DE3340711A1 - Process for the preparation of paraffinic hydrocarbon solvents from vegetable oils - Google Patents

Abstract

Process for the preparation of paraffinic hydrocarbons of a higher fatty acid glycerol ester which is catalytically cracked by a catalyst containing Y-zeolite aluminosilicate, cobalt molybdenum or nickel molybdenum.

Description

description

The present invention relates generally to a method of manufacture of paraffin hydrocarbons from vegetable oils.

Paraffinic hydrocarbons, also known as alkanes, are compounds of hydrogen and carbon that have structures in which the carbon atom only forms simple valence bonds and those in open chains are arranged, which can be straight or branched. The ratio of carbon atoms to hydrogen atoms in all paraffinic hydrocarbons can be expressed are given by the general formula CnH2n + 2 are paraffinic hydrocarbons generally characterized by a lack of noticeable chemical reactivity as well as the lowest specific weight of the liquid hydrocarbons (the range is from about 0.62 to 0.77). Paraffinic hydrocarbons come in petroleum and natural gas and can be separated from petroleum by fractional Distillation. Van Nostrand's Scientific Encyclopedia, 5th Ed., Pp. 1294-1299. the physical properties of paraffinic hydrocarbons make these compounds well suited for use as an organic solvent. In terms of the exhaustible The nature of natural petroleum and its currently highly volatile cost, as well as the fact that certain regions and countries are very small or minimal Having quantities of natural petroleum there is a need for a process that economically produces alternative paraffinic hydrocarbons Can produce sources of raw material. Such a process must be economical produce paraffinic hydrocarbons from raw materials that are both easily accessible or replaceable as well as not prohibitively expensive.

In the present invention, paraffinic hydrocarbons are used made from higher fatty acid glycerol esters in a catalytic cracking process, where Y-zeolite, cobalt-molybdenum or nickel-molybdenum together with aluminum oxide is used.

In the process of the present invention are either saturated or unsaturated fatty acids sufficient as raw material. That is why there is a hydrogenation not mandatory. A saturated fatty acid glycerol ester can be obtained from biological sources such as coconut oil and an unsaturated fatty acid glycerol ester can be obtained from biological sources such as a medicinal nut oil (physic nut oil). While using such renewable sources, one can supply of paraffinic hydrocarbons are produced in countries that do not have any have natural oil deposits. Furthermore, according to the method of the present Invention of the raw material required to produce paraffinic hydrocarbons to produce, not a non-renewable source that depletes over time will. Therefore, it is the first object of the present invention to make paraffinic Manufacture hydrocarbons from biological materials.

These and other objects and advantages of the present invention will become apparent to those skilled in the art in connection with the following description the before to th embodiment.

In the preferred embodiment of a method in accordance with the present invention, a glycerol ester of a higher fatty acid becomes catalytic cracked by a catalyst in which the support is aluminum oxide, the aluminum silicate Y zeolite in crystal form or contains cobalt-molybdenum or nickel-molybdenum. The content of the The aluminosilicate Y zeolite catalyst should be between approximately 5 and 50% by weight, with the range from 10 to about 30% by weight being preferred. Of the The cobalt content of the catalyst should be between approximately 3 to 10% by weight, with the range from 4 to about 6 weight percent being preferred. The nickel content of the catalyst should be between about 3 and 10% by weight, with the range from about 4 to 6 % By weight is preferred. The molybdenum content of the catalyst should be between about 10 and 20% by weight, with the range of about 13 to 18% by weight being preferred.

During the process of the present invention, the reaction pressure, which is used in the reactor which is mainly used by hydrogen will be between about 9.8 and 196 bar (10 and 200 kg / cm2), the range being from about 29.4 to 147 bar (30 to 150 kg / cm2) is preferred. The reaction temperature of the reactor should be between about 30,000 and 6000C, preferably between 350 and 4500C.

The invention is carried out using a few examples.

The oil product in the following examples was collected at a Temperature up to 330 "C and the product was analyzed by gas chromatography.

Example l In this example recorded in Table 1, Paraffinic hydrocarbons are produced from coconut oil, the saturated one Fatty acid glycerol esters to about 91% by weight and unsaturated fatty acid glycerol esters contains about 8 wt .-%. The boiling point of the raw material was about 2900C to 552 "C. The catalytic cracking was carried out inside a fixed bed reactor, in the reaction pressure was about 147 bar (150 kg / cm2) with a hydrogen flow rate of 1200 ml H2 per ml feed material. The reaction temperature was between held around 400 "C and 410" C and the l.h.s.v. (liquid hourly space velocity) was held at about 0.3 per hour. The catalyst used in the first example was used, Y-zeolite-alumina and the yield was paraffinic Hydrogen was 58.4 wt% with other hydrocarbons being about 1.5 wt% of the product included. The paraffinic hydrocarbons that were obtained had carbon numbers between 4 and 19.

