CLIAMS:1. A process for the production of bio-oil; said process comprising the following steps:

a. preparing and/or collecting a biomass slurry;
b. adding a first catalyst composition in an amount ranging from 1 to 20 wt% with respect to the biomass in said slurry to obtain a mixture;
c. heating the mixture at a temperature ranging from 200 to 350o C and at a pressure ranging from 70 to 250 bars for a time period ranging from 10 to 180 minutes to obtain a mass containing crude bio oil, a residue and the catalyst;
d. separating the crude bio oil from said mass to obtain a separated crude bio oil and a sludge containing the residue and the catalyst, extracting said separated crude bio oil with at least one solvent and evaporating said solvent to obtain a solvent free crude bio oil;
e. subjecting said solvent free crude bio oil to a reaction in the presence of a second catalyst composition and a hydrogen source at a temperature ranging from 200 to 450 0C and at a pressure ranging from 70 to 250 bars for a time period ranging from 10 to 180 minutes to obtain bio-oil, a residue and the catalyst.

2. The process as claimed in claim 1, wherein the method step (d) further comprise recovering said catalyst from said sludge.

3. The process as claimed in claim 1, wherein the concentration of the biomass in the slurry ranges from 5 to 35 wt%.
4. The process as claimed in claim 1, wherein the biomass is selected from the group consisting of organic waste, agricultural residue, urban refuse, land and water based plant material and microorganism.

5. The process as claimed in claim 1, wherein the biomass is at least one algae division selected from the group of divisions consisting of Rhodophyta, Chlorophyta, Phaeophyta, Chrsophyta, Cryptophyta, Dinophyta, Tribophyta, Glaucophyta, Charophyta, Ochrophyta, Protista and Blue green algae (Cyanobacteria).

6. The process as claimed in claim 1, wherein the biomass is at least one algae selected from the group consisting of Spirulina, Nannochloropsis, Chlorella, Euglena, Microcystis, Dictyosphaerium Anabaena, Nodularia, Oscillatoria, Spirogyra, hydrodictyon, Chara, Nitella, Oedognium and Phormidium.

7. The process as claimed in claim 1, wherein the second catalyst employed in step (e) is a fresh catalyst or the first catalyst recovered from the sludge formed in step (d).

8. The process as claimed in claim 1, wherein the carbon content of said crude bio oil ranges between 74 and 80 %.

9. The process as claimed in claim 1, wherein the first or the second catalyst composition comprise:
i. at least one metal in an amount of 0.1 to 15 wt. %, wherein the metal is selected from the group consisting of group Ib, group IIb metals, group IVb metals, group Vb metals, group VIb metals, group VIIb metals, group VIII metals and noble metals;
ii. at least one support in an amount of 30 to 96 wt%; and
iii. at least one solubilizing agent in an amount of 4 to 50 wt. %, said solubilizing agent selected from the group consisting of ammonia solution, piperidine, pyrrolidine, morpholine, piperazine hydrate, 2-methylcyclohexyl amine, cyclohexylamine and hexamethyleneimine.

10. The process as claimed in claim 9, wherein said support is selected from the group consisting of alumina, silica, zirconia, alumina-silica, zeolite and molecular sieves.

11. The process as claimed in claim 9, wherein said support comprises a) 30 to 100 wt% of at least one carrier selected from the group consisting of alumina, silica, zirconia, alumina-silica, zeolite and molecular sieves; b) 0.001 to 70 wt% of at least one binder selected from the group consisting of aluminophosphate, psuedoboehmite, alumina oxide, silica and ludox silica solution.

12. The process as claimed in claim 9, wherein said support comprises a) 30 to 100 wt% of at least one carrier selected from the group consisting of nano-structured aluminum oxide, nano-structured silicon oxide, nano-structured zirconium oxide, nano-structured cerium oxide, nano-structured titanium oxide, nano-structured tantalum oxide; b) 0.001 to 70 wt% of at least one binder selected from the group consisting of aluminophosphate, psuedoboehmite, alumina oxide, silica and ludox silica solution.

13. The process as claimed in claim 9, wherein said support comprises a) 30 to 100 wt% of at least one carrier selected from the group consisting of mesoporous zeolites, mesoporous alumino silicate, mesoporous silicalite, mesoporous molecular sieves; b) 0.001 to 70 wt% of at least one binder selected from the group consisting of aluminophosphate, psuedoboehmite, alumina oxide, silica and ludox silica solution.

14. The process as claimed in claim 9, wherein the metal is selected from the group consisting of nickel (Ni), molybdenum (Mo), cobalt (Co), copper (Cu), silver (Ag), zinc (Zn), zirconium (Zr), vanadium (V), tungsten (W), rhenium (Re), platinum (Pt), palladium (Pd), ruthenium (Ru) and rhodium (Rh).

15. The process as claimed in claim 9, wherein the support is in the form of extrudates, spheres, pellets and powder.

16. The process as claimed in claim 9, wherein the support is in the form of extrudates and has a length ranging from 4 to 6 mm, a diameter ranging from 1 to 2 mm and a surface area ranging from 25 to 1000 m2/gm; and the support in the form of spheres and pellets has a diameter ranging from 3 to 10 mm.
17. The process as claimed in claim 9, wherein the catalyst composition is characterized by:
i. total acid strength ranging from 0.05 to 3.5 mmole/gm of ammonia; and
ii. pore width ranging from 1 to 20 nm. ,TagSPECI:This application is a patent of addition with respect to main Indian Patent Application No. 2899/MUM/2013 dated 06.09.2013, the entire contents of which, are specifically incorporated herein by reference.
FIELD:
The present disclosure relates to a process for the production of crude bio oil and its up-gradation to bio-oil using a catalyst composition.

BACKGROUND:
Definitions:
Biomass:
The term biomass in the context of the present disclosure means materials such as organic waste, urban refuse, wood, agricultural crops or wastes, municipal wastes and the like, which can be used as a source of fuel or energy.

