Development of (γ-Al2O3-Zeolite Y)/α-Al2O3-HPCM Catalyst based on Highly Porous α-Al2O3-HPCM Support for Decreasing Oil Viscosity
Round 1
Reviewer 1 Report
I think the quality of this manuscript is not enough to be published in Catalysts. The contents of this manuscript are considered to be more a technical report than a research paper. In addition, there are so many typo and grammatical errors and the level of English is very low. It is recommended that the manuscript should be reviewed by a native English speaker before submission.
Author Response
Dear Reviewer, we have corrected the errors that were indicated. All corrections are highlighted in the manuscript.
Author Response File: 
Author Response.pdf
Reviewer 2 Report
This paper describes the high porous celled catalyst for the oil viscosity decrease. The catalyst was synthesized by a template synthesis, and the catalyst activity was determined in the experiments to the heavy oil viscosity decrease having the dynamic viscosity about 3000 cPs. The catalyst was characterized using XRPD, SEM, specific surface area, pore volume, pore size analysis and TPD etc. The traditional granular catalyst (i.e., the thermal process) was also used for comparison.
The methodological approach seems effective and appropriate. The paper was well organized and the results are important for the field of catalyst engineering, energy and environmental science. There is no problem regarding English. Therefore, I feel this paper should be acceptable after minor revision in view of the following specific comments.
(1) It would be interesting if the authors could describe the study implications for now and the future.
(2) The lettering in Figure 1 is not clear (or the font size is small), and difficult to read. Please revise.
Author Response
Dear reviewer, we have corrected the errors that were indicated. All corrections are highlighted in the manuscript.
Author Response File: Author Response.pdf
Reviewer 3 Report
file attached
Comments for author File: Comments.pdf
Author Response
Dear Reviewer, we have corrected the errors that were indicated. All corrections are highlighted in the manuscript.
Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
Lines 12-13: The author wrote “α-Al2O3” and zeolite Y was applied on the α-Al2O3-HPCM surface. However, the catalyst was denoted as “γ-Al2O3” (85%)-zeolite Y (15%)/α-Al2O3-HPCM). Which one is right between “α-Al2O3” and “γ-Al2O3”? Line 18: Is “50” cPs right? On Table 3, it is 40 cPs. In addition, what means “micron/h”? Is it same to “mL/h” on Table 3? Lines 25-33: It is desirable to make the three paragraphs into one paragraph. Line 34: Remove the second “use”. Line 46: Revise “transition the metals” to “transition metals”. Line 56: Is “3000” cPs right? Is not “2500”? Lines 54-57: Is it first time to synthesize the HPCM catalyst in this work? And also is the first time it is applied to the process of decreasing oil viscosity? If yes, the authors can emphasize these points in the introduction part. If not, the relevant literature should be referred here. Lines 91-102: See lines 91 to 97 and lines 97 to 102. One of them should be removed. Lines 119-121: The authors said the reactions were conducted with an isothermal (and isobar) flow (and it should be a fixed-bed) reactor as shown in Figure 2. In the condition of 400 oC and 1 kgp/sm2, is the heavy oil with 2500 cPs (at 20 oC) liquid or gas phase? In other word, is it liquid or gas phase reaction? If the phase is liquid, is there no problem with channeling in the flow fixed-bed reactor? Lines 122-126: The weight of catalyst is different, 8.7 g vs 1.25 g. In addition, the weight ratio of catalyst to feed is also different, 2.5:1 vs 11.7-14.6:1. Why? How these values can be determined? Without the specific basis, there is no meaning that the discussion of catalytic comparison between the traditional granular catalyst and the newly synthesized HPCM catalyst on Tables 3-5. Lines 132-145: What means “d/l”? Because the XRD data (Figures 3-5) are shown as 2-theta (degree), it is better to use “2-theta” rather than “d/l” or “d” values in their discussion. Line 134: The two words “and” are quite weird. Lines 137-139: It is quite confusing that “the highly porous catalyst for the highly porous support and the highly porous support with supported active component”. Lines 139-145: The authors discussed first highly porous support (Figure 5) and then highly porous catalyst (Figure 4). Thus, the order of figures should be changed. Lines 153-170: It looks quite confusing for the readers. The materials were named as “highly porous support” and “highly porous catalyst” but their textural characterization results showed “no porosity”. The authors should be more kind and appropriate about this point for the readers. Line 155: What means “sm3/g”? Is not “cm3/g”? Line 162: “Table 2” should be changed to “Table 1”. Line 167: Replace a Russian letter in Table 1. Line 173: Because NH3-TPD is not a spectroscopy, “spectrum” is not appropriate. Lines 176-177: Is it true that 21, 28, and 51% for weak, medium, and strong, respectively? Figure 7 doesn’t look like that. Line 185: “Thermoprogrammed desorption of ammonia” can be removed. Line 187: Is “Average” right? Is not “Medium”? What means “mkmol/m2”? Lines 191-192: The figure number 8A,B, 8C,D should be checked. Line 215: Change “mL/hour” to “mL/h”. Line 230: Is “147” right? Is not “137”? Line 248-249: Change “TPD-NH3” to “NH3-TPD”.Author Response
Lines 119-121: The authors said the reactions were conducted with an isothermal (and isobar) flow (and it should be a fixed-bed) reactor as shown in Figure 2. In the condition of 400 oC and 1 kgp/sm2, is the heavy oil with 2500 cPs (at 20 oC) liquid or gas phase? In other word, is it liquid or gas phase reaction? If the phase is liquid, is there no problem with channeling in the flow fixed-bed reactor?
