CU23154A3

Process for conversion of heavy hydrocarbons into liquids

Abstract

The present invention relates in general to a process related to the conversion of hydrocarbons with impurities and / or light hydrocarbon charges that can be separated into fractions of conventional products.

CU23154A3, drawing sheet 1 — Sheet 1 of 2

Term

No projected expiry on record.

9 claims: 4 independent, 5 dependent

1
A process for the conversion of hydrocarbon containing high-density heavy load to a less viscous, light, oxygenated liquid such as gasoline, comprising the following steps:1. Un proceso para la conversión hidrocarbón que contienen carga pesada de alta densidad a un líquido ligero oxigenado menos viscoso como gasolina, aceite comprendiendo los siguientes pasos: a) precalentamiento de residuos pesados de hidrocarbón que comprenden residuos de alta viscosidad, residuos atmosféricos (Rat) o residuos bajo vacío ( RsV) a una temperatura de 4 0 0°C a 460°C. a) preheating of heavy hydrocarbon residues comprising high viscosity residues, atmospheric residues (Rat) or residues under vacuum (RsV) at a temperature of 4 0 0 ° C to 460 ° C. b) Precalentar separadamente el flujo a una temperatura de 600°C a 800°C. b) Preheat the flow separately to a temperature of 600 ° C to 800 ° C. c) Pulverizar dichos residuos pesados de hidrocarbón precalentado dentro de un inyector mientras también, c) Spray said heavy pre-heated hydrocarbon waste into an injector while also, d) alimentar dicho flujo precalentado a dicho inyector a un radio de 0.7 de flujo al carbón. d) feeding said preheated flow to said injector within 0.7 radius of flow to carbon. e) alimentar dicho hidrocarbón calentado e inyectar el flujo directamente desde el inyector en un reactor vacío no catalítico a una temperatura de 430°C a 480°C y a una presión de 2,000 a 3,000Kpa. e) feeding said heated hydrocarbon and injecting the flow directly from the injector into a non-catalytic empty reactor at a temperature of 430 ° C to 480 ° C and a pressure of 2,000 to 3,000Kpa. f) Decrease the pressure in a radius of 100 to 100% and, f) Disminuir la presión en un radio de 100 a lOOOKpa y, g) Proporcionando dicha carga de molécula oxigenada ligera de hidrocarbón presión al reactor directamente a un extractor. g) Providing said load of light oxygenated hydrocarbon pressure molecule to the reactor directly to an extractor.
4
El proceso según reivindicación No 1 donde dicha carga pesada de hidrocarbón comprende H2O. Four. The process according to claim No. 1 wherein said heavy hydrocarbon load comprises H2OR.
6
The process as characterized because they comprise impurities aluminum, sediments sedic. 6. El proceso según caracterizado porque comprenden impurezas aluminio, sedimentos sálica. claim No. 1 said heavy residues of nickel, sodium, sulphide, vanadium and reivindicación No 1 dichos residuos pesados de níquel, sodio, de sulfuro, vanadio y
9
13.41 CRUDEFEED, 13.41 CRUDEFEED, RECYCLE 14 RECYCLE 14 EXTRACTIVE EXTRACTIVE DISTILLATION DISTILLATION EMULSION EMULSION BREAKER BREAKER CUT6 CUT5 CUT4 CUT3 CUT2 CUT1 CUT6 CUT5 CUT4 CUT3 CUT2 CUT1 FIG. 1 l FIG.1 l r \ r\ 5' 5'

Independent claims4

992 paragraphs in 80 sections, as filed

(57) Summary:

The present invention generally relates to a process related to the conversion of hydrocarbons with impurities and / or light hydrocarbon charges that can be separated into fractions of conventional products 4. ·: <·

FIELD OF THE INVENTION

The general with more hydrocarbons that can be convincing in the present invention is related to the conversion of hydrocarbons and, in particular, to the conversion of impurities into light hydrocarbons separated into product fractions.

It is well known that all refining processes leave heavy residues that are poorly meltable or solid, which have few users and sell little. It is also known that oil wells often contain deposits containing crude oil that are characterized by a high content of metals such as nickel and vanadium, sediments and sludge, sulfur and salt, to mention only the main impurities, which are poisons for any type of catalyst In addition, regardless of what has been done, it is impossible to completely avoid the deposits of these components in everything that comes into contact with these crudes. In this way, it is understood that yes-. a catalyst is used, its entire surface and pores will be covered quickly and thevThe catalyst will be completely depleted: therefore it will only take up space in the reactor and still at risk of plugging it if grains accumulate in the catalyst by means of cement consisting of sediments, nickel, vanadium, asphalts, produced coal, etc.

Processes such as the FCC are known, which aims to adjust carbon deposits by burning them in a regenerator, but requires a complex circulation of the catalyst between the reactor and the regenerator. In addition, the circulation of this catalyst generates delicate erosion problems, both through the actual wear of the material itself, which is sometimes drilled, as well as the wear of the catalyst that once used produces dangerous powders for any person that no filter has the ability to stop, no matter how big or advanced it is. In addition to all the restrictions that are found and the commitments that are made, this type of unit can only treat vacuum distillates (DsV), that is, by removing the waste (RsV) in which the waste is emptied from the feed load they concentrate metals, sediments, etc. In addition, the regenerator that calcines the coke that forms imposes a minimum temperature of the order of 700 ° C so that combustion can occur. The catalyst leaving the regenerator is sent to the reactor at this excessive temperature, which results in an abundant production of gaseous products, as well as very aromatic heavy products that lose a significant amount of hydrogen during the first contact with the catalyst that was too hot. . On the other hand, it is impossible to change the distribution spectrum of liquid conversion products, which are also accompanied by a significant amount of gas Ci, C2 and LPG C3, C4.

The FCC only rearranges the distribution of carbon and hydrogen in the molecules: it takes hydrogen in the molecules of high molecular weight (high boiling temperature) to generate light molecules, but hydrocarbons C4, C3, C2 and in particular, Ci (CH4) take a large portion of hydrogen. There is even a discharge of pure hydrogen. As a consequence, the heavy fractions known as HCO are poor in hydrogen and cannot be recycled for a new conversion. Therefore, the conservation of a good hydrogen / carbon ratio during conversion is vital.

The objective of hydrofractioning is precisely to increase the H / C ratio by adding hydrogen to the feed load in an efficient manner. This hydrogen-consuming process requires the use of a hydrogen production unit that uses a lot of energy and as a starting point material containing gaseous hydrocarbons is used (usually with a discharge of C02 yes CnH (2n+2)) · In addition, hydrogen becomes reactive only at pressures greater than 100 bar; This imposes a construction with a very large thickness. The combination of the presence of hydrogen at temperatures of the order of 450 ° C to 150 bar presents considerable problems of realization and technology, in particular with regard to the nature of the special steel alloys that are suitable for this type of applications. On the other hand, the conversion products saturated with hydrogen have high paraffin content and, therefore, give low octane gasolines. Therefore, it is necessary to use a catalytic reformer that removes hydrogen in order to increase the octane rating. In these operations it seems paradoxical to begin by adding hydrogen with great difficulty to the products and then having it removed. Thus, it is easy to understand why it is important to avoid useless operations when they are related to hydrogen content.

Some research efforts were carried out to generate active hydrogen, designated as Η., In order to incorporate it into low hydrogen content feedstocks. The generation of H. requires a large consumption of energy that returns at the time to the final reaction and explodes the hydrocarbon molecules in

<td>question,</td><td>possibly</td><td>with</td><td>carbon release</td><td>In</td>

<td colspan="2">consequence instead</td><td>from</td><td>incorporate hydrogen to</td><td>the</td>

<td>load of</td><td>feeding,</td><td>he</td><td colspan="2">generate unsaturated gases</td>

<td>(for the</td><td>general between</td><td> 20</td><td>and 4 0% of the load</td><td>from</td>

feed) discarding total hydrogen.

A research work was carried out that considers the use of superheated hydrogen between 1100 and 1200 ° C at 40 bar, with disintegration times of 60 seconds for hydrocarbons tsar oil residues and heavy oils, for example, those of B.SCHÜTZE and H.HOFMAN reported in Erdól und Khole-Erdgas-Petrochemie vereinigt mit BrennstoffChemie 1983, 36 No.10, 457-461. The results obtained always include high proportions of gas (12 to 27%) and a large amount of coke. From the thermodynamic point of view, these two approaches are inefficient, as confirmed by all the practical results obtained (excessive production of gas and coke).

It is well known that the molecules that constitute the residue can be thermally stirred under vacuum with a VISCOSITY REDUCER (known as a visbreaker) in order to break the viscosity. This generates a small additional production of feed load, which is usually converted with the FCC process. Then we have a viscosity reducer residue that is usually known as an instant viscosity reducer residue (RVR), which can only be used as a heavy industrial fuel if light products such as diesel or LCO (FCC diesel) are added in order of achieving a normal viscosity.

These examples illustrate the complexity of refining operations with complicated treatments and retreatment. The physical state of the material (liquid, solid or gaseous) should receive a lot of attention under normal conditions of temperature close to 20 ° C and pressures close to 1 atmosphere.

COKERS (COKERS) that treat the waste to release liquids while rejecting solid coal are also known, which will have the same applications as coal (also the same difficulties).

There is also knowledge of the attempts that have been carried out with the FLEXICOKER, which currently consist of gasifying the coke that is produced. Gasification requires an installation as large as that required for coking. This saturates the refinery with a lousy combustible gas that must be exported or used for purposes other than those that are strictly required for refining operations (that is, to produce electrical energy).

It is also known that attempts to convert the RsV known as the HYCON PROCESS would consume approximately 2.3% of the hydrogen. He

41% converted must be processed through the FCC, with all the consequences already mentioned in relation to it, in particular with respect to the direct escape of H2 and the loss of hydrogen contained in gases such as CH4 and C2H6.

These two processes are too complex and in the end too difficult to implement in an efficient refining plant.

FW and UOP indicated on October 27, 1997, that they had implemented a catalytic process called AQUACONVERSION PROCESS for the catalyst in collaboration with UNION CARBIDE. In practice, the specific general problems of the catalysts remained intact. ELF ANTAR also demanded the preparation of an Aquazol product that contained between 10 and 20% water, stable only from 15 days to one month.

SUMMARY OF THE INVENTION

One or more of the problems noted above can be solved by the modalities of the present invention.

With respect to Figure 1, one embodiment comprises a process for the conversion to liquids (gasoline, diesel, fuels) of hydrocarbons that are solid or have a high boiling temperature, containing metals, sulfur and sediments, with the help of water or oxygenated gas superheated properly between 600 and 800 ° C. The process comprises preheating a feed load 5 in a heater 8 at a temperature below the temperature selected for a reactor 0. This feed load is injected by injectors 4 into the empty reactor 10 (ie, without catalyst). The feed charge is treated with a jet of superheated steam or gas from a superheater 2 to activate the feed charge. The products activated in the feed load are allowed to stabilize in the reactor at the selected temperature and at the selected pressure and then passed through a series of extractors 13 to separate light and heavy hydrocarbons and demetalize the feed load. Useful products that appear in the form of water / hydrocarbon emulsions are usually demulsified in demulsifier 16 to form water containing different impurities. The light phase that contains the final hydrocarbons.

BRIEF DESCRIPTION OF THE DRAWINGS

Other objects and advantages of the invention will become apparent upon reading the following detailed description and by referring to the accompanying drawings, in which:

Figure 1 is an illustration of the process diagram of a unit according to an embodiment of our process for steam conversion of products containing hydrocarbons.

Figure 2 is an illustration of an extractor / separator used in one mode.

Figure 3 is an illustration of a reactor employed in one embodiment.

Figure 4 is an illustration of the process diagram of a unit according to one modality of our process for steam conversion of products containing hydrocarbons, in a non-arid country.

Figure 5 is an illustration of the same diagram implemented in a desert area poor in aquatic resources.

Figure 6 is an illustration of the same diagram implemented in order to convert excess gases from a drilling well or from a refinery into liquids.

<td>Figure 7</td><td>is a</td><td>illustration of a</td><td>plant</td>

<td colspan="3">industrial pilot to convert distillates and</td><td>oils</td>

<td colspan="3">heavy in light distillates, where the</td><td>plant</td>

<td>pilot works at a</td><td colspan="3">total supply speed of</td>

<td>5 kg / h or 2 kg / h of</td><td>residue</td><td colspan="2">at atmospheric pressure or</td>

<td>1.5 kg / h of waste a</td><td>empty.</td><td></td><td></td>

<td>The figure</td><td>8 is</td><td>an illustration</td><td>of a</td>

<td>process diagram</td><td>in other</td><td>modality.</td><td></td>

<td>The figure</td><td>9 is</td><td>an illustration</td><td>of a</td>

<td>process diagram</td><td>in other</td><td>modality.</td><td></td>

Figure 10 is an illustration of an industrial pilot plant in another embodiment.

While the invention is susceptible to various modifications and alternative forms, specific embodiments of the masses are shown in the drawings as an example and will be described herein in detail. However, it should be understood that the drawings and the detailed description thereof are not intended to limit the invention to the particular form set forth, but rather, the intention is to cover all modifications, equivalents and alternatives that remain within of the spirit and scope of the present invention as defined by the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED MODES

Several modalities can be characterized in the different characteristics described below, which can be considered together or separately, this list is provided for information purposes, without being exclusive.

(1) Feeding charges are taken as they appear. In the refinery, our process, which will be referred to as CPJ, can accept either crude oil, atmospheric residue (Rat), vacuum residue (RsV) or heavy distillates.

(2) The process never uses a vacuum process that requires large distillation columns that must also withstand the crushing force of atmospheric pressure.

(3) The feed feed introduced is treated with gases or vapors that act as energy vectors.

* If the process is carried out in a refinery, the preferred steam is water vapor.

* If the process is carried out in a desert or arid area, the preferred gases are N2 + CO2 (that is, taken directly from the gases that leave the furnaces).

* Any combination is possible and has been tested. For example:

- in a refinery that has a hydrogen unit, CO can be used2 discarded by a decarbonation unit;

- a mixture of C0 gas can be used2 + H20 (steam) ;

- a mixture of CO can be used2 + xH2 from the Benffield hydrogen production unit prior to decarbonization, a mixture that provides some advantages in the octane rating of the gasolines produced;

- CO mixtures are appropriate2+ xH2 or CO2+ H2+ H2OR.

The most favorable gases or vapors will contain oxygen and / or hydrogen. These components can be combined or mixed, for example:

X-OH, H2OC, CO2, CO2 + H2, CO + H2O <=> CO2 + H2O, CO + 2H2 <=> -CH2- + H2O or even CO2+ H2 from a Bensfiel unit after the conversion change and before the decarbonation unit in a hydrogen production unit. The n2 Pure is acceptable but not very convenient. It can be selected only accompanied by CO2 that preferably originates in combustion gases.

The direct introduction of O2 Requires special injection precautions. For example, it is possible to inject 2CH4+ O2 -> 2CO + 4H2 + Heat with a pre-injector. (In this case, 0 is not required2 pure. The air (O2 + 4N2) It's enough) .

It is possible to consider this alternative to absorb excess light gases (Ci, C2) in primary chemical energy, the material is partially recovered in a special extractor between 200 and 220 ° C, 20 to 30 bar. This shows another aspect of the great flexibility of the CPJ process. Sulfur does not hinder the process and may even be convenient (except when considering corrosion resistance).

(4) The gases are heated, preheated or prepared in classic ovens.

(5) The new feed load and any of the recycled components are properly heated in a conventional oven or through the pipes of the classic heat exchangers.

(6) The feed charge is fed to the reactor by an injector that generates intimate contact between the preheated feed charge and a gas stream, properly preheated (or superheated in the case of pure steam) during expansion. This injector also has the purpose of generating a free jet of material and gas, which does not come into contact with any material barrier, in order to facilitate the initiation of the reactions. The energy supply determined by the temperature, the flow rate and the expansion speed in the injector, releases a usable amount of mechanical energy that provides the necessary and barely sufficient energy supply to initiate the reactions without removing the peripheral hydrogen from the molecules and without generating an energy such that the molecule can break into many small fragments, as can happen in FCC.

(7) The disintegration reactor is an empty vessel. Catalyst is not used. This reactor allows the reactions initiated by the injector to develop, to achieve equilibrium. The absence of material in the reactor has the advantage that there is no stagnation point for the reagents, which cause too long a decay time and, consequently, give rise to carbon deposits.

(8) The products, steam and gas then expand at a pressure close to atmospheric pressure, when leaving the fractionation reactor. If 2CH is entered4 + O2 or 2 CO + 4H2 in order to recover a carbon of gaseous origin, the disintegration reactor outlet is cooled between 200 and 220 ° C without reducing the pressure, which makes it possible, as a secondary capacity, to establish the equilibrium of the reactions for the addition of CO2 + H2, which give -CH2-, which binds to the material contained in the emulsion H20 / hydrocarbon used in this case.

The CO mix2 + H2 You can also provide a functional block: -C: Ó

Η '' H which is added to unsaturated bonds to give aldehydes, the simplest example is:

H2C: CH2 + CO + H2 ==> 3HC-CH2-C: O

All these reactions contribute to generate liquids and eliminate or block the generation of gas. The products then expand to atmospheric pressure.

(9) In all cases, they are cooled adequately and devices are separated by a series of specials that provide separation of heavy liquid phases from light gas phases at temperatures properly selected according to the physical characteristics of the products.

(10) Heavy products that do not meet the selected standard are recycled with the new feed load.

(11) Light products that meet the selected standard are extracted. In the presence of steam, they are in the form of very stable water / hydrocarbon emulsions, which can break easily.

(12) In all these processes the fragmentation of heavy molecules happens in a controlled manner. Approximately, it is possible to say that the weight of the molecules is divided by 2 in each run in the injector, with a conversion speed of (1l / e = 0.63). Therefore, this process hardly changes the H / C ratio of the products.

(13) The control of the breakdown of molecules makes it possible to avoid the production of gases by never implementing the energy required for their formation and by selecting conditions for the equilibrium of the molecules in the reactor that do not favor the appearance of those gases.

(14) The useful products can be either hydrated and constituted by the emulsion mentioned in 11, or anhydrous and obtained by means of dehydration with extraction.

None of the aforementioned processes is critical in itself and can be compensated by the others to the detriment of reduced production, impairment of conversion speeds, high energy consumption or large production of solid coal.

According to another series of characteristics of one modality, much attention is paid to the restrictions of the material during treatment.

Although this only means an attempt of gross and imperfect explanation, it is possible to imagine that heat, in its thermal aspect, is stored in the form of mechanical vibrations of the molecules. The vibrations generate mechanical restrictions that due to the inertia related to the mass, are higher in the middle part of the molecule, if the vibrations are moderate. These restrictions then cause a break in the middle part of the molecule. The more the molecule heats up (or more generally, the more energy of any kind it must store), the more it will vibrate. In this regard, it will vibrate according to harmonic patterns with several antindes and vibration depressions such as those observed in a piano string or a flag string that flies under strong winds or also in a long waving rod. Since vibration depressions form the basis of maximum restrictions, the molecule will fragment at these points, one third, one quarter, etc. of its length This explains that if a molecule is overheated (if too much energy is transmitted to it), it will break into very small fragments, which generate CH4 and even coal

With this brief explanation, it is also possible to understand that as the length of the molecule increases (the one with more mass and the heaviest), it will have more vibration elements and the central elements that gather the side elements that are agitated will be subject to bigger restrictions to keep those side elements together. When the restrictions are too large, the molecules break.

This example makes it possible to explain that as the molecule gets heavier, it is less able to withstand heat without fractionation. To illustrate the concept, the CH4 cannot withstand temperatures greater than 700 ° C and heavy waste cannot withstand temperatures greater than 430 ° C. If the selection of the devices is considered, these restrictions are also reflected by the maximum acceptable thermal fluxes expressed in Kcal / hour / square meter or also by the acceptable temperature differences between the hot wall and the cold fluid. Critical values depend on the products considered to be characterized by their physical state (liquid, solid, vapor) under operating conditions. In this way, it is very important to obtain a practical knowledge of what can happen with the products that are treated.

The following example will explain the risks with simple molecules as common as C10H8, consisting of two aromatic nuclei

Note that each cycle of 6 aromatic carbons is designated as A, A for the cycle, is used .. for double bonds in each core.

Á: Á indicates that two carbons Á are attached.

If Á: Á gets too hot, it loses hydrogen and becomes more reactive, thus producing:

A: A

4A: Á

A: A

C10H8 + C10H8 => C20H12 + 2H2

If = 80'CT eb = 218 ° C d = 0.963 π = 1.60 (Iiq) lf = 278 ° C

T eb = 350 (sublimated) d = 1.36 α = 1.88

We go from a liquid / solid to a very hard solid. (From what has already been said, it is necessary to observe that the molecules with 20 carbon atoms constitute the products that are generally known as diesel or light domestic fuel). Thus, another characteristic of a modality is to prevent such situations from occurring.

It was observed that the newly fragmented chains were naturally reactive at right angles with respect to the fragment and that the polar molecule HÓH (water) was easily attached to these fragments, such as ÓCÓ (carbon dioxide).

Another feature of one modality is to introduce oxygen into the conversion process.

In order to better understand the special nature and high inventive activity of this process, an attempt will be made to provide an explanation of what should be done and what should be avoided. To the

<td>effect,</td><td>again</td><td colspan="2">an example will be selected</td>

<td>family</td><td>c20.</td><td></td><td></td>

<td>C20H14Ó2</td><td>Tf = 300 ° C</td><td>T eb = Sublime</td><td>Ho, Á: Á-Á: Á, 6H</td>

<td>C20H14</td><td>Tf = 188 ° C</td><td>T eb = 452 Sublima</td><td>A: Á-Á: A</td>

Substituting hydrogen with a lateral OH is not good (the melting temperature ranges from 188 ° C to 300 ° C). If O eliminates a CC bond, a favorable effect is obtained (the melting temperature ranges from 188 ° C to

81 ° C).

It will now be considered the case in which the C molecule20Hi4 is weakened by an appropriate temperature that causes its vibration and we send a molecule of HÓH (H20) to the central link:

<td>T eb = 452 sublime</td><td>Teb = 295 ° C</td><td>Teb = 2I8 ° C</td>

The presence of water is very favorable in the products that are formed. If we consider the C molecule20H14 quite compact, joined by 2 H20, we have:

C20H12 + 2H2O - »

H H

Á _ A

A - A or

Η * Ή

Tf = 278 ° CT eb = 350 Sub d = 1.36 π = 1.88

C10H78H

Á: Á-8H + C10H78H

Tf = 123 ° CT eb = 295 ° C d = 1.0ln = 1.62 + Á: Á-8H

Tf = 123 ° C Teb = 295 ° C d = 1.01 π = 1.62

This example clearly shows all the advantages that can be obtained from steam.

Through thermodynamic considerations, it is also possible to determine that the free solid carbon that can be formed is oxidized between 600 and 700 ° C, according to the following reactions:

CO2 + C »-»

H2O + CS ->

2C0 AS = 42.14 AH = 41.23 Tcq = 705 ° C

CO + H2 AS = 3 3.04 AH + 31.40 Teq = 677andC where AS is the entropic variation, AH the enthalpy and Teq the equilibrium temperature at a pressure of 1 bar.

There is another possible explanation for the favorable effect of H20 and C02, which when applied to the injector correctly, tend to remove solid carbon that can be inadvertently formed.

As can be seen in the examples, the measurement of physical characteristics and in particular, the index of refraction, makes it possible to follow the direction of the evolution of the conversion products and direct this conversion.

It will be easier to understand the objective of a modality that consists in the operation under conditions that prevent the loss of hydrogen, since this loss of hydrogen generates unsaturated components that give rise to nuclei of low fusion capacity.

If we consider the straight chain described below, when it is heated to high temperature, it begins to lose hydrogen according to the following scheme:

Η ,, Η Η ,, Η Η ,, Η

H, CCC

Ή H ”H ΗΉ

Then the unsaturated chain bends and closes:

AS AH

Teq: 941 ° K (668 ° C) -20.65 -19.44

H., H HC-CJI! \ 4í Tf Teb S AHf °

HC CH +6.5 81 71.18 -29.4

H '\ /

HC-CH

Η 'Η'

The melting temperature is between -95 ° C and + 6 ° C with only 6 carbons. Thus we discovered that, on the one hand, there were never approximations at temperatures of the order of 650 ° C and on the other, the energy required in this case should not be supplied; the thermodynamic values indicated above provide orders of magnitude. In addition, it is observed that when the dehydrogenation process begins, the reactions are canceled because the cyclization releases energy.

Below is what could happen if there were a more violent energy supply:

<td colspan="2">H H C i \</td><td>H H C</td><td>H H CH</td><td>Tf</td><td>Teb 95</td><td>S ° 69</td><td>THERE* 92.83</td><td> -39.96</td>

HC

<td>The close:</td><td colspan="2">highly chain</td><td colspan="2">dehydrogenated</td><td>he</td>

<td>C</td><td>C</td><td>CH Tf</td><td>Teb</td><td>S ° THERE *</td><td></td>

H, C 'Η

H? EXTRACTION from a STRAIGHT CHAIN:

Generate approximately & SH2 = -30.19 and requires approximately: & H / H2=+32.18

Closing a cycle releases energy (and reduces the & S by approximately 2 0.5).

After the initial conditioning of the appropriate products thanks to our injection, a modality makes it possible to initiate and activate the reactions while complying with the preceding rules and orders of magnitude that should not be exceeded.

Another advantage will be presented in the presence of H20, which behaves similarly to a cyclisation reaction blocker.

Heavy crudes contain very few simple and straight molecules; they contain numerous complex polyaromatic molecules that are more or less linked together, as can be seen in the following molecule that condenses easily and forms 2 to 3 nuclei, according to the following scheme:

Á-C: C-Á -> H2 + A \ Á / Á 9.1 / 8.7 956 ° K 1I9.Q / + 46.8 32.21 / 0.0 96.7 / 55.5 683 ° C

H,, HC = C / \ TfTeb S ° AHf ° dn

HC CH 124 307 119.0 +46.8 0.970 1.6264 \\ U <------------------------- CC

H. / C = C

Η, / Ή CC // w

HC CU \ /

C = C Η 'Ή

Ή Η,, Η

C- C

-> H2 + Η, / \ Ji

CC cc // \\ // \

HC CC C, H \ / \ /

C = C CC ff Ή Η 'Ή

TfTeb S ° ΑΗΡ dn 101340 96.7 55.5 1,181.67

As already mentioned, it is observed that the creation of a third central nucleus significantly increases the density of this molecule.

With the steam of H20 It is possible to operate in stages in order to fragment this 14-carbon molecule and even show how to resorb a light 3-carbon molecule that would otherwise produce gases.

Ito Stage: Weakening of the central unsaturated bond:

AS / AH

Á> -CH: CH- <Á + H20 -> Á> -CHóH-CH2- <A -29.96 / -12.50

Tf-124 Tcb-307 * C Tf-68 Teb-170/15

2to Stage: Central fractionation of the molecule:

Á> -CH5H-CH2- <A 4 A> -CH0 + H3C- <A + 26.27 / + 39.31

Tf ~ -26Teb “¡78 Tf« -94Tcb-H0

3 to Stage: Fusion and waste of HoO (sure it is presented)

Á> -CHÓ + C3H8 4 Á> -C2-CH: CH2 + H2O -2.04 / 44.36

Tf «-33 Teb-190»

4to Stage: Cycling of unsaturated branches (natural)

WMNWH a »

Tf = 124 Teb-307 ^ C

FPL

A> -C2-CH.CH2 A Á: C¡c6Csat -15.44 / -19.90

TF - 43 Téb = l95

Á> -CH: CH- <Á + C3H8 -> Á: C¡6sat + Á> -CH3 -21.17 / -7.45

TP-43 Tcb-195 Tf - 94 Teb = l 10

Light diesel Fuel possible to observe that the intermediate steps of the reaction are carried out with moderate energy levels and that the total reaction develops as if the water supplied at the beginning is recovered at the end (similar to the action of a catalyst).

It is also appropriate to note, since it is one of our interests and a characteristic of our process, that the initial melting temperature of 127 ° C, after the first stage decreases to 26 ° C, then to -33 ° C, in the fourth stage the temperature was -43 ° C and finally in the fifth stage, products with a melting temperature of -94 ° C were obtained.

Thus, there is a continuous decrease in this melting temperature during the intermediate stages of the total reaction. The experiment showed that there was a very low production of gas and coal and that it was possible to completely convert products of the type of so-called vacuum residues or asphalts into liquid hydrocarbons.

The case of straight chains (with 14 unsaturated carbons for this example) will now be considered:

Without h2Or we have:

Cél4 C7H16 -C2Ó7B12 36.04 / 19.57

Apparently the fractionation in presence

<td>of H20 he</td><td>carries</td><td>finished</td><td>according</td><td>The following scheme:</td>

<td>What does it give in</td><td>total</td><td>. Cell4</td><td> -></td><td>C7H16 + C2Ó7HI2 36.04 / 19.57</td>

satisfy

It is noted that in these operations, it was first necessary: to open a CC link that required approximately 40 to 60 Kcal (activation); and finally a supply of 20 Kcal / fraction (specific net energy).

Remember that the extraction of an H2 requires approximately & H / H2= + 32Kcal and that if this is carried out bad results are obtained.

Therefore, it was necessary to find a set of devices that made possible the different ones as well as the specifications stated above, which was achieved through the proper preheating of the feed load, followed by the activation that originated from the expansion in the injector, in this case the products subject to conversion could have, in terms of equivalent temperature, a very short stay in an interval in which they are unstable, since the fragmentation consumes the energy that causes the reactants to return to the stable condition and a desired interval in the reactor where they can achieve thermodynamic equilibrium (a cook would say: let them simmer).

These reactions and their mechanisms are provided here only as an attempt to explain why we get unexpected conversion results with our process.

The in-depth analysis of the results of our tests taught us to define how a given feeding load could be treated and also what were the problems related to the structure of the complex matter constituted by these heavy products; Everything that has been provided before constitutes only a guideline for the necessary adjustments.

It is clear that all these experiments were used in order to constitute a database of physical and thermodynamic properties, of which an extract is provided below for information purposes, for families of 1 to 10 carbons per molecule.

Physical and thermodynamic properties Family (0

Name Tf ° C TebtoCSc ΑΗΡ dn TccK Pe Vc zc

CH4 -186 -165.0 44.49-17.89 0.415 .gas .. 190.7 45.8 99 0.290 CO -199 -191.0 47.30-26.41.0.793 .gas .. 133.0 34.5 93 0.294 H2CÓ -92 -21.0 52.26-28.00 0.815 .gas .. 410.0 67.0112 0.223 H3C6H-97.1 64.7 57.00-48.05 0.812 1.3288 513.2 78.5118 0.220 HCÚoH +8.3 100.7 59.40-90.50 1.220 1.3714 581.0 71.8 117 0.176

Physical and thermodynamic properties Family (10)

Pj-Mend _______________

Units ° C ° C cal / m Kcal / m <-¿ 20 ° C-> andK bar ccing / m

Name Tf Teb S ° AHÍ® dn = l, Te Pe Vc PM zc = 0.Slr

----------------------------(neither)..................

C10H8 nl4 80 218 80.5 36.1 0.963.5898 748 40.0413 J28.269 A: Á CI0HI2 «98-36 207 <83.2 4.2> 0.970.5414 <7I7 33.0478> I32 .268 ÁCy6 C10H14 ni 89 .. 200 <84.5-11.7 XJ.934.526 <K7O7 30.6 500> 134 .264 2Á-6H C10H18 d6 -43 195 87.1 -43.6 0.897 .4810 687 25.8 543 138.249 2Cy6 C10H18 d74 -36 174 125.3 9.85 0.766.4265 623 25.8 587 138.297 SC10 C10H20 d66 -66 171 129.2 -293 0.741 .4215 616 25.0 592 140.292 éClO CI0H22 d20 -30 174 130.2 -59.7 0.730 .4102 619 20.8 602 142.246 nClO

C10H20O 18 -5 208 137.7 -78.9 0.830.4287 636 24.4 605 156.278 Aid. C10H216H d57 +7 229 142.1 -96.40.830.4372 667 29.8 619 158 .337 ale. C10H19Ó6H d42 32 270 1423 -143.0.886.4288 717 29.4 644 172 322 Acid

Observe the classification:

Oxygenated / Alkanes / Alkenes / Alkynes / Cycle / Aromatic

The abbreviations are:

Tf: Melting temperature S °: Standard entropy d: Density

Te: Critical temperature

Teb: Boiling temperature AHF °: Standard formation enthalpy n: refractive index Pe: critical pressure

See: Critical volume zc: Compressibility factor

Str: Structure, abbreviated

Aromatic core, Cycle saturated Acetylenic, ethylenic, n normal paraffin OR double bond oxygen, OH functional group OH

These data help to monitor, know or predict the state of matter in the different conditions of its treatment, as well as possible thermodynamic equilibria. These data also allow to predict the chemical irreversibilities that are responsible for the production of coal and the elimination of hydrogen, in particular. In conclusion, a guideline will be described that will greatly help the analysis of these problems, considered with a new approach from a mechanical point of view.

If an isoC is considered4 cycle C6 First, the molecule must be turned to transform it from the free state and naturally deployed to the folded state, which requires energy. If each end of the isoC branch is then removed4, near the core cycle C6, also eliminating the corresponding hydrogen, two new carbon-carbon bonds are established. The molecule thus formed with only 10 carbons is a true cage that has the amazing physical properties indicated below.

C10H16a742 Tf-268 Teb = Sublima

Density »1,070 n = 1.5680

C10H20e686 Tf = -94

Teb = 171

Density = 0.795 n = l.4386

The references given are from: Handbook Chemistry and Physics.

.CH i

CH 9\, H 0 ° CH or Ή or

CH J~ H

H * \ ·

HC

H \ ° cand H " i *: CH

Molecule:

H H

CH

H.7 <Cycle C6> -CC, H H '\

CH

H H

HCH

Represented in the deployed state

HCH * ♦. *

C i \

Η H

C10H20c686 Tf = -94

Teb = l? L

Density- = 0.795 1.4386 *

Η * \ ·

HC

Η \

C Η «β ·;

CH · * / Η • “CH • ο

Η ,, Η CH Η, Ζ <CycIoC6> -CC, H

Η '\

ΗΗ • · Η Η Represented in the • β \ ¡bending state

HCH ° .CH «« O * CH • Φ

CH *. ·

C / \

Η H ° CH

Z \

Η H

C10HI6 a742 Tf = 268 Teb-Sublima Density = 1,070

Molecule:

n = 1.5680

H \

CH »~ a · j •: CH * ·· / H • CH ♦” • ° H • · /

HC- · —.CH * oo • CH • »

HC ° ° β· ° · °° CH ♦; ♦ \ Observe the JAULA structure

CH / \

Η H

H * \ ·

HC: CH

H'NIttMU * ·

Molecule Ref. A742 with:

6 carbon cycles

Note that these cage-like molecules (particularly if they are aromatic) become true nests or sandwiches for metals and organometallic, which will be described below.

CONTROL OF THE APPEARANCE OF GAS. COKE OR WASTE FROM

SOLID COAL

An amazing feature of this process is that it makes it possible to convert asphalts without generating significant amounts of coal or gas. An attempt will be made to explain why this result can be obtained, based on the knowledge acquired while trying to interpret our observations.

With appropriate means (mechanical, thermal,

<td>electric</td><td>or</td><td>chemists,</td><td>etc. )</td>

<td>to transfer</td><td>a</td><td>Energy,</td><td>to</td>

<td>(variation</td><td>from</td><td>enthalpy),</td><td>according</td>

according to the terms that are generally used in thermodynamics. The experience in monitoring the state of the material led us to adopt, on a continuous basis, a variation key for that state that can be summarized as AS, the entropy variation. In fact, when referring to the tables that have already been presented, it is possible to observe the existence of very strong correlations between SXL and the physical parameters of fusion and boiling and more generally, the parameters are characteristic of the change of state or The organization of matter. In order to explain the ideas, an unsaturated molecule containing 14 carbons will be selected.

<td>ENTRY</td><td colspan="2"><---------- OUTPUT - -----></td><td rowspan="2">ACE</td><td rowspan="2">AH</td><td rowspan="2">Teq'c</td>

<td></td><td colspan="2">** L¡quldcr · * '- *** GAS ** »* ·». *, + * »***</td>

<td>CÉ14H28 ==> ——— v ------ Tf = -13 Teb = 251 “d = 0.771 n-1.433 5</td><td>Cé7H14 + Cé7HI4 Tf-I l9Teb = 94 ° d-0.697 n = 1,400</td><td>... 36.06 V— Liquid</td><td> 19.18</td><td> —</td><td> 269°</td>

<td></td><td>Tf — 81 ° Teb = 93.8 ° Liquid</td><td>—V— Gas</td><td> -----</td><td></td><td> 720°</td>

This table shows that as the level of energy applied increases, the number of fragmented molecules increases, as well as the amount of fragments generated, which means that the greater the disorder generated (the AS increases), the greater the amount of CH4 generated and greater the amount of hydrogen removed. In addition, the AH / AS ratio gives the Tee temperature at which the reagents reach a natural equilibrium under the pressure of 1 bar. If only liquids are desired, the entire process develops as if it were limited to 20 kcal / molecule, as already indicated somewhere. (As already mentioned, this also explains why an FCC with its catalyst regenerated at more than 700 ° C will eliminate hydrogen and CH4. In fact, no catalyst can change this state. This can only favor the intermediate states and their speed, allowing the reagents to achieve thermodynamic equilibrium depending on the reactor temperature).

Another characteristic of one modality is that it makes it possible to control the rate of conversion into liquid without generating excess amounts of light gases such as methane or ethane. An attempt will be made to provide an explanation that was generated during the different tests that were carried out, in relation to chemical irreversibilities (which apparently are not mentioned very frequently).

One of the characteristics of our process is basically the fact that it fragments the molecules in two and begins again in order to preserve the domain of the process.

It can be thought that in order to accelerate the process, the solution is simply to apply more energy, which would actually generate a large number of light molecules, as indicated in the preceding table, including a large amount of gas, assuming that always it was possible to polymerize it in order to return to the liquids. However, it would be impossible to perform this operation in an appropriate manner due to chemical irreversibilities (which no catalyst will be able to overcome).

To illustrate, suppose that the generation of liquids from methane, ethane, etc. is considered. In this case, the intention would be to carry out reactions such as:

THESE REACTIONS ARE IRREVERSIBLE since there is NO NEGATIVE Teq. It would never be possible to carry out follow-up reactions in a reversible way:

(A) (B) (C)

Teb

Normal state

Cnl =? -> H2 - Cn2 =? => H2 - Cn4 -? »> ΙΙΤΚ Í84 ° K 272 ° K

GAS GAS GAS

H2 + Cn8 i

298 ° K

399andK

LIQUID (1) ch4

It is necessary to accept the in this process, summed up inevitable formation in the total reaction:

from

C ') C4H10 + C4H10-> C7H16 + CH4 AS = -1.53 AH = -2.48 Teq = 1620andK

O: 2 Cn4 ==> Cn7 and Cnl Kcq (600andC) = 1.93 (This reaction is possible because Teq is positive) (2) if thermodynamic reversibility is violated with energy: according to reaction C: hydrogen must be removed

C) C4H10 + C4H10 ==> C8HI8 + H2 AS = -0.54 ΑΗ = + 10.48 Teq — 194OO3K (This reaction is irreversible because Teq is negative)

C Even the transition through gas synthesis, which begins with the following reaction:

GH4 + 1/2 02 - »> CO + 2H2 AS = + 42.7 AH = -8.52, (The reaction can be explosive) is irreversible and will lead to low efficiency

<td>global in</td><td>liquefaction with</td><td>methanol</td><td>o Fischer-</td>

<td>Tropsch</td><td></td><td></td><td></td>

<td>C</td><td>can be carried</td><td>finished</td><td>only with</td>

<td>reactions</td><td>secondary crue</td><td>produce</td><td>C2H2, in</td>

<td>particular.</td><td></td><td></td><td></td>

<td colspan="3">PRACTICAL CONCLUSION: in Drimer</td><td>term is</td>

You must avoid gas generation. That is precisely what our process does.

CARBON DEPOSITS

Our experience in controlling the appearance of coke, led us to assume that there were two main sources: massive deposits through polyaromatic nuclei and pulverulent coal through gases.

It is very easy to visualize that if the material is polymerized in several adjacent polyaromatic cores, since the carbons are directly linked to each other and comprise few hydrogen bonds or none as already observed, the melting temperature increases with the number of cores and reduction of the H / C ratio (Ci0H8 Tf = 80 ° C, C20H12 Tf = 278 ° C, etc.); we are getting closer to a solid coal.

This can be examined for information purposes, with our method for the study of chemical irreversibilities.

<td></td><td>TO</td><td>in order to exemplify, it</td><td>will take something</td><td>from</td>

<td>benzene</td><td>and</td><td>It will try to divide it.</td><td>It is noted</td><td>a</td>

<td>fusion</td><td>from</td><td>the molecules, accompanied</td><td>once again</td><td>from</td>

an elimination of H2, according to the following reaction:

[IJ Á A = -> A> - <A + H2 -J.I7 3.46

The reaction is irreversible since Teq cannot be negative. The following secondary reaction should be added:

(2] Á ==> 6Cgas + 3H2 +259.4 +1010

In order to obtain AS = 0.0 it is necessary to take 1.17 / 259 from reaction (2), or:

[3] 0.0045 A -> 0.0045 6Cgas - 0.013H2 +1.17 + 4.55

Which give rise to the global reaction:

(1J to + Á *

[3] 0.0045 Á ===> A> - <Á + H2 -1.17 +3.46 => 0.0045_6Cgas »0.013H2 +1.17 +4.55

2.0045 A => Á> - <Á + 1.01.H2 + 0.004 (6Cgas) 0.00 + 8.01 and the return of 6Cgas in Csol = Coke

0.0046Cgas ·> 0.004.Coque -1.16 -4.55

2.0045 A «=> A> - <A -1.OI.H2-0.004.Coque -1.16 + 3.46

The experimental data of 750 ° C with 50% conversion in 40 s confirm the projected values found before and thus reinforce our belief regarding what should be avoided.

The notion of irreversibility provides a good projection of coke production considered the most difficult side reaction.

The second form of appearance of pulverulent deposits of carbon 10 is the acetylenic route, of which some data are indicated below for informational purposes, for 4CH4.

(21) 4CH4 => 2C2H6 + 2H2

-----------------------...---------------------- Teq ° C

AS = -3.S4 aH = + 31.OS -.% '= K (22) 4CH4 = -> (23J4CH4 =>

(24) 4CH4 - =>

(25) 4CH4 =>

Note: TfdeC: sublimates to ............................................ ...................... 3379 ° C

THERMAL DECOMPOSITION OF CH,:

Reaction (24) indicates that above 565 ° C, CH4 It decomposes with slow kinetics, (approximately 1 hour at 800 ° C), as required to enter the gaseous state summarized in the reaction (25).

Therefore, the relationship that causes the appearance of pulverulent coal seems to be:

CH4 => C2H4 => C2H2 * “=> Powder Csol

C6H6 - «> Mass Csol Polymerization

In any case and in practice:

(1) In all cases, the formation of saturated light gases should be avoided.

(2) The appearance of free hydrogen is a basic sign.

(3) The formation of unsaturated light gases and hydrogen constitutes an alarm sign.

(4) The generation of acetylene is a serious alarm sign.

(5) The aromatization monitoring by means of the refractive index is very useful in order to determine if the process is being carried out correctly.

EMULSIONS

One of the characteristics of our process is that it uses oxygenated intermediates, which when converted to steam naturally produce stable water / hydrocarbon emulsions.

It has long been known that the combustion of difficult fuels is greatly improved with the addition of 5 to 10% water. This addition, during the first stages of combustion, provides the fractionation of heavy molecules, while preventing their polymerization to polyaromatics, which would produce nodules of soot or pulverized coal.

On August 5, 1997, ELF presented to the press the product called Aquazol, which contains between 10 and 20% water, indicating that the main problem was to guarantee the stability of the mixture. At present, this stability can only be guaranteed for 15 days to 1 month, despite resorting to a special mixing procedure and in particular thanks to special additives.

The interest expressed directly by the intermediate emulsions produced by our process is understandable, since these emulsions can become the main objective of these applications.

We have emulsions that are already 8 years old and still remain stable, this shows that the difficulties encountered by ELF were controlled.

These advantages can be explained through the internal molecular bonds that in the anhydrous state would be unsaturated and remain partially bound to the water. It would also be possible to propose all the oxygenated intermediaries that we previously presented, for the control of fractionation operations between 440 and 600x, which have a favorable balance between 200 and 220 ° C, the operating temperature of our extractor.

In any case:

(1) Stable water / hydrocarbon emulsions are obtained whose water content can be determined in a simple way by setting the proportion H in the conversions2O / (X), in the gases used in the conversion, X is preferably C02 - Y: and it can be any gas N2, H2, etc. This means that dry gas (taken at less than 200 ° C at 1 bar) from combustion is appropriate.

(2) The products formed (gasoline, especially kerosene) contain binding water.

(3) Limited for reasons of simplicity and ease of implementation to use only water vapor, with our process it is possible to obtain, depending on the selected conditions, oxygenated and hydrated products; or mainly anhydrous products.

Actually, when water vapor is used, useful recipes appear in the form of emulsions that produce:

a light emulsion called clear: d = 0.89 to 0.92 a heavier mayonnaise emulsion: d = 0.93 to 0.96 which are clearly separated from an excess of process water d = l.0 (if this excess exists, which is not the case in the example below).

Mayonnaise (in which the 8-year-old samples have not changed) is easily broken by different mechanical means, for example, by passing it through a series of cross-linked pieces of fabric (an operation known as extrusion). Dry sand immediately breaks the emulsion; there are additional mechanical possibilities, for example, sliding balls in the emulsion, etc.

evaluation given below is an example of the characteristics of these emulsions, with P-annotations. Weight in g

V: Volume in cm

Dp / V: Density = Weight / Volume gives: Density (read by densitometer) dn: Deviation read by refractometer indicating refractive index n.

MAYONNAISE

Total

Ptara

Total mayonnaise Water extracted

1700.01163.8 698.31 = 444.13 =

Net Weight 1001.69

719.67

Dp / v

0.9656 da dn

3.5 1.50625

Clara HC extracted

Direct clear HC 731.36282.02

311.412= 419.95

13.0 1.50099

0.8916 0.902 13.3 1.50310

Total HC: 701.97

Total WATER / HC ratio: 719.67 / 701 97 = 1.02

<td>With the</td><td>terms</td><td>from</td><td>operation</td>

<td>selected to be</td><td>will describe in</td><td>other</td><td>part, the</td>

<td>useful products no</td><td>contain nothing</td><td>from</td><td>free water</td>

(aqueous phase d = 1.0).

The distillation of the direct and extruded clear phase gave the following results:

DISTILLATION 1 Summary WITHOUT SAND and without agitation

Recipes Volumes Weight

<td>Ptot fraction</td><td>Tweet</td><td>Pp</td><td colspan="2">Vr V. water</td><td>V. HC</td><td>HC. dry</td><td>Dp / v</td><td>dn</td><td>N</td>

<td>Regurgitated:</td><td> 93.11</td><td> 75.02</td><td> 18.09 20,2</td><td> 3.0</td><td> 17.2</td><td> 15.09</td><td> 0.877</td><td> 12.3</td><td> 1.49360</td>

93.76 7.9 85.86

DISTILLATION 2 Summary WITH SAND and without agitation

Flask: 202.78

Flask + Support: 214.21

Flask + Support + 309.95g load feeding

Power load: 95.74g

Sand 300 μ: 610.34 g to cover liquids (total weight compromised)

Recipes Volumes Weight

<td colspan="2">Ptot fraction</td><td>Pair</td><td>Pe</td><td>Vt</td><td colspan="2">V. water V. HC</td><td colspan="2">HC.secoDp / V</td><td>dn</td><td colspan="2">N</td>

<td></td><td></td><td>Total·-</td><td colspan="2"> ------>82.63</td><td></td><td> 2.2</td><td></td><td> 80.43</td><td></td><td></td><td></td>

Residue: 95.74 - 82.63-13.11

0.901 19.0

In significant regurgitation the first case, accompanied by water released in the abundant form a violent amount, shows that there is water of union with moderate chemical forces. During the distillation of the liquids submerged under the sand, there is a weaker depolymerization and a reduced release of water. In any case, this shows that: (1) the 262 g of mayonnaise hydrocarbons have the capacity to bind with 719 g of extruded water or 2.5 times its weight in water; and (2) clear and extruded hydrocarbons, in this case, already contain 3 to 9% of H2Or united. Therefore, it can be seen that our process can naturally provide oxygenated compounds or stable water / hydrocarbon emulsions.

We check that the water in the exit process did not have any alcohol or any other carbon compound, by processing its distillation, which is summarized below.

PROCESS WATER ANALYSIS BY DISTILLATION WITH 15

DISHES

Feed load 100 cc Traffic starts 99 ° C distills between 100 ° C and 101 ° C

97.81 g as clear water that contains some milky flocculant turbidity

Waste 225.93

- 224.89 = 1.04 Dark coffee

Not combustible

With small black nodules

It is also observed that water extracts different elements from the treated feed load.

This water has an acidic pH that indicates that it has absorbed SH2 or some other acidic element of the feed load. All this constitutes a set of favorable elements that our process provides, which applies steam whose extractive activity is increased with the injection temperature and the successive purification operations in the extraction zone.

OXYGENATION CONTROL OR PRODUCT HYDRATION

Other features of this system may include: controlling the hydration of emulsions or preventing it; and control the oxygenation of products or prevent it. We will indicate how these results can be obtained with our device. It should be noted that thanks to our extractor you can select the standard of useful products and recycle those that are outside. Therefore, we will consider the case of the standard (selected objective) of oxygenated gasoline or diesel and hydrated emulsion without free water.

It is clear that it is necessary to avoid sending too much process water to treat the feed load, although a sufficient quantity must be sent. It was found that a good water / feed load ratio (treated atmospheric residue) was of the order of 1 by weight. (Which was what was found in the evaluation of the results presented before). If the objective is to move towards oxygenated compounds, it is clear that if said compounds are not oxygenated they are considered outside, especially if the objective is to produce automotive gasoline or diesel fuel fractions.

Therefore, we have the idea, which is characteristic of one modality, of making a first conversion of atmospheric waste into distillates

PI-360 with the extractor-contactor heater at approximately 200 ° C and then reprocess these refined (200-) in their current state, through the installation.

In fact, during this recycling, equivalents of heavy but atmospheric distillates were converted into lighter diesel or gasoline type products. The steam provided for these operations is also sufficiently reactive to generate the chemical additions shown in the distillation of the products (direct distillation or sand distillation).

The inverse standard will now be considered, for example, to satisfy the refining specification of an exit site, which requires non-hydrated standard products (called dry). Therefore, the present process will avoid recycling the anhydrous products formed (200-), which would tend to hydrate and form oxygenated compounds. In this case, the operation is carried out by recycling only the extracts (200+) with the new feed load consisting of waste or any other feed load to be converted (200 is a value that can vary depending on the recycling as desired)

In order to understand this, a vacuum residue will be taken that will not produce any atmospheric distillate during the first generation. It should be noted that a very rough scheme is the following relationship:

RsV ===> DsV

DsV ===> Rat

The following is a total conversion test RsV (precursor) that gives DsV 8th generation), followed by Rat (second generation). Within this type of recycling and the selected conditions, the conversion products were not hydrated, as indicated by their distillation carried out after the separation of water / hydrocarbons from the emulsions. Therefore, distillation does not produce water (unlike the previous case, where an attempt was made to establish the same). This indicates that the problem is under control.

CONVERSION WITH RECYCLING EXTINCTION:

<td colspan="2" rowspan="2">Final conversion during flow Useful global reference (3) - (4)</td><td colspan="4">Total exhaustion of resources</td>

<td rowspan="2">Summary:% by weight</td><td rowspan="2">% in weigh</td><td rowspan="2">dn</td><td rowspan="2">n</td>

<td>Atm fraction.</td><td>Dp / v weight</td>

<td>Residue</td><td> = 4.70</td><td> 9.63</td><td> 100%</td><td></td><td></td>

Total-> 48.76 (Losses: 1.24) ★ Λ ***** ·· *** · **** · *********************** ******************** * ★ * <* ♦ ***** »******* <

The minutes of distillation of the 5 conversion products contained in the clear and extruded phase (see table I) show that there is no water release that can be measured. The release of white vapors or crackling between 80 ° C, 130 ° C,

150 ° C, 250 ° C, 290 ° C, clearly demonstrate the key points of water release that were easily found in the treatment that was intended to achieve hydration and oxygenated products; but here they are quantitatively negligible. Its total can be assessed by excess, by establishing that at most they are equal to the losses observed or 3.8%. (It should also be noted that the transfer of samples from the recipe cylinder to the appropriate cylinder, in order to take a more accurate measurement of volume and weight to obtain density

Dp / v, should be performed with losses of 0.3 g for very light liquids, approximately 0.75 g for the atmospheric fraction 300+ and 2.15 g for atmospheric waste, due to flow problems associated with increased viscosity and surface tension . This gives an idea of the effect of the union of the products on the walls, which increases with the density and refractive index).

Finally, for information purposes, when considering these tests, it should be noted that the main characteristics of the vacuum residue were: density 1.01, refractive index 1,594, solid state.

REACTORS-EXTRACTORS and DISTILLATION DEVICES OF

PRODUCTS

Our reports on the distillation of conversion products mention the regurgitation of products, the emergence of released water, crackling, etc. which if they were presented in a classic distillation unit would cause the distillation plates and their packaging to burst. According to a new characteristic of one modality, a device was conceived that not only had the ability to perform this distillation work without the aforementioned problems, but also functioned as a true reactor-extractor of the mixer-decanter type.

With reference to Figure 2, the principle is as follows: preheated or properly cooled products are shipped in a double-deck cylinder containing steam saturation water, in which it sets the cover temperature simply by setting the chamber pressure; steam is produced when heat is released; steam is consumed when heat is absorbed; The presence of saturation water provides significant heat transfers with the inner vessel of the reactor-extractor.

In this double vertical cover that is almost isothermal with the temperature defined by the saturation water temperature, a tube or a series of vertical tubes was installed, which emerges at half the height of the double cover. Therefore, the upper section is empty. Act as a select a ba jao

baffle-decanter at the rate of rise of light gas products, which allows heavy liquid products in the form of fog or dew to descend to the bottom. For this purpose, the rate of descent of heavy or liquid products only needs to be greater than the rate of rise of lighter products. In addition, this space acts as a relief for any sudden burst of water or violent release that may not be adequately controlled. Since it is empty (there is no packing in this area) there is no material risk. Heavy or liquid products remain at the bottom of the roof, between the roof and the vertical tubes. When all the space between the cover and the tubes is filled, the heavy products are spilled into the vertical tubes and collected at their bottom outlet, therefore, this extraction is automatic and natural.

The incoming products, liquids or gases, are injected at the bottom of the double deck in the heavy or liquid phase at a very moderate speed. Therefore, they are dispersed in the heavy phase, mixed therein under local conditions of temperature and pressure; thus, the mass transfer happens through the contact surfaces and is regulated by differences in concentration in relation to the equilibrium of the stationary phase and the dispersed phase that enters. These balances are defined both by the physical separation of the phases in reciprocal presence, and by the licit chemical equilibria under existing local conditions. The incoming products enrich the heavy phase and the transferred heavy compounds are drained. These reappear with the light compounds that can be formed, in the light phase that fills the upper part of the roof, where they decant and separate from the liquid portions or from the heavy mist that falls to the bottom. This device is especially favorable because it is capable of carrying out the equivalent of a distillation while operating as a liquid-liquid extraction for oils or asphalts or as a chemical reactor. In fact, aromatic products such as furfural have well-known extraction potentials to extract aromatic products in the preparation of lubricants. In any case, it allows us to separate the effluents that leave the reactor at our convenience, in a safe and risk-free manner.

When several of these devices are distributed in series, a series of separations are made that perfectly define the nature of the products extracted by the tubes, as the refined products are sent to the next device for the definition of another extract.

It should be noted that with the operating conditions used, the separation of atmospheric distillates from the atmospheric residue is carried out at 200 ° C at 1 bar, while in the classical distillation column it would be carried out at 360 ° C.

The configuration provided is for information purposes only and should not be considered limiting, as it can be done with numerous variations. For example, for the 2 Kg / h pilot test, since the heat losses were very high, the electric heating of the extractors was adopted, where the temperature was regulated by the intensity of the heater for a given speed and a load of feed given. The same system allowed to carry out the process extractions and the associated atmospheric distillations of the finished products in order to treat quantities of up to 50 kg.

This technological device can satisfy several purposes, in particular chemical conversions. We will explain its application to the conversion of a gaseous mixture to liquids.

It has been seen that our emulsions were stable and that the clear products could be oxygenated or hydrated and that they were also related to the temperature (and the operating pressure) of the reactor-extractor key that separates the useful products from the recycling standard. This unexpected effect leads to an explanation that could help define the size of the equipment and set operating conditions while minimizing practical experimentation.

THE ACTION OF STEAM ON DOUBLE LINKS DOES NOT

SATURATED

Consider a chain that contains a carbon-carbon double bond symbolized as CeC. In the presence of steam, the following reaction may occur:

<td></td><td>-CcC- - H2O</td><td>= -> Alcohol</td><td colspan="2">AS AH</td><td>Teq</td>

<td></td><td>Examples:</td><td></td><td>ACE</td><td>AH</td><td>Teq</td>

<td>CI8H36</td><td>+ H2O ==></td><td>Alcohol 08</td><td>-32.15 / -15.03 194 ° C</td><td></td><td></td>

It is important to underline that under these conditions, it is possible to convert ethylene into alcohol, which explains why gas production can be limited. It is also observed that heavy alcohols naturally form under the operating conditions of the reactor-extractor, which operates specifically at the temperature that is favorable to achieve this type of conversion.

This makes it easy to understand why our emulsions are stable and why our process can produce oxygenated compounds. In fact, if emulsion stability is considered, heavy alcohols behave as a third-party solvent between water and hydrocarbons, since alcohols are miscible with water through their oH function and with hydrocarbons through The basic hydrocarbon chain. When considering the fact that the binding forces involved in the emulsion are weak because their origin is more physical than chemical, it is easy to understand that the emulsion can be easily broken by simple mechanical means that we have discovered.

METALS WITH INORGANIC DEPOSITS / EMULSIONS

COMPLEXES

The vacuum residue that was converted contained the impurities summarized in the following table, which also presents its distribution.

FRACTIONATION OF RsV. Kuwait for EXTRACTION C3-C5

<td>POSITION</td><td>• DAO C3</td><td>* ExC4 * ExC5</td><td>• Asp C5 · -RsV</td><td> *</td>

<td>Density 20 ° C</td><td> •0.896 * 1.000</td><td> •1.047 * 1.067</td><td> * 1.010 *</td><td></td>

<td>Refrac. n. 20 ° C</td><td> * 1.519 · 1.592</td><td> • 1.624 * 1.641</td><td> • 1.59415 ·</td><td></td>

<td>TfC</td><td> *50 · 60</td><td> • 100</td><td>• 146 * + 4landC ♦</td><td></td>

<td>Sediments</td><td> •</td><td> *</td><td> * ·</td><td>* 0.096% Pds *</td>

<td>Sulfur% RsV</td><td> • 0.53 · 1.62</td><td> •1.62 * 1.23</td><td> * 5.0 ♦</td><td></td>

<td>Nickel ppmRsV</td><td> • 0.2 * 10.2</td><td> • 14.4 · 17.2</td><td> • 42 ·</td><td></td>

<td>Vanadium ppmRsV</td><td> • 1.0 * 32.3</td><td> •47.2 * 55.5</td><td> * 136 ·</td><td></td>

<td>NaCl% by weight</td><td> * _</td><td> « _</td><td> *0.0003 · 0.0107 ·</td><td> 0.0110 *</td>

<td>The</td><td colspan="2">combustion of</td><td>fuels</td><td>heavy gives</td>

ashes that usually have the following relative composition (without SO4) :

SiO2: 32,

Fe2O3: 25, Na: l6,

Go: 14

Ni: 6, Al: 6,

Thus, the feed charges to be converted contain vanadium, nickel, sodium, iron, aluminum, sulfur, etc., which must at least be taken into account in the conversion and preferably should be eliminated.

It is observed that one of the first negative effects of metals is the generation of 20 solid compounds due to the formation of eutectic between 520x and 600 ° C, for example, SiO2+ NaO2, V2OR5+ Na2O, V2OR5+ NiO2i the most meltable acts as a fusion agent of the least fuse that follows.

It seems that the free compounds such as those indicated below are evacuated by the effluents from the reactor in the solid state.

Compounds

SiO2

SiS2

Tf Teb D n

1700 2230 2.32 1.4840 >1090 2.020

In any case, if the operation is carried out with a reactor at a temperature that is too high, deposits are observed that contain the eutectic that are formed, which will be deposited on the reactor walls, therefore, this limitation does not have nothing to do with the chemistry of conversion; This only relates to the nature of the impurities of the feed load. In fact, it is not the presence of these impurities that constitutes an impediment, it is their accumulation in the reactor operation, any or the extractor in which it would tend to plug it, blocking possible operation until they were removed. Thus, there is a new characteristic of one modality, which limits the operating temperature of the reactor depending on the impurity content, in the case of the vacuum residue, below 500orC.

The SiO2 it is extracted slightly by steam of H2Or dry (see table below).

<td colspan="2">Solubility SIO2 / H2O</td><td></td><td>YES2 / H2O ppm</td>

<td>Ρ H2O liq., Sat.</td><td></td><td>H2O steam, sat</td><td>Dry H2O steam</td>

<td>Temp. atm.</td><td>Concent</td><td>YES2 / H2O ppm to Tsat.</td><td>400 ° C 500 ° C 600 ° C</td>

Oxides like V205 yellowish red or the V2OR3 Of a darker color, they have a significant water solubility that contributes to their extraction in our extractor. Vanadium-sodium compounds such as NaVO4 or NaVO3 they are also soluble in water, as well as NiSO4 yellow or NiCl3 green and FeCl2. By extracting the different oxides, water counteracts the formation of the eutectic mentioned above and also reduces the speed of their deposits in the reactor, the presence of water and the oxygenation of hydrocarbons in the reactor contributes to the formation of compounds such as: C6H5SW3> 2Fe, 3H2O (coffee) O

C6HsSW3> 2Ni, 6H2O o c2H3Óó> 2Ni (green), which also has water solubility, partial but significant.

This explains the color of the water collected after the separation of water / hydrocarbons, as well as the appearance of flocs with a density greater than that of water. After avoiding deposits in the reactor due to metals, it was observed that they were concentrated in polyaromatic hydrocarbons

I read the heavy ones that tended to form cages, as clearly demonstrated by vacuum residue analysis.

The following table describes some Si and Fe compounds that mainly appear in DsV and RsV.

<td>Compounds</td><td>P.M</td><td>Tf</td><td>Teb</td><td></td><td>d</td><td>Π</td>

<td colspan="5">This property is exploited to extract them in</td>

<td>1 point 13.4</td><td>of the</td><td>process that</td><td>It constitutes</td><td>other</td>

<td>feature of</td><td>a</td><td>modality.</td><td></td><td></td>

<td>As well</td><td>he</td><td>has observed</td><td>that even</td><td>the</td>

<td colspan="2">lightweight components</td><td>that could</td><td colspan="2">to have formed</td>

they remained primarily bound to carbon-free silica to form liquids with a boiling temperature PI-150 ° C, as shown in the

<td>following</td><td colspan="4">table:</td>

<td>Compounds</td><td>Tf</td><td>Teb</td><td>D</td><td>n</td>

LEAD TETRAETYL FOR GASOLINE (for purposes of illustration, the remarkable physical properties of lead tetraethyl are indicated).

<td>These of iron:</td><td>are</td><td>Some</td><td>compounds</td><td>organometallic</td>

<td>Compounds</td><td>P.M</td><td>TfO</td><td>Teb</td><td>N Color</td>

<td>C4H6Fe (CO) 3</td><td> 193</td><td> 19</td><td></td><td>Yellow</td>

<td>C6H4SFe (CO) 2</td><td> 220</td><td> 51</td><td>I went up.....</td><td>Light red</td>

<td>C5H9C5H4) FeO5H5</td><td> 254</td><td> 16</td><td> · >. ..·*</td><td>RedLiq.</td>

<td>HbOCH2C5H4> 2Fe</td><td> 302</td><td> 140</td><td> ....</td><td>Reddish brown</td>

<td>C6H5C5H4> 2, Fe</td><td> 338</td><td> 154</td><td> .... «...</td><td>Yellow</td>

<td>Fluorescent green</td><td></td><td></td><td></td><td>Yellow</td>

<td>C6H5> 2, C5H3> 2, Fe</td><td> 490</td><td> 220</td><td> ....</td><td>Red / AmariHo</td>

<td>These</td><td>by</td><td colspan="2">they are usually</td><td>liquids and it</td>

extract according to our process at 100 or 200 ° C.

These explanations are provided for informational purposes only, in order to get an idea of the observed phenomenon.

It was also observed that very polyaromatic molecules that could form cages, which would result in a very high refractive index, had a solvent force capable of extracting unwanted molecules. This explains our technique, which consists of maintaining a strong stationary liquid phase at 13.4 whose activity is increased by temperature; This phase also originates from components of the residue under vacuum.

COMMENTS REGARDING THE FINAL STABILIZATION OF

THE FORMED PRODUCTS

There is always a residue of products to

<td>temperature Useful as:</td><td>low boil</td><td>in</td><td>the</td><td>products</td>

<td>Compounds</td><td>PM Tf Teb</td><td>d</td><td>n</td><td>Colour</td>

<td colspan="2">Alcohols are added that react according to the following</td><td colspan="2">to these scheme:</td><td>compounds</td>

-CeC- + H2O <-► Alcohol AS = -32 AH = -15 Teq200 ° C

Consequently, the final separation cannot be a simple distillation due to changes in the dissolved solid / gas phase ratio or when it follows a dehydration. In fact, what refiners know as water breakthrough, which destroys the packaging of a classic distillation unit, could be presented. In our reference distillations, we observe these effects at the aforementioned temperatures, in the form of violent regurgitation, sudden dehydration, crackling accompanied by the release of white vapors, etc. This is why the extraction device has been adopted to carry out this final stabilization operation with total safety. This device allows to separate all the products or approximately 100 kg, without finding any problem.

DESCRIPTION AND PERFORMANCE OF INJECTION ASSOCIATED WITH

THE REACTOR

It was already indicated previously that the function of the injector was to transfer the maximum usable energy contained in the vapors or gases, to the feed load to be converted on the one hand and on the other generate a close contact between the steam and the feed load, preferably without any material coming into contact with the metal walls.

The results obtained are the following:

The feeding load that is actually a heavy phase in relation to gases or vapors, is divided into pairs of jets atomized by mechanical means, fixed laterally in opposite directions and arranged according to Figure 3, flowing from the top to the bottom and meet on the injector shaft. Through mutual deviation, they flow axially at a moderate speed, without coming into contact with any material.

The purpose of mechanical atomization is to generate small fine droplets, preferably some fog, so that in this way a maximum surface area of the feed load containing the hydrocarbon is developed. The atomization must be supported by approximately 5% of superheated HP vapor that contributes to the nebulization of the feed load (as is well known with respect to the injector heads of heaters and furnace burners).

In this flow, the steam or gas jet is placed during the expansion, its energy is mainly transformed into kinetic energy to the greatest extent possible and at high speed.

By injecting the high speed steam jet into the atomized jet of the feed load, the mechanical cutting force of that jet is obtained, with the transfer of energy that contributes to the activation of the reactions, all these operations are carried out at very high speeds, without making contact with the walls of the material and practically at the temperature desired in the reactor.

The calculation of valves and nozzles is easily performed, according to techniques that are specific for steam turbines or hydraulic turbines, taking into account the multi-phase state of the feed load.

DISPOSITION OF THE INJECTORS IN THE REACTOR FOR

FACILITATE YOUR MECHANICAL CLEANING

The reactor is empty. Most of the solid carbon formed is eliminated by the effluents that leave the reactor, which constitutes a great advantage of this process. However, a small portion is deposited on the walls and tends to accumulate. Therefore, these carbonaceous deposits of metal oxide compounds contained in the feed charge must be removed at convenient intervals. The presence of non-combustible oxides requires the use of mechanical means such as washing or purification, sandblasting and other means. At this point, it is necessary to open the reactor while avoiding any internal part or protruding edge.

Therefore, the injectors are arranged laterally, opposite each other, towards the external part of the reactor, in pairs, so that the reactor once opened can keep its walls completely free. By removing the top of the reactor and then the bottom part, the reactor ring is exposed, which can be easily cleaned by any mechanical means.

This device is particularly advantageous, especially when compared to the problems presented by reactors adapted with packaging (Visbreaker Soaker) or loaded with catalysts with or without circulation.

INJECTOR AND DISINTEGRATION CAMERA

A critical problem is knowing how to define the conditions for the injection of products in order to facilitate the proper start of useful reactions and define the conditions required to achieve the balance of stable products leaving the disintegration chamber. This practical definition constitutes a unique concept of a modality, it consists mainly of defining the key parameters that regulate that process in a practical way. An example will be described where the residue is treated under vacuum in order to obtain a production of light diesel and kerosene.

First the waste will be considered under vacuum.

Its density and refractive index provides valuable information regarding its structure thanks to the technical know-how of the process. An extraction of asphalts at C3, C4, C5 Specify this structure in terms of the molecules to be treated. Preferably, a global sample will be taken and a thermal stability test (or conversion by thermal fractionation) will be performed that is moderate and easy to carry out.

If RsV is the amount of waste involved and is operated at a temperature T, it is observed that RsV disappears and that other products are formed according to the following relationship:

-t / Ts d (RsV) / dt = RsV e Ts is a unit of time

For example, for the residue for which all conversion results will be given below, we find:

Temperature T ° C Ts seconds:

430 460 490

700 140 40

Experience leads us to think that this reaction speed was related to the imbalance between the composition of the products and the one that would exist if things were allowed to develop without any time constraint.

If RsVeq is the residue that would be in equilibrium with all the products generated, it would be obtained:

d {RsV) / dt Ts (RsVeq-RsV) To

That is a specific unit of time for each product.

In addition, the conditions of the mechanical breakdown of the molecules that have already been explained in detail, are related to the interatomic cohesive forces of the component molecules and to the fact that the matter in question exceeds the maximum acceptable deformation.

This result is an effort E equal to: E = force x deformation. It is believed that there is a general relationship between Ts and temperature T, with constant universal R of the perfect gases, in the form of:

-T (R / E)

Ts = To e

Thus, we have a simple means to evaluate the E value, which we assign to the vacuum vacuum, in fact, according to our hypothesis and considering two pairs of temperature measurements Ts (l), TI; Ts (2), T2, you get:

R (TI - T2)

E - ---------------- with ·: £ Logaritmo neper £ (Ts (l) / Ts (2))

In our case, with TI = 430 ° C, Ts (l) = 700s,

T2 = 490 ° C, Ts (2) = 40s, we find that the value of E is approximately 42 kcal / mol. This means that if you do not have the ability to use this energy, nothing will happen instantly in the reactor (it also means that if a lot of energy is transferred to the molecule, this molecule will disintegrate).

The preheating of the feed load and the reactor temperature will now be checked.

If an effort of 42 kcal / mol has been provided without converting it to heat, the average RsV molecule breaks into only 2 fragments due to lack of energy. First, it is necessary to prevent the two fragments produced from being reunited immediately. Again, this is the function of the injector, which inserts gaseous molecules during fragmented, the expansion between the formed fragments. This insertion is facilitated by the fact that the H vapor20 or the C0 gas2 they can react chemically with the broken ends of the molecules.

According to one modality, in order to achieve this with almost total certainty, it is necessary to have as many gaseous molecules as there are carbon pairs, to generate this situation. If steam is the only element used, the ratio between water (18 g / mol) and hydrocarbons (CHx 13 14) should ideally be of the order of 18 / (2x13) by weight or approximately 0.7.

Since the RsV molecules are there it is necessary to place them in a stable thermodynamic equilibrium. At this point, a period of time Ts is required, which depends mainly on the temperature. Based on the experimental data Ts, it would be preferable to adopt the highest possible temperature in order to reduce the duration of the operations, but it was found that this cannot be done without incurring risks.

Cl4H28 ~> Cái3H24 + CH4 CH4 - »4Csol + 8H2 The polyaromatic polymerizes massive carbon.

Thanks to the reagents used, mainly steam, these side reactions can be partially blocked but never by

Thus, at 460 ° C we have

565 ° C complete. Thus, the final choice becomes a commitment based primarily on accepted solid coal. In practice, it is negligible at 440 ° C. At 520 ° C, its accumulation in the reactor requires frequent purification for disposal; otherwise, if it is not done, it can become an impediment, possibly filling the reactor completely.

A temperature between 460 ° C and 470 ° C was adopted, which gave good results. It was observed that the pressure had a very favorable effect on the reaction rate. It is very important at first to go from 1 to 20 or 30b, this effect drops later, reaches a maximum of 150b and decreases above 200 bar. For this reason, pressures of 20 or 30 bar were adopted, which allowed dividing approximately 2 times the Ts times that we would have at 1 bar. Therefore, at 470 ° C, we would have approximately 25 seconds to achieve equilibrium in the reactor.

With regard to the control of reactions, our goal is to fragment the molecule into two,

<td>during each</td><td>run.</td><td>This</td><td colspan="2">requires a net worth</td><td>from</td>

<td>20 kcal / mol</td><td>such</td><td>as</td><td>he</td><td>indicated before.</td><td>Yes</td>

<td>we supply</td><td colspan="2">40 kcal / mol</td><td>for</td><td>the activation,</td><td>is</td>

<td colspan="2">enough to start</td><td colspan="2">starting</td><td>of a load</td><td>from</td>

<td>feeding</td><td colspan="2">preheated</td><td>to 470</td><td>° C to obtain</td><td>he</td>

desired result.

In fact, when starting from this temperature that is slightly lower than the desired temperature of the decay chamber, when the activation energy is added, the molecule would have a thermal temperature that is higher than what it would have in its normal state, but it would fragment by absorbing 20 kcal / mol, finally by leaving it at the desired temperature for the remaining operations necessary to reach equilibrium.

Once this is well understood, if the previously defined steam (or gas) flow rate, necessary to effectively close the broken ends, is taken into account, it is possible to deduce the value of the enthalpy of the steam that is sent to the injector.

In order to reach 470 ° C in the disintegration tank, considering the recirculations and the different energy transfer values achieved, it is necessary to consider steam superheat temperatures of the order of 600-650 ° C for the RsV.

Once the energy balance is achieved and recycling is completed, it would be convenient to adopt a vapor pressure of the order of 60b, superheated to 600 ° C. Our injection nozzle then adiabically releases steam from 60 bar to 30 bar at 470 ° C, and has 60 kcal / kg available mechanically as kinetic energy in the steam jet of the order of 700 m / s. Thus, we obtain steam at the desired temperature in the reactor. At this temperature, there is no risk at all of roasting the hydrocarbons, which receive usable energy as kinetic energy, which will cut the hydrocarbons mechanically.

Usually, preheating will be approximately 20 ° C or tank temperature

25 ° C less than the decay or approximately 445-450 ° C. This is particularly favorable for the operation of the waste preheating furnace and prevents any coking problem. In fact, it is known that visbreaker ovens should heat this same type of waste at 460 ° C and that the risk of coking appears above this temperature. With these operating conditions, coking was never found in our oven.

In any case, once the steam flow rate and the operating speed of the unit have been set, the steam overheating and the preheating of the feed load are adjusted to achieve the thermal balance defined by the tank temperature of disintegration In practice, the preheating of the feed load is set at 20 ° C or 25 ° C below the temperature of the reactor outlet, the flow rate of the steam furnace heating fuel is adjusted by the outlet temperature of the reactor.

The example we provided earlier for the vacuum residue can be generalized without taking into account the feeding load. The main key parameter is the reactor temperature, which increases when the products are lighter. For example, with very heavy vacuum distillates, we will have temperatures of the order of 500 ° C, which will increase to 520 ° C for light vacuum distillates or very heavy atmospheric diesel.

EXAMPLES OF APPLICATIONS

Figure 4 represents the process diagram of a unit according to our process for steam conversion of products containing hydrocarbons, in a non-arid country.

Figure 5 represents the same diagram implemented in a desert area poor in aquatic resources.

Figure 6 represents the same diagram implemented in order to convert excess gases from a drilling well or from a refinery into liquids.

Figure 7 represents a pilot plant that operates at a total supply rate of 5 kg / h or 2 kg / h of waste at atmospheric pressure or 1.5 kg / h of waste in vacuum. The pilot plant also converts distillates and heavy oils into light distillates.

STEAM CONVERSION

In this version, see Figure 4, the water is introduced into [0] by means of the pump [1], in a tube furnace [2] heated by a burner [3]; superheated steam is sent to the injector [4].

<td>store</td><td>in</td><td colspan="2">the tank</td><td>[6], which receives</td><td>the recycled</td>

<td>[14] in</td><td>he</td><td>which</td><td colspan="2">mix, pump</td><td>by means of the</td>

pump [17] that sends it to the oven [8] that preheats everything and sends it to the inlet of the injector [4], when operating as described, injects everything into the reactor [10].

Under the control of the pressure measurement [20], the valve [12] discharges the effluents from the reactor when released into the exhaust system [13], which operates at a pressure similar to atmospheric pressure.

The extractor system, which has already been described, comprises a series of extractions {13.1 to 1.5}, which are set from room temperature to 360 ° C.

[13.1] is at the local ambient temperature, [13.2] is set at 100 ° C, [13.3] is used to separate useful products (usually atmospheric distillates) from atmospheric residues that were not completely converted. The output [13.4] can also fulfill this purpose and in all cases interrupt the final separation of [13.3].

The outlet [13.5] extracts the heaviest products that are heavily loaded with polyaromatic and solid carbon precursor metals.

A portion [13.52] is removed to prevent its accumulation in the facility and is used to form heavy fuels as long as they are still acceptable in this fuel, while the remaining portion [13.51] is recycled in [14], in preparation for A new conversion.

Useful products [13.2] and [13.1] appear in the form of fairly stable emulsions. They are usually combined (but can be separated if light products are desired) and sent to the system [15] that breaks the emulsions mechanically. These broken emulsions are sent to a classic decanter that separates hydrocarbons [16.1] from water [16.2] and the heaviest phases (sludge and sediments) [16.3] are extracted.

The hydrocarbon fraction [16.1] is sent to the extractor [18] that separates hydrocarbons that may be oxygenated or hydrated. (A classic distillation would have the risk of dangerous water breakthrough).

The normal outputs are:

[18.1] PI-100 [18.2] 150-200 [18.3] 200-250 [18.4] 250-300 [18.5] 300-350 [18.6] 350+ (atmospheric residue)

The cut-off points can be changed by changing the temperature of the extractors, as already explained somewhere.

Heavy fuels consist of output products [18.6] (atmospheric waste) and extracts [13.52]. Carbonic residues (loaded with metals) [15] are used as fuels to feed preferably the burner [9] of the furnace [8] and the non-condensable gases are sent as primary fuel to the different furnace burners, the rest is taken of heavy fuel. Finally, the small amount of non-condensable gas and small carbon deposits produced by the unit's self-consumption are resorbed in this way, which leaves the maximum amount of liquid products demanded by users.

In principle, this installation presents no risk. All predominant reactions are endothermic, therefore stable. The presence of process water vapor makes it possible to quell any potential fire hazard. The small gas production does not give rise to any significant degassing, in the case of an incident.

The retention (amount of matter retained in the reactors) is relatively modest, which of supply approximately allows quick starts and interruptions of the unit. The unit is automatically stabilized and self-regulating according to the technique adopted, in particular, the extractors that operate through the natural flow of the extracts. All these qualities provide extreme ease of operation and driving (especially when compared to units that can be replaced, such as an FCC with its catalyst circulation problems between the RISER reactor and its air regenerator at a pressure of 3 bar , with its hydrocyclone problems to eliminate catalyst fines, etc.).

ARID AREAS INSTALLATION

If there is no water available, its absence can be easily compensated through the use of hot gases produced from a simple combustion that involves CO2 + H2O + N2.

In this case, the furnace [2] of Figure 4 is replaced with the furnace [68] of Figure 5. This furnace receives the liquid (or gaseous) fuel [61] that is pumped or compressed by means of [60 ], is sent to the burner [64] which also receives compressed air [63] through the compressor [62] and then sent as fuel to the burner [64]. The temperature of the gases produced (fumes) is adjusted to the required value by deviating more or less from the convection zone that cools these gases mixed with the gas that exits the radiation at 900 ° C, if it is thermally charged properly. In fact, the flow rate of the fuel is set according to the desired amount of gas. An oxygen meter sets the oxidizing air necessary to avoid any excess, while the preset temperature [54] of the gases supplied controls the bypass valve [67] that regulates that temperature. In this version, the amount of water applied is reduced compared to the case of Figure 4, which runs completely with steam. The devices [15] and [16] are reduced, but instead it is necessary to provide an air compressor that is more complex and less economical in terms of power consumed than a water furnace supply pump. The rest of the installation remains identical to the previous one. This application is very simple and very safe.

It requires the constant monitoring of combustion in the furnaces (flame detector) to prevent any uncontrolled and untimely combustion in the event that the flame goes out, which could be caused by the fusion of the reactor. (Note that the reactor can be removed from time to time by the controlled combustion of air from carbonaceous deposits, since solid deposits would then be easily removed by hammering or sandblasting).

RESORTION OF LIGHT GASES IN THE REFINERY OR IN A

OIL FIELD OR TO MAXIMIZE THE MAXIMUM

GASOLINE PRODUCTION

This case is illustrated in Figure 6. As we saw earlier, the process moves towards the phases of oxygenation and hydration that are favorable at approximately 200 ° C in the extractor. Instead of injecting H2Or in the unsaturated links of the conversion products, under the same conditions it is possible to graft -CH2- resulting from the high initial reaction temperature:

2CH4 + O2—> 2CO + 4H2 which produces a low temperature at 200 ° C:

CO + 4 H2 «=> 2-CH2- + 2 H2O

Since the nature of the gas is less important at elevated temperatures than the energy it carries, this mixture is appropriate for the projected conversions of heavy products and as already mentioned, its unsaturated chains constitute a good basis for the union of -CH2- which is favorably formed at 200 ° C at a pressure of 20 to 30 bar, in reactors that already contain hydrocarbons, installation of this type is illustrated in Figure 6.

A schematic, the

From a gas generation point of view it is the same as in the case of Figure 5. Only the combustion regulation changes. The oxygen meter is adjusted with a device to measure CO2 which will eventually regulate the oxygen (or air) fed to the burner.

The installation remains identical to the previous ones and the only difference is the reactor output [10]. The effluents that leave the reactor do not expand and are maintained at a pressure of the order of 25 bar. They are cooled by means of a heat exchanger [82] and then go to an extractor [84] that works in the same way as [23] and [24]. [84] is in the optimum temperature and pressure conditions to carry out the useful reactions and will be sized accordingly. By regulating the pressure [74], the valve [85] is operated, which discharges the reactor [84], partially returns to the initial process [13] here at [83] at atmospheric pressure and the outputs [13.3 are available] ], [13.2] and [13.1] that function as previously mentioned in the case of Figure 4.

The partial self-thermal oxidation of gases requires continuous monitoring of this combustion, as well as rapid means of degassing in the event of an incident (hydraulic protection and significant flame, to handle any contingency). Experience in this field leads us to think that this technique will be reserved for large units where all safety measures and precautions can be taken and satisfied.

In the case of gasoline, more advanced gas or fuel oxidation can be adopted in order to obtain C02 + H20 (total oxidation) or C02 + H20 + CO + H2 (partial oxidation), mixtures that are favorable to improve the conversion speed to light products and the octane number of gasoline. In this case, the security requirement of the facilities, once again, is total, with the usual refining techniques.

These three variations illustrate the flexibility of the possible adaptation of our process and the equipment with which it is implemented, depending on the needs that must be met and the restrictions imposed.

EXAMPLES OF RESULTS OBTAINED WITH OUR PLANT

INDUSTRIAL PILOT

The pilot plant of which an illustration is provided in Figure 7 makes it possible to carry out all the operations that have been considered.

For reasons of space and cost, operations [15] and [16] for the separation and extrusion of hydrocarbons from emulsions were not carried out continuously, but as a retreat at the end of a controlled cycle according to the diagram of the process in Figure 8.

In the same way, the stabilization (some type of reactive distillation) that gives the final products, was carried out in our installation as a retreat and in a continuous way according to the diagram of Figure 9. In this case, the reactor (atmospheric pressure) it constitutes only one transfer line between the furnace [8] and the extractor [13], which replaces the total [18] of an installation, completely in line according to Figures 4, 5 and 6.

The pilot plant comprises a distribution tube that allows the loading of H gases2, CO2, N2, air or CH4.

The pilot plant is illustrated in Figure 10 in a simpler and closer way to industrial applications. This converts the feed loads only with steam. [2] is the simple tube furnace for water. [1] is the booster pump that collects from a tank in which the level is measured in order to determine the injected water. [3] is the simple tube oven that heats the feed load injected by the pump [7]. [6] is the new feed load and the recycling tank (which must be carefully monitored in order to conserve liquids, so that they can be pumped). This tank is measured with bubbles that provide the weight of the treated feed load. [4] is the injector that has been described before. [10] is the reactor sized according to the method described in the patent. [12] is the reactor discharge valve, which regulates its pressure. [13] is a set of extractors as already defined. Its temperature is set as necessary from one extractor to another. [28] is a positive displacement meter of the GAS output placed behind a de-siculator.

[39] is another condensate collector. [13.1 to 13.5] are the discharge outputs of the extract.

Temperatures are measured with mercury thermometers placed in deep wells. Pressures are measured by conventional manometers.

Treatment and measurement of the conversion products formed

Exit gases:

Exhaust gases [13], after they are de-skewed and cooled to room temperature, go to a precision positive displacement meter followed by a gas sampling system in 11.2-liter flexible chambers (previously evacuated by a pump blades that creates very good vacuum).

The density of the gas can be determined by simple weighing of the chamber (taking into account the tare), which, based on the volume of the gases produced, directly indicates the mass of the exhaust gases. The composition of the gases that were sampled is obtained by any appropriate technique. In our case, since there may be large capacity chambers, gases can be extracted, cooled by liquefaction with liquid nitrogen and distilled naturally during reheating. If hydrogen were released in the reactions, it would be easy to determine why it would not be trapped in liquid nitrogen and would give permanent gases with a molecular weight of 2. This industrial procedure allows an unquestionable industrial analysis of the exhaust gases.

From a practical point of view, the gas flow makes it possible to verify the proper establishment of the operating energy conditions of the injector and consequently of the reactor, since we know that the production of hydrocarbon-containing gases must be minimal (objective: zero ). Therefore, the gases consist mainly of SH2, C02 and CO, which can be easily determined by simple means.

Liquid products formed:

These products appear after a brief decantation, in the form of: a light mobile phase called clear; a stable emulsion called mayonnaise; and a phase of free water that sometimes covers the sediments of the flocculant mud called flocs.

The proportion of these different phases or emulsions varies according to the feeding load and the operating conditions. Often the emulsion phase predominates and may still be the only phase present. In all cases, the emulsion is extruded through the means described above, produces a clear phase (resulting from mayonnaise) and dirty water (colorful and acidic). The direct clear phase and the clear mayonnaise phase constitute the output products in [16.11], which contain the useful conversion products (which may be hydrated or oxygenated as indicated above).

These products are then separated continuously, according to the process diagram in Figure

9. They are heated in the oven [8] to 360x at approximately 1 bar, after which they pass to [10], which acts as a transfer line, to finally produce [13.5-18.5] the atmospheric residue; [13.4-18.4], fraction 300-360; [13.318.3], fraction 200-300; [13.2-18.2], the fraction

100-200; [13.1-18.1], the PI-100 fraction. The cutting points can be changed by changing the temperature of the extractors. We intentionally modified the cuts to 5 because they were sufficient in the first phase of conversion of Figure 7. Thus, we obtained significant quantities of products in which all the desired evaluations and measurements could be performed.

The detailed characteristics of the products formed are obtained through classical distillation, without agitation or packaging, in order to observe the phenomenon of dehydration of these products, which can release water. The measurements of the index of refraction and density give us information about the structure of the products formed and as a consequence of the good performance of the conversion.

This is especially important for recycling, having the assurance that it does not polymerize to form some polyaromatic that could degenerate into massive coke.

EXAMPLES OF THE RESULTS OBTAINED

<td></td><td>CONVERSION</td><td>FROM WASTE TO</td><td>EMPTY. RsV</td><td></td>

<td> [5]</td><td>Augmentation</td><td>RsV, Allment 100.0</td><td>4 = 1.01 SOLID</td><td>n = l, 594</td>

<td></td><td>Csol</td><td> 3.0</td><td>Solid combust</td><td> 3%</td>

<td> [41]</td><td>Cgas</td><td> 4.0</td><td>2 gas combustion.</td><td> 2%</td>

<td> [16.3]</td><td>+ Miscellaneous:</td><td> 4.0</td><td></td><td></td>

<td> [13.52]</td><td>Purges</td><td> 3.5</td><td>1 FUEL</td><td> •</td>

<td> [18-5]</td><td></td><td> 8.5</td><td>/heavy</td><td> 12%</td>

[18.] to 18.4] Dat:

77.0

0.839 DISTILLED atm.

CONVERSION Fraction atm. % by weight DpAZ n

<td>Dp / v</td><td>is</td><td>the density</td><td colspan="2">of the quotient</td>

<td>Weight / Volume,</td><td>da es</td><td>the same density</td><td>taken in</td><td>a</td>

<td>densitometer</td><td></td><td></td><td></td><td></td>

<td>The</td><td>points</td><td>key of this</td><td>conversion</td><td>he</td>

set forth below:

Reference

<td>dd process</td><td>Nature</td><td>d: Density</td><td colspan="2">n: refraction</td>

<td> [0]</td><td>Natural H2O</td><td> 1.00</td><td></td><td></td>

<td>Feeding:</td><td></td><td></td><td></td><td></td>

<td> [5]</td><td>Food RsV</td><td> 1.01</td><td></td><td>1,594 SOLID</td>

<td> [50]</td><td></td><td>Dv / P</td><td>gives</td><td>α</td>

<td> [16.1]</td><td>clear</td><td> 0.893</td><td> 0906</td><td> 1.51671</td>

<td> [16.2]</td><td>Mayonnaise</td><td> 0.977</td><td></td><td> 1.51252</td>

<td></td><td>Clara extracted 0.925</td><td> 0,933</td><td> 1.51567</td><td></td>

[16.11: Clear + clear extracted from [13.1-13.2]% in the fraction

<td>CONVERSION</td><td>Fracc atm.</td><td colspan="2">% by weight Dp / V</td><td>n</td>

RECYCLED: MAIN FLOW

Atm residue 9.28% in the fraction [13.3] 200 ° C

VERY SLOW FLOW: RECYCLED + PURGE [13.4] 36O ° C fraction DsV% weight Dp / vn

<td></td><td></td><td colspan="2">% in fraction</td><td></td><td></td><td></td>

<td colspan="4">fraction dsV% weight Dp / v</td><td></td><td>Π</td><td></td>

[13.5] 470 ° C NOTHING ..................................-........ .................................................. .....

It is noted that fraction [13.4] contains an RsV portion and (250-300) DsV that extracts metals and polyaromatics. A portion thereof is removed to purge the reactor. The 3.5% adopted gave us good results.

<td> 2</td><td>ATMOSPHERIC WASTE CONVERSION</td><td>470 ° C reactor</td>

<td> [16.3]</td><td>+ Miscellaneous:</td><td> 3.0</td>

<td> [13-52]</td><td>Purges</td><td> 2.0</td>

<td></td><td>Total Souls Dist .:</td><td> 81.0</td>

Fixed n = 1.5576

With bus solid 2 gas with bus. 1.5% \ FUEL / heavy 11.5% in alment

<td colspan="2">f 16.11; Clear + clear ex. as of [13.1 -13.2]</td><td colspan="4">% in food</td>

<td></td><td>CONVERSION Fracc. atm. % weight</td><td>Dp / v</td><td colspan="3">n</td>

Atm residue 9.50 (5) Rat feed, feed_100.0 ¢ = 0.97 Fixed n-1.5576 [5] Rat fraction DsV% weight Dp / V n

<td colspan="2">RECYCLED: MAIN FLOW</td><td colspan="2">% in fraction</td>

<td> [13-3]</td><td>200 ° C</td><td>tails. DsV% weight Dp / v Pl -200 6.95 200-250 28.14 0.867</td><td>n 1,503 1,509</td>

<td>- VERY SLOW LUXURY: RECYCLED + PURGE</td><td></td><td>% in fraction</td>

<td> [13-4]</td><td>36 ° C</td><td colspan="2">fraction dsV% weight Dp / v</td><td></td><td>n</td>

<td> [13-5]</td><td>470 ° C</td><td>NOTHING ........................</td><td> ··«« 1 ··«·***·······<« ···«</td><td> ---------------</td><td> ---------------</td>

<td></td><td>With</td><td>clarity is</td><td>observe</td><td>what</td><td>the metals</td>

heavy polyaromatics are concentrated in the RsV of the extract [13.4], whereby a portion of this extract is purged. Recycling decreases compared to the case in which only the

RsV; Therefore, the treatment capacity is its nominal value of 2 kg / h of atmospheric waste.

PRODUCTION OF HYDROGEN COMPOUNDS OR

HYDRATED EMULSION

When performing a first run of atmospheric residue conversion, direct clear products + emulsions are obtained. It was considered to process them again through the pilot plant in order to oxygenate or hydrate them during this new conversion.

Sand distillation of the direct clear product and the extruded phase after this second conversion gave the following results:

<td></td><td></td><td colspan="2">Recipes: Weight</td><td>density</td><td colspan="2">refractive index</td>

<td>Section</td><td>Vt</td><td>Steam</td><td>V.HC</td><td>HC, dry</td><td>Dp / v</td><td>or</td>

Sand-free distillation of the same feed load produced:

H2O = 7.9 g for: 85.86 g of dry HC. This clearly shows that oxygenated and hydrated products were formed, which are first depolymerized at similar temperatures between 120 and 250 ° C at 1 bar. In addition, it is well known that water binds to ethylenic bonds according to reactions of the following type:

-CeC- + H2O

AS alcohol

AH

Tcq

H H

H, Ó, H CC f \

RR '

H

Η ,, Ο Η ,, Η -32 C -C / \

RR '

468 ° K (200 ° C)

C2H4

C18H36

Examples: AS AH + H2O - => H3C-CH6H -29.96 / 10.9 90 ° C + H2O - => Alcohol C18 -32.15 /-15.03 194 ° C

Tcq

The equilibrium temperature of these reactions is specifically achieved at ib, at approximately 200 ° C for heavy alcohols and at 200 ° C for light alcohols.

Experience clearly demonstrates that we have oxygenated and hydrated hydrocarbons, which is confirmed by the chemical equilibrium temperatures of the water with the corresponding alcohols.

The presence of hydrated and oxygenated products is favorable for the quality of the products that are formed, in particular gasoline.

Oxygenation or hydration are also favorable for combustion, both in furnaces and diesel engines. In addition, because of their polar characteristics due to the OH function, these products act as the third solvent between water and the hydrocarbon hydrocarbon chain, which makes it possible to obtain emulsions that are quite stable over time (our samples of more 8 years have not changed).

CONVERSION OF THE LAST DISTILLATED HEAVY VACUUM called 80, Kuwait, of the Oil Plan BP reactor

Dunkirk 500 ° C

These controlled operating conditions were selected in order to verify the increase in productivity and test the speed control of the deposits in the reactor. In addition, the technique for the liquid-liquid extraction of furfural from the feed load and effluents, allowed us to analyze the structure of the products formed and confirm our operating practices and calculation of dimensions for the units designed according to our process.

<td colspan="2">Power: 80, K</td><td> 100.0</td><td colspan="2">d = 0.936 SOLID n = 1.530</td>

<td>[15] Csol</td><td></td><td> 3.0</td><td>Fuel solid</td><td> 3%</td>

<td>[41] Cgas</td><td></td><td> 4.0</td><td>2 gas combustion.</td><td> 2%</td>

<td>[16.3] + Miscellaneous:</td><td> 0.5</td><td></td><td></td><td></td>

<td>[13.52] Purges</td><td></td><td> 3.5</td><td>\ GAS</td><td></td>

<td> [18.5]</td><td></td><td> 11.2</td><td>/heavy</td><td> 14.7%</td>

<td>Total Atmos Dist .:</td><td></td><td> 77.8</td><td>in allment</td><td></td>

<td colspan="2">[16.11: Clear + clear extr. as of [13.1-13.2]</td><td></td><td>% in food.</td><td></td>

<td>CONVERSION</td><td>Fracc atm.</td><td>% weight</td><td>Dp / v</td><td>n</td>

<td> (-18.53</td><td colspan="2">Atm residue 11.20</td><td></td><td></td>

[5]

Feeding:

80, K

100.0 d- 0.936 SOLID n = l .530

Furfural extraction by extraction

<td>fraction:</td><td>PAIR :</td><td>PA:</td><td>AN:</td><td>NB *</td><td></td>

<td>% weight</td><td> 13</td><td> 21 :</td><td> 21 :</td><td> 46 ♦</td><td></td>

<td>RECYCLED: MAIN FLOW</td><td></td><td></td><td>d</td><td>n</td><td></td>

<td colspan="2">VERY SLOW FLOW: RECYCLED + PURGE</td><td></td><td>d</td><td></td><td>n</td>

<td colspan="2">A few polyaromatic: not extracted [13.5]</td><td>470 * C</td><td colspan="2">(returned in [13.4])</td><td></td>

<td>It is noted</td><td colspan="2">clearly</td><td>what</td><td>the</td><td>metal</td>

<td colspan="2">heavy and polyaromatic</td><td>he</td><td colspan="2">concentrate</td><td>in</td>

extract [13.4], for this reason a portion of this extract is purged. The conversion is carried out with a low recycling, thanks to the operating conditions adopted, in particular a reactor approximately 500 ° C.

It should be noted that there is a very significant production of gasoline (27.55% by weight PI-200 ° C, from a

which compares very favorably with FCC gasolines).

CONVERSION WITH MIXTURES OF VARIOUS GASES AND THE EFFECT OF

THE NATURE OF THE FOOD LOAD IN THE

REACTOR TEMPERATURE

In order to work in arid areas where water is rare and in order to improve the quality of gasoline, the alternative offered by our process was studied, which consists of working with various permanent gases or mixtures that are easy to produce, for example, oven gases.

Some units, such as the decarbonation unit of the BENFIEL unit in a hydrogen production complex, discard large amounts of CO2 whose use could finally be considered.

Another of our interests was to verify our knowledge and experience in the operation with light vacuum distillates or heavy atmospheric diesel, in order to obtain light diesel or gasoline or in other terms, in order to meet the unbalanced market demand for these products. In reality, our unit makes it possible to favor the production of either diesel or gasoline as desired, which cannot be achieved with existing conversion units that have a fixed distribution of the products they generate.

Therefore, an ELF ENGINE OIL was selected as the feed load to be converted, which is common and easy to find in all supermarkets and has a density of 0.885 and a refractive index n = 1,488 (average values).

We know that CO2 He was a good candidate for conversions; that the mixture CO2 + H2Or it presented potential advantages; that the mixture CO2 + H2 might be convenient, but with the H2 he ran the risk that he is not very reactive and participated in the reactions only through his physical attributes; that the N2 It might be adequate but, when used alone it did not protect against coking. All these combinations were explored.

We were able to verify that it was very practical to adopt a reactor temperature of 520 to 530 ° C.

Without recycling, the conversion observed was as follows:

[5] [16.11]

CONVERSION OF OIL TO PURE C02 WITHOUT RECYCLING

<td>CONVERSION</td><td>Fraction</td><td></td><td>% weight</td><td></td><td>Dp / v</td><td>n</td>

<td colspan="3">Total Atmospheric Distillate</td><td></td><td> 43.10</td><td></td><td></td>

52.79 0.878

0.91 0.861 [13-3] [13.4] [13.5]

CONVERSION OF OIL TO CO2 + H2O WITH RECYCLING

<td></td><td>CONVERSION</td><td>Fraction</td><td>% weight</td><td></td><td>Dp / v</td>

CONVERSION OF OIL TO CO2 + H2O WITHOUT RECYCLING

<td> [16.11]</td><td>CONVERSION Fraction% weight</td><td></td><td>Dp / v</td><td></td><td>n</td>

The H2Or it tends to retard the appearance of light fractions, as expected. There are no significant differences that distinguish the behavior of these gas mixtures.

From the point of view of the octane index, the classification is done in ascending order of CO2, C02 + H20, CO2 + H2, without any important distinction. Care should be taken to avoid excess gas flow of C02 + H2Or, that would reduce conversions as pure losses.

CONVERSION OF OIL TO CO2 + H2O WITH RECYCLING

<td>f5]</td><td>Feeding:</td><td>MOTOR OIL</td><td> 100.00</td><td colspan="2">d-0.886 n = 1.49148</td>

<td> [15]</td><td>Csol</td><td></td><td> 0.5</td><td>burns solid</td><td> 03%</td>

<td> [41]</td><td>Cgas</td><td></td><td> 3.2</td><td>combustion gas 1.6%</td><td></td>

<td> [16.3]</td><td>+ Miscellaneous:</td><td> 0.0</td><td></td><td></td><td></td>

<td> [13.52]</td><td>Purges</td><td></td><td> 0.5</td><td>\ GAS</td><td></td>

<td> [18-5]</td><td></td><td></td><td> 6.3</td><td>/HEAVY</td><td> 6.8%</td>

<td colspan="2">[18.1 - I8.4JDat:</td><td> 89.5</td><td></td><td>DISTILLED atm.</td><td></td>

<td colspan="2">CONVERSION</td><td>Fracc atm. % weight</td><td></td><td>Dp / V n</td><td></td>

This oil is converted to 30% gasoline

PI-200

These different examples show that very different feeding loads can be converted, in a very safe way and with excellent results. (The tests with N2 pure showed that there was a significant tendency to coking).

10 DEPOSITS IN THE REACTOR

We select ELF engine oils as test feed loads in examples 6, 7, 8 and 9, considering in particular that we would only be limited by chemical considerations for an analysis of the conversion of light fractions. Basically the conversions with permanent gases were carried out, in particular the C02 and the hydrogen supplied by Air Liquide and commercially available demineralized water, with an oven temperature of 530 ° C.

We begin by providing the deposits by controlled combustion according to the technique that is specific for hydrocarbons, while the combustion front is carefully monitored. Some unexplained problems related to loss of local feed load remained in the reactor.

Therefore, it was decided after a long controlled run: (1) to carry out careful combustion; and (2) open the reactor and its injector. The injector was clean.

Then the deposits deposited in the reactor were removed, by means of the well-known hammering technique and a gray powder was also extracted by means of a hole. Neither the encrustations nor the dust were combustible.

151.2 solids were collected for a feed load of 62300 g, which gives a solid deposit / feed load ratio of 0.24%. The origin of these deposits can only be the treated oil and they appeared only as accumulation.

(In our waste conversion tests, we adopted the mechanical purification technique to extract solid and carbonaceous residues from the reactor, which was a more difficult but more precise operation that indicated the amount by weight of the deposit formed. These deposits can then be analyzed for practical purposes).

eleven DEMETALIZATION FOR WASTE EXTRACTION OR

POWER LOADS

These are the properties of a Kuwait RsV that we would use as the reference feed load in our conversions.

A fractionation by means of extraction with propane C3, butane C4 and pentane C5 It makes it possible to separate the components of this residue under vacuum, according to its nature, which varies from DAO (deasphalted oils) to very hard asphalts (Asp C5) .

RsV FRACTIONATION BY EXTRACTION C3-C5 6/1

RsV

<td>POSITION % RsV LOAD FOOD.</td><td>• DAOC3 • 18.7</td><td> ♦ •</td><td>ExC4 33.7</td><td> * «</td><td>Ex CS 30.4</td><td> * *</td><td>AspC5 17.5</td><td>I 100% RsV</td><td> * ♦</td>

<td>Density 20 "C</td><td> •0.896</td><td> *</td><td> 1.000</td><td> *</td><td> 1.047</td><td> *</td><td> 1.067</td><td> ! 1.010</td><td> *</td>

<td>Refrac index 20 "C</td><td> • 1.519</td><td> *</td><td> 1.592</td><td> *</td><td> 1.624</td><td> *</td><td> 1.641</td><td> ! 1.59415</td><td> *</td>

<td>Sediments</td><td> *</td><td> *</td><td></td><td> *</td><td></td><td> *</td><td></td><td>1 0.09% Pds</td><td> *</td>

<td>Sulfur% RsV</td><td> • 0.53</td><td> •</td><td> 1.62</td><td> •</td><td> 1.62</td><td> *</td><td> 1.23</td><td>r 5th</td><td> *</td>

<td>Nickel ppm RsV</td><td> * 02</td><td> *</td><td> 10.2</td><td> *</td><td> 14.4</td><td> *</td><td> 17.2</td><td> ! 42</td><td> *</td>

<td>Vanadium ppm RsV</td><td> • 1.0</td><td> »</td><td> 323</td><td> *</td><td> 47.2</td><td> *</td><td> 55.5</td><td>I 136</td><td> *</td>

<td>NaCI% by weight</td><td> *</td><td> ♦</td><td> -</td><td> *</td><td> 0.0003</td><td> *</td><td> 0.0107</td><td> ! 0.0110</td><td>ib</td>

It is observed that metals (nickel, vanadium) are concentrated in the most polyaromatic products with a high refractive index n and with the highest density. The same applies to salts and sulfur.

These components constitute an impediment because they are poisons for any subsequent catalytic refining treatment that could be performed. Polyaromatics containing these components are coking precursors and when mixed increase the viscosity of the products to the point that they can no longer be pumped, thereby greatly reducing the quality of the fuels used for their own applications. For these reasons, it would be necessary to extract them separately.

The conversion of this residue in vacuo (RsV) described in example No. 1 provides the following extract of the extraction [13.4]:

VERY SLOW FLOW: RECYCLED + PURGE% in fraction [13.4] 360'C fraction DsV% weight Dp / vn

PI-195 Nothing .........................................

195-250 8.63 0.859 1.49888

250-300 4333 0.904 1.53737

RsV.4 48.04 1.625

When referring to densities and refractive indices, it is observed that the extract [13.4] is practically and exclusively composed of EXC4, EXC5 and AspC5.

However, the analysis of the extract [13.3] shows that it contains virtually no components containing metals, salts, sulfur, etc., since its heaviest fraction is DAO and 10% of RV.3 is equivalent to EXC3.

100

RECYCLING: MAIN FLOW% in fraction

<td colspan="2">fraction.DsV% weight</td><td>Dp / v</td><td></td><td>n</td>

[13.5] 470®C NOTHING ........................................... ........................................

(The extractor [13.5] operates as a safety device)

At 360 ° C and at atmospheric pressure, the EXTRACTOR [13.4] demetalizes the feed load in an efficient and controlled manner by concentrating metals, salts and sulfur in a well-defined extract [13.4] that constitutes a new characteristic of a modality.

CONTENTS OF METALS AND OTHER IMPURITIES OF CRUDES AND

WASTE

<td></td><td colspan="2">When fractioning</td><td>a residue</td><td colspan="3">to typical vacuum, to</td>

<td>through</td><td>of techniques</td><td>from</td><td>refinement</td><td>very</td><td>known</td><td>with</td>

<td>propane</td><td>C3butane</td><td>c4,</td><td>pentane C5</td><td>, he</td><td>they get</td><td>the</td>

<td colspan="2">following extracts</td><td>and</td><td>refined:</td><td></td><td></td><td></td>

<td colspan="3">POSITION * DAO C3 * ExC4</td><td>* ExC5</td><td> *</td><td>Asp C5</td><td></td>

<td>Sediments * *</td><td> * *</td><td> *</td><td>0.096% Pds *</td><td></td><td></td><td></td>

<td>Sulfur% RsV0.53</td><td> * 1.62</td><td></td><td> * 1.62</td><td> *</td><td> 1.23 *</td><td>5.0% Pds *</td>

<td>Nickel ppmRsV * 02</td><td> ‘ 10.2</td><td> * 14.4</td><td> *17.2 *</td><td> 42</td><td> *</td><td></td>

<td>Vanadium ppm RsV * 1.0</td><td> *32.3</td><td> *47.2</td><td> •55.5 *</td><td> 136</td><td> •</td><td></td>

<td>NaCl% by weight * -</td><td> * *</td><td> 0.0003</td><td> * 0.0107 * - *</td><td colspan="2"> 0.0110 *</td><td></td>

DAO is the product called deasphalted oil; ExC4 is the extract with C4; ExC5 is the extract with Cs and AspC5 is the corresponding residual asphalt obtained.

101

The metals, NaCl and sulfur, are concentrated in quite aromatic heavy molecules with a low hydrogen content.

In combustion these residues give ashes that have a typical relative composition, as indicated below:

Ashes: SiO2: 32 Faith2OR3: 25 Na: 16 Va: 14 Ni: 6

At: 6

In addition, it is known that eutectic (glass) appear approximately between 550 and 660 ° C.

Silica + Sodium carbonate -> Classic glass (Silicate)

Silica + V2OR5 -> Vanadium glass

Silica + Nickel -> Nickel glass

Silica + Ashes -> Glass with iron, Ni, etc.

Therefore, it is observed that any catalyst is necessarily overloaded with glass by metals.

Since our disintegration reactor is empty, it can withstand long cycles without quickly forming deposits on its walls, as was also observed with respect to other considerations, which should work in this case approximately between 460 and 480 ° C. Therefore, metals are transported and extracted using the heaviest liquid products.

The motor oils that became

102 require a reactor between 500 and 520 ° C. Actually it was observed that there were few non-combustible deposits on the walls of the decay reactor.

This led us to generalize the technique for mechanical cleaning of the extraction of carbonaceous residues accompanied by metal deposits, preferably by combustion (which leaves metal deposits and ashes on the walls). Since the disintegration reactor is empty, no problems were found here to perform this mechanical debugging and descaling operation. Sulfur presents no problem.

While the present invention has been described with reference to particular modalities, it will be understood that the modalities are illustrative and that the scope of the invention is not limited thereto. Many variations, modifications, additions and improvements to the modalities described are possible. These variations, modifications, additions and improvements may be within the scope of the invention as described in detail in the following claims.

Contents80

45 members in 25 offices

This recordMember, by publication datePriority claim15 more offices are in the list below

Priority claims8

Priority claims
Document	Office	Kind	Date
9812983	France	A	1998-10-16
9812983	France	A	1998-10-16
40593499	United States of America	A	1999-09-27
40593499	United States of America	A	1999-09-27
FR09405934A	–	–	–
FR19980012983	–	–	–
FR9812983A	–	–	–
US19990405934	–	–	–

Members45

Family members, oldest first
Document	Office	Kind
CA2346181A1	Canada	A1	2000-04-27
WO0023540A1	World Intellectual Property Organization (WIPO)	A1	2000-04-27
FR2785289A1	France	A1	2000-05-05
AU6418599A	Australia	A	2000-05-08
NO20011828D0	Norway	D0	2001-04-10
NO20011828L	Norway	L	2001-06-11
ID29093A	Indonesia	A	2001-07-26
BR9915551A	Brazil	A	2001-07-31
EP1129153A1	European Patent Office (EPO)	A1	2001-09-05
KR20010089310A	Republic of Korea	A	2001-09-29
EA200100399A1	Eurasian Patent Organization (EAPO)	A1	2001-10-22
CN1323338A	China	A	2001-11-21
PL347248A1	Poland	A1	2002-03-25
EA003082B1	Eurasian Patent Organization (EAPO)	B1	2002-12-26
JP2003525310A	Japan	A	2003-08-26
EP1342773A2	European Patent Office (EPO)	A2	2003-09-10
NZ510706A	New Zealand	A	2003-09-26
EP1342773A3	European Patent Office (EPO)	A3	2003-11-19
US2004065589A1	United States of America	A1	2004-04-08
AU773537B2	Australia	B2	2004-05-27
UA66875C2	Ukraine	C2	2004-06-15
GEP20043409B	Georgia	B	2004-07-12
AP1341A	African Regional Intellectual Property Organization (ARIPO)	A	2004-12-13
US2005211602A1	United States of America	A1	2005-09-29
US2005276735A1	United States of America	A1	2005-12-15
US6989091B2	United States of America	B2	2006-01-24
EP1129153B1	European Patent Office (EPO)	B1	2006-04-26
AT324422T	Austria	T	2006-05-15
DK1129153T3	Denmark	T3	2006-05-29
PL191375B1	Poland	B1	2006-05-31
DE69931064D1	Germany	D1	2006-06-01
OA12680A	African Intellectual Property Organization (OAPI)	A	2006-06-20
CU23154A3This record	Cuba	A3	2006-07-18
PT1129153E	Portugal	E	2006-07-31
ES2258341T3	Spain	T3	2006-08-16
DE69931064T2	Germany	T2	2006-08-31
FR2785289B1	France	B1	2007-01-05
KR100684141B1	Republic of Korea	B1	2007-02-20
CA2346181C	Canada	C	2007-06-26
JP4080162B2	Japan	B2	2008-04-23
CN100489066C	China	C	2009-05-20
US2010260649A1	United States of America	A1	2010-10-14
US7967954B2	United States of America	B2	2011-06-28
BR9915551B1	Brazil	B1	2011-07-26
US2012055847A1	United States of America	A1	2012-03-08

Abstract

Term

FIELD OF THE INVENTION

DESCRIPTION OF THE RELATED TECHNIQUE

SUMMARY OF THE INVENTION

BRIEF DESCRIPTION OF THE DRAWINGS

DETAILED DESCRIPTION OF THE PREFERRED MODES

A: A

A: A

A: A

H H

C10H78H

H, CCC

AS AH

HC-CH

HC

C- C

AS / AH

FPL

HC

H H

CH

CH

H H

HCH

HC

HC: CH

CONTROL OF THE APPEARANCE OF GAS. COKE OR WASTE FROM

SOLID COAL

(A) (B) (C)

GAS GAS GAS

CARBON DEPOSITS

THERMAL DECOMPOSITION OF CH,:

EMULSIONS

MAYONNAISE

PROCESS WATER ANALYSIS BY DISTILLATION WITH 15

DISHES

OXYGENATION CONTROL OR PRODUCT HYDRATION

CONVERSION WITH RECYCLING EXTINCTION:

PRODUCTS

THE ACTION OF STEAM ON DOUBLE LINKS DOES NOT

SATURATED

METALS WITH INORGANIC DEPOSITS / EMULSIONS

COMPLEXES

COMMENTS REGARDING THE FINAL STABILIZATION OF

THE FORMED PRODUCTS

DESCRIPTION AND PERFORMANCE OF INJECTION ASSOCIATED WITH

THE REACTOR

DISPOSITION OF THE INJECTORS IN THE REACTOR FOR

FACILITATE YOUR MECHANICAL CLEANING

INJECTOR AND DISINTEGRATION CAMERA

-T (R / E)

R (TI - T2)

EXAMPLES OF APPLICATIONS

STEAM CONVERSION

ARID AREAS INSTALLATION

RESORTION OF LIGHT GASES IN THE REFINERY OR IN A

OIL FIELD OR TO MAXIMIZE THE MAXIMUM

GASOLINE PRODUCTION

EXAMPLES OF RESULTS OBTAINED WITH OUR PLANT

INDUSTRIAL PILOT

EXAMPLES OF THE RESULTS OBTAINED

RECYCLED: MAIN FLOW

PRODUCTION OF HYDROGEN COMPOUNDS OR

HYDRATED EMULSION

AH

H H

RR '

H

RR '

C2H4

C18H36

80, K

CONVERSION WITH MIXTURES OF VARIOUS GASES AND THE EFFECT OF

THE NATURE OF THE FOOD LOAD IN THE

REACTOR TEMPERATURE

CONVERSION OF OIL TO PURE C02 WITHOUT RECYCLING

PI-200

10 DEPOSITS IN THE REACTOR

POWER LOADS