent from the spray dryer may be washed to remove any excess sodium silicate prior to the next step of the proce~s.
However, this step is not e~sential.
In the second step of the process, the effluent from the spray dryer i8 calclned at a temperature of about 1800 to 1900, preferably 1850F., for a period of about 2 to 4 hours, preferably about 3 hours. ~sufficient quantity of water is added to prepare a sodium hydroxide solution containing about 12 to 16~ sodium hydroxide with solutions of 13 to 15% being preferred. A sufficient quantity of this solution is added to provide about 0.5 to 1 mole of Na20 per mole of alumina in the mi~rospheres, prefer-ably about O.q moles of Na20 per mole of alumina. A
quantity of meta~oalin equal to about 1 to _lQ% of the reactant mixture is added to assure that sufficient quantity of metakoalin is present, thus assuring conversion of ~bout 10 to ~Q % of the kaolin to the faujasitic ~eolite. The essential feature of the disclosed process is the improve~
ment in the amount of zeolite and the quality of the pro-duct by the use of nucleation centers. ' The nucleation centers are colloidal particles having a size between 0.005 and 0.05 microns having the composition 0.9 ~ 0.1 Na20:A]203:2.3-2.7 SiO2r Broadly speaking, these nucleation centers are p~epared as follows:
(a) An Na20-A1203-SiO2 mi~ture is prepared Erom sodium aluminate, sodium silicate, sodium hydroxide and water to provide a composition of:
15 ~ 2 Na20 14 + 2 SiO2 350 ~ 50 H20 The composition is prepared by mixing the ingredienks at a temperature of or below about 35C.
(b) The reactant mixture is aged at a temperature of or below about 25C. for at least 2 hours.
The nucleation centers prepared by this process do not exhibit ~ crystalline pattern when examined by standard X-ray diffraction techniques. Although these nucleation centers have one silica-alumino ratio, they can be used to form faujasites having any silica to alumina ratio from 2 to about 5. The silica to alumina ratio of the nucleation centers does not have to correspond to the silica to alumina ratio of the desired product.
The nucleation centers are added a~ about 0.2 to percentage of the total alumina in the reactant mixture.
In the next step of the process the mixture is hot aged atQa temperature of about 150 to 220, preferably about 180F., for periods of a~out 14 to 16 hours to convert generally about 10 to 50 % of the clay to the faujasitic zeolite. The mixture is filtered, the mother liquor is discarded and the filtrate washed.
In the next step of the pxocess the Na20 content of the washed p~oduct is reduced to less than 1% by ~ither of two processes. In the first process the product is ex-changed with a rare earth salt solution followed by cal-cination. Because of its ready availability, th~ commercially available rare earth chloride is normally prepared at a 2 to 20 weight percent rare earth OEhloride solution. The exchange is caxried out by mixing the particles in the fluidizable siæe range with the solution. After the base ions have been removed, the product i5 washed with water and ~ried at 110C. The catalyst is then ready for use in a catalytic ao~version system. The finished catalyst con-tains 2 to 10 percent rare earth oxide.
In the second process the product is exchanged twice with ammonium sulfate solution and once with rare earth salt solution. The exchanged product is then water washed.-This process is shown in the drawing.
Our invention is illustrated by the following specific but not limiting examples.
Example 1 0 This example illustrates a method of preparing nucleation centers.
~A) A total of 29 grams of sodium aluminate (Na20, A1203.~H20.~ ~as dissolved in 368 yrams of water.
Sodium silicate solution comprising 420 grams of sodium silicate (28.5~ Si~2. 7% Na20) 112 grams of NaOH and 100 grams of H20 was prepared. The solutions were cooled to 0C., mixed and aged by storing for 1 hour at 0C.
The mixture was then aged for about 16 hours at about 20C~
The resulting nucleation cen~ers at a particle si~e of ~o about 0.01 microns with a silica to alumino ratio of about 2.5 and no detectable crystallinity.
Example 2 This example illustrates the preferred method of preparing the catalysts of our invention.
