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Article
Peer-Review Record

The Composition and Structure of Ultra-Dispersed Mixed Oxide (II, III) Particles and Their Influence on In-Situ Conversion of Heavy Oil

Catalysts 2020, 10(1), 114; https://doi.org/10.3390/catal10010114
by Irek I. Mukhamatdinov *, Aliya R. Khaidarova, Rumia D. Zaripova, Rezeda E. Mukhamatdinova, Sergey A. Sitnov and Alexey V. Vakhin
Reviewer 1: Anonymous
Reviewer 2: Anonymous
Reviewer 3: Anonymous
Catalysts 2020, 10(1), 114; https://doi.org/10.3390/catal10010114
Submission received: 20 December 2019 / Revised: 8 January 2020 / Accepted: 10 January 2020 / Published: 13 January 2020
(This article belongs to the Special Issue Heavy Oil In Situ Upgrading and Catalysis)

Round 1

Reviewer 1 Report

The article is dealing with the composition and structure of ultra-dispersed mixed oxide particles and their influence on the in-situ conversion of heavy oil. Therefore hydrothermal-catalytic experiments were carried out and viscosity measurements as function of reaction time were performed. Different aspects are highlighted such as the change in composition of different oil fractions and changes in the used catalysts as well as mechanistic aspects.

I included a list of comments and suggestions for a better understanding.

 

Line 16: The particle size of catalysts was investigated

Line 17:  the aggregates of 200 nm are formed  

Line 49: The most 48 significant reduction was in the content of alcohol-benzene resins

Line 68: temperature of 360 °C

Line 86: 5000 rpm

Line 91: by subsequent elution with aliphatic and aromatic hydrocarbons. Which elution solvents?

Line 97: previously dehydrated neutral aluminium oxide. Under which conditions?

Line 101: SEM analysis. More information of experimental conditions for SEM and sample reparations are required.

Line 105: the products of thermo-catalytic treatments were studied dependent on the time of laboratory stimulation. Not clear to me, should be reformulated (the products of thermo-catalytic treatments were studied as function of time during laboratory simulation experiments?).

Line 107: Figure 2 should be reorganised: left (250 °C) and right (300 °C) for better comparison.

Line 111: where the given temperature was constantly at 250 °С are presented

Line 118: as heteroatom containing bonds destruct  are cleaved.

Line 118: decomposition reactions

Line 120: These bonds are cleaved

Line 121: The hydrogen donor prevents the formation of free radicals that further could be recombine. The hydrogen donor deactivates free radicals that are formed during thermolysis of asphaltenes and other oil components of oil.  

Line 127: Figure 3 should be reorganised as in Figure 2 (see my remarks) for a better comparison

Line 130: Moreover, deposition of carbonic formations carbonaceous residues and concentration of sulfuric enrichment of sulphur compounds

Line 133: and the content of resins is reduced by the same amount

Line 145: SEM images of the initial catalyst particles (a), and after experiments at 6 (b), 12 (c) and 24 (d) (temperature 300 °C).

Line 151: non-Newtonian fluid

Line 158: steam injection with catalysts

Line160 and line 174: at 250 °C and at 300°C

Line 164: thermal degradation instead of destruction

Line165: with lower molecular mass

Line 168: hydrogen donor

Line169: prevents high molecular weight hydrocarbon formation from polymerization

Line 171: Moreover, the intermolecular interactions of aggregate combinations is weakened and increases the solubility of disperse medium and supports the dispersing of asphaltene aggregates.

Line 176: Tables 2 and 3

Line 180: Generally, maghemite is not stable under the heat treatment. Hence, in the big temperature interval, starting from 200 °С, maghemite converts into hematite [19].

Line 182:  During the catalytic aquathermolysis of oil, the reduction of maghemite to magnetite is due to the interaction of iron oxide with water steam occurs

Line 185: in Tables 2 and 3: the products

Line 191: heavy oil components are converted

Line 197: all maghemite is converted into magnetite

Line 201: depends on conditions of hydrogenation process

Line 203: The catalytic activity of pyrites is higher than pyrrhotines due to the decomposition of pyrite with release of hydrogen sulphide.

