SPECIAL REPORT: Cracking

the

Pyrolysis

Code

Special Report: Cracking the Pyrolysis Code

Table of Contents

Introduction ............................................................................................................................ 1

The Case for Pyrolysis of Waste Tires and Other Feedstock ................................................ 3

Waste Tires ...................................................................................................................... 3

Pyrolysis ........................................................................................................................... 4

Gasification Technologies ............................................................................................... 4

Tire Pyrolysis ................................................................................................................... 5

Other Feedstocks .............................................................................................................. 6

The CTSW Solution ............................................................................................................... 7

The CTSTC Thermal Conversion Plant Technology....................................................... 7

Plant Operation ................................................................................................................ 9

Feedstock ....................................................................................................................... 10

End Market and Customers ............................................................................................ 10

Pyro Oil .......................................................................................................................... 12

Emissions and Permitting .............................................................................................. 12

Capital and Funding ....................................................................................................... 12

Management ................................................................................................................... 13

Special Report: Cracking the Pyrolysis Code

Introduction

In the spring of 2011, Louisiana’s largest tire processor, Clean Tech Solutions Louisiana (CTSL), a

subsidiary of Clean Tech Solutions Worldwide (CTSW), will launch the nation’s first Total Solutions

Pyrolysis System for waste tires, using a pyrolysis system installed in more than 100 locations around

the world. Regarding the economic and social value of converting society’s waste tires into useful

products and energy for communities worldwide, Lloyd Ward, CEO of CTSW, says: “We are extremely

excited to introduce our technology and business model in the U.S., in a way that recovers economically

valuable materials from waste tires and industrial wastes, solves an environmental problem, and creates

jobs.”

Annual waste produced in the U.S. alone is estimated at more than 400 million tons. Much of this waste

contains materials and energy that can be recovered and reused. The pyrolysis process – with its ability

to thermally decompose organic material into gas, oil, carbon and other products – holds the key to

harvesting the economic value of everyday waste.

Many unsuccessful attempts to commercialize thermal decomposition processes have been made, over

the years. The high failure rate can be attributed to:

Unreliable feedstock arrangements

Unproven, poorly understood, and costly pyrolysis technologies

Emissions and permitting uncertainties

Undeveloped end markets for pyrolysis by-products

Inexperienced management teams

Inability to define capital needs and raise capital

By contrast, the system that will be installed in Louisiana addresses and resolves all of these issues.

Today, the company has improved pyrolysis technology and developed a business model that “cracks

the pyrolysis code” and creates a viable environmental and business solution for the future. This

technology is already in operation around the world, and because of a continuous improvement in

technology and low cost manufacturing, it is now coming to the U.S.

This report discusses critical elements of the business model, including a total solution that enables a

financially-successful application of the technology, while helping to solve some of our most

challenging environmental issues. Specifically, the CTSW group of companies want to answer the

questions:

What is pyrolysis technology, and how does it work?

How do we create an economic benefit from waste tires and other feedstock?

2

How do states, cities and businesses build a sustainable system to protect the environment from the

growing volume of waste tires generated – worldwide – every day?

What elements influence the successful application of pyrolysis technology?

Who is bringing this technology to the U.S.?

Waste tire processing, one of the most difficult environmental issues of today, will be the basis for most

of this discussion, but the potential for other feedstocks is also discussed.

3

The Case for Pyrolysis of Waste Tires and Other Feedstock Waste Tires The U.S. generates an estimated 300 million waste tires, with another 1 to 3 billion tires already

stockpiled in landfill operations. Despite using recycled waste tires for fuel and commercial products,

illustrated in Figures 1 – 3, waste tires remain one of our biggest disposal challenges because of their

volume and non-degradability. In landfills, waste tires are often home for pests and insects, and are

known to be a noxious fire hazard that can burn for months.