A quantity of clay was mixed with 2 weight percent sodium silicate (as SiO2) and ~pray dried. This spray dried material was calcined at 185~CF for about 3-hours and thell was separated into coarse fractions having a - 6 ~
particle size of 40 to 250 microns and fine particles having particle sizes of 5 to 40 microns. A sodium hydroxide solution was made up by adding 25g grams of sodium hydroxide to 1360 grams of water and cooling to 100F. Five hundred grams of the coarse, calcined kaolin and 500 grams of the fines from this calcination along with 51.5 gram~ of metakaolin were added to a resin kettle containing the sodium hydroxide along with 50 ml ~finucleation centers. The temperature was increased to 180F. and maintained at that temperature for a period of four hours. At the end of this time the product was quenched~in hot water, washed twice with hot deionized water and exchanyed with a rare earth chloride solutionO The product had the following analysis: Table I
Total Volatiles 5.70 A123 51.2 Na20 .62 2~ so4 .106 RE203 ~.51 Surface Area 228.M /g Average Bulk Density 0~2/g/cc Compacted Density 0.703 g/cc The activity of the catalyst was compared to a conventional alumina gel catalyst containing 12 to 20 percent zeolite.
The catalyst is found to have activity o~ 76.6 as compared to 66.9 for the standard. The gtandard i8 a conventional gel type silica-alumina cracking catalyst containing 12 to 20 percent zeolite.
~3'~
Example 3 This example illustrates an alternate method of preparing the catalyst.
A sodium hydroxide solution was prepared by dis-solving 259 grams of sodium hydroxidc' in~l360 grams of water. The solution was cooled to 100F. and 500 grams of the coarse material described in Example 2 and 500 grams of the fine material described in Example 2 t~g~ther with 51.5 grams of metakaolin was added. A total of 50 ml of nucleation centers were then added and the product stirred thoro~gh]y and aged at room temperature for a period of 12 hours. At the end of this time the temperature was increased to 180~and the temperature maintained for 14 hours. At the end of this time the material was quenched, washed with deionized ~ater and exchanged with rare earth chloride solution as in Example 2. The catalyst had the following pxoperties:
Table II
Total Volatiles 5.32 A1203 9.
Na20 .57 S04 .071 RE23 4.52 Surface Area 296 ~ /g Average Bulk Density 0.66 g/cc Compacted Density 0.76 g/cc The activity of ~he c~talyst was determined using the process described in Example 2. The catalyst is found to ' - 8 -have an activity of 74.1 as compared to 69.2 for the standard.
It is obvious from these data that a product of comparable quality can be prepared without a cold age step.
The products recovered from the processes of Exa~ple 2 and Example 3 were comparable in quality.
ExamPle 4 This example illustrates the improvemen~ i~ the activity of the catalyst that is obtained by rare earth exchange. In thiS run, a quantity of catalysts prepared by the general technique described in Example 3 was rare earth exchangéd with a solution containing 2,4,6,8,10 and 15 lbs. or rare REC13 . 6 H20 per 100 pounds of catalyst.
Following the exchange, the samples were rinsed with hot water and dried. The samples are then pilled and treated with steam at a pressure of 15 psi and a temperature of 1350F. fox a period of 8 hours, The micro activity of the various samples was determined using the standard micro activity test. The test was carried out at a temperature of 900F., a weight hourly space veloci~y of 16 and a catalyst to oil ratio of 3 using a standard West Texas gas oil feb~ The physical and chemical data for the mat~rial before exchange are shown in Table III and for the earth exchanged material are shown in Table IV.
g _ . ~ .
.
, `:
Table III
Ph~cal ~ Chemical Properties of Fresh Catalyst Ch emi cal Pr~r ti es IrY Wt.7~Total Yolatiles~
A1 Z03' 1~ . 5 3 RE203 .
Na 2 , . , 021 Phys i c al Proper ti es ABD: gr/cC(Av Bulk Density) .76 CD: gr/Cc~compact BulkDens-ie~2 ~I: (Davison Index~ L 7 ~.
