Description:FIELD OF THE INVENTION
[0001] The present invention relates to the field of catalysis and fuel production, specifically to a process for co-processing syngas and bio-oils to produce hydrocarbons using a heterogeneous catalyst. The invention majorly focuses on converting renewable feedstocks, such as bio-oils and syngas, into sustainable fuels capable of handling multiple feedstocks and producing a range of hydrocarbon products.

BACKGROUND OF THE INVENTION
[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] The global energy landscape is undergoing a significant transformation due to the urgent need to reduce greenhouse gas (GHG) emissions, particularly carbon dioxide (CO2). International agreements, such as the COP22 and subsequent climate accords, have pushed industries, governments, and researchers to develop alternative fuels that can help mitigate the environmental impact of fossil fuel consumption. One of the primary challenges in this context is the development of sustainable, renewable fuels that can replace or complement traditional petroleum-derived fuels while reducing CO2 emissions.
[0004] Biofuels and synthetic fuels derived from renewable feedstocks are viewed as promising alternatives. However, existing methods for producing these fuels have notable limitations. Among the most well-known processes for converting feedstocks into hydrocarbons are the Fischer-Tropsch (FT) process and the Hydrotreated Esters and Fatty Acids (HEFA) process.
[0005] The FT process is a well-established method for converting syngas (a mixture of carbon monoxide (CO) and hydrogen (H2)) into hydrocarbons. Syngas can be derived from various sources, including natural gas, coal, and biomass through gasification. The FT process, however, has limitations in terms of selectivity. It tends to favor the production of lower-molecular-weight hydrocarbons, such as light gases, and has a relatively low selectivity for longer-chain hydrocarbons, which are needed for the production of fuels like diesel and jet fuel. Furthermore, traditional FT catalysts, while effective for syngas conversion, are not designed to handle the co-processing of bio-derived feedstocks.
[0006] Regarding HEFA, the process is primarily used to convert bio-oils, such as vegetable oils or animal fats, into renewable fuels like diesel and aviation turbine fuel (ATF). This process involves hydrotreating the bio-oil, typically using hydrogen gas, to remove oxygen and convert the feedstock into hydrocarbons. However, the HEFA process also has its limitations. It generates by-products such as CO and CO2, which can reduce overall carbon conversion efficiency and contribute to emissions. Additionally, HEFA is often constrained by the availability of bio-oil feedstocks, which can be subject to seasonal variability and fluctuations in supply due to agricultural and climate conditions.
[0007] Further, one of the major challenges in relying solely on bio-oil feedstocks for renewable fuel production is their limited and uncertain supply. Bio-oils are often derived from agricultural products such as palm oil, jatropha, and other oilseeds, many of which are seasonal and subject to regional climate variations. This makes it difficult to ensure a consistent, year-round supply of bio-oils for industrial-scale fuel production. Moreover, the competition between food and fuel crops, as well as the impact of land-use change, adds further complexity to the large-scale adoption of bio-oils as a primary feedstock for renewable fuel production.
[0008] A review of prior art reveals that patents exist for both the FT and HEFA processes individually, but there is limited information on their integration or co-processing. Some patents discuss bio-oil hydrotreating or syngas-based fuel production, but none have addressed the possibility of co-processing syngas and bio-oils in the same reactor.
[0009] Given the limitations of the FT and HEFA processes, there is a clear need for a more flexible and efficient process that can handle multiple feedstocks, including syngas and bio-oils, either independently or co-fed, to produce hydrocarbons and fill the gap by disclosing a novel catalyst system and process that allows for the co-processing of these two feedstocks, enabling the efficient production of hydrocarbons with improved selectivity and yield.

OBJECTIVE OF THE INVENTION
[0010] An objective of the present invention is to develop a flexible process that can co-process syngas and bio-oils for the production of sustainable hydrocarbons, including fuels such as diesel, ATF, and gasoline.
[0011] An objective of the present invention is to overcome the limitations of traditional FT and HEFA processes by integrating the two feedstocks.
[0012] An objective of the present invention is to perform insitu conversion of CO and CO2 released during conversion of bio-oils to hydrocarbons which helps in increasing the overall carbon conversions and producing sustainable hydrocarbons and fuels.
[0013] An objective of the present invention is to enhance the selectivity and yield of hydrocarbon products, particularly those in the higher carbon range, by leveraging syngas-induced reaction intermediates (SIRI).
[0014] An objective of the present invention is to provide a process that can operate under varying parameters and conditions utilizing various kind of feedstock compositions to ensure year-round fuel production from renewable sources.

