GB2132222A

GB2132222A - Process for producing petrol

Info

Publication number: GB2132222A
Application number: GB08326312A
Authority: GB
Inventors: Yasuo Takabori; Yoshihisa Saeki; Tooru Tomii; Tsuguo Kimura
Original assignee: Honda Motor Co Ltd
Current assignee: Honda Motor Co Ltd
Priority date: 1982-10-02
Filing date: 1983-09-30
Publication date: 1984-07-04
Also published as: GB8326312D0; PH21593A; MY8700274A; JPS6033153B2; JPS5962694A; GB2132222B

Abstract

A fatty acid glycerine ester (such as coconut oil, hydrogenated coconut oil or physic nut oil) is catalytically cracked in a reaction chamber by a catalyst containing Y zeolite alumina-silica, to produce a petrol with an octane number greater than 90.

Description

SPECIFICATION A process for producing petrol This invention relates generaliy to a process for producing petrol.

Petrol (known in the United States as gasoline) is a petroleum fuel having an octane number of at least 60.

It is made up of a mixture of volatile hydrocarbons suitable for use in a spark-ignited internal combustion engine, as defined in The Condensed Chemical Dictionary, 9th Edition, p.407. The major components of petrol are branched-chain alkanes (often known as branched-chain paraffins), cycloalkanes (often known as cycloparaffins), alkenes (often known as olefins), and aromatics. There are several processes for producing petrol, including distillation orfractionation both yielding a straight-run productofa relatively low octane number which is primarily used for blending; thermal and catalytic cracking; reforming; polymerization; isomerization; and dehydrocyclization.Of these processes, all butthe first are various means of converting hydrocarbon gases into motor fuels by modifications of chemical structure, the modifications usually involving catlysts. Although the overwhelming present source of petrol is crude oil, it may also be produced from shade oil and tar sands, as well as by hydrogenation or gasification of coal.

As noted in Van Nostrand's Scientific Encyclopedia, 5th Edition, pp. 1745 to 1749, the composition of petrol has varied over the years. In the infancy of automobile transportation, petrol was a relativelysimple mixture of petroleum fractions derived from straight-run and thermally-cracked stocks. Over the years, there was an increase in the compression ratio of internal combustion engines so as to improve the overall engine performance and efficiency. As the compression ratio increased,thefuel octane number also had to increase in orderto prevent pre-ignition (also known as knocking).

Additives were eventually developed which increased the octane number. Additives were also found to perform otherfunctions, such as the prevention of: carburettor icing and fouling; fuel system corrosion; and poorfuel distribution. As ecological problems are now a major concern, the use of lead alkyls as fuel additives is beginning to decline and catalytic converters are being installed in automobile engines. With unleaded petrol and the new anti-pollution standards, it became more expensive to produce a petrol of a purity which would not poison a catalytic converter butstill be of a sufficiently high octane numberto deliver good performance. In addition, the curtailed use of certain fuel additives, such as lead alkyls, has increased the cost of such high octane petrol.

The cost of petrol is also influenced by the world market price for petroleum fuels. Since petroleum fuels are created over a very long period oftime, petroleum reserves are considered to be a depletable natural resource. As such, the price of petroleum fuels is effected by the world supply and world demand for such fuels, as well as current production capacity.

Additionally, the supply of petroleum fuels is subject to depletion over a long period oftime.

In view of the depletable natureofnatural petroleum, as well as thefactthat certain regions and countries contain very small or negligible quantities of natural petroleum,there have been attempts to produce petrol from biologically renewable sources.

However,the prior attempts to produce petrol from biological oils have rendered unsatisfactory results since any product similar to petroleum which has been obtained has suffered from undesirable qualities which would prevent the productfrom being used in a petrol engine. In orderforsuch a productto be of a sufficiently high qualityto be used in a petrol engine, the product must meet certain minimum requirements, a partial list of which includes a reasonable octane number, low corrosion tendency, distillation condition and purity (to prevent catalytic converter poisoning).

Thus, there exists a need for a process which can economically produce petrol from biological compounds such that the petrol produced is of sufficient purity and high octane number so as to power modern automobiles containing engines with catalytic converters. There also exists a need for a replaceable source of petrol.

According to the present invention, there is a process for producing a petrol with an octane number greaterthan 90, which process comprises catalytically cracking a fatty acid glycerine ester with a catalyst having, in a carrier, Yzeolite alumina-silica in a crystalline form.

