Title of Invention	"A NOVEL PROCESS FOR THE PREPARATION OF LPG AND GASOLINE & DIESEL FROM VACUUM GAS OIL"
Abstract	A novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil by separating vacuum gas oil compound into saturated and aromatics compounds by well known SARA (saturates, aromatics, resins and asphalenes) method, fractionating the components into saturates and aromatics on alumina, then separating saturates into normal paraffins, iso-paraffins & cyclo paraffins using molecular sieve 5A° by known methods, heating different fractions at a temperature in the range of 100-150°C and injected through a preheater maintained at a temperature of 600°C and cracked in a metallic reactor in presence of zeolitic cracking catalyst at temperature 450-482°C at a weight hourly space velocity in the range of 16-160 h-1 and a reaction time of 50-75 seconds, collecting the gasoline & diesel in an ice cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%.

Title of Invention

"A NOVEL PROCESS FOR THE PREPARATION OF LPG AND GASOLINE & DIESEL FROM VACUUM GAS OIL"

Abstract

A novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil by separating vacuum gas oil compound into saturated and aromatics compounds by well known SARA (saturates, aromatics, resins and asphalenes) method, fractionating the components into saturates and aromatics on alumina, then separating saturates into normal paraffins, iso-paraffins & cyclo paraffins using molecular sieve 5A° by known methods, heating different fractions at a temperature in the range of 100-150°C and injected through a preheater maintained at a temperature of 600°C and cracked in a metallic reactor in presence of zeolitic cracking catalyst at temperature 450-482°C at a weight hourly space velocity in the range of 16-160 h-1 and a reaction time of 50-75 seconds, collecting the gasoline & diesel in an ice cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%.