Crude bio oil:
The term crude bio oil used in the context of the present disclosure means an oil or biofuel derived from biomass and which can be used as an alternative to petroleum fuel.
Biomass, a renewable energy source, can either be used directly via combustion to produce heat, or indirectly after converting it to various forms of biofuels. Biofuels are derived from biomass and are intended to provide an alternative to petroleum fuels. Conversion of biomass to biofuel can be achieved by different methods which are broadly classified into thermal, chemical and biochemical methods.

Fossil fuels such as petroleum, natural gas and coal are typically formed through the processes of thermochemical conversion (TCC) from biomass buried beneath the ground.
TCC is a chemical reforming process of biomass in a heated and usually pressurized, oxygen deprived enclosure, where long - chain organic compounds break into short - chain hydrocarbons such as syngas or oil. TCC is a broad term that includes gasi?cation, including the Fisher - Tropsch process, direct liquefaction, hydrothermal liquefaction and pyrolysis.
Pyrolysis is a heating process of dried biomass to directly produce syngas and/or oil. Both gasi?cation and pyrolysis require dried biomass as feedstock and the processes occur in an environment higher than 600 °C.

Hydrothermal liquefaction is promising technology for converting high-moisture waste biomass into energy dense “crude bio oil” that can be used for direct combustion or refined for transportation grade fuels.

HTL, also called hydrous pyrolysis, is a process for the reduction of complex organic materials such as bio - waste or biomass into crude oil and other chemicals.

Hydrothermal Liquefaction (HTL) technique, which involves the application of heat and pressure on the biomass medium, has an advantage that the lipids and other organic components can be efficiently converted while the biomass is in wet condition. During HTL, high moisture biomass is subjected to elevated temperature (250-400oC) and pressure (up to 225 bars) in order to break down and reform the chemical building blocks into crude bio oil. HTL of biomass gives only crude bio oil that need to be further treated /refined to get the finished crude oil products. The hydrothermal process breaks down bio macromolecules in the wet biomass and promotes heteroatom removal.

Some of the representative patent documents which suggest conversion of biomass to upgraded bio-oil via crude bio oil are discussed herein below.
US20120055077 suggests a method of producing an upgraded bio-oil from a wet biomass which involves heating the wet biomass at a first temperature (200 to 400° C) and a first pressure (0.1 to 25 MPa) for a time period ranging from 10 to 200 minutes to form a crude bio-oil and heating the crude bio-oil and water at a second temperature and a second pressure for a time period of at least 30 minutes to form the upgraded bio-oil, wherein the second temperature is greater than the first temperature and is at least 300 °C.

As per the procedure suggested in US20120055077, the biomass is subjected to heat twice i.e. heating at a first temperature and at a first pressure followed by heating at a second temperature and at a second pressure. The first heating is below supercritical condition, whereas the second heating is above supercritical condition. Further, the crude bio oil is converted into bio-oil in the presence of water. Still further, the catalysts employed in the process suggested by US 20120055077 are heterogeneous catalyst containing Pd/C, Pt/C, Ru/C, Ni/SiO2—Al2O3, sulfided CoMo/?-Al2O3, zeolite, activated carbon, and combinations thereof.

Considering the complexity associated with the suggested process, there is a need for a simple, energy efficient, time saving and high yielding process for the conversion of biomass to crude bio oil and its up-gradation to bio-oil. Accordingly, the present disclosure provides a process in which the upgradation of crude bio oil to bio-oil can be carried out in the absence of solvent using a catalyst which can be easily recovered and recycled and the steps of preparing crude bio oil from biomass and bio-oil from crude bio oil can be carried out at similar temperature and pressure conditions.

OBJECTS:

Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:

It is an object of the present disclosure to provide a process for the production of crude bio oil and its up-gradation to bio-oil using a regenerable and recyclable catalyst.
It is another object of the present disclosure to provide a simple, energy efficient, time saving and high yielding process for the production of crude bio oil and its up-gradation to bio-oil.
It is another object of the present disclosure to provide a process in which the upgradation of crude bio oil to bio-oil is carried in the absence of solvent.
It is another object of the present disclosure to provide a process in which the temperature and pressure parameters for the conversion of biomass into crude bio oil and subsequent upgradation of crude bio oil to bio-oil are same.
It is a still another object of the present disclosure to provide a process which is capable of producing bio-oil compatible with crude used in the refinery process.
It is yet another object of the present disclosure to provide a process which is capable of producing bio-oil containing high carbon content.
It is yet another object of the present disclosure to provide a process which is capable of producing bio-oil which is free from heteroatoms such as oxygen, nitrogen, sulfur and phosphorus.

Other objects and advantages of the present disclosure will be more apparent from the following description which is not intended to limit the scope of the present disclosure.

SUMMARY:

The present disclosure relates to a process for the conversion of crude bio oil into bio oil. The crude bio oil is prepared in accordance with the process using the catalyst composition as disclosed in the co-pending patent application 2899MUM2013, to which this patent application is a patent of addition. In accordance with the present disclosure the temperature and pressure parameters for preparing bio oil are similar or slightly higher than that required for the preparation of crude bio oil from crude biomass. Further, the preparation of crude bio oil from crude biomass in accordance with the process of the present disclosure is carried out in the absence of a solvent. The purpose of upgrading the crude bio oil to bio oil is to make the bio oil compatible with the petroleum crude oil. This is achieved by removing heteroatoms such as nitrogen, oxygen and sulphur by subjecting the crude oil to upgradation process of the present disclosure.
BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS:
The disclosure will now be explained in relation to the non-limiting accompanying drawings, in which:
Figure 1- illustrates GCMS chromatogram of crude bio oil;
Figure 2- illustrates GCMS chromatogram of bio oil;
Figure 3- illustrates the preparation of crude bio oil; and
Figure 4- illustrates the preparation of bio-oil.