The process of the present invention preferably comprises: passing a fatty acid glycerine ester mixture, wherein the fatty acid moiety contains from 6to 36 carbon atoms, into a reaction chamber having a catalyst containing Yzeolite alumina-silica in a carrier; catalytically cracking the mixture at a temperature in the rangefrom 350into 650"C, atan applied pressure lowerthan 10 kg/cm2; and then removing a cracked mixture containing a petrol from the reaction chamber.

In the process of the present invention fatty acid glycerine esters with either generally saturated or unsaturated fatty acid moieties are satisfactory as a raw material. Therefore, hydrogenation is not re quired. A generally saturated glycerine ester may be obtained from a biological source, such as coconut oil, and an unsaturated glycerine ester may be obtained from biological sources, such as physic nut oil. By utilizing such renewable sources, a supply of petrol may be produced in countries having no natural petroleum deposits. Further, according to the process of the present invention, the raw material required to produce petrol is a renewable resource which wili not be depleted overtime.

Thus the present invention makes it possible to produce a petrol, suitablefor use in motor engines, from biological materials.

According to the preferred embodiment of a process in accordance with the present invention, a glycerine ester mixture wherein the fatty acid moiety contains from 6to 36 carbon atoms is catalytically cracked by a catalyst which contains Y zeolite alumina silica in a carrier. TheY zeolite alumina-silica content of the catalyst is preferably in the range from 5 to 50 percent by weight, with a range of 1 to 30 percent by weight being more preferred. Preferably, when the catalyst is used in a moving bed reactor, the catalyst is in a powderform, whereas when the catalyst is used in a fixed bed reactor, the catalyst is shaped in a cylindrical or spherical shape. During the process of the present invention, the reaction pressure applied in the reaction bed is preferably less than 10 kg/cm2.A pressure which is less than 2 kg/cm2will usually be satisfactory. The reaction temperature of the reaction bed is preferably in the range from 350"C to 650"C, a more preferred reaction temperature being in the range from 450into 550 C. The ratio of the catalyst weight to the glycerine ester weightfor a moving bed reactorshould be in the rangefrom 3:1 to 12:1,with a preferred ratio being in the range from 8:1 to 10:1. For a fixed bed reactor, for every one to five parts by weight of the catalyst, one part by weight of the mixture is fed per hourto the reaction chamber, with a preferred value of 1 to 3 parts by weight of the catalyst for every one part by weight of the mixture fed per hour.

When the catalytic reaction takes place underthe conditions noted above, gas, water and coke are all formed besides a low boiling point oil. Thereafter, the oil is distilled and the distillate is tested for its quality as a petrol in thetemperatu re range from 25"C to 200"C after treatment by caustic soda.

The fatty acid glycerine ester may have one, two or three fatty acid moieties per glycerine moiety.

The invention will be further illustrated in the working examples that follow. However, the following examples are provided for illustration only, and are not intended to limit the scope ofthe present invention.

EXAMPLE 1 In this example, the results of which tabulated in thefollowingTable, petrol was producedfrom unrefined coconut oil which contained generally satu rated fatty acid glycerine ester. The catalytic cracking was performed inside a moving bed reaction chamber with a catalyst containing Y Zeolite alumina-silica powder.

After one run of cracking, the gasolineyeild was 34 percent byweightwith an octane number of 94. After also analyzing the distilled products, it was found that the petrol productwas of sufficiently high quality, so as to power a motor engine, wfthoutfurthertrnatment.

In a usual catalytic cracking reaction,the uncracked oil remaining afterthe first run would have to be recracked so asto increase the yield of the petrol.

EXAMPLE 2 In this example, the cracking run was performed underthe same conditions as stated in Example 1, except that hydrogenated coconut oil was utilized as the raw stock material. The hydrogenated coconut oil represented an example of highly saturated high grade fatty acid glycerine ester. The results of one run of catalytic cracking, which are set forth in the Table, were as good as the results obtained in Example 1.

EXAMPLE 3 In this example, physic nut oil was used as an example of an unsaturated fatty acid glycerine ester.

The catalytic cracking was performed on a fixed bed inside a reaction chamber, with cylindrically shaped catalytic particles (1.5 mm diameter, 3 mm length) containing Y zeolite alumina, with a reaction temperature of approximately 500"C and for every 1.2 kilograms of catalyst, one kilogram of physic nut oil was fed per hour.

When a physic nut oil was used on a moving bed reactor operated under conditions substantially simi- larto those stated in Example 1, a petrol of an octane number of 93 was obtained. After analyzing the distilled products, it was found thatthe petrol product could be used as a fuel for a petrol motor engine after the product was subjected to a simple treatment with caustic soda to remove impurities.

Comparison Example For the purposes of comparisonra Middle East heavy gas oil was catalytically'crnckedundercondi- tions substantially the same as those state in Example 1 above. In this comparison example, a moving bed was also utilized and the resultwas based upon one reaction run. The gasoline obtained had an octane numberof 91.

TABLE Example 1 Example 2 Example 3 Comparison Example -

Raw oil coconut oil hydrogenated physic nut oil Middle East heavy coconut oil gas oil saturated saturated saturated aromatic hydrocarbon glycerine ester glycerine ester glycerine ester and saturated Component 91 wt. % 98 wt. % 77 wt. % hydrocarbons unsaturated unsaturated unsaturated glycerine ester glycerine ester glycerine ester 8 wt. % 2 wt. % 23 wt. % Boiling Point 290 - 552 338 - 549 356 - 562 300 - 500 ( C) Catalytic Bed moving bed moving bed moving bed fixed bed moving bed Catalytic Y zeolite Y zeolite Y zeolite Y zeolite Y zeolite Agent silica alumina silica alumina silica silica silica alumina alumina alumina Reaction Temperature 485 500 500 500 485 ( C) Reaction Pressure normal normal normal normal normal Ckg/cm 937.8'C) Petrol yield 34 35 35 30 50 (weight percent Octane Number 94 92 91 93 91 (research method) Reaction (pH) neutral neutral neutral neutral neutral Distillation Condit ons: 10% Distillation 34 35 38 40 48 Temperature 508 Distillation 81 83 96 95 102.5 Temperature 90% Distillation 167 166 154.5 155 191 Temperature 97% Distillation 192 194 187 190 214.5 Temperature Residue Oils (Vol. %) 0.5 0.5 0.5 0.5 0.5 Copper strip corrosion t b t a t a t a t a (3h &commat; 50 C) Vapour2Pressure 0.72 0.69 0.54 0.57 0/51 (kg/cm &commat;37.8 C) Existent Gum (mg/100ml) 0.64 0.67 0.72 0.65 0.82 Tetra Ethyl Lead 0.0 0.0 0.0 0.0 0.0 ml/l

Claims

1. A process for producing a petrol with an octane numbergreaterthan 90, which process comprises catalytically cracking a fatty acid glycerine ester with a catalyst having, in a carrier,Yzeolite alumina-silica in a crystalline form.

2. A process according to Claim 1, wherein the carriercomprisesalumina.

3. A process according to Claim 1, wherein the carrier comprises silica.

4. A process for producing a petrol, which comprises: passing a fatty acid glycerine ester mixture, wherein the fatty acid moietycontainsfrom 6to 36 carbon atoms, into a reaction chamber having a catalyst containing Yzeolite alumina-silica in a carrier; catalytically cracking the mixture at a tem perature in the range from 350into 650 C, at an applied pressure lowerthan 10 kg/cm2; and then removing a cracked mixture containing a petrol from the reaction chamber.

5. A process according to Claim 4, wherein the catalyst in the reaction chamber is in the form of a moving bed and the catalyst is a powder.

6. A process according to Claim 5, wherein the weight ratio of catalyst to the glycerine ester is in the rangefrom3:1 to 12:1.

7. A process according to Claim 4, wherein the catalyst in the reaction chamber is in the form of a fixed bed, and the catalyst is shaped in the form of a cylinder.

8. A process according to Claim 4, wherein the catalyst in the reaction chamber is in the form of a fixed bed, and the catalyst is shaped in the form of a sphere.

9. A process according to Claim 7 or 8, wherein, for every one to five parts by weight of the catalyst, one part by weight ofthe mixture is fed per hourto the reaction chamber.

10. Aprocessaccordingto anyoneofClaims4to 9, wherein the mixture contains a generally saturated glycerine ester.

11. A process according to Claim 10, wherein the saturated glycerine ester comprises coconut oil.

12. A process according to any one of Claims 4to 9, wherein the mixture contains an unsaturated glycerine ester.

13. A process according to Claim 12, wherein the unsaturated glycerine ester comprises physic nut oil.

14. A process according to any one of Claims 4to 13, wherein the Yzeolite alumina-silica constitutes from 5 to 50 percent by weight of the catalyst.

15. A process according to any one of Claims 4to 14, which also includes treating the cracked mixture with an effective amount of a base to remove a sufficient quantity of impurities to enable the cracked mixtureto be used as a fuel in an automobile petrol engine.

16. Aprocessaccordingto Claim 1 or4,substantially as described in any one of the foregoing Examples 1 to 3.

17. Petrol whenever produced by a process according to any preceding claim.