SUMMARY OF THE INVENTION
[0015] In an aspect, the present invention presents a novel method for the co-processing of syngas and bio-oils to produce hydrocarbons, addressing the growing need for sustainable and renewable fuel sources in light of global commitments to reduce carbon emissions. By integrating the use of heterogeneous solid catalysts which can perform both FT and HEFA reactions simultaneously, this process not only enhances the efficiency of hydrocarbon production but also provides flexibility in handling various feedstocks.
[0016] In an aspect of the present invention, it discloses a method for co-processing syngas and bio-oil for the production of hydrocarbons, comprising the steps of:
i. preparing a heterogeneous solid catalyst comprising metals;
ii. supplying syngas with an H2/CO ratio of approximately 1.7 as reactant 1;
iii. supplying bio-oil, selected from used cooking oils, pyrolytic oils, or plant-based oils, as reactant 2; wherein reactant 2 is selected from, but not limited to tri-glycerides, fatty acids, carboxylic acids or a combination thereof.
iv. co-feeding the syngas and bio-oil into a fixed bed reactor;
i. conducting the reaction at a temperature of approximately 200-500°C;
ii. conducting the reactions at a pressure 0-60 bar.
[0017] recovering and obtaining hydrocarbons, including products in the boiling ranges of diesel, ATF, and gasoline.
[0018] Various objects, features, aspects, and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

BRIEF DESCRIPTION OF FIGURES
[0019] The accompanying drawings are included to provide a clear understanding of the present invention and a detailed description, and they constitute a part of this complete specification.
[0020] FIG. 1a illustrates the system used for the process claimed.
[0021] FIG. 2 illustrates the FTIR plot for example 6.
[0022] FIG. 3 shows Acid number for example 6.
[0023] FIG. 4 illustrates Simdist plot of Example 6.
[0024] FIG. 5 shows FTIR plot for example 7.
[0025] FIG. 6 shows Acid number for example 7.
[0026] FIG. 7 shows Simdist plot for example 7.
[0027] FIG. 8 shows Iodine number plot for example 7.
[0028] FIG. 9 shows FTIR plot for example 8.
[0029] FIG. 10 shows Acid number for Example 8.
[0030] FIG. 11 shows Simdist plot of Example 8.
[0031] FIG. 12 shows FTIR plot for example 9.
[0032] FIG. 13 shows Acid number for example 9.
[0033] FIG. 14 shows Sim dist plot for example 9.
[0034] FIG. 15 shows Iodine number of example 9.
[0035] FIG. 16 shows FTIR plot for example 10.
[0036] FIG. 17 shows Acid number for example 10.
[0037] FIG. 18 shows Simdist plot of Example 10.
[0038] FIG. 19 shows Iodine number plot of Example 10.
[0039] FIG. 20 shows FTIR plot of example 11.
[0040] FIG. 21 shows Acid number for example 11.
[0041] FIG. 22 shows Simdist plot for example 11.
[0042] FIG. 23 shows Iodine number plot for example 11.

