8. V K Joshi -TKIS · • Constraints on caustic soda production due to negative price for chlorine...

Chlorine Derivatives

07 – 08th March, 2017 | AMAI Conference | Vadodara

Mr. V. K. Joshi, Sr. General Manager, & Head - Sales (BU- Electrolysis, Polymer & Fertiliser)

An overview

2 | 07 – 08th March, 2017 | AMAI Conference | Vadodara

Introduction to Thyssenkrupp organisation


Leading engineering expertise from one source

Fiscal Year 2015/16

thyssenkrupp: a global corporation

80

employees

€39,263mnproduction sites, offices and service location

all over the world

R&D spending

> 2,200Sales

~156,000~18,000

~2,000€778mn

Present in nearly countries

industrial property

rights in reporting period

patents in total


thyssenkrupp – Industries we serve

of our employees are engineers and technicians

machines and systems in use worldwide

chemical installations constructed worldwide

>17,600

Almost 70%

More than

Over 2,500

years of engineering excellence

200


RC North America

RC CIS

RC Maghreb

RC Sub-Saharan Africa

RC APAC

Europe

RC Gulf States

RC South America

RC India

thyssenkrupp - We are present wherever our customers need usRegional cluster organization


thyssenkrupp Industrial Solutions - Business Units

Cement Technologies

Industrial Specialties

Fertilizer & SyngasTechnologies

Service

Electrolysis & Polymers Technologies

Marine SystemsSystem EngineeringMining Technologies

Network of Excellence


Projects Executed Over 600 projects

Types of Contracts EPC-LSTK / EPCM, PMC, Reimbursable Services, Open Book Estimates

Formation Erection Office 1965Branch Office 1970Indian Company 1977

thyssenkrupp Industrial Solutions (India) (Former Uhde India Private Limited)At a glance : History, Formation, Capacity, Contracts

Quality Assurance,Health Safety & Environment

ISO 9001 : 2008ISO14001 : 2004, BS OHSAS 18001 : 2007

Caustic Soda /Chlorine Plants / Projects

Is key business area, with 80% Market share of Membrane Cell Technology Market In India


Chlorine – Challenges & Opportunities

• Challenges:

• Increasing volatility of demand / price for liquid chlorine product

• Outlets for Chlorine either non-existent or limited at many locations

• Difficulties with long distance transportation / associated environmental

considerations

• Significant impact on project feasibility / operating cost due to the above

• Constraints on caustic soda production due to negative price for chlorine

• Opportunities:

• Integration of downstream Chlorine based products can offer good value addition

• Integrated approach offers better potential for optimising operating costs

• Downstream products can offer valuable options and can be strategy drivers for

future business growth as forward integration


Some Examples of Chlorine Based Products

Ethylene Dichloride (EDC) / VCM / PVC

Epichlorohydrin (ECH)

Sodium Hypochlorite

Bleaching Powder

Poly Aluminium Chloride (PAC)

Chlorinated Paraffin Wax

Thionyl Chloride Monochloro Acetic Acid

Calcium Chloride) ChlorosulphonicAcid

Hydrochloric Acid Chloromethane (Silicone

Polymers)

Chlorine Consumption Options:

Though various options are also available, this presentation is focused on

select options having good Chlorine Consumption potential such as:

- Ethylene Dichloride (EDC)

- Chloromethanes (CLM)

- Chlorinated Paraffin Wax (CPW)

- Chlorinated Polyvinyl Chloride (CPVC)

- Chlorinated Aromatics (CLB/ CLT)

- Phosphoric Acid - by HCl route (PA)


Cl2

EDC

CLM

CPVC

CPW

PA

Ethylene

Dichloride

CLBT


Chlorine + Ethylene

EDCEDC VCM PVC

• EDC is produced by the chlorination of ethylene through directchlorination or oxy-chlorination

• tkIS AG (former ThyssenkruppUhde GmbH) has exclusivepartnership with Vinnolit for EDC Process technology (and also forVCM / PVC processes)

• Key issues� Availability of Ethylene at competitive Price

� Availability / Cost of Power,

� Stringent environmental and health regulations for Chlorine & Ethylene

� Either captive or external consumption for VCM / PVC

EDC Value Chain


EDC Process – Direct Chlorination – Vinnolit Technology

• Innovative Boiling Reactor with natural convection flow in an external

reactor loop (results in significant reduction in energy consumption)


EDC Trends

• The projected annual market growth rate

(global) of 3.47% over the period 2014-

2019

• In 2015, over 98% of EDC produced is

used towards making VCM, which in

turn is used to produce PVC

• The global consumption of PVC is

estimated to grow at a CAGR of 5.6%

between 2016 and 2021

• The global EDC market shows immense

growth potential also because of the

emergence of certain trends such as the

use of bio-ethylene as a potential

feedstock for EDC


Cl2

EDC

CLM

CPVC

CPW

PA Chloromethanes

CLBT


Overview

• Chloromethanes (CLM) belong to a group of organic compounds called halo alkanes.

• These are typically produced by chlorinating Methanol. There are four Chloromethanes which

are made in a sequence.

• Based on the number of Chlorine molecules in its structure, the CLM’s are classified as

follows:

• Their end uses are mainly in pharmaceuticals, agrochemicals and refrigerant gases. HFC32 –

a refrigerant gas is made from C3 and C4. CFCs and HCFCs (previous generation of

refrigerant gases) were made from CLM.

• Typical Chlorine consumption Potential of CLM’s (T/T)

C1 Methyl chloride

C2 Methylene dichloride

C3 Chloroform

C4 Carbon tetrachloride

CLM name Cl2 consumption Norm

(T/T of product)

MDC 0.9

Chloroform 1.3

CCl4 1.5


CLM Market trends

Global Scenario

• The global CLM market was estimated at USD 1,400 million as of 2012 and is projected to

reach USD 1,800 million by 2018 growing at a CAGR of 4.2%The increase in global demand

for Silicone is expected to drive this growth

• Asia Pacific is expected to be the major growth center due to increasing industrial activities

and minimum regulations, with China and India leading the demand

• Globally, Akzo Nobel, Dow Chemicals, Solvay SA and Shin Etsu are the major producers of

Chloromethanes

Indian Scenario

• Based on recent developments as summarised below, it appears that CLM has a growing

demand in Indian market & could be a good alternative for Cl2 consumption over the next

years.

• India is a net importer of MDC (100 KTPA).

• Provisional anti-dumping duty imposed on import of Dichloromethane (Methylene Chloride)

from China and Russia to India for a period of 5 years.

• The existing & new manufacturers of CLM In India are given below •Sources: Business Standard , Pharma Technologist


Company Current

Capacity

(TPA)

Key LocationRemark

Gujarat Alkalies &

Chemicals Ltd.

(GACL)

37,950Vadodara, Gujarat

Dahej project

Existing plant of ~40 KTPA at Vadodara (built by Uhde)

Chemplast Sanmar 34,850 Mettur, Tamil Nadu

SRF Ltd. 40,000Bhiwadi, Rajasthan

Dahej project

• Existing plant of identical capacity

• New Plant To meet need of its Pharma customers for

Methylene Dichloride (MDC).

• MDC is a raw material in production of HFC 32, a

refrigerant for room air-conditioners.

Gujarat Fluoro

Chemicals87,500 Dahej, Gujarat

Meghmani Finechem - Dahej, Gujarat

• Captive Cl2 consumption

• Cl2 consumption from Pharma and agro & refrigerant

gases

Sree Rayalaseema

Alkalies & Allied

Chemicals

140 TPDKurnool, Andhra

Pradesh

commissioned in March 2016

Existing Chloromethane Capacity in India


Cl2

EDC

CLM

CPVC

CPW

PA

Chlorinated PVC

CLBT


• Overview

• It is a thermoplastic which is prepared by chlorination of PVC by application of thermal heat or Photo

chlorination

• It is generally used in production of plastic pipes, fittings and industrial liquid handling. CPVC can typically

tolerate high temperatures

• In India CPVC pipes compete with conventional PVC pipes and Galvanized Iron (GI) pipes. They occupy a

5% (but fast growing share) of the Indian pipe market by volume

• Global scenario

• CPVC resin is made by Lubrizol (claims 85% market share globally), Arkema of France and Kaneka

of Japan

• Recent developments:

• Presently, there are couple of C-PVC producers in India and regular imports of either the resin or

the compounds occur from China, Japan and France

• August 2016: Astral ties up with Japan's Sekisui Chemical for CPVC compound. Sekisui makes

CPVC resin and compounds at Map Ta Phut in Thailand and can export duty free to India because

of the FTA

• January 2016: Lubrizol is the first major global producer of CPVC to establish operations in India

(Dahej facility) with a capacity to produce approximately 55,000 metric tons of compounds annually,

and have invested more than USD 50 million in this plant pledging strong commitment to the Indian

market


CPVC - Overview

• 2014 : DCW established the first of CPVC plants in India (10000 TPA, based on

Arkema technology) & also a compounding line. tkIS India (former Uhde India)

engineered & implemented both the projects

• Future Prospects

• Due to its wide acceptance for domestic plastic Pipes, the future of CPVC in India

looks very bright.

• Typical Chlorine consumption Potential:

approx. 0.75 T / T

By-products / MT of CPVC

− HCl as 100% - 0.25 T

− Cl2 as 100% - 0.3 T (recycled)


Process description

• Chlorinated polyvinyl chloride (CPVC) is PVC is chlorinated via a free radical

chlorination reaction typically initiated by application of thermal or UV energy

utilizing various approaches. In the process, Chlorine gas is decomposed into free

radical Chlorine, which is then reacted with S- PVC in a post-production step,

essentially replacing a portion of the Hydrogen in the PVC with chlorine

• Pre dried S-PVC is sucked into the reactor first fluidized with Nitrogen.

• Depending on the method, a varying amount of Chlorine is introduced

progressively into the process according to a measured way to fine-tune the final

properties. The reaction temperature increases due to exothermic heat of reaction

due to thermal or photo chlorination reaction.

• The heat of reaction and the heat from the UV lamps are removed by means of

cooling water.

• The chlorine content in the product may vary from manufacturer to manufacturer;

the base can be as low as PVC 56.7% to as high as 74% by mass, although most

commercial resins have Chlorine content from 63% to 69%. Under normal

operating conditions, C-PVC becomes unstable at 70% mass of chlorine.


Cl2

EDC

CLM

CPVC

CLBT

CPW

PA

Chlorobenzene, Chlorotoluene


PR NewswireReport Linker

Overview of Chlorobenzenes

• Chlorination of benzene yields Monochlorobenzene (MCB) and

dichlorobenzenes (ortho, para).

• Nitration, Amination and hydrogenation reactions on chlorobenzenes yield a host

of economically useful products starting from Nitro-chlorobenzenes (ortho, para)

and Dinitro-chlorobenzenes (2,5 & 3,4).

• The products are used in synthesis of agrochemicals, pharmaceuticals and

personal care products

Overview of Chlorotoluenes

• Chlorination of toluene produces a chlorinated mass which is distilled to get

benzyl cyanide, benzyl chloride, Benzaldehyde and Benzal chloride

(Chlorotoluene family).

• Chlorotoluenes are used in the manufacturing of agro chemicals, paints,

perfumes, bulk drug intermediates etc.


Global Market for Chloro benzenes

• In 2015, global Chlorobenzene market is estimated to be over USD 1,780 mn. The

biggest markets globally are Asia Pacific, wherein China is the largest market with ~60%

share of the APAC region

• In 2015, mono chlorobenzene segment was the largest amongst various types of

Chlorobenzenes with a share 71% in volume and over 67.7% in terms of value in 2015

• The Para dichlorobenzene segment is anticipated to witness the highest growth (6.7%

in terms of value).

• During the 2016 - 2022 period, the increasing production of polyphenylene sulfide

(PPS) in China, Japan, and the U.S. is fueling the demand for Para dichlorobenzene

Global Market for Chloro Toluenes

• The global Chlorotoluene market is estimated to be around USD 740 mn in 2016,

growing from USD 660 mn in 2011, at an estimated CAGR of 2.43% between 2011 and

2016


Indian scenario

• Indian chlorotoluenes market size is around 60000 TPA

• Major Manufacturers of Chlorobenzene:

• Deepak Nitrite

• Aarti Industries and

• Kutch Chemical Industries

• Major Manufacturers of Chlorotoluene

• Lanxess (formerly Gwalior Chemical) in Nagda,

• KLJ Organics in Jhagadia, Kadillac Chemicals in Baroda, and

• Sanghvi Organics in Panoli are manufacturing

• Chlorine consumption

• 1 T of benzyl chloride consumes 1.6 T of chlorine

• Typical plant sizes

• Typical plant capacities for chlorobenzenes are around 30000 TPA and for chlorotoluenes

around 10000 TPA


Cl2

EDC

CLM

CPVC

CPW

PA

Ethylene

Dichloride

CLBT


Chlorinated Paraffin Wax (CPW)

Secondary Plasticiser in PVC/Polymer products

Flame Retarding Agent in PVC/Polymer products

High Pressure Lubrication

Sealants

CPW Applications

• CPW’s are processed from the chlorination

of the following paraffin ranges:

• L – Grade : C10 – C13 (Short Chain)

• M – Grade : C14 – C17 (Med. Chain)

• H – Grade : C18 – C30 (Long Chain)

• These are further divided based on the %of

chlorine content into three types viz.

• < 40% chlorine

• 40 – 70% chlorine

• > 70% chlorine

• Based on the paraffin range, different

varieties of CPWs are produced which vary

in volatility, thermal stability, viscosity,

refractive index, free mineral acidity, and

colour.

• The commercial grade used is 40 – 70%.

Increasing the quantity of chlorine by weight

to more than 70% affects the viscosity and

limits the applications.


CPW Production Process

Exothermic Reaction

By-product HCl

AbsorptionStabilisation

Chlorine

Paraffin

HCl

(~32%)

CPW

Oil (e.g. soyabean)

• Batch process

• Typical Chlorine Consumption: 1 ton / ton CPW

• CPW is an ideal investment opportunity in the small and medium

scale sector.

Off-gases


CPW Trends

• Around 300,000 tons are consumed in India -

Global CPW volumes are at least 2 to 3 times

higher

• The CPW market in India is estimated to be

growing at ~ 9% per annum. KLJ Organics,

Aditya Birla and K G Industries are some of

the largest producers of CPW in India

• Typical plant capacity is in the range of 30

TPD

• In recent times, the export of the product have

been steadily going up, as Indian production is

competitive.

• Considering the likely growth rate in demand,

additional capacity can be created to meet the

demand in the local regions and exploit the

export opportunities

Source: Transparency Market Research Analysis,

2015

Global Chlorinated Paraffins

Market Volume Share, by

Application, 2014


Cl2

EDC

CLM

CPVC

CPW

PA

Ethylene

Dichloride

CLBT


Overview

• Brief manufacturing Process:

• Phosphoric acid (H3PO4) is an inorganic acid which is manufactured by treating phosphate rock

(apatite) with an acid- either sulphuric or hydrochloric.

• The acid comes in 4 grades: Merchant grade, Tech Grade (TG), Food Grade (FG) and Pure Grade

(PG)

• Merchant grade Phos. Acid using the Sulphuric Acid route is typically used in fertilizer applications.

• Technical grade Phos. Acid (85%) is made using HCl.

• Phosphoric acid using HCl has a long history in India with track record in Karwar (BILT then Solaris &

now part of Birla group) and Vadodara (GACL).

• Global scenario

• Global phosphoric acid production capacity was estimated at 4.5 million tons in 2011.

• In 2015, 85% of the of world phosphoric acid production was for captive consumption and only 15 %

was estimated to be traded in the international market.

• Indian scenario

• India was the world’s top importer of phosphoric acid (2.5 MT), accounting for close to half of world

imports. We get our supplies from Morocco, Senegal, Jordan and Tunisia. Europe is also a major

importing region due to its own limited phosphate rock capacity.

• Western region dominates the Indian Phosphoric acid market owing to a large phosphate fertilizer

production.

Sources: Potash Corp, Hindu Business Line


• Recent developments in India for Phos. Acid based on HCl

route:

• Phos. Acid by HCl route can be a good alternative to consume Chlorine (as HCl) for Caustic soda & Chemical producers (e.g. Isocyanate producers)

• Particularly for those having surplus HCl, as selling HCl generated from a manufacturing process can be an issue & this route can consume a good amount of HCl.

• Typical HCl consumption (T/T)

• 4 T of HCl are consumed for every T of Phos. Acid.Uses of Technical grade PA Uses of Food Grade PA

Metal pre-treatment to acidify food products like colas

Sugar refining to make phosphates used in a variety

of food products like

cheese,

bakery products,

yeast,

jams,

jellies and

refined sugar

Anodizing

Waste water treatment

Soaps and detergents

Tea leaf processing


Conclusions / Observations

• Effective Chlorine utilisation, though it appears challenging, is achievable

• Due to “localised” Chlorine demand, it is worth performing proper market / feasibility study for downstream options before embarking on a caustic soda project or expanding an existing plant

• For new caustic soda projects, downstream integration is recommended from the beginning as it allows planning infrastructure (e.g. utility / offsites) for downstream plants and save on additional spending later on

• A “single window” engineering contractor able to offer / arrange both reliable process technology and project implementation would be ideal solution for Indian Chlor alkali companies looking to venture into Chlorine based downstream products


Thank You

8. V K Joshi -TKIS · • Constraints on caustic soda production due to negative price for chlorine...

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