Project-wise Reports of Sectorial Monitoring Committee

1. Project Title: Development of Advanced Carbon Materials from Petroleum Derived Feed Stocks and Explore their Applications (CSC- 0121) (AdCarbMate)

2. Project Details:

·~: -No-da_f.i.ab·---··-1-C-SII:~--=--inCilan_i .. nstitute of Petroleum (C-Si-R -li-P) ,-Dehraduri---·-·---,

1

t:~crpatrng - - ~ ~;;!~~;entrai- Eie-ctrochemTcaiReSe;;;:ch-instltUie(csTR---=-~1

[~~~~~:~~~~~-r- ---·ror-Man~orsrlva~tava-----·-·-·-·--·~----·-··-·-·---------- - --- - - -~~~~-=-=-~~~=----~

! Taskforce ! I I Chairman I I f---··-··--·-·--·----+-·-··---·-·-·-·----·------·----------·~----·-----------·------···-···-···-···-···--·······-···-····------····-··-·····--·--·-·-·-·-··-···1

~~~~:-~_~1~5-s~_-5_~j~~-~-;;_ha_s~_: __ i: __ ~!_!2_--~_-w_~_ki_n~~-"~-·~~:~!_-____ ·-~-------~----_·_--l L~~~~-~~~-=~~-~-d_J .. R~-- ~3 9~~~-:~~-~---~?.-~-~~~)· - ··-·· ···- ·· --- ··- ···- -·-·····-- ·· ···· ··--· ····---- ·----·- · - - --- ··· ·-··-··.... . .. -............. J ! Fund utilized ! Rs 239.747 Lakh (2012-16) _j i-~····-·-··· ·· ····-- ... - .... , .. ,._._,,. ..... _ ... , .. _,,,._ ,. .......... l ....... _ .... _ .... _, _____ ............ _ .. ___ ,. ___ ,. ______ .. __ ,.,.,., _______ ...... ---·--···-----·---·- ··- ··- -·--- ·- ··- ··- ··- ··- ··- ·--- ----·--·

3. Periodic Key Recommendations of Task Force/RC/Monitoring Committee

;-··-·--~----··~--- - . I - -··-·-·---~~-------··---···-·-··---·-··---··--·-··-~--··--··~-··--·--·•·• ;

i ! • ! • 1 Proposed Rev1sed i i S.No i Key Recommendations i Act1on taken on I . i . ! I i f k l Dehverables 1 Deliverable I 1 • o Tas 1 Key · ; 1 ! i ! (approved !

I I Force/~C/Monitoring I Recommendations I I by Task ! : I Comm1ttee i · Force) ! ~---.. - ...... ---t ...................... -.... - ........ -----.. ··---·- .......... _ ............ J ................................................ _. · ...................... - ............. .L. ......... - .......... .. ..... ........ . ...- .......... _ ......... J. .... _________ .. ___ .. ___ .. _______ ... I i l i WP-2 I · i 1 1 • Focus of the project l i ! . • j i l I should be on the ! • Asphalt extraction !

I production of usable I and quality testing l I i l amount of carbon !

1

1

1

1

9naranpohtuebnees and I

from I petroleum/

petrochemical

residues/asphaltenes I 1 • CSIR-IIP should I i provide the carbon ! II j

material to CSIR-CECRI ·,: . I t I for evaluation of i L ... -....... ____ L _______ ______ _ _ ____ j__

•

I I•

i

j Feasibility study for l

j

preparation of I 1

carbon nanotubes ! j

(CNT) from asphalt i i i

Refinement of the i process

I WP-3

! I • Production I

of ! i i i

.. --·- ·- ·- ·- ·- --·.J.··- ···-------- -.... __ _j

1

r---~·-M----,.···-M-•~~-•->•'--••• • ••••-•••• •••-·~~--·•-•••••"-'''-''''--'•'M-•••-••,•••·--~·-·-- -· .. •-·-·---- ··-•·---,-------

1 ! electro -chemical I i asphalt ------,.. -·-·- ·-·- .. ~

! I i ; I · applications '

I i

I . CSIR-IIP

provided the

petroleum pitch

I to CSIR-CECRI

for eva luation

I I

•

•

I.

Production

carbon

through

processing

Production

carbon

through

cata lytic

processing

of

materials

thermal

of

materials

thermo-

Development of

Lab scale process

for carbon

nanomateria Is

(graphene)

Papers

Patents

(2-3)

I WP-4

i • I

•

•

Preparation of

petroleum derived

precursor isotropic

pitches for

development of

mesophase pitches

Preparation of

petroleum derived

mesophase pitches

for development of

advanced carbon

materials

Preparation of

carbon wool and

its carbon wool -

CNT composites

using petroleum

derived pitches

WP-5

i J. • Evolve carbon 1

_____ .. __ ..... 1 .. _,, _____ ,,_ .... _.,,_,,, ... ..... -.... ---.. ·-··-···-- ________ , _____ ,,_,_, ___ , _ ___ , _ __ ___ ,, -·-·---------·-·- ·---.. ~ ... i ____ ...J

2

·~ forms from IIP for _, ..... --·-·r----···~-·-··-·-·-·-·-.. -- .. - ... _ ................ _,_ .. ,,_,,, ......... _ ..... ,_._,, __ ,,_ .... - ... ·-·~·-·-·- -·-·-···-·-·-··-··-·-·--,----···-·-·-l

1 device applications

I

• Development of

novel carbon­

based materials for

batteries and

supercapacitors _, __ ., _ _______ ,_j ____ , -. ,,_ .. _ ,, __ .,_..!

4. Project Achievements:

s. No.

Deliverables I promised ! ! start

[

OeliverabJes Achieved at

1 • Asphalt

j extraction

'I and quality

testing

•

•

•

•

Feasibility of

the process of

formation of

carbon

nanotube

from asphalt

Refinement

of t he

process

"

Production of

asphalt

Production of

carbon

materials

through

thermal

processing

Production of

carbon

materials

thro·ugh

thermo-

cata lytic

• Achieved

• Achieved

• One patent filed

• Under progress

• Ach ieved (<10%)

• <1% upto 1100° C degree thermal

processing

• Achieved

• Lab process developed

llf not achieved, I reasons thereof

3

applications • N-containing carbon/ graphene nano­composites was developed w1th a large specific capacitance of 296 F/g for supercapacitor applicatiOns • Development

of novel

carbon-based

materials for

batteries and

supercapacit

ors

(Generally, carbon based materials used in supercapacitors are with a speet{ic capacitance of 200 - 300 F/g, compared to that the observed specific capacitance (296 Fig) of N-containing carbon/graphene nona­composites which is high)

• Porous carbon (CMK-3) with a specific surface area of 835 m2/g by replica synthesis using mesoporous silica (SBA-15) as hard template was obtained and their performance in supercapacitors are to be measured.

• NiCo204-CNF nanocomposite was prepared using hydrothermal and supercritical fluid processmg and the resulted materials prepared in supercritical fluid processing method showed high specific capacitance of 600 F/g in aqueous electrolytes.

(The supercritical fluid processing is expensive and has some practical difficulties compared to hydrothermal or any other techniques due to the high pressure (Mpa) and high temperature requirement. However, there are few commercial plants in Korea for the production of battery materials such as LiFeP04. Here, we have shown that the nano· composite prepared by this technique has good performance than the some materials prepared in hydrothermal.

Generally, carbon based motertals used in supercopacitors are with a speet{ic capacitance of 200-300F/g, compared to that the observed specific capacitance of NiCo~,rCNF nona-composite 600 Fig is high)

t NiCo204(SCF), NiCo204 (HT) N1Co204·

CNF (SCF) and NiCo20 4-CMK·3 (HT) I showed coerci~e field (H,) values of

5

L.. ...... _ ... ____ ,.J .......................... ..

2900, 3250, 1800 and 826 Oe, respectively, at 5 K. By coupling NiCo204 with CNF and CMK-3 reduced the saturation magnetization and coercive field resulting in the soft

magnetic _ nature of the I nanocompos1tes

• Asymmetric RGO-PEDOT.PSS//GO­CNF-Mn02 withHigh Energy density of 35 Wh/Kg is obtained using 1.8V aqueous based supercapacitor

• Achieved - The specific capacitance of Nitrogen doped graphene (NDG) is found to be 103 F/ g at a current density of 0.5 mAcm2

• The NDG I product exhibi ts a remarkably high energy density of 97 Wh/kg, which is double that of conventional lead-acid batteries. It can be tested at a large- I format device.

