DE3335688A1 - Process for producing gasoline from biomass - Google Patents

Abstract

A process for producing high octane gasoline is described. The process is characterised in that a high-grade fatty acid glycerol ester is cracked using a supported Y-zeolite/alumina/silica catalyst. The reaction is preferably carried out at 350 to 650 DEG C at a pressure of less than 10<6> Pa.

Description

Gasoline is a petroleum fuel with an octane rating of at least 60, which consists of a mixture of volatile hydrocarbons suitable for use in a spark ignited Internal combustion engine are suitable as defined in The Condensed Chemical Dictionary, 9th Edition, p. 407 will. The main components of gasoline are branched-

10 chain paraffins, cycloparaffins, olefins and aromatics.

There are several methods of making gasoline that use distillation or fractionation to produce a gasoline Relatively low octane straight run product primarily used for trimming include; thermal and catalytic cracking; Reform; Polymerization; Isomerization; and dehydrocyclization. from These methods, besides the first, are all different means of converting hydrocarbon gases into motor fuels by modifying the chemical structure, the modifications usually using catalysts. Although the predominant current source of gasoline is petroleum, it can also be obtained from shale oil and tar sands as well as by hydrogenation or gasification of coal.

As in Van Nostrand's Scientific Encyclopedia, 5th Edition, S. 1745. To 1749 is established, and what is expressly referred to here, the composition of Motor fuels changed over the years. In the early days of car transportation, gasoline was a relatively simple mixture of petroleum fractions from straight-run and thermally cracked material. Over the years that increased Compression ratio of gasoline to increase overall engine performance and efficiency. The rise of the Compression ratio required an increase in the octane

pay to prevent knocking.

For this reason, additives have been developed to increase the octane number. Additives also began to perform other functions, such as for example the prevention of carburetor icing and pollution, of corrosion of the fuel system, and of poor fuel distribution. With the increasing importance of ecological problems, the use of lead alkylene began Fall as fuel additives and catalytic converters have been built into automobile engines. With unleaded gasoline and The new environmental protection requirements was the production of a gasoline of a purity that a catalytic converter not poisoned, and yet it has a sufficiently high octane number to achieve good performance, always more expensive. In addition, the limited use of certain fuel additives, such as. B. lead alkyls, the cost for such a high-octane gasoline.

The price of gasoline is also determined by the world market price for Petroleum fuels affected. Because petroleum fuel Produced over a very long period of time, it is believed that the petroleum reserves are a depleted natural one Source are. The price of petroleum fuel is therefore determined by world supply and world demand for such fuels are regulated, as well as by the respective production capacity. In addition, there is the supply of petroleum fuel subject to exhaustion for a long period of time.

in view of the limited availability of natural Petroleum as well as the fact that different regions and countries have very little or minimal amounts of natural Having owned petroleum, attempts have been made to produce gasoline from bio-renewable sources. The previous Attempts to produce gasoline from biological

oils, however, have shown inadequate results in that any product obtained similar to petroleum is undesirable Has properties that prevent the product from being used in a gasoline engine. So that such a product has sufficient properties for use in a gasoline engine, it must meet various minimum requirements some of which the octane number, corrosion tendency, distillation conditions and purity (to prevent the Poisoning a catalytic converter).

There is therefore a need for a method that can economically produce gasoline from biological compounds can be produced, and with which a gasoline of sufficient purity and high octane number can be obtained,

15 um as sufficient fuel for modern cars

to be able to serve catalytic converters. In addition, there is a need for a substitute source for gasoline.

According to the invention, a gasoline of sufficient purity and a sufficiently high octane number is produced from a high-grade fatty acid glycerol ester mixture having carbon numbers of the fatty acid from 6 to 36 in a catalytic cracking process which uses Y-zeolite-alumina-silica.
25th

The subject matter of the invention is a method according to claim and 4. Expedient embodiments of this method are the dependent claims 2, 3 and 5 to 16 can be found.

In the process of the invention, either saturated or unsaturated fatty acid compounds are a sufficient starting material. Therefore, hydrogenation is not required. A saturated glycerol ester can be obtained from a biological Source, e.g. B. from coconut oil, and an unsaturated one Glycerine ester can be obtained from biological sources

will hold like ζ. B. from Physcia nut oil (physcic nut oil). By using such renewable sources, gasoline supply can be created in countries that do not have natural petroleum deposits. In addition, according to the method of the invention is that for production The feedstock needed by gasoline is not a non-renewable one Source that becomes exhausted over time.

A first object of the present invention is therefore to produce gasoline for use in internal combustion engines made of biological materials.

