Title of Invention	A PROCESS FOR THE CONVERSSION OF HEAVY NORMAL PARAFFINS (HNP) TO LPG AND LIQUID TRANSPORTATION FUEL
Abstract	The present invention provides a process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting heavy normal paraffin's C14- C18 with the dealuminated zeolite-Y as a catalyst at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160h-1 for a period ranging from 20 - 150 sec. if desired separating LPG and liquid transportation fuel by conventional methods.

Title of Invention

A PROCESS FOR THE CONVERSSION OF HEAVY NORMAL PARAFFINS (HNP) TO LPG AND LIQUID TRANSPORTATION FUEL

Abstract

The present invention provides a process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting heavy normal paraffin's C14- C18 with the dealuminated zeolite-Y as a catalyst at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160h-1 for a period ranging from 20 - 150 sec. if desired separating LPG and liquid transportation fuel by conventional methods.

Full Text	This invention relates to a process for the conversion of Heavy Normal Parafins (HNP) to LPG and liquid transportation fuels. Heavy ricrm.i.1 paraffins are utilized commercially for the production of internal olefins by catalytic dehydrogenaticn (molex process) and sec-alcohols by boric acid protected oxidation (Easkhirov process). However, these paraffins can be cracked in presence of a suitable acidic catalyst and the products formed are LPG and liquid transportation fuel. Conventional methods for the production of LPG and liquid transportation fuel are through distillation of crude oil, catalytic and steam cracking of vacuum gas oil naphth as feedstocks. The objective of the present invention is to provide a process for the conversion of heavy normal praffins (C 14 to C 18 range) to LPG and liquid hydrocarbon type of fuel using dealumi-nated zeolite-Y as a catalyst. We have developed a process for the conversion of heavy normal paraffins to LPG and liquid fuel by catalyatic cracking in presence of dealuminated zeolite-Y.. The reaction conditions are: Temperature - 2 85 to 410 ° C Weight Hourly Space Velocity (WHSV) - 16 to 160 h-1 Reaction Time - 20 to 15C seconds. Accordingly, the present invention provides a process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting neavy normal paraffin's C14- CI8 with the dealuminated zeolite-Y as a catalyst at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160IT1 for a period ranging from 20-150 sec. if desired separating LPG and liquid transportation fuel by conventional methods. kerosene and diesel fractions. The gaseous products are LPG, trace amounts of dry gas (H2 + C1, + C2) • Small amount of coke is also produced as by product during the reaction. Heavy normal paraffins, n-paraffin mixture in the range of C14 to Cl8 produced by Indian petrochyemical Limited, Baroda, India with the following characteristics was used as the feed. Bioling range : 260-340° C Composition (wt%) C14 - 16.6 C15 - 38.5 C16 - 24.8 C1? - 12.8 C18 - 5.3 C18 - 1.9 Aromatics - 0.1 Zeolite Y dealuminated to levels of 40 and 60% was used as catalyst. The novel zeolite Y delauminated catalysts is subject matter of our co-pending patent application No. 1247/Del/95 .- Cracking experiments were conducted in a micro processor controlled auto MAT fixed bed unit with facility to estimate the coke make in situ. The dealuminated zeolite -Y sample (0.5 ± 0.02g) diluted by quartz powder (1.5g, 80-100 mesh) was loaded in the reactor. The catalyst bed was heated to 300 ± 2°C in a stream of nitrogen (30 cm-3 min ) for 15 minutes. A constant quantity (1.285 ± 0.05 g) of the paraffin feed preheated to 200°C was injected into the reactor while varying the time on stream. The catalyst bed was then stripped with nitrogen (3 0cm° min -1) for 15 minutes. The liquid product was collected in an ice cooled receiver and analysed by simulated distillation gas chro-nanagraaphg. Thegaseous product were analysed by gas chromatography using a squalane column at ambient temperature. The coke laden catalyst was regenerated at 650°C in a stream of air (50 cm3 min-1 ) for 30 minutes or so, till the carbon dioxide content in the outgoing flue gases was less than 0.1 %. The gaseous enroute were, passed through a converter at 450°C containing cupric oxide to oxidise any carbon