I 5. Outcome and Outputs from the Project !

1- ·---·-···-r--······-···-.......... - .. ·-··- ·· , a. Outcomes

·-· ---1-! ! ! !

1 -··-~e:d-(s) Number with TRL

t ---_1

·- ............ - ............................ ,

identifie~:-'f WP-2 : Synthesis of 'Carbon Nanotubes' and and names j 'Carbon Fiber Analogue' utilizing asphaltene

i and resins from heavy ends of crude oil !

• Asphaltenes were separated and demetalized • A Reactor was set-up for preparing Carbon

Nano-Tubes (CNT) ' . I

Carbon Nano-Tubes (CNT) and Carbon Nano Granules have successfully been synthesized from Asphaltenes and Maltenes {TRL-2) Polymer stacking of asphaltene has been done with three different monomers (TRL-2)

,. i I

(At present, data on production of Carbon Nona-Tubes (CNT) for a short term reaction time of 1 hr

I have been generated Now, the work is going on to I check the CNT yield in 6 hr reaction time. Then, it ! is planned to perform 12 hr continuous run

... I ~erime_'!]~to J!.roduc:._f!._C}!Id separa~5._NT! __ Corbon

6

,.--·-·-··-·-r·-··-·-·-···-·-.. - ... - .. _-,-_,_,_,,,_,_, _____ , __ ,, ___ ,_~--------·-·-·---·-·------·-.. - ·- ·- --·, I ! i i Nona-Granules (CNGs) as well as Graphitic l I ! l Carbon Sheets. After examining the production : i ' !

' 1 capacity level of CNT and other Carbon Nono-1 materials, scale-up possibilities for

i

I . . I I i i

l.__ ___ _j _______________ j ________ _

1 commercialization of process will be examined) 1

I

i (WP-3) Development of process for I production, extraction and utilization of i 'Graphene' from heavy petroleum ends J Development of process for production, j extraction and utilization of 'Graphene' from ·

I heavy petroleum ends

Developed a process for the preparation of layered sp2 carbon nanomaterial from heavy petroleum ends (TRL-1)

I I (Potential usages of layered sp2 materials may be I 1 explored) !

I (WP-4) Development of petroleum derived I Carbon Wool and its Carbon Nanotubes ] Composite !

j • Prepared isotropic pitch from different petro leum feed stocks. (TRL-2)

! • Prepared mesophase pitch from petroleum i

feed stock/isotropic pitch for development of carbon materials (TRL-2)

! 1 • Prepared 'Carbon Wool' from petroleum

derived pitches (TRL-1)

J (Petroleum pitches ore comparable with the I I pitches available in the market. Further, Carbon I Wool is a new kind of material not reported in l I Google Search and Google Potent Search. Such I I type of product is not available in the world i market as well as in Indian market. Carbon Wool !

1 may have some industrial applications such as 1 adsorbent, material for gas storage or any other. If · I it works well as on adsorbent, it may replace the i existing carbon based adsorbents for various I applications. About 2-3 years time will be required j J to develop Carbon Wool product) '

i (WP-5) To exploit novel carbonaceous i materials for electrochemical applications I I . b . d . I J re atmg to attenes an super-capac1tors 1 ! , ______ _j

7

r ..... -............... 1 .... .. . .... _ ..... .......... ........................... .. .. .................... - ............... 1 .. -. --i~~t-~-~-pi·~-... -plt~h · ca.;b·~~- suppJi;;~T"-by- llP--~~-~

found to be suitable for use in lithium-ion i batteries and the Nitrogen-doped graphene 1

was found to be good electrodes for i I

supercapacitors (TRL-2) i

I (The reversible capacities are higher than those I j generally reported for both lithium and sodium I I intercalation. Once, the material passes validation I i in terms of irreversible capacity, cycle life and fade, l ! it can be taken up as a candidate. For example, j i the TAPSUN program uses a carbon paper that j l gives a reversible capacity of only 220 mAh/g; ! ; once optimized, liP's pitch carbon may be used in 1

__ ·· - · • • .. .. M ·· · · ··-·-·· - ··· -·······-··· --· • ..... • ... .. ..... _ .. _ ...... - .................. -... .. Lf~-~ P {Ci_~€!_91!_1}_~-~!!:.P..Clt!_.Pq_p~r)_ .. _ . _ ... .. __ ... _______ , ____ _! I Technology/Product I Product I Lab Scale Process Development I 2

3

4

developed: Number i ' · • WP-2 :Carbon Nano-Tubes (CNT) and Carbon I

and names with TRL j 1 Nano Granules have successfully been !