DETAILED DESCRIPTION:
The co-pending patent application No. 2899/MUM/2013 overcomes the drawbacks associated with the known hydrothermal liquefaction methods for the conversion of biomass to crude bio oil, such as time consumption, energy consumption and low yield and discloses a simple, energy efficient, time saving and high yielding process for hydrothermal conversion of biomass to bio- crude. 2899/MUM/2013 particularly provides a method for the preparation of a catalyst at a room temperature having improved catalytic activity when used for hydrothermal conversion of biomass to crude bio oil. However, the crude bio oil obtained is incompatible with petroleum crude oil as it contains free fatty acids, N-containing heterocyclic compounds, polycyclic aromatics, unsaturated compounds and other undetectable heavier molecules. To make the crude bio oil compatible with the petroleum crude oil, the crude bio oil needs to be upgraded.

The present disclosure focuses on the upgradation of crude bio oil to bio oil.
Particularly, the present disclosure provides the up-gradation of crude bio oil to bio-oil in the absence of solvent which is carried out essentially at temperature and pressure conditions similar to those of conversion of biomass to crude bio oil.
Accordingly, the present disclosure provides a process for the production of crude bio oil and its up-gradation to bio-oil. The process involves the following steps.
In the first step, slurry of a bio-mass is prepared in a medium. The concentration of the biomass in the slurry ranges from 5 to 35 wt%. The biomass utilized for preparing slurry includes but is not limited to organic waste, agricultural residues, urban refuse, land-and water-based plant material and microorganism and the medium includes water or demineralized water. In one embodiment, the biomass is algae division selected from the group of divisions consisting of Rhodophyta, Chlorophyta, Phaeophyta, Chrsophyta, Cryptophyta, Dinophyta, Tribophyta, Glaucophyta, Charophyta, Ochrophyta, Protista and Blue green algae (Cyanobacteria).
Particularly, the algae is selected from the group consisting of Spirulina, Nannochloropsis, Chlorella, Euglena, Microcystis, Dictyosphaerium Anabaena, Nodularia, Oscillatoria, Spirogyra, Hydrodictyon, Chara, Nitella, Oedognium, Phormidium and the like.
In the second step, a first catalyst composition is added to the slurry to obtain a mixture. The amount of the first catalyst composition added to the slurry ranges from 1 to 20 wt. % with respect to the biomass.
The first catalyst composition useful for the purpose of the present invention includes at least one metal, at least one support and at least one solubilizing agent.
The metal used in the first catalyst composition includes but is not limited to group Ib metals, group IIb metals, group IVb metals, group Vb metals, group VIb metals, group VIIb metals, group VIII metals and noble metals. Particularly, the metal is selected from the group consisting nickel (Ni), molybdenum (Mo), cobalt (Co), copper (Cu), silver (Ag), zinc (Zn), zirconium (Zr), vanadium (V), tungsten (W), rhenium (Re), platinum (Pt), palladium (Pd), ruthenium (Ru) and rhodium (Rh).

In accordance with the present disclosure the source of the metal is selected from a group of compound containing cation which includes but is not limited to nickel (Ni), molybdenum (Mo), cobalt (Co), zinc (Zn), zirconium (Zr), vanadium (V), tungsten (W), rhenium (Re), platinum (Pt), palladium (Pd), ruthenium (Ru) and rhodium (Rh); and anion which includes but is not limited to chlorides, bromides, fluorides, iodides, sulfates, phosphates, phosphonates, nitrates, nitrites, carbonates, acetates, bicarbonates, hydroxides and oxides.
The amount of a metal in the catalyst composition ranges from 0.1 to 15 w/w %.

Non-limiting examples of the solubilizing agent present in the catalyst composition includes ammonia solution, piperidine, pyrrolidine, morpholine, piperazine hydrate, 2-methylcyclohexyl amine, cyclohexylamine and hexamethyleneimine. Preferably, the solubilizing agent is hexamethyleneimine. The amount of the solubilizing agent in the catalyst composition of the present disclosure ranges from 4 to 50 wt. %.
The amount of the support in the first catalyst composition ranges from 30 to 96 wt%.
In one embodiment the support is selected from the group consisting of alumina, silica, zirconia, alumina-silica, zeolite and molecular sieves.

In another embodiment the support comprises at least one carrier which includes but is not limited to alumina, silica, zirconia alumina-silica, zeolite and molecular sieves in an amount from 30 and 100 wt% with respect to the support and at least one binder which includes but is not limited to aluminophosphate, pseudoboehmite, alumin oxide, silica and ludox silica solution in an amount from 0.001 to 70wt% with respect to the support.

Alternatively, the support contains at least one carrier which includes but is not limited to nano-structured aluminum oxide, nano-structured silicon oxide, nano-structured zirconium oxide, nano-structured cerium oxide, nano-structured titanium oxide, nano-structured tantalum oxide in an amount from 30 and 100 wt% with respect to the support and at least one binder which includes but is not limited to aluminophosphate, pseudoboehmite, alumina oxide, silica and ludox silica solution in an amount from 0.001 to 70wt% with respect to the support.

Still alternatively, the support contains at least one carrier which includes but is not limited to mesoporous zeolites, mesoporous alumino silicate, mesoporous silicalite, mesoporous molecular sieves in an amount from 30 and 100 wt% with respect to the support and at least one binder which includes but is not limited to aluminophosphate, pseudoboehmite, alumina oxide, silica and ludox silica solution in an amount from 0.001 to 70 wt% with respect to the support.
The support employed in the catalyst preparation is in the form selected from the group consisting of extrudate, sphere, pellet and powder. The support utilized has a surface area ranging from 25 to 1000 m2/g, whereas the spheres and pellets have a diameter of 3 to 10 mm.

In one embodiment the support is in the form of extrudates having lengths ranging from 4 to 6 mm and diameter ranging from 1 to 2 mm.

In another embodiment the support is prepared using at least one carrier, at least one binder and at least one peptizing agent. The peptizing agent is selected from the group consisting of phosphoric acid, acetic acid and combination thereof.

In the third step, the mixture is heated at a temperature ranging from 200 to 350o C and at a pressure ranging from 70 to 250 bars for a time period ranging from 10 to 180 minutes to obtain a mass containing crude bio oil, a residue and the catalyst. Optionally, the mixture is heated in the presence of at least one hydrogen source selected from the group consisting of H2 and CH4.

