WO1997019148A1

WO1997019148A1 - Refining of oil and petroleum materials

Info

Publication number: WO1997019148A1
Application number: PCT/GB1996/002866
Authority: WO
Inventors: Sergey Vladimirovich Trifonov; Vladimir Georgievich Andrienko; Evgeny Grigorevich Gorlov; Olga Zinovevna Elina; Valery Anatolievich Donchenko; Albert Pavlovich Avdoshin; Jury Germanovich Soone; Larisa Vladimirovna Bolxhovitina
Original assignee: Bryson, Julian; Spickernell, James; Woodcock, Ian; Djeiranishvili, Nougzar; Boutine, Sergei
Priority date: 1995-11-20
Filing date: 1996-11-20
Publication date: 1997-05-29
Also published as: AU7632296A; WO1997019149A1; AU4460396A

Abstract

There is disclosed a method and apparatus for refining petroleum materials in which the petroleum materials are mixed with an organomineral bearer prior to being passed through a thermal reactor so as to undergo thermo-cracking. The organomineral bearer may be a powder or granular material comprising, or derived from, sapropelite, sapropelic coal, shale, rabdopissite, liptobiolite and/or sapromyxite. The organomineral bearer serves to improve the efficiency of the isolation of distilled fractions from the petroleum materials.

Description

REFINING OF OIL AND PETROLEUM MATERIALS

The present invention relates to a method and apparatus for processing and refinement of oil/petroleum raw materials. In particular, but not exclusively, it relates to the thermo-cracking of oil/ petroleum raw materials such as crude oil (especially heavy bituminous oil) and heavy residual raw materials such as mazut, half-tar, tar and/or heavy gasoils produced by catalytic or hydro-cracking.

It is known that m order to generate light oil products, petroleum materials (such as oil residua or oil tar mixed with bituminous coal) are supplied into a processing plant in which hydro-cracking of the received suspension is carried out (as described, for example, m US 4,394,248) . This known process works adequately m industry standard plants, but production of benzine (by which is meant light petroleum distillates m the gasoline and naphtha range) and diesel fractions from oil residua is not high m these plants. Furthermore, used suspension is subject to exfoliation, which complicates the execution of tne hydro-cracking

Plant for the thermo-cracking of heavy residual petroleum materials (such as mazut, which is a petroleum product remaining after the distillation of benzine and kerosene, also known as black oil) are widely known. These contain a furnace for the heating of o l raw materials, a thermal reactor, a rectification column and a separator, which separates benzine fractions from benzine steams (i.e. the vapour phase) Mazut is supplied to and heated in the furnace and then transferred into the thermal reactor where it is subject to thermal cracking. The resulting products are then introduced into the feeding zone of the rectification column, where separation into benzine and diesel fractions (the selecting stage is executed m the upper part of the rectification column) and cracking of residua are carried out. Benzine steams are cooled down in heat exchangers and are transferred into the separator, where a separation of rich (fatty) gases (such as, for example, natural gases containing significant amounts of liquefiable hydrocarbons) from the benzine fractions takes place. Further details are disclosed in "Album with technological schemes of oil and gas processing" edited by B .1.Bondarenko, 1983, Publishing House "Chimiya", Moscow, p.25. It is important to note that the thermo-cracking plant discussed above generate light oil products which do not exceed lp-12% of the raw materials. It is desirable to provide means for the thermo- cracking of petroleum materials which allows the increased extraction of light oil products, for example by additional processing of thermo-cracking products. According to a first aspect of the present invention, there is provided a plant for the thermo-cracking of oil raw materials which contains a furnace for their heating and a thermal reactor (the point of entry to the reactor is connected with the point of exit of the furnace for the heating of oil raw materials) , rectification column and separator which separates benzine fractions from benzine steams. The plant also contains a device for the additional isolation of distilled fractions from the products of thermal cracking (the entry port of the device is connected with the exit port of the thermal reactor, and the exit port of the device is connected with the feeding zone of the rectification column) , and a mixer (the exit port of which is connected to the entry port of the furnace for heating of oil raw materials) , oil raw materials being given into one entry port of the mixer and a solid organomineral bearer m powder form being introduced through another entry port . The bearer ensures the additional isolation of distilled fractions from oil raw material and interacts with the latter. According to a second aspect of the present invention, there is provided a method of refining petroleum materials, comprising the steps of thermo- cracking the petroleum materials so as to generate thermo-cracking products and then separating the said products into predetermined fractions, characterised m that prior to the thermo-cracking step, the petroleum materials are mixed with an organomineral bearer.

According to a third aspect of the present invention, there is provided an apparatus for refining petroleum materials comprising a thermal reactor and fractionmg means, wherein, m use, petroleum materials undergo thermo-cracking m the thermal reactor sc as to generate thermo-cracking products which are separated into predetermined fractions m the fractioning means, characterised in that the apparatus further comprises a mixer m which the petroleum materials are mixed with an organomineral bearer prior to being passed into the thermal reactor when the apparatus is in use.

According to a fourth aspect of the present invention, there is provided a mixer for use in a petroleum-refining apparatus, the mixer being adapted, m use, to mix petroleum materials with an organomineral bearer and to pass this mixture to a thermal reactor. The organomineral bearer serves to increase the efficiency of the isolation of distilled fractions from the petroleum materials. Preferably, the quantity of organommeral bearer used m the mixture does not exceed 15% of the quantity of petroleum materials. Advantageously, the organomineral bearer comprises a powder or granular material derived from coal. Particularly suitable materials include sapropelite or sapropelic coal (sapropilyt) , shale, rabdopissite (rabdopissyt) , liptobiolite and/or sapromyxite (sapromixit) . After the petroleum materials have been mixed with the organomineral bearer, they may be passed to a furnace for heating before being introduced into the thermal reactor for thermo-cracking The products of thermo-cracking may be passed to a separating means m which they are separated into a gaseous phase including rich (fatty) gases and a liquid phase including kerosene and diesel fractions The gaseous phase may then be passed to a further separating means in which benzine fractions and rich (fatty) gases are separated, and the liquid phase may then be passed, preferably by way of a valve or throttle, to a rectification column m which kerosene fractions, diesel fractions and cracking residua are separated.

For a better understanding of the present invention, and to show how it may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, m which.

FIGURE 1 shows m schematic form a plant for refining petroleum materials m accordance with the present invention; and

FIGURE 2 shows a functional scheme of the plant of Figure 1.

As shown in Figures 1 and 2 , a plant for the thermo-cracking and/or refining of petroleum materials (oil raw materials) comprises a heating furnace 1, an exit port of which is connected with an entry port of a thermal reactor 3 via conduit 2 The plant also contains a rectification column 4 which separates the mixture of thermo-cracking products An exit port 5 of the rectification column 4 is used to take out cracking residua, exit port 6 to take out kerosene fractions, and exit port 7 to take out diesel fractions.

The plant also contains a separator 8 which separates benzine fractions from the mixture of thermo-cracking products. An exit port 9 of the separator 8 is used to take out benzine fractions, and exit port 10 to take out rich (fatty) gases

The plant further contains a device 11 for the additional isolation of distilled fractions from the products of thermal cracking An entry port of the device 11 is connected by conduit 12 with the exit port of the thermal reactor 3. One exit port of the device 11 is connected with a feeding zone of the rectif cation column 5 by conduit 13, and another exit port is connected to the separator 8 by conduit 14 A mixer 15 is mounted m front of the furnace 1.

An exit port of the mixer 15 is connected by conduit 16 with an entry port of the furnace 2. Petroleum materials are supplied into one entry port 17 of the mixer 15, and a solid powder-type organommeral bearer (such as sapropelite, shale, rabdopissite, liptobiolite and/or sapromyxite) is supplied into another entry port 18 of the mixer 15.

The device 11 for the additional isolation of distilled fractions from the products of thermal cracking contains, as shown in Figure 2, a separator 19 (the entry-port of which corresponds to the entry port of the device 11) and is connected by conduit 12 with the thermal reactor 3 One exit port the upper part of the separator 19 is the exit port of the device 11 shown Figure 1. This exit port is connected by conduit 14 with the separator 8 which separates benzine fractions from the vapour phase Another exit port 20 the lower part of the separator 19 is connected with a throttle 21, an exit port of the latter being connected with a feeding zone of the rectification column 4 by conduit 22. In use, petroleum materials, such as mazut or tar, are passed through conduit 17 mto the mixer 15. Other heavy petroleum materials, such as crude oil (especially heavy bituminous oil) , half-tar, heavy gasoils of catalytic and hydro-cracking can also be used.

A solid powder-type organommeral bearer (for example, sapropelite powder) is introduced to the entry port 18 of mixer 15 Other natural materials and/or compositions, such as shale, rabdopissite, liptobiolite or sapromyxite can also be used. These bearers, when mixed with petroleum materials the mixer 15, provide physical and chemical conditions for the additional isolation of distilled fractions from petroleum materials which enrich the gaseous and liquid fractions taken from the petroleum materials. For this purpose the mixture of petroleum materials and the organommeral bearer is passed through conduit 16 mto the furnace 1 for heating, and then passed through conduits 12 and 13 mto the thermal reactor 3

Decomposition of the petroleum materials with the formation of a mixture of thermo-cracking products is carried out the thermal reactor 3 The mixture is passed through conduit 12 into the separator 19 of the device 11 for additional isolation of distilled fractions .

If a high pressure is maintained m separator 19, the gaseous phase which contains rich (fatty) gases and benzine fractions is separated from the liquid phase which contains kerosene and diesel fractions, cracking-residua and a solid phase.

The gaseous phase is passed through conduit 14 from the separator 19 into the separator 8, where rich (fatty) gases (which are taken from the exit port 10 of the separator 8 from benzine fractions, which m their turn are taken from the exit port 9 of the separator 8) are separated.

The liquid phase is passed from the separator 19 by the throttle 21 and is passed through conduit 22 into the feeding zone of the rectification column 4, where it is separated by rectification into kerosene and diesel fractions and crackmg-residua, which may be used as oil bitumen The device 11 allows additional benzine and diesel fractions to be isolated from the mixture of cracking products, thereby enabling the increased production of light o l products of up to 40%, depending on the original quantity of petroleum materials used.

The invention can be used to produce, among other products, benzine, kerosene and diesel oil with the simultaneous production of mazut and o l bitumens for roads and building purposes.

In the table below, there is shown a comparison of the existing "socking-visbreaking" method of petroleum refinement with the results which may be achieved by the method of the present invention:

Prior art Method of the method present invention

(sockmg- (using crumbled up visbreaking) shale as the bearer)

Products :

End of gas: 2.1% gas: 4 6% weight, boiling - weight, benzine fraction.

165°C benzine 8.8% fraction : 4.4%

165 - 350°C diesel diesel fraction: 55% fraction - 12 6%

350 - 420°C vacuum vacuum distillate - distillate - 11,5%

16.3%

Product of vacuum vacuum residue : heavy residue : 18 5% mixed with residue over 64.6% on de- unlimited part of

420°C oxidation shale, after de- oxidation - prepared road bitumen (asphalt concrete) with high adgasmg characteristics

Deasphaltis- no data Full de-asphalt sa- ation, de- tion and full de- metallisa- metallisation of tion benzine fraction, diesel fraction and vacuum gas oil Desulphatis- no data Full de-asphaltisa- ation tion and full de- metallisation of benzine fraction, diesel fraction and vacuum gas oil

Pressure of 2.5 atm 0.5 - 2.0 atm the process

Temperature 430°C 415°C of the process

Claims

CLAIMS :

1. A method of refining petroleum materials, comprising the steps of thermo-cracking the petroleum materials so as to generate thermo-cracking products and then separating the said products into predetermined fractions, characterised in that prior to the thermo-cracking step, the petroleum materials are mixed with an organommeral bearer.

2. A method according to claim 1, wherein the organomineral bearer is m the form of a powder or granular material.

3. A method according to claim 2, wherein the organom eral. bearer is derived from coal .

4. A method according to claims 1, 2 or 3 , wherein the organomineral bearer is comprises at least one member selected from the group consisting of: sapropelite, sapropelic coal, shale, rabdopissite, liptobiolite and sapromyxite.

5. A method according to claims 1, 2 or 3 , wherein the organomineral bearer is derived from at least one member selected from the group consisting of: sapropelite, sapropelic coal, shale, rabdopissite, liptobiolite and sapromyxite.

6. A method according to any of the preceding claims, wherein the quantity of organomineral bearer mixed with the petroleum materials does not exceed 15% of the quantity of petroleum materials .

7. A method according to any of the preceding claims, in which the thermo-cracking products are passed to a separator m which a gaseous phase including rich (fatty) gases is separated from a liquid phase including kerosene and diesel fractions.

8. An apparatus for refining petroleum materials, comprising a thermal reactor and fractioning means, wherein, in use, petroleum materials undergo thermo-cracking m the thermal reactor so as to generate thermo-cracking products which are separated into predetermined fractions the fractioning means, characterised m that the apparatus further comprises a mixer which the petroleum materials are mixed with an organomineral bearer prior to being passed mto the thermal reactor when the apparatus is in use .

9. A apparatus as claimed in claim 8, further comprising a separator mto which, in use, the thermo- cracking products are separated mto a gaseous phase including rich (fatty) gases and a liquid phase mcludmg kerosene and diesel fractions.

10. A mixer for use in a petroleum-refining apparatus, the mixer being adapted, m use, to mix petroleum materials with an organom eral bearer and to pass this mixture to a thermal reactor.