Jl (Jersey Index) SA : mZ/gr (Surface Area) 3~8 N2 pore ~Jol . : cc/gr . 35 H20 pore ~rol.: cc/gr .~4 APS :.(Av. Particle Size) 6 Table IV
Acti~th Content RE Cl3` 1~ H20 Treat v~, RE20 0 lb . /lO0 lb . cat . 0 58 . 2 2 ~.8 . 71.8 2.4 75.
6 2.8 78.6 5,o 80.5 ~ 5.6 80.5 .
.
It is apparent from a review of thesie data that adding as little as O.~percent rare earth oxide to the catalyst improves the conversion substantially. There is however, very little improvemen~ when the rare earth content is increased from 5 to 5.6 percent.
~ , .
This example illustrates the improvement in the activity of a catalyst prepared by the general technique described in Example 3 which has been steam deactivated prior to rare earth exchange. (From a commercial aspect, this would correspond to a typical equilibrium catalyst) The exchange levels of 2,4,6,8,10 (similar to example 3) RE~13, 6H20 per lO0 pounds of catalyst were made followed by washing with hot water and drying. The microactivity of this sample was then determined at a temperature of 900F., a weight hourly space velocity of 16 and a catalyst to oil ratio of 3 using a standard West Texas gas oil feed.
The activity level as a function of rare earth content for each sample is summarized in Table V.
:
Tab e V
RECl3 . 6 H20 Treat~Conversion 0 lb/lO0 lb. cat. 74.5 2 75.0 4 74.9 6 78.8 8 79.9 .
... :
- .. ~
The improvement in activity is not as dramatic as was found for a fresh catalyst, however,the increase is still significant and occurs essentially at the same level of exchange (viz. 6 lbs/100 lbs. of catalyst).
~ 2 - ~
~L~7~
thereto, the mixture is heated to a temperature of 150 to 212F
for about 14 to 16 hours to convert from abou~ 10% to 50%
of the clay to faujasite zeolite and rare earth exchanging the product obtained to impart a rare earkh oxide conten-t of about 2 to 10% by weight, drying and recovering the product.
We have found that a catalyst having improved properties over the catalyst described in the Hayden Patents can be prepared by mixing sodium silicate with clay, spray drying the mixture, water washing the effluent to remove a large . .
.
- 2a -`:`
J~ ~3 b '~
portion of the sodium silicate and calcining at 1800 to 1900F., preferably 1850F. This product is mixed with water, sodium hydroxide and metakoalin. We have found that the process of ~ayden et al. is greatly improved if nucle-ation centers are added to the reactant mixture. If the reaction mixture is then hot aged at a temperature of 150 to 212F. at preferably 180F. for a period of 14 to 16 hours to complete zeolitization. Under these conditions approximately 10 to 50% of the clay is converted to the zeolite. The product is then filtered, water washed and the sodium content of the product reduced by exchanging with a mixed rare earth salt solution. The rare earth exchanged product is flash dried and the catalyst recovered.
Detailed Description of the In_ention The first step of the process is preparation of the spray dryer feed. In our process we mix raw clay with an inorganic oxide binder, such as sodium silicate, for example. Since calcined koalin is the clay that is most easily converted to ~eolite, we prefer to use koalin clay.
The clay is ground ~o a relatively fine powder prior to mixing with the binder. ~her commercially available fine sized clays,such as halloysite, for example, give satisfactory results. The sodium silicate binder is added as about 2 to 10% of the weight of the clay to a~sure that the product recovered from the spray dryer consists of particles in the fluidizable size range. The effluent from the spray dryer may be washed to remove any excess sodium silicate prior to the next step of the proce~s.
However, this step is not e~sential.