During the course of heating the biomass breaks down and reforms the chemical building blocks into crude bio oil. The catalyst hydrothermal process employing the catalyst of the present disclosure breaks down the bio macromolecules present in the biomass and promote removal of heteroatoms to result into crude bio oil. The crude bio oil obtained contains free fatty acids, N-containing heterocyclic compounds, polycyclic aromatics, unsaturated compounds and other undetected heavier molecules and therefore, is not suitable for application. To make the crude bio oil suitable for applications it is upgraded to bio oil by subjecting crude bio oil to reduction process. The crude bio oil before subjecting to the reduction process is separated from the mass to obtain separated crude bio oil and a sludge containing the residue and the catalyst. The crude bio oil is extracted using at least one solvent and then the solvent is evaporated to obtain solvent free crude bio oil. Simultaneously, the catalyst is recovered from the sludge. The recovery of the catalyst comprises the steps of separating the catalyst from said residue, calcining at a temperature of 500 to 7000C for a time period of 3 to 7 hours followed by reduction using hydrogen at a temperature of 400 to 6000C for a time period of 2 to 5 hours to obtain a recovered catalyst. The recovered catalyst can be recycled for the production of crude bio oil or bio-oil or both.
Finally, the solvent free crude bio oil is subjected to reaction in the presence of a second catalyst composition and hydrogen source at a temperature ranging from 200 to 450 0C and at a pressure ranging from 70 to 250 bars for a time period ranging from 10 to 180 minutes to obtain bio-oil, a residue, the catalyst. The catalyst employed for reduction of crude bio oil to obtain bio-oil is a fresh catalyst having composition as that of the first catalyst or a recovered catalyst from the sludge.

The catalyst employed for the production of crude bio oil and up-gradation of the crude bio oil to bio-oil is characterized by:
i. total acid strength ranging from 0.05 to 3.5 mmole/gm of ammonia; and
ii. pore width ranging from 1 to 20 nm.

The yield of the crude bio oil obtained by the process of the present disclosure using the catalyst composition as specified above ranges from 45 % to 80 % and the carbon content of said crude bio oil ranges from 74 to 80 %.
The yield of the bio-oil obtained by the process of the present disclosure using the catalyst composition as specified above ranges from 50 to 70%.
The catalyst compositions of the present disclosure are highly stable during the hydrothermal liquefaction.

Further, the recovered catalyst of the present disclosure exhibits X-ray diffraction (XRD) pattern similar to the fresh catalyst reflecting the retention of crystalline structure of the catalyst after regeneration. The Brunauer, Emmett and Teller (BET) surface area, metal concentration and decomposition behaviors of the regenerated catalysts are similar to that of fresh catalysts showing that texture of the catalysts is retained during regeneration of the catalyst.

Still further, the recovered catalyst can be recycled for at least 5 times with a performance similar to the fresh catalyst.

The present disclosure is further described in light of the following examples which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure.

Example 1:
Preparation of a catalyst composition
Solution A was prepared by dissolving cobalt acetate (0.863 gm) in water (10ml) at 30oC for 10 minutes. Separately, solution B was prepared by dissolving ammonium molybdate (10.41 gm) and hexamethyleneimine (7 gm) in water (70ml) at 60oC for 30 minutes at 300 rpm.
Solution A and B were then mixed together at 30oC. To this alumina powder (10 gm) was added and mixed for 2 hours to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined at 600oC for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (CoMo/Al2O3).

Example 1A
The process of example 1 was repeated except that 8 gm of ammonia solution (25 %) was used instead of hexamethyleneimine (7 gm).

Example 1B
The process of example 1 was repeated except that 8 gm of cyclohexylamine was used instead of hexamethyleneimine (7 gm).
Example 1C
The process of example 1 was repeated except that 8 gm of ammonia solution (25 %) was used instead of hexamethyleneimine (7 gm) and zirconia powder was used instead of alumina extrudate.
Example 1D
The process of example 1 was repeated except that 8 gm of cyclohexylamine was used instead of hexamethyleneimine (7 gm) and zirconia powder was used instead of alumina extrudate.
Example 1E
The process of example 1 was repeated except that zirconia powder was used instead of alumina extrudate.

Example 2:
Preparation of a catalyst composition
Solution A was prepared by dissolving nickel nitrate (1.011 gm) in water (10ml) at 30oC for 10 minutes. Separately, solution B was prepared by dissolving ammonium molybdate (10.41 gm) and hexamethyleneimine (7 gm) in water (70ml) at 60oC for 30 minutes at 300 rpm.
Solution A and B were then mixed together at 30oC. To this alumina powder (10 gm) was added and mixed for 2 hours to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined at 600oC for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (NiMo/Al2O3).
Example 2A
The process of example 2 was repeated except that 7 gm of ammonia solution (25 %) was used instead of hexamethyleneimine (7 gm).

Example 2B
The process of example 2 was repeated except that 7 gm of cyclohexylamine was used instead of hexamethyleneimine (7 gm).

Example 3:
Preparation of catalyst composition
Solution A was prepared by dissolving rhodium chloride (0.381 gm) and hexamethyleneimine (7 gm) in water (100 ml) at 30oC for 30 minutes at 300 rpm. To this zirconia powder (10 gm) was added and mixed for 2 hours at 30 oC to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined at 600oC for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (Rh/zirconia).

Example 4A:
Catalytic Hydrothermal Liquefaction using Nannochloropsis
21 g Nannochloropsis as 20% slurry in water was loaded in an HTHP reactor (capacity: 300ml). 10 wt. % of powdered CoMo/Al2O3 catalyst (1.897 g w.r.t. ash and moisture free algae) of the present disclosure was added to the reactor. The reactor was then closed. Leak check was done using nitrogen at 120 bar. Nitrogen pressure was released and the required amount of hydrogen (35 bar) was filled and heated to reaction temperature (350°C) with 500 rpm stirring speed. Upon reaching the temperature, the reactor was kept under the same condition for 30 min. It was then cooled with chilled water facility and the gas was collected for gas analysis. The reactor was opened and the product was collected in a beaker. Oil, aqueous and solid phases were separated and measured individually. The mixture was filtered using a Buckner flask. The obtained powder was washed with Dichloromethane and water and then dried. The liquids (oil and aqueous phase) were separated by solvent extraction method.

Example 4B:
Catalytic Hydrothermal Liquefaction using Chlorella
21 g chlorella as 20% slurry in water was loaded in an HTHP reactor (capacity: 300ml). 10 wt. % of powdered CoMo/Al2O3 catalyst (1.897 g w.r.t. ash and moisture free algae) of the present disclosure was added to the reactor. The reactor was then closed. Leak check was done using nitrogen at 120 bar. Nitrogen pressure was released and the required amount of hydrogen (35 bar) was filled and heated to reaction temperature (350°C) with 500 rpm stirring speed. Upon reaching the temperature, the reactor was kept under the same condition for 30 min. It was then cooled with chilled water facility and the gas was collected for gas analysis. The reactor was opened and the product was collected in a beaker. Oil, aqueous and solid phases were separated and measured individually. The mixture was filtered using a Buckner flask. The obtained powder was washed with Dichloromethane and water and then dried. The liquids (oil and aqueous phase) were separated by solvent extraction method.

Example 5
The process of example 4A and 4B was repeated using 10 wt. % of powdered NiMo/Al2O3 catalyst obtained in example 2.

Example 6
The process of example 4A and 4B was repeated using 10 wt. % of powdered Rh/ZrO2 catalyst obtained in example 3.

Example 7:
Catalytic Hydrothermal Liquefaction using Spirulina
23 g of Spirulina as 20% slurry in water loaded in a reactor (HTHP reactor, capacity: 300ml). 10 wt. % of powdered CoMo/Al2O3 catalyst (1.897 g w.r.t. ash and moisture free algae) of the present disclosure was added to the reactor. The reactor was then closed. Leak check was done using nitrogen at 120 bar. The nitrogen pressure was released and the required amount of hydrogen (35 bar) was filled and heated to reaction temperature (350°C) with 500 rpm stirring speed. Upon reaching the temperature, the reactor was kept under the same conditions for 30 min. It was then cooled with chilled water facility and the gas was collected for gas analysis. The reactor was opened and the product was collected in a beaker. Oil, aqueous and solid phases were separated and measured individually. The mixture was filtered using a Buckner flask. The powder was washed with Dichloromethane and water and dried. The liquids (Oil and aqueous phase) were separated by gravimetric method.

Example 8
The process of example 7 was repeated using 10 wt. % of powdered NiMo/Al2O3 obtained in example 2.

Example 9
The process of example 7 was repeated using 10 wt. % of powdered Rh/ZrO2 obtained in example 3.

The comparative results of % HTL oil yield for conventional methods (without catalyst/ with commercial catalysts) vis-à-vis catalysts of the present disclosure are provided in the Table No. 1:
Yield (%) of HTL oil was calculated as weight of oil product X 100 / weight of moisture and ash free algae in the HTL slurry.

Table No. 1
Catalysts % Crude Bio Oil yield
Nannochloropsis Spirulina Chlorella
Without catalyst 58 46 -
CoMo/Al2O3 (Commercial) 68 48 -
NiMo/Al2O3 (Commercial) 65 48 -
Present (CoMo/Al2O3 + hexamethyleneimine) Example 1 73 57 59
Present (NiMo/Al2O3 + hexamethyleneimine) Example 2 69 55 56
Present (Rh/ZrO2 + hexamethyleneimine)
Example 3 71 55 45
Present (CoMo/ZrO2+ hexamethyleneimine) Example 1E 71 61 -
Present (CoMo/Al2O3 + 25% ammonia solution)
Example 1A 63 51 49
Present (CoMo/Al2O3 + cyclohexylamine)
Example 1B 60 50 50
Present (NiMo/Al2O3+ 25% ammonia solution)
Example 2A 60 51 48
Present (NiMo/Al2O3+ cyclohexylamine)
Example 2B 61 52 49
Present (CoMo/ZrO2+ 25% ammonia solution)
Example 1C 63 - -
Present (CoMo/ZrO2+ cyclohexylamine)
Example 1D 61 - -

From the results, it is clear that % HTL oil yield by the process of the present disclosure which utilizes a catalyst comprising a solubilizing agent is 48 to 73 %. Whereas, the % HTL oil yield using the commercial catalyst (which is devoid of a solubilizing agent) ranges from 48 to 68 %.
It is particularly found that when a catalyst comprising hexamethyleneimine as a solubilizing agent is utilized for liquefaction of high lipid Nannochloropsis algae, % HTL oil yield is 69 to 73 %. Thus, when hexamethyleneimine is used as a solubilizing agent, the process of the present disclosure provides high yield of crude bio oil than the crude bio oil yield obtained by the process which utilize commercial catalyst.
The following examples illustrate preparation of the extruded form of the catalyst composition using extruded support which may be recycled and regenerated as per process of the present disclosure:
Example-10: Preparation of support
Example 10
A: Alumina support preparation (10 g batch)
Pseudoboehmite (4.0 g) and alumina (7.0 g) were taken. To this, 6 ml of diluted solution of orthophosphoric acid was mixed to obtain aluminophosphate gel. This gel was mixed in a mortar-pestle and pegged to extrudable dough.

B: Alumina support preparation (10 g batch)
Pseudoboehmite (4.0 g) and alumina (7.0 g) were taken. To this, 7 ml of diluted solution of acetic acid was mixed to obtain aluminum acetate gel. This gel was mixed in a mortar-pestle and pegged to extrudable dough.

C: Zirconia support preparation (10 g batch)
Zirconium hydroxide powder (14.0 g) and Pseudoboehmite alumina (4.0 g) were mixed. Diluted solution of orthophosphoric acid (6 ml) was added while mixing to prepare Zirconium phosphate gel. This gel was mixed in a mortar-pestle and pegged to extrudable dough.

D: Zirconia support preparation (10 g batch)
Zirconium hydroxide powder (14.0 g) and Pseudoboehmite alumina (4.0 g) were mixed. Diluted solution of acetic acid (7 ml) was added while mixing to prepare Zirconium acetate gel. This gel was mixed in a mortar-pestle and pegged to extrudable dough.

