Abbreviated process to custom-make titanium silicate based catalysts with variegated physico-chemical properties

Abstract

An abbreviated, energy efficient and manipulative process and recipe using a novel binder-combination, to custom-make shaped TS-1 product wherein, their physico-chemical attributes can be engineered, variegated or optimized independent of one another, according to specific stipulations for diverse catalytic reactions that employ them.

Claims

1. A method of making a shaped Titanium Silicalite-1 product, comprising the steps of: i) providing powdered raw Titanium Silicalite-1 material having undergone calcination; ii) adding to the Titanium Silicalite-1 material from step (i), a binder composition comprising a combination of one or more Oligomeric silicate and one or more alcohols, and at least one hydrolysing agent, the one or more alcohols generated as a result of hydrolysis of the one or more Oligomeric silicate; iii) forming the Titanium Silicalite-1 material mixture from step (ii) into a dough; iv) fabricating the dough from step (iii) into a shaped Titanium Silicalite-1 product; v) drying the shaped Titanium Silicalite-1 product from step (iv) at a temperature elevated from ambient temperature for a pre-determined period of time; wherein the properties of the shaped Titanium Silicalite-1 product are engineered by regulating one or more of the following, factors or suitable combinations thereof: (i) an amount of the at least one hydrolysing agent that is added; (ii) stage(s) of the reaction when the at least one hydrolysing agent is added; (iii) an amount of water along with the at least one hydrolysing agent; (iv) an amount of the binder composition added; (v) a duration of mixing of the binder composition and the at least one hydrolysing agent; (vi) drying time and temperature.

2. The method of claim 1 wherein the binder composition comprises Ethyl silicate 40, ethanol, and liquor ammonia, and further wherein the ethanol generated during the reaction is retained and not distilled out prior to shaping the dough into extrudates/other shapes.

3. The method of claim 2 wherein for every 1 Kg of raw Titanium Silicalite-1 powder comprising 70 to 90 Wt % catalyst further comprising at least one of: (a) adding Ethyl Silicate 40 comprising an SiO2 content of 5 to 50 Wt %; (b) adding demineralized water in an amount of 80 to 400 ml; (c) adding Ammonia being, 5 to 25 N and 1 to 6 ml; (d) the pre-determined drying time in step (v) being 2 to 24 hours; (e) the elevated temperature in the drying step (v) being 80 to 130 degree C.; (f) calcining the Titanium Silicalite-1 for 2 to 12 hours; (g) calcining the Titanium Silicalite-1 at a temperature of 400 to 600 deg. C; (h) adding a blowing agent to further engineer or optimize Titanium Silicalite-1 combination attributes to match a given stipulation, being 1 to 20 wt %.

4. The method of claim 1 wherein, the said binder composition allows for turning out extrudates, tablets and pellets from both calcined as well as non-calcined raw TS-1 material.

5. The method of claim 1 wherein the properties of the shaped Titanium Silicalite-1 product can be engineered or optimized by employing one or more of the following steps, or any desirable combination thereof: (i) a crushing strength and a bulk density can be gradually increased with increase in the binder composition content; (ii) the crushing strength and the bulk density can be gradually decreased with increasing water content; (iii) the crushing strength and the bulk density can be gradually decreased with increasing the content of the hydrolyzing agent; (iv) the crushing strength and the bulk density can be gradually decreased with increasing stirring time during hydrolysis of the binder composition; (v) the crushing strength and the bulk density can be gradually decreased with increasing drying time.

6. The method of claim 1 wherein physico-chemical properties of the end product are engineered or optimized by employing one or more of the following steps, or any desirable combination thereof: (a) addition of a blowing agent to the binder composition alone or either with water or Ethyl silicate, to sustain a given value of crushing strength while varying a bulk density alone, which can be increased with decreasing a blowing agent content, (b) addition of a blowing agent during mixing to make the dough not in combination with either Ethyl silicate or water, to drastically decrease a crushing strength alone, (c) addition of the blowing agent along with ethyl silicate during the mixing to make the dough, to acutely increase the bulk density alone.

7. A process as claimed in claim 6 wherein the blowing agent is a carbohydrate.

8. A process as claimed in claim 1 wherein the availability of Titanium catalyst is increased by reducing the binder composition content.

9. A process as claimed in claim 1 wherein pore volume distribution is regulated by varying the hydrolysis time duration.