Line 204: The hydrogen sulphide may be the source for hydrogen transfer to radicals of degradation products of heavy oil

Line 208: where ?• is the radical of degradation products of heavy oil and ?1? is the hydrogen donor.

Line 215: the catalyst is composed of ultra-dispersed particles with the size of 200 nm size

Line 218: The SEM results

Line 221: It probably corresponds

Line 222: such as carbenes and carboids: carbenes and carboids are rather to be considered as precursors since they are highly reactive intermediates. Please comment.

Line 222: They are formed after the thermal cracking of asphaltenes as a result of the loss of alkyl substitutes and functional groups

Line 225: The physical simulation

Line 226: The catalyst was a mix of iron oxides (II, III), with ultra-dispersed particles

Line 230: the cleavage of C-S bonds in high molecular weight components

Line 274: 14.Vakhin, A.V

Line 291: Heavy Oil in a Catalytic Aquathermolysis System. Petroleum Chemistry

Line 300: oil-soluble catalyst precursor mixtures. Journal

Author Response

Line 16: The particle size of catalysts was investigated

Reply: Corrected.

Line 17: the aggregates of 200 nm are formed

Reply: Corrected.

Line 49: The most 48 significant reduction was in the content of alcohol-benzene resins

Reply: Corrected.

Line 68: temperature of 360 °C

Reply: Corrected.

Line 86: 5000 rpm

Reply: Corrected..

Line 91: by subsequent elution with aliphatic and aromatic hydrocarbons. Which elution solvents?

Reply: Hexane for saturates, toluene for aromatic and toluene+methanol for resins.

Line 97: previously dehydrated neutral aluminium oxide. Under which conditions?

Reply: At 450 degrees for 3 hours.

Line 101: SEM analysis. More information of experimental conditions for SEM and sample reparations are required.

Reply:

MERLIN Field Emission Scanning Electron Microscope (FE-SEM) from Carl Zeiss was used to analyze the morphology and elemental composition of sample surfaces. 

The measurement accuracy is in the range of 0.01-1 %. The elemental analysis was carried out under 20 kV accelerating and working voltages. This avoids the minimal errors. The sounding depth was about 1 µm.   

Line 105: the products of thermo-catalytic treatments were studied dependent on the time of laboratory stimulation. Not clear to me, should be reformulated (the products of thermo-catalytic treatments were studied as function of time during laboratory simulation experiments?).

Reply: the products of thermo-catalytic reactions after various treatment time were analyzed by several methods (SARA composition, oil viscosity and etc.) 

Line 107: Figure 2 should be reorganised: left (250 °C) and right (300 °C) for better comparison.

Reply: Corrected.

Line 111: where the given temperature was constantly at 250 °С are presented

Reply: Corrected.

Line 118: as heteroatom containing bonds destruct  are cleaved.

Reply: Corrected.

Line 118: decomposition reactions

Reply: Corrected.

Line 120: These bonds are cleaved

Reply: Corrected.

Line 121: The hydrogen donor prevents the formation of free radicals that further could berecombine. The hydrogen donor deactivates free radicals that are formed during thermolysis of asphaltenes and other oil components of oil.

Reply: Corrected.

Line 127: Figure 3 should be reorganised as in Figure 2 (see my remarks) for a better comparison

Reply: Corrected.

Line 130: Moreover, deposition of carbonic formations carbonaceous residues and concentration of sulfuric enrichment of sulphur compounds.

Reply: Corrected.

Line 133: and the content of resins is reduced by the same amount

Reply: Corrected.

Line 145: SEM images of the initial catalyst particles (a), and after experiments at 6 (b), 12 (c) and 24 (d) (temperature 300 °C).

Reply: Corrected.

Line 151: non-Newtonian fluid.

Reply: Corrected.

Line 158: steam injection with catalysts.

Reply: Corrected.

Line160 and line 174: at 250 °C and at 300°C

Reply: Corrected.

Line 164: thermal degradation instead of destruction

Reply: Corrected.

Line165: with lower molecular mass

Reply: Corrected.