DETAILED DESCRIPTION OF THE INVENTION
[0043] The following is a full description of the disclosure's embodiments. The embodiments are described in such a way that the disclosure is clearly communicated. The level of detail provided, on the other hand, is not meant to limit the expected variations of embodiments; rather, it is designed to include all modifications, equivalents, and alternatives that come within the spirit and scope of the current disclosure as defined by the attached claims. Unless the context indicates otherwise, the term "comprise" and variants such as "comprises" and "comprising" throughout the specification are to be read in an open, inclusive meaning, that is, as "including, but not limited to."
[0044] When "one embodiment" or "an embodiment" is used in this specification, it signifies that a particular feature, structure, or characteristic described in conjunction with the embodiment is present in at least one embodiment. As a result, the expressions "in one embodiment" and "in an embodiment" that appear throughout this specification do not necessarily refer to the same embodiment. Furthermore, in one or more embodiments, the specific features, structures, or qualities may be combined in any way that is appropriate.
[0045] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0046] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference.
[0047] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations.
[0048] It should also be appreciated that the present invention can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0049] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
Definitions
[0050] For the purpose of the present invention, Syngas may be defined as a mixture of CO and H2, with or without CO2, produced through but not limited to the gasification of biomass, coal, Natural gas or other carbonaceous materials, or through steam reforming of natural gas or through conversion of CO2 to syngas. Further, the syngas originated from any source may be used to perform the invention.
[0051] For the purpose of the present invention, bio-oil may be defined as oils derived from biological sources, including used cooking oils, pyrolytic oils, and plant-based oils such as jatropha, sunflower, and palm oils comprising of tri-glycerides, fatty acids, carboxylic acids or a combination thereof.
[0052] For the purpose of the present invention, Co-processing may be defined as the simultaneous conversion of syngas and bio-oils into hydrocarbons using a single catalyst and reactor system.
[0053] In a general embodiment, the present invention relates to a method for co-processing syngas and bio-oil for the production of hydrocarbons, comprising the steps of:
i. preparing a heterogeneous solid catalyst
ii. supplying syngas with an H2/CO ratio of approximately 1-7 as reactant 1;
iii. supplying bio-oil, selected from used cooking oils, pyrolytic oils, or plant-based oils, as reactant 2; wherein reactant 2 is selected from, but not limited to tri-glycerides, fatty acids, carboxylic acids or a combination thereof.
iv. co-feeding the syngas and bio-oil into a fixed bed reactor;
v. conducting the reaction at a temperature ranging from 200-500°C;
vi. conducting the reactions at a pressure 0-60 bar.
vii. recovering and obtaining hydrocarbons, including products in the boiling ranges of diesel, ATF, and gasoline or as any other hydrocarbon stream.
[0054] In another embodiment, the syngas is sourced from, but not limited to, biomass or coal or Natural gas or a combination thereof.
[0055] In another embodiment, the syngas is produced via the reverse water gas shift reaction, converting CO2 to CO.
[0056] In another embodiment, the bio-oil is a pyrolytic oil generated from the pyrolysis of biomass.
[0057] In another embodiment, the bio-oil is an oil derived from biological feedstocks which is edible or non-edible.
[0058] In another embodiment, the bio-oil is a used cooking oil.
[0059] In another embodiment, the reactor effluent comprises hydrocarbons in the boiling ranges of diesel, ATF, and gasoline.
[0060] In another embodiment, the hydrocarbons produced are subjected to hydrogenation or hydro-treating to further refine the product.
[0061] In another embodiment, the reactant 1 is syngas, which primarily consists of CO and H2, potentially containing CO2 and other impurities.
[0062] In another embodiment, the syngas as reactant 1 may be generated through various methods, including, but not limited to the gasification of biomass or coal, reforming of natural gas
[0063] In another embodiment, the syngas can also be produced by converting CO2 into CO via reverse water-gas shift reactions, utilizing CO2 captured from stack emissions or process emissions, either with or without treatment.
[0064] In another embodiment, the Bio-oils, including but not limited to edible and non-edible oils, are designated as reactant 2.
[0065] In another embodiment, the bio-oils mentioned may include used cooking oils, fresh cooking oils, pyrolytic oils (derived from biomass pyrolysis), and plant-based oils such as jatropha, karanja, cashew nut shell liquid, sunflower, palm, and groundnut oils, along with re-processed and refined oils with an initial biological origin.
[0066] In another embodiment, a reactor is employed for the conversion of reactants 1 and 2 as co-fed inputs for hydrocarbon production, utilizing the catalyst produced from the method disclosed herein.
[0067] In another embodiment, a process utilizing a reactor for converting the aforementioned reactant 1 into hydrocarbons over the catalyst produced from the method disclosed herein.
[0068] In another embodiment, the process employing a reactor for converting the aforementioned reactant 2 into hydrocarbons over the catalyst produced from the method disclosed herein.
[0069] In another embodiment, the products generated from the processes in the disclosure may include hydrocarbons, fuels, solvents, petrochemicals, and chemical feedstocks.
[0070] In another embodiment, the processes outlined in the present disclosure may utilize reactors such as, but not limited to, slurry reactors, continuous stirred tank reactors (CSTRs), fixed bed reactors, or fluidized bed reactors to achieve the desired objectives.
[0071] In another embodiment, the constituents may undergo post treatment like distillation, purification, hydrogenation and hydro-treating before the separation of desired streams or their components.
[0072] In another embodiment, the constituents may also be subjected to hydrogenation and hydro-treating after the separation of desired streams or their components.
[0073] In another embodiment, the constituents can be treated through hydrogenation and hydro-treating within the same reactor.
[0074] In another embodiment, the catalysts obtained from the process herein may illustrate the capability to process syngas to fuels where hydrogen concentrations can be adjusted based on the conditions and parameters of the process requirements.
[0075] In another embodiment, the catalysts obtained by the process disclosed herein may effectively process bio-derived oils independently.
[0076] In another embodiment, the catalysts obtained by the process disclosed herein may process bio-derived oils in conjunction with hydrogen, with varying gas / oil ratios based on process requirements.
[0077] In another embodiment, the catalysts obtained by the process disclosed herein may handle the co-feeding of syngas and bio-derived oils, with the conversion reactions for each proceeding independently.
[0078] In another embodiment, the intermediates produced in may undergo oligomerization reactions to yield higher hydrocarbons.
[0079] In another embodiment, the reactor effluent may consist of hydrocarbons, oxygenates, CO, CO2, and water.
[0080] In another embodiment, the effluents described are processed in a downstream separation section.
[0081] In another embodiment, the by-products obtained can be recycled back to the reactor to improve conversions.
[0082] In another embodiment, the by-products can be partially recycled back to the reactor to enhance conversions.
[0083] In another embodiment, the by-products may be considered as product streams, which are managed appropriately or treated before being released into the atmosphere.
[0084] In another embodiment, the hydrocarbons produced or separated can serve commercial or intermediate applications, including but not limited to drop-in fuels, sustainable fuels, renewable fuels, synthetic fuels, petrochemicals, and petrochemical feedstocks and solvents, depending on their physicochemical properties.
[0085] It is understood that in developing a viable co-processing route, the choice of catalyst is critical. Conventional FT catalysts are designed primarily for syngas conversion and may not be effective for bio-oil deoxygenation. Conversely, catalysts used in the HEFA process may not be well-suited for syngas conversion. The present invention addressed this challenge though a heterogenous catalyst that can handle both syngas and bio-oils, either separately or together, in a single reactor. These catalysts not only facilitate the FT reaction but also assist in the cracking, hydrogenation and deoxygenation of bio-oils, enhancing hydrocarbon selectivity and yield.
[0086] Further, Co-processing syngas and bio-oils in a single reactor presents a promising solution. Syngas can be produced from a variety of sources, including non-food biomass, waste materials, and even CO2 captured from industrial emissions, providing a versatile feedstock that complements the bio-oils. Moreover, by integrating the processing of syngas and bio-oils, it is possible to leverage the strengths of both feedstocks while mitigating their individual limitations.
[0087] Accordingly, the integration of syngas and bio-oil co-processing opens new possibilities for enhancing hydrocarbon production. Both FT and HEFA processes generate intermediates such as methylene (-CH2) and methyl (-CH3) groups, which are crucial for carbon chain propagation in the formation of larger hydrocarbon molecules. The co-feeding of syngas and bio-oils allows these intermediates to interact, potentially reducing the number of methylene units needed from syngas alone and increasing the yield of higher carbon number hydrocarbons, such as diesel and jet fuel.
[0088] Furthermore, the co-processing of these feedstocks enables the utilization of syngas as a hydrogen source for the deoxygenation of bio-oils. This could lead to improved efficiency and lower hydrogen consumption, reducing overall process costs. By integrating the two feedstocks, the process also creates a pathway for utilizing CO and CO2, which are often by-products of bio-oil conversion, as valuable reactants in the syngas conversion process.
[0089] As the development of a flexible and efficient process for co-processing syngas and bio-oils is crucial for the future of sustainable fuel production, the present invention addresses the limitations of existing processes and provide a novel catalyst formulation capable of handling multiple feedstocks. The present invention also offers a significant advancement in the production of renewable hydrocarbons. The integration of syngas and bio-oil processing allows for the optimization of feedstock use, enhancing the overall efficiency of fuel production while contributing to global efforts to reduce carbon emissions.
[0090] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. The scope of the invention is determined by the claims that follow. The invention is not limited to the described embodiments, versions, or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
EXAMPLES
[0091] The present invention is further explained in the form of the following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limitations upon the scope of the invention.
[0092] Though the catalyst recipe i.e., composition, constituents, preparation techniques be varied, the current invention discloses couple of such potential recipes which can be used for conversion of syngas and bio-oils as a proof of the novel approach.
Example 1: Formation of Reaction intermediates
This shows the possible conversion route(s) involved in co-processing of bio-oil and syngas to hydrocarbon.
Equation 1

Equation 2

HEFA reaction
Equation 3

Equation 4

[0093] From the above reactions, it is evident and important to note that the Reaction intermediates like ‘E’ are commonly formed in both approaches which are further referred in discussions irrespective of the source. In co-processing this intermediate can react with CO through CO insertion mechanism as shared below and produce hydrocarbons.
Equation 5

At the same time as Intermediate E and F are available on the catalyst, These can react to produce Ketones (hydrocarbons)
Equation 6

Subsequently the intermediate E in both the processes are similar which can react to form alkanes. As these intermediates are identical they can undergo self or cross oligomerization reactions. Self is intermediate from same feedstock, while Cross is intermediate formed from different feedstock.
Equation 7

[0094] Analysis of reactor effluents were performed for identifying these intermediates and thereby establishing the proof of possible formation.
[0095] The bi-functional catalysts is referred as co-processing catalyst as syngas and bio-oil reacts simultaneously over the same catalyst. This catalyst comprises of constituents which can convert syngas to hydrocarbons and also bio-oils to hydrocarbons.
Example 2: Catalyst preparation:
[0096] Catalysts are prepared through wet-impregnation techniques. Where in solution of metal salts was prepared and is added to the support. This preparation technique is an open art and procedures are well established in books and literatures. In the examples the concentration of metals is shared and the amount of salt required for the targeted metal quantity need to be calculated.
[0097] In another approach, constituents other than support are co-precipitated, dried and calcined to form Part A of the catalyst. This is mixed with supports forming a CoMIX catalyst.
Example 3: Preparation of supports
[0098] Commercially available supports are used in the catalyst preparation. Supports in pellets / extrudate form are procured and are powdered. The powdered support is dried at 120oC before adding the metal solution, this drying is to remove moisture from the support.
Example 4: Catalyst activation
[0099] The catalyst produced is loaded into the reactor and is initially subjected to insitu activation (activated within the reactor) using 10% Hydrogen and balance nitrogen. The activation process involves controlled temperature raise and holdup which took about 48 hours for completion. The purpose of activation process is to convert catalyst from its oxide form to active phase. In the current experiments catalyst is reduced to metallic form.
[00100] Note: catalyst can also be active in sufided, carbide and oxide phases as well, but activation media will get changed accordingly. The objective of activation is to ensure that the catalyst is in desired active state as required
Example 5: Experimental setup
[00101] The developed catalyst is tested in a fixed bed reactor setup, whose typical configuration is as shared in FIG. 1. This is an open art involving conventional equipment(s). In the depicted bio-oil and syngas (a and b) are fed to reactor consisting of catalyst bed. The reactor temperatures in the test setup are maintained through heater while commercially it can be through any other means. Post reaction the reactor effluent (d) is a cocktail of products, unreacted constituents and by-products. These reactor effluents are initially separated using a phase separator where these are cooled and are flashed for separation. The gases and liquid streams may still consist of products, unreacted constituents and by-products which are further purified and converted to finished products using various techniques. Further, while discussing the examples, these liquid (f) and gaseous (e) streams shall be referred as product streams.
[00102] The operating conditions of the reactors are dependent on the kind of bio-oil and the targeted products. For example, if lighter bio-oils are used then the temperatures can be below 300oC also but most of the reported bio-oils crack at above 350oC. During the preliminary experiments the feedstock cracking characteristics are evaluated at temperatures ranging from 250-400oC . Though the operating conditions can be beyond 400 C, but in the current experiments this was limited to 400oC due to setup limitations. Furthermore, lowering the temperatures will also provide advantage in metallurgy and energy savings.
Example 6: Cobalt and Y-Zeolite based catalyst with co-processing feed
[00103] A catalyst with composition Co-Zn-Yzeolite catalyst is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 350oC, 30barg pressure at Gas/oil ratio of 380 (Gas / oil ratio is volumetric ratio of Syngas /Used cooking oil at which they are being fed to the reactor) where in the feed syngas is having a H2:CO ratio of 2:1. A space velocity LHSV of 725 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and WHSV of 6.07 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00104] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where in presence of various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category.
[00105] FIG. 2(g) and FIG. 2(h) shows the presence of esters in feed UCO, which were completely converted with formation of carboxylic acid in product stream. As a result, a comparative increase in carboxylic acid content was seen as observed in FIG. 2(h). The formation of these carboxylic acids can be validated with increase in Acid number as shared in FIG. 3. These carboxylic acids are intermediates and get converted to hydrocarbons during the process which can be observed from FIG. 2(c).
[00106] From FIG. 2 and FIG. 3 it is evident that UCO conversion and hydrocarbon formation took place. This change imparted an effect on boiling point distribution of liquid product in comparison to the feed. This can be inferred from FIG. 4, where a miniscule change and improved diesel range yield can be inferred.
[00107] In order to prove co-processing along with UCO conversions, it was important to ascertain the conversion of CO as well. In the current example, a negative CO conversion was reported. This is because during deoxygenation of UCO, CO released through decarbonylation route got added to the gaseous reactor effluent.
[00108] It is important to note that this CO is in feed and also generated as an intermediate. So, the amount of CO released and consumed during the process cannot be calculated. But for proof-of-concept CO should get reacted with UCO or with its intermediates. This can be established through FIG. 2 (i) where ketones are formed through CO insertion. The reaction chemistry establishes the pathway for conversion of esters to carboxylic acids which in turn get converted to alcohols and then to hydrocarbons. but the ketone formation is possible through CO insertion approach.
Example 7: Cobalt and gamma alumina-based catalyst recipe 1 with co-processing feed.
[00109] A catalyst with composition Co-Pt-Gamma Alumina is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 350oC, 30barg pressure at Gas/oil ratio of 380 (Gas / oil ratio is volumetric ratio of syngas/Used cooking oil at which they are being fed to the reactor) where in the syngas has H2:CO ratio of 3:1. The increase in hydrogen concentration is expected to improve CO conversions. A space velocity LHSV of 640 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and a WHSV of 5.93 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00110] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where in presence of various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category. FIG. 5(g) and FIG. 5(h) shows a minuscule conversion of esters in feed UCO to carboxylic acids, while as discussed earlier apart of carboxylic acids might have also got converted to products. This is validated with the alkenes formation identified in FIG. 5(c). As an increase in carboxylic acid content is inferred in FTIR plots, the next evaluations deal with this validation. This is done by comparing the acid number of feed and reactor liquid effluent stream. The increase in carboxylic acid content should increase the acid number and the same is inferred from FIG. 6. This justifies the conversion of esters to carboxylic acids and then to hydrocarbons. From FIG. 5 and FIG. 6 it is evident that the s conversion and hydrocarbon formation took place. This change imparted on boiling point distribution of liquid product in comparison to the feed. This can be inferred from FIG. 7, where a miniscule change and improved diesel range yield can be inferred.
[00111] While conversion of UCO is discussed herein, it is also important to ascertain the conversion of CO as well. Unlike the previous example in the current study CO was not released, but was rather consumed. The formation of ketones in FIG.5 (i) establishes the formation of ketones which are formed through CO insertion as per the reactors discussed earlier. Though there is no much change in the yields, but the CO conversion got improved to 90%. Despite of such high conversions the low yields are due to formation of lighter hydrocarbons and formation of higher hydrocarbons through CO insertion route. Iodine number of liquid product is analyzed to assess the hydrogenation capabilities of the catalyst and is as shared in FIG. 8. The unsaturation levels in product were less than the feed. Further experiments are conducted to focus on improved yields.

Example 8: Cobalt and gamma alumina-based catalyst recipe 2 with co-processing feed.
[00112] A catalyst with composition Co-Ni-Gamma Alumina catalyst is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 400oC, 30barg pressure at Gas/oil ratio of 1935 (Gas / oil ratio is volumetric ratio of syngas/Used cooking oil at which they are being fed to the reactor) where in the syngas has H2:CO ratio of 2:1. Lower hydrogen concentrations are targeted to reduce the formation of lighter hydrocarbons. A space velocity LHSV of 910 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and a WHSV of 1.47 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00113] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category.
FIG. 9(g) and FIG. 9(h) shows a minuscule conversion of esters in feed UCO to carboxylic acids, while apart of carboxylic acids might have also got converted to products, but the same is ruled out as there was no alkane and alkene formation identified in FIG. 9(b, c, d, e). But a slight increase in carboxylic acid content is inferred is FIG. 9(h) the same resulted an increase in acid number as shared in FIG. 10.
[00114] From FIG. 9 and FIG. 10 it is evident that negligible UCO conversion took place, however any conversion through CO will result a change in boiling point distribution of feed and liquid product effluent. This distillation curve is also important to assess the yield of fuel range hydrocarbons. from FIG. 11 wherein we can find almost no change in boiling point distribution and a slight CO conversion was also observed signifying the consumption of CO released during the UCO conversion.
Example 9: Iron and gamma alumina-based catalyst recipe 1 with co-processing feed.
[00115] A catalyst with composition Fe-Co-K-Gamma Alumina catalyst is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 400oC, 30barg pressure at Gas/oil ratio of 1364 (Gas / oil ratio is volumetric ratio of syngas/Used cooking oil at which they are being fed to the reactor) where in the syngas has H2:CO ratio of 2:1. A space velocity LHSV of 846 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and a WHSV of 1.87 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00116] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category.
[00117] FIG. 12(g) and FIG. 12(h) shows conversion of esters in feed UCO to carboxylic acids, while apart of carboxylic acids might have also got converted to products, as there was some alkene formation identified in FIG. 12 (c). the conversion of esters to carboxylic acid content is also validated through increase in acid number as shared in FIG.13.
[00118] From above results it is evident that UCO conversion took place. The cracking induced in the reaction and the formation of alkenes resulted a change in boiling point distribution of liquid product with respect to feed and the same can be inferred from FIG. 14. This also shows that major fraction of ATF and Diesel range molecules along with a miniscule amount of gasoline are present in the liquid product. Due to the involvement of cracking reactions and a significant hydrocarbon yield, iodine number is analysed for assessing the hydrogenation characteristics. Though FIG. 15 shows improved iodine numbers when compared to feed but inorder to use as fuel the liquid product need to undergo post treatment.
[00119] Furthermore, the objective of Co-processing is to convert CO and CO2 along with UCO. The formation of Ketones identified from FTIR analysis in FIG. 12 (i) establishes the support required for involved CO insertion reactions. Furthermore, the studies reported a CO conversion of about 25% under the conditions and catalyst discussed in this example. Which implies that the catalyst was able to convert all the CO release during UCO conversion along with a considerable fraction of feed CO.
[00120] Example 10: Iron and gamma alumina-based catalyst recipe 2 with co-processing feed.
[00121] A catalyst with composition Fe-Co-K-Mo-Gamma Alumina catalyst is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 400oC, 30barg pressure at Gas/oil ratio of 4762 (Gas / oil ratio is volumetric ratio of syngas/Used cooking oil at which they are being fed to the reactor) where in the syngas has H2:CO ratio of 2:1. A space velocity LHSV of 1000 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and a WHSV of 1.07 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00122] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category.
