IN202121044692A 审中 用于利用 co2 合成甲醇、从碳氢化合物原料发电的集成工艺和 cu/zn 基催化剂
BRIEF DESCRIPTION OF THE DRAWING: To further clarify advantages and aspects of the present integrated process, a more particular description of the present integrated process will be rendered by reference to specific embodiments thereof, which is illustrated in the appended drawing(s). It is appreciated that the drawing(s) of the present integrated process depicts only typical embodiments of the invention and are therefore not to be considered limiting of its scope. Figure 1: illustrates a schematic process flow diagram depicting an integrated process scheme for the generation of electricity through gasification of the hydrocarbon feedstock along with conversion of CO2 to methanol; Figure 2: illustrates a schematic process flow diagram depicting CO2 to methanol conversion process setup; Figure 3(a): illustrates an XRD chromatogram of Cu/Zn/Al catalyst; Figure 3(b): illustrates a surface morphology (SEM image) of Cu/Zn/Al catalyst; Figure 4(a): illustrates an XRD chromatogram of Cu/Zn/Ce catalyst; Figure 4(b): illustrates a surface morphology (SEM image) of Cu/Zn/Ce catalyst; Figure 5(a): illustrates an XRD chromatogram of Cu/Zn/Zr/Ga catalyst; and Figure 5(b): illustrates a surface morphology (SEM image) of Cu/Zn/Zr/Ga catalyst; BRIEF DESCRIPTION OF THE INVENTION: Solid hydrocarbon feedstocks like coal, petcoke and biomass waste have a huge energy potential. For instance, biomass waste is a major source of renewable energy that is leaving the value chain untapped. The unbalanced waste management practice creates many threatening problems such as (i) huge land area occupied by landfill sites, (ii) Groundwater depletion due to accumulated wastes, (iii) greenhouse gas emissions from numerous waste filling sites, (iv) Marine life threats and many others. On the other side, the huge energy potential of biomass wastes provides an immediate solution to address this waste management problem by bringing the valuable energy from these wastes back to the cycle, i.e., practicing the so called ‘circular economy’. For years, solid wastes are mainly recycled, piled up in landfill sites or incinerated but all these conventional methods further create air pollution and greenhouse gas emission problem. However, thermal treatment of the waste material gives better control in energy recovery besides the huge volume reduction of the solid wastes. Incineration, pyrolysis, and gasification comprises the well-established thermal treatment methods. Incineration though harnesses certain segment of the energy potential also creates emission threats. Thus, pyrolysis and gasification are commercially way forward in waste to energy treatment with controlled emissions. However, in gasification almost 72% of the energy can be recovered with an investment of only 28% energy and the control of gasification process is much simpler compared to that of pyrolysis. Therefore, developing advanced ‘waste to energy’ gasification technology with integrated carbon looping is vital in achieving low-carbon targets especially, in hydrocarbon feedstock management and biomass waste management. The oxygen-based gasification process to produce methanol through heat, power and hydrocarbon feedstock integration provides a better solution for the above cited issues. According to the main embodiment, the present disclosure provides an integrated process and system for utilizing hydrocarbon feedstock in methanol synthesis through CO2 conversion as well as electricity generation. The integrated approach of the present disclosure suggests a superior alternative to use the waste biomass, coal or petcoke for electricity generation and also utilizing CO2 produced in process to methanol production. The present process utilizes multiple feedstocks for gasification using oxygen as a gasifying agent instead of air and the resultant product syngas is used as a fuel for power production. A portion of the exhaust gas from the power generation unit, containing CO2 and H2O streams is recycled back to the gasification unit for conversion to CO. The remaining gas is cooled for the removal of water and the resultant CO2 stream is sent to the methanol generation unit. The electricity produced is further used in an electrolyzer, especially, during non-peak hours for the production of H2 (with O2 as by-product) which is sent to the methanol reactor. The current approach provides a superior way for CO2 utilization to methanol as compared to the syngas-to-methanol pathway. Further, the integration of oxygen produced from the electrolyzer, as a by-product in the electrolyzer unit with both the gasification and power generation units where it is used as a gasifying agent and combustion agent respectively, reduces the capital cost as there is no need for an exclusive air separation unit. Further, this integration makes use of the by-product oxygen from electrolyzer unit as a reactant which otherwise would have been discarded. The figure-1 explains the current invention of an advanced waste to energy conversion through carbon looping. The biomass feedstock basically includes agricultural residues, organic fractions of municipal solid wastes, paper, cardboard, plastic, food waste, green waste etc. The hydrocarbon feedstock to the gasification unit in the current scheme can be coal, petcoke or waste biomass. The solid hydrocarbon feedstock after suitable size reduction is fed to the gasification unit. The gasifying agent can be air, oxygen or steam. However, the oxygen and steam have considerable advantages over air as the gasifying agent. In the proposed present process and system, the oxygen is chosen as the preferred gasifying agent. In the present process the gasification products include a syngas mixture mainly consisting of CO, H2, CO2, CH4 etc. This product syngas mixture is used as a fuel for power generation. The combustion process in the power generation unit is supplied with oxygen (produced in the electrolyzer unit) as the combustion agent. A portion of the exhaust gases from the power generation unit, containing CO2 and H2O as primary constituents is recycled back to the gasification unit for further conversion into CO and H2. Wherein, the CO2 gets converted to CO inside the gasification chamber as per the Boudouard reaction. The H2O in the recycle gas acts as a gasifying agent along with O2 thereby promoting the formation of H2 of higher heating value. The remaining portion of the exhaust gas is cooled for removing the water content thereby producing a resultant pure CO2 stream. The CO2 stream thus produced is sent to the methanol generation system for further hydrogenation. In an embodiment, during the peak hours, the electricity generated through this integrated gasification unit is sent to the main grid, attending the energy consumption of residential homes and industries. The electricity from the power generation unit can be sent to the electrolyzer during off-peak hours for generation of hydrogen. In the electrolyzer, demineralised water is split into H2 and O2 stream using the generated electricity from the power generation unit. The O2 stream from the electrolyzer is used in both the gasification and combustion units as mentioned above. This integration process as disclosed herein serves the purpose of cost reduction (of an exclusive air separation unit for O2 production), by-products recycling (using the by-product O2 stream from electrolyzer as the high-quality oxidizing agent) and exclusion of a separate CO2 capture system. Further, the H2 stream from the electrolyzer is sent to the methanol reactor in the required stoichiometric proportion for production of methanol. The figure-2 depicts a CO2 to methanol system setup which includes a feed section, a reactor section and product separation section. The feed section includes CO2, H2 and N2 streams. The CO2 line includes a booster and heat traced line. All the gas feeds are fitted with pressure regulators, hand valves and mass flow controllers for ensuring the required feed ratio of CO2:H2 to the inlet of the reactor. The N2 gas stream is used for diluting the hydrogen stream during catalyst activation. All the gas streams to the reactor inlet are sufficiently pure (99.9 to 99.999%). The reactor is adapted to convert CO2 to methanol and selected from a fixed-bed reactor, a down-flow reactor and/or a single pass configuration. The flow rates of the individual gas streams are controlled by mass flow controllers. CO2 and H2 in the required composition are premixed before the reactor inlet. The reactor is heated through electrical furnace and the surface of the reactor is insulated to avoid heat loss. The product stream from the reactor outlet passes to the condenser followed by gas-liquid separator. The condenser has a cooling range of (00C to 200C) and liquefies the water and methanol product from the unconverted gas stream. In the gas-liquid separator, the product liquid stream gets segregated from the gas effluent stream at a pressure of 10 to 20 bar. The liquid product stream is then depressurized through a pressure control valve and passed on to the product vessel for further analysis. The gas stream passes through a wet gas flow meter for the flow measurement and analyzed for individual gas compositions and recycled back to the reactor for converting CO2 to methanol, wherein, a Cu/Zn-based catalyst provides conversion of CO2 to methanol. There are very limited studies on Cu/Zn-based catalyst and their preparation process, and the present disclosure specifically provides preparation process of Cu/Zn-based catalyst by using carbamide as an ideal chemical solution. The current process aims at the facile and accelerated precipitation reaction of the Cu/Zn-based catalyst in autoclave reactor under high temperature autogenic pressure conditions. Different heterogeneous catalyst systems of copper, zinc, Alumina, cerium, zirconium and gallium are used for catalysts synthesis with improved properties like better metal ions dispersion, high surface area and high thermal stability. Accordingly, the present disclosure provides a Cu/Zn-based catalyst for methanol synthesis through direct hydrogenation reaction of CO2. The said Cu/Zn-based catalyst comprises a nitrate or an acetate salt of copper, zinc, and one or more nitrate salts of metals selected from alumina, cerium, zirconium, gallium. Further, the Cu/Zn-based catalyst as disclosed herein includes a nitrate or an acetate salt of copper, zinc, and a nitrate salt of alumina, forming a copper/zinc/alumina catalyst, wherein, copper, zinc, alumina each are in weight% ratio of 6.5:2.5:1. Further, the Cu/Zn-based catalyst as discussed herein includes a nitrate or an acetate salt of copper, zinc, and a nitrate salt of cerium, forming a copper/zinc/cerium catalyst, wherein, copper, zinc, cerium each are in weight% ratio of 2.7:3.5:1. Further, the Cu/Zn-based catalyst as disclosed herein includes a nitrate or an acetate salt of copper, zinc, and a nitrate salt of zirconium, and/or gallium, forming a copper/zinc/zirconium/gallium catalyst, wherein, copper, zinc, zirconium, gallium each are in weight% ratio of 5.5:3:1:0.5. Further, the Cu/Zn-based catalyst as disclosed herein shows 10.42 to 19.97 weight% loss at a reaction temperature of 9000C and surface area is 87 to 103 m2/gm. Furthermore, the present disclosure provides a process for preparing the Cu/Zn-based catalyst, wherein, the process comprises a precipitation reaction of a reaction mixture of a nitrate salt, or an acetate salt of metals selected from copper, zinc, and one or more nitrate salt of metals selected from alumina, cerium, zirconium, gallium. Wherein, the said precipitation reaction is carried out in an autoclave reactor under 1000C to 1400C temperature condition and 25 bar autogenic pressure condition. The precipitation reaction of the said reaction mixture is initiated by adding an aqueous solution of carbamide which acts as mild precipitating agent and lifts the pH of the reaction mixture to 13.9. Methanol production, catalyst, and operating parameters: The different catalysts are experimented for methanol production by varying operating parameters like temperature, pressure, CO2:H2 ratio and GHSV. The temperature range can vary from 2000C to 3200C more specifically between 2200C to 2800C. The pressure can vary from 10 to 200 bar more specifically from 40 to 60 bar; the methanol formation is favored at higher pressures according to Le-Chatelier’s principle. The CO2:H2 ratio can vary from 1:2 to 1:10, more specifically from 1:3 to 1:5. The GHSV which is the gas hourly space velocity is varied from 2000 to 10000 hr-1, more specifically in the range from 4000 to 6000 hr 1. Example-1 Cu/Zn/Al catalyst synthesis: The catalyst precursor powder Cu/Zn/Al was prepared with the high pressure solvothermal hydrolysis method. The matrix of the catalyst composition (wt.%) is 6.5:2.5:1. The catalyst is synthesized through the following steps, 1. The autoclave reactor is charged with an aqueous solution containing Cu(CH3CO2)2.H2O(3.72 M), Zn(CH3CO2)2.2H2O (1.40M) and Al(NO3)3.9H2O (1.31M) mixed in an molar ratio of 0.11:0.04:0.04. The pH of the resultant reaction mixture is 6.5. 2. An aqueous solution of carbamide (0.26 mole content) is added as a mild precipitating agent which lifts the pH value of the mixture to 13.9. 3. The autoclave is tightly closed and run for set 1000C-1400C temperature for 4 hours under autogenic pressure (25 bar). During the reaction, metal ions are precipitated by the hydroxide ions that are formed by precipitant. 4. The precipitated product was aged overnight, filtered and washed with distilled water until neutral (pH 7) reaction medium is obtained. 5. The obtained precipitates were dried in an oven at 1000C-1400C for 4 hours and then calcined at 2200C for 4 to 5 hrs. 6. Final Cu/Zn/Al catalyst is obtained as course black powder and is characterized by XRD (phase analysis), ICAP (metal content analysis), SEM (morphology analysis), TGA (thermal stability) and Surface area (morphology analysis). Cu/Zn/Al catalyst testing: The Cu/Zn/Al catalyst as disclosed herein is tested under various temperatures, pressures, GHSVs and CO2:H2 ratios as per the procedure described under detailed description of figure 1 and figure 2. The highest CO2 conversion and methanol selectivity obtained for this catalyst was shown to be 65.56% and 21.49%. The table-1a below enlists the CO2 conversion, methanol selectivity and methanol yield obtained for this catalyst at varying operating conditions. Table-1a Catalyst composition: X% Cu/ y% Zn/ z% Al CO2 conversion, % Methanol selectivity, % Methanol Yield, % T= 260°C, P= 60 bar, GHSV= 5250 hr-1, CO2: H2= 1:3 57.74 15.27 8.82 T= 260°C, P= 40 bar, GHSV= 5250 hr-1, CO2: H2= 1:3 28.14 19.79 5.57 T= 260°C, P= 50 bar, GHSV= 5250 hr-1, CO2: H2= 1:3 30.71 20.48 6.29 T= 260°C, P= 70 bar, GHSV= 5250 hr-1, CO2: H2= 1:3 40.52 21.49 8.71 T= 240°C, P= 70 bar, GHSV= 5250 hr-1, CO2: H2= 1:3 65.56 12.46 8.17 Cu/Zn/Al catalyst physico-chemical properties: Various physico-chemical properties of the Cu/Zn/Al catalyst are determined through the standard and general test methods such as Inductively coupled plasma (ICP-AES), Thermo gravimetric analysis (TGA), Surface Area (SA), XRD (X-ray diffraction), Scanning electron microscope (SEM) analysis. Test results are presented in the below table-1b. Table-1b S. No. Property Cu/Zn/Al 1. ICAP (%) Cu - 41.32 Zn - 15.60 Al - 8.37 2. TGA (wt. loss, wt. %) (RT - 9000C) 11.04 3. Surface Area (m2/gm) 103 Example-2 Cu/Zn/Ce catalyst synthesis: The catalyst precursor powder Cu/Zn/Ce was prepared with the high pressure solvothermal hydrolysis method. The matrix of the catalyst composition (wt.%) is 2.7:3.5:1. The catalyst is synthesized through the following steps, 1. The autoclave reactor is charged with an aqueous solution containing Cu(CH3CO2)2.H2O(2.64M), Zn(CH3CO2)2.2H2O (3.42M), Ce(NO3)2.6H2O (0.44M) mixed in an molar ratio of 0.079: 0.101: 0.013. The pH of the resultant reaction mixture is 6.5. 2. An aqueous solution of carbamide (0.26 mole content) is added as mild precipitating agent which lifts the pH of the mixture to 13.9. 3. The autoclave is tightly closed and run for set 1000C-1400C temperature for 4 hours under autogenic pressure (25 bar). During the reaction, metal ions are precipitated by the hydroxide ions that are formed by precipitant. 4. The precipitated product was aged overnight, filtered and washed with distilled water until a neutral (pH 7) reaction medium is obtained. 5. Obtained precipitates were dried in an oven at 1000C-1400C for 4 hours and then calcined at 2200C for 4 to 5 hrs. 6. Final Cu/Zn/Ce catalyst is course black powder, characterized by XRD (phase analysis), ICAP (metal content analysis), SEM (morphology analysis), TGA (thermal stability) and Surface area (morphology analysis). Cu/Zn/Ce catalyst Testing: The Cu/Zn/Ce catalyst of the present invention is tested under various temperatures, pressures, GHSVs and CO2: H2 ratios as per the procedure described under detailed description of figure 1 and figure 2. The highest CO2 conversion and methanol selectivity obtained for this catalyst was shown to be 50.86% and 60.18%. The table-2a enlists the CO2 conversion, methanol selectivity and methanol yield obtained for this catalyst at varying operating conditions. Table-2a Catalyst composition: X% Cu/ y% Zn/ z% Ce CO2 conversion, % Methanol selectivity, % Methanol Yield, % T= 320°C, P= 65 bar, GHSV= 5242 hr-1, CO2: H2= 1:3 20.55 60.18 12.37 T= 320°C, P= 60 bar, GHSV= 5242 hr-1, CO2: H2= 1:5 23.82 42.74 10.18 T= 320°C, P= 60 bar, GHSV= 4250 hr-1, CO2: H2= 1:3 15.41 59.44 9.16 T= 320°C, P= 60 bar, GHSV= 7250 hr-1, CO2: H2= 1:3 50.86 12.47 6.34 T= 280°C, P= 60 bar, GHSV= 5242 hr-1, CO2: H2= 1:3 20.9 29.23 6.11 Cu/Zn/Ce catalyst physico-chemical properties: Various physico-chemical properties of the Cu/Zn/Ce catalyst are determined through the standard and general test methods such as Inductively coupled plasma (ICP-AES), Thermo gravimetric analysis (TGA), Surface Area (SA), XRD (X-ray diffraction), Scanning electron microscope (SEM) analysis. Test results are presented in the below table-2b. Table-2b S. No. Property Cu/Zn/Ce 1. ICAP (%) Cu - 27.3 Zn - 37.4 Ce - 8.42 2. TGA (wt. loss, wt. %) (RT - 9000C) 10.42 3. Surface Area (m2/gm) 87 Example-3 Cu/Zn/Zr/Ga catalyst synthesis: The catalyst precursor powder Cu/Zn/Zr/Ga was prepared with the high pressure solvothermal hydrolysis method. The matrix of the catalyst composition (wt.%) is 5.5:3:1:0.5. The catalyst is synthesized through the following steps, 1. The autoclave reactor is charged with an aqueous solution of metal salts containing Cu(NO3)2.3H2O (1M), Zn(NO3)2.6H2O (1M), ZrO(NO3)2.H2O and Ga(NO3)2.3H2O (1M) mixed in an molar ratio of 0.34:0.18:0.043:0.028. The pH of the resultant reaction mixture is 6.5. 2. An aqueous solution of carbamide (0.26 mole content) as mild precipitating agent was added, lifting pH of the mixture to 13.9. 3. The autoclave is tightly closed and run for set 1000C-1400C temperature for 4 hours under autogenic pressure (25 bar). During the reaction, metal ions are precipitated by the hydroxide ions that are formed by precipitant. 4. The precipitated product was aged overnight, filtered and washed with distilled water up to neutral (pH 7) reaction medium. 5. Obtained precipitates were dried in oven at 1000C-1400C for 4 hours and then calcined at 2200C for 4-5 hrs. 6. Final Cu/Zn/Zr/Ga catalyst is a course black powder and is characterized by XRD (phase analysis), ICAP (metal content analysis), SEM (morphology analysis), TGA (thermal stability) and Surface area (morphology analysis). (Cu/Zn/Zr/Ga Testing) The Cu/Zn/Zr/Ga catalyst of the present invention is tested under various temperatures, pressures, GHSVs and CO2:H2 ratios as per the procedure described under detailed description of figure 1 and figure 2. The highest CO2 conversion and methanol selectivity obtained for this catalyst was shown to be 25.74% and 41.45%. The table-3a enlists the CO2 conversion, methanol selectivity and methanol yield obtained for this catalyst at varying operating conditions. Table-3a Catalyst composition: X% Cu/ y% Zn/ z% Zr/c% Ga CO2 conversion, % Methanol selectivity, % Methanol Yield, % T= 340°C, P= 60 bar, GHSV= 8000 hr-1, CO2: H2= 1:3 23.42 38.47 9.01 T= 300°C, P= 60 bar, GHSV= 8000 hr-1, CO2: H2= 1:3 21 41.45 8.7 T= 380°C, P= 60 bar, GHSV= 8000 hr-1, CO2: H2= 1:3 25.74 32.23 8.29 T= 260°C, P= 60 bar, GHSV= 8000 hr-1, CO2: H2= 1:3 16.82 36.7 6.17 T= 340°C, P= 60 bar, GHSV= 5000 hr-1, CO2: H2= 1:3 15.64 37.36 5.84 Cu/Zn/Zr/Ga catalyst physico-chemical properties: Various physico-chemical properties of the Cu/Zn/Zr/Ga catalyst are determined through the standard and general test methods such as Inductively coupled plasma (ICP-AES), Thermo gravimetric analysis (TGA), Surface Area (SA), XRD (X-ray diffraction), Scanning electron microscope (SEM) analysis. Test results are presented in the below table-3b. Table-3b S. No. Property Cu/Zn/Zr/Ga 1. ICAP (%) Cu - 40.7 Zn - 8.5 Zr - 4.2 Ga - 2.04 2. TGA (wt. loss, wt. %) (RT - 9000C) 19.97 3. Surface Area (m2/gm) 90 Catalyst physical property characterization methods Inductively coupled plasma (ICP-AES) and Thermo gravimetric analysis (TGA) were performed by standard test methods while the Surface Area (SA), XRD (X-ray diffraction), Scanning electron microscope (SEM) analysis were performed by general procedure. For validation, instrument model numbers as used hereinafter are for reference only. Inductively coupled plasma (ICP-AES) Inductively coupled plasma (ICP) optical emission spectroscopy was used for the determination of metal content of the catalyst. The measurements were performed with a Perkin Elmer Optima 8300 DV spectrometer using ASTM D8088-16. Thermo gravimetric analysis (TGA) This test method is an empirical technique in which the mass of a substance, heated from room temperature to 9000C at a heating rate of 100C min-1 under N2 atmosphere. TGA profile of the catalyst was recorded by TG model 2950 Hi Resolution modulated TGA by ASTM E1131 – 20 test methods. Surface Area The surface area of prepared catalyst was measured by Micromeritics BELSORB-Max PC000668 instrument through adsorption desorption measurements. The sample was degassed under vacuum at 4000C for 2 hours prior to adsorption measurements to evacuate the physisorbed moisture. XRD (X-ray Diffraction) The X-ray diffraction (XRD) patterns of catalysts were recorded on PAN Analytical Empyrean X-ray diffractometer (XRD) with Cu-K radiation at 45 kV and 40 mA. The catalyst powder was grinded fine to ensure random orientation of the molecules so that there are sufficient number of crystals to generate detectable signals of all angles respective to all the components present in the catalyst. The overall peak intensities are often used to estimate the amount of specific crystalline phases. Scanning electron microscope (SEM) SEM analysis was used to study the surface morphologies of catalysts. The topographical images of the catalyst sample were captured by type JSM-6610LV, JEOL, Japan coupled with X-ray energy dispersive spectroscopy. The morphology was observed using an energy dispersive X-ray system. The above disclosed Cu/Zn-based catalysts and their use in the present process and system provides various technical advantages as outlined hereinafter. The catalyst synthesis process involves gradual in-situ dissolution of carbamide under pressure. With the increase of process temperature to 1200C, the degree and rate of precipitating agent increases and results in high surface area and well dispersed small sized Cu/Zn particles. Further, carbamide acts as mild precipitating agent with gradual dissolution effectively controls the nucleation rate of the reaction and results in uniform multi-component dispersion. The prepared catalyst has improved catalytic activity.The use of non-toxic, harmless carbamide compounds as precipitating agent merits to environmentally friendly catalyst for methanol synthesis. Further, the catalyst preparation process does not produce wastewater to the environment unlike the other conventional basic precipitants (NaOH, Na2CO3) and the precipitant aqueous solution can be stored, dosed and decomposed quite easily. Effluent recovered after catalyst washing can be served as N-based fertilizer. The catalyst synthesized through the above novel method gives better single pass CO2 conversion and methanol yield of 65.56% and 12.37 % respectively at the optimized process conditions including temperature, pressure, CO2:H2 ratio and GHSV. Further, the catalyst synthesis process is simple, requires less quantity of metal loading and less reaction time. The catalyst synthesis process is cost effective due to use of inexpensive mild carbamide precipitant. Present in–situ hydrolysis of precipitating agent under pressure provides uniform metal ions dispersion and high surface area catalyst with enhanced catalytic activity. Further, the carbamide precipitant does not require extra storage and special handling care. In general, prepared catalyst is thermally stable up to 8000C in comparison to commercial catalysts. Introduction of carbamide as precipitant, increases the activity of the catalyst. The catalyst for methanol synthesis gives better CO2 conversion at the optimized process conditions. Regarding the hydrocarbon gasification process provided by the present disclosure, it is noted that the oxygen supplied gasification units and combustion units require a dedicated air-separation unit (ASU) for the supply of pure oxygen. The cost of these ASUs account for almost 30% of capital cost since the separation of oxygen from atmospheric air is highly energy intensive. The suggested integration scheme provides a superior option for pure oxygen supply by integrating the electrolyzer unit with the gasification and combustion units thereby neglecting the usage of expensive ASU. Therefore, employing the pure oxygen gas which is a by-product of the electrolyzer unit, as an oxidizing agent in the gasification and combustion units addresses the higher capital investment of the otherwise non-integrated system. Further, the oxygen is a superior gasifying agent as well as combustion agent not only because of the better gasification and combustion efficiencies, but also it produces a product gas mixture comprising fewer impurities. However, air supplied units produce a product mixture comprising 40 to 60% N2. This is a drawback because the air contains up to 79% nitrogen, leading to the produced gas being highly diluted (with low heating value 3.5–7.8 MJ/m3), which increases the cost of gas separation. Therefore, the usage of air as gasification/ combustion agent is often limited to on-site heat and power generation. Further, the increase in the oxygen proportion of air improves the oxidation of tar and char compounds, which diminishes the char and tar content while producing CO and CO2. Thus, the drawbacks of air gasification/combustion like low combustion efficiency, low heating value product gas, high proportion of impurities and deprived oxidation of tar and char compounds in the product gas mixture are addressed by the selection of pure oxygen. Further, in the conventional process of hydrocarbon feedstock gasification, the air combusted unit in power generation produces a gas mixture which needs to be removed of N2 impurities followed by the separation/capture of CO2. This leads to additional cost to the overall system. However, the suggested integration scheme rules out the need for additional impurities separation cost. The CO2 separation from the combustion exhaust gas can be achieved through a simple cooling unit which primarily removes the water content from the exhaust stream. Furthermore, in the present integrated process a portion of the exhaust stream from the power generation unit is recycled back to the gasification unit. The exhaust stream from the power generation unit predominantly contains CO2 and H2O. Recycling a portion of this stream, aids in the conversion of CO2 to CO according to the Boudouard gasification reaction. Therefore, the CO2 emissions from the combustion unit are utilized in the gasification unit for further production of valuable syngas. Also, the H2O composition in the exhaust gas will act as a superior gasifying agent in addition to oxygen, as steam gasification produces a greater amount of H2 with a higher heating value. This is attributed to steam's role in promoting the water-gas shift and steam reforming reactions. In addition, steam decreases the mass yield of tar and char in the final product mixture. Accordingly, from the resultant stream of the combustion exhaust gases, pure CO2 stream is obtained post cooling without capture and the pure H2 stream is obtained from the electrolyser unit. The usage of these streams for direct hydrogenation to produce methanol is proven to be advantageous over the direct usage of syngas to produce methanol. CO2-to-methanol reaction is more selective towards methanol thereby resulting in fewer by-products, and the reaction conditions are milder because CO2 to methanol reaction is less exothermic compared to the syngas to methanol reaction. Further, the present integrated process also offers better carbon utilization compared with conventional syngas. Also, the freedom of adjusting the feed gas stoichiometric ratio depending on the catalyst requirements is superior in the present integrated process, wherein, CO2 and H2 are added as separate pure streams when compared to the syngas which is generated as a mixture of gases in the conventional processes. The CO2 stream from the oxygen-combusted power generation unit is used for methanol generation rather than discarding as exhaust gas. Therefore, the otherwise polluting greenhouse gas is utilized to produce cleaner fuel/chemical – methanol through the catalytic hydrogenation process.
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