monooxide to carbon dioxide. The yield of coke was computed from the flow rate of the flue gases at the exist and the carbon dioxide content monitored by an on-line IR analyser. Cracked product consists of trace amount of dry gas (a mixture of H2 + C1, + C2) , LPG (a mixture of C3 and C4) , hydrocar bons boiling in gasoline range (IBP-150°C). The FBP of the cracked liquid product was around 320-330°C and the product boiling in the range of 150-330°C is suitable for use as kerosene and diesel. Reactions like isomerisation, H-transfer and cyclisa-tion occur to a significant extent. The liquid product will be a mixture of normal and isopraffins, olefins, naphthenes and aro-matics in varying amount. This makes the gasoline boiling range product rich in olefins and aromatics which are potential contributor to octane number. H-transfer reaction is known to be suppressed duringing catalytic cracking in presence of delaumi-nated zeolite-Y. The diesel range product has limited concentration of aromatics, which guards the product cetane value within acceptable limit. The LPG produced is highly olefinic which makes it guite useful as the raw material for a number of petrochemical products. The following examples illustrate the process of invention and should not be construed to limit the scope of the present invention. Example-1 A mixture of n-paraffins was subjected to fixed bed catalytic cracking in presence of 40% dealuminated zeolite-Y. Data from a typical experiment having catalyst to feed ratio of 0.389, reaction temperature of 3000 C, WHSV 160h and reaction time 58 seconds showed the following product selectivities (wt%). Dry gas - 0.05 LPG - 3.91 Gasoline - 6.55 Kerosene and diesel - 87.70 Coke - 1.7 9 Example-2 Using the feed and catalyst as in Example-1, at the same temperature and catalyst/feed ratio, by varying the reaction time -1 to 129 sees and WHSV 72h , the following product selectivities (wt%) was obtained. Dry gas - 0.10 LPG - 5.19 Gasoline - 12.05 Kerosene and diesel - 80.48 Coke - 2.18 Example-3 Using the feed as mentioned in Example-1, 60% dealuminated o zeolite-Y at reaction temperature of 300 C, catalyst feed ratio -1 0.389, reaction time 67 sees and WHSV 138h gave the product selectivities (wt%) as given below : Dry gas - 0.07 LPG - 2.8 5 Gasoline - 4.68 Kerosene and diesel - 90.82 Coke - 1.5 8 Example-4 Using the feed described in Example-!, catalyst as in o Example-3, at reaction temperature of 300 C, catalyst feed ratio -1 0.389, reaction time 140 sees and WHSV 66h gave the following product selectivities (wt%). Dry gas - 0.09 LPG - 3.41 Gasoline - 6.75 Kerosene and diesel - 88.10 Coke - 1.6 5 Example-5 Using the feed, catalyst and catalyst to feed ratio as o described in Example-1, at reaction temperature of 400 C, WHSV -1 160h and reaction time 58 seconds showed the following product selectivities (wt%). Dry gas - 0.10 LPG - 5.5 0 Gasoline - 7.75 Kerosene & diesel - 84.85 Coke - 1.9 0 Example-6 Using the feed, catalyst and catalyst to feed ratio as o described in Example-3, at reaction temperature of 400 C, reaction time 6 7 sees and WHSV 13 8h gave the product selectivities (wt%) as given below : Dry gas - 0.12 LPG - 3.5 0 Gasoline - 5.50 Kerosene and diesel - 89.18 Coke - 1.70 We Claim: 1. A process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting heavy normal paraffin's C14- C18 with the dealuminated zeolite-Y as a catalyst as herein before described at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160h_1 for a period ranging from 20 - 150 sec. if desired separating LPG and liquid transportation fuel by conventional methods. 2. A process as claimed in claim 1, wherein the reaction is carried out preferably at a temperature ranging from 285-325 °C. 3. A process as claimed in claim 1-2 , wherein reaction is carried out preferably at space velocity 65-160h-1. 4. A process as claimed in claim 1 -3, wherein the reaction is carried out preferably at reaction time 59-140 sec. 5. A process as claimed in claims 1-4, wherein the modified zeolite- Y catalyst is diluted with inert material, such as quartz and used in amounts ranging from 0.01 - 1.0 gram by weight. 6. A process for the conversion of (HNP) in C14 - C18 range to LPG as liquid transportation fuel substantially as herein described with reference to the examples.