Figure 1. Figure 2. Figure 3. Waste Tires Shredded Tires Close-up of Shredded Tires

Most states have instituted a system to control the disposal of these tires through a network of tire

processors and haulers who get paid tipping fees for tire disposal. Landfill and the sale of shredded tires

as civil engineering materials or industrial Tire Derived Fuel (TDF) are typical disposal methods for

waste tires. In 2003, 130 million scrap tires (45% of waste tires generated) were used as fuel in the

cement, pulp and paper utilities, and other industries, according to the EPA. Today, there is some

uncertainty in the TDF industry regarding

possible legislation that would restrict its use

as a fuel.

Direct recycling of waste tire materials takes

the form of crumb rubber and the waste tire

shreds used in civil engineering materials, such

as rubber modified asphalt, sub-grade fill, and

embankments. Recycled materials are also

used in applications such as carpet padding,

automotive parts, and mulch.

Thermal decomposition of waste tires through

an environmentally-friendly, efficient pyrolysis

process could not only recover valuable

elements and chemicals for industrial use, as

shown in Figure 4, but could help to solve

waste tire disposal challenges.

Figure 4. Estimated percentage of recovered elements

4

Pyrolysis

Pyrolysis is the thermal decomposition of organic material in the absence of oxygen. It is not a new

discovery. Its earliest uses were in making charcoal, a concentrated carbon residue that burns at an

elevated temperature, making it useful for industrial processes and cooking. It is possible to use

pyrolysis with a variety of feedstocks, including tires, biomass, paper, and some plastics.

The pyrolysis process takes place when a feedstock is heated to high temperatures – above about 600° F

– in the absence of oxygen. This process thermally depolymerizes the feedstock and gasifies the organic

elements, creating a hydrocarbon gas that can be burned as fuel, or condensed and converted into oil.

Usable carbon char is also generated in this process. Since oxygen is not present during the process and

it is totally closed, emissions are very low, especially when compared to burning TDF.

The characteristics of the pyrolysis products are related to the process temperature, rate of temperature

increase, and retention time. In general, lower process temperatures produce more oil, and less gas,

while higher temperatures tend to create more gas. Pyrolysis processes are characterized by time and

temperature regimens, which produce different product characteristics.

Temperature Range °C Time End Products

Carbonization 325-500 Days Charcoal

Pressure Carbonization 450 Minutes to 2 hrs Charcoal

Slow Pyrolysis 400-600 Minutes – several

hours Char, Oil, Gas

Fast Pyrolysis 650-3000 Less than 1 second Oil, Gas

Vacuum Pyrolysis 350 - 500 Seconds Oil

Gasification Technologies

Another technology that has been experimented with over the years is Gasification, a close relative of

pyrolysis. Gasification is similar to pyrolysis in that it thermally decomposes organic materials. It

differs from pyrolysis in that the gasification process takes place with a controlled amount of oxygen or

steam present, usually operating at higher temperatures than pyrolysis.

Gasification systems are designed to maximize the amount of gas produced. The gasses are combustible

and are generally used for energy and producing power. This gas can be used directly to produce heat or

used as a fuel for gas engines and gas turbines to generate electricity; in addition, it can also be used as a

feedstock (syngas) in the production of chemicals, e.g., methanol.

The greatest technical challenges for the development of this technology are the cost and complexity of

its systems, and adequately cleaning the tars and particulates from the producer gas, to enable efficient,

economical system operation. (Tars and particulates have to be removed from the producer gas before

entering a gas turbine or engine, so that it can operate without plugging piping and filters with materials

that may be carcinogenic.)

Much research is being done today to find answers to these challenges and to create an understanding of

the time, temperature, and residence time of a wide variety of feedstocks. Further development of

5

gasification technology must come with a breakthrough in cost so that its benefits can be more broadly

applied.

Tire Pyrolysis

The system being installed in Louisiana is an example of a simple, affordable technology that has

proven itself around the world as an effective means of recovering carbon, oil, and steel from waste

tires.

Previous attempts to thermally decompose tires have not produced an optimum solution in the U.S. or

any other country where there are large numbers of vehicles. Addressing the need for a total solution,

Bill Petrich, Senior Advisor for CTSW, states: “Previous attempts at used tire thermal conversion were

exercises in poorly understood science, poorly understood markets for harvested products and under-

capitalized resources. Technical talent, coupled with the administrative and financial responsibility

absolutely required for this type of project, has only been realized in the last few years.”

Better understood science and an effective pyrolysis process would make pyrolysis systems

economically attractive for converting waste tires to a source of fuel and useful industrial materials, and

help solve the environmental issues associated with waste tires.

Pyrolysis of waste tires creates numerous financial and environmental benefits. Recovered carbon

products can be used in industrial applications to replace the more expensive virgin carbon black

material. The revenue opportunity for both carbon and oil depend largely on the degree of processing

and enhancement of the materials. Market pricing of carbon today is between $.05 per lb. to over $5.00

per pound, again depending on the degree of processing. Similarly oil can be used as an intermediate

fuel oil feedstock, or a chemical feedstock. Market prices for fuel range from $.80 to $1.25 per gallon,

and even higher for fuel use as a chemical feedstock.

The environmental benefits include a landfill volume reduction, and the potential for a better emissions

and energy profile than virgin carbon black plants. Every pound of virgin carbon black produced

generates over 2 pounds of CO2. By contrast, the CTSTL technology produces a fraction of that

number per pound of carbon produced. The ability to burn some of the process oil and pyro gas to fuel

the process and to generate electricity lowers operating costs. So in addition to the economic value of

the recovered carbon, oil and steel, the process has a relatively positive impact on the environment.

On average, for every 1,000,000 waste tires processed through a well-designed pyrolysis system, the

following benefits are realized:

Carbon 3,375 tons

Oil 44,000 barrels

Steel 788 tons

Landfill reduction 83,000 cu. yd

CO2 reduction vs. Tire Derived Fuels combustion Lower

CO2 reduction per pound of Carbon vs. Virgin Carbon Black production Lower

Energy Reduction per pound of Carbon vs. Virgin Carbon Black production Lower

6

In most states in the U.S., waste tire processors and investors can add to their existing operations and

realize additional financial returns by installing a pyrolysis process. A typical pyrolysis process is

illustrated in Figure 5.

Figure 5. Process flow diagram

Other Feedstocks

Other waste carbon-based feedstocks are plentiful and can be converted to usable products through

pyrolysis processes. Therefore, installing a pyrolysis system that can handle a variety of feedstocks is

advantageous.

Biomass and Municipal Solid Waste (MSW) are two examples. Biomass includes plant, wood, crop

residues, solid waste, animal waste, sewage, and waste from food processing. Biomass pyrolysis

generally produces less carbon than waste tires, and its oil has more oxygen content, more water, and is

more acidic. Post-processing of the oils can upgrade its characteristics to increase energy density and

reduce its corrosiveness.

MSW is a heterogeneous feedstock that includes organic and inorganic wastes, hospital waste, plastics,

metals, and paper. The carbon-based wastes that are a part of this feedstock can be pyrolyzed to produce

oil, gas and char. MSW installations usually require capital invested in sorting systems to get to a more

homogeneous feedstock where pyrolysis systems operate more efficiently.

In the sections that follow, how the new Louisiana pyrolysis plant brings a solution to the business and

technical challenges relating to profitable thermal conversion of waste materials is presented.

7

The CTSW Solution

The CTSW group of companies offers a complete solution for waste tire pyrolysis. After searching the

world for pyrolysis technologies, CTSW has found not only the technology, but has also structured a

solid business model around it. This model clearly shows the benefits of these installations for

municipalities, tire processors, and investors. Further, its versatile technology has the potential to serve

industries that produce other feedstocks. The total solution includes solutions to some of the challenges

that have been barriers for previous efforts.

Clean Tech Solutions Louisiana (CTSL) has purchased the Jupiter™ pyrolysis process that was

developed in China by the Ruixin Environmental Specialty Equipment Manufacturing Company

(RESEM), a joint venture between CTSW and the Shangqiu Rui Xin Equipment Company, the Chinese

partner. RESEM was founded in 2004 and has sold more than 100 thermal conversion systems through

Asia, the Middle East and Europe.

Many engineering, business and regulatory questions must be answered in order to commercialize a

pyrolysis system successfully. The following sections present an overview of the technical and business

plans that can now be made available to other business concerns in the U.S., and in other countries. The

key elements to these plans include:

Pyrolysis Technology

Feedstock

End Markets and Customers

Emissions and Permitting

Capital and Funding

Management

The CTSTC Thermal Conversion Plant Technology

As a part of the JV operation, CTSW has worked within RESEM to upgrade the pyrolysis system to the

10-ton Jupiter system that meets emissions and other U.S.-required standards. The components of the

upgrade and details of the full commercial process are shown below.

Upgrade Full Commercial Process

Stainless steel reactor and condenser components

PLC control system for time and temperature control (complete with Internet monitoring capability)

Integrated pyro gas management system

Enhanced emissions control system

Waste tire shredding equipment

Automatic in-feed conveyors

Self-generated utilities system for electricity and steam

Highly effective emission control system

Carbon processing and handling equipment

Warehousing

Figures 6 and 7, below, show plants in Korea and Inner Mongolia.

8

Figure 6. Plant in Korea

Figure 7. Plant in Mongolia

CTSL’s engineering process includes foundation designs, flow diagrams, P&ID’s, plant layout

arrangements, equipment lists and other engineering information. A typical process arrangement for the

thermal conversion system is shown in Figure 8, below.

Figure 8. CTSW typical plant

The technology is versatile, with capabilities to handle more than one feedstock. It uses the pyrolysis

catalytic reforming approach to convert waste tires into sellable products that include finely milled

carbon char, three cuts of oil, pyrolysis gas, and high quality tensile steel. The technology operates in a

9

batch mode, and decomposes the waste tires to molecular gas and oil in an oxygen-free, externally-

heated reaction vessel in a temperature-controlled process. The typical thermal conversion cycle occurs

over a 14-hour period (including loading and unloading). At the end of the batch cycle, condensed oil,

carbon and steel are collected and stored for sale.

Plant Operation

The plant operating process consists of the following steps:

1. Waste tire receiving

2. Waste tire shredding and inventory storage, as required

3. Waste tire shred feed into the Thermal Conversion Reactor

4. Thermal Conversion Reactor operation

5. Condensing, processing and storage of light-cut, mid-cut and heavy-cut oil

6. Carbon char processing (i.e., metal removal, milling, pelletizing, blending, and packaging)

7. Carbon, oil and steel finished product storage

8. Emissions control system for the combustion chamber

9. Excess gas combustion system and emissions control system

10. Self-generated steam and electricity with excess pyro gas and oil.

Shredded tires are transported to the reactor via an in-feed conveyor. This conveyor contains a weigh

scale for accurate tracking of feed quantities. The conveyor feed is monitored from the control room.

The typical loading process takes less than 30 minutes.

Some of the oil and pyro gas generated in the thermal conversion process is used to provide the energy

input for pyrolysis. Stored oil from the process is used to start the combustion process until pyro gas

generation is sufficient to fuel the thermal conversion process. A stainless steel reactor drum rotates in

order to maximize heat transfer characteristics. In addition, steam and electricity for utilities can be

generated on the plant site, with surplus pyro gas and the combining of the light and heavy pyro oil

recovered from the pyrolysis process.

Heat exchangers and condensers used in the oil recovery system are

water-jacketed tanks, supplied by water from the water box. A cooling

tower controls water supply temperature. To optimize process

conditions, a secondary oil processing step can be provided to enhance

odor and flashpoint characteristics of the mid-cut oil, increasing the

market demand and price for the recovered oil.

Complete control of time and temperature in the reactor ensures product

decomposition and consistency in product quality. A Programmable

Logic Controller (PLC) system (screen shown in Figure 9) can monitor

and control the entire process from a central control room.

Figure 9. PLC screen

10

After processing, the carbon char is removed from the reactor through a vacuum suction system and

delivered to the carbon processing area. The high tensile steel remaining in the reactor, after the pyro-

carbon is discharged, is collected and stored for sale.

Typically, operating crews consist of five to seven people per shift, including process operations and

maintenance.

Feedstock

Successful pyrolysis projects must have a reliable, ongoing source of feedstock. CTSW targets its

offering to those companies that already have control of a waste tire or other feedstock, or that have a

significant environmental issue to solve with their current disposal methods. CTSW also has established

a network of possible feedstock suppliers for companies that would like to get into the business.

End Market and Customers

Significant knowledge and relationships in the carbon and oil markets (for sales of the end products) are

essential to successful and profitable operation of a thermal conversion site. For example, to sell

recovered carbon end product, customers will need to run a gauntlet of tests and evaluations to prove the

raw material’s performance in each application and recipe.

Carbon Solutions LLC is the registered CTSW company leading the efforts to qualify recovered

carbon for various customer applications. Carbon Solutions will work with customers in various ways

to secure customers for their end products. These relationships range from working in an advisory

capacity to, potentially, offering a guaranteed off-take of carbon for qualified customers who do not

want to take the risks associated with selling recovered carbon into the carbon market. Carbon Solutions

can provide end market development support through its relationships with global “end use” customers.

The steel market is straightforward and easily accessible.

Carbon Solutions has invested significant time and financial resources to understand the process of

thermal conversion of tires, including how tires are manufactured, the blend of elastomers used in tire

construction, the additive materials beyond carbon black (e.g., oil and zinc oxide), accelerating

chemistries, and cure systems.

Recognizing that the process was one of the keys to achieving consistent and predictable products from

the harvest, Carbon Solutions and its technical staff accumulated data from several pyrolysis

technologies, and then isolated the specific variables that are involved in their unique process:

Time, temperature, pressure, dwell time

Composition variables, such as ratio of poly-isoprene to styrene-butadiene in the recipe

Sulfur in all variations used for cure mechanisms

Reactivity, release and re-combination with oxygen

Surface conditions of carbon-black as originally formulated, and how this property is affected by

heat, pressure, sensitivity to other elements, such as zinc.

11

Carbon Solutions has differentiated itself by recognizing the need to continue research and development,

well beyond the simple thermal conversion attempted by others. Strategic partners, including academic

affiliations at the university level, and trade association cooperation in the adhesives, coatings, sealants,

latex, rubber and plastic areas are part of the planning and execution of the Carbon Solutions program.

We know of no other recycling company providing speakers, data sharing and cooperative research

efforts, to this extent.

Preliminary market research on the products developed through Carbon Solutions has enabled the

company to identify a number of markets previously unrecognized by predecessors, including:

Use of evolved gas as feedstock for the development of new chemistries.

Recognition that condensate products can be influenced to intermediate, reactive moieties of much

higher value than simply “fuel oil.”

Modeling of the “char” fraction reveals an entirely new family of chemistries; other attempts believed

that this material would simply be used again in tire rubber.

Use by industrial markets, never envisioned by earlier attempts, include but are not limited to:

Reinforcement engineered materials for elastomers, thermoplastic and thermosetting resins,

including EPDM, urethane and epoxy systems

Color for ceramic, plastic, paint, ink, coatings and graphic arts application including glass

Electro-chemical functions only recently identified

Dispersions in organosols (plastisols used in “casting” and “mold making” specialties)

Soil amendments through mechanism of carbon sequestration, unique to Carbon Solutions

Activation with co-carbon elements, unique to Carbon Solutions and their strategic partner, for

water and air cleansing

Distillation carrier for recovery of aromatic and aliphatic hydrocarbons, resulting in clear, water

white, reusable solvents.

In addition, the CTSTC system provides the following:

A method of size reduction (milling) that is a critical processing step in meeting customer

specifications. The ability to “size-reduce” has resulted in a new family of “meta-materials”

affecting the way materials can be used in formulated products.

A post-formation “enhancement” of carbon small-particle clusters that increases the marketability

and value of products developed through CTSTC technology. Improved physical and chemical

properties, including electrical conductivity, magnetic performance, higher water resistance or water

acceptability, oil rejection or acceptance, predictable hardness performance with new rubber and

plastics are being developed. Below are the four basic application categories for recycled carbon:

Series 100 - Reinforcement products and carbon-black extenders for rubber.

Series 200 - Color for color concentrate in thermoplastic and thermosetting resins.

12

Series 300 - Activated and co-activated products for air and water cleansing.

Series 400 - Specialty applications

Pyro Oil

Similar to the efforts in developing high quality carbon products, CTSTC has invested in understanding

oil chemistries produced by the waste tire pyrolysis process. Components of the process are shown in

Figures 10 and 11.

Through sampling and gas chromatography, CTSTC has created a detailed mapping of compounds and

has applied for Toxic Substances Control Act (TSCA) permits for the sale of these materials. CTSTC

also has explored the catalyst chemistry and steam stripping systems to enhance the oil flashpoint and

odor properties. CTSTC’s pyro oil is branded: Carbonol™. Carbon Solutions is developing a network

of pyro oil customers for Carbonol.

Emissions and Permitting

The Jupiter model pyrolysis system is designed to meet U.S. emissions standards. However, each state

and each country has regulatory oversight for emissions. Therefore, numerous standards exist. One of

the first questions prospective customers in the U.S. ask is, “does this process meet emissions standards

requirements so that I can get the permits I need to implement this process in the U.S.?” Because the

closed, oxygen-free process environment generates low emissions, the answer is “yes.” In fact, for

plants up to 60TPD, this process qualifies as a small or minor emitter.

The CTSW group has developed a large body of information about this process to assist customers with

the applications process for permits in any state. In addition, a body of information regarding all permits

necessary to operate the plant has been developed.

Capital and Funding

Before embarking on a new pyrolysis project, a complete understanding of the capital and working

capital requirements for the project, as well as return on investment, is critical. CTSW has developed

capital cost data for engineering and installation of a turnkey project.

For analyzing project financials, CTSW has developed an Excel-based financial model that can provide

pro forma financial analyses with any carbon and oil pricing, capital, and operating cost assumptions.

Figure 10. Partial carbon collection Figure 11. Oil storage tank

13

Most importantly, CTSW’s direct experience in working with federal, state, and local governments to

gain access to grant funds and tax incentives, can assist customers in creating a strong financial pro

forma. This knowledge can be the key to creating stronger profits and returns.

Management

Perhaps no other asset is as valuable as the capability, knowledge and experience of the people who do

the research and deliver the project. CTSW has assembled a world class network of experts, engineers,

suppliers, and marketing and sales professionals. The CTSW group is led by a former CEO of a Fortune

500 company, and its senior management team members are accomplished in all phases of the work

required for successfully commercialized pyrolysis. This team brings this knowledge in responding to

prospective customer inquiries.

CTSW has also established Clean Tech Solutions Technology Company (CTSTC) for equipment sales,

along with its carbon sales organization (Carbon Solutions), led by accomplished leaders and experts.

CTSW’s management approach is one of the company’s strongest assets. The management approach

consists of working with customers on three options:

Customers can purchase one of the four lines of CTSTC for installation in their facilities, with

consulting support from CTSW, as needed.

CTSW can perform a feasibility study for any customer who needs answers to questions involving

commercialization in their location(s).

CTSW can provide the turnkey system plus operations personnel at the customer’s site, to mine their

feedstock. Thus, customers who do not have installation and operations capabilities can still reap the

benefits of an on-site pyrolysis system.

The creative approaches described in this paper are based on actual experience with the technical and

management aspects of pyrolysis systems. CTSW is now in the process of establishing a consulting

company to assist customers with the options listed above.

For further information, please call 318.876.3100 Lloyd Ward CTSW

Greg Jordan CTSW