10. The method of claim 1 wherein the process employed to make shaped Titanium Silicalite-1 products obviates the need for spray-drying and remotion of alcohol generated during the process.

11. The method of claim 1, in which the Titanium silicate-1 product is a catalytic Titanium silicate-1 molecular sieve, and wherein physico-chemical attribute combinations of the Titanium silicate-1 product are defined by: (1) the Titanium silicate-1 product is in the form of extrudates, wherein, (a) bulk density is in the range of 0.58 to 0.62 kgs/lit. and crushing strength in the range of 4 to 7.5 Kgs; or (b) bulk density is in the range of 0.57 to 0.65 kgs/lit. and crushing strength in the range of 3.5 to 4.5 Kgs; or (c) bulk density is greater than 0.65 kgs/lit. and crushing strength greater than 7.5 Kgs; or (d) bulk density is lesser than 0.58 kgs/lit. and crushing strength lesser than 3.5 Kgs; or (e) Ti content is in the range of 1.4 wt % to 2.0 wt % with bulk density 0.54 to 0.67 kgs/lit and crushing strength 2.7 to 12.5 Kgs; or (f) Micropore volume is 78 to 97%, Meso and macro-pore volume 22 to 3%, with bulk density 0.6 to 0.62 kgs/lit and crushing strength 7.2 to 6.3 Kgs; or (2) the Titanium silicate-1 product is in the form of tablets or pellets, wherein, (g) bulk density is in the range of 0.62 to 0.69 kgs/lit. and crushing strength in the range of 3.6 to 6.8 Kgs; or (h) bulk density is in the range of 0.62 to 0.67 kgs/lit. and crushing strength in the range of 3.0 to 4.0 Kgs; or (i) bulk density is greater than 0.65 kgs/lit. and crushing strength greater than 5.0 Kgs; or (j) bulk density is lesser than 0.65 kgs/lit. and crushing strength lesser than 4.0 Kgs.

12. The method of claim 1, further comprising the step, after step (iv), of cutting, granulation, compacting or other fabrication operation.

13. The method of claim 1, wherein the dough from step (iii) is fabricated into a shaped Titanium Silicalite-1 product by extrusion, pelleting or tableting.

14. The method of claim 3, wherein the blowing agent includes starch.

15. The method of claim 3, wherein the SiO2 content is 10 to 30 Wt %.

16. The method of claim 3, wherein the demineralized water is in an amount of 160 to 320 ml.

17. The method of claim 3, wherein the Ammonia is 10 to 18 N and 1 to 3 ml.

18. The method of claim 3, wherein the pre-determined drying time in step (v) is 6 to 12 hours.

19. The method of claim 3, wherein the elevated temperature in the drying step (v) is 100-120 degree C.

20. The method of claim 3, wherein the Titanium Silicalite-1 is calcined for 4 to 6 hours.

21. The method of claim 3, wherein the Titanium Silicalite-1 is calcined at a temperature of 450 to 550 deg. C.

22. The method of claim 3, wherein the blowing agent ranges from 5 to 10 percent by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) It is pertinent to mention that although this specification makes reference to TS-1 in the description and the examples of the invention, the novel process recipe and methods for manipulation/engineering of the physico-chemical attributes to custom-make shaped TS-1, without limitation, extend to all (silica based) carriers for other catalysts as well. For the purposes of this specification, the term Binder composition or binder in the context of the instant invention means and includes the binder-combination comprising a mixture of (a) one or more Oligomeric silicate, (b) one or more alcohols and, (c) at least one hydrolysing agent either in a pre-mixed condition or sequentially, in addition to optionally (d) other additive/s, wherein, any combination thereof acts as a binder or increases binding strength of the end product.

(2) As mentioned, this invention provides a process wherein powdered Titanium Silicalite-1 material is converted into a shaped Titanium Silicalite-1 product by the application of a novel binder. The dough obtained after the application of the binder(s) to the powdered raw TS-1 material is subjected to a fabrication operation to give the said shaped product. Said fabrication operation may be either an extrusion operation to give an extrudate product or a granulation operation followed by compaction to give a pellet or tablet product.

(3) In the preferred process of the invention, the powdered raw TS-1 is taken and contacted with the Binder composition of the invention which is a combination of primarily, ethyl silicate, water, ammonia and Ethyl alcohol/ethanol. The said ethyl silicate (ETS-40) contains about 40% by wt of silica. ETS 40 is taken and a hydrolysing agent is added. This initiates the hydrolysis. Ethanol is generated as a result of the said hydrolysis which forms the said Binder composition.

(4) The hydrolysis is allowed to proceed till a pre-determined stage i.e typically hydrolysis of ETS-40 from 10 to 90% level and at that stage the binder-hydrolysis agent mixture is added to the raw TS-1 material. Said addition is carried out over a predetermined period of time. This is the preferred arrangement of the invention. Within the scope of the invention, the binder-hydrolysis agent mixture may be partly or fully hydrolyzed at the time of the addition thereof to the raw TS-1 powder.

(5) Therefore the terms binder, and binder composition used in the description of the embodiments and examples of this invention, unless incoherent with the context, shall mean a combination of ETS-40, silica, Ethanol, water, ammonia with or without other additives. One of the objectives of the process of the invention is to extend the said hydrolysis process and to let it spill over beyond the said initial operation(s) wherein the raw TS-1 material, ETS-40, the hydrolysing agent and the optional ethanol are brought together and the dough formed. Said initial operations broadly comprises mixing of the components which may be carried out in any suitable mixing equipment. Different arrangements are possible for the bringing together of the TS-1 mixture components and are all within the scope of the invention. Preferably, an Eirichmixer or a mix muller is used. Said initial operations may also comprise optionally kneading, homogenising, densification and other operations.

(6) One aspect of the control of the formation of the TS-1 product of the invention is by regulating the degree of hydrolysis of the binder precursor i.e stirring/hydrolysis time before the addition thereof to the raw TS-1 material and by regulating the addition of the binder-hydrolyzing agent mixture to the TS-1 material.

(7) As mentioned, the shaped TS-1 product characteristics such as BD, CS, pore volume distribution and Ti availability, can be influenced by varying the parameters of the hydrolysis process of the ETS-40-ethanol binder, in particular by changing the duration of the process in the pre-dough and post-dough stages. Higher degree of hydrolysis prior to the adding of the ETS-40, aq. NH3, and ethanol mixture to the TS-1 and HPMC mixture tends to reduce CS and BD of the final extrudate product. Extending said ETS-40 hydrolysis into the curing and drying stages tends to alter the CS, pore volume distribution and the BD.

(8) The degree of said hydrolysis can be controlled by the quantity of the hydrolysingagent(aq. ammonia) added and the stirring time allowed for hydrolysis before the said addition of the ETS-40 mixture to the said powder mixture. It may be noted that the progress of the hydrolysis reaction affects the subsequent condensation reactions; the greater the extent of the hydrolysis the greater will be the polymerization (condensation) of the silica species i.e more of Q3 and Q4 silica species are formed.

(9) The amount of the binder and the amount of the hydrolyzing agent used have an effect on the properties of the final TS-1 shaped product. Water comes into the reacting system through the application of the binder as an aqueous solution and also the application of the hydrolysis agent such as when aqueous ammonia is adopted as the hydrolysing agent. Also, water may be required to be added to adjust the dough consistency.

(10) The effect of binder and the amount of the hydrolyzing agent on product properties depend on whether the process adopted for said shaped TS-1 product is the extrusion route, or the granulation route or tableting/pelleting route.

(11) Said Effects in the Case of the Extrusion Route are as Follows;

(12) In the experiment of the invention employing the said extrusion route the dough was extruded with 3 mm diameter size.

(13) Where the binder solution is added first to the TS-1 material, the control is achieved by the regulation of the rate of addition of the hydrolyzing agent to the binder-TS-1 mixture. A pre-determined degree of hydrolysis, that is, a pre-determined progress of the said hydrolysis is planned to be achieved by the time of the completion of the said initial operations, that is, up to dough formation. The remainder of the hydrolysis reaction is then required to be completed in the post shaping stages. To achieve good control over this part of the said hydrolysis process, this invention provides for a stage of curing/drying operation. Duration of the curing stage, properties can be carefully controlled so as to achieve the desired physicochemical properties in the final shaped TS-1 product. The term post-addition stage shall also be understood to mean post-shaping operation stage.

(14) This invention has found that providing for a greater degree of said hydrolysis in the post-addition stages, that is, in the said curing stage results in enhanced crushing strength (CS) of the shaped TS-1 product. CS and BD (Bulk Density) of the product were found to increase with increasing binder content. The binder amount remaining the same, administering thereof to the raw TS-1 powder in the form of a more dilute aqueous solution i.e more water content, results in decrease in CS and BD.

(15) The amount of the hydrolyzing agent, which is ammonia in the preferred embodiment, was found to affect the CS and BD both of which were found to decrease with increasing ammonia content.

(16) The Effects When the Granulation Route is Adopted are Found to be as Follows:

(17) In this investigation, the dough was subjected to drying and granulation. The granulated material was then compacted into tablets/pellets of 3 mm dia. size.

(18) No significant effect was observed on the shaped TS-1 product properties upon variation of the amount ammonia, the hydrolysing agent added to the raw powdered TS-1.

(19) In this investigation wherein said tablets were produced, starch was added to the dough mixture as a blowing agent so as to obtain a lighter and more porous shaped-TS-1 product having a lower BD. Addition of starch as blowing agent or extrusion aid affected the CS and BD significantly. The effect of starch addition to the dough was further investigated as follows; two methods of starch addition were studied. In one method starch was added to the dough mixture together with water. In another experiment, the starch was added as such and not in combination with any other component.

(20) Addition of starch by itself caused a sharp drop in BD. BD was found to decrease with increasing starch quantity. It was observed that the CS achieved was highest when the starch addition was done together with water, all other factors such as the starch quantity remaining the same. Addition of the starch directly had a very strong effect on the BD leading to a substantial decrease in BD.

(21) Within the scope of the invention, other additives may be added to the TS-1 and binder mixture. Such additives may include forming additives, viscosity-enhancing additives, additives for increasing the stability/activity of final product.

(22) Preferably, HPMC(Hydroxyl propyl methyl cellulose) is added to the TS-1. The binder composition is added to convert the mixture into dough (paste). A kneading operation is not necessary in the shaped TS-1 process of the invention but can be optionally adopted if desired. Said paste is homogenized in a mixing operation preferably carried out in an Eirich mixer or a Mix Muller. Additional operations such as mixing, homogenizing, densification, kneading may be incorporated optionally if found necessary/useful.

(23) The dough is then extruded using a suitable extruder. Any of the known extruders in the art may be used. Preferably, a Ram extruder or a screw (single, double) or piston type extruder is used. The extruded material is cut into pieces of desired length. The cutting operation may be carried out on the extruder by suitable adjustment of the knife or die cutter or other such cutting devices. Alternatively, other cutting means may be adopted. Said cutting may also be carried out as a separate operation.

(24) Said catalyst pieces are dried by any of the known procedures for drying using any of the known equipment. The dried pieces are then calcined. During calcining the HPMC and ammonia are substantially eliminated. The product is shaped TS-1 product and contains silica that comes from the added ETS-40.

(25) Drying time has considerable influence on the extrudate characteristics. During the drying of the green extrudates, further hydrolysis and subsequent polymerization of silica is affected resulting in binding with TS-1 particles. The water required for the progress of the hydrolysing reaction during these stages comes from the green extrudate material. If hydrolysis time is reduced a large-pore extrudate is obtained, the CS value remaining substantially the same.

(26) In order to provide a clearer understanding of the invention and without any limitation to the scope of the invention, a few of the embodiments thereof are described hereinbelow as examples to show variegated attributes of TS-1 product.

EXAMPLES

Preparation of TS-1 Based Extrudates

(27) Preparation of Extrudates with BD in the Range of 0.58 to 0.62 kgs/lit.and CS in the Range of 4 to 7.5 Kgs:

Example 1

(28) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 0.5 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 6 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 1.

Example 2

(29) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 3 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density.

(30) The properties of the same are tabulated in the Table 1.

(31) TABLE-US-00001 TABLE 1 Properties of TS-1 based extrudates with BD in the range of 0.58 to 0.62 kgs/lit and CS in the range of 4 to 7.5 Kgs: TS-1 Powder Binder wt % in composition Ethyl silicate hydrolysis conditions Ave. final content DM Liq. drying Crushing Bulk Ex catalyst (SiO2 wt water Ammonia HPMC Stirring time, strength Density No. (wt %) %) (ml) (ml) (g) time (h) (h) (Kgs) (Kg/lit) 1 80 20 200 2 20 0.5 6 7.2 0.6 2 80 20 200 2 20 3 12 4 0.6
Preparation of Extrudates with BD in the Range of 0.57 to 0.65 kgs/lit.and CS in the Range of 3.5 to 4.5 Kgs:

Example 2

(32) As described above. The properties of the same are tabulated in the Table 2.

Example 3

(33) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 2.