In the second step of the process, the effluent from the spray dryer i8 calclned at a temperature of about 1800 to 1900, preferably 1850F., for a period of about 2 to 4 hours, preferably about 3 hours. ~sufficient quantity of water is added to prepare a sodium hydroxide solution containing about 12 to 16~ sodium hydroxide with solutions of 13 to 15% being preferred. A sufficient quantity of this solution is added to provide about 0.5 to 1 mole of Na20 per mole of alumina in the mi~rospheres, prefer-ably about O.q moles of Na20 per mole of alumina. A
quantity of meta~oalin equal to about 1 to _lQ% of the reactant mixture is added to assure that sufficient quantity of metakoalin is present, thus assuring conversion of ~bout 10 to ~Q % of the kaolin to the faujasitic ~eolite. The essential feature of the disclosed process is the improve~
ment in the amount of zeolite and the quality of the pro-duct by the use of nucleation centers. ' The nucleation centers are colloidal particles having a size between 0.005 and 0.05 microns having the composition 0.9 ~ 0.1 Na20:A]203:2.3-2.7 SiO2r Broadly speaking, these nucleation centers are p~epared as follows:
(a) An Na20-A1203-SiO2 mi~ture is prepared Erom sodium aluminate, sodium silicate, sodium hydroxide and water to provide a composition of:
15 ~ 2 Na20 14 + 2 SiO2 350 ~ 50 H20 The composition is prepared by mixing the ingredienks at a temperature of or below about 35C.
(b) The reactant mixture is aged at a temperature of or below about 25C. for at least 2 hours.
The nucleation centers prepared by this process do not exhibit ~ crystalline pattern when examined by standard X-ray diffraction techniques. Although these nucleation centers have one silica-alumino ratio, they can be used to form faujasites having any silica to alumina ratio from 2 to about 5. The silica to alumina ratio of the nucleation centers does not have to correspond to the silica to alumina ratio of the desired product.
The nucleation centers are added a~ about 0.2 to percentage of the total alumina in the reactant mixture.
In the next step of the process the mixture is hot aged atQa temperature of about 150 to 220, preferably about 180F., for periods of a~out 14 to 16 hours to convert generally about 10 to 50 % of the clay to the faujasitic zeolite. The mixture is filtered, the mother liquor is discarded and the filtrate washed.
In the next step of the pxocess the Na20 content of the washed p~oduct is reduced to less than 1% by ~ither of two processes. In the first process the product is ex-changed with a rare earth salt solution followed by cal-cination. Because of its ready availability, th~ commercially available rare earth chloride is normally prepared at a 2 to 20 weight percent rare earth OEhloride solution. The exchange is caxried out by mixing the particles in the fluidizable siæe range with the solution. After the base ions have been removed, the product i5 washed with water and ~ried at 110C. The catalyst is then ready for use in a catalytic ao~version system. The finished catalyst con-tains 2 to 10 percent rare earth oxide.
In the second process the product is exchanged twice with ammonium sulfate solution and once with rare earth salt solution. The exchanged product is then water washed.-This process is shown in the drawing.
Our invention is illustrated by the following specific but not limiting examples.
Example 1 0 This example illustrates a method of preparing nucleation centers.
~A) A total of 29 grams of sodium aluminate (Na20, A1203.~H20.~ ~as dissolved in 368 yrams of water.
Sodium silicate solution comprising 420 grams of sodium silicate (28.5~ Si~2. 7% Na20) 112 grams of NaOH and 100 grams of H20 was prepared. The solutions were cooled to 0C., mixed and aged by storing for 1 hour at 0C.
The mixture was then aged for about 16 hours at about 20C~
The resulting nucleation cen~ers at a particle si~e of ~o about 0.01 microns with a silica to alumino ratio of about 2.5 and no detectable crystallinity.
Example 2 This example illustrates the preferred method of preparing the catalysts of our invention.
A quantity of clay was mixed with 2 weight percent sodium silicate (as SiO2) and ~pray dried. This spray dried material was calcined at 185~CF for about 3-hours and thell was separated into coarse fractions having a - 6 ~
particle size of 40 to 250 microns and fine particles having particle sizes of 5 to 40 microns. A sodium hydroxide solution was made up by adding 25g grams of sodium hydroxide to 1360 grams of water and cooling to 100F. Five hundred grams of the coarse, calcined kaolin and 500 grams of the fines from this calcination along with 51.5 gram~ of metakaolin were added to a resin kettle containing the sodium hydroxide along with 50 ml ~finucleation centers. The temperature was increased to 180F. and maintained at that temperature for a period of four hours. At the end of this time the product was quenched~in hot water, washed twice with hot deionized water and exchanyed with a rare earth chloride solutionO The product had the following analysis: Table I
Total Volatiles 5.70 A123 51.2 Na20 .62 2~ so4 .106 RE203 ~.51 Surface Area 228.M /g Average Bulk Density 0~2/g/cc Compacted Density 0.703 g/cc The activity of the catalyst was compared to a conventional alumina gel catalyst containing 12 to 20 percent zeolite.