These and other objects and advantages of the present invention are clarified in connection with the following description of preferred embodiments.

In the preferred embodiment of the process according to the invention, a glycerol ester of a high-grade fatty acid having a carbon number of 6 to 36 is catalytically cracked with a catalyst which contains Y-zeolite-aluminum oxide-silicon dioxide. The Y-zeolite-aluminum oxide-silicon dioxide content of the catalyst should be between approx. 5 to 50% by weight, a range of 10 to approx. 30% by weight being preferred. When the catalyst is used in a fluidized bed reactor, the catalyst is in the form of a powder, when the catalyst is used in a fixed bed reactor, the catalyst is cylindrical or spherical in shape. During the process of the present invention, the pressure applied to the reaction bed is less than 10 Pa (10 kg / cm ² ) · A pressure of less than 2 × 10 Pa (2 kg / cm ² ) is usually sufficient. The reaction temperature of the reaction bed is between 350 and approx. 650 ^° C., and the preferred reaction temperature between approx. 450 to 550 ^° C. The ratio of the catalyst weight to the glycerol ester weight should be

335668

bed reactor between 3: 1 to 12: 1, with the preferred ratio between 8: 1 to 10: 1. For a fixed bed reactor the ratio of catalyst weight to glycerol ester weight should be between about 1 to 5 / hour, with a preferred feed rate between 1 to 3 / hour.

When the catalytic reaction takes place under the above-mentioned conditions, gas, water and coke are formed besides a low-boiling oil. The oil is then distilled and the distillate is ^{tested for its quality as gasoline between temperatures of 25 °} C. to 200 ^° C. after treatment with sodium hydroxide.

The invention is further illustrated by the following exemplary embodiments. The following examples serve but only for illustration, without restricting the invention thereto.

Example I.

In this example, illustrated in column 1 of Table 1, gasoline made from unrefined coconut oil becomes the saturated one Contains fatty acid glycerol esters. The catalytic cracking is carried out in a fluidized bed reaction chamber a Y zeolite-alumina-silica powder catalyst carried out. After one pass of cracking, the gasoline yield is 34% by weight, with an octane number of 94. According to analysis of the distillation conditions it was found that the product is of sufficient quality for without further treatment has use in an internal combustion engine. in an ordinary catalytic cracking reaction this can Uncracked oil remaining after the first run cracked again to increase the yield of gasoline will.

33356R8

Example II

In this example, the cracking run will be among the same Conditions as in Example I except that hydrogenated coconut oil was used as the starting material. The hydrogenated coconut oil is an example of a highly saturated one high grade fatty acid glycerol ester. The results of a run of catalytic cracking disclosed in Column 2 of Table 1 were as good as the results obtained in Example I.

10 Example III

In this example, Physcia nut oil was used as an example of an unsaturated fatty acid glycerol ester. Catalytic cracking was in a fixed bed in a reaction chamber with a cylindrical (diameter 1.5 mm, 3 mm length) Y-zeolite-alumina at a reaction temperature of about 500 ⁰ C and a feed rate of 1.2 kg per kg of catalyst weight Physcia- Nut oil performed per hour.

When Physcia nut oil is fed to a fluidized bed reactor operating under substantially similar conditions, as shown in Example I, a gasoline with an octane number of 93 was obtained. After analyzing the Distillation conditions have found that the product can be used as fuel for a gasoline engine, after subjecting the product to a simple cleaning with sodium hydroxide to remove impurities became.

30 Comparative Example I.

For comparison purposes, a heavy gas oil was chosen from the middle East (Middle East heavy gas oil) is catalytically cracked under conditions which are essentially the same as in example I were. In this example

a fluidized bed reactor is also used and the result is based on a reaction run-through. The received gasoline had an octane rating of 91.

Ex. I. Tab] Example II .Ie 1 Example III Fixed bed Comparative
ex. I. 1
d Coconut-
oil hydrogenated co-
coconut oil Physcia nut oil Y zeolite Si
silicon dioxide
Alumina heavy gas oil
from the middle
ren east 1 crude oil saturated Gly
cerinester
91% by weight
unsaturated
Glycerol ester
8% by weight saturated Gly
cerinester
98% by weight
unsaturated
Glycerol ester
2% by weight saturated glycerol ester
77% by weight
unsaturated glycerol ester
23% by weight 500 aromatic coals
hydrogen and ge
saturated coals
hydrogen component 290-552 338-549 356-562 normal 300-500 Boiling point ( ⁰ C) 30th Catalytic
Cracking conditions Fluidized bed Fluidized bed Fluidized bed Fluidized bed Catalyst bed Y zeolite
Silicon dioxide
Alumina Y zeolite silicon
cium dioxide-aluminum
minium oxide Y zeolite silicon
cium dioxide-aluminum
minium oxide Y zeolite silicon
dioxide-alumina catalyst 485 500 500 485 Reaction temp. ( ⁰ C) normal normal normal normal Reaction pressure
(kg / cm ² (337.8 ° C) 34 35 35 50 Benz xn yield
(Wt%) quality

CO CO CO

cn cn co

Ex. I. Table I. (Continuation) 93 Comparative example I. 94 Example II Example III neutral 91 Octane number
(Research method) neutral 92 91 neutral reaction neutral neutral 40 distillation 34 95 . 48 10% distillation temp. 81 35 38 155 102.5 50% distillation temp. 167 83 96 190 191 90% distillation temp. 192 166 154.5 0.5 214.5 ! 97% distillation temp.
i 0.5 194 187 1 a 0.5 Residual oils
(% By volume) 1 b 0.5 0.5 0.57 1 a Copper streak corrosion
(3 h 5O ⁰ C) 0.72 1 a 1 a 0.65 0.51 Vapor pressure
(kg / cm ² β37.8 ⁰ C) 0.64 0.69 0.54 0.0 0.82 Existing rubber
(mg / 100 ml) 0.0 0.67 0.72 0.0 Tetraethyl lead (ml / 1) 0.0 0.0

CO CO CO

Claims (16)

Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber Dr.-Ing. H. Liska, Dipl.-Phys. Dr. J. Prechtel SMCT 8000 MUNICH S6 1 Π <Jgp JQOO POST BOX S60 820 · · QJ MOl IIS TRASSK 22 TKUTON (0 89) 9S0352 TUIKX 522621 TI II GIiAMM PATIiNTWKICKMANN MUNICH Honda Giken Kogyo Kabushiki Kaishaae, 27-8 , Shibuya-ku, Tokyo, Japan Process for the production of gasoline from biomass Patent claims 1.1 Method of making gasoline with an octane rating greater than 90, characterized in that it contains the following stages: catalytic cracking of a high-grade Fatty acid glycerol esters with a catalyst with a carrier, the Y-zeolite-alumina - silica in a crystalline Contains shape. 2. The method according to claim 1, characterized in that the carrier contains aluminum oxide. 3. The method according to claim 1, characterized in that the carrier contains silicon dioxide. 4. Process for the production of gasoline, characterized in that that it contains the stages: Passing a high grade fatty acid glyceride mixture having fatty acid carbon numbers in the range of 6 to 36 into a reaction chamber having a catalyst containing Y-zeolite-alumina-silica in a carrier; catalytic cracking of the mixture at a temperature between approx. 350 ^° C. and 650 ^° C. at a pressure lower than 10 Pa (10 kg / cm ² ) and with an effective feed rate; and subsequently removing a cracked mixture containing gasoline from the reaction chamber.
10 5. The method according to claim 4, characterized in that the reaction chamber is a fluidized bed and the catalyst is a powder. 15 6. The method according to claim 5, characterized in that the ratio of catalyst weight to Glycerol ester weight is between 3: 1 and 12: 1. 7. The method according to claim 4, characterized in that g e k e η η - 20 shows that the reaction chamber is a fixed bed and the catalyst has the shape of a cylinder. 8. The method according to claim 7, characterized in that the feed speed between 2 5 1 to 5 parts by weight of catalyst to 1 part by weight of the mixture per hour. 9. The method according to claim 4, characterized in that the reaction chamber is a fixed bed and the catalyst has the shape of a sphere. 10. The method according to claim 9, characterized in that the feed speed between 1 to 5 parts by weight of catalyst to 1 part by weight of the mixture per hour. ο r ~ c ο ο ,: ■ -j üüö 11. The method according to claim 4, characterized in that the mixture is a saturated glycerol ester contains. 12. The method according to claim 11, characterized in that the saturated glycerol is coconut oil contains. 13. The method according to claim 4, characterized in that g e k e η η - draws that the mixture is an unsaturated glycerol ester contains. 14. The method according to claim 13, characterized in that the unsaturated glyceride Physcia- 15 contains nut oil (physcic nut oil). 15. The method according to claim 4, characterized in that the Y-zeolite-aluminum oxide silicon oxide comprises about 5 to 50 weight percent of the catalyst. 16. The method according to claim 4, characterized in that it contains the further stage in which the cracked mixture with an effective amount of a base to remove a sufficient amount of impurities treated to enable the cracked mixture to be used as fuel in a car gasoline engine,