WO2012035540A1

WO2012035540A1 - Process for the production of acrolein and reusable catalyst thereof

Info

Publication number: WO2012035540A1
Application number: PCT/IN2010/000755
Authority: WO
Inventors: Ganapati Dadasaheb Yadav; Suraj Onkar Katole; Rajesh Vishnudev Sharma
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-09-16
Filing date: 2010-11-19
Publication date: 2012-03-22
Anticipated expiration: 2013-03-16

Abstract

Calcinated catalyst composition is designed and developed comprising composition of d-block transition metals, p-block metal and silicon as base metal atom along with oxygen wherein catalyst specific surface area is in the range 50 m²/g to 1000 m²/g. Composition of d-block transition metals and p-block metal atom are specifically selected for calcinated catalyst composition as per requirement of specific catalytic reaction. By using calcinated catalyst composition, aqueous glycerol solution is converted under mild reaction conditions to give high purity acrolein.

Description

"PROCESS FOR THE PRODUCTION OF ACROLEIN AND REUSABLE CATALYST THEREOF"

This application claims priority from Indian patent application INDIA 2562/MUM/2010 Date of Priority : 16/09/2010

FIELD OF INVENTION

The present invention is related to calcinated catalyst composition comprising divalent metal, trivalent metal, tetravalent metal and hexavalent metal and or mixture thereof with silicon as base metal wherein said catalyst composition has specific surface area is in the range of 50 m²/g to 1000 m²/g. Such high specific surface area calcinated catalyst composition is useful in many solid catalysed reactions. In one of the process wherein acrolein production by using calcinated catalyst composition to give high glycerol conversion with high acrolein selectivity. Calcinated catalyst composition is easily separable, regenerable and reusable in acrolein production process.

BACKGROUND OF INVENTION

Heterogeneous solid catalyst are always been great area of interest to researcher. Thus many efforts have been made to design of better Heterogeneous solid acid catalyst with high specific area which can be easily separable, regenerable and reusable. Many inventors claim for better heterogeneous catalyst with various support but they have their own drawbacks for different reaction system.

On other hand production of acrolein with the help of different solid acid catalyst is well known but regeneration and reusability of the catalyst, with high conversion of glycerol and high selectivity for reaction with eco-friendly green technologies have given threshold challenges.

Acrolein is also known as 2-propenal, acryaldehyde, aqualin, allyl aldehyde, having colorless to light yellow liquid. Its boiling point is 52.5°C, melting point is - 88°C and vapor density is 1.94 (Air =1). Acrolein is a key intermediate for the synthesis of methionine, is a synthetic protein used as a substitute of fishmeal. Acrolein is used for preparation of a wide variety of value-added specialty and fine chemicals. Acrolein finds direct application in medicine, water treatment, and petroleum industry as biocide. Refined acrolein is used for the synthesis of agrochemical methionine, fragrances and dyes. It also acts act as a precursor for the production of acrylic acid esters, super absorber polymers and detergents. A new direct route of aqueous glycerol to acrolein is always welcome, as it will avoid multi-step energy incentive processes with waste reduction. The oxidation of propylene with the atmospheric oxygen produces acrolein is the most commonly used process. This process demand propylene as starting material which is obtained by steam cracking of petroleum fraction. Under the threat of depletion of petroleum and global warming, it becomes necessary to have acrolein process based on renewable resources such as glycerol. Acrolein can be synthesis by double dehydration of glycerol by using either homogeneous or heterogeneous solid acid catalysts.

The utilization of glycerol for the synthesis of value added chemicals is a theme of great Industrial interest because glycerol is formed in large amounts during the production of biodiesel from natural triglycerides.

Patent No. US2010/0113838 Al discloses process for production of acrolein in vapour phase dehydration of glycerol in the presence of rare earth metal salt crystals of phosphoric acid, as Nd (Neodymium) is a rare earth metal atom. At a temperature in the range of 350°C to 450° C it gives glycerol conversion is 100 % and acrolein selectivity is 77 % after 3 hours, and it gives glycerol conversion is 100 % and acrolein selectivity is 68 % after 7 hours.