Line 168: hydrogen donor

Reply: Corrected.

Line169: prevents high molecular weight hydrocarbon formation from polymerization.

Reply: Corrected.

Line 171: Moreover, the intermolecular interactions of aggregate combinations is weakened and increases the solubility of disperse medium and supports the dispersing of asphaltene aggregates.

Reply: Corrected.

Line 176: Tables 2 and 3.

Reply: Corrected.

Line 180: Generally, maghemite is not stable under the heat treatment. Hence, in the big temperature interval, starting from 200 °С, maghemite converts into hematite [19].

Reply: Corrected.

Line 182:  During the catalytic aquathermolysis of oil, the reduction of maghemite to magnetite is due to the interaction of iron oxide with water steam occurs.

Reply: Corrected.

Line 185: in Tables 2 and 3: the products.

Reply: Corrected.

Line 191: heavy oil components are converted.

Reply: Corrected.

Line 197: all maghemite is converted into magnetite.

Reply: Corrected.

Line 201: depends on conditions of hydrogenation process

Reply: Corrected.

Line 203: The catalytic activity of pyrites is higher than pyrrhotines due to the decomposition of pyrite with release of hydrogen sulphide.

Reply: Corrected.

Line 204: The hydrogen sulphide may be the source for hydrogen transfer to radicals of degradation products of heavy oil.

Reply: Corrected.

Line 208: where ?• is the radical of degradation products of heavy oil and ?1? is the hydrogen donor.

Reply: Corrected.

Line 215: the catalyst is composed of ultra-dispersed particles with the size of 200 nm size

Reply: Corrected.

Line 218: The SEM results

Reply: Corrected.

Line 221: It probably corresponds.

Reply: Corrected.

Line 222: such as carbenes and carboids: carbenes and carboids are rather to be considered as precursors since they are highly reactive intermediates. Please comment.

Carbenes and carboids are high-carbon products of high-temperature treatment of oil and its residue. Carbenes are not dissolved in  carbon tetrachloride, while carboids in carbon disulphide.   

Line 222: They are formed after the thermal cracking of asphaltenes as a result of the loss ofalkyl substitutes and functional groups

Reply: Corrected.

Line 225: The physical simulation

Reply: Corrected.

Line 226: The catalyst was a mix of iron oxides (II, III), with ultra-dispersed particles

Reply: Corrected.

Line 230: the cleavage of C-S bonds in high molecular weight components

Reply: Corrected.

Line 274: 14.Vakhin, A.V

Reply: Corrected.

Line 291: Heavy Oil in a Catalytic Aquathermolysis System. Petroleum Chemistry

Reply: Corrected.

Line 300: oil-soluble catalyst precursor mixtures. Journal

Reply: Corrected.

Reviewer 2 Report

In general this is a well composed paper describing a novel and original investigation that is within the remit of the journal.   With that assessment, the paper should be published if some significant questions can be answered satisfactorily.

The authors report that they recovered the nanoparticle catalysts by extraction with toluene.   This raises questions of the extent to which the toluene processing has altered the constituency of the thermolysis/catalytically processed crude oil, after the reaction.

Toluene is a solvent for many aromatic hydrocarbons, could also have extracted some of the higher molecular weight components, such as asphaltenes.   So was the toluene recovered analysed for content of other extracts?

Toluene is soluble in crude oils to some extent, and acts as a plasticisizer  thinner, hence should decrease the apparent viscosity of the resultant material.  To what extent was toluene dissolved in the crude oil from the extraction contacting?   How much toluene was recovered?

Until these questions are addressed, the variation in the composition and the constitutive properties material are in doubt, as there is an uncontrolled variable.   One might argue that in any industrial process that would be used to recover the nanoparticles there would be a similar set of influences, but the extractive recovery is an inherently important issue that has been sidestepped by the authors.  It must certainly be addressed so that the audience are not misled about the reaction dynamics by the additional processing stage. 

Author Response

In the given sentence, the order of the methods was not properly described.  Once the catalytic aquathermolysis process was stopped, the oil from the reactor was put into the centrifuge tube in order to separate it from the water and catalyst particles. Then, the separated oil was sent for further analyzes.