Example 4

(34) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 3 ml of 14 N liquor ammonia. This solution was stirred for 3 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density.

(35) The properties of the same are tabulated in the Table 2.

(36) TABLE-US-00002 TABLE 2 Properties of TS-1 based extrudates BD in the range of 0.57 to 0.65 kgs/lit. and CS in the range of 3.5 to 4.5 Kgs: TS-1 Powder Binder wt % in composition Ethyl silicate hydrolysis conditions final content DM Liq. drying Ave. Bulk Ex. catalyst (SiO2 water Ammonia HPMC Stirring time, Crushing Density No. (wt %) wt %) (ml) (ml) (g) time (h) (h) strength (Kg/lit) 3 80 20 200 2 20 1 12 4.5 0.62 2 80 20 200 2 20 3 12 4 0.6 4 80 20 200 3 20 3 12 3.85 0.57
Preparation of Extrudates with BD Greater Than 0.65 kgs/lit.and CS Greater Than 7.5 Kgs:

Example 5

(37) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 0.5 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 3.

Example 6

(38) For making binder solution for 1 Kg TS-1 powder, 1071 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from Eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 3.

(39) TABLE-US-00003 TABLE 3 Properties of TS-1 based extrudates with BD greater than 0.65 kgs/lit. and CS greater than 7.5 Kgs: TS-1 Powder Binder wt % in composition Ethyl silicate hydrolysis conditions Ave. final content DM Liq. drying Crushing Bulk Ex. catalyst (SiO2 wt water Ammonia HPMC Stirring time, strength Density No. (wt %) %) (ml) (ml) (g) time (h) (h) (Kgs) (Kg/lit) 5 80 20 200 2 20 0.5 12 12.8 0.66 6 70 30 200 2 20 1 12 12.5 0.67
Preparation of Extrudates with BD Lesser Than 0.58 kgs/lit.and CS Lesser Than 3.5 Kgs:

Example 7

(40) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 400 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density.

(41) The properties of the same are tabulated in the Table 4.

Example 8

(42) For making binder solution for 1 Kg TS-1 powder, 278 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. The same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 4.

(43) TABLE-US-00004 TABLE 4 Properties of TS-1 based extrudates with BD lesser than 0.58 kgs/lit. and CS lesser than 3.5 Kgs: TS-1 Powder Binder wt % in composition Ethyl silicate hydrolysis conditions Ave. final content DM Liq. drying Crushing Bulk catalyst (SiO2 wt water Ammonia HPMC Stirring time, strength Density Sr No. (wt %) %) (ml) (ml) (g) time (h) (h) (Kgs) (Kg/lit) 7 80 20 400 2 20 1 12 3.5 0.58 8 90 10 200 2 20 1 12 2.7 0.54
Preparation of Extrudates Containing Ti Content in the Range of 1.4 wt % to 2.0 wt %

(44) Refer Examples 3, 8 and 6 as described above. The said product from these examples was characterized for crushing strength and bulk density and Ti content. The properties of the same are tabulated in the Table 5.

(45) TABLE-US-00005 TABLE 5 Properties of TS-1 based extrudates with varying Ti content/binder content. content TS-1 Powder Binder wt % in composition Ethyl silicate hydrolysis conditions Ave. final content DM Liq. drying Ti Crushing Bulk catalyst (SiO2 water Ammonia HPMC Stirring time, content strength Density Sr No. (wt %) wt %) (ml) (ml) (g) time (h) (h) (wt %) (Kgs) (Kg/lit) 3 80 20 200 2 20 1 12 1.82 4.5 0.62 8 90 10 200 2 20 1 12 1.96 2.7 0.54 6 70 30 200 2 20 1 12 1.48 12.5 0.67
Preparation of Extrudates with Varying Pores Size Distribution.

Examples 1

(46) As described above. The properties of the same are tabulated in the Table 6

Example 9

(47) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 4 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and the same was removed from eirich mixer and transferred to a single screw extruder fitted with a 3 mm multi hole die at the mouth piece. The dough was extruded to make 3 mm green extrudates. These green extrudates were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the green extrudates were dried at 120 C. in an air oven for 6 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 extrudates constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 6.

(48) TABLE-US-00006 TABLE 6 Properties of TS-1 based extrudates with different prore volume distribution. TS-1 Meso Powder Binder and wt % in composition Ethyl silicate hydrolysis conditions Ave. macro- final content DM Liq. Stirring Crushing Bulk Micropore pore Ex catalyst (SiO2 water Ammonia HPMC time drying strength Density volume volume No. (wt %) wt %) (ml) (ml) (g) (h) time, (h) (Kgs) (Kg/lit) (%) (%) 1 80 20 200 2 20 0.5 6 7.2 0.6 78 22 9 80 20 200 2 20 4 6 6.3 0.61 97 3

Preparation OF TS-1 Based Tablets/Pellets

(49) Preparation of Pellets/Tablets with BD in the range of 0.62 to 0.69 kgs/lit.and CS in the Range of 3.6 to 6.8 Kgs:

Example 10

(50) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and mixed further for 30 minutes. Dough was transferred to an air oven and dried at 120 C. for 12 hours. Post drying, the lumps obtained were pressed through a granulater of 1 mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the feed was converted to tablets having both dia and length 3 mm. These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 7.

Example 11

(51) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 3 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. A dough was obtained after 30 minutes and mixed further for 30 minutes. Dough was transferred to an air oven and dried at 120 C. for 12 hours. Post drying, the lumps obtained were pressed through a granulater of 1mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the feed was converted to tablets having both dia and length 3 mm. These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 7.

Example 12

(52) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr . 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. 100 g starch powder was mixed with 400 ml DM water, and added to the Eirich mixer containing TS-1 powder with binder solution and mixed for 30 minutes. Dough obtained after 30 minutes was transferred to an air oven and dried at 120 C. for 12 hours.

(53) Post drying, the lumps obtained were pressed through a granulater of 1 mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the feed was converted to tablets having both dia and length 3 mm These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 7.

Example 13

(54) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Erich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. 100 g starch powder was added to the Eirich mixer containing TS-1 powder with binder solution and mixed for 30 minutes. Dough obtained after 30 minutes was transferred to an air oven and dried at 120 C. for 12 hours. Post drying, the lumps obtained were pressed through a granulater of 1 mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the teed was converted to tablets having both dia and length 3 mm. These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 7.

(55) TABLE-US-00007 TABLE 7 Properties of TS-1 based tablets/pellets with BD in the range of 0.62 to 0.69 kgs/lit. and CS in the range of 3.6 to 6.8 Kgs: TS-1 Powder Binder wt % composition Ethyl silicate hydrolysis conditions Ave. in final content DM Liq. Starch drying Crushing Bulk Example catalyst (SiO2 water Ammonia HPMC powder Stirring time, strength Density No. (wt %) wt %) (ML) (ML) (g) (g) time (h) (h) (Kgs) (Kg/lit) 10 80 20 200 2 20 0 1 12 5.3 0.69 11 80 20 200 3 20 0 1 12 5 0.69 12 80 20 200 2 20 100 1 12 6.8 0.62 13 80 20 200 2 20 100 1 12 3.6 0.62
Preparation of Pellets/Tablets with BD in the Range of 0.62 to 0.67 kgs/lit.and CS in the Range of 3.0 to 4.0 Kgs:

Example 13

(56) As described above. The properties of the same are tabulated in the Table 8.

Example 14

(57) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. 50 g starch powder was added to the Eirich mixer containing TS-1 powder with binder solution and mixed for 30 minutes. Dough obtained after 30 minutes was transferred to an air oven and dried at 120 C. for 12 hours. Post drying, the lumps obtained were pressed through a granulater of 1 mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the feed was converted to tablets having both dia and length 3 mm. These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 8.

(58) TABLE-US-00008 TABLE 8 Properties of TS-1 based tablets/pellets with BD in the range of 0.62 to 0.67 kgs/lit. and CS in the range of 3.0 to 4.0 Kgs: TS-1 Powder Binder wt % composition Ethyl silicate hydrolysis conditions Ave. in final content DM Liq. Starch drying Crushing Bulk Example catalyst (SiO2 water Ammonia HPMC powder Stirring time, strength Density No. (wt %) wt %) (ML) (ML) (g) (g) time (h) (h) (Kgs) (Kg/lit) 13 80 20 200 2 20 100 1 12 3.6 0.62 14 80 20 200 2 20 50 1 12 3.6 0.67
Preparation of Pellets/Tablets with BD Greater Than 0.65 kgs/lit.and CS Greater Than 5.0 Kgs:

Example 15

(59) For making binder solution for 1 Kg TS-1 powder, 625 g ethyl silicate 40 was taken in a 2 liter poly propylene container. To this was added 200 ml DM water and 2 ml of 14 N liquor ammonia. This solution was stirred for 1 hr and then 100 g of starch powder was added to this solution. This solution was further mixed for 30 minutes. 1 Kg TS-1 powder was mixed with 20 g of HPMC in an Eirich mixer for 15 minutes. To this mixture the binder solution was added slowly, while agitation was on in the Eirich mixer. Binder solution was mixed with TS-1 powder and HPMC in the Eirich mixer for 30 min. Dough obtained after 30 minutes was transferred to an air oven and dried at 120 C. for 12 hours. Post drying, the lumps obtained were pressed through a granulater of 1 mm dia (BSS 16 mesh) to make feed granules. This feed was then transferred to a tableting machine where in the feed was converted to tablets having both dia and length 3 mm. These tablets were allowed to age for 12 hours at room temperature in an open atmosphere. Post ageing, the tablets were dried at 120 C. in an air oven for 12 hours, followed by calcinations in air flow at 550 C. for 3 hrs at a heating rate of 1.5 C./minute. Calcined TS-1 tablets constituted the shaped TS-1 product. The said product was characterized for crushing strength and bulk density. The properties of the same are tabulated in the Table 9.

(60) TABLE-US-00009 TABLE 9 Properties of TS-1 based tablets/pellets with BD greater than 0.65 kgs/lit. and CS greater than 5.0 Kgs: TS-1 Powder Binder wt % composition Ethyl silicate hydrolysis conditions Ave. in final content DM Liq. Starch drying Crushing Bulk Example catalyst (SiO2 water Ammonia HPMC powder Stirring time, strength Density No. (wt %) wt %) (ML) (ML) (g) (g) time (h) (h) (Kgs) (Kg/lit) 15 80 20 200 2 20 100 1 12 6.8 0.68
Preparation of Pellets/Tablets with BD lesser than 0.65 kgs/lit.and CS Lesser Than 4.0 Kgs:

Example 13

(61) As described above. The properties of the same are tabulated in the Table 10.

(62) TABLE-US-00010 TABLE 10 Properties of TS-1 based tablets/pellets with BD lesser than 0.65 kgs/lit. and CS lesser than 4.0 Kgs. TS-1 Powder Binder wt % composition Ethyl silicate hydrolysis conditions Ave. in final content DM Liq. Starch drying Crushing Bulk Example catalyst (SiO2 water Ammonia HPMC powder Stirring time, strength Density No. (wt %) wt %) (ML) (ML) (g) (g) time (h) (h) (Kgs) (Kg/lit) 13 80 20 200 2 20 100 1 12 3.6 0.62

(63) Within the scope of the invention, the binder may comprise a mixture of ETS-40 and other suitable binder materials. A number of suitable binder materials are known in the art and any of them can be in mixture with ETS-40, which is within the scope of the invention. Although the extrusions and tablets/pellets mentioned in the examples/tables can be formed with 3 mm diameter, the diameter can be varied from 1.5 mm to 4.5 mm which is within the scope of the invention. The length of the extrudates can be controlled by fitting a die cutter at the extruder outlet and controlling the length by rmp of die cutter, which is also within the scope of the invention. The length of tablets can be controlled by choosing the appropriate die/device during the tabeletting, which is also within the scope of the invention.

(64) In summary, the advantages of the process of the invention over the prior art processes, are: (i) Custom-making shaped TS-1 product with targeted physico-chemical attributes according to stipulations of various industrial processes employing Titanium catalysts; (ii) the adoption of a novel binder composition; (iii) a novel process engineering technique of the invention wherein superior control and optimization of the properties of the shaped TS-1 product is possible by means of novel steps in the process of the invention. Said properties over which control can be exercised are CS, BD, pore volume distribution and Ti availability/dispersibility of active sites. Said control being exercised by regulating the degree of hydrolysis of the ETS-40ethanol-ammonia-water binder composition. In the novel method both the primary-hydrolysis, that is the degree of hydrolysis before the addition of the ETS-40 mixture to the TS-1 and the secondary-hydrolysis that occurs during the various processing operations in making the dried/calcined shaped TS-1 product are controlled; (iv) the shaped TS-1 process of the invention can be worked with both calcined raw TS-1 powder or non-calcined powder, unlike the prior-art processes. (v) the process step of spray drying in prior art processes being obviated by the unique process-recipe of this invention. (vi) the process step of removing ethanol from the reaction mixture is also obviated.