[00123] FIG. 16(g) and FIG. 16(h) shows near complete conversion of esters in feed UCO. Though as per pervious examples and involved chemistry esters first get converted to carboxylic acids and the Two other intermediates before getting converted to hydrocarbons. But unlike earlier examples in this case, a negligible amount of carboxylic acid presence was observed as shown herein the present disclosure and in FIG. 16(h). Which leaves an impression that either carboxylic acid is not formed or it is also completely converted into hydrocarbons. But a slight increase in acid number be inferred from FIG. 17 which signifies the formation of carboxylic acids during the process.
[00124] As per reaction pathway the carboxylic acids was converted to alcohols before converting to hydrocarbons and presence of these alcohols in liquid product are validated from FIG. 16(f), while the miniscule amount supports that these intermediates are also converted to subsequent products. The overall impact of these can be seen in FIG. 18 where almost 80% of the product is falling under fuel range with a considerable yield of gasoline and ATF.
[00125] Due to the involvement of cracking reactions and a significant hydrocarbon yield, iodine number is analyzed for assessing the hydrogenation characteristics. FIG. 19 shows improved iodine numbers when compared to feed and are very close to the fuel range specifications, but in order to use as fuel the liquid product need to undergo post treatment. But this showcases the good hydrogenation characteristics and the same can be observed from FIG. 16(d) through reported formation of alkanes.
[00126] Furthermore, the objective of Co-processing is to convert CO and CO2 along with UCO. The formation of Ketones identified from FTIR analysis in FIG. 16 (i) establishes the support required for involved CO insertion reactions. The low intensity of peak resembled maximum conversion of these ketones also to products. Furthermore, the studies reported a CO conversion of about 45% under the conditions and catalyst discussed in this example. Which implies that the catalyst was able to convert all the CO release during UCO conversion along with a considerable fraction of CO fed through syngas.
Example 11: Iron and gamma alumina-based catalyst recipe 2 as in example 18 with Co-processing feed and temperature of 375oC
[00127] A catalyst with composition Fe-Co-K-Mo-SiO2 catalyst is loaded into a fixed bed reactor. Post activation catalyst is evaluated at 375oC, 30barg pressure at Gas/oil ratio of 4762 (Gas / oil ratio is volumetric ratio of syngas/Used cooking oil at which they are being fed to the reactor). A space velocity LHSV of 647 h-1 (this is the volumetric ratio of total feed to catalyst) is maintained and a WHSV of 1.07 (this is the mass flowrate of feed per hour / weight of catalyst). The experiments were conducted for 17 hours and samples are collected for analysis.
[00128] The liquid product is analyzed using FTIR (Fourier Transform Infrared Spectroscopy) where various hydrocarbon with and without functional groups were identified. These FTIR plots are compared with that of feed to identify the conversions with respect to class and category
[00129] FIG. 20(g) and FIG. 20(h) shows near complete conversion of esters in feed UCO. Though as per pervious examples and involved chemistry esters first get converted to carboxylic acids and the two other intermediates before getting converted to hydrocarbons. In this case also we can see a negligible amount of carboxylic acid presence in FIG. 20(h). Which leaves an impression that either carboxylic acid is not formed or it is also completely converted into hydrocarbons. But a slight increase in acid number be inferred from FIG. 21 signifying the formation of carboxylic acids during the process.
[00130] As per reaction pathway, the carboxylic acids gets converted to alcohols and we can see negligible amount of alcohol presence in FIG. 20(f) stating almost complete conversion of alcohols. The overall impact of these can be seen in FIG. 22 where almost 80% of the product is falling under fuel range with a considerable yield of gasoline and ATF.
[00131] Due to the involvement of cracking reactions and a significant hydrocarbon yield, iodine number is analyzed for assessing the hydrogenation characteristics. FIG. 23 shows improved iodine numbers when compared to feed and are very close to the fuel range specifications, but in order to use as fuel the liquid product need to undergo post treatment. The formation of alkenes was identified through FTIR plots in FIG. 20(c).
[00132] Furthermore, the objective of Co-processing is to convert CO and CO2 along with UCO. The studies reported a CO conversion of about 8% under the conditions and catalyst discussed in this example. Which implies that the catalyst was able to convert all the CO release during UCO conversion along with a portion of CO fed through syngas.
[00133] From the distillation curves the fraction of reactor effluent in the boiling range of various fuels is summarized below.

Table 1 : Yield summary of the examples based on simdist plots
Gasoline Till ATF Till Diesel >375C
Feed 0 0 3.33 96.67
Example 5 0 2.30 20.76 79.24
Example 6 8.95 22.88 35.97 64.03
Example 7 0.00 1.23 5.43 94.57
Example 8 2.77 24.45 64.93 35.07
Example 9 9.49 49.54 77.49 22.51
Example 10 4.13 29.52 72.43 27.57

[00134] The reaction chemistry enlightens the possibility of multiple functional group constituents during the conversions. The presence of these is validated through FTIR studies for which experiments are conducted at varying conditions for validating the pathway through identification of intermediates
[00135] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.

ADVANTAGES OF THE PRESENT INVENTION
[00136] The present invention establishes the possibility of co-processing both syngas and bio-oils
[00137] This approach can help in converting CO2 to CO and then to products thereby can be a potential technology for carbon capture and utilization techniques.
[00138] The present invention also provides a process for producing hydrocarbons using a wide variety of bio-oils and syngas, allowing for continuous operation despite seasonal or geographic feedstock variability.
[00139] By co-processing syngas and bio-oils, the process increases the production of higher carbon number hydrocarbons such as diesel and ATF.
[00140] The use of renewable feedstocks like bio-oils and syngas derived from CO2 capture contributes to reducing carbon emissions, aligning with global sustainability goals.
[00141] The developed catalyst system optimizes reaction conditions to balance the production of hydrocarbons from both feedstocks, enhancing overall process efficiency.
[00142] The ability to process syngas produced from CO2 further supports global efforts to mitigate climate change.
The process helps to reduce CO and CO2 released during bio-oil conversions.
, Claims:1. A method for co-processing syngas and bio-oil for the production of hydrocarbons, comprising the steps of:
i. preparing a heterogeneous solid catalyst;
ii. converting the catalyst to its active phase;
iii. supplying syngas with an H2/CO ratio of approximately 1-7 as reactant 1;
iv. supplying bio-oil as reactant 2;
v. co-feeding the syngas and bio-oil into a fixed bed reactor;
vi. conducting the reaction at a temperature ranging from 200-550°C;
vii. conducting the reaction at a pressure in the range of 0-60 bar.
viii. recovering and obtaining hydrocarbons, including products in the boiling ranges of diesel, ATF, and gasoline.
2. The method as claimed in claim 1, wherein the bio-oil is selected from, but not limited to used cooking oils, pyrolytic oils, or plant-based oils
3. The method as claimed in claim 1, wherein said reactant 2 is selected from, but not limited to tri-glycerides, fatty acids, carboxylic acids or a combination thereof.
4. A method for converting syngas and bio-oil into hydrocarbons, comprising:
i. using syngas, primarily comprising CO and H2, with or without CO2, as a reactant;
ii. using bio-oil as a co-reactant, where the bio-oil includes used cooking oils, pyrolytic oils, or other plant-based oils;
iii. co-feeding the syngas and bio-oil over a heterogeneous catalyst.
iv. conducting the reaction in a single reactor or a system comprising multiple reactors or a combination of multiple types of reactors under conditions suitable for hydrocarbon production.
5. The method as claimed in claim 4, wherein the reactor effluent comprises hydrocarbons including hydrocarbons in the boiling ranges of diesel, ATF, and gasoline.
6. The method as claimed in claim 4, wherein the hydrocarbons produced may be treated / purified before using as finished product.
7. The method as claimed in claim 4, wherein the organic compounds produced may be treated / purified before using as finished product.
8. The method as claimed in claim 4, wherein the syngas and UCO are fed into the reactor separately and allowed to react and interact in a same reactor.
9. The method as claimed in claim 8, wherein a part of required syngas is fed along with UCO and the rest is fed separately at single or multiple points into the reactor.
10. The method as claimed in claim 8, wherein feeding syngas constituents into the reactors is performed independently as individual gases.