The catalyst is found to have activity o~ 76.6 as compared to 66.9 for the standard. The gtandard i8 a conventional gel type silica-alumina cracking catalyst containing 12 to 20 percent zeolite.
~3'~
Example 3 This example illustrates an alternate method of preparing the catalyst.
A sodium hydroxide solution was prepared by dis-solving 259 grams of sodium hydroxidc' in~l360 grams of water. The solution was cooled to 100F. and 500 grams of the coarse material described in Example 2 and 500 grams of the fine material described in Example 2 t~g~ther with 51.5 grams of metakaolin was added. A total of 50 ml of nucleation centers were then added and the product stirred thoro~gh]y and aged at room temperature for a period of 12 hours. At the end of this time the temperature was increased to 180~and the temperature maintained for 14 hours. At the end of this time the material was quenched, washed with deionized ~ater and exchanged with rare earth chloride solution as in Example 2. The catalyst had the following pxoperties:
Table II
Total Volatiles 5.32 A1203 9.
Na20 .57 S04 .071 RE23 4.52 Surface Area 296 ~ /g Average Bulk Density 0.66 g/cc Compacted Density 0.76 g/cc The activity of ~he c~talyst was determined using the process described in Example 2. The catalyst is found to ' - 8 -have an activity of 74.1 as compared to 69.2 for the standard.
It is obvious from these data that a product of comparable quality can be prepared without a cold age step.
The products recovered from the processes of Exa~ple 2 and Example 3 were comparable in quality.
ExamPle 4 This example illustrates the improvemen~ i~ the activity of the catalyst that is obtained by rare earth exchange. In thiS run, a quantity of catalysts prepared by the general technique described in Example 3 was rare earth exchangéd with a solution containing 2,4,6,8,10 and 15 lbs. or rare REC13 . 6 H20 per 100 pounds of catalyst.
Following the exchange, the samples were rinsed with hot water and dried. The samples are then pilled and treated with steam at a pressure of 15 psi and a temperature of 1350F. fox a period of 8 hours, The micro activity of the various samples was determined using the standard micro activity test. The test was carried out at a temperature of 900F., a weight hourly space veloci~y of 16 and a catalyst to oil ratio of 3 using a standard West Texas gas oil feb~ The physical and chemical data for the mat~rial before exchange are shown in Table III and for the earth exchanged material are shown in Table IV.
g _ . ~ .
.
, `:
Table III
Ph~cal ~ Chemical Properties of Fresh Catalyst Ch emi cal Pr~r ti es IrY Wt.7~Total Yolatiles~
A1 Z03' 1~ . 5 3 RE203 .
Na 2 , . , 021 Phys i c al Proper ti es ABD: gr/cC(Av Bulk Density) .76 CD: gr/Cc~compact BulkDens-ie~2 ~I: (Davison Index~ L 7 ~.
Jl (Jersey Index) SA : mZ/gr (Surface Area) 3~8 N2 pore ~Jol . : cc/gr . 35 H20 pore ~rol.: cc/gr .~4 APS :.(Av. Particle Size) 6 Table IV
Acti~th Content RE Cl3` 1~ H20 Treat v~, RE20 0 lb . /lO0 lb . cat . 0 58 . 2 2 ~.8 . 71.8 2.4 75.
6 2.8 78.6 5,o 80.5 ~ 5.6 80.5 .
.
It is apparent from a review of thesie data that adding as little as O.~percent rare earth oxide to the catalyst improves the conversion substantially. There is however, very little improvemen~ when the rare earth content is increased from 5 to 5.6 percent.
~ , .
