AU6092080A - Fuel for i.c. engines - Google Patents

Description

COMMONWEALTH OFIAUSI RAt sA c t19' 2 L

APPLICATION FOR A STANDARD PATENT (Combined Form Convention and Non-Convention)

4/We JOHNSON, MATTHEY CO., LIMITED, a British company, of 43 Hatton Garden, London, EClN 811, England,

.300 hereby apply for the grant of a Stan ',1rd Patent for an invention entitled 0

0 which is described in the accompanyn Completex02 Specification. 3

see*

2. This application is a Convention Application and is based on the application(s) for a

303 patent or similar protection made in......Great Britain

on 3 0th .July 1.979 *,numbered 792.6477 and

numberedbe e n

on nu m bered

:Ocoe 3. My/Our address for service is-, Care of COWIE, THOMSON CARTER Patent V

Attorneys, of Suite 5, 65 Queens Road, Melbourne, Australia, 3004

DATED this 28th day of July 1980.

f~AT2c1.E COWIE,. THOMSON CARTER. 3oJ UL 09 By:

Patent Attorneys for JOHNSON, MATTHEY CO., LIMITED.

To the Commissioner of Patents, COMMONWEALTH OF AUSTRALIA

COWIE, THOMSON CARTER Patent Attorneys,

Fornms 7 and 8 COMMONWEALTH OF AUSTRALIA Patents Act 1952-1962 COWIE, THOMSON CARTER Patent Attorneys Suite 5, 65 Queens Road Melhourne, 3004 60920/so Australia

Declaration in Support of an Application for a Patent (Combined Form Convention and Non-Convention)

Strike out for In support of the Convention* application made for a patent for an non-convention invention entitled.... "PETROLEUM

S.F. ROBINSON Manager (Patents Dept) I, of *o* Johnson, Matthey Co., Limited, of 43 Hatton Garden, *e London ECIN. 811 z....England, oe do solemnly and sincerely declare as follows:- 1 "I'm poaZl

a (or in the case of an application by a body corporate) 1. I am authorised authorised by by. the applicant for the patentxad _q .Matt n I.hn e-.Yy Co. Limit ed to make this declaration on its behalf.

StriIeout, Para. 2. 2. The basic application(s) as defined by section 141 of the was made at Act were roroon-contention in Gre at...B rit ain of00

on the.. 3.0 day of. Ju ly 19.7 o 0 0 by Johnson t he. and on day of S 0: by an d *o S on th e. d ay o f. 19 o by

3. x^ a re tiB co !s x antats Km iaen a s!Bsicm a l. iSBEm

(or, where a person other than the inventor is the applicant) 3. ALAN...FRANCZ D.IW.ELI....and .R of o Galsworthh. Drive 26 Caversham Park Village Rea.dicr, a.t.lin.g. Qx. OX9 5JP, England, respectively,

re the actual inventor(s) of the invention and the facts upon which m I ~said entitled to make the applicati are as follows The said company is the assignee of the invention from the said actual inventors. Strik out Para. 4. was the first 4. The basic application(s) referred to in paragraph 2 of this Declaration were for aon-convcntion application(s) made in a Convention country in respect of the invention the subject of the application.

DECLARED AT Reading ,2 1 day of August 19

__Sigatreof Declarant

J (12) PATENT ABSTRACT (11) AU-A1-60 920/80 (19) AU

(54) FUEL FOR I.C. ENGINES (71) JOHNSON, MATTHEY CO. LTD. (21) 60,920/80 (22) 30.7.80 (24) 30.7.79 (31) 7926477 (32) 30.7.79 (33) GB (43) 5.2.81 3 C10L 1/06 C10L 1/30 (51) CO1L 1/20 (72) Diweli, A.F. and Harrison, B. (74) CM (57) Claim A petroleum fuel suitable for use in internal combustion

engines which have a catalytic converter for exhaust emission

control includes a compound of lead and from 0.1 to 0.8 theories

of 1,2-dichloroethane.

n .1 3-1

Form PATENTS ACT 1952-1973

COMPLETE SPECIFICATION (ORIGINAL) FOR OFFICE USE Class: Int. Cl: *one

S7. Application Number: Lodged: 0. 0.

0

0

.00. Complete Specification-Lodged: *000 Accepted: Published: Priority:

0 Related Art: 000.

TO BE COMPLETED BY AP~PLICANT- SOS* Name of Applicant: JOHNSON, MATTHEY CO., LIMITED, a B.ritish company, *SS* 5 of 43 Hatton Garden, London, ECIN 8ER, England.

o

Address oY Applicant:

Actual Inventor: ALAN FRANCIS DIWELI BRIAN HARRISON

Care of: COWIE, THOMSON CARTER, Address for Service: Patent Attorneys, Suite 5, 65 Queens Road, Melbourne, Vic., 3004, Aus tr aF1-. Complete Spe-.fication for the invention entitled: PETROLEUM FUEL

The following statement is a full description of this invention, including the best method of performing it known to me:- *-I

-1i-

"Petroleum Fuel"

This invention relates to petroleum fuel for internal combustion engines and in particular for engines fitted with a catalytic exhaust purification unit. The petroleum fuel used in spark-ignition internal com-

D. 5 bustion engines, is graded by its octane number which is the percentage by volume of 2,2,4-trimethylpentane (iso octane) in a mixture of 2,2,4-trimethylpentane and iormal heptane

which has the same knocking characteristics as che fuel under e* test. The knock of an internal combustion engine is the

'IT charactcristic metallic noise which results from out of sequence detonation, i.e. the spontaneous combustion of the compressed charge before it can be ignited by the spark. In an attempt to prevent knocking, anti-knock substances such as tetraethyl lead or tetramethyl lead are added to the fuel. Other addi- tives are often present in the fuel in addition to the anti- 0

knock substances to aid removal of the lead compounds from the vicinity of the cylinder and valves and into the exhaust gas stream. Two such additives commonly called "scavengers" are 1,2-dichloroethane (ethylene dichloride, EDC) and 1,2-dibrom-

oethane (ethylene dibromide, EDB). When a catalytic exhaust gas purification unit is positioned in the exhaust gas stream, a lead-free petroleum fuel has to be used to prevent poisoning of the catalytic components, such as platinum metal in the unit. The present invention provides a petroleum fuel which

contains a lead compound as an anti-knock component and a scavenger and which will either not poison a platinum-contain- ing catalycic exhaust gas purification unit or will at least poison it to a lesser extent or at a slower rate.

In EEC countries the proposed level of lead in petroleum -1 fuel from January 1981 is a maximum of 0.4gl and a minimum -i of 0.1 5 gl The amount of the scavenger present in the petroleum fuel is measured in 'theories' where a 'theory' is the amount of scavenger that theoretically will react with all the lead presernt to form a compound that is easily removed from the engine and into the exhaust gas stream. Petroleum on'" 'fuel as used in the U.K. (herein referred to simply as "conventional motormix") at present normally contains theory of 1,2-dibromoethane and 1 theory of 1,2-dichloroethane as ee. scavengers.

According to one aspeccof the present invention a petroleum fuel suitable for use in internal combustion engines which have a catalytic converter for exhaust emission control includes a compound of lead and from 0.1 to 0.8 theories of 1,2-dinhloroethane.

According to another aspect of the invention we provide a process of operating a spark-ignition internal combustion

engine having a plaLinum group metal-containing catalytic exhaust gas purification unit through which the exhaust gas from the engine is passed, the petroleum fuel used in the operation of the engine containing tetramethyl lead or tetraethyl lead and 0.1 to 0.8 theories of 1,2-dichloroethane. Preferably the lead content of the fuel is in the range from 0.15 to 0.4 grams per litre measured as lead, the lead being present as one or more of the anti-lnock agents referred to above. Within the above-stated range of 0.1 0.8 theories of 1,2 dichloroethane we particularly prefer 0.4 to 0.6 theories. To study the effect of exhaust gases from the combustion of a petroleum fuel containing lead compounds and other additives, such as lead scavengers, tests were carried out on a catalyst using a rig built to produce simulated exhaust gas from an internal combustion engine. The rig has a modified pulse flame reactor such that fuel can be injected into the reactor, mixed with air and ignited, by means of a propane gas pilot light, in a double conical combustion chamber. The catalyst can be placed in one of two positions downstream of the combustion chamler. The fuel inlet was 10 adjusted so that substantially stoichiometric combustion of z the fuel took place. A further addition of air, commonly called 'secondary air', was added to the exhaust gas stream after the combustion chambei so that there was a 0.5% excess of oxygen present in the exhaust gas stream as it passed over the catalyst. Nitorgen oxides were also added with the secondary air so that there was a concentration of approxi- mately 2,000 ppm of nitrog-n oxides in the exhaust gas stream. The duration of each test was 8 hours, the hydrocarbon and carbon monoxide levels present in the exhaust gas stream being measured, before and after the catalyst, at hourly intervals. Before each test the rig was run for two hours with a non-active catalyst support in position to allow the reactor walls to come to equilibrium with the lead species present in the exhaust gas stream. The catalyst support used was a cylindrical ceramic one 9 with a cell density of 300 cells/in a length of 3 inches and a diameter of 2 inches. The catalytic metal used was 3 platinum at a loading of 40g/ft 3 An intermediate layer of alumina was present between the support and the catalytic layer.

The first series of tests used a petroleum fuel con- -i taining 0.4gl- of lead, present as tetramethyl lead and a

lead scavenger 1,2 dibromoethane present at the following

levels, 2 theories, 1 theory, theory and zero. The inlet

temperature was kept at 630 0 C for all the tests. The effect

of exhaust gases, obtained by burning such a petroleum fuel,

on'the catalyst is shown in Figure 1 in which rate of loss

S of catalytic conversion effi.iency is shown for various exhaust gas components. A second series of tests used a petroleum fuel con- taining 0.4gl of lead, present as tetramethyl lead, and a

lead scavenger 1,2-dichloroethane present at a number of

levels, 2 theories, 1 theory, theory and zero. The effect

of exhaust gases, obtained by burning such a petroleum fuel,

on the catalyst is sho'T in Figure 2 in which rate of loss of catalytic conversion efficiency is shown for various exhaust

gas components. A comparison of the effect of the two lead scavengers,

1,2-dibromoethane and 1,2-dichloroethane, on the conversion

efficiency of the catalyst is given in Figure 3 in which rate of loss of efficiency of catalytic conversion of

methane is shown. A further series of tests was carried out using a 50 hour

aged catalyst (aged on a 1.8 litre British Leyland Dolomite

engine) and conducted on a 1.8 litre Dolomite engined Marina motor car using ECE-15 tests with the following results:

Conversion HC CO

0.4g/l Pbr a conventional motor mix of 1 EDC+j EDB measured in theories 2.6 79.2

0.4g/l+ theory EDC 27.3 77.1

From the above results it will be appreciated that an

improved performance was obtained, particularly regarding

hydrogen removal, when the theory EDC scavenger was used

as compared with the conventional motor mix. In the above

ECE means the Economic Commission for Europe whereas ECD and EDB have the meanings prevLously assigned to them in this

specification.

The actual catalyst was a conventional 400 cell per

square inch ceramic monolith 6" x 4" diameter having a first

10 Cnd washcoat layer of alumina at a loading of 1.78 grams per

S cubic inch and a second and catalytic layer of platinum at a

loading of 40 grains/cubic foot.

So

g

Claims (1)

The claims defining the invention are as follows:

1. A petroleum fuel suitable for use in internal combustion

engines which have a catalytic converter for exhaust emission

control includes a compound of lead and from 0.1 to 0.8 theories

of 1,2-dichloroethane.

2. A petroleum fuel according to claim 1 wherein the lead

content of the fuel is within the range from 0.15 to 0.4 grams

per litre measured as lead.

S3. A petroleum fuel according to claim 2 wherein the lead

content of the fuel is present in the form of an anti-knock

compound selected from the group consisting of tetraethyl lead

and tetramethyl lead.

4. A petroleum fuel according to any one of claims 1 to 3

containing 0.4 to 0.6 theories of 1,2 dichloroethane. 5. A process of operating a spark ignition internal combustion

engine having a platinum group metal containing catalytic exhaust

gas purification unit through which the exhaust gas from the

engine is passed, the petroleum fuel used in the operation of

.the engine containing z compound of lead and from 0.1 to 0.8

theories of 1,2-dichloroethane.

6. A process according to claim 5 wherein the lead content

is within the range from 0.15 to 0.4 grams per litre measured

as lead.

7. A process according to claim 5 or claim 6 wherein the lead

content of the fuel is present in the form of an anti-knock

compound selected from the group consisting of tetraethyl lead

and tetramethyl lead.

8. A process according to claims 5, 6 or 7 containing 0.4

to 0.6 theories of 1,2 dichloroethane.

9. A process according to any preceding claim wherein the

catalytic exhaust purification unit comprises a monolith

having a plurality of channels for the passage of the exhaust

gas therethrough, a first layer of a refractory material

applied to the channel walls and a second layer of a platinum

group metal applied to the first layer. 10. A process according to claim 9 wherein the monolith is

made from a ceramic material having 400 channels per square

inch of cross-sectional area with a first layer of alumina

and a second layer of platinum.

11. A process according to claim 9 wherein the monolith

is made from a metal.

DATED this 28th day of July, 1980.

•JOHNSON, MATTHEY CO., LIMITED.

COWIE, DPATTN TTHOMSON TRDEM"R ATTO..J CARTER K

MELBO, SUITE 5, 653004, AUSFRALA QUEENS MELBOIOHNS, E, 3004, AU CRO.!D RALIA

POISONING OF HC CO OXIDATION BY LEAD BROMIDE SPECIES

0

Ui

j +30 CH4 S. LLJ SSSD

Li

UH

C)H

a 00 01 LL

Sc

0/2 1 1112 2 Theory 1,2-dibromoethane(EDB)

Fi g.1.

POISONING OF HCO OXIDATION BY LEAD +131 CHLORIDE SPECIES

CH4 0000

0000

0 0

*0*

C2 H6 @S S S 50

OeSS**

1 1 2 Theory 1,2-dichtooethane(EDC)

Fi g.2.