12.00 progress in radiation methods for petroleum processingiiaglobal.com/uploads/yuriy...

Yuriy Zaikin and Raissa Zaikina

PetroBeam, Inc., USAwww.petrobeam.com

Progress in Radiation Methods for Progress in Radiation Methods for Progress in Radiation Methods for Progress in Radiation Methods for Petroleum ProcessingPetroleum ProcessingPetroleum ProcessingPetroleum Processing

9212 Falls of Neuse RoadRaleigh, NC 27615

151 Heartland Blvd,Edgewood, NY 11717

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� Demand for the new type of technology Demand for the new type of technology Demand for the new type of technology Demand for the new type of technology for oil processingfor oil processingfor oil processingfor oil processing

�PetroBeamPetroBeamPetroBeamPetroBeamTMTMTMTM technology: technology: technology: technology: general characteristic and fundamentalsgeneral characteristic and fundamentalsgeneral characteristic and fundamentalsgeneral characteristic and fundamentals

�Applications of Applications of Applications of Applications of PetroBeamPetroBeamPetroBeamPetroBeamTMTMTMTM Process: Process: Process: Process: upgrading of heavy and highupgrading of heavy and highupgrading of heavy and highupgrading of heavy and high----paraffin oilparaffin oilparaffin oilparaffin oil

� Advantages of the Advantages of the Advantages of the Advantages of the PetroBeamPetroBeamPetroBeamPetroBeamTMTMTMTM technologiestechnologiestechnologiestechnologies

Demand Demand Demand Demand for the new type of technology for the new type of technology for the new type of technology for the new type of technology for heavy oil processingfor heavy oil processingfor heavy oil processingfor heavy oil processing

Traditional methods of deep oil processing Traditional methods of deep oil processing Traditional methods of deep oil processing Traditional methods of deep oil processing are usually efficient only for oil feedstock with density up to are usually efficient only for oil feedstock with density up to are usually efficient only for oil feedstock with density up to are usually efficient only for oil feedstock with density up to 0.90 g/cm30.90 g/cm30.90 g/cm30.90 g/cm3 , , , , …………

………… hydrocarbonhydrocarbonhydrocarbonhydrocarbon feedstockfeedstockfeedstockfeedstock ofofofof higherhigherhigherhigher densitydensitydensitydensity suchsuchsuchsuch asasasas heavy crude oil, heavy heavy crude oil, heavy heavy crude oil, heavy heavy crude oil, heavy residua of oil primary processing, wastes of oil extraction and residua of oil primary processing, wastes of oil extraction and residua of oil primary processing, wastes of oil extraction and residua of oil primary processing, wastes of oil extraction and bitumenbitumenbitumenbitumen withwithwithwith highhighhighhighcontentscontentscontentscontents ofofofof pitchespitchespitchespitches, , , , asphaltenesasphaltenesasphaltenesasphaltenes, , , , isisisis difficult for upgrading and difficult for upgrading and difficult for upgrading and difficult for upgrading and undesirableundesirableundesirableundesirable forforforforconventionalconventionalconventionalconventional refineriesrefineriesrefineriesrefineries....

Demand Demand Demand Demand for the new type of technology for the new type of technology for the new type of technology for the new type of technology for heavy oil processingfor heavy oil processingfor heavy oil processingfor heavy oil processing

Despite the impressing success in exploration and development of the huge world bitumen and heavy oil reserves, such as Athabaska oil sand, still high capital and operation costs restrain generous efforts of high capital and operation costs restrain generous efforts of high capital and operation costs restrain generous efforts of high capital and operation costs restrain generous efforts of synthetic oil producers.synthetic oil producers.synthetic oil producers.synthetic oil producers.

Huge capital investment into presently Huge capital investment into presently Huge capital investment into presently Huge capital investment into presently technology used for upgrading heavy oil technology used for upgrading heavy oil technology used for upgrading heavy oil technology used for upgrading heavy oil and bitumen product to make it market and bitumen product to make it market and bitumen product to make it market and bitumen product to make it market

valuable and commercially transportable valuable and commercially transportable valuable and commercially transportable valuable and commercially transportable is caused by fundamental peculiarities of is caused by fundamental peculiarities of is caused by fundamental peculiarities of is caused by fundamental peculiarities of used classic thermal and used classic thermal and used classic thermal and used classic thermal and thermocatalyticthermocatalyticthermocatalyticthermocatalytic

processing.processing.processing.processing.One of the main problemsOne of the main problemsOne of the main problemsOne of the main problems to be solved is to be solved is to be solved is to be solved is combination of combination of combination of combination of high processing ratehigh processing ratehigh processing ratehigh processing rate and and and and sufficient conversion degreesufficient conversion degreesufficient conversion degreesufficient conversion degree with with with with maximum simplicitymaximum simplicitymaximum simplicitymaximum simplicity and and and and economic economic economic economic efficiencyefficiencyefficiencyefficiency at at at at minimum energy expenseminimum energy expenseminimum energy expenseminimum energy expense

Radiation Methods for Oil ProcessingRadiation Methods for Oil ProcessingRadiation Methods for Oil ProcessingRadiation Methods for Oil ProcessingHardly achievable in frames of conventional methods, these goalsHardly achievable in frames of conventional methods, these goalsHardly achievable in frames of conventional methods, these goalsHardly achievable in frames of conventional methods, these goals

can be efficiently realized by application of electron beams forcan be efficiently realized by application of electron beams forcan be efficiently realized by application of electron beams forcan be efficiently realized by application of electron beams foroil feedstock processing. oil feedstock processing. oil feedstock processing. oil feedstock processing.

The great potentialities of these methods for heavy oil processing come from the higher efficiency of

energy transfer to hydrocarbon molecules and radiation ability to initiate and to propagate of highinitiate and to propagate of highinitiate and to propagate of highinitiate and to propagate of high----

rate selfrate selfrate selfrate self----sustainable chain sustainable chain sustainable chain sustainable chain reactions in hydrocarbons at reactions in hydrocarbons at reactions in hydrocarbons at reactions in hydrocarbons at

lowered temperatures and nearly lowered temperatures and nearly lowered temperatures and nearly lowered temperatures and nearly atmospheric pressure.atmospheric pressure.atmospheric pressure.atmospheric pressure.

It is convenient to consider the mechanism of the PetroBeam process by

analogy with the well-known methods of conventional thermal cracking

(TC) and radiation-thermal cracking (RTC).

PetroBeamTM process*) is a self–sustaining chain cracking reaction of hydrocarbon molecules decomposition at lowered temperatures down to room temperature

Technology Fundamentals

Similar to these conventional methods,

PetroBeamTM process proceeds by the radical mechanism.

*) US patent application P79993US00GP.


Two steps of crackingThe thermal cracking of hydrocarbons usually takes place at high temperatures (for example, 500-6000C for heptane). According to the generally accepted theory, this process is accomplished in two stepstwo stepstwo stepstwo steps:1111. Initiation of the reaction by radicals. Initiation of the reaction by radicals. Initiation of the reaction by radicals. Initiation of the reaction by radicalsproducedproducedproducedproduced by dissociation of a molecule of the starting compound; and2222. Propagation of the chain.Propagation of the chain.Propagation of the chain.Propagation of the chain.


RTC mechanism• The chain propagation process results in formation of a reactionThe chain propagation process results in formation of a reactionThe chain propagation process results in formation of a reactionThe chain propagation process results in formation of a reaction

product molecule and of a new large radical.product molecule and of a new large radical.product molecule and of a new large radical.product molecule and of a new large radical. It can dissociate into an olefin molecule and a shorter, more reactive radical which will be able to propagate the chain.

• The initiation step requires the activation energy of about 250 about 250 about 250 about 250 kJ/molekJ/molekJ/molekJ/mole, i.e. the thermally activated reaction can proceed at an appreciable rate only at the temperatures of 500-6000C. RTC releases this most energy-consuming stage of the chain cracking reaction.

• The chain propagation step, controlled by dissociation of the The chain propagation step, controlled by dissociation of the The chain propagation step, controlled by dissociation of the The chain propagation step, controlled by dissociation of the radical, requires the activation energy of radical, requires the activation energy of radical, requires the activation energy of radical, requires the activation energy of about 80 kJ/moleabout 80 kJ/moleabout 80 kJ/moleabout 80 kJ/mole,,,, i.e. it i.e. it i.e. it i.e. it requires a much lower temperature.requires a much lower temperature.requires a much lower temperature.requires a much lower temperature.


Two main conditions and two stages are necessary Two main conditions and two stages are necessary Two main conditions and two stages are necessary Two main conditions and two stages are necessary for chain cracking reaction:for chain cracking reaction:for chain cracking reaction:for chain cracking reaction:

1 2

Radiation-chemical yields of the reaction productsRadiolysis (without chain reactions ) - 3-5 molecules per 100 eV

RTC – up to 20,000 molecules per 100 eV

Formation and maintenance of Formation and maintenance of Formation and maintenance of Formation and maintenance of relatively low concentration of relatively low concentration of relatively low concentration of relatively low concentration of chain carriers ( light radicals of chain carriers ( light radicals of chain carriers ( light radicals of chain carriers ( light radicals of

type) necessary type) necessary type) necessary type) necessary for cracking initiation;for cracking initiation;for cracking initiation;for cracking initiation;

Formation and maintenance of the certain Formation and maintenance of the certain Formation and maintenance of the certain Formation and maintenance of the certain concentrations of excited molecules concentrations of excited molecules concentrations of excited molecules concentrations of excited molecules necessary for chain propagation necessary for chain propagation necessary for chain propagation necessary for chain propagation (interaction of radicals with excited (interaction of radicals with excited (interaction of radicals with excited (interaction of radicals with excited molecules and their disintegration).molecules and their disintegration).molecules and their disintegration).molecules and their disintegration).

•••

523,, HCCHH


RTC theory assumed that concentration of excitedmolecules suffficient for the noticeable rate of chain

cracking reactions can be created only by thermal activation of hydrocarbon molecules at the

temperature not lower than 3500C.

Radiation generation of the excited molecular states was neglected because the lifetime of the excitedstates was supposed to be too low (10-15-10-14 s)

alhtough there were studies indicating to the existence of the long-living excited molecules,

especially in aromatic hydrocarbons.


Generally, the rate of radiation-induced cracking is proportional to the concentration of radiation-generated radical chain carriers [R] and

concentrations of excited molecules C* :

2/1

)(•

D[R] ~

As a result, the assumed dependence of the cracking rate on the dose rate is

2/1

)(•

DW ~

W ~ [R] C*= [R] (C*therm + C*rad ),

In RTC theory, C*rad is neglected and the steady state radical

concentration is proportional to square root of the dose rate:


C*rad ~

The theory of PetroBeam process takes into account interaction of radical chain carriers with radiation-excited molecules or with hydrogen atoms in

the isolated pairs “hydrogen atom-unstable radical” generated by ionizingirradiation. Concentration of these reactive particles responsible for chainpropagation is

•

D

It results in a stronger dose rate dependence of the cracking rate :

2/1)(

•

D

2/3

)(•

DW = A (T) + B

Our analysis of the available data on radiation-induced cracking of model

hydrocarbons and different types of petroleum feedstock in a wide range of

temperature and irradiation parameters has confirmed the dose rate dependence

predicted by this equation.


This effect of dose rate on

the efficiency of oil processing was used in

PetroBeam process.

Efficiency of PetroBeam process application at lowered

temperatures depends on the structural state of oil processed.


The described above regularities get upset for the

heaviest types of oil feedstock characterized by

availability of dense radiation-resistant low-temperature colloid structures. In this case, dose

and dose rate dependences of the cracking rate

become more complicated and additional

factors limiting oil conversion, such as critical ranges of irradiation dose and dose rate and

critical thickness of the irradiated layer, should

be taken into account.

To overcome these limitations To overcome these limitations To overcome these limitations To overcome these limitations associated with lowassociated with lowassociated with lowassociated with low----temperature temperature temperature temperature structures and to make radiation structures and to make radiation structures and to make radiation structures and to make radiation processing of heavy oil and bitumen processing of heavy oil and bitumen processing of heavy oil and bitumen processing of heavy oil and bitumen highly efficient, highly efficient, highly efficient, highly efficient, PetroBeamPetroBeamPetroBeamPetroBeam technology technology technology technology uses additional methods for oil uses additional methods for oil uses additional methods for oil uses additional methods for oil structural destabilization.structural destabilization.structural destabilization.structural destabilization.

These methods include preliminary and under-beam mechanical agitation of oil feedstock, acoustic processing, oil bubbling with special agents, gas or steam injection to the reaction zone, etc.

Technology FundamentalsTechnology FundamentalsTechnology FundamentalsTechnology Fundamentals

Applications of the PetroBeam process

The tests of the PetroBeam pilot line in IBA Industrial, NY, have demonstrated its ability to production of high-quality synthetic oil

from bitumen and heavy oil residua without any

coke production.

Mass balances

Typical mass balance for

PetroBeam processing of heavy oil

at lowered temperatures

(in respect to the feedstock mass):

97-98% - liquid product of oilradiation processing;

2-3% - gases

The typical content the gaseous fraction is:

4-7 mass % hydrogen, 35-40 mass % methane, 18-21 mass % ethane, 10-12 mass % butane, 10-12 mass % ethylene, 8-12 mass % propylene

and other hydrocarbon gases.

Synthetic Oil

Gases

hydrogen,

methane,

ethane,

butane,

ethylene,

propylene

and other

hydrocarbon

gases

The high-viscous crude oil

was processed with

3 MeV electrons at the PetroBeam

facility in flow

conditions

at the temperature

of 1200C.

Crude oil- 17.5 API0

PB product - 27API0

0

10

20

30

40

50

SB-200C 200-250C 250-360C 360-450C >450C

Yie

ld,

ma

ss

%

feedstock

D=12kGy

D=20kGy

Fractional content of high-viscous crude oil

and product of its radiation processing


The high-viscous crude oil

was processed with 3

MeV electrons

at the PetroBeam

facility in flow

conditions

at the temperature

of 800C

0

10

20

30

40

50

SB-200C 250-350C 350-500C > 500C

Yie

ld, m

ass%

feedstock

D=14kGy

Fractional content of high-viscous crude oil

and product of its radiation processing


The high-paraffin crude oilused in our experiments is

relatively light (32 API0) but its

solidification temperature is as high

as 300С.

0

10

20

30

40

SB-250C 250-350C 350-460C > 460C

yie

ld,

ma

ss

%

feedstock

D=8.5 kGy

Fractional contents of high-paraffin crude oil and

the product of its radiation processing

Due to the irreversible changes in oil fractional

contents, its solidification

temperature decreased

down to -100C.


Together with the high concentration of heavy paraffins,

this type of oil contains a considerable amount of pitches

and asphaltenes.

The high-viscous heavy fuel oil

(oil #6)was processed at the

PetroBeam pilot line.

Conversion of 35%

for the heavy residue

boiling out above

4500C was reached

at the electron

irradiation dose of

24 kGy .

Fractional contents of oil#6 and

product of its PetroBeamTM processing at 1200C

Conversion heavy residua (>450C) - 35%

D=24 kGy

0

10

20

30

40

SB-250 250-350 350-450 450-550 550-650 >650

Yie

ld,

ma

ss

%

feedstock ( 15API)

PB product (25 API)

The changes in the fractional

contents of the feedstock were

accompanied by the drop in the

product viscosity by 86%.


0

1

2

3

4

5

0 50 100

T,C

Vis

co

sit

y, P

a s

feedstock

product

The bitumenwas characterized by

the density of 0.9781

g/cm3 (API gravity

13.20) and the

kinematic viscosity of 2912 cSt. The C/H ratio

was 8.7.

Fractional contents of bitumen and product

of its PetroBeam processing at 1450C

Conversion of heavy residue - 34%

D=21 kGy

0

10

20

30

40

50

60

70

SB-250C 250-350C 350-550C >550C

Yie

ld, m

ass%

feedstock(13API)

PB product(22API)

PetroBeamTM

process provides

efficient upgrading

even for the

heaviest types of

oil feedstock


0

1

2

3

4

20 40 60 80 100

T,C

vis

co

sit

y, 1

03 m

Pa

s

product

feedstock

Energy consumption

Thermal cracking

(TC)

Radiation-thermal

cracking (RTC)

The process is thermally activatedThe process is thermally activatedThe process is thermally activatedThe process is thermally activated(1) Activation energy for cracking initiation is (1) Activation energy for cracking initiation is (1) Activation energy for cracking initiation is (1) Activation energy for cracking initiation is about about about about 250 kJ / mole250 kJ / mole250 kJ / mole250 kJ / mole; ; ; ; (2) Activation energy for chain continuation is (2) Activation energy for chain continuation is (2) Activation energy for chain continuation is (2) Activation energy for chain continuation is about about about about 80 kJ / mole.80 kJ / mole.80 kJ / mole.80 kJ / mole.

The process is radiationThe process is radiationThe process is radiationThe process is radiation----initiated and thermally initiated and thermally initiated and thermally initiated and thermally activatedactivatedactivatedactivated

((((1111)))) EEEEnnnneeeerrrrggggyyyy ffffoooorrrr ccccrrrraaaacccckkkkiiiinnnngggg iiiinnnniiiittttiiiiaaaattttiiiioooonnnn iiiissss aaaabbbboooouuuutttt 0.4 kJ / mole0.4 kJ / mole0.4 kJ / mole0.4 kJ / mole....

(2) Activation energy for chain continuation is (2) Activation energy for chain continuation is (2) Activation energy for chain continuation is (2) Activation energy for chain continuation is about about about about 80 kJ / mole80 kJ / mole80 kJ / mole80 kJ / mole. . . .

PetroBeamTM process

The process can be radiation The process can be radiation The process can be radiation The process can be radiation ––––activated.activated.activated.activated.The total consumption of radiation energy (dose The total consumption of radiation energy (dose The total consumption of radiation energy (dose The total consumption of radiation energy (dose of electron irradiation) is of electron irradiation) is of electron irradiation) is of electron irradiation) is 1111----10 kJ/mole10 kJ/mole10 kJ/mole10 kJ/mole

Advantages of the PetroBeamTM Process

Energy savings

In conditions favorable for low-temperature cracking, the doses of electron

irradiation required for high conversion of heavy oil are about 20 kGy, i.e.

the process requires energy consumption about 20 kJ/kg

compared with about 2000 kJ/kg characteristic for thermal cracking of

heavy oil or 1200-1600 kJ/kg characteristic for thermocatalytic or

radiation-thermal cracking.

Operating Temperatures (oC)

for the PetroBeam™ processcompared

to thermal cracking (TC),thermal catalytic cracking (TCC),

and

low temperature cracking (LTC)

0

100

200

300

400

500

600

TC TCC LTC PetroBeam™

PetroBeamTM Technology

� The PetroBeamTM process provides tremendous energy savings.

�It provides high-rate processing of heavy oil and bitumen at temperatures lower than 1500C and at nearly atmospheric pressure without application of catalysts.

�The PetroBeamTM process is highly economic due to low

capital and operating cost.

� It is characterized by versatility, easy scalability and ersatility, easy scalability and

integrabilityintegrability into existing refinery operationsinto existing refinery operations

The tests of the technology at the PetroBeam pilot line have demonstrated its high efficiency for upgrading the heaviest types of

petroleum feedstock.

12.00 progress in radiation methods for petroleum processingiiaglobal.com/uploads/yuriy...

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