This example illustrates the improvement in the activity of a catalyst prepared by the general technique described in Example 3 which has been steam deactivated prior to rare earth exchange. (From a commercial aspect, this would correspond to a typical equilibrium catalyst) The exchange levels of 2,4,6,8,10 (similar to example 3) RE~13, 6H20 per lO0 pounds of catalyst were made followed by washing with hot water and drying. The microactivity of this sample was then determined at a temperature of 900F., a weight hourly space velocity of 16 and a catalyst to oil ratio of 3 using a standard West Texas gas oil feed.
The activity level as a function of rare earth content for each sample is summarized in Table V.
:
Tab e V
RECl3 . 6 H20 Treat~Conversion 0 lb/lO0 lb. cat. 74.5 2 75.0 4 74.9 6 78.8 8 79.9 .
... :
- .. ~
The improvement in activity is not as dramatic as was found for a fresh catalyst, however,the increase is still significant and occurs essentially at the same level of exchange (viz. 6 lbs/100 lbs. of catalyst).
Claims (5)
1. Process for preparing a zeolitic cracking catalyst which comprises:
(a) mixing clay with about 2 to 10 weight percent sodium silicate binder and spray drying, (b) calcining the spray dried material at a temperature of 1800 to 1900°F for about 2 to 4 hours, (c) preparing a reactant solution containing sodium hydroxide, metakaolin and nucleation centers and adding the calcined clay thereto, (d) heating to a temperature of 150 to 212°F
for about 14 to 16 hours, to convert from about 10% to 50%
of said clay to faujasite zeolite, and, (e) rare earth exchanging the product of stage (d) to impart a rare earth oxide content of about 2 to 10% by weight, drying and recovering the product.
(a) mixing clay with about 2 to 10 weight percent sodium silicate binder and spray drying, (b) calcining the spray dried material at a temperature of 1800 to 1900°F for about 2 to 4 hours, (c) preparing a reactant solution containing sodium hydroxide, metakaolin and nucleation centers and adding the calcined clay thereto, (d) heating to a temperature of 150 to 212°F
for about 14 to 16 hours, to convert from about 10% to 50%
of said clay to faujasite zeolite, and, (e) rare earth exchanging the product of stage (d) to impart a rare earth oxide content of about 2 to 10% by weight, drying and recovering the product.
2. The process according to Claim 1 wherein the reactant solution contains a quantity of Na2O sufficient to provide a concentration of 0.5 to 1 mole of Na2O per mole of alumina, 2 to 10 weight percent metakaolin and 0.2 to 1 weight percent nucleation centers.
3. The process according to Claim 1 wherein the rare earth exchange is carried out with a rare earth chloride solution.
4. The process according to Claim 1 wherein the clay is calcined at 1850°F. for about 2 to 4 hours.
5. The process according to Claim 1 wherein the reactant mixture is heated to about 180°F.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55087875A | 1975-02-14 | 1975-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071611A true CA1071611A (en) | 1980-02-12 |
Family
ID=24198939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,970A Expired CA1071611A (en) | 1975-02-14 | 1976-01-21 | Resid fluid cracking catalyst |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS51106690A (en) |
| CA (1) | CA1071611A (en) |
| GB (1) | GB1524123A (en) |
| NL (1) | NL7601444A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454241A (en) * | 1982-05-24 | 1984-06-12 | Exxon Research And Engineering Co. | Phosphorus-containing catalyst |
| US4465780A (en) * | 1982-10-14 | 1984-08-14 | Exxon Research & Engineering Co. | Phosphorus-containing catalyst |
| ES2079941T3 (en) * | 1992-04-27 | 1996-01-16 | Grace W R & Co | CATALYTIC CRAYING CATALYSTS AND ADDITIVES. |
-
1976
- 1976-01-21 CA CA243,970A patent/CA1071611A/en not_active Expired
- 1976-02-12 NL NL7601444A patent/NL7601444A/en not_active Application Discontinuation
- 1976-02-13 GB GB580676A patent/GB1524123A/en not_active Expired
- 1976-02-14 JP JP1536976A patent/JPS51106690A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7601444A (en) | 1976-08-17 |
| GB1524123A (en) | 1978-09-06 |
| JPS51106690A (en) | 1976-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |