Deoxy-liquefaction of Corn Stalk in Subcritical Water with Hydrogen Generated in Situ via Aluminum–Water Reaction

In situ shale or kerogen oil production is a promising approach to developing vast oil shale resources and increasing world energy demand. In this study, cyclic subcritical water injection in oil shale was investigated in laboratory conditions as a method for in situ oil shale retorting. Fifteen non-extracted oil shale samples from Bazhenov Formation in Russia (98 °C and 23.5 MPa reservoir conditions) were hydrothermally treated at 350 °C and in a 25 MPa semi-open system during 50 h in the cyclic regime. The influence of the artificial maturation on geochemical parameters, elastic and microstructural properties was studied. Rock-Eval pyrolysis of non-extracted and extracted oil shale samples before and after hydrothermal exposure and SARA analysis were employed to analyze bitumen and kerogen transformation to mobile hydrocarbons and immobile char. X-ray computed microtomography (XMT) was performed to characterize the microstructural properties of pore space. The results demonstrated significant porosity, specific pore surface area increase, and the appearance of microfractures in organic-rich layers. Acoustic measurements were carried out to estimate the alteration of elastic properties due to hydrothermal treatment. Both Young’s modulus and Poisson’s ratio decreased due to kerogen transformation to heavy oil and bitumen, which remain trapped before further oil and gas generation, and expulsion occurs. Ultimately, a developed kinetic model was applied to match kerogen and bitumen transformation with liquid and gas hydrocarbons production. The nonlinear least-squares optimization problem was solved during the integration of the system of differential equations to match produced hydrocarbons with pyrolysis derived kerogen and bitumen decomposition.

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Enhanced Biodiesel and Ethyl Levulinate Production from Rice Bran through Non Catalytic In Situ Transesterification under Subcritical Water Ethanol Mixture

Materials Science Forum ◽

10.4028/www.scientific.net/msf.964.97 ◽

2019 ◽

Vol 964 ◽

pp. 97-102

Author(s):

Siti Zullaikah ◽

Sri Utami ◽

Rifky Putra Herminanto ◽

M. Rachimoellah

Keyword(s):

Ethyl Acetate ◽

Rice Bran ◽

Subcritical Water ◽

Rice Bran Oil ◽

Ethyl Esters ◽

Ethanol Mixture ◽

Ethyl Levulinate ◽

Polarity Index ◽

Transesterification Method

In-situ transesterification method without catalysts to produce biodiesel (fatty acid ethyl esters, FAEE) from rice bran using subcritical water ethanol mixture has been investigated. This method was found to be efficient since the rice bran oil (RBO) extraction and reaction of RBO into FAEE occur simultaneously. In this process other chemical (ethyl levulinate, EL) was also formed along with FAEE. EL can be used to improve the biodiesel quality by improving the low temperature properties of biodiesel. In this study effect of co-solvent types (without co-solvent, ethyl acetate, chloroform, and n-hexane) and water ethanol ratio (20%, 40%, 50%, 60% and 80%, v/v) on the content and yield of FAEE and EL at subcritical water ethanol mixture (T= 160°C, P= 80 bar, and t= 2 h) were investigated systematically. The content and yield of FAEE and EL obtained was found to be affected by the type of co-solvent. The content of FAEE and EL obtained without co-solvent (ethanol and water polarity index were PI=5.2 and PI=10.2, respectively) and with co-solvent of ethyl acetate (PI= 4.4), chloroform (PI= 4.1) and n-hexane (PI= 0.1) were 55.80% and 3.92%, 68.63% and 1.15%, 65.56% and 2.14%, and 62.00% and 0.93%, respectively. Higher polarity index of co-solvent extracted more RBO, as consequent the yield of FAEE (79.79%) obtained was higher using ethyl acetate as co-solvent. This data also suggested that RBO contains more free fatty acids (FFA= 63.59%) rather than of triglycerides (TG= 24.94%).The content and yield of FAEE and EL decreased with increasing water ethanol ratio. The highest content of FAEE (60.57%) and EL (8.48%) and yield of FAEE (78.03%) and EL (10.92%) were obtained using water ethanol ratio of 20%, v/v.

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An improvement study of biodiesel production from rice bran via non-catalytic in-situ transesterification using a subcritical water-methanol mixture

IOP Conference Series Materials Science and Engineering ◽

10.1088/1757-899x/543/1/012068 ◽

2019 ◽

Vol 543 ◽

pp. 012068

Author(s):

M Yasmin ◽

F D Alfaty ◽

H S Pradipta ◽

M Rachimoellah ◽

S Zullaikah

Keyword(s):

Rice Bran ◽

Subcritical Water ◽

Biodiesel Production ◽

In Situ Transesterification ◽

Methanol Mixture

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Enhanced Biodiesel and Ethyl Levulinate Production from Rice Bran through Non Catalytic In Situ Transesterification under Subcritical Water Ethanol Mixture

Materials Science Forum ◽

10.4028/www.scientific.net/msf.964.234 ◽

2019 ◽

Vol 964 ◽

pp. 234-239

Author(s):

Siti Zullaikah ◽

Sri Utami ◽

Rifky Putra Herminanto ◽

M. Rachimoellah

Keyword(s):

Ethyl Acetate ◽

Rice Bran ◽

Subcritical Water ◽

Rice Bran Oil ◽

Ethyl Esters ◽

Ethanol Mixture ◽

Ethyl Levulinate ◽

Polarity Index ◽

Transesterification Method

In-situ transesterification method without catalysts to produce biodiesel (fatty acid ethyl esters, FAEE) from rice bran using subcritical water ethanol mixture has been investigated. This method was found to be efficient since the rice bran oil (RBO) extraction and reaction of RBO into FAEE occur simultaneously. In this process other chemical (ethyl levulinate, EL) was also formed along with FAEE. EL can be used to improve the biodiesel quality by improving the low temperature properties of biodiesel. In this study effect of co-solvent types (without co-solvent, ethyl acetate, chloroform, and n-hexane) and water ethanol ratio (20%, 40%, 50%, 60% and 80%, v/v) on the content and yield of FAEE and EL at subcritical water ethanol mixture (T= 160°C, P= 80 bar, and t= 2 h) were investigated systematically. The content and yield of FAEE and EL obtained was found to be affected by the type of co-solvent. The content of FAEE and EL obtained without co-solvent (ethanol and water polarity index were PI=5.2 and PI=10.2, respectively) and with co-solvent of ethyl acetate (PI= 4.4), chloroform (PI= 4.1) and n-hexane (PI= 0.1) were 55.80% and 3.92%, 68.63% and 1.15%, 65.56% and 2.14%, and 62.00% and 0.93%, respectively. Higher polarity index of co-solvent extracted more RBO, as consequent the yield of FAEE (79.79%) obtained was higher using ethyl acetate as co-solvent. This data also suggested that RBO contains more free fatty acids (FFA= 63.59%) rather than of triglycerides (TG= 24.94%). The content and yield of FAEE and EL decreased with increasing water ethanol ratio. The highest content of FAEE (60.57%) and EL (8.48%) and yield of FAEE (78.03%) and EL (10.92%) were obtained using water ethanol ratio of 20%, v/v.

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Solubility and dissolution mechanism of 4-chlorotoluene in subcritical water investigated in a fused silica capillary reactor by in situ Raman spectroscopy

Fluid Phase Equilibria ◽

10.1016/j.fluid.2016.05.018 ◽

2016 ◽

Vol 425 ◽

pp. 93-97 ◽

Cited By ~ 10

Author(s):

Ke Bei ◽

Chuanyong Zhang ◽

Junliang Wang ◽

Kai Li ◽

Jinghui Lyu ◽

...

Keyword(s):

Raman Spectroscopy ◽

Subcritical Water ◽

Fused Silica ◽

Dissolution Mechanism ◽

In Situ Raman Spectroscopy ◽

In Situ Raman ◽

Fused Silica Capillary ◽

Silica Capillary

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Characterization of subcritical water oxidation with in situ monitoring and self-modeling curve resolution

Analytica Chimica Acta ◽

10.1016/s0003-2670(03)00354-4 ◽

2003 ◽

Vol 485 (1) ◽

pp. 73-87 ◽

Cited By ~ 8

Author(s):

Paul J. Gemperline ◽

Yu Yang ◽

Zhihui Bian

Keyword(s):

Water Oxidation ◽

Subcritical Water ◽

In Situ Monitoring ◽

Curve Resolution

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Synthesis and application of functionalized ionic liquids as solvent to corn stalk for phenolic resin modification

e-Polymers ◽

10.1515/epoly-2014-0195 ◽

2015 ◽

Vol 15 (3) ◽

pp. 195-201 ◽

Cited By ~ 1

Author(s):

Liying Guo ◽

Bin Zhang ◽

Shiyang Bai ◽

Xiuyun Ma ◽

Zhiming Wang

Keyword(s):

Mechanical Properties ◽

Ionic Liquids ◽

Phenolic Resin ◽

Corn Stalk ◽

X Ray Diffraction ◽

Scanning Calorimetry ◽

X Ray ◽

H Nmr ◽

Good Solubility

AbstractThree functionalized ionic liquids (ILs) of [HeMIM]Cl, [CeMIM]Cl, and [AeMIM]Br that can dissolve corn stalk were synthesized and characterized via Fourier transform infrared spectroscopy (FTIR) and 1H NMR. The dissolved corn stalk was in situ blended with phenol and formaldehyde to produce modified phenolic resin composites. The resulting composites were characterized via FTIR, differential scanning calorimetry, and X-ray diffraction analysis, and tested for their mechanical properties. In addition, the effects of ILs on the dissolution rate of corn stalks and on the mechanical properties of the modified phenolic resin were investigated as well. The results showed that the synthesized ILs presented good solubility toward corn stalk at the optimum temperature of 90°C. After modification with corn stalk dissolved in ILs, the mechanical properties of phenolic resin were significantly improved. At the same conditions, the phenolic resin modified with [AeMIM]Br presented the lowest concentration of free formaldehyde and the best mechanical properties, in which the tensile strength and impact strength were improved from 3.28 MPa and 0.93 kJ/m2 to 9.36 MPa and 5.74 kJ/m2, respectively, but the hardness only changed slightly.

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