Patent No. WO 2009/127889 Al discloses process for dehydration of glycerol in the gas phase in the presence of cesium salt of tungustophosphoric acid (CsPW), wherein acrolein yield is 92.9% with 100% glycerol conversion, after 7 hours of reaction. At a temperature in the range of 260° C to 350° C with pressure lower than 3 arm.

Patent No. WO 2007/058221 discloses a process for producing acrolein by dehydration reaction of glycerin in gas-phase in the presence of heteropolyacid used as a solid acid catalyst. The heteropolyacid is those of group 6 elements such as tungstosilicic acid, tungstophosphoric acid and phosphomolybdic acid. These heteropolyacids are supported on bi-elemental pore silica carrier and produce acrolein at a yield of 86%. This dehydration reaction of glycerin, however, is effected without oxidation gas but using nitrogen stream as carrier gas, so that deposition of carbon increase seriously and hence there is a problem of deterioration in time of stability, activity selectivity of the catalysis.

Patent No. WO 2007/119528 discloses acrolein is usually produced using a catalyst for promoting intramolecular dehydration of glycerin, using yttrium salt crystals, lanthanum salt crystals, cerium salt crystals, or samarium salt crystals of phosphoric acid are used as a catalyst. In the process for producing acrolein using these salt crystals, when glycerin gas is employed as a raw material, the deposition of carbonaceous substance on the surface of a catalyst, which is one of the factors for the deactivation of the catalyst, is suppressed. Similarly to how the suppression of such a deposition is being desired in the production of acrolein, a process for producing acrolein in high yield is also inevitably desired.

Ferdi Schuth et al. " Journal of catalysis 269 (2010) 71-79" discloses reaction in gas phase dehydration of glycerol over small sized HZSM-5 with high aluminum content appears to be most promising catalyst, it gives 100% glycerol conversion with 65% of acrolein selectivity at atmospheric pressure. Wataru Ueda et al. "Journal of catalysis 268 (2009) 260-267" discloses reaction in gas phase dehydration of glycerol over vanadium phosphate oxide (VPO) catalyst, on a fix- bed reactor. At 300°C glycerol conversion is 100% with 66% selectivity of acrolein, by using oxygen as a carrier gas, at atmospheric pressure.

All these catalytic conversions of glycerol to acrolein suffer from disadvantages like harsh reaction conditions, moderate yield and non reusability of the catalyst.

OBJECTIVE OF THE INVENTION

Objective of the present invention is to design calcinated heterogeneous solid acid catalyst composition having high specific area and which can be easily separable, regenerable and reusable.

Another objective of the present invention is to design catalyst having specific surface area is in the range of 50 m²/g to 1000 m²/g.

Another objective of the present invention is to develop process for the production of acrolein by vapor phase dehydration of aqueous glycerol solution with the said calcinated catalyst composition.

Yet another objective of the present invention is to develop process operated at low temperature as compare to other processes reported in the scientific literature.

Yet another objective of the present invention is to develop an economical viable process for the production of acrolein.

SUMMARY OF INVENTION

The present invention calcinated catalyst composition is designed and developed comprising at least O.OOlto 2.00 mass percent of aluminium, at least 5.0 to 15.0 mass Percent of zirconium, at least 5.0 to 15.0 mass percent of tungsten with hexagonal mesoporous silica (HMS) as base metal is used. Wherein HMS composition is designed and developed comprising at least 10 to 50 mass percent of silicon and at least 30 to 60 mass percentage of oxygen wherein catalyst specific surface area is in the range 50 to 1000 m²/g.

In group of invention, Process for production of Acrolein has been designed and developed wherein aqueous glycerol solution is dehydrating in presence of calcinated catalyst composition with or without solvent.

In the group of invention, Process for production of acrolein has been designed and developed by reacting gas phase aqueous glycerol solution in presence of calcinated catalyst composition. Further pure acrolein is separating from final mixture by distillation at 45-55 °C temperature. BRIEF DESCRIPTION OF DRAWINGS

Drawing 1: SEM (Scanning Electron Microscope) images of fresh and regenerated

catalyst.

Drawing 2: NH₃-TPD (Temperature Program Desorption) of fresh and regenerated

catalyst.

Drawing 3: FT-IR spectrum of catalyst

Drawing 4: ASAP (Surface area and pore size analysis) of fresh and regenerated catalyst. Drawing 5: XRD analysis of the catalyst

Drawing 6: EDX (Elemental analysis) of fresh, used and regenerated catalyst.