The oil was in gas-liquid form in the reactor under 400 oC and 1 kgp/sm2. In this work the highly porous celled material was used. The primary advantage of this materials is the random position of the cells. This cells position provides the uniform mass transfer of the total volume of the loadable catalyst based on the highly porous support compared to the catalyst which has the honeycombed structure.
Lines 122-126: The weight of catalyst is different, 8.7 g vs 1.25 g. In addition, the weight ratio of catalyst to feed is also different, 2.5:1 vs 11.7-14.6:1. Why? How these values can be determined? Without the specific basis, there is no meaning that the discussion of catalytic comparison between the traditional granular catalyst and the newly synthesized HPCM catalyst on Tables 3-5.
In the experiments the traditional catalyst was used in amount of 8.7 g, which amounts 10.5 ml. Therefore, in the highly porous catalyst tests the was used 10.5 cm too. But due to its highly porous structure the highly porous catalyst mass was 1.25 g. In the traditional granular catalyst and highly porous catalyst tests the oil feed speed was constant 20 mL/h (which amounts 19.6 g/h). The oil feed speed in the c.u. was measured as the ratio of the oil input amount g/h to the loading catalyst mass. Accordingly this ratio the feed speed in the c.u. in the granular catalyst presence was 2.3, and for the highly porous catalyst – 16.
Lines 176-177: Is it true that 21, 28, and 51% for weak, medium, and strong, respectively? Figure 7 doesn’t look like that.Line 185: “Thermoprogrammed desorption of ammonia” can be removed.
We recalculated the data. Thank you.
Other errors have been corrected in the article.
Author Response File: 
Author Response.docx
Reviewer 3 Report
file attached
Comments for author File: Comments.pdf
Author Response
Lines 119-121: The authors said the reactions were conducted with an isothermal (and isobar) flow (and it should be a fixed-bed) reactor as shown in Figure 2. In the condition of 400 oC and 1 kgp/sm2, is the heavy oil with 2500 cPs (at 20 oC) liquid or gas phase? In other word, is it liquid or gas phase reaction? If the phase is liquid, is there no problem with channeling in the flow fixed-bed reactor?
The oil was in gas-liquid form in the reactor under 400 oC and 1 kgp/sm2. In this work the highly porous celled material was used. The primary advantage of this materials is the random position of the cells. This cells position provides the uniform mass transfer of the total volume of the loadable catalyst based on the highly porous support compared to the catalyst which has the honeycombed structure.
Lines 122-126: The weight of catalyst is different, 8.7 g vs 1.25 g. In addition, the weight ratio of catalyst to feed is also different, 2.5:1 vs 11.7-14.6:1. Why? How these values can be determined? Without the specific basis, there is no meaning that the discussion of catalytic comparison between the traditional granular catalyst and the newly synthesized HPCM catalyst on Tables 3-5.
In the experiments the traditional catalyst was used in amount of 8.7 g, which amounts 10.5 ml. Therefore, in the highly porous catalyst tests the was used 10.5 cm3 too. But due to its highly porous structure the highly porous catalyst mass was 1.25 g. In the traditional granular catalyst and highly porous catalyst tests the oil feed speed was constant 20 mL/h (which amounts 19.6 g/h). The oil feed speed in the c.u. was measured as the ratio of the oil input amount g/h to the loading catalyst mass. Accordingly this ratio the feed speed in the c.u. in the granular catalyst presence was 2.3, and for the highly porous catalyst – 16.
Lines 176-177: Is it true that 21, 28, and 51% for weak, medium, and strong, respectively? Figure 7 doesn’t look like that.Line 185: “Thermoprogrammed desorption of ammonia” can be removed.
We recalculated the data. Thank you.
Other errors have been corrected in the article.
Author Response File: Author Response.docx
Round 3
Reviewer 1 Report
the authors' answers to my questions and issues, and the revision of manuscript are not enough for me. My decision is the result of comprehensive judgment. For example, I cannot clearly understand their answer to the question no. 10, which I raised in the second round revision. “… the was used 10.5 cm too.” What that means? Then, is the base area of cylinder 1 cm2? Where is the information? Even if it is clear, the authors should have described this point to the revised manuscript. Furthermore, in the second version manuscript, the weight ratio of catalyst to feed was written as 2.5:1 and 11.7-14.6:1. But, in the third version manuscript, those are changed to 2.3:1 and 16:1 without any explanation
Author Response
This answer is included in paragraph 2.3. Heavy oil viscosity reduction tests. If you or the reviewer have questions, we will try to give a more detailed answer. We also inform you that we have made changes to the calculation of the specific oil feed speed . For granular and highly porous catalysts, this value is 2.2 and 15.4 h-1. Calculations are presented in paragraph 2.3.
An adjustment of the article is below.
The value of the catalyst loading was 10.5 cm3, which is equivalent of 8.7 g if used the granular catalyst. The same value of the catalyst loading (10.5 cm3) in the case of the highly porous catalyst using conformed the weight 1,25 g. This value is 7 times smaller than the using granular catalyst loading. At that the delivery rate was same in both the granular and the highly porous catalyst 20 mL/h (19.23 g/h, ρ20= 0.9617 g/cm3). The specific oil feed speed (υoil) from the ratio the oil feed speed (Voil) 19.23 g/h to the catalyst loading mass (mcat) showed the specific feed speed (υoil) of the granular catalyst was 2.2 h-1 (υoil=Voil/mcat=19.23/8.7) and the highly porous catalyst was 15.4 h-1 (υ=19.23/1.25).
