Refining India 2022 Newspaper

and Petrochemical Plants and Petrochemical Plants and Petrochemical Plants

refining india 2022

Smarter and safer sulphur for refinery and petrochemical plants with SULSAFE New Generation of Sulfiding Agents VALUE PROPOSITION New Generation of Sulfiding Agents VALUE PROPOSITION New Generation of Sulfiding Agents VALUE PROPOSITION

g Technology Technology Technology

DA 2600 dif DA 2600 diff DA 2600 diffe

Benefits in P Benefits in Pe New Generation o VALUE PRO • Enhanced Ethyle • Reduced CO & • Persistent Sulfide • Variable chain • Sustained gen radiant coil. • Enhanced Ethy • Reduced CO & • Persistent Sulfid • Enhanced Ethy • Reduced CO & • Persistent Sulfide • Variable chain • Sustained gene radiant coil. Smarter & Safer Su and Petroche Benefits in Pet • Variable chain le • Sustained gener radiant coil.

DORF KETAL cost ratio paradigm. s safety. s performance. t In-situ Sulfidation. ce Sulfidation. cost ratio paradigm. safety. performance. In-situ Sulfidation. e Sulfidation. ost ratio paradigm. afety. performance. n-situ Sulfidation. e Sulfidation.

Greener Technology

Reliable Supply

Greener Technology

Im-proved Heath & Safety Im-proved Heath & Safety Im-proved Heath & Safety

Reliable Supply

High Performance High Performance High Performance

Attractive ROI%

SULSAFE TM The Path breaking Technology DMDS DMDS SULSAFE TM DMDS SULSAFE TM Flash Point ( o C) Vapor Pressure (psi 25°C) • Polymeric Sulfur. • Breaks the US$/kg Sulfur cost ratio paradigm. • Improvement in process safety. 62 0.1 – 0.2 Eye Irritation Respiratory Irritation No No Oral Toxity Limit (LD50 ppm) • Enhancement in process performance. • SA 400 Series for Catalyst In-situ Sulfidation. • DA 2600 series for Furnace Sulfidation. 7150 Easy Flash Point ( o C) 15 Vapor Pressure (psi 25°C) 0.55 Eye Irritation Yes Respiratory Irritation Yes|Toxic Oral Toxity Limit (LD50 ppm) 300 to 500 Handling& Storage Difficult Handling& Storage Difficult Handling& Storage Difficult Flash Point ( o C) Vapor Pressure (psi 25°C) 62 0.1 – 0.2 Eye Irritation Respiratory Irritation No No Oral Toxity Limit (LD50 ppm) 7150 Easy Flash Point ( o C) 15 Vapor Pressure (psi 25°C) 0.55 Eye Irritation Yes Respiratory Irritation Yes|Toxic Oral Toxity Limit (LD50 ppm) 300 to 500 Flash Point ( o C) Vapor Pressure (psi 25°C) 62 0.1 – 0.2 Eye Irritation Respiratory Irritation No No Oral Toxity Limit (LD50 ppm) 7150 Easy Flash Point ( o C) 15 Vapor Pressure (psi 25°C) 0.55 Eye Irritation Yes Respiratory Irritation Yes|Toxic Oral Toxity Limit (LD50 ppm) 300 to 500

Benefits in Catalyst Sulphidation • Optimum availability on catalyst surface • Better sulphur laydown efficiency on catalyst • Complete catalyst activation • Safer activation for sustained hydrodesulphurisation • Better hydrogen purity • Less SOx emission • Equivalent dosage to DMDS • Unmatched health, safety, and environ- mental benefits Demonstrated up to 2% improved C4- yield Demonstrated up to 2% improved C4- yield High Performance Attractive ROI% Demonstrated up to 2% improved C4- yield

Refiners and petrochemical operators are looking for a sustainable replacement for dimethyl disulphide (DMDS), which is known to be hazardous in the indus- try. Ethylene producers want to improve ethylene yield and eliminate CS₂ impu- rity added with thermal decomposition of DMDS. Dorf Ketal has developed a green polymeric sulphiding agent (SULSAFE) under the ‘Make in India’ initiative to over- come concerns with safety, domestic availability, and efficiency problems of DMDS. Pilot study results of SULSAFE and DMDS in ethylene have quantified the increased ethylene yield and CS₂ reduc- tion with SULSAFE. Demonstrated in eth- ylene furnaces across globe, the green technology also can replace DMDS in hydrotreater catalyst sulphidation appli- cation, proven in a pilot-scale hydrotreater. Benefits in petrochemical furnaces • Demonstrated up to 2% improved C₄ yield • Extended furnace run length • Effective CO control with less addition of sulphur than DMDS • Improved coke control visible from reduced H₂ make • CS₂ generation with SULSAFE is nil • Sustainable DMDS replacement • Toxicity and irritation levels are lower • No odour issues • No handling issues from drum disposal • Easier to control and verify injection rates minimal manual intervention in the field for feed preparation and monitoring of the plant. The plant was commissioned jointly by the BPCL R&D team and Kochi Refinery. When designing the formula for hygiene- grade SAP, certain points should be high- lighted. Development must keep in mind the health aspects while maximising the efficiency of the product. The product developed by BPCL meets all the critical parameters of international benchmarks, like residual monomer, absorption under load, and centrifugal retention capac- ity. The product is already on the market, thereby realising the dream of Atmanirbhar Bharat (self-reliant India). The Process A typical process for the commercial production of superabsorbent polymer includes: • Feed preparation : Acrylic acid is par- tially neutralised with caustic and diluted with water CATALYST SULFIDED WITH DMDS CATALYST SULFIDED WITH SULSAFE TM SA400 45.15% 45.60% 43.61% C2H4 C2H6 CATALYST SULFIDED WITH SULSAFE TM SA400 45.15% 45.60% 43.61% C2H6 CATALYST SULFIDED WITH SULSAFE TM SA400 45.15% 43.61% C2H6

e Study Study

e Study

Ethylene & Ethane Yields-Same Agent Dosage thylene & Ethane Yields-Same Agent Dosage ylene & Ethane Yields-Same Agent Dosage

2% 3% 4% 5% 6%

Extended Furnace Run-length

45.60%

44.54%

Handling & Storage N 2 Blanket (Pressurized Vessel)

Green Techno

C2H4

N 2 Blanket (Pressurized Vessel)

Yes

SULSAFE TM DMDS * For pictorial representation only Pilot Furnace Study SULSAFE TM DMDS * For pictorial representation only SULSAFE TM DMDS * For pictorial representation only

DMDS SULSAFE DA 2628 DMDS SULSAFE DA 2628 DMDS SULSAFE DA 2628

Sustainable DMDS replacement SULSAFE TM

Sustainable DMDS replacement

Toxicity & irritation levels are lower

Light Diesel

Odor Description

Pungent

Odor Description

Pungent

Odor Description

Pungent

Flash Point ( o C)

SA 400 Series for catalyst in-situ sulphidation Vapor Pressure (psi 25°C) 0.1 – 0.2

ater Study ter Study er Study

Ethylene Success Story Ethylene Success Story Ethylene Success Story

Benefits in Benefits in Benefits in C No

CO & Coke Formation- Same Agent Dosage New generation of sulphiding agents

Ethylene & Ethane Yields-Same Agent Dosage

• Overcome reaction exotherm and min- imise the risk of irreversible catalyst reduction • Less excess sulphur, fewer SOx emis- sions from decreased or eliminated flaring of recycle gas • Offers uniform sulphur distribution and consistent H₂S availability in a wide range of temperatures • Can reduce the need for hydrogen make-up DA 2600 series for Furnace Sulphidation • Same level of CO formation and slightly lower coke • Better sulfur laydown efficiency on catalyst LAYDOWN EFFICIENCY • Better sulfur laydown efficiency on catalyst LAYDOWN EFFICIENCY • Better sulfur laydown efficiency on catalyst LAYDOWN EFFICIENCY CATALYST ACTIVATION • Presents slightly higher yields of unsaturated molecules. Around 2% of ethylene yield increase was observed. • Lower SO generation, reducing acid load to downstream unit • Optimum availability on catalyst surface availability on catalyst surface availability on catalyst surface 7150 Easy • Optimum • Safer Eye Irritation Respiratory Irritation No Oral Toxity Limit (LD50 ppm) Handling & Storage N 2 Blanket (Pressurized Vessel) No Odor Description Light Diesel • Optimum • Safer

• Mixed Feed Cracker, Technip Design. • R/L increased by 30-50%. • CO generation reduced by 11% as compared to DMDS. • Mixed Feed Cracker, Technip Design. • R/L increased by 30-50%. • CO generation • Mixed Feed Cracker, Technip Design. • R/L increased by 30-50%. • CO generation reduced by 11% as compared to DMDS. Pilot furnace study results reduced by 11% as compared to DMDS. 0.0100 13.80 0.0067 13.61 13.80 13.61 8 10 12 14 0.0000 0.0050 0.0100 0.0150 0.0200 CO (%) Coke (gr) DMDS SULSAFE DA 2628 CO (%) Coke (gr) 0.0200 0.0150 0.0100 0.0050 0.0100 0.0067 0.0000 14 12 10 8 DMDS SULSAFE DA 2628

42% 43% 44% 45% 46%

46% 45% 44% 43% 42%

• Complete catalyst activation • Safer activation for sustained hydrodesulf urization activation for sustained hydrodesul urization activation for sustained hydrodesulf urization SULSAFE TM * For pictorial repres

• Complete catalyst activation

45.60% 45.60%

• Complete catalyst activation

Run Length Data 45.15% 45.15%

Run Length Data

44.54%

43.61%

Base Line Period SULSAFE TM

43.61%

71.00

61.00

C2H4

C2H6

54.00

53.00 CH

54.00

53.00

52.00

DMDS SULSAFE DA 2628

SULSAFE DA 2628

DMDS

43.00

ESH ALYST H LYST ST

CATALYST SULFIDED WITH DMDS

37.00

30 Pilot Hydro-treater Study 30 30

CATALYST ACTIVATION Ethylene Suc CATALYST ACTIVATION

1 2 3 4 5 6 7 8 RUN 1 2 3 4 5 6 7 8 RUN 1 2 3 4 5 6 7 8 RUN

• Mixed Feed Cracker, Technip Design. • R/L increased by 30-50%. • CO generation reduced by 11% as compared to DMDS.

GAS-OIL FEED

DMDS RUN PRODUCT

SA 400 RUN PRODUCT

FRESH CATALYST

CATALYST SULFIDED WITH DMDS

CATALYST SULFIDED WITH SULSAFE TM SA400

Contact: suhasnair@dorfketal.com

Pilot hydrotreater study results

• Polymerisation : Acrylic acid and sodium acrylate, in water solution, are polymer- ised using various free radical initiators in the presence of cross-linkers • Drying : The gel containing >60% water is dried at high temperature to remove the water • Milling : Post drying, the solid is milled to the desired particle size • Surface treatment: The polymer is stitched on the surface to impart physical strength to the swollen SAP particles Processing equipment also plays a major role in achieving the target specifications. Thus, technology development involved using state-of-the-art process equipment for high throughput processing, maximum monomer conversion, and off-spec mini- misation, which is pertinent in the SAP industry to achieve low unit manufactur- ing costs. The present technology devel- oped at BPCL R&D has taken care of all these aspects by employing indigenously designed industry-representative pre-pol-

BPCL despatches first indigenous superabsorbent polymer

cess technology. BPCL is in a particularly advantageous position as it is backwards integrated into the acrylic value chain. The commercial-scale plant based on in-house technology and acrylic acid feedstock from KR-PDPP is thus expected to drastically drive down the cost of SAP production and boost the hygiene industry in India.

ymerisation and post-polymerisation pilot equipment to enhance the overall econom- ics of the process. Major suppliers of SAP in India are Sumitomo, Nippon Shokubai, LG, Sumitomo Seika, and various Chinese suppliers. The significant growth in SAP demand has recently created the need to build large, grassroots SAP plants incorporating the newest and most cost-competitive pro-

Contact: dlcrdcsupport@bharatpetroleum.in