E: Zeolite support preparation (10 g batch)
To make zeolite extrudates, Pseudoboehmite alumina (4.0 g) and diluted solution of orthophosphoric acid (6 ml) were mixed thoroughly with a mixture of zeolite powder (7.0 g) and hydroxypropylmethyl cellulose (HPMC, 0.1 g) in a mortar-pestle and pegged to extrudable dough.

Upon making the above said dough, it was passed through extruder/nodulizer and obtained extrudates like wires. It was then dried at room temperature for 2 hours followed by 120oC for 6 hours. Finally, it was calcined at 540 – 600oC in presence of air for 6hours in an air flow.

Example 11
A]
Preparation of a catalyst composition
Dispersion A was prepared by dissolving cobalt acetate (0.863 g) in water (10ml) at 30oC for 10 minutes. Separately, dispersion B was prepared by dissolving ammonium molybdate (10.41 g) and hexamethyleneimine (7 g) in water (70ml) at 60oC for 30 minutes at 300 rpm.
Dispersions A and B were then mixed together at 30oC. To this alumina support of example 10 A (10 gm) was added and mixed for 2 hours to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined in presence of air at 600oC for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (CoMo/Al2O3).
B]
The process of example 11A was repeated except that 8 g of ammonia solution (25 %) was used instead of hexamethyleneimine (7 g).
C]
The process of example 11A was repeated except that 8 g of cyclohexylamine was used instead of hexamethyleneimine (7 g).

Example 12
A]
The process of example 11A was repeated except that 8 g of ammonia solution (25 %) was used instead of hexamethyleneimine (7 g) and zirconia support of example 10C was used instead of alumina support.

B]
The process of example 11A was repeated except that 8 gm of cyclohexylamine was used instead of hexamethyleneimine (7 g) and zirconia support of example 10 C was used instead of alumina support.

C]
The process of example 11A was repeated except that zirconia support of 10D was used instead of alumina support.

D] The process of example 11A was repeated except that Zeolite support of example 10 E was used instead of alumina support.

Example 13:
A] Preparation of a catalyst composition
Dispersion A was prepared by dissolving nickel nitrate (1.011 g) in water (10ml) at 30oC for 10 minutes. Separately, dispersion B was prepared by dissolving ammonium molybdate (10.41 g) and hexamethyleneimine (7 g) in water (70ml) at 60oC for 30 minutes at 300 rpm.
Dispersions A and B were then mixed together at 30oC. To this alumina support of example 10 A (10 g) was added and mixed for 2 hours to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined at 600oC in presence of air for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (NiMo/Al2O3).
B]
The process of example 13A was repeated except that 7 g of ammonia solution (25 %) was used instead of hexamethyleneimine (7 g).
C]
The process of example 13A was repeated except that 7 g of cyclohexylamine was used instead of hexamethyleneimine (7 g).

Example 14:
Preparation of catalyst composition
Dispersion A was prepared by dissolving rhodium chloride (0.381g) and hexamethyleneimine (7 g) in water (100 ml) at 30oC for 30 minutes at 300 rpm. To this zirconia support obtained in 10C (10 g) was added and mixed for 2 hours at 30 oC to obtain a mixture. The liquid from the mixture was discarded and the remaining mass was dried at room temperature for 2 hours. This mass was further dried at 120oC for 10 hours and calcined in presence of air at 600oC for 6 hours. The resulting calcined mass was subjected to reduction in the presence of hydrogen at 500oC for 4 hours to obtain the catalyst (Rh/Zirconia).

Example 15:
Catalytic Hydrothermal Liquefaction using Nannochloropsis
21 g Nannochloropsis as 20% slurry in water loaded in an HTHP reactor (capacity: 300ml). 10 wt. % of extruded CoMo/Al2O3 catalyst, obtained in example 11A (1.897 g w.r.t. ash and moisture free algae) of the present disclosure was added to the reactor. The reactor was then closed. Leak check was done using nitrogen at 120 bar. Nitrogen pressure was released and the required amount of hydrogen (35 bar) was filled and heated to reaction temperature (350°C) with 500 rpm stirring speed. Upon reaching the temperature, the reactor was kept under the same condition for 30 min. It was then cooled with chilled water facility and the gas was collected for gas analysis. The reactor was opened and the product was collected in a beaker. Oil, aqueous and solid phases were separated and measured individually. The mixture was filtered using a Buckner flask. The powder was washed with Dichloromethane and water and dried. The liquids (oil and aqueous phase) were separated by solvent extraction method.

Example 16
The process of example 15 was repeated using 10 wt. % of extruded NiMo/Al2O3 catalyst, obtained in example 13A.

Example 17
The process of example 15 was repeated using 10 wt. % of extruded Rh/ZrO2 catalyst obtained in example 14.

Example 18:
Catalytic Hydrothermal Liquefaction using Spirulina
23 g of Spirulina as 20% slurry in water was loaded in a reactor (HTHP reactor, capacity: 300ml). 10 wt. % of extruded CoMo/Al2O3 catalyst, obtained in example 11A (1.897 g w.r.t. ash and moisture free algae) of the present disclosure was added to the reactor. The reactor was then closed. Leak check was done using nitrogen at 120 bar. The nitrogen pressure was released and the required amount of hydrogen (35 bar) was filled and heated to reaction temperature (350°C) with 500 rpm stirring speed. Upon reaching the temperature, the reactor was kept under the same conditions for 30 min. It was then cooled with chilled water facility and the gas was collected for gas analysis. The reactor was opened and the product was collected in a beaker. Oil, aqueous and solid phases were separated and measured individually. The mixture was filtered using a Buckner flask. The powder was washed with Dichloromethane and water and dried. The liquids (Oil and aqueous phase) were separated by gravimetric method.

Example 19
The process of example 18 was repeated using 10 wt. % of extruded NiMo/Al2O3 obtained in example 13A.

Example 20
The process of example 18 was repeated using 10 wt. % of extruded Rh/ZrO2 obtained in example 14.