DETAILED DESCRIPTION OF THE INVENTION

Our fossil raw materials are diminishing day by day and, under the threat of depletion of petroleum and global warming it becomes necessary to shift the non renewable to the renewable feedstock base, Glycerol is one of the potential renewable resources is obtained as a by-product in hydrolysis of fat, soap-manufacturing process and production of biodiesel. In the biodiesel production processes the ratio of biodiesel to crude glycerol produced are about 9:1, therefore, a new application of glycerol needs to be found. Dehydration of glycerol produces important commodity chemicals like acrolein. It is an important bulk chemical used as a feedstock for acrylic acid production, pharmaceuticals intermediates, fiber treatments, and methionine (used in animal feed). The most significant application of acrolein is an herbicide to control the growth of aquatic plants. Thus there is need to design Heterogeneous solid acid catalyst composition having high specific area and which can be easily separable, regenerable and reusable.

In the present invention, calcinated catalyst composition has been developed which comprises aluminium, zirconium, tungsten, and oxygen with silicon (hexagonal mesoporous silica) as base metal is used and has specific surface area is in the range 50 to 1000 m²/g. Such high specific surface area of calcinated catalyst composition can be use in many solid catalysed reactions.

Thus, heterogeneous catalyst of the present invention is calcinated catalyst composition which comprising at least O.OOlto 2.00 mass percent of aluminium, at least 5.0 to 15.0 mass percent of zirconium, at least 5.0 to 15.0 mass percent of tungsten, at least 10.0 to 50.0 mass percent of silica, and at least 30.0 to 60.0 mass percent of oxygen, and has specific surface area is in the range 50 to 1000 m²/g.

One of embodiments of the invention is that in the calcinated catalyst composition, metal ions used can be in form of nitrate, oxide, chloride, oxychloride, carbonate, acetate, isopropoxide, sulphate, hydroxide salts of metal ions.

One of the embodiments of calcinated catalyst composition wherein mass percent of silicon metal is varied from at least 10.0 to 50.0 of total mass percent of calcinated catalyst composition according to type of solid acid catalyzed reaction. One of the embodiments of calcinated catalyst composition is that metals can be present in the form of its oxides and /or in its metal compound form, according to type of solid acid catalyzed reaction.

One of the embodiments of calcinated catalyst composition is that metals can be supported on hexagonal mesoporous silica (HMS) to give high specific surface area.

One of the embodiments of calcinated catalyst composition is that it comprises oxygen varied from 30.0 to 60.0 mass percent of total mass percent of calcinated catalyst composition according to type of solid acid catalyzed reaction.

Calcinated solid acid catalyst has varying ratio of aluminum, zirconium, tungsten, silica and oxygen metal ion. The catalyst is found to have excellent activity towards dehydration reactions. Also this catalyst can be activated and reused for the same or different reactions.

Thus resulting calcinated catalyst composition has pore diameter in the range of 3.0 nm to 12.0 nm and pore volume in the range of 0.20cmVg to 0.50cmVg.

General method for production of calcinated catalyst composition comprises reaction of dodecyl amine with alcohol like ethanol along with water followed by addition of tetraethyl orthosilicate under vigorous stirring. The reaction mixture is aged for 10 to 30 hours at temperature range 15 to 110 °C. The clear liquid above the white colored precipitate is decanted and the precipitate of resultant is dried. The dried resultant is calcined at high temperature to give catalyst base.

Such catalyst base is mixed with aqueous metal salt solutions by incipient wetness technique, after addition of the solid, resultant is dried in an oven at 110°C for at least 1 to 4 hours, the dried material is hydrolyzed by ammonia gas and washed with deionised water until neutral filtrate is obtained, then material is filtered and dried in oven for at least 20 to 30 hours at 110° C, then add tungustic acid at least 0.05 gm to 0.20 gm by grinding technique on previously prepared material of at least 0.5 gm to 1.5 gm, followed by hydrothermal treatment and then it is calcined at 750° C for at least 1 to 5 hours.

One of the embodiments of the present invention for process for manufacture of acrolein wherein reaction of aqueous glycerol solution with said heterogeneous calcinated solid acid catalyst is carried out.