level of Development I · synthesized from Asphaltenes and i

I . l

'·

Maltenes(TRL-2) I W P-3 :Developed a process for !

preparation nanomaterial ends(TRL-1)

I of layered sp2 carbon 1

from heavy petroleum l ! i

(WP-4) : Prepared isotropic and mesophase l pitches of different properties from different i petroleum feed stocks. (TRL-2); Prepared I Carbon Wool from pitches(TRL-1) I

i i • (WP-5) : Isotropic pitch carbon supplied by I

! liP was found to be suitable for use in 1

lithium-ion batteries and the Nitrogen-doped 1

graphene was found to be good electrodes i I

.. ..... -............. ___ .. ,_ .. ___ ...... ... _ -l---·· ... :~~-~~~-~~-~~~acito~~~~~~--------.. ·-·---------~ Technology/Product j I transferred: Number 1 ,:i.

and names with I name of licensee(s) I i

-- --f -- -- ----i Facility created: I • Number and names i with uniqueness & '

1 utility

A High Temperature Reactor (Model 4598HPHT SS Parr Reactor) was purchased. (Cost Rs 15 lakh) - This equipment was utilized to prepare graphene from heavy

. ~------- · J ---·--·

1 petroleum ends

·-·-··--J.~--.. -~_I::IJ9.h -~-~-'!1J?.~~!!~~~~_na~~_jl~ree zone

8

r-·-·----~-.. -----.. --.. -------.. ·----.. ··r-.................... ....... ···-·-·---·-·· .... ··~- -· ......... ---~-p-iit····f~-~~;~~--~ith·-;dj~~t~-b·i~-t~b~ di~-;;;-~"t;) .. ,i . I

1 was purchased from Thermcraft USA (Cost Rs I

i r-·

I

l 6 lakh) - This equipment was utilized to make 1 carbon nano-tubes (CNT) from heavy end of I crude oils •

• Electrochemical Charge-discharge I cycler/battery tester (Maccor, SERIES 4000, 1

2015), Total Cost ~ 55 lakhs; This equipment I was utilized for characterization of cycling j

1 1 behavior and cycle life test for devices l ~-----·--.. -.. -----r-·-·-.. -... -... ... .. ... -... -..... _ ......... .......... -----.. ----····-·-·-.. ···-··-· ... ----.. -·--------.. ·-:··-··-·-.. -.... -.......................... _ ............... ---.... -.... 1 1 5 1 Sponsored projects I I I obtained (with .

II ! d ., j

~---+----__ ! eta1 s) ---· i I I i - ----1 1 1 6 I External Cash Flow I

[ 1 I (ECF) generated I f---l..---·-· _____ .. _, _____ ·!-··-··--·-··- ... ----.. ---··-·----.. - ... - .. ___________ , ________ , _______ , ___________________ , .................. , _____ ,,_. ____________ , __ 1

· ! 1 NA I I 7 I Societal impact i I created (quantified

I I data) ~-~·---- I

b. Outputs -,-1 Periodic l Submitted

r---+--------L--.. -- --·-!

1 Reports

;----t--2 ____ ~ublications I Total number i. !

_________ j • 3 Research Papers Published I • 1 Communicated I • 2 Manuscript of Research Papers Under I

preparation !

I I

1. Nitrogen-doped grapheneas electrode j material with enhanced energy density for j next-generation supercapacitor I application, ECS J. Solid State Sci. Tech. 4 1

i M88-M92 (2015).

I 2. Embedded Iron Nanoparticles in Carbon

'I Nanogranules for Direct Synthesis of I

lower Olefins,Chemistty Select 1, 14736 -I

''I

I 4741 (2016)

3. Graphene-polypyrrolenanocomposite for I I supercapacitors,J. Nanosci. Nanotech. 17 I I 1267-1274 (2017). I

..____l ___________________ l __ ---·----·-· ____ l !__A2Y-mmetric RGO-PEDOT.PSS//GO-CNF- 1

9

-'--i

i ii.

Mn02 for high energy supercapacitors (communicated)

5. Graphene quantum dots from incipient kish graphite and silicon GQD composites prepared therefrom. Mater. Chem. Phy s. (Under preparat ion)

6. Kaolinite-graphene oxide composite as super adsorbent for removal of Rhodamine 6G from aqueous solution (Under preparation)

I Cumulative IF (as per 1

3·214

2015 figures ) ;

I ___ J __ ~~----~~·:·~· ~~- -----j~_-___ -____ -___ -__ -... -. -... -... -..... -.. -.-........ -... -........... _·-·-··-··-··-·····--·-···-··-···-···-·· Average IF/scientist l 0.40lB IV.

3

l------1

Patents (or other 1 I

forms of IP generated 1

L____ -. ~:S~~n;setc~:p~~~:~~' l---·· --·- .. ---- .. -------·---·-·-. j I. Filed 1 Patents have been filed in India

I l I I

l ~-

, 1. A process for the preparation of layered I sp2 carbon nanomaterial from heavy ~~ petroleum ends, Babita Behera, Piyush

Gupta, S S Ray, L N Shivkumar Konthala

i Arvind Kumar, Manoj Srivastava, Y K Sharma I ! Appl No 4190Del2015 dt 21.12.2015 i l (At present, process is successful only at o lob 1

scale. The mechanism of formation of sp2 carbon I ] materials is to be understood for fine-tuning of the I process before proceeding for any I commercialization. VefY few papers and patents

are available worldwide. University of Idaho, Moscow has o similar potent technology, where

i they hove stated sulfur cofactor additives for 1 obtaining grophene (GUITAR) materials from

1 asphalt by o USA potent and o paper in Carbon I

1 Journal)

! 2. Heavy petroleum residue derived I sp2 carbon nanogranules for improved I synthesis of light olefins (134 NF 2016) ,

____ I (This Potent is first of its kinq. Further research I 10

r···-·-···-------··,.·-···--------·--·-----'-·--·-··----- ·r-·- ···-·-·- ·--·- .. -·-·-.. - ·-··-"-··r-·--·oo-oo-··- .. --·-··-····-.. ------·-·-·-~. I i 1 work is required to prepare a better product with J

I i · I some modifications i. e. combining metals with i ' I ; f i 1 CNGs by in-situ doping for use as a catalyst for

I the synthesis of light olefins. The 2-3 years time I will be required to assess the commercialization

, I possibilities of the current work) f-·----.. -·4-.. -·---···-···-··-·-----···--· ··- ·-···-··-··- ·- ·----r-------·- -------··--···--··- - ···--------1 ! I i -i i ii. Granted 1

r-~~~~-t==~==~~~·~ =~-~=~+===~~-~ -~=-===~ · I 4 I Human Resource 1 1

, generated 1

:------r------ i. f .. ~h D fellows (g ive Ph I Two Ph Ds are completed with partial fi ~ancial , i I Ds completed & 1 support from this project

: i 1

pursuing separately) j

:------~L ______ --i~--~~~ject fellows ·-·-~ }-·--·--·--··-----~-·-----·--·---··--·-·-··- ····--.... - .. --·-··-·---·----·+-····---- - ··-·-·- ------- - --·-- - ------1 l ! iii. Ski lls imparted _ j Four Project fellows were engaged in different

I ! work packages of the project and trained for R & Including skill set I D work in the area of Carbon Materia ls developed for

l ! I technical services/ 11 ..• ·.

! I . Consultancy/ training

j I J purposes 1 !------··---+----- ·---·-··--- ··- --- ----·-·- ... -·-··----·-·---·-·~·-·---·-·-·· -·· .. ·-··--·- -- ··- ··-.. ··- ··-·-···----

; I c. External collaborations i ! I established I L --------···--'··-- ····-·---····-····- --··-- .. ·--··-··-··------····-·····-···-······--····--"·-····- ·-·--·-- ··-----·J------·--·---.. --····-··-----.. --·---·-·---·---.. -----·-----·-----·---·-·----·--·-

11

S.No lead/Techno! Salient TRl of the IP Status of Status of ogy /Product Features of the lead/ lead/Technolog DPR/Commerc (listed above lead/Technolog Technology y/Product ial Technical in outcomes) y/ Product /Product Report of

lead/ Technology/ Product

WP-2 Synthesis of • Asphaltenes 1 Patent Filed 'Carbon were separated

Nanotubes' and demetalized

• A Reactor was and 'Carbon set-up for

Fiber preparing

Analogue' Carbon Nano-

utilizing Tubes (CNT)

• Carbon Nano-asphaltene Tubes (CNT) and and resins Carbon Nano

from heavy Granules have (TRl-2) ends of crude successful ly

oil been synthesized from Asphaltenes and Maltenes

• Polymer stacking of asphaltene has been done with three different monomers

(TRL-2)

12

... (TRL-1) 1 Patent Filed • ~c!>S for the

preparation of -- ··"'n, layered

extraction sp2 carbon and nanomatenal utilization of from heavy

'Graphene' petroleum ends

from heavy petroleum ends Development of process for production, extraction and utilization of 'Graphene' from heavy petroleum ends

WP-4 Development • Prepared1sotrop (TRL-2) of petroleum ic pitch from

derived different petroleum feed

Carbon Wool stocks.

I and its • Prepared Carbon mesophase (TRL-2) Nanotubes pitch from I

Composite petroleum feed stock/isotropK pitch for development of carbon materials

• Prepared 'Carbon Wool' from petroleum (TRL-1) deO...ed p1tches

13

WP-5 To exploit • Isotropic pitch (TRl-2) novel carbon supplied

carbonaceous by liP was found to be suitable

materials for for use in

electrochemic l ithium-ion

al batteries and the

applications Nitrogen -doped graphene was

relating to found to be batteries and good elect rodes

super- for

capacitors supercapacitors

6. Sectoral Monitoring Committee Recommendations on Lead/Technology/Product (listed above):

For each Lead/Technology/Product provide details separately:

Criteria SMC Recommendations

Name of Lead/Technology Carbon wool from petroleum pitch /Product

Is the lead/ Yes Technology /Product worth taking up further?

What is the further R&D Tailo r to applications and scale up efforts that need to be put by CSIR/CSIR laboratories?

Global benchmarking of the No manufacturer of carbon woo l. It is expected to lead/Technology /Product substitute activated carbon. specifically wrt specifications and cost

Is the No lead/Technology /Product worthy of commissioning a DPR at this stage?

What are the likely resources Road ma p fo r creating a platfo rm for applications in 3

and time duration required years for taking forward the identified lead/

14

Technology/Product to the desired TRL?

Potential stake holders who Oil and Gas, Water treatment and strategic sector may be appropriate to partner technically as well as financially

Suggestion for plausible road map towards further development of lead/technology/product for achieving desired TRL

GO/NO GO further GO development

Other suggestions, if any, related to benefits/usage/ commercialization

7. Identified "lessons to be learnt", especially from shortcomings/failures.

8. Comments on financial progress on the project- fund availability and utilization of fund in the project:

Financial progress is satisfactory and the investment made are justified.

9. SectoraiMonitoring Committee Recommendations on Facility creation or other outcomes:

10. Grading of Project Execution: Outstanding/ Excellent/ Very Good/ Good/ Satisfactory/ Un-satisfactory

VERY GOOD

11. Additional comments, if any:

High density graphite and pyrolytic carbon to be explored with strategic sector user.

In context of very large refining capacity in India, the lead needs to be given priority with resources.

15

~k..rh ~·A:~.~~o- ~ .... Dr. S.Srikanth Prof. Amol A. Gokhale

(Convener) (Member) (Member)

~ ~....t- ~J~~ lot . Seshadri Dr R N Das Dr Samir V Kamat

(Member) (Member) (Member)

~ Director, CSIR-NIIST Director, CSIR-AMPRI Director, CSIR-CECRI

(TF Chairman-Member) (TF Chairman- Member) (TF Chairman-Member)

Direct~ ~ Director, CSIR-IMMT ShriAjit Singh

(TF Chairman-Member) (TF Chairman- Member) (Member)

Dr.Bal~ ~ (Chairman)

16