Full Text

This invention relates to a process for the conversion of Heavy Normal Parafins (HNP) to LPG and liquid transportation fuels.
Heavy ricrm.i.1 paraffins are utilized commercially for the production of internal olefins by catalytic dehydrogenaticn (molex process) and sec-alcohols by boric acid protected oxidation (Easkhirov process). However, these paraffins can be cracked in presence of a suitable acidic catalyst and the products formed are LPG and liquid transportation fuel. Conventional methods for the production of LPG and liquid transportation fuel are through distillation of crude oil, catalytic and steam cracking of vacuum gas oil naphth as feedstocks.
The objective of the present invention is to provide a process for the conversion of heavy normal praffins (C 14 to C 18 range) to LPG and liquid hydrocarbon type of fuel using dealumi-nated zeolite-Y as a catalyst.
We have developed a process for the conversion of heavy normal
paraffins to LPG and liquid fuel by catalyatic cracking in
presence of dealuminated zeolite-Y.. The reaction conditions are:
Temperature - 2 85 to 410 ° C
Weight Hourly Space Velocity (WHSV) - 16 to 160 h-1
Reaction Time - 20 to 15C seconds.
Accordingly, the present invention provides a process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting neavy normal paraffin's C14- CI8 with the dealuminated zeolite-Y as a catalyst at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160IT1 for a period ranging from 20-150 sec. if desired separating LPG and liquid transportation fuel by conventional methods.
kerosene and diesel fractions. The gaseous products are LPG, trace amounts of dry gas (H2 + C1, + C2) • Small amount of coke is also produced as by product during the reaction.
Heavy normal paraffins, n-paraffin mixture in the range of
C14 to Cl8 produced by Indian petrochyemical Limited, Baroda,
India with the following characteristics was used as the feed.
Bioling range : 260-340° C
Composition (wt%) C14 - 16.6 C15 - 38.5 C16 - 24.8 C1? - 12.8 C18 - 5.3 C18 - 1.9 Aromatics - 0.1
Zeolite Y dealuminated to levels of 40 and 60% was used as catalyst. The novel zeolite Y delauminated catalysts is subject matter of our co-pending patent application No. 1247/Del/95 .-
Cracking experiments were conducted in a micro processor controlled auto MAT fixed bed unit with facility to estimate the coke make in situ. The dealuminated zeolite -Y sample (0.5 ± 0.02g) diluted by quartz powder (1.5g, 80-100 mesh) was loaded in the reactor. The catalyst bed was heated to 300 ± 2°C in a stream of nitrogen (30 cm-3 min ) for 15 minutes. A constant quantity (1.285 ± 0.05 g) of the paraffin feed preheated to 200°C was injected into the reactor while varying the time on stream.
The catalyst bed was then stripped with nitrogen (3 0cm° min -1) for 15 minutes. The liquid product was collected in an ice cooled receiver and analysed by simulated distillation gas chro-nanagraaphg. Thegaseous product were analysed by gas chromatography using a squalane column at ambient temperature. The coke laden catalyst was regenerated at 650°C in a stream of air (50 cm3 min-1 ) for 30 minutes or so, till the carbon dioxide content in the outgoing flue gases was less than 0.1 %. The gaseous enroute were, passed through a converter at 450°C containing cupric oxide to oxidise any carbon monooxide to carbon dioxide. The yield of coke was computed from the flow rate of the flue gases at the exist and the carbon dioxide content monitored by an on-line IR analyser.
Cracked product consists of trace amount of dry gas (a mixture of H2 + C1, + C2) , LPG (a mixture of C3 and C4) , hydrocar bons boiling in gasoline range (IBP-150°C). The FBP of the cracked liquid product was around 320-330°C and the product boiling in the range of 150-330°C is suitable for use as kerosene and diesel. Reactions like isomerisation, H-transfer and cyclisa-tion occur to a significant extent. The liquid product will be a mixture of normal and isopraffins, olefins, naphthenes and aro-matics in varying amount. This makes the gasoline boiling range product rich in olefins and aromatics which are potential contributor to octane number. H-transfer reaction is known to be suppressed duringing catalytic cracking in presence of delaumi-nated zeolite-Y. The diesel range product has limited concentration of aromatics, which guards the product cetane value within acceptable limit. The LPG produced is highly olefinic which makes it guite useful as the raw material for a number of petrochemical products.
The following examples illustrate the process of invention and should not be construed to limit the scope of the present invention.
Example-1
A mixture of n-paraffins was subjected to fixed bed
catalytic cracking in presence of 40% dealuminated zeolite-Y.
Data from a typical experiment having catalyst to feed ratio of
0.389, reaction temperature of 3000 C, WHSV 160h and reaction
time 58 seconds showed the following product selectivities (wt%).
Dry gas - 0.05
LPG - 3.91
Gasoline - 6.55
Kerosene and diesel - 87.70
Coke - 1.7 9
Example-2
Using the feed and catalyst as in Example-1, at the same
temperature and catalyst/feed ratio, by varying the reaction time
-1 to 129 sees and WHSV 72h , the following product selectivities
(wt%) was obtained.
Dry gas - 0.10
LPG - 5.19
Gasoline - 12.05
Kerosene and diesel - 80.48
Coke - 2.18
Example-3
Using the feed as mentioned in Example-1, 60% dealuminated
o zeolite-Y at reaction temperature of 300 C, catalyst feed ratio
-1 0.389, reaction time 67 sees and WHSV 138h gave the product
selectivities (wt%) as given below :
Dry gas - 0.07
LPG - 2.8 5
Gasoline - 4.68
Kerosene and diesel - 90.82
Coke - 1.5 8
Example-4
Using the feed described in Example-!, catalyst as in
o Example-3, at reaction temperature of 300 C, catalyst feed ratio
-1 0.389, reaction time 140 sees and WHSV 66h gave the following
product selectivities (wt%).
Dry gas - 0.09
LPG - 3.41
Gasoline - 6.75
Kerosene and diesel - 88.10
Coke - 1.6 5