On the other hand, the lower part of centrifuge tube where the catalyst particles are precipitated in oil phase were washed with toluene and centrifuged. The last was repeated until a clear toluene solution was formed in centrifuge tube. After every washing cycle, the solution of crude oil dissolved in toluene was discharged from centrifuge tube and it was filled by pure toluene solution. Then the catalyst particles were dried in an oven.

Reviewer 3 Report

I recommended paper entitled The Composition and Structure of Ultra-Dispersed  Mixed Oxide (II, III) Particles and Their Influence On  In-Situ Conversion of Heavy for publication in Catalysts journal after carried out following issues:

What is current pressure and temperature in Ashal’cha reservoir? Please refer oil viscosity in reservoir temperature. Please present viscosity axis in log scale in all figures. Describe methodology, how catalysts will be put in reservoir.    In Fig.4 please add reference or label to a) and b) subfigures Did you evaluate stability of oil – catalysts binary system in term of settlement ? It is possible to update your methodology to avoid using hydrogen as a particle donor? Hydrogen can affect in oil properties, thus effect of catalyst is hard to separate.

Author Response

The pressure and temperature in Ashalcha field after steam injection is about 20 atm and 180C, correspondingly. The viscosity of oil in reservoir conditions (before stem injection process) is about 1000 mPa.s. However, the viscosity was measured starting from 10C in order to consider the transportation of crude oil. Providing viscosity axis in log scale can alter the visibility of the obtained effect. However, there is no need in reduction of viscosity by several times in order to increase the oil recovery. Even a slight decrease in the content of resins and asphaltenes is important for increasing the oil flow in a porous medium.

The technology of catalyst injection is identical to the tehnology of  CSS (Cyclic Steam Stimulation): steam injection – catalyst suspension injection – steam injection – soak period for several weeks or months -  oil production from the same well.

In fig. 4 shows where what connection (geometric figure) and the duration of the reaction (6, 12, 24 hours in colored lines).

No, we did not evaluate the stability of oil – catalysts binary system in term of settlement. We did not use the gaseous hydrogen, instead we use naphthenic and aromatic compounds – benzene fraction. Such hydrogen donors are necessary to avoid the recombination of radicals after the cracking, hydrogenolysis and hydrocracking reactions.  

Round 2

Reviewer 1 Report

The authors have implemented corrections and additional information. I have only two minor remarks.

 

Line 132: thermal degradation instead of destruction of aliphatic side chains

Line 144: Tables 1 and 2

Author Response

corrections made

Author Response File: Author Response.pdf

Reviewer 2 Report

The authors have responded to my critique about their ambiguity of the description of the processing steps with

"In the given sentence, the order of the methods was not properly described.  Once the catalytic aquathermolysis process was stopped, the oil from the reactor was put into the centrifuge tube in order to separate it from the water and catalyst particles. Then, the separated oil was sent for further analyzes.

On the other hand, the lower part of centrifuge tube where the catalyst particles are precipitated in oil phase were washed with toluene and centrifuged. The last was repeated until a clear toluene solution was formed in centrifuge tube. After every washing cycle, the solution of crude oil dissolved in toluene was discharged from centrifuge tube and it was filled by pure toluene solution. Then the catalyst particles were dried in an oven."

However, it does not appear that their description has changed in the paper (nothing highlighted in yellow) that explains this clarification.   I believe the authors' should be much more explicit about what they did -- put this description, as well as to the implications for the fidelity of the nanoparticle separation -- into the paper.   Glossing over the issue is not in the spirit of primary disclosure -- a peer should be able to reproduce what was done, so the description must be clear, and assess the level of faithfulness of the experimental methodology and results to the support the hypotheses stated.   The authors have apparently paid "lip service" only to my concerns, so I cannot recommend for publication unless they make alterations to the description of the methodology as they have conceded, and modifications to the discussion to clarify the implications for the level of fidelity of their comparison to "without the active principle".

Author Response

description of the methodology done

Author Response File: Author Response.pdf

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