Example 21
Recovery of the catalyst
The solid residue obtained in example 15 was subjected to sieving to separate the catalyst. The obtained catalyst was then subjected to calcination at 6000C and then subjected to reduction in the presence of hydrogen at 5000C to obtain a catalyst ready for recycle.

Example 22
The process of example 21 was repeated except that the solid residue obtained in example 16 was used.

Example 23
Recycling of the catalyst
The catalyst recovered as per example 21 was used for hydrothermal liquefaction of microalgae. The process of example 15 was repeated.

The comparative results of % crude bio oil yield are provided in the Table No. 2.

Table No. 2:

Runs Crude Bio Oil Yield (%)
Algae, Nannochloropsis Algae, Spirulina
CoMo/Al2O3 obtained in example 11 NiMo/Al2O3
obtained in example 13 CoMo/Al2O3
obtained in example 11 NiMo/Al2O3
obtained in example 13
Catalyst – 1( Fresh) 70 68 57 55
1st Regeneration 69 68 57 56
2nd Regeneration 70 67 58 57
3rd Regeneration 68 69 56 55
4th Regeneration 69 68 56 56
5th Regeneration 70 68 57 55

The comparative properties of the fresh and recovered catalyst are provided in Table No. 3.

Table No. 3:
Sr. No. Catalyst Name XRD (Crystallinity) BET, m2/g Pore volume (cc/g) Pore diameter (Å) NH3-TPD (mmol/g) TGA (% wt loss upto 900°C)
1 Catalyst-1 (Fresh)
, prepared as per example 11A Quasi crystalline 176 0.496 98 0.842 7.20
2 Catalyst-2 (Regenerated), prepared as per example 21 Quasi crystalline 170 0.479 101 0.813 9.55
3 Catalyst-3 (Fresh) prepared as per example 13A Quasi crystalline 181 0.503 96 0.812 11.42
4 Catalyst-4 (Regenerated) prepared as per example 22 Quasi crystalline 165 0.455 100 0.805 9.28

Yield (%) of crude bio oil was calculated as weight of oil product X 100 / weight of moisture and ash free algae.
From the results, it is clear that % crude bio oil yield by using the regenerated catalyst of the present disclosure is similar to that of fresh catalysts.

The following examples illustrate preparation of the catalyst composition using nano-structured support of the present disclosure.
Preparation of nano-structured support:
Example 24:
Solution A was prepared by dissolving 8 g of Pluronic-123 (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) in 75 g of ethyl alcohol.
Separately, Solution B was prepared by dissolving 16 g aluminum iso-propoxide (Al(OPri)3 in the mixture of 10 ml 60% nitric acid and 70 g ethyl alcohol.
Solution B was added to Solution A with stirring. Stirring was continued for 4 h at room temperature. The resultant solution was kept in oven at 60°C for 72 h for evaporation of ethanol and for crystallization. The final powdered nano-structured aluminum oxide was further dried at 110°C for 6 h. The nano-structured material was obtained by removing Pluronic-123 by calcining at 540°C for 6 h under the flow of air.
This calcined material was used as a support for the preparation of a catalyst composition by the process as described for examples 11-14.
Example 25:
In-situ synthesis of mono or multi metallic catalysts of nano-structured aluminum oxide were synthesized by following the same method as described in Example 24. The required amounts of metal salts such as cobalt acetate or nickel acetate with ammonium molybdate, etc. were added during preparation of Solution B. After metal loading, samples were calcined at 540°C in air and followed by reduced at 500°C in H2.
Example 26:
For the preparation of nano-structured zirconium oxide, Solution A was prepared by dissolving 7.5 g of Cetyltrimethylammonium bromide (CTAB) in 25 g of distilled water. Further, 0.5 g of trimethylammonium hydroxide (TMAOH) was added and stirred for 30 min. Solution B was prepared by mixing 53 g of 1-butanol with 33g of 80% solution of zirconium (iv) butoxide. Solution B was added drop wise into solution A with vigorous stirring to obtain a gel. pH of the gel was adjusted to 10.5 – 11. Gel was stirred for 2 h at RT and then it was transferred to 500 ml round bottom flask and refluxed at 90°C for 48 h to obtain nano-structured zirconium oxide was collected by filtration and washing using distilled water. Solid powder of nano-structured zirconium oxide was dried at 110°C for 6 h and calcined at 600°C for 6 h under the flow of air.
This calcined material was used as catalyst support for the preparation of a catalyst composition by the process as described for examples 11-14.
Example 27:
In-situ synthesis of mono or multi metallic catalysts of nano-structured zirconium oxide were synthesized by following the same method as described in Example 26. Metal salts such as cobalt acetate or nickel acetate with ammonium molybdate, etc. were prepared as solution C and added upon addition of solution B into solution A. After metals loading, samples were calcined at 540°C in air and followed by reduced at 500°C in H2.
The catalysts synthesized in examples 24- 27 were used for the conversion of Bio-mass to crude bio-oil as per the procedure described in example 4 for algal species Nannochloropsis and example 7 for algal species Spirulina. The results are depicted in Table No. 4.
Table No. 4:
Catalyst Name Algae Species CBO Yield, %
No Catalyst Spirulina 48
CoMo/gamma Alumina Spirulina 57
CoMo/Nano-structured alumina (Example 24) Spirulina 56
In-situ CoMo/Nano-structured alumina (Example 25) Spirulina 60
CoMo/Nano-structured zirconia (Example 26) Spirulina 59
In-situ CoMo/Nano-structured zirconia (Example 27) Spirulina 62