EXAMPLE 1 II In this example, the catalyst used was Cobalt-molybdenum in spherical form. The same raw material was put into a fixed bed reactor introduced with a l.h.s.v. from 1.0 per hour. The reaction temperature was kept at about 3800C, while the pressure inside the reactor was about 29 bar (30 kg / cm2) was obtained with a hydrogen flow rate of 500 ml H2 per ml of raw material. The product obtained was rich in straight chain hydrocarbons in which the Carbon number was between 6 and 19.

Example 1 III In this example, the same raw material was used used as in the first two examples. The catalyst in this example was nickel-molybdenum in a cylindrical shape. A fixed bed reactor was used by maintaining the pressure at about 29 bar (30 kg / cm2) with a hydrogen flow rate of 500 ml H2 per ml of raw material. The reaction temperature was maintained at about 3800C and the l.h.s.v. was 1.0 per hour. The resulting product was rich in straight chain Hydrocarbons with a carbon number between 6 and 19.

EXAMPLE 1 IV Medicinal nut oil was used in this example as an example of an unsaturated fatty acid glycerol ester. Catalytic cracking was carried out in a fixed bed within a reactor with a Y-zeolite-alumina catalyst. The reaction temperature was maintained at about 3900C while the reaction pressure was held at about 147 bar (150 kg / cm2). The l.h.s.v. was 0.3 per hour and the resulting product was rich in paraffinic hydrocarbons with a Carbon number between 5 and 19.

Comparative Example 1 For comparative purposes, a top residue oil was used from the Middle East catalytically cracked in a fixed bed reactor, the one Cobalt molybdenum alumina Had catalyst. The reaction temperature was kept at about 3900C, while the reaction pressure was 147 bar (150 kg / cm2) was maintained at a hydrogen flow rate of 930 ml H2 per ml of feed. The l.h.s.v. was held at 0.3 per hour. The yield obtained was only 17 % By weight of paraffinic hydrocarbons.

V e r g 1 e i c h s b e i s p i e 1 II In this example, the Upper residual oil from the Middle East reused in a fixed bed reactor, which now had a Y-zeolite-alumina catalyst. The reaction temperature was kept at about 3900C with a reaction pressure of 147 bar (150 kg / cm2) and a hydrogen flow rate of about 1200 ml H2 per ml of raw material. The l.h.s.v. was 0.3 per hour. The yield of paraffinic hydrocarbons was 24.4 Wt%.

Table 1 Comparative comparative Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 @ J Coconut oil med. Nut oil at above the residual oil Robmaterial fatty acid components fatty acid components from the middle saturated fatty acid glycerol esters 77% by weight unsaturated 77% by weight East saturated hydrocarbon saturated fatty acid glycerol - 8% by weight saturated 23% by weight substances and aromatic cabbage @@ ester hydrogen Boiling point of 290 ~ 552 minimum 350 minimum 330 Robmaterials (° C) Reaction conditions- Y-zeolite- cobalt-molybdenum-nickel-molyb- cobalt-molyb- Y-zeolite- Danish aluminum Y zeolite aluminum oxide Danish aluminum aluminum oxide gene catalyst aluminum oxide aluminum oxide oxide Reaction temperature ° C 400 ~ 410 380 380 390 390 390 Reaction pressure bar (kg / cm²) (150) 147 (30) 29 (30) 147 (150) 147 (150) 147 (150) Yield.wt% 58.4 72.5 70.8 70.7 17.0 24.4 Content of paraffin KW 04 0.2 0.2 05 0.6 0.2 0.2 0.2 06 1.0 0.5 0.6 9.9 0.1 0.4 07 1.9 5.6 5.3 1.6 0.1 0.5 08 4.0 4.6 5.0 1.6 0.3 0.5 09 2.1 3.8 4.1 1.5 0.3 0.7 010 2.7 2.5 2.5 2.1 0.2 0.9 011 19.8 21.5 20.8 2.2 0.3 1.1 012 10.1 12.9 12.0 1.4 0.5 0.8 013 5.0 6.3 6.2 1.0 0.6 1.0 014 3.0 4.2 3.8 0.9 0.6 1.0 015 2.0 2.7 2.5 4.0 0.8 1.3 016 1.6 1.7 1.8 11.2 1.1 1.5 017 1.8 2.5 2.3 10.8 1.2 1.8 018 1.0 1.6 1.5 29.9 1.0 1.2 019 0.1 0.3 0.3 0.3 0.4 0.5 other week 1.5 1.8 1.9 1.1 9.5 10.8

Claims (21)

Claims process for the production of paraffinic hydrocarbons, it is noted that a higher fatty acid glycerol ester catalytic cracking is carried out with a catalyst selected from the group consisting made of Y-zeolite-aluminum oxide, cobalt-molybdenum-aluminum oxide and nickel-molybdenum-aluminum oxide. 2. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that the fatty acid glycerol ester is unsaturated. 3. The method according to claim 2, d a d u r c h g e k e n n z e i c h Not that the unsaturated fatty acid glycerol ester comprises medicinal nut oil. 4. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that the fatty acid glycerol ester comprises a saturated glycerol ester. 5. The method according to claim 4, d a d u r c h g e k e n n z e i c h Not that the saturated glycerol ester comprises coconut oil. 6. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that Y zeolite-alumina is about 5 to 50 weight percent of the catalyst matters Cobalt makes up about 3 to 10% by weight of the catalyst, nickel about 3 to 10 % By weight of the catalyst and molybdenum about 10 to 20% by weight of the catalyst matters. 7. The method of claim 1, d a d u r c h g e- k e n n z e i c h n e t that a yield of paraffinic hydrocarbons of more than 50 % By weight is obtained by the process. 8. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that a reaction temperature of about 3000C to 6000C is maintained in the reactor will. 9. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that a reaction pressure between about 9.8 to 196 bar (10 and 200 kg / cm2) is maintained in the reactor. 10. Process for the production of paraffinic hydrocarbons, it is noted that a higher fatty acid glycerol ester is passed into a reaction chamber which has a catalyst selected from the group consisting of Y-zeolite- aluminum oxide-silica, cobalt-molybdenum or nickel- Molybdenum; the fatty acid glycerol ester at a temperature between about 3000C and 6000C, with an applied pressure between about 9.8 and 196 bar (10 kg / cm2 and 200 kg / cm2) and an effective feed rate; is catalytically cracked and then the cracked mixture that removes the paraffinic hydrocarbons from the reactor contains is removed. 11. The method according to claim 10, d a d u r c h g e k e n n z e i c That is, the reactor is a fixed bed and the catalyst is in the form of a cylinder Has. 12. The method according to claim 10, d a d u r c h g e k e n n z e i c That is, the reactor is a fixed bed and the catalyst is in the form of a ball Has. 13. The method according to claim 10, d a d u r c h g e k e n n z e i c h n e t that the effective l.h.s.v. is between about 0.3 and 1.0 per hour. 14. The method according to claim 10, d a d u r c h g e k e n n z e i c Not that the fatty acid glycerol ester is unsaturated. 15. The method according to claim 14, d a d u r c h g e k e n n z e i c Note that the unsaturated fatty acid glycerol ester comprises a medicinal nut oil. 16. The method according to claim 10, d a d u r c h g e k e n n z e i c Not that the fatty acid glycerol ester contains a saturated glycerol ester. 17. The method according to claim 15, d a d u r c h g e k e n n z e i c Note that the saturated glycerol ester contains coconut oil. 18. The method according to claim 10, d a d u r c h g e k e n n z e i c Note that Y-zeolite-alumina-silica is about 5 to 50 percent by weight of the catalyst makes up, cobalt makes up about 3 to 10% by weight of the catalyst, nickel makes up about 3 to 10% by weight of the catalyst and molybdenum about 10 to 20% by weight of the catalyst matters. 19. The method according to claim 10, d a d u r c h g e k e n n z e i c h n e t that a yield of paraffinic hydrocarbons by the process is obtained which is greater than 50 wt .-%. 20. The method according to claim 10, d a d u r c h g e k e n n z e i c Note that a reaction temperature of about 3000C to 6000C is maintained in the reactor will. 21. The method according to claim 10, d a d u r c h g e k e n n z e i c h n e t that a reaction pressure of about 9.8 to 196 bar (10 to 200 kg / cm2) in the reactor is maintained.