According to one of the embodiments of the present invention for process for production of acrolein, wherein reaction of aqueous glycerol solution with calcinated catalyst composition can be carried out in absence of any solvent.

One of the embodiments of the present invention for acrolein production is, the calcinated catalyst composition is used in the range of about 0.5 gm to 5.0 gm. One of the embodiments of the present invention is to react aqueous glycerol solution with said calcinated solid acid catalyst in the temperature range of 80°C to 600 °C, preferably in the range 200°C to 450°C.

One of the embodiments of the present invention is the glycerol feed flow rate is in the range of 5.1 ml/h to 20.4 ml/h, preferably is that 5.1 ml/h.

One of the embodiments of the present invention for process for production of acrolein is that nitrogen flow rate as a carrier gas is in the range of 0.72 lit/h to 3.0 lit h, preferably in the rang of 1.3 to 1.5 lit/h.

One of the embodiments of the present invention for process for production of acrolein is that glycerol concentration is used in the range of 10 to 50 mass percent, preferably in the range of 10 to 20 mass percent.

One of the embodiments of the present invention for process for production of acrolein is that said calcinated solid acid catalyst is easily separable, regenerable and reusable up to in the range of 2 to 15 times, preferably in the rang of 2 to 8 times.

One of the embodiments of the present invention for process for production of acrolein is that reaction of aqueous glycerol solution with said calcinated solid acid catalyst is carried out for time of 1 to 100 hours, preferably for 1 to 22 hours, depending upon the reaction conditions.

The process of the invention may be carried out at desired temperature range of 80°C to 600 °C, preferably in the range 200°C to 450 °C wherein reaction is performed at pressures less than, greater than or equal to atmospheric pressure, with nitrogen as a carrier gas.

The production of acrolein is that the dehydration of aqueous glycerol solution was carried out at atmospheric pressure on down flow fixed bed haste alloy HC-276 reactor having 25.4mm ID and 300mm length with as upstream vaporizer and downstream condenser. The liquid feed is fed by double piston (Well Chrom HPLC-pump K-120) pump to the vaporizer by using N₂ as a carrier gas. The catalyst is loaded in the form of powder or pellets to form catalytic bed. The temperature of the bed is maintained with the help of PID controller. The product is condensed in a trap by circulating chilled water, or dry ice-acetone mixture, temperature is maintained in the range of at least -7 to 5° C. Analysis is carried out by using Chemito GC 1000 equipped with an FID detector by using BPX-50 capillary column (30 m).

Present invention for acrolein production in vapour phase dehydration of aqueous glycerol solution under mild reaction conditions using heterogeneous solid acid catalyst as follows

Hydroxyacetone

Glycerol dehydration to acrolein

A few of the numerous examples for catalyst preparation and process for manufacture of acrolein is listed below.

EXAMPLE 1: CATALYST PREPARATION

Preparation of Hexagonal mesoporous silica (HMS): A solution of 500g Hexadecyl amine in ethanol 4180 ml is added to 2960 ml distilled water. Silica precursor such as tetraethyl orthosilicate (2080 g) is added to it. The material was aged for 24 h at 30 °C. The solid material is filtered and dried at 40 °C for 12 h. The resulting material is subjected to calcined at 650 °C for 3 h.

Preparation of calcinated solid acid catalyst: 2.39 gm of zirconium oxychloride and 0.11 gm of aluminum nitrate were dissolved in aqueous solution and added to 5.0 gm of precalcined HMS by incipient wetness technique, after addition this solid material is dried in an oven at 110° C for 3 hours. The dried material is hydrolysed by ammonia gas and washed with deionised water until a neutral filtrate is obtained, then it is filtered, dried in an oven for 24 hours at 110° C. The generation of super acidic centers in to this material is made by grinding tungustic acid 0.1078 gm with 0.9 gm of zirconium hydroxide and aluminum hydroxide on HMS, followed by hydrothermal treatment³ and then it is calcined at 750° C for 3 hours.

This calcinated solid acid Catalyst is characterized completely by the following techniques:

SEM (Scanning Electron Microscope) images of fresh, and regenerated calcined catalyst as shown in Drawing 1.

NH₃-TPD (Temperature Programmed Desorption) data of catalyst, as shown in Drawing 2.

FT-IR (Fourier Transform Infrared) spectrum of catalyst, as shown in Drawing 3. It gives this information, 3451 cm^"1 = H-bonding stretching vibrations of OH group, 1637 cm^"1 = characteristic bands of H₂0 molecules due to - OH bending frequency, 1088,804,462 cm^"1 = evidence of silica presence in the materials.

ASAP (Surface area and pore size analysis) of fresh and regenerated catalyst as shown in Drawing 4.

XRD (X-ray Diffraction analysis) Analysis of the catalyst shows the said catalyst is mesoporous in nature, as shown in Drawing 5.

EDX (Elemental analysis) of the catalyst, it shows the said catalyst comprises of oxygen, aluminium, silicon, zirconium, and tungsten, as shown in Drawing 6.

ASAP (Surface area and pore size analysis), results are as follows

BET surface area: 278 m²/g.

Adsorption average pore diameter: 7.3 nm.

Total pore volume: 0.39 cm³/g.

EXAMPLE 2

The reactions are carried out on fix bed catalytic reactor with nitrogen as carrier gas. Specifications of fix bed reactor, uses for all reactions are given in detailed description of invention. In between the glass wool, 1 g of calcined catalyst is fixed, in the middle of the reactor, with glass beads as packing material above and below the catalyst in to the reactor. The reactor is fed with an aqueous glycerol solution 20% by weight of glycerol at a mean feed flow rate of 10.2 ml/h, with the N₂ flow rate is 1.5 lit/h, preheater temperature is 275° C. The aqueous glycerol solution is vaporized in the preheater and then passed over the catalyst bed. The effect of temperature of the reactions is studied form 250°C to 325°C, for 4 h. The sample is then analyzed by gas chromatography equipped with flame ionization detector, With BPX-50 capillary column. Then acrolein is distilled off from reaction liquid products at 45-55 °C temperature to get the desired pure acrolein.

CHART 1

250 C 275 C 300 C 325 C

B %Conversion of glycerol B % Selectivity of acrolein

EXAMPLE 3

The reactions are carried out with different amount of glycerol concentration, on fix bed catalytic reactor with nitrogen as carrier gas. In between the glass wool, 1 g of calcined catalyst is fixed, in the middle of the reactor, with glass beads as packing material above P T/IN2010/000755 and below the catalyst in to the reactor. Feed flow rate is 10.2 ml/h, N₂ flow rate is 1.5 lit/h, preheater temperature is 275° C. and reactor bed temperature is 275°C, the aqueous glycerol solution is vaporized in the preheater and then passed over the catalyst. Reactions are carried out for 4 h. The effect of glycerol concentration is studied with 10%, 20% and 50% (w/w).

EXAMPLE 4

Reactions are carried out with different amount of calcined catalyst loadings 2.0, 1.0 and 0.5g to get WHSV of 5.37, 10.74 and 21.78 respectively. The reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate is 10.2 ml/h, N₂ flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C. Reactions are carried out for 16h, herewith shown the difference in the conversion and selectivity for different WHSV is as follows.

CHART 4

( ) 5 Tirffe (h) ¹⁵ 20

0.5 g CILO g A2.0 g

EXAMPLE 5

Reactions are carried out with different feed flow rate ranging from 5.1 - 20.4 ml/h, of aqueous glycerol solution. 1.0 g of calcined catalyst is loaded into the fix bed reactor. The reactor is fed with an aqueous glycerol solution 20% by weight of glycerol with N₂ flow rate is 1.5 lit/h. preheater temperature is 275°C and reactor bed temperature is 275 °C, reactions are carried out for 4 h.

CHART 5

5.1 ml/h 10.2 ml/h 20.4 ml/h

B %Conversion of glycerol ■ % Selectivity of acrolein

EXAMPLE 6

Reactions are carried out with Different N₂ flow rate ranging from 0.72 - 3.0 lit/h. 1.0g of calcined catalyst is loaded into the fix bed reactor. The reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, preheater temperature is 275°C and reactor bed temperature is 275 °C.The reactions are carried out for 4 h. CHART 6

0.72 lit h 1.5 lrt h 3.0 lit/h

B %Conveision of glycerol ■ % Selectivity of acrolein

EXAMPLE 7

In this reaction stability and activity of the catalyst is evaluated by time on stream (TOS) data. 2.0g of calcined catalyst is loaded into the fix bed reactor. The reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, N₂ flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C. Reaction is carried out for 100 h.