Example-5
Using the feed, catalyst and catalyst to feed ratio as
o described in Example-1, at reaction temperature of 400 C, WHSV
-1 160h and reaction time 58 seconds showed the following product
selectivities (wt%).
Dry gas - 0.10
LPG - 5.5 0
Gasoline - 7.75
Kerosene & diesel - 84.85
Coke - 1.9 0
Example-6
Using the feed, catalyst and catalyst to feed ratio as
o described in Example-3, at reaction temperature of 400 C,
reaction time 6 7 sees and WHSV 13 8h gave the product
selectivities (wt%) as given below :
Dry gas - 0.12
LPG - 3.5 0
Gasoline - 5.50
Kerosene and diesel - 89.18
Coke - 1.70

We Claim:

1. A process for the conversion of heavy normal paraffin's (HNP) in C14 to C18 range to LPG and liquid transportation fuel which comprises reacting heavy normal paraffin's C14- C18 with the dealuminated zeolite-Y as a catalyst as herein before described at a temperature in the range of 285-410°C, space velocity in the range of 16 - 160h_1 for a period ranging from 20 - 150 sec. if desired separating LPG and liquid transportation fuel by conventional methods.
2. A process as claimed in claim 1, wherein the reaction is carried out preferably at a temperature ranging from 285-325 °C.
3. A process as claimed in claim 1-2 , wherein reaction is carried out preferably at space velocity 65-160h-1.
4. A process as claimed in claim 1 -3, wherein the reaction is carried out preferably at reaction time 59-140 sec.
5. A process as claimed in claims 1-4, wherein the modified zeolite- Y catalyst is diluted with inert material, such as quartz and used in amounts ranging from 0.01 - 1.0 gram by weight.
6. A process for the conversion of (HNP) in C14 - C18 range to LPG as liquid transportation fuel substantially as herein described with reference to the examples.

Documents:

1305-del-1998-abstract.pdf

1305-del-1998-claims.pdf

1305-del-1998-correspondence-others.pdf

1305-del-1998-correspondence-po.pdf

1305-del-1998-description (complete).pdf

1305-del-1998-form-1.pdf

1305-del-1998-form-19.pdf

1305-del-1998-form-2.pdf

« Previous Patent

Next Patent »

Patent Number

196975

Indian Patent Application Number

1305/DEL/1998

PG Journal Number

41/2008

Publication Date

10-Oct-2008

Grant Date

30-Mar-2007

Date of Filing

15-May-1998

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH, an Indian registred body incorporated under the Registration of Societies Act (Act XXI of 1860)

Applicant Address

RAFI MARG, NEW DELHI- 110001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	RAJENDRA PRASAD BADONI	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA.
2	MOOL CHAND	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA
3	UMA SHANKAR	INDIAN INSTITUTE OF PETROLEUM, DEHRADUN-248005, INDIA

PCT International Classification Number

C10G 11/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA