DE1057710B - Improved radiochemical hydrocarbon conversion process - Google Patents

Description

kl. 23 b 1/04

INTERNAT. KL. C 10 g

BUNDESKEPUBLIK ^ GERMANY

GERMAN ejyk PATENT OFFICE INTERPRETATION PAPER 1057 710

E 14307 IVc / 23 b

REGISTRATION DATE: JUNE 21, 1957

NOTICE THE REGISTRATION AND ISSUE OF THE OUTLOOK: 2 1. M A I 1 9 5 9

The invention relates to the conversion of hydrocarbon oils in the liquid phase by irradiation in the presence of a gel-like hydrocarbon conversion catalyst which adsorbed Contains water.

In the hydrocarbon conversion process of the present invention, a hydrocarbon oil is converted into liquid phase in a reaction zone by exposure to high-energy ionizing radiation, especially with ^ rays, in the presence of a highly porous hydrocarbon conversion catalyst of the solid gel type, e.g. B. Silica - clay, which contains at least 5% adsorbed water.

In particularly preferred embodiments of the invention, the conversion ^{temperature is kept below 260 °} C., the radiation from a nuclear reactor is used and a petroleum distillate is subjected to the conversion.

It has now been found that the presence of adsorbed water on the surface of a highly porous hydrocarbon conversion catalyst on the gel type greatly influences the amount and type of products obtained when the catalyst is used one by irradiation with y-rays or neutrons used hydrocarbon conversion process; the intimate contact of the water with the catalyst surface and the oil to be converted has a noticeable influence on the result of the conversion.

For best results, it is recommended to keep the Umwandlungstcmpcratur below 26O ⁰ C and maintain a pressure, the conditions for the liquid phase be ensured by the substantially.

The feedstocks suitable for the invention include hydrocarbon oils liquid under normal conditions, such as e.g. B. unprocessed crude oils, distillates and residues, asphalt, shale oils, coal tar, synthetic oils and the like. Particularly good results are achieved with relatively clean petroleum distillates that _{boil in the range between C 4} hydrocarbons and 566 ° C.

The preferred catalyst of the present invention is a gel-type hydrocarbon conversion catalyst known in the art which is useful in hydrocarbon conversion processes such as gas oil cracking, heavy gasoline reforming, polymerization, and desulfurization. A gel type catalyst is e.g. B. the solid obtained on drying a hydrated oxide such as alumina, silica, zirconia, titania, magnesia, zinc aluminate, and mixtures of these materials. However, other known improved radiochemical hydrocarbon conversion processes can also be used

Applicant:

Esso Research and Engineering Company, Elizabeth, N.J. (V.St.A.)

Representative:

Dr. W. Beil and A. Hoeppener, lawyers, Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority: V. St. v. America June 21, 1956

John P. Longwell, Scotch Plains, N.J., Peter J. Lucchest, Cranford, N.J.,

and Robert B. Long, Wanamassa, N. J.

(V. St. A.),
have been named as inventors

Types of porous conversion catalysts such as activated charcoal can be used.

The porous hydrocarbon conversion catalyst can be of natural origin such as bauxite be produced or, for example, by the alcoholate clay method or by precipitation from an aluminum sulfate solution. A common type of catalyst is that for gas oil cracking used silica-alumina catalyst.

These catalysts are preferably highly porous and have a surface area of more than 50 m ² / g and a pore volume of more than 0.2 ccm / g. These properties can be determined by known methods, e.g. B. by calcining, chemical treatment, regulation of the rate of precipitation and the like. The catalysts preferably have a size of 0 ' to 1000 μ; however, larger particles, e.g. JB. Pills or pellets, are used.

In preferred embodiments of the invention, the catalyst has an additional component on. This can be a common component that affects the conversion, such as a Hydrogenation component, e.g. B. platinum, molybdenum, palladium, nickel, rhodium and ruthenium or their Oxides or sulfides, hande-lrif the component can

S. 909 527/394

however, it can also be added to improve the properties of the catalyst, e.g. B. in the case of silica or the salts or oxides of potassium, calcium and magnesium. The added component can also be so-called »radiochemical accelerators «, such as e.g. B. Boron 10 and Lithium 6 . which emit ct particles of high intensity when capturing a neutron, or comprise materials which emit y-rays of high intensity when capturing neutrons, e.g. Yy. Cadmium, o you, home to the capture of neutrons / g radiation emitters . These materials can be used as pure elements or isotopes, or as compounds. Although they are preferably applied to the catalyst surface, they can, however, also be used on inert substances or in solutions; for example, tri-n-dodccyl borate can be used.

The following explanation of the drawing serves to explain the invention.

The feed coming from 1 is shown in the drawing guided through line 2 into a radiation zone 3. The water-containing catalyst according to the invention is mixed with the oil coming from 4 through the line 5. The one containing the catalyst ül is irradiated in the radiation zone 3.

The radiation can come from waste material from nuclear reactors, such as spent fuel, or from man-made cesotopes, such as cobalt 60. In this embodiment of the invention, the reaction pieces are simply guided past the radiation source in suitable tubes or containers. The intensity of the radiation source is preferably so great that there is a γ-flow of at least about to ⁵ X-rays / h in the reaction zone. The conditions are preferably chosen so that the oil ^{receives a radiation amount of at least 10 3} X-rays.

However, it is highly recommended that the conversion be carried out in a nuclear reactor, e.g. B. a nuclear reactor. The stream of Rcaktionstcilnehmcr containing the catalyst is passed through the reactor or around the fissile material in suitable tubes and is thereby subjected to a cncrgicreichen ionizing radiation comprises y and neutron rays. Braking substances such as carbon, light or heavy AVasscr or hydrocarbons can be used. In some cases the feed stream itself can serve as a braking substance.

When using a nuclear reactor, the reaction zone, apart from the above intensity of the / rays, is preferably ^{exposed to a neutron flux of at least 10 8} Ncutroncn / cm ² / scc and the conditions are designed so that the reactants have an amount of ^{neutrons of at least 10 "1 cg /} g / scc received.

In the drawing, a suspensoid system is shown, ie. The next catalyst is conveyed in suspension in the liquid reaction component through the reaction zone , then recovered and returned. However, the catalyst can also be present in the irradiation zone 3 in the form of a quiescent bed, a bed that sinks under the force of gravity, or a fluidized bed. It can be continuously removed from the irradiation zone either together with the reactant or separately for regeneration, re-treatment, etc. If desired, it can be regenerated periodically or continuously on site in the irradiation zone 3.

As already stated above, the conditions in the irradiation zone 3 are preferably such that a liquid phase is maintained; the temperature is maintained to obtain a good product distribution below 26O ⁰ C. The pressure can be up to 7 kg / cm ² and more. The time required to achieve the above amounts of radiation is usually 60 to 10 ⁶ minutes. The flow rate is normally

ίο 0.01 to 100 vol./vol./h. The proportions of Catalyst to oil are usually between 0.1: 1 and 10: 1.

The irradiated material is transported through line 6 from zone 3 to separation zone 7. the Separation zone contains means for recovering the catalyst, for example by distillation and filtration. The recovered catalyst is returned in this example through line 8, however, it can also be discarded. The recovered catalyst can first, for example by burning off, steam treatment, chemical treatment, etc. for removal of impurities and to improve its properties are treated before being returned will.

The separation zone 7 can also be a device for the removal and / or neutralization of radioactive Contain waste products. Such a device can allow containers to decay which include radioactivity, ion exchangers, distillation columns and solvent extraction systems.

The hydrocarbon products are in the Zone 7 separated by conventional devices. So you can do distillation, extraction, crystallization and adsorption use. If desired, part of the product can be returned through line 9. The treated product is removed through line 10. According to the invention, the contains in the irradiation zone 3 catalyst used at least 5%, preferably more than 25%, adsorbed water. By doing This water content on the catalyst is obtained by the "suspensoid system" shown get water from a spring. 11 added to the recycled catalyst. The water can according to any Procedure, e.g. B. by immersing the catalyst or spraying, can be added. A becomes the catalyst ζ B. in a quiescent bed, kept essentially permanently in zone 3, the water content of the catalyst can be maintained by adding water to the feed adds or water directly into the zone containing the catalyst, preferably in amounts of more than 2 percent by weight based on the feed material. This can be periodic or happen continuously.

In some cases the adsorption of water on the catalyst can be promoted by using certain materials, for example CaSO ₄ or other anhydrous salts, which can be easily hydrated. These can be on the surface of the catalyst or added together with the water.

, Example

The following oils were treated: Oil A. Hydrogenated, boiling between 121 and 260 ° C Luminous oil with an aniline point of around 62.8 ° C, a specific gravity of 0.7976 and a refractive index 1.4407 at 20 °.

oil B. Untreated, paraffinic petroleum gas oil with the following data: specific gravity 0.8724, bromine number 1.25 centigrams / g, Saybold Second Universal viscosity 34.4 at 98.9 ° C, viscosity index 67 and sulfur content 0 , 14 percent by weight. Distillation properties: At normal pressure were at 315.5 ° C and 5% at 371 ⁰ C abdestillicrt 90%.

were distilled off oil C. Slight residue from West Texas oil with an initial boiling point of 284 ⁰ C, of which 50% at 51O ⁰ C. The density was 0.9285, the refractive index 1.5162 and the sulfur content 2.53%. The residue contained 0.001% Ni, 0.00244% V and 0.000296% Fe. The oil has a C: Η ratio of 7.43. The catalysts used were alumina, silica-alumina, and platinum-on-clay earth.

Alumina catalysts. An excess of ammonia water was added to an aluminum alcoholate solution. The aqueous layer containing the toner dehydrosol as a slurry was separated. The slurry was dried at 121 ⁰ C and calcined for 4 hours at 593 ° C. The product had a surface area of 100 to 200 m ² / g.

Silica-alumina catalysts. A silica gel was immersed in an aluminum sulfate solution, then treated with ammonia and then washed free of sulfate. The product was dried and calcined at 649 ° C for 3 hours. Its surface area was about 500 m ² / g.

No protection is claimed for the catalyst production in the context of the present process.

Platinum-on-alumina. This was a commercially available alcoholate-alumina catalyst containing 0.6 percent by weight platinum and 0.6 percent by weight chlorine. The catalyst was used in the form of 4.76 x 3.17 mm cylinders with a surface area of 300 m ² / g and a pore size of 50 to 80 Å. These catalysts were impregnated with water by allowing a known amount by weight of water to be adsorbed by a known amount by weight of the above-described catalyst. An air-cooled research reactor powered by natural uranium and braked with graphite was used to irradiate these samples. At the time of the experiments, this atomic pile was working with a total output of 24 megawatts, with the following radiation distribution being obtained at the point where the oils were irradiated:

Slow neutron flux (0.03 eV)

= 2.5 · 10 ¹² neutrons / cm ² / s fast neutron flux () IMeV)

= 0.5 · 10 ¹² neutrons / cm ² / s y radiation = 1.7 · 10 ^e X-rays / h

The core of the reactor consisted of a graphite grid about 6-6-6 m in size with evenly spaced horizontally within the reactor, extending from the north to the south surface of the core of aluminum-plated uranium rods with a diameter of 25 mm. This core was completely surrounded by a 1.52 m thick protective wall made of concrete. The openings for receiving the samples were 10-10 cm in size and horizontal and extended through the 1.52 m thick concrete wall through and 3 m from the outer surface of the core into the carbon core. The normal operating temperatures in these openings were 121 to 204 ⁰ C.

The irradiation was carried out in the following way:

Three 0.95-1 samples were irradiated simultaneously by placing them in three ventilated aluminum containers with a diameter of 75 mm placed on a horizontal aluminum slide was. The aluminum vent tubes extended from the vapor phase of the containers the core out and through the concrete wall to a sample collection system, · in "the gases and condensable liquids measured and collected

ίο were. The samples were made by filled the hopper with the solids, the empty space evacuated in the container and sucked the oil into the container using the vacuum. Samples were then purged with purified nitrogen and placed in the reactor during scheduled shutdowns introduced, irradiated for 10 days each and during the subsequent shutdown from the Pile away.

Table 1 gives the ratio of CH ₃ - to

CH ₂ groups in the products obtained on irradiation of oil A.

Tabel 1 Pt _a - boiling range
of the product
⁰ C 27 »/ 0 H ₂ O
on clay No
catalyst 0.80 -18 to 135
30 135 to 171
171 to 204
-18 to 221
221 to 315 1.52
1.28
1.01 0.64

Table 1 shows that the products obtained from hydrogenated luminous oil in the presence of water are highly branched and contain a large amount of iso-compounds. The ratio of C Ii ₃ : CH ₂ was measured by nuclear magnetic resonance.

Table 2 shows that the irradiation in the presence of a catalyst containing adsorbed water which has the specific effect of yielding highly unsaturated cracking material, such as by the high bromine numbers will be shown.

It was also found that the presence of water on the catalyst for the formation of a significant amount of oxygen-containing organic compounds (acids, esters, ketones) in these low temperatures is responsible. By infrared analysis it was found that, although the Feed streams did not contain oxygenated hydrocarbons, the various product fractions however, substantial amounts of such

• Contained 55 bonds.

In particular, the product boiling between -18 and 315.5 ° C (about 13% based on feed) of irradiation of Oil A with the alumina catalyst containing 27% water contained about 20% carbonyl compounds, as shown by infrared analysis. These carbonyl compounds were not found in blank tests carried out without water. The analysis of the product boiling between -18 and 315.5 ° C (approx. 10 percent by weight, based on the use) which is produced when the oil is irradiated ^! B using a catalyst consisting of alumina and 27 weight percent water also showed about 20% carbonyl compounds, while no such compounds were obtained in blank tests.

Tabel

oil B

oil C

Temperature, ⁰ C

Pressure, kg / cm ²

Time, days

catalyst

Volume ratio of catalyst to oil Initial water on the catalyst. Conversion to gas, weight percent

to 204
normal

10
Si

1: none 20%
7.9

Products

Boiling point, ⁰ C

Percentage by weight, based on use ...

Aromatics, percent by volume

Olefins, percent by volume

Saturated compounds, volume percentage.

Bromine number

Boiling point, ⁰ C

Percentage by weight, based on use ...

Aromatics, percent by volume

Olefins, percent by volume

Saturated compounds, volume percentage.

Bromine number

-18 to 221

14.8

12.3

72.9

3.05 b s 343

9.4
35.9
54.7
29.0

8.8 9.4

34.6 50.6

56.6 40.0

1.03 27.0 ² )

¹ J silica-alumina.

² ) The aqueous layer obtained when the mixture of oil B and water was irradiated showed a metal content that was one

36% removal of Fc and a slight removal of V and Ni from the residue.

177 to 204
normal

10

Si: Al!)
1: 1

none
1.2

20%

-18 to 315

8.0
24.1
30.4
45.5
31

2.6
21.8
42.7
37.5
36

Claims (13)

Patent claims: 1. Improved radiochemical hydrocarbon conversion process, characterized in that a hydrocarbon oil is irradiated in the liquid phase in a reaction zone in the presence of a highly porous hydrocarbon conversion catalyst which contains at least 5% adsorbed water. 2. The method according to claim 1, characterized in that that a solid catalyst of the Gcltype is used which becomes more hydrated by drying Alumina, silica, zirconium, titanium, magnesia, zinc aluminate or mixtures of these materials has been obtained. 3. The method according to claim 1, characterized in that a catalyst made of alumina with a surface area of more than 50 m ² / g is used. 4. Driving up according to claim 1 to 3, characterized in that a porous hydrocarbon conversion catalyst is used, the particle size of which is between 0 and 1000 μ and which has a surface area of more than 50 m ² / g. 5. The method according to claim 1 to 3, characterized in that a catalyst is used also an added component that affects the conversion, such as elementary Platinum, molybdenum, palladium, nickel-rhodium or ruthenium or their oxides or sulfides. 6. The method according to any one of claims 1 to 5, characterized in that there is a catalyst used from alumina and an added hydrogenation component. 7. The method according to any one of claims 1 to 5, characterized in that there is a catalyst made of clay and added silica used as a cracking component. 8. The method according to any one of claims 1 to 6, characterized in that there is a catalyst with a radiochemical accelerator which, when capturing a neutron, has a higher α-particle Emitted intensity, such as boron 10 or lithium 6, or materials that when a neutron is captured high intensity y-rays such as B. cadmium, or ^ rays emit used. 9. The method according to claim 5, characterized in that the radiochemical accelerator used as pure isotopes or as compounds. 10. \ ^ crfahren according to claim 1 to 7, characterized characterized in that the amount of adsorbed water on the catalyst is preferably more than 25%. 11. The method according to claim 1, characterized in that one is used as a hydrocarbon oil Petroleum distillate boiling between the boiling point of (^ hydrocarbons and 564 ° C) is used. 12. retraction according to claim 1, characterized in that the reaction temperature is kept below 26O ⁰ C. 13. The method according to claim 1, characterized in that the method is continuous is carried out, the catalyst remains in the reaction zone and that in the reaction zone incoming feed material contains at least 2% by weight of water. 1 sheet of drawings ® 909 527/394 5.59