No Catalyst Nannochloropsis 58
CoMo/gamma Alumina Nannochloropsis 68
CoMo/Nano-structured alumina (Example 24) Nannochloropsis 67
In-situ CoMo/Nano-structured alumina (Example 25) Nannochloropsis 70
CoMo/Nano-structured zirconia (Example 26) Nannochloropsis 65
In-situ CoMo/Nano-structured zirconium oxide (Example 27) Nannochloropsis 68
CoMo/Nano-structured zirconium oxide (Example 26) Nannochloropsis* 75
*Slurry concentration – 35%
The following example illustrates preparation of the catalyst composition using mesoporous zeolite support of the present disclosure.
Example 28:
For the preparation of meso-porous zeolite, Solution A was prepared using 6 g of Cetyltrimethylammonium bromide (CTAB) in 450 g of distilled water. Further, 28.5 ml of ammonium hydroxide (NH4OH) was added and stirred for 30 min. In the above solution, 8 g of zeolite power was added, stirred at room temperature for 20 min and then hydrothermally treated at 120 - 180°C for 10 – 24 h. This was cooled, filtered and washed to obtain final meso-porous zeolite in the powder form. The powder was dried at 110°C for 6 h and calcined at 600°C for 6 h under the flow of air. This calcined material was used as catalyst composition by the process as described for examples 11-14.
The catalysts synthesized in examples 28 was used for the conversion of Bio-mass to crude bio-oil as per the procedure described in example 4 for algae species Nannochloropsis and example 7 for algae species Spirulina. The results are depicted in Table No. 5.
Table No. 5:
Algae Catalyst CBO Yield, %
Nannochloropsis No Catalyst 57
Nannochloropsis Neat Meso-porous Zeolite 61
Nannochloropsis CoMo/Meso-porous Zeolite
(Example 28) 71
Spirulina No Catalyst 46
Spirulina Neat Mesoporous Zeolite 50
Spirulina CoMo/Mesoporous Zeolite
(Example 28) 61

Upgradation:
To obtain desired upgraded crude bio oil which will be equivalent to petroleum crude oil, upgradation of crude bio oil to bio-oil is essential. During the upgradation reaction, maximum numbers of heteroatoms were removed from oil components so that hydrocarbons only with carbon and hydrogen are obtained.

Example 29:
CoMo/Al2O3 catalyst described in Example 1 was used for upgradation study. In a typical experimental condition, 40 g of Spirulina crude bio oil of Example 7 was loaded in the reactor with 10 wt.% of catalysts. Leak check was done using nitrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (425°C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 30
NiMo/Al2O3 catalyst described in Example 2 was used for upgradation study. In a typical experimental condition, 40 g of Spirulina crude bio oil of Example 8 was loaded in the reactor with 10 wt.% of catalysts. Leak check was done using hydrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (375 °C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 31
CoMo/Al2O3 catalyst described in Example 1 was used for upgradation study. In a typical experimental condition, 25 g of Nannochloropsis crude bio oil of Example 15 was loaded in the reactor with 10 wt.% of catalysts. Leak check was done using nitrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (425°C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 32
NiMo/Al2O3 catalyst described in Example 2 was used for upgradation study. In a typical experimental condition, 40 g of Nannochloropsis crude bio oil of Example 16 was loaded in the reactor with 10 wt.% of catalysts. Leak check was done using nitrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (375°C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 33
In-situ synthesized CoMo/nano-structured Al2O3 catalyst described in Example 25 was used for upgradation study. In a typical experimental condition, 40 g of Spirulina crude bio oil of Example 8 was loaded in the reactor with 10 wt.% of catalyst. Leak check was done using hydrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (375 °C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 34
In-situ synthesized CoMo/nano-structured Zirconia catalyst described in Example 27 was used for upgradation study. In a typical experimental condition, 40 g of Spirulina crude bio oil of Example 8 was loaded in the reactor with 10 wt.% of catalyst. Leak check was done using hydrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (375 °C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties.

Example 35
CoMo/mesoporous zeolite catalyst described in Example 28 was used for upgradation study. In a typical experimental condition, 40 g of Spirulina crude bio oil of Example 8 was loaded in the reactor with 10 wt.% of catalyst. Leak check was done using hydrogen. Required amount of hydrogen (35 – 50 bars) was filled and heated to reaction temperature (375 °C) with 500 rpm stirring speed. Upon reaching the temperature, reaction conditions were maintained for 30 min. The reactor was then cooled with chilled water and gas was collected for analysis. Upgraded bio oil, solid mass and catalyst were collected separately. Upgraded bio oil was subjected to Simulated Distillation to ascertain its chemical properties and results are provided in Table No. 6.
Table No. 6:

Catalyst crude bio oil used UBO yield (%) Solid yield (%)
CoMo/Al2O3 Spirulina crude bio oil of example 7 70 18
NiMo/Al2O3 Spirulina crude bio oil of example 8 65 28
CoMo/Al2O3 Nannochloropsis crude bio oil of example 4 52 36
NiMo/Al2O3 Nannochloropsis crude bio oil of example 5 65 27
In-situ CoMo/Nano-structured alumina (Example 25) Spirulina crude bio oil of example 7 63 27
In-situ CoMo/Nano-structured zirconia (Example 27) Spirulina crude bio oil of example 7 67 22
CoMo/Mesoporous Zeolite
(Example 28) Spirulina crude bio oil of example 7 66 25

The obtained crude bio oil and bio-oil were subjected to high temperature distillation separately. The results of high temperature simulated distillation patterns of CBO (crude bio oil) and UBO are provided in Table No. 7.
Table No. 7:
Recovered Mass (%) Temp (°C) for CBO Temp (°C) for UBO
1 145 63
10 212 158
20 260 205
30 304 236
40 351 268
50 380 287
60 416 309
70 461 347
80 510 401
90 570 488
100 704 683

Technical advance and economic significance:
The present disclosure provides a simple, energy efficient, time saving and high yielding process production of crude bio and its up-gradation to bio-oil using a fresh or re-generated catalyst.
The present disclosure provides a process which is capable of producing bio-oil compatible with petroleum crude oil.
The present disclosure provides a process which is capable of producing bio oil containing high carbon content.
The present disclosure provides bio-oil which is free from heteroatoms such as oxygen, nitrogen, sulfur and phosphorus.
The upgradation of crude bio oil to bio-oil in accordance with the present process is carried out in the absence of solvent.
The process steps of conversion of biomass into crude bio oil and subsequent upgradation of crude bio oil to bio-oil are carried out at same temperature and pressure conditions.

Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired objects or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.