CHART 7

CHART 8

— l Conversion (%) -Selectivity (%)

EXAMPLE 8

Reactions are carried out for catalyst regeneration and reusability study, after completion of the reaction, the catalyst is removed from the reactor and washed with methanol up to 3 to 4 times, to remove the adsorbed polymerized material from the catalyst. Then c Catalyst is subjected to calcinations at 550 °C for 3 h, in the flowing air to burn off coke present on the catalyst. There is an inevitable loss of catalyst particles during these operations. Hence, actual amount of catalyst used in the next batch is almost 10% less than the previous batch. The loss of the catalyst is made up with fresh catalyst. Catalyst reusability is performing reactions by using 1.0g of calcined catalyst is loaded into the fix bed reactor. The reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, N₂ flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C. Reactions are carried out up to 16 h. for 6 times in a row.

CHART 9

■ Seriesl

□ Series2||

2 3 4 5

Catalyst Reuse

(%) Glycerol conversion (Seriesl)

(%) Acrolein selectivity (Series 2)

10

Claims

We Claims:

1) Calcinated heterogeneous catalyst composition comprising metals as at least 0.001 to 2.00 mass percent of aluminium, at least 5.0 to 15.0 mass percent of zirconium, at least 5.0 to 15.0 mass percent of tungsten, at least 10.0 to 50.0 mass percent of silicon, and at least 30.0 to 60.0 mass percent of oxygen, and has specific surface area is in the range 50 to 1000 m7g.

2) Calcinated heterogeneous catalyst composition according to claim 1, wherein metals are used in the form of one, two, or more kinds of salts selected from nitrate, oxide, chloride, oxychloride, carbonate, acetate, isopropoxide, sulphate, hydroxide, salts of metal ions.

3) Calcinated heterogeneous catalyst composition according to claim 1, wherein metals are in the form of its oxides, metals and/or mixture of thereof.

4) Calcinated heterogeneous catalyst composition according to claim 1, wherein composition has pore diameter in the range of 2.0 nm to 12.0 nm and pore volume in the range of 0.10 cm³/g to 0.50 cm³/g.

5) Calcinated heterogeneous catalyst composition according to claim 1, wherein metals are supported on hexagonal mesoporous silica to give high specific surface area.

6) Calcinated heterogeneous catalyst composition according to claim 1, wherein calcinations is carried out under an atmosphere of air, inert gas or a mixture of oxygen and inert gas, the calcinations is effected at temperature in the range of 200° C to 1000° C, more preferably in the range of 400 °C to 750 °C for 0.5 to 10 hours, more preferably in the range of 2 to 5 hours.

7) Process for production of acrolein on fixed bed vapour phase reactor with said calcinated catalyst under inert atmosphere as claimed in claim 1 to 6 comprises steps of :

(a) Dehydrating glycerol having concentration in the range of 5 to 80 % (w/w) in water (aqueous glycerol), in the presence of said calcinated catalyst composition with or without solvent under nitrogen or argon atmospheric condition.

(b) Separation of pure acrolein from final reaction mixture.

8) Process for production of acrolein as claimed in claim 7, wherein calcinated catalyst composition is used in the range of 0.1 to 30% with respect to glycerol weight. 9) Process for production of acrolein as claimed in claim 7, wherein reactions are carried out in the temperature range of 80°C to 600 °C, more preferably 200 °C to 450 °C.

10) Process for production of acrolein as claimed in claim 7, wherein reactions are carried out at pressure less than, greater than or equal to atmospheric pressure, with nitrogen as a carrier gas.

11) Process for production of acrolein as claimed in claim 7, wherein reactions are carried out for period of time 1 to 100 hours, more preferably for 1 to 22 hours depending upon the reaction conditions.

12) Process for production of acrolein as claimed in claim 7, wherein said calcinated catalyst is easily separable, regenerable and reusable for 2 to 15 times, more preferably in the range of 2 to 8 times.

13) Process for production of acrolein as claimed in claim 7, wherein separation of pure acrolein from final reaction mixture is carried out by distillation at 45-55 °C.

14) Process for production of acrolein and calcinated catalyst as claimed in above claims and examples herein.