Full Text	This invention relates to a novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil. In particular, the invention relates to a process for the cracking of hydrocarbon concentrates i.e. straight chain paraffins, iso+cycloparaffins and monoaromatics into LPG, gasoline and diesel. The invention more specifically relates to a process for the cracking of hydrocarbon concentrates in terms of hydrocarbon types i.e., straight chain paraffins, iso + cyclo paraffins and monoaromatics derived from Bombay high vacuum gas oil (VGO) of the hydrocarbon types given in Table-1 in presence of proven commercial cracking catalyst of the characteristics given in Table-2 into high value products like LPG, gasoline and diesel. Fluidized Catalytic Cracking (FCC) has proven to be a major process to convert vacuum distillates and residues into valuable products such as gasoline, diesel and LPG. FCC in its modern version is not only providing diesel and high octane gasoline, it is also meeting other challenges by providing building blocks for petrochemicals and antiknock extenders (MTBE, TAME, ETBE in the form of propylene, isobutylene and isomylene. Indian FCC Units are specifically geared to maximize light cycle oil (LCO) a diesel blending component. Projections of fuels demand in India shows that gasoline will become surplus in later years as refinery throughputs are increased. For the same period, diesel is expected to grow 37% and LPG consumption 41%. Therefore, values of products for Indian refiners increase continuously from distillate through gasoline to more olefinic LPG. Presently there is great pressure on FCC units to maximize middle distillates and olefmic LPG. The refiner can maximize these streams by using a novel catalyst, optimising process parameters within unit constraints and, hardware modifications through combined technologies as well as by revamp of existing units. The other variable i.e. the feedstocks characteristics can also influence the product yields and its pattern dramatically. The feedstock composition interms of hydrocarbon type distribution, such as straight-chain, iso+cycloparaffins and aromatics can completely alter the product slate. In cracking reactions a desired product can be maximized by using a feedstock having maximum number of precursors which will endup in forming that particular product. Refineries are generally faced with difficulties in the availability of feedstocks with desirable hydrocarbon types distribution. Due to this the refiners prefer to look for other variables such as selection of a right type of catalyst, hardwares and process parameters optimisation to suit the crackability of feedstocks to maximise a particular product in greater demand. To overcome these problems, the present invention suggests the use of hydrocarbon concentrates in terms of hydrocarbon types derived from the vacuum gas oil by the separation scheme presented in the following section. Thus the present invention provides a process for the cracking of hydrocarbon concentrates with identified and well defined requirements of hardwares and process parameters to maximise a particular product in greater demand. SEPARATION SCHEME A novel separation scheme which is experimentally convenient, less time consuming, repeatable and gives compound types with no chemical alteration has been used for the separation of hydrocarbon types from VGO. The well known SARA (saturates, aromatics, resins and asphaltenes) method was employed. Hydrocarbon were further separated into saturate and various aromatic concentrates on alumina. Saturates were further fractionated into normal paraffins and iso-paraffins plus cyclo paraffins using molecular sieve 5A°. The present invention provides a process for the conversion of various hydrocarbon concentrates prepared by using a separation scheme, discussed above into distillates and LPG fuel using commercially proven cracking catalyst. The novelty of the process lies in the cracking of hydrocarbon concentrates separated from vacuum gas oil, which is not known in the prior art. Accordingly the present invention provides a novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil which comprises (a) separating vacuum gas oil into saturated compounds and aromatic compounds by well known SARA (saturates, aromatics, resins and asphalenes) method, (b) fractionating the components into saturates and aromatics on alumina, then separating saturates in to normal paraffins, iso-paraffins & cyclo paraffins using molecular sieve 5 A° by known methods, (c) heating different fractions obtained in step (b) at a temperature in the range of 100-150°C and injected through a preheater maintained at a temperature of 600°C and cracked in a metallic reactor in presence of zeolitic cracking catalyst such as herein described at temperature 450-482°C at a weight hourly space velocity in the range of 16-160 h-1 and a reaction time of 50-75 seconds, (d) collecting the resultant liquid product of step (c ) i. e. agasoline & diesel in an ice cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%. According to further embodiment of the invention catalyst used is zeolitic commercial cracking catalyst with surface area 90-100 m2/g, zeolite content 10-15%, rare earth loading with 1.25-1.5 %, pore volume 0.15-0.20 ml/g, unit cell size with 24.34 to 24.38 and acidity mmoles/g of 0.33 to 0.35. The reaction time ranges preferably 50-75 sec. Table-1 Hydrocarbon Type Composition of VGO (Table Removed) TabIe-2 Physico-Chemical Characteristics of the Catalyst (Table Removed) DETAILS OF CONVERSION PROCESS The feed i.e. various hydrocarbon concentrates (1.33 gm ± 0.03) were heated in the range of 100-150°C and injected through a preheater (600°C) to the metallic reactor packed with 4 grams of catalyst and heated to 450- 482°C. After the reaction of the feed with the catalyst, product in the form of gas, liquid and coke is obtained. The liquid product was collected in an ice cooled receiver and analyzed by simulated distillation gas chromatograph. The gaseous products were analyzed by gas chromatography using squalane column at ambient temperature. The coke laden catalyst was regenerated at 650°C in a stream of air (50 cm3 min-1) for about 30 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%. Cracked products consists of the following useful products apart from others such as dry gas (DG) (H2, H2S, CH4, C2H6 and C2H4) and clarified oil regarded as unconverted and amount of material on distillation curve boiling above 370°C. LPG Comprises C3H8, C3H6, C4H10, C4H8 which are primary products important as domestic fuel and feedstock to downstream petrochemical industry. Gasoline Product which is quantitated as the amount of C5+ material in the reactor effluent gas plus the amount of liquid boiling upto 150°C on the distillation curve of effluent liquid. TCO Total cycle oil product, the yield is determined from distillation curve within the boiling range 150-370°C, a useful diesel blending component. Conversion Defined as fraction boiling below 216°C, including DG and coke yield. The following examples illustrates the process of invention and should not be construed to limit the scope of present invention. Example-1 n-paraffins mixture obtained from VGO was subjected to fixed bed cracking using commercially proven zeolite based cracking catalyst. Data from a typical experiment having catalyst to feed ratio of 4.8, reaction temperature 482°C and reaction time of 75 seconds showed the following product selectivities. MAXIMISATION OF LPG AND GASOLINE Feed N-paraffins concentrates Products (Table Removed) Example-2 Using iso-plus cycloparaffins as feed and catalyst at the reaction temperature of 482°C, catalyst/feed ratio of 4.8 and reaction time of 75 seconds the following product selectivities were obtained. MAXIMIZATION OF LPG AND GASOLINE Feed I so-Plus Cycloparaffins Products Dry Gas 1.7 LPG 17.4 Gasoline 53.3 (C5-150) Diesel 22.2 (150-370°C) Example-3 Using Aromatics concentrate as feed and commercially proven cracking catalyst at the reaction temperature of 482°C, catalyst/feed ratio of 4.8 and reaction time of 75 seconds showed the following product selectivities maximising the yield of diesel. MAXIMIZATION OF DIESEL Feed Aromatics Concentrates Products Dry Gas 2.4 LPG 9.0 Gasoline (C5-150°C) 14.6 Diesel (150-370°C) 41.2 The advantages of the present invention are : 1. The present invention eliminates the problem associated with the availability of feed stocks with desired hydrocarbon types distribution. 2. The present invention eliminates the problem of selecting a right type of catalyst to suit the crackability of feed stocks to maximise a particular product in greater demand. 3. The present invention eliminates the problem of hard wares and process parameters for the maximisation of particular product in greater demand. 4. The present invention has the advantage as the particular hydrocarbon concentrates separated from VGO can be cracked to LPG, gasoline and diesel as per the requirements using similar catalyst, hard wares and reaction conditions. WE CLAIM: 1 . A novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil which comprises (a) separating vacuum gas oil into saturated compounds and aromatic compounds by well known SARA (saturates, aromatics, resins and asphalenes) method, (b) fractionating the components into saturates and aromatics on alumina, then separating saturates in to normal paraffins, iso-paraffins & cyclo paraffins using molecular sieve 5 A° by known methods, (c ) heating different fractions obtained in step (b) at a temperature in the range of 100-150°C and injected through a preheater maintained at a temperature of 600°C and cracked in a metallic reactor in presence of zeolitic cracking catalyst such as herein described at temperature 450-482°C at a weight hourly space velocity in the range of 16-160 h-1 and a reaction time of 50-75 seconds, (d) collecting the resultant liquid product of step (c ) i. e. gasoline & diesel in an ice cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%. 2. A process claimed in claim 1 where in catalyst used is zeolitic commercial cracking catalyst with surface area 90-100 m2/g, zeolite content 10-15%, rare earth loading with 1.25-1.5 %, pore volume 0.15-0.20 ml/g, unit cell size with 24.34 to 24.38 and acidity mmoles/g of 0.33 to 0.35. 3. A novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil substantially as herein described with reference to examples 1 to 3.

Full Text

This invention relates to a novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil. In particular, the invention relates to a process for the cracking of hydrocarbon concentrates i.e. straight chain paraffins, iso+cycloparaffins and monoaromatics into LPG, gasoline and diesel. The invention more specifically relates to a process for the cracking of hydrocarbon concentrates in terms of hydrocarbon types i.e., straight chain paraffins, iso + cyclo paraffins and monoaromatics derived from Bombay high vacuum gas oil (VGO) of the hydrocarbon types given in Table-1 in presence of proven commercial cracking catalyst of the characteristics given in Table-2 into high value products like LPG, gasoline and diesel.
Fluidized Catalytic Cracking (FCC) has proven to be a major process to convert vacuum distillates and residues into valuable products such as gasoline, diesel and LPG. FCC in its modern version is not only providing diesel and high octane gasoline, it is also meeting other challenges by providing building blocks for petrochemicals and antiknock extenders (MTBE, TAME, ETBE in the form of propylene, isobutylene and isomylene. Indian FCC Units are specifically geared to maximize light cycle oil (LCO) a diesel blending component.
Projections of fuels demand in India shows that gasoline will become surplus in later years as refinery throughputs are increased. For the same period, diesel is expected to grow 37% and LPG consumption 41%. Therefore, values of products for Indian refiners increase continuously from distillate through gasoline to more olefinic LPG. Presently there is great pressure on FCC units to maximize middle distillates and olefmic LPG. The refiner can maximize these streams by using a novel catalyst, optimising process parameters within unit constraints and, hardware modifications through
combined technologies as well as by revamp of existing units. The other variable i.e. the feedstocks characteristics can also influence the product yields and its pattern dramatically. The feedstock composition interms of hydrocarbon type distribution, such as straight-chain, iso+cycloparaffins and aromatics can completely alter the product slate. In cracking reactions a desired product can be maximized by using a feedstock having maximum number of precursors which will endup in forming that particular product. Refineries are generally faced with difficulties in the availability of feedstocks with desirable hydrocarbon types distribution. Due to this the refiners prefer to look for other variables such as selection of a right type of catalyst, hardwares and process parameters optimisation to suit the crackability of feedstocks to maximise a particular product in greater demand. To overcome these problems, the present invention suggests the use of hydrocarbon concentrates in terms of hydrocarbon types derived from the vacuum gas oil by the separation scheme presented in the following section. Thus the present invention provides a process for the cracking of hydrocarbon concentrates with identified and well defined requirements of hardwares and process parameters to maximise a particular product in greater demand. SEPARATION SCHEME
A novel separation scheme which is experimentally convenient, less time consuming, repeatable and gives compound types with no chemical alteration has been used for the separation of hydrocarbon types from VGO. The well known SARA (saturates, aromatics, resins and asphaltenes) method was employed. Hydrocarbon were further separated into saturate and various aromatic concentrates on alumina. Saturates
were further fractionated into normal paraffins and iso-paraffins plus cyclo paraffins using molecular sieve 5A°.
The present invention provides a process for the conversion of various hydrocarbon concentrates prepared by using a separation scheme, discussed above into distillates and LPG fuel using commercially proven cracking catalyst. The novelty of the process lies in the cracking of hydrocarbon concentrates separated from vacuum gas oil, which is not known in the prior art.
Accordingly the present invention provides a novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil which comprises
(a) separating vacuum gas oil into saturated compounds and aromatic compounds by
well known SARA (saturates, aromatics, resins and asphalenes) method,
(b) fractionating the components into saturates and aromatics on alumina, then
separating saturates in to normal paraffins, iso-paraffins & cyclo paraffins using
molecular sieve 5 A° by known methods,
(c) heating different fractions obtained in step (b) at a temperature in the range of
100-150°C and injected through a preheater maintained at a temperature of 600°C
and cracked in a metallic reactor in presence of zeolitic cracking catalyst such as
herein described at temperature 450-482°C at a weight hourly space velocity in
the range of 16-160 h-1 and a reaction time of 50-75 seconds,
(d) collecting the resultant liquid product of step (c ) i. e. agasoline & diesel in an ice
cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream
or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing
flue gas was less than 0.1%.
According to further embodiment of the invention catalyst used is zeolitic commercial cracking catalyst with surface area 90-100 m2/g, zeolite content 10-15%, rare earth loading with 1.25-1.5 %, pore volume 0.15-0.20 ml/g, unit cell size with 24.34 to 24.38 and acidity mmoles/g of 0.33 to 0.35. The reaction time ranges preferably 50-75 sec.
Table-1 Hydrocarbon Type Composition of VGO

(Table Removed)
TabIe-2 Physico-Chemical Characteristics of the Catalyst

(Table Removed)
DETAILS OF CONVERSION PROCESS
The feed i.e. various hydrocarbon concentrates (1.33 gm ± 0.03) were heated in the range of 100-150°C and injected through a preheater (600°C) to the metallic reactor packed with 4 grams of catalyst and heated to 450- 482°C. After the reaction of the feed with the catalyst, product in the form of gas, liquid and coke is obtained. The liquid product was collected in an ice cooled receiver and analyzed by simulated distillation gas chromatograph. The gaseous products were analyzed by gas chromatography using squalane column at ambient temperature. The coke laden catalyst was regenerated at 650°C in a stream of air (50 cm3 min-1) for about 30 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%.
Cracked products consists of the following useful products apart from others such as dry gas (DG) (H2, H2S, CH4, C2H6 and C2H4) and clarified oil regarded as unconverted and amount of material on distillation curve boiling above 370°C.
LPG
Comprises C3H8, C3H6, C4H10, C4H8 which are primary products important as domestic fuel and feedstock to downstream petrochemical industry. Gasoline
Product which is quantitated as the amount of C5+ material in the reactor effluent gas plus the amount of liquid boiling upto 150°C on the distillation curve of effluent liquid. TCO
Total cycle oil product, the yield is determined from distillation curve within the boiling range 150-370°C, a useful diesel blending component.
Conversion
Defined as fraction boiling below 216°C, including DG and coke yield. The following examples illustrates the process of invention and should not be construed to limit the scope of present invention.
Example-1
n-paraffins mixture obtained from VGO was subjected to fixed bed cracking using commercially proven zeolite based cracking catalyst. Data from a typical experiment having catalyst to feed ratio of 4.8, reaction temperature 482°C and reaction time of 75 seconds showed the following product selectivities.
MAXIMISATION OF LPG AND GASOLINE
Feed N-paraffins concentrates
Products

(Table Removed)

Example-2
Using iso-plus cycloparaffins as feed and catalyst at the reaction temperature of 482°C, catalyst/feed ratio of 4.8 and reaction time of 75 seconds the following product selectivities were obtained. MAXIMIZATION OF LPG AND GASOLINE
Feed I so-Plus Cycloparaffins
Products
Dry Gas 1.7
LPG 17.4
Gasoline 53.3
(C5-150)
Diesel 22.2
(150-370°C)
Example-3
Using Aromatics concentrate as feed and commercially proven cracking catalyst at the reaction temperature of 482°C, catalyst/feed ratio of 4.8 and reaction time of 75 seconds showed the following product selectivities maximising the yield of diesel. MAXIMIZATION OF DIESEL
Feed Aromatics Concentrates
Products
Dry Gas 2.4
LPG 9.0
Gasoline (C5-150°C) 14.6
Diesel (150-370°C) 41.2

The advantages of the present invention are :
1. The present invention eliminates the problem associated with the availability of
feed stocks with desired hydrocarbon types distribution.
2. The present invention eliminates the problem of selecting a right type of catalyst
to suit the crackability of feed stocks to maximise a particular product in greater
demand.
3. The present invention eliminates the problem of hard wares and process
parameters for the maximisation of particular product in greater demand.
4. The present invention has the advantage as the particular hydrocarbon
concentrates separated from VGO can be cracked to LPG, gasoline and diesel as
per the requirements using similar catalyst, hard wares and reaction conditions.

WE CLAIM:
1 . A novel process for the preparation of LPG and gasoline & diesel from vacuum gas oil which comprises
(a) separating vacuum gas oil into saturated compounds and aromatic compounds by
well known SARA (saturates, aromatics, resins and asphalenes) method,
(b) fractionating the components into saturates and aromatics on alumina, then
separating saturates in to normal paraffins, iso-paraffins & cyclo paraffins using
molecular sieve 5 A° by known methods,
(c ) heating different fractions obtained in step (b) at a temperature in the range of 100-150°C and injected through a preheater maintained at a temperature of 600°C and cracked in a metallic reactor in presence of zeolitic cracking catalyst such as herein described at temperature 450-482°C at a weight hourly space velocity in the range of 16-160 h-1 and a reaction time of 50-75 seconds,
(d) collecting the resultant liquid product of step (c ) i. e. gasoline & diesel in an ice cold receiver, regenerating the coke laid on catalyst surface at 650°C in a stream or air (50cm3 mm-1) for 20-40 minutes till the carbon dioxide content of outgoing flue gas was less than 0.1%.
2. A process claimed in claim 1 where in catalyst used is zeolitic commercial
cracking catalyst with surface area 90-100 m2/g, zeolite content
10-15%, rare earth loading with 1.25-1.5 %, pore volume 0.15-0.20 ml/g, unit cell
size with 24.34 to 24.38 and acidity mmoles/g of 0.33 to 0.35.
3. A novel process for the preparation of LPG and gasoline & diesel from vacuum
gas oil substantially as herein described with reference to examples 1 to 3.

Documents:

245-del-2000-abstract.pdf

245-del-2000-claims.pdf

245-del-2000-correspondence-others.pdf

245-del-2000-correspondence-po.pdf

245-del-2000-description (complete).pdf

245-del-2000-form-1.pdf

245-del-2000-form-19.pdf

245-del-2000-form-2.pdf

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Patent Number

221449

Indian Patent Application Number

245/DEL/2000

PG Journal Number

31/2008

Publication Date

01-Aug-2008

Grant Date

23-Jun-2008

Date of Filing

16-Mar-2000

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110 001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	NEERAJ ATHEYA	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
2	CHANDRA DUTT SHARMA	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
3	DHIRENDRA SINGH ASWAL	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
4	UMA SHANKER	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
5	RAJENDRA PRASAD BADONI	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
6	BRIJ MOHAN LAL BHATIA	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.

PCT International Classification Number

C01G 11/05

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA