FR2785289A1 - Hydrocarbon conversion into distillable light products for oil refinery, comprises load treating with jet having energy causing it to reach activation energy for its molecules to split - Google Patents

Abstract

Hydrocarbons are converted into distillable light products by treating a hydrocarbon load with a jet having first amount of energy, thus, transferring at least a portion of the energy to it. The energy transfer causes the load to reach an activation energy at which at least a portion of its molecules split into lighter molecules. The load is demetallized through extractor series. Hydrocarbons are converted to distillable light products by preheating a hydrocarbon load to a first temperature, treating the load with a jet, stabilizing the load at a second temperature in a reactor, expanding the load at a second pressure, and passing the load through a series of extractors. The hydrocarbon contain residues or heavy distillates which may be laded with impurities. The jet has a first amount of energy. A portion of the first amount of energy is transferred to the load causing it to reach an activation energy at which at least a portion of its molecules split into lighter molecules. The reactor is operated at a first pressure. At least one of the extractors demetallizes the load. At least one of the reactors produces water/hydrocarbon emulsions. An Independent claim is included for a device comprising a hollow reactor body, at least one inlet, a nozzle, and at least one outlet.

Description

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 Deep conversion combining the demetallization and conversion of crude, heavy residues or oils to light liquids, using pure or impure oxygen compounds (H20, CO2, CO, accompanied by H2, N2 SH2 etc.). It is well known that all refining processes leave heavy residues, weak fusible or solid, which find few users and few outlets.

It is also well known that oil drilling often falls on deposits which give roughs characterized by a very high density and a very high viscosity, difficult to transport as such.

These Crudes are also characterized by a high content of metals such as Nickel and Vanadium, sediments and sludge, sulfur, salt to name only the main impurities, which are as many poisons for any possible catalyst.

Moreover, whatever one does, it is impossible to completely avoid deposits of these components on anything that comes into contact with these crudes.

It is thus understood that if any catalyst is used, all its surface, all its pores are quickly covered and that the catalyst becomes totally dead: it then only occupies the space in the reactor, even risking to plug it if the catalyst grains are agglomerated by the cement that consists of sediments, nickel, vanadium, asphalts, carbon produced, etc.

Processes such as FCC are known which try to accommodate carbon deposits by burning them in a regenerator, but this requires a complex circulation of the catalyst between the reactor and the regenerator. In addition, the circulation of said catalyst creates thorny erosion problems both in wear of the material itself which sometimes happens to be perforated, that the catalyst that is worn gives dust dangerous for any human being and no filter as voluminous and perfect as it is, it can not stop.

As a result of all the constraints encountered and the compromises to be made, in fact, this type of unit can only treat vacuum distallates, that is to say by removing from the charge the vacuum residues in which the metals are concentrated. sediments etc ..

 Furthermore, the regenerator which burns the formed coke imposes a minimum temperature of about 700 C for the combustion to take place. The catalyst leaving the regenerator, sent into the reactor at this temperature which is too high, leads to an abundant production of gaseous products on the one hand and, on the other hand, to very aromatic heavy products having lost a lot of hydrogen during the first contact with the catalyst too hot.

 In addition, it is impossible to change the distribution spectrum of liquid conversion products which, moreover, are accompanied by a large quantity of Cl C2 gas and LPG C3, C4.

According to a feature of our invention, the production of gasoline and gas oil can be varied by stopping conversion to the gas oil level or the contrary by continuing the conversion of gas oils into gasolines.

The FCC is only rearranging the distribution of carbon and hydrogen in molecules: it takes hydrogen in molecules with high molecular weight (high boiling temperature) to create light molecules, but C4, C3 , C2 and especially Cl (CH4) take up a large part of the hydrogen. There is even rejection of pure hydrogen. It follows that the cuts

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 heavy oils known as HCOs are low in hydrogen, can not be recycled for further conversion.

It will be seen that one of the characteristics of our invention is precisely to control the contacting of the products to be treated with the gases which initiate the reactions and this without excessive energy transfer leading to the excessive creation of gases C1, C2 and the creation of molecules that are poor in hydrogen.

Conservation during conversion of a good Hydrogen / Carbon ratio is therefore crucial.

Hydrocracking is precisely aimed at improving the H / C ratio by effectively adding hydrogen to the load.

This process consuming hydrogen requires to be equipped with a hydrogen production unit which is a strong consumer of energy and gaseous hydrocarbon material (with, in general, C02 discharge if starting from CnH (2n + 2) ).

In addition, hydrogen becomes reactive only at pressures greater than 100 bar, this imposes a construction with very high thicknesses. The conjunction of the presence of hydrogen at temperatures of the order of 450 C under 150 bar to fix the ideas, poses thorny problems of realization and technology, especially on the nature of special alloy steels suitable for these jobs.

In addition, the conversion products saturated with hydrogen are very paraffinic and consequently give gasoline having a bad octane number.

It is then necessary to use a catalytic reformer which removes hydrogen to raise the octane number.

 It is paradoxical in these operations to begin by laboriously introducing hydrogen into the products, and then be led to remove it.

It is therefore understood that it is important in all these operations to avoid unnecessary operations on the hydrogen content. This is what our invention realizes directly.

Some research has been done in trying to create hydrogen, called H, for incorporation into hydrogen-poor feeds.

The creation of the said H. requires a great energy that is restored at the time of the final reaction and "shatter" the relevant hydrocarbon molecules to release the carbon.

It follows that instead of incorporating hydrogen into the feed, unsaturated gases (usually 20-40% of the feedstock) are created by globally rejecting hydrogen.

Other investigations have been made on the use of superheated hydrogen at 1100-1200 C at 40 bars with residence times of 60 seconds for hydropyrolysing oil and heavy oil residues, such as those of B. SCHOTZE and H. HOFMAN reported in Erdol und Knhle-Erdgas -Petrochemie vereinigt mit Brennstoff-Chemie 1983, 36 N 10, 457-461.

The results obtained always include high proportions of gas (12 to 27%) and a lot of coke.

These two paths are thermodynamically dead-end, as confirmed by the practical results obtained (excessive production of gas and coke).

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It is well known that by purely thermal means using a VISCOREDUCTEUR (or Visbraeker) one can "shake" the molecules that make up the residues under vacuum to "break" the viscosity. This creates a small additional load generation that is generally converted to the FCC. Then there remains a viscorreducer residue generally called flashed visbreaking residue (RVR) which in turn can be used as heavy industrial fuel oil supplemented with light products of the type Diesel or LCO (FCC Diesel) to have normal viscosity.

These examples show the complexity of refining operations with nested processing and reprocessing.

Much attention must in fact be given to the physical state of the material (solid or gaseous liquid) under normal conditions of temperature close to 20 C and pressure close to 1 atmosphere.

We also know the COKERS which treat the residues to deliver liquids but reject solid carbon which will have the same uses as the coal (and with the same difficulties) We also know the attempts of improvement made with the FLEXICOKER which consists in fact to gasify the coke produced. Gasification requires an installation as important as useful coking. It saturates the refinery with a combustible fatal gas that must be exported or used for purposes other than those strictly necessary for refining operations (for example, to produce gasoline). electricity).

We still know the attempted hydroconversion of RSV known by the name of HYCON PROCESS which consumes about 2.3% of hydrogen. The 41% converted must in turn pass to the FCC with all the consequences that have been mentioned in this regard, especially regarding the direct leakage of H2 and the loss of hydrogen contained gases such as CH4, C2H6.

These two processes are too complex and ultimately difficult to integrate into an effective refining scheme.

FW and UOP reported on October 27, 1997 that they have developed a catalytic process called AQUACONVERSION PROCESS in collaboration with UNION CARBIDE for the catalyst. In use the general problems relating to the catalysts remain intact.

It is still claimed by ELF ANTAR the preparation of an Aquazole containing 10 and 20% water, stable simply from 15 days to a month, while one of our intermediate products is an emulsion that has a proven stability of over 8 years.

 The review we have just done allows us to better understand the extent, originality, and contributions of our invention.

Our invention is characterized by the various points below which can be taken separately or in combination, this list being given for information only and not limiting.

1 / Charges are taken as they appear.

In a refinery, our process that we will call CPJ in short,

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 can accept indifferently crude, atmospheric residue (Rat), vacuum residue (RsV) or heavy distillates.

 On an oil field, he takes directly the crude leaving the well.

2 / Our process never uses vacuum processes that lead to voluminous distillation towers that must withstand moreover the crushing of the atmospheric pressure.

3 / The introduced charge is treated with gases or vapors which serve as energy vector.

 * If you are in a refinery, the steam is preferably water vapor.

* If you are in an arid or desert region, the gases are preferably N2 + CO2 (that is to say, taken directly from the smoke coming from the ovens) * Any combination is possible and has been tried: - For example in a refinery having a unit of hydrogen, it is possible to take the CO 2 released by the BENFFIELD unit for decarbonation of hydrogen, - the CO 2 gas + H 2 O (vapor) mixture - the CO 2 + xH 2 mixture leaving the unit of hydrogen production
Benffield before decarbonation, a mixture that provides some advantages for the octane number of the species produced.

 The mixtures CO 2 + xH 2 or CO 2 + H 2 + H 2 O are suitable.

 The most favorable gases or vapors will contain Oxygen and / or Hydrogen.

These elements can be linked, or in a mixture like for example:
X-OH, H20C, CO2, CO2 + H2, CO + H2O # == # CO2 + H2O, CO + 2H2 # == # -CH2- + H2O or CO2 + H2 from a BENSFIEL unit after SHIFT CONVERSION and before decarbonation in a hydrogen production unit.

 Pure N2 is acceptable, but not very favorable. It will only be taken with CO 2 from combustion fumes preferably.

 The direct introduction of 02 requires special precautions of injection.

For example we can inject 2CH4 + 02 => 2CO + 4H2 + Heat using a pre-injector. [In this case we do not need pure 02. The air (02 + 4N2) does the trick. ] This variant could be considered to absorb a surplus of light gases (C1, C2) in primary chemical energy supply, the material being partially recovered in a special extractor to 200 C-220 C, 20- 30bars.

This shows another aspect of the extreme flexibility of the CPJ process.

Sulfur, which is a close relative of Oxygen in the periodic table of elements, is not troublesome and would be even beneficial (except with regard to resistance to corrosion).

The gases are heated, preheated or prepared in conventional ovens.

 5 / The fresh feedstock and the possible recycles are cnntibly preheated in a conventional oven or by conventional heat exchanger trains.

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6 / The charge is injected into the reactor by an injector which intimately contacts the preheated charge in a jet of the gases during expansion suitably preheated (or superheated if it is pure water vapor)
This injector also aims to create a free jet of material and gas that does not touch any material wall to facilitate the initiation of reactions.

 The energy inputs fixed by the temperature, the flow rate and the rate of expansion in the injector release a quantity of usable mechanical energy which makes it possible to provide the energy necessary and just sufficient to initiate the reactions without being able to pull the Peripheral hydrogen molecules and without having an energy such that the molecule can be broken into tiny fragments, as is done in an FCC.

7 / The Reactor Maturation is an empty capacity.

 No catalyst is used.

 This reactor allows the reactions initiated by the injector to be in equilibrium.

 The pressure reduces the necessary volume on the one hand and on the other hand increases the speed of equilibrium.

 The absence of any material in the reactor has the advantage of not having breakpoints reagents leading to too long residence time and consequently carbon deposits.

8 / The products, Steam and Gas are then expanded at a pressure close to atmospheric pressure leaving the cracking reactor.

 If 2CH4 + 02 or 2CO + 4H2 has been introduced for the recovery of carbon of gaseous origin, the outlet of the maturing reactor is cooled to 200 -220 ° C. without breaking the pressure, which makes it possible, in a secondary capacity, to equilibrates the addition reactions of CO + H2 giving-CH2- which is grafted onto the material contained in the H20 / Hydrocarbon emulsion retained in this capacity.

CO + H2 can still give a functional block - C: 0
HH which is added on unsaturated bonds to give aldehydes, the simplest example being:
H2C: CH2 + CO + H2 ===> 3HC-CH2-C: All these reactions help to create liquids by eliminating or blocking the creation of gases.

The products are then relaxed at atmospheric pressure.

9 / In all cases they are suitably cooled and separated by a series of special devices allowing the separation of the heavy liquid phases of the light gaseous phases at temperatures suitably selected according to the physical characteristics of the products.

10 / Non-standard heavy goods chosen are recycled with the fresh load.

11 / The Light Products conforming to the chosen standard are extracted. In the presence of water vapor they come in the form of water / water emulsions.

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 carbide very stable, but easy to break.

12 / The breaking of heavy molecules is done in a controlled way in all these processes.

 Basically, say that the weight of the molecules is divided by 2 at each passage in the injector, with a conversion rate of (1-1 / e = 0.63).

 This process therefore changes very little the H / C ratio of the products.

13 / The control of the rupture of the molecules makes it possible to avoid producing gases, on the one hand by never using the energy required to their formation and on the other hand by choosing the conditions of equilibrium in the reactor unfavorable to their appearance.

14 / Useful products can be; - Or hydrated and compound by the emulsion mentioned in 11 - or anhydrous and obtained by extractive dehydration.

None of the above processes is critical in itself and can be overtaken by others to the detriment of lower performance, higher conversion rates, higher energy consumption, or higher production. Solid Carbon.

According to another series of features of our invention, great attention is given to the constraints of the material being processed.

Although this is only a very crude and imperfect explanation, one can imagine that heat in its thermal aspect is stored in the form of mechanical vibrations of the molecules.

The vibrations generate mechanical stresses which, because of the inertia linked to the mass, are maximum in the middle of the molecule, if the vibrations are moderate. These constraints then lead to a break in the middle of the molecule.

The more one heats the molecule (or more generally, the more it is stored energy of any kind), the more it will vibrate.For that it will vibrate on harmonic modes with several bellies and vibrational troughs as each could observe it on a piano string or the halyard of a flag fluttering in a very strong wind, or on a long rod that one agitates. The vibration hollows being the seat of the maximum stresses the molecule will break at these points there, the third, the quarter, etc. of its length.

This gives an image that explains that if we heat too much (if we transmit too much energy) to a molecule it will break up into tiny pieces that stop at CH4 and even at Carbon C.

With this summary explanation, we can still understand that the longer a molecule is so massive and heavy the more it has vibrating elements, the more the central elements retemant the many lateral elements that are agitated must force to retain them.

If they force too much, they crack.

This image makes it possible to explain that the heavier the molecule, the less it supports the heat without cracking.

To fix the ideas the CH4 supports badly temperatures of more than 700 C

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 and heavy residues, temperatures of over 430 C.

In the choice of devices, these constraints are still reflected by the maximum allowable heat flux expressed in Kcal / hour / square meter, or by the allowable temperature differences between the hot wall and the cold fluid.

The critical values depend on the considered products characterized by their physical state (Liquid, Solid, Steam) in the working conditions.

It is therefore very important to have a working knowledge of what can happen with the treated products.

The following example will make the stakes understand with just as common molecules as C10H8 consisting of two aromatic nuclei.

 We will note each cycle of 6 aromatic carbons A, A for the ring, for the double bonds in each ring.

 A: A here: indicates two carbons of A are linked.

If A: A is too heated, it loses hydrogen and becomes very reactive, we then have:

<Tb>
<tb> A: A <SEP> A: A
<tb> +
<tb> A <SEP>: A <SEP> A <SEP>: A
<tb> ClOH8 <SEP> + C10H8 <SEP> === # <SEP> C20H12 <SEP> + <SEP> 2H2
<tb> tf <SEP> = <SEP> 80 C <SEP> tf <SEP> = 278 C
<tb> Tb = 218 C <SEP> Tb = 350 (Sublime)
<tb> d <SEP> = 0.963 <SEP> d <SEP> = 1.36
<tb> n <SEP> = 1.60 (liq) <SEP> n <SEP> = 1.88
<Tb>
We go from a solid / liquid to a very hard solid.

(Note in passing that the 20-carbon molecules are the products commonly called gas oil or light domestic fuel.) A new feature of our invention is therefore to prevent such situations from occurring.

It was found that the freshly broken chains were naturally very reactive to breakage and that the polar molecule HöH (UAE) only wanted to attach to these breaks, just like ÖCÖ (carbon dioxide).

Another feature of our invention is to introduce oxygen into conversion processes
To better perceive the originality and inventive height we will try to give an explanation of what we must try to do and what not to do.

For this purpose we will take another example in the C20 family:

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<Tb>
<tb> C20H1402 <SEP> Tf = <SEP> 300C <SEP> Tb = Sub <SEP> Ho, A: AA: A, ôH
<tb> C20H14 <SEP> Tf = <SEP> 188 C <SEP> Tb = 452Sub <SEP> A: AA: A
<tb> C20H140 <SEP> Tf = <SEP> 81 C <SEP> Tb = 264 / 15mm <SEP> A: A-O-A: A
<Tb>

C20H14 + H20 ====> C10H7ÔH + C10H8 H H 0 A:A - A:A A:A-ôH + A:A Tf =188 C Tf =123 C Tf = 80 C Téb=452sub Téb=295 C Téb=218 C d =1,30 d =1,01 d =0,963 n =1,76 n =1,62 n =1,60 liq La présence de l'eau est hautement bénéfique sur les produits formés. Replace a hydrogen with a lateral OH is bad (the melting temperature has risen from 188 C to 300 C)
If 0 suppresses a DC bond, it has a beneficial effect (the melting temperature goes from 188 C to 81 C). Let us now take the case where the molecule C20H14 is weakened by a suitable temperature which sets it in vibration and sends a HHO molecule ( H20) on the central link:

C20H14 + H20 ====> C10H7OH + C10H8 HH 0 A: A - A: AA: A-OH + A: Tf = 188C Tf = 123C Tf = 80C Tb = 452bubbub = 295b Tb = 218 C d = 1.30 d = 1.01 d = 0.963 n = 1.76 n = 1.62 n = 1.60 liq The presence of water is highly beneficial on the products formed.

C20H12 +2H20 ====> C10H7ÔH + C10H7ÔH H H A A ====> A:A-ôH + A:A-ôH A - A o H' 'H Tf =278 C Tf =123 C Tf =123 C Téb=350Sub Téb=295 C Téb=295 C d =1,36 d =1,01 d =1,01 n =1.88 n =1,62 n =1,62 Cet exemple montre clairement tout le profit quel'on peut tirer de la vapeur d'eau. Take again the molecule very collected C20H12 attacked by 2 H20, one has:

C20H12 + 2H20 ====> C10H7OH + C10H7OH HHAA ====> A: A-OH + A: A-OH A - A o H '' H Tf = 278 C Tf = 123 C Tf = 123 C Tb = 350Sub Teb = 295 C Teb = 295 C d = 1.36 d = 1.01 d = 1.01 n = 1.88 n = 1.62 n = 1.62 This example clearly shows all the benefits that can be derived from water vapor.

By thermodynamic considerations, it can also be defined that the free solid carbon that can be formed is oxidized at about 600-700 C depending on the reactions:

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C02 + Cs ===> 2CO AS=42,14 AH=41,23 Téq= 705 C H20 + Cs ===> CO +H2 AS=33,04 AH+31,40 Téq= 677 C avec AS variation d'entropie , AH d'enthalpie et Téq la température d'équi- libre sous une pression de 1 bar.

C02 + Cs ===> 2CO AS = 42.14 AH = 41.23 Teq = 705 C H20 + Cs ===> CO + H2 AS = 33.04 AH + 31.40 Teq = 677 C with AS variation d entropy, AH enthalpy and T eq the equilibrium temperature under a pressure of 1 bar.

There is still a possible explanation of the beneficial effect of H 2 O and CO 2 which suitably used in the injector tends to remove the solid carbon that may be inadvertently formed.

As can be seen from these examples, the measurement of the physical characteristics and particularly the refractive index makes it possible to follow the direction of the evolutions of the conversion products and to control the latter.

We will better understand the object of our invention which is to work in conditions avoiding losses of hydrogen, because this loss of hydogen creates unsaturates that evolve towards weak nuclei.

Puis la chaîne insaturée se plie et se ferme : AS AH
Téq: 941 K (668 C) -20,65 -19,44

La température de fusion passe de -95 C à + 6 C avec seulement 6 carbones. If we take the straight chain below, brought to high temperature, it will start to lose hydrogen, according to the diagram:

Then the unsaturated chain folds and closes: AS AH
Téq: 941 K (668 C) -20.65 -19.44

The melting temperature goes from -95 ° C. to + 6 ° C. with only 6 carbons.

It was therefore found that at no time should we approach these temperatures of the order of 650 C on the one hand, nor be able to provide the required energy in this case, on the other hand; thermodynamics given above giving orders of magnitude.

In addition, it is found that if we started to dehydrogenate, the reaction is racing because cyclization releases energy.

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Here's what could happen if you had a more violent energy intake:

La chaîne fortement déshydrogénée se ferme : AS AH Tég-33810K -20,4 -68,98

ARRACHER UN H2 à une CHAINE DROITE :
CREE environ: &S/H2= +30,19 et DEMANDE environ : &H/H2= +32,18 Fermer un cycle libère de l'énergie ( et diminue &$ de 20,5 environ) Notre invention ,après une mise en condition initiale des produits convenables grâce à notre injecteur permet de réaliser l'initiation et l'activation des réactions en respectant les règles ci-dessus et les ordres de grandeurs à ne pas dépasser.

The strongly dehydrogenated chain closes: AS AH Teg-33810K -20.4 -68.98

STOP H2 an RIGHT CHAIN:
CREATE about: & S / H2 = +30,19 and DEMAND about: & H / H2 = +32,18 Close a cycle releases energy (and decreases & $ 20,5 approx) Our invention, after a conditioning initial of the suitable products thanks to our injector allows to realize the initiation and the activation of the reactions by respecting the rules above and the orders of quantities not to be exceeded.

We will now give another interest of the presence of H20 which somehow behaves as a blocker of cyclization réartions.

Heavy crudes contain very few simple and straight molecules, they contain many polyaromatic complex molecules more or less bound together as can be seen on the molecule below which easily condenses and goes from 2 to 3 nuclei according to the following diagram :

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On constate au passage que la création d'un troisième noyau central augmente fortement la densité de cette molécule.

It can be seen in passing that the creation of a third central nucleus greatly increases the density of this molecule.

With H20 vapor, one can operate by step to break this molecule of 14 carbons and even show how can be absorbed a light molecule of 3 carbons which otherwise would have given gas.

A>-CH:CH-<A + H20 ===> l>-CHH-CH2-<( -29,96 / -12,50 Tf=124 Téb=307 C Tf=68 Téb=170/15 2 Etape : CRAQUAGE CENTRAL de la molécule: A>-CHôH-CH2-<A ===> A>-CHO + H3C-<A +26,27 / +39,31 Tf=-26 Téb=178 Tf=-94 Téb=110 3 Etape : FUSION et REJET de H20 (réalisés à coup sûr) A>-CHO + C3H8 ===> A>-C2-CH:CH2 + H20 -2,04 / -14,36 Tf=-33 Téb=190 4 Etape : Cyclisation Branche Insaturée (naturelle) A>-C2-CH:CH2 ===> A:Cyc6Csat -15,44 / -19,90 Tf=-43 Téb=195 A>-CH:CH-<A + C3H8 ===> A:Cy6sat + A>-CH3 -21,17 / -7,45 rrnnnnVnnrrrrn nrrnnvwnn nnnllnn Tf=124 Téb=307 C Tf=-43 Téb=195 Tf=-94 Téb=110 FOL Golécrer Essence 1 Step: embrittlement The unsaturated central link: AS / AH

A> -CH: CH- <A + H20 ===>l> -CHH-CH2 - <(-29.96 / -12.50 Tf = 124 Teb = 307 C Tf = 68 Teb = 170/15 2 Step : CENTRAL CRACKING of the molecule: A> -CH6H-CH2- <A ===>A> -CHO + H3C- <A +26,27 / +39,31 Tf = -26 Tb = 178 Tf = -94 Teb = 110 3 Step: FUSION and RELEASE H20 (definitely) A> -CHO + C3H8 ===>A> -C2-CH: CH2 + H2O -2.04 / -14.36 Tf = -33 Tb = 190 4 Step: Cyclization Branch Unsaturated (natural) A> -C2-CH: CH2 ===> A: Cyc6Csat -15.44 / -19.90 Tf = -43 Teb = 195 A> -CH: CH- < A + C3H8 ===> A: Cy6sat + A> -CH3 -21.17 / -7.45 rrnnnnVnnrrrrn nrrnnvwnn nnnllnn Tf = 124 Tb = 307 C Tf = -43 Tb = 195 Tf = -94 Tb = 110 FOL Golecrer gasoline

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 It can be seen that the intermediate stages of the reaction are carried out with moderate energies and that everything happens as if the water engaged at the beginning is restored at the end (in the manner of a catalyst).

Note also, which is one of our concerns and a characteristic of our process, that the initial melting temperature of 127 C after the first step is down to -26 C, then -33 C; in the fourth step it was -43 C and finally in the fifth stage products are obtained which have a melting temperature of -94 C.

There is therefore a continual decrease of this melting temperature during the intermediate stages of the progress of the overall reaction.

Experience has shown that we have very low gas and carbon production and that we can completely convert products such as Vacuum Residues or Asphalts into liquid hydrocarbons.

Now take the case RIGHT CHAINS (with 14 unsaturated carbons for this example): Without H20 we have: AH Cel4 =====) C7H16 + C2é7H12 36,04 / 19,57
The cracking in the presence of H 2 O seems to be according to the following scheme:

<Tb>
<tb> AS <SEP> close
<tb> Cel4 <SEP> (C14-H28) <SEP>=====><SEP> Ce7-H13). <SEP> + <SEP> (C7-H15) <SEP> 43.71 <SEP> / <SEP> 59.98
##
<tb> .C7H15 <SEP> +. <SEP> H <SEP>=====><SEP> C7H16 <SEP> -30.72 <SEP> / -87.3
<tb> Ce7Hl3δH <SEP>====><SEP> C2e7-H12 <SEP> + <SEP> H20 <SEP> 21.14 <SEP> / <SEP> 9.0
<tb> Let <SEP> at the <SEP>total;
<tb> Cel4 <SEP>=====><SEP> C7H16 <SEP> + <SEP> C2d7H12 <SEP> 36.04 <SEP> / <SEP> 19.57
<Tb>
It can be seen that in these operations it was necessary: first: - OPEN A DC CONNECTION which requires approximately 40 to 60 KCAL (ACTIVATION 1 and finally: - PROVIDE ABOUT 20 KCAL / CUT (SPECIFIC NET ENERGY) It must be remembered that 'RESTORE H2 REQUEST approximately: & H / H2 = +32 KCAL and if this is done we get bad results.

It was therefore necessary to find a set of devices to best respect the various specifications above, which we obtain by means of an adequate preheating of the load, followed by an activation favored by a relaxation in the injector , the products to be converted can have in term of temperature equivalent a very short excursion in a field where they are unstable, the rupture consuming the energy which brings the reactants back to the stable and desired domain of the reactor in which they are then placed. to thermodynamic equilibrium (a cook would say: to make them properly "simmer").

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These reactions and their mechanisms are only given here to try to understand why we are getting unexpected results of conversion with our process.

 The in-depth examination of the results of our tests taught us how to treat a given load and also the problems related to the structure of the complex material of these heavy products, all of which has been said above. being a guide to the necessary adjustments.

It is quite obvious that we took advantage of all these experiments to build a database of thermodynamic data and physical properties of which here is an extract for information for families with 1 and 10 carbons per molecule: Physical and Thermodynamic Properties *** ******************** Family (1) name Tf C Teb CS AHf dn Tc K Pc Vc zc CH4-186 -165.0 44,49-17,89 0.415 .gau .. 190.7 45.8 99 0.290 CO -199-191.0 47.30-26.41. 0.793 .gases 133.0 34.5 93 0.294 H2CO 92 -21.0 52.26 -28.00 0.815 .gass .. 410.0 67.0 112 0.223 H3CÔH -97.1 64.7 57.00 -48.05 0.812 1.3288 513.2 78.5 118 0.220 HCOÔH +8.3 100.7 59.40-90.50 1.220 1.3714 581.0 71.8 117 0.166 ******* ************************************************** ************** Physical and Thermodynamic Properties ********************** Family (10)

<Tb>
<tb> PJ-Mend
<tb> units <SEP> C <SEP> C <SEP> cal / m <SEP> Kcal / m <SEP><-to<SEP> 20 C <SEP>-><SEP> K <SEP> bar <SEP > CC / m <SEP> g / m
<tb> Names <SEP> Tf <SEP> Tb <SEP> S <SEP> AHf <SEP> d <SEP> n = 1, <SEP> Tc <SEP> Pc <SEP> Vc <SEP> PM <SEP> zc = 0, <SEP> Str
<tb> ----------- <SEP> --- <SEP> ---- <SEP> ---- <SEP> ------ <SEP> ---- - <SEP> (n-1) <SEP> --- <SEP> ---- <SEP> ---- <SEP> --- <SEP> ---- <SEP> --C10H8 <SEP > nl4 <SEP> 80 <SEP> 218 <SEP> 80.5 <SEP> 36.1 <SEP> 0.963 <SEP>, 5898 <SEP> 748 <SEP> 40.0 <SE> 413 <SE> 128 <SEP>, 269 <SEP> TO: A
<tb> C10H12 <SEP> t98-36 <SEP> 207 <SEP><83.2<SEP>4.2> 0.970 <SEP>, 5414 <717 <SEP> 33.0 <SE>478> 132 <SEP >, 268 <SEP> Cy6
<tb> C10H14 <SEP> n189 <SEP> .. <SEP> 200 <SEP><84.5<SEP>-11.7> 0.934 <SEP>, 5260 <707 <SEP> 30.6 <SEP> 500 > 134 <SEP>, 264 <SEP> 2A-6H
<tb> C10H18 <SEP> d6 <SEP> -43 <SEP> 195 <SEP> 87.1-43.6 <SEP> 0.897 <SEP>, 4810 <SEP> 687 <SEP> 25.8 <SEP> 543 <SEP> 138 <SEP>, 249 <SEP> 2Cy6
<tb> C10H18 <SEP> d74-36 <SEP> 174 <SEP> 125.3 <SEP> 9.85 <SEP> 0.766 <SEP>, 4265 <SEP> 623 <SEP> 25.8 <SEQ> 587 <SEP> 138 <SEP>, 297 <SEP> aClO
<tb> C10H20 <SEP> d66-66 <SEP> 171 <SEP> 129.2-29.3 <SEP> 0.741 <SEP>, 4215 <SEP> 616 <SEP> 25.0 <SE> 592 <SEP> 140 <SEP>, 292 <SEP> eClO
<tb> C10H22 <SEP> d20-30 <SEP> 174 <SEP> 130.2-59.7 <SEP> 0.730 <SEP>, 4102 <SEP> 619 <SEP> 20.8 <SEP> 602 <SEP> 142 <SEP>, 246 <SEP> nC10
<tb> C10H200 <SEP> d18 <SEP> -5 <SEP> 208 <SEP> 137.7-78.9 <SEP> 0.830 <SEP>, 4287 <SEP> 636 <SEP> 24.4 <SEP> 605 <SEP> 156 <SEP>, 278 <SEP> Ald.
<Tb>

C10H21OH <SEP> d57 <SEP> +7 <SEP> 229 <SEP> 142.1-96.4 <SEP> 0.830 <SEP>, 4372 <SEP> 667 <SEP> 29.8 <SE> 619 <SEP> 158 <SEP>, 337 <SEP> ale.
<Tb>

C10H190OH <SEP> d42 <SEP> 32 <SEP> 270 <SEP> 142.3-143, <SEP> 0.886 <SEP>, 4288 <SEP> 717 <SEP> 29.4 <SE> 644 <SE> 172 <SEP>, 322 <SEP> Acid
<Tb>

~~~~~~~~~~~ ~~~ ~~~~ ~~~~ ~~~~~~ ~~~~~ (n~1) ~~~ ~~~~ ~~~~ ~~~ ~~~~ ~~~ ********************************************************************** Noter le classement : Alcanes/ Acénes/ Alcyne/ Cyclo/ Aromatiques Les notations sont :
Tf : température de fusion , Téb : température d'ébullition
S : Entropie Standard , AHF : Enthalpie Standard de formation d : densité , n : Indice de réfraction
Tc: Température critique , Pc : Pression critique
Vc: Volume critique , zc : Facteur de compressibilité
Str : Structure en abrégé :
A noyau aromatique , Cy Cycle saturé ä acétylénique , é éthylénique , n normal paraffinique 0 oxygène en double liaison , öH groupe fonctionnel OH ( Ces données concourent à suivre, connaître, ou prévoir l'état de la matière dans les conditions diverses où on la traite, ainsi que les équilibres thermo dynamiques possibles . Ces données nous permettent aussi de prévoir

~~~~~~~~~~~ ~~~~~~~ ~~~~ ~~~~~~ ~~~~~ (n ~ 1) ~~~ ~~~~ ~~~~ ~ ********* ***************************** Note the classification: Alkanes / Acenes / Alcyne / Cyclo / Aromatic The ratings are:
Tf: melting temperature, Tb: boiling temperature
S: Entropy Standard, AHF: Standard formation enthalpy d: density, n: Refractive index
Tc: Critical temperature, Pc: Critical pressure
Vc: Critical Volume, zc: Compressibility Factor
Str: Abbreviated structure:
Aromatic ring, Cy Acetylenic saturated, ethylenic, normal paraffinic 0 double bonded oxygen, OH functional group (These data combine to follow, know, or predict the state of the material in the various conditions in which it is present. as well as the possible thermodynamic equilibrium, which also allows us to predict

<Desc / Clms Page number 14>

 the chemical irreversibilities responsible for carbon production and hydrogen rejection in particular) Finally, we will show a guideline that we used a lot in the analysis of these problems, seen in a new light mechanic.

Let's take an isoC4 cyclo C6:
At first, the molecule must be twisted from the expanded, free and natural form to the folded form, which requires energy.

 If then we remove each end of the folded isoC4 branch, close to the C6 cyclo ring and also removing the corresponding hydrogen, we establish two new carbon-carbon bonds.

The molecule thus formed with only 10 carbons is a real cage with the following astonishing physical properties: C10H16 a742 Tf = 268 Teb: Sublime Density = 1.070 n = 1.5680 C10H20 c686 Tf = -94 Teb: 171 Density = 0.795 n = 1,4386 conparées to the starting molecule.

The benchmarks we have given are those of: Handbook Chemistry and Physics

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C10H20 c686 Tf=-94 Téb:171 Densité= 0,795 n=l,4386 H Molécule : \ H,,H C H C,H * ou / H, / * Ç -H <CycloC6>-C-C,H H * * /H H' \ \ * * Ç -H C,H H- Ç * H"H * ... * H H Représentée * * \ / repliée * H--H . -H * * o * * C - H * * o H - C -H * C- H * :* / \ C H H \ H H

(;lUtilb a t4 'l'I=6b23 TeD: :5UDllme venSHe= 1, u tU n=l,5auu H \ Ç H Molécule Réf a742 *-o * , / ayant: * <1-H 4 jC-H H * 0* /H rrrrnnmnn \ * * o -H et H- * 4 Cycles à 6Carbones ...1 .., .. *..: *0 H * * 0 / * H - ~0 - -. -H * * o 0 * * C - H * * 0 fj ~ O 0*0 0 0 or H * :* \ Remarquer la structure C H " CAGE / \ H H Notons que ces molécules cages,(particulièrement si elles sont aromatiques), deviennent de véritables "nids"ou"sandwiches" pour les métaux et les organe-métalliques dont on va parler maintenant.

C10H20 c686 Tf = -94 Teb: 171 Density = 0.795 n = 1.4386 H Molecule: H, HCHC, H * or H, / -H <CycloC6> -CC, HH * * / HH ' \ * * Ç -HC, HH- * H * H * ... * HH Represented * * \ / collapsed * H - H. -H * * o * * C - H * * o H - C - H * C- H *: * / \ CHH \ HH

## STR1 ## where ## STR1 ## is a compound of the formula ## STR1 ## wherein: ## STR2 ## H * 0 * / Hrrrnnmnn \ * * o -H and H- * 4 Cycles to 6Carbones ... 1 .., .. * ..: * 0 H * * 0 / * H - ~ 0 - -. - H * * o 0 * * C - H * * 0 fj ~ O 0 * 0 0 0 or H *: * \ Note the structure CH "CAGE / \ HH Note that these molecules cages, (especially if they are aromatic), become real "nests" or "sandwiches" for the metals and metal-organ that we are going to talk about now.

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CONTENT IN CONTAINERS AND OTHER IMPURITIES OF BRUTS and RESIDUES By fractionating a typical vacuum residue by the well-known refining techniques, with Propane C3, Butane C4, Pentane C5, the following extracts and raffinates are obtained:

<Tb>
<tb> POSITION <SEP> * <SEP> DAO <SEP> C3 <SEP> * <SEP> ExC4 <SEP> * <SEP> Ex <SEP> C5 <SEP> * <SEP> Asp <SEP> C5 <SEP > * <SEP>"""""" RSV <SEP> *
<tb>% <SEP> LOAD <SEP> RSV <SEP> * <SEP> 18.7 <SEP> * <SEP> 33.7 <SEP> * <SEP> 30.4 <SEP> * <SEP> 17 , 5 <SEP> * <SEP> 100 <SEP>% <SEP> RSV <SEP> *
<tb> Sediment <SEP> * <SEP> * <SEP> * <SEP> * <SEP> 0.096% Wt <SEP> *
<tb> Sulfur <SEP>% Rsv <SEP> * <SEP> 0.53 <SEP> * <SEP> 1.62 <SEP> * <SEP> 1.62 <SEP> * <SEP> 1.23 <SEP> * <SEP> 5.0 <SEP>% WPS <SEP> *
<tb> Nickel <SEP> ppmRsv * <SEP> 0.2 <SEP> * <SEP> 10.2 <SEP> * <SEP> 14.4 <SEP> * <SEP> 17.2 <SEP> * <SEP> 42 <SEP> *
<tb> Vanadium <SEP> ppmRsv * <SEP> 1.0 <SEP> * <SEP> 32.3 <SEP> * <SEP> 47.2 <SEP> * <SEP> 55.5 <SEP> * <SEP> 136 <SEP> *
<tb> NaCl <SEP>% <SEP> Wt <SEP> * - <SEP> * - <SEP> * <SEP> 0.0003 * <SEP> 0.0107 <SEP> * <SEP> 0.0110 <SEP> *
<tb> --------------- <SEP> -------- <SEP> ------- <SEP> ------- <SEP> -------- <SEP> -------------- *
<tb> H / C <SEP> * <SEP> * <SEP> 1.64 <SEP> * <SEP> 1.35 <SEP> * <SEP> 1.22 <SEP> * <SEP> 1.18 <SEP> * <SEP> H / C = 1.33 <SEP> * <SEP> *
<Tb>
DAO is the product called Desasphalted Oil; ExC4 is the C4 extract; ExC5 extract C5 and Asp C5, the resulting residual asphalt.

The metals, NaCl, Sulfur, are concentrated in the highly aromatic heavy molecules low in hydrogen.

These residues give by combustion ashes which have a typical relative composition indicated below:
Ashes: Si02: 32 Fe203: 25 Na: 16 Va: 14 Ni: 6 Al: 6 Now we know that towards 550 -600 C appear eutectics (glasses)
Silica + Classic Glass Soda (Silicate)
Silica + V205 Vanadium glass
Silica + Nickel ==> Nickel glass
Silica + Ash ==> Iron Glass, Ni, Etc ..

We see that any catalyst is inevitably "sent" by metals.

Our maturation reactor being Vacuum endures long steps without rapid deposits on the walls, because on the other hand, it was found that for other considerations, it should operate in this case to 460 -480 C.

The metals are therefore driven and extracted by the heaviest liquid products.

Engine oils have been converted which, they have an interest in having a reactor at 500 - 520 C. It was found that there were small incombustible deposits on the walls of the maturing reactor.

This has led us to generalize the technique of mechanical cleaning of extraction of carbon residues accompanied by metal deposits, preferably burning (which leaves deposits of metals and ash on the walls).

 Again, the maturation reactor being empty, there is no difficulty to conduct this operation of scraping and peeling mechanical.

Sulfur is not a problem.

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 CONTROL OF THE APPEARANCE OF GAS, COKE or SOLID CARBON RESIDUES One of the surprising characteristics of our process is to allow to convert asphalts without significant carbon creation or gas rejection.

We will try to explain why this result can be obtained, the light of knowledge that we have acquired by trying to interpret what we observed.

With an appropriate means (mechanical, thermal, electrical or chemical ..), we can always transfer an energy that we will call AH (variation of enthalpy) according to the terms adopted in thermodynamics.

Our experience in monitoring the state of matter has led us to constantly ask a key variation of this state that can be summarized by AS the variation of entropy. Indeed, by referring to the tables that we have already presented, one realizes that there are very strong correlations between S and the physical parameters of fusion and boiling and more generally of changes of state or of organization of the material.

To clarify the ideas, we will take an unsaturated molecule with 14 carbons ************************************ ***********************************

<Tb>
<tb> ENTER <SEP># ----------- <SEP> OUTPUTS <SEP> AS <SEP> AH <SEP> Teq C
<tb> *************** <SEP> ******** Liquid ********* <SEP> GAS <SEP> **** * <SEP> ***** <SEP> *****
<tb> Cel4H28 <SEP>====><SEP> Ce7H14 <SEP> + <SEP> Ce7H14 <SEP> ... <SEP> 36.06 <SEP> 19.18
<tb> ------- v -------- <SEP> ------- v ------- <SEP> --- v --- <SEP> ----- <SEP> ----- <SEP> 269
<tb> Tf = -13 <SEP> Teb = 251 <SEP> Tf = -119 <SEP> Teb = <SEP> 94 <SEP> Liq
<tb> d = 0.771 <SEP> n = 1.4335 <SEP> d = 0.697 <SEP> n = 1.400
<tb> Cel4H28 <SEP> ====) <SEP> Ce12H24 <SEP> + <SEP> Ce2H4 <SEP> 33.83 <SEP> 22.33
<tb> ------- v -------- <SEP> ------- v ------- <SEP> --v-- <SEP> - --- <SEP> ----- <SEP> 387
<tb> Tf = -35 <SEP> Tb = 213 <SEP> Gas
<tb> d = 0.755 <SEP> n = 1.430
<tb> C18H28 <SEP>====><SEP> C11H24 <SEP> + <SEP> CH4 <SEP> 36.39 <SEP> 26.54
<tb> ------- v -------- <SEP> ------- v ------- <SEP> --v-- <SEP> - --- <SEP> ----- <SEP> 456
<tb> Tf = -5 <SEP> Tb = 234 <SEP> Gas
<tb> d = 0.784 <SEP> n = 1.43
<tb> C13H28 <SEP> ==== # <SEP> C14HJ26 <SEP> + <SEP> H2 <SEP> 27.41 <SEP> 39.50
<tb> ------- v -------- <SEP> ------- v ------- <SEP> --v-- <SEP> - --- <SEP> ----- <SEP> 1168
<tb> Tf = -0 <SEP> Tb = 252 <SEP> Gas
<tb> d = 0.789 <SEP> n = 1.439
<tb> C13H28 <SEP> ==== # <SEP> C7H12 <SEP> + <SEP> C7H14 <SEP> + <SEP> H2 <SEP> 63.48 <SEP> 64.02
<tb> ------- v -------- <SEP> ------- v ------- <SEP> --v --- <SEP> - -v-- <SEP> ----- <SEP> ----- <SEP> 720
<tb> Tf = -81 Tb = 93.8 <SEP> Liq. <SEP> Gas
<Tb>
************************************************** *********************** This table shows us that the more we bring energy, the more we break the molecules, the more we create fragments it is to say that the more we create disorder (which increases AS), the more we create CH4 and finally the more we reject hydrogen.

 In addition, the quotient AH / AS gives us the Teq temperature at which the reactants are naturally at equilibrium under a pressure of lbar.

<Desc / Clms Page number 18>

 If one wishes to have only liquids, everything happens as if one were to limit oneself to 20 kcal / molecule as already indicated elsewhere.

(This also explains in passing why a FCC with its regenerated catalyst at over 700c will reject hydrogen and CH4.) No catalyst can change this state of affairs .11 can only favor intermediate steps and their speed, allowing the reactants to make up the equilibrium thermodynamic equilibrium according to the temperature of the reactor) Another characteristic of our invention is that it makes it possible to control the degree of conversion into liquid without creating an excess of light gases such as methane, ethane. We will try to give an explanation which appeared to us during the various tests that we made, relating to the chemical irreversibilities (which seem not to be often evoked) One of the characteristics of our process is schematically to split in two the molecules and start over to stay in control of the process flow.

Some might say that, to go faster, it is necessary to use more energy which actually allows to create more light molecules as shown in the table above, including a lot of gas, thinking that then it will still be possible to polymerize them to return to liquids. We then come up against a total impossibility of carrying out this operation properly as a result of the chemical irreversibilities (no catalyst will be able to circumvent it) To fix the ideas suppose that we envisage to create liquids starting from methane, ethane etc. ..

(A) (B) (C) Cnl =?=) H2 + Cn2 =?=> H2 + Cn4 =?=> H2 + Cn8 Téb 117 K 184 K 272 K 399 K Etat normal GAZ GAZ GAZ 298 K LIQUIDE Conséquences : 1 / Il faut ACCEPTER la CREATION FATALE du CH4 dans ce procédé,schématisée par la réaction globale C': C') C4H10 + C4H10 ===) C7H16 + CH4 AS=-1,53 AH=-2,48 Téq=1620 K soit: 2 Cn4 ===) Cn7 et Cnl Kéq(600 C)=l,93 ( Cette réaction est possible car Téq positive ) Our wish would then be to carry out reactions such as: A) CH4 + CH4 == ?? ==> C2H6 + H2 AS = -1.95 AH = + 15.54 Teq = -7669 KB) C2H6 + C2H6 ==? ? ==> C4H10 + H2 AS = -3.38 AH = + 10.33 Teq = -3056 KC) C4H10 + C4H10 == ?? ==> C8H18 + H2 AS = -O, 54 AH = + 10.48 Teq = -19400 K
THESE REACTIONS ARE IRREVERSIBLE because NEGATIVE TESTING DOES NOT EXIST and we will never be able to reversibly carry out the following reactions:

(A) (B) (C) Cnl =? =) H2 + Cn2 =? => H2 + Cn4 =? => H2 + Cn8 Teb 117 K 184 K 272 K 399 K Normal state GAS GAS GAS 298 K LIQUID Consequences: 1 / It is necessary to ACCEPT the FATAL CREATION of CH4 in this process, schematized by the global reaction C ': C') C4H10 + C4H10 ===) C7H16 + CH4 AS = -1,53 AH = -2,48 Teq = 1620 K = 2 Cn4 ===) Cn7 and Cnl Keq (600 C) = 1.93 (This reaction is possible because Teq positive)

<Desc / Clms Page number 19>

2 / IF THERMODYNAMIC REVERSIBILITY IS VIOLATED WITH ENERGY: according to the reaction C ": It MUST REJECT HYDROGEN C") C4H10 + C4H10 ===> C8H18 + H2 AS = -0.54 AH = + 10 , 48 Teq = -19400 K (This reaction is irreversible because Teq is negative) C "/ Even the passage through Synthesis gas which starts with the reaction below:
CH4 + 1/2 02 === # CO + 2H2 AS = + 42.7 AH = -8.52, (reaction which can be explosive) is IRREVERSIBLE and will lead to an overall IMPROPER EFFICACY in liquefaction by methanol or Fischer -Tropsch.

 This can only be done with parasitic reactions giving C2H2 in particular.

PRACTICAL CONCLUSION: IT SHOULD BE PREVENTED IN THE FIRST PLACE TO CREATE GASES.

 This is exactly what our process does.

 CARBON DEPOSITS The experience of controlling the appearance of coke led us to think that there were two main origins: - a massive deposits path via the polyaromatic nuclei - a pulverulent carbon path via the gases.

It is rather easy to conceive by a simple visual design that if the material polymerizes into numerous contiguous polyaromatic nuclei, the carbons then being directly bonded to each other and having no or little hydrogen bonding, as we have already seen, the temperature melting point increases with the number of nuclei and the decrease in the H / C ratio (C10H8 Tf = 80 C C20H12 Tf = 278 ° C); we are getting closer and closer to a solid coal.

This can be further examined with our method of studying chemical irreversibilities as an indication.

To fix ideas, take benzene and try to crack it.

Cette réaction est irréversible car téq ne peut être négative. Il faut rajouter la réaction parasite fatale:

Pour avoir AS = 0.0 ,il faut prendre 1,17/259 de la réaction (2],soit:

D'on la réaction globale: A fusion of the molecules with one more rejection of H2 is observed, according to the reaction:

This reaction is irreversible because teq can not be negative. We must add the fatal parasitic reaction:

To have AS = 0.0, it is necessary to take 1,17 / 259 of the reaction (2), ie:

From the global reaction:

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<Tb>
<tb> [1] <SEP> + <SEP> ==== # <SEP> A) - <A <SEP> + <SEP> H2-1.17 <SEP> +3.46
<Tb>
<tb> [3] <SEP> 0.0045 <SEP> A <SEP> ==== # <SEP> 0.0045 ~ 6Cgas <SEP> + <SEP> 0.013H2 <SEP> +1.17 <SEP > +4.55
<tb> 2.0045 <SEP> A <SEP> ====) <SEP>A> - <A <SEP> + 1.01.H2 <SEP> + <SEP> 0.004 <SEP> (6Cgaz) <SEP> 0.00 + 8.01
<tb> and <SEP> the <SEP> return <SEP> of <SEP> 6Cgaz <SEP> in <SEP> Csol = Coke
<tb> 0.0046Cgaz <SEP>====><SEP> 0.004.Coke <SEP> -1.16-4.55
<tb> 2.0045 <SEP> A <SEP> ==== # <SEP> Ä # - # Ä <SEP> + 1.01.h2 <SEP> + 0.004.Coke <SEP> -1.16 <SEP> +3.46
<Tb>
Experimental data at 750 C with Conversion 50% in 40 s confirm the predicted values found above and thus reinforce us in what not to do.

THE CONCEPT OF IRREVERSIBILITY ALLOWS A GOOD PREDICTION OF COKE PRODUCTION CONSIDERED AS THE HARDEST PARASITE REACTION.

The second way of appearance of the powdery deposits of carbon is the acetylene path, of which some indicative data are recalled for 4CH4 involved.

<Tb>
<Tb>

CH4 ===> C2H4 ===> C2H2 ===) Csol pulvérulent \ \ C6H6 ==> Polymérisation CSol Massif Quoiqu'il en soit et dans la pratique: 1 / Dans tous les cas la création de gaz légers saturés est à éviter . * ------------------------------------------------- ------------- TEQ <SEP> C
<tb> (21) <SEP> 4CH4 <SEP> === # <SEP> 2 <SEP> C2H6 <SEP> + <SEP> 2H2 <SEP> AS = <SEP> -3.84 <SEP> AH = +31.08 <SEP> - /// K
<tb> -.............................................. ................ ***** -
<tb> (22) <SEP> 4CH4 <SEP> === # <SEP> C2H4 <SEP> + <SEP> 2H2 <SEP> + <SEP> 2CH4 <SEP> AS = + 27.89 <SEP> AH = + 48.66 <SEP> 1472 C
<tb> (23) <SEP> 4CH4 <SEP> === # <SEP> C2H2 <SEP> + <SEP> 3H2 <SEP> + <SEP> 2CH4 <SEP> AS = + 55.65 <SEP> AH = + 89.95 <SEP> 1343 C
<tb> (24) <SEP> 4CH4 <SEP> === # <SEP> 4Csol <SEP> + <SEP> 8H2 <SEP> AS = + 85.2 <SEP> AH = + 71.4 <SEP> 565 C
<tb> (25) <SEP> 4CH4 <SEP> === # <SEP> 4Cgaz <SEP> + <SEP> 8H2 <SEP> AS = 230.76 <SEP> AH = 793.16 <SEP> 3164C
<tb> Note: <SEP> TfdeC: sublime <SEP> to ...., ................ <SEP> 3379 C
<Tb>
THERMAL DECOMPOSITION OF CH4: Reaction (24) indicates that above 565C CH4 decomposes with slow kinetics, about 1 hour at 800C), because in fact it is necessary to go through the gaseous state summarized by the reaction (25) The filiation scheme showing the pulverulent carbon seems to be:

CH4 ===> C2H4 ===> C2H2 ===) Csol powder \ \ C6H6 ==> Polymerization CSol Massif In any case and in practice: 1 / In all cases the creation of saturated light gases is to avoid .

2 / The appearance of free hydrogen is a bad sign.

3 / The creation of unsaturated light gases and hydrogen is an alert.

4 / The creation of acethylene is a serious alarm.

5 / The monitoring of aromatization via the refractive index is very useful to know if the processes are going well.

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EMULSIONS One of the features of our process is the use of oxygenated intermediates, which when converted to steam naturally give stable Water / Hydrocarbon emulsions.

It has long been known that the combustion of difficult fuels is greatly improved by adding 5 to 10% water.

This contribution during the first moments of the combustion makes it possible to crack the heavy molecules while avoiding their polymerization in polyaromatics which would give nodules of soot or pulverulent carbon.

ELF presented to the press on August 5, 1997 a product called Aquazole containing 10 to 20% of water, indicating that the major problem is the guarantee of the stability of the mixture .Currently this stability can be assured only of 15 days to one month despite the use of a special mixing procedure and especially thanks to special additives.

We understand all the interest directly present in the intermediate emulsions produced by our process, emulsions which can become a main objective for these applications.

We have emulsions that are already 8 years old and are still stable: this shows that we dominate the difficulties faced by ELF.

These advantages can be explained by internal molecular bonds which, in the anhydrous state, are unsaturated and have remained partially bound to water. We could also highlight all the oxygenated intermediates that we have already presented in the literature. control of the cracking operations towards 440 - 600 which have a favorable balance towards 200 -220 C operating temperature of our extractor.

Anyway: 1 / We obtain stable emulsions EAu / Hydrocarbon whose water content can be fixed simply by fixing in our conversions the ratio H20 / (X), in the gases used in our conversion, X being preferably C02 + Y, Y can be any N2 gas, H2 etc ...

This means that the dry smoke (taken before 200 C under lbar) from combustion is the case.

2 / The products formed (Essences, Kero in particular) contain bound water.

3 / While imposing itself to use only water vapor for reasons of simplicity and ease of implementation, our process allows to obtain according to the adopted settings: - either oxygenated and hydrated products.

 - essentially essentially anhydrous products.

Indeed the useful recipes are presented, when working with water vapor, in the form of emulsions which give: a light emulsion called "light": d = 0.89 to 0.92 an emulsion "mayonnaise" heavier: d = 0.93 to 0.96 which are frankly separated from an excess of water-process d = 1.0 (if this excess exists, which is not the case in the example below) below)

<Desc / Clms Page number 22>

The "mayonnaise" (of which 8-year-old samples have not moved) is broken easily by various mechanical means such as forced passage through a series of crossed canvases (operation that we will call extrusion). The dry sand immediately breaks the emulsion, there are still other mechanical possibilities such as rolling balls in the emulsion, etc.

P Poids en g V Volume en Cm3 , Dp/V : densité =Poids/Volume da : Densité (lue par densimètre ) dn déviation lue du réfractomètre donnant l'indice de réfraction n. Here is an example of the analysis of the characteristics of these emulsions, with the notation:

P Weight in g V Volume in Cm3, Dp / V: density = Weight / Volume da: Density (read per densimeter) dn deviation read from the refractometer giving the refractive index n.

MAYONNAISE Ptotal Ptare Net weight Dp / V da dn n Total mayonnaise: 1700,0 - 698,31 = 1001,69 0,9656 13,5 1,50625 Extruded water 1163,8 - 444,13 = 719, 67 ~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ********** - # --- --- # ------------ Hc light extruded: 282.02 13.0 1.50099 BC clear direct: 731.36- 311.412 419.95 0.8916 0.902 13.3 1, 50310 ***************** ********** total 701,97 UAE / HCototal ratio 719,67 / 701,97 = 1.02 With the operating conditions adopted , which will be described elsewhere, useful products did not contain free water (aqueous phase d = 1.0).

The distillation of the direct and extruded clear phase gave the results below: Summary DISTILLATION 1 WITHOUT SAND and without agitation ********** ~ Recipes ~: Volumes Weight Cut Ptot Ptar P g Vt V.eau V. HC HC, dry Dp / V dn N PI - 115 74.95 73.01 1.94 2.4 0.9 1.5 1.04 0.693 8.2 1.44963 Regurgite; 93.11 75.02 18.09 20.2 3.0 17.2 15.09 0.877 12.3 1.49360 200 - 250 84.43 78.06 6.37 8.2 ... 8.2 6 , 37 0.777 9.5 1.46368 250 - 300 91.86 76.73 15.13 17.4 4.0 13.4 11.13 0.830 11.3 1.48297 300 - 360 115.28 77.01 38 , 27 43.8 43.8 38.27 0.874 12.4 1.4946 360 89.15 75.44 13.96 15.5 ... 15.5 13.96 0.901 19.3 1.56567 93.76 7,9 85,86 Summary DISTILLATION 2 IN SAND and without agitation *********** Balloon: 202,78 Balloon + Suport: 214,21 Ball + Sup + Charg: 309,95 g loaded 95,74 g Sand 300, W 610.34 g to cover liquids (total weight engaged)

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~Recettes~: ~Volumes~~ Poids Coupe P.tot P.tar P.g V.t V.ean V.HC HC.sec Dp/V dn N PI - 120 72,50 70,06 2,44 3,25 0,9 2.25 1,54 0,684 6,5 1,43112 120 72,8 72,50 0,3 0,3 0,3 .. - 120 -200 81,17 76,99 4,18 5,6 -.- 5,6 4.18 0,746 8,2 1,44963 200 -250 85,44 78,06 7,38 9,1 1,0 8,1 6,38 0,790 9,5 1,46368 250 -300 95,14 72,87 22,27 26,1 -.- 26,1 22,27 0,853 11,2 1,48191 300 -360 119,05 72,99 46,06 53,0 -.- 53,0 46,06 0,869 12,6 1,49677 Total --------- >82,63 2.2 80,43 Résidu: 95,74 - 82,63= 13,11 0,901 19,0 1,56268
La régurgitation abondante dans le premier cas accompagnée d'une notable quantité d'eau relarguée brutalement démontre que l'on a de l'eau liée avec des forces chimiques modérées .

~ Recipes ~: ~ Volumes ~~ Weight Section P.tot P.tar Pg Vt V.ean V. HC HC.sec Dp / V dn N PI - 120 72.50 70.06 2.44 3.25 0.9 2.25 1.54 0.684 6.5 1.43112 120 72.8 72.50 0.3 0.3 0.3 .. - 120 -200 81.17 76.99 4.18 5.6 -.- 5, 6 4.18 0.746 8.2 1.44963 200 -250 85.44 78.06 7.38 9.1 1.0 8.1 6.38 0.790 9.5 1.46368 250 -300 95.14 72.87 22 , 27 26.1 -.- 26.1 22.27 0.853 11.2 1.48191 300 -360 119.05 72.99 46.06 53.0 -.- 53.0 46.06 0.869 12.6 1 , 49677 Total ---------> 82.63 2.2 80.43 Residue: 95.74 - 82.63 = 13.11 0.901 19.0 1.56268
The abundant regurgitation in the first case accompanied by a notable quantity of suddenly salted water demonstrates that one has water bound with moderate chemical forces.

 By carrying out the distillation of the liquids embedded in the sand, there is a less pronounced "depolymerization" and a weaker release of water.

Anyway this shows us that: 1 / 262g of hydrocarbons "mayonnaise" are able to ally with 719 g of extruded water, or 2.5 times its weight in water.

2 / The "clear and extruded" hydrocarbons already contain in this case 3 to 9% bound H2O.

It can therefore be seen that our process can naturally provide oxygenated compounds or stable water / hydrocarbon emulsions.

Chargé lOOcc 97,81 g Le trafic amorce à 99 C distille entre 100 C et 101 C en eau claire contenant un petit voile floculeux laiteux Résidu 225,93 - 224,89 = 1,04 g Brun foncé Incombustible Avec de petits nodules noirs ****************************************************************************
On voit aussi que l'eau extrait des éléments divers de la charge traitée . We ensured that the outgoing water-process did not carry alcohol or any other carbon compound, proceeding to its distillation summarized below:
WATER-PROCESS ANALYSIS BY 15-tray DISTILLATION

Charged 100cc 97.81 g The traffic primer at 99 C distills between 100 C and 101 C in clear water containing a small milky flocular veil Residue 225.93 - 224.89 = 1.04 g Dark brown Incombustible With small black nodules * ************************************************** *************************
It can also be seen that the water extracts various elements of the treated feedstock.

 This water has an acidic pH that tells us that it has absorbed SH2 or any other acidic element of the charge.

 All this constitutes a set of favorable elements provided by our process using ean steam whose extractive activity increases with the injection temperature and the successive washes in the extraction zone.

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 CONTROL OF THE OXYGENATION OR MOISTURIZATION OF PRODUCTS Another characteristic of our invention is: to control the hydration of the emulsions, or to avoid it.

 - to control the oxygenation of the products, or to avoid it.

We will indicate how to obtain these results with our equipment.

 Recall that with our extractor we can choose the standard of useful products and recycle those that are out of the ordinary.

 So let's take the standard case (chosen objective) Essences or Oxygenated diesel and hydrated emulsion without free water.

 It falls under the direction that one should not send too much water-process to treat the load it is necessary enough.

It has been found that a good ratio WATER / Charge (treated atmospheric residue) was of the order of 1 by weight (This is what appears in the analysis of the results presented above)
If the objective is to go to oxygenated compounds, it is clear that if they are not they are out of the ordinary, especially if we aim to produce gasoline or gasoline type coupes.

 So we had the idea, which is a feature of our invention, to make a first conversion of the atmospheric residue to PI-360 distillates, our extractor-contactor-decanter being set to 200 C, then to iron all these Raffinats (200-) as is, in our facility.

 In fact, during this recycling, equivalents of heavy but atmospheric distillates are converted into lighter products such as gas oil and gasoline. The steam which facilitates these operations, is moreover sufficiently reactive to create the chemical additions highlighted in the distillations of the products (direct distillation or under sand).

Now let's take the opposite standard, for example to satisfy a refining specification of an existing site, which requires standard non-hydrated products (so-called dry products).

So we go in our process to avoid recycling the anhydrous products formed (200-) which tends to hydrate and create oxygenates.

In this case we will operate by recycling only the extracts (200+) with the fresh feed consisting of residues or any load to be converted (200 being a value that may vary depending on the desired recycling).

To understand this well, let's take a Vacuum Residue that will not give an atmospheric distillate in first generation.

Un essai de conversion totale de RSV (père) qui donne DSV (fils) puis qui donne un RaT ( petit-fils) est détaillé ci-après. Recall that a very rough schema is the following filiation:

A total conversion test of RSV (father) that gives DSV (son) and then gives a RaT (grandson) is detailed below.

With this type of recycling and the settings adopted, the conversion products have not been hydrated as shown by their distillation after separation of water and HC from the emulsions. Here, the distillation does not produce water, (contrary to the previous case where one sought to fix it).

 This shows that this problem is well controlled.

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Coupe Atm Pds Dp/v % Pds &%Pds dn n PI -150 = 1,70 0,6872 3,49 3,49 6,5 1,43112 150-200 = 3,89 0,7720 7,98 11,46 7,7 1,44420 200-250 = 8,07 0,8200 16,55 28,01 8,2 1,44963 250-300 =24,96 0,8692 51,19 79,20 9,8 1,46691 300-320 = 5,44 0,8685 11,16 90,36 11,5 1,48511 Résidu = 4,70 9,63 100% Total-----------------) 48,76 (Pertes: 1,24 ) *************************************************************************** Les minutes de la distillation des produits de conversion contenus dans la phase claire et extrudée (voir tableau I ), montrent que l'on n'a pas de relargage mesurable d'eau. On aperçoit bien par les lâchers de vapeurs blanches ou crépitements vers 80 C ,130 C, 150 C, 250 C, 290 C les points-clés de relargage d'eau rencontrés de façon notable dans le traitement avec objectif hydratation et produits oxygénés ;mais ici ils sont quantitativement négligeables .On pourra évaluer leur total par excès en disant, qu'ils sont au plus, égaux aux pertes observées ,soit 3,8 % pour fixer les idées. CONVERSION with EXTINGUISHING RECYCLING: End Conversion to Total Resource depletion-Benchmark (3) - (4) Global useful Summary:

Cut Atm Pds Dp / v% Wt &% Wt dn n PI -150 = 1.70 0.6872 3.49 3.49 6.5 1.43112 150-200 = 3.89 0.7720 7.98 11, 46 7.7 1.44420 200-250 = 8.07 0.8200 16.55 28.01 8.2 1.44963 250-300 = 24.96 0.8692 51.19 79.20 9.8 1, 46691 300-320 = 5.44 0.8685 11.16 90.36 11.5 1.48511 Residue = 4.70 9.63 100% Total ---------------- -) 48.76 (Losses: 1.24) ************************************** ************************************* Minutes of the distillation of the conversion products contained in the phase clear and extruded (see Table I), show that there is no measurable release of water. The release of white vapors or crackling at 80 ° C., 130 ° C., 150 ° C., 250 ° C., 290 ° C. is clearly visible in the key points for the release of water which are noticeably encountered in the treatment with objective hydration and oxygenated products. here they are quantitatively negligible. We can estimate their total excess by saying that they are at most equal to the losses observed, or 3.8% to fix the ideas.

(It should be noted in passing that the transfer of samples from the test specimen into the appropriate test piece to make a more accurate measurement of the volume and weight giving the density Dp / v, is done with losses which are 0.3 g for very light liquids, they are increased to 0.75g for the 300+ atmospheric cut and 2.15 g for the atmospheric residues, due to the flow difficulties related to the increase of the viscosity and to the surface tensions. gives an idea of the attachment effect of the products on the walls which increases with the density and the index of refraction).

Finally for the record, in these tests, remember that the main characteristics of the treated vacuum residue were:
Density 1.01, refractive index 1.594, solid state.

 REACTORS-EXTRACTORS and DISTILLATORY APPLIANCES OF PRODUCTS Our distillation reports of conversion products mention "Regurgitation of products, salted water shots, crackling, etc., which, if they occurred in a conventional distillation unit would "blow up" all distillation trays and their packing.

 According to a new feature of our invention we imagined a device that not only could do this work of distillation without these troubles, but which, moreover, worked as a true reactor-type extractor mixer-decanter, The principle is as follows:

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The suitably preheated or cooled products are sent to a jacketed cylinder containing saturated water with its vapor, which sets the temperature of this jacket simply by setting the pressure of the chamber.

Steam is produced if heat is released.

There is steam consumption if you absorb heat.

The presence of saturating water allows large heat transfers with the internal contents of the reactor-extractor.

In this double vertical envelope, almost isothermal at the temperature defined by the temperature of the saturating water, we dispose a tube or a series of vertical tubes, which rise, to fix the ideas, to the middle of the height of the double envelope.

The upper part is empty.

It serves as a tranquilizer-decanter by choosing a low ascending speed of light products or gases, allowing heavy or liquid products in fog or rain, to fall down.

For that it is enough that the speed of fall of the heavy or liquid products is higher than the speed of rise of the lighter products.

In addition, this space serves as a relaxation for any untimely phenomenon of water blow or brutal release that one would have poorly mastered.

Being empty (no packing in this area), we have no material risk. The heavy or liquid products stay in the bottom of the envelope between the envelope and the vertical tubes.

When all the space between the envelope and the tubes is full, the heavy products are poured inside the vertical tubes and are collected at their lower exit. This extraction is thus automatic and natural.

Incoming products, liquid or gas, are injected at the bottom of the jacket in the heavy or liquid phase at a very moderate speed.

They are therefore dispersed in the heavy phase, mix with it under conditions of temperature and local pressure; the mass transfers are then made by the contacted surfaces and are governed by the differences in concentrations relative to 1 equilibrium of the stationary heavy phase and the incoming dispersed phase.

These balances are defined both by the physical phase separation in the presence and by the legal chemical equilibrium in the existing local conditions.

The incoming products enrich the heavy phase and are depleted of the heavy components transferred. With the light components possibly created, they are found in the light phase that fills the top of the envelope or they decant by separating liquid parts or heavy mists that fall.

This device is particularly advantageous because it can achieve the equivalent of a distillation while working as one would do in liquid-liquid extraction for oils or asphalts, or a chemical reactor.

 Indeed, aromatic products such as furfural have well-known extracting powers for extracting aromatic products in the preparation of lubricants.

Whatever the case, it allows us to separate our suitability, safely and safely, from the effluents leaving the reactor.

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By putting several of these devices in series, a series of separations is carried out which perfectly defines the nature of the products extracted by the tubes, the refined products being sent to the following device to define another extract.

It should be noted that with the working conditions employed, the separation of Atmospheric Distillates from the Atmospheric Residue is 200 C under 1 bar whereas it would be carried out at 360 C in a conventional distillation tower.

The configuration given is indicative and not limiting and can be made in many variants.

For example for our pilot from 2 to 5 kg / h, the heat losses being very strong, we adopted an electric heating of the extractors, the temperature being regulated by the intensity of the heating for a determined pace and a determined load.

The same system allowed us to carry out process extractions and atmospheric servicing distillations of our finished products to treat quantities up to 50kg.

This technological device can thus serve several purposes, in particular for purposes of chemical conversions.

We will explain its application to conversions into liquids of a gas mixture.

We have just seen that our emulsions were stable and that the clear products could be oxygenated or hydrated and were also related to the temperature (and the operating pressure) of the reactor-extractor-key separating the products useful "to the standard" of the recycles.

This unexpected effect prompted us to look for an explanation helping us to size the equipment and to set the operating conditions with the minimum of practical experiments.

Here are the results of this review especially on
THE STEAM ACTION ON UNSATURATED DOUBLE BINDINGS Either a chain containing a carbon-carbon double bond denoted by CE.

Il est parculièrement remarquable de constater que dans ces conditions on peut convertir : In the presence of water vapor the reaction below will be able to proceed:

It is remarkable to note that under these conditions we can convert:

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 - Ethylene alcohol, which explains that we can limit the production of gases on the one hand, - that heavy alcohols form naturally in the working conditions of the reactor-extractor which operates precisely at favorable temperature to achieve this type conversion on the other hand.

It is easier to understand why our emulsions are stable and why our process can produce oxygenates.

Indeed, with regard to the stability of the emulsions, the heavy alcohols behave as third solvents between water and hydrocarbons, the alcohols being miscible with water by their ÖH function and miscible with hydrocarbons by their hydrocarbon base skeleton.

* If we remember that the bonding forces used in the emulsion are low because they have a more physical than chemical origin, it is understood that the emulsion can be "broken" quite easily by simple mechanical means that we discovered.

INORGANIC DEPOSITION METALS // COMPLEXES EMULSIONS
The vacuum residue that we converted contained the impurities summarized in the table below which, in addition, gives their distribution.

FRACTIONING of the RSV, Kuwait by EXTRACTION C3-C5.

<Tb>
<Tb>

POSITION <SEP> * <SEP> DAO <SEP> C3 <SEP> * <SEP> ExC4 <SEP> * <SEP> Ex <SEP> C5 <SEP> * <SEP> Asp <SEP> C5 <SEP> * <SEP>"""""" RSV <SEP> *
<tb>% <SEP> LOAD <SEP> RSV <SEP> * <SEP> 18.7 <SEP> * <SEP> 33.7 <SEP> * <SEP> 30.4 <SEP> * <SEP> 17 , 5 <SEP> * <SEP> 100 <SEP>% <SEP> RSV <SEP> *
<tb> Density <SEP> 20 C <SEP> * <SEP> 0.896 <SEP> * <SEP> 1,000 <SEP> * 1,047 <SEP> * <SEP> 1,067 <SEP> * <SEP> 1,010 <SEP> *
<tb> n <SEP> refrac <SEP> 20 C <SEP> * <SEP> 1.519 <SEP> * <SEP> 1.592 <SEP> * <SEP> 1.624 <SEP> * <SEP> 1.641 <SEP> * <SEP> 1.59415 <SEP> *
<tb> Tf C <SEP> * <SEP> 50 <SEP> * <SEP> 60 <SEP> * <SEP> 100 <SEP> * <SEP> 146 <SEP> * <SEP> + <SEP> 41 C <SEP> *
<tb> Sediment <SEP> * <SEP> * <SEP> * <SEP> * <SEP> 0.096% Wt <SEP> *
<tb> Carb <SEP> Res <SEP>% Rsv <SEP> * <SEP> 0.62 <SEP> * <SEP> 2.96 <SEP> * <SEP> 8.09 <SEP> * <SEP> 8.23 <SEP> * <SEP> 19.9 <SEP> *
<tb> Sulfur <SEP>% Rsv <SEP> * <SEP> 0.53 <SEP> * <SEP> 1.62 <SEP> * <SEP> 1.62 <SEP> * <SEP> 1.23 <SEP> * <SEP> 5.0 <SEP> *
<tb> Nickel <SEP> ppmRsv * <SEP> 0.2 <SEP> * <SEP> 10.2 <SEP> * <SEP> 14.4 <SEP> * <SEP> 17.2 <SEP> * <SEP> 42 <SEP> *
<tb> Vanadium <SEP> ppmRsv * <SEP> 1.0 <SEP> * <SEP> 32.3 <SEP> * <SEP> 47.2 <SEP> * <SEP> 55.5 <SEP> * <SEP> 136 <SEP> *
<tb> NaCl <SEP>% <SEP> Wt <SEP> * - <SEP> * - <SEP> * <SEP> 0.0003 * <SEP> 0.0107 <SEP> * <SEP> 0.0110 <SEP> *
<tb> VISCO <SEP> Cst <SEP> 100 C * <SEP> * <SEP> * <SEP> * <SEP> * <SEP> 1402 <SEP> Cst <SEP> *
<tb> H / C <SEP> * <SEP> 1.64 <SEP> * <SEP> 1.35 <SEP> * <SEP> 1.22 <SEP> * <SEP> 1.18 <SEP> * <SEP> H / C = 1.33 *
<tb> *********************************************** ******************
<Tb>
The combustion of heavy fuels gives ash which typically has the relative composition below (except S04):
SiO2: 32, Fe203: 25, Na: 16, Va: 14, Ni: 6, Al: 6, Our charges to be converted therefore contain Vanadium, Nickel, Sodium, Iron, Aluminum, Sulfur, etc. ..of which one must at least accommodate in the conversion and which one should preferably eliminate.

We have observed that one of the first detrimental effects of metals is to give solid compounds due to eutectics which are formed between 520 and 6,000 (such as SiO 2 + Na 2 O, V 2 O 5 + Na 2 O, V 2 O 5 + NiO 2, the most fuse melting to the following less fuse.

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It appears that free compounds such as those listed below are removed by the reactor effluents in the solid state.

Compounds Tf Teb D n SiO2 1700 2230 2.32 1.4840 SiS2> 1090 2.020 Anyway, if one operates with a reactor at too high temperature, one observes deposits containing the formed eutectics which will be deposited on the walls of the reactor. reactor.

 This limitation therefore has nothing to do with the chemistry of the conversion, but is only related to the nature of the impurities in the charge.

Indeed, it is not the presence of these impurities which is troublesome, it is their accumulation in the reactor or the extractor of guard which tends to clog them thus blocking any exploitation possible until they are not eliminated.

There is therefore a new feature of our invention which limits the operating temperature of the reactor as a function of the content of impurities, in the case of the residue under vacuum below 500 C.

Solubilité Si02/H20 Si02/H20 ppm P H201iq,sat H20vap,sat H20vap Sèche Temp atm Concent Si02/H20ppm àTsat 400 C 500 C 600 C 100 C 1 500 0,02 0,2 0,5 0,9 200 15 1000 0,2 1,5 5,0 10,0 235 30 1300 1,1 4,5 11,0 40,0 Les Oxydes tels que V205 de couleur jaune ronge ou V203 de couleur plus noire ont une solubilité notable dans l'eau ce qui concourt à les extraire dans notre extracteur. Si02 is slightly extracted with dry H20vap (see table below)

Solubility SiO2 / H2O SiO2 / H2O ppm H201iq, sat H20vap, sat H20vap Dry Temp atm Concient SiO2 / H2Oppm to Tsat 400 C 500 C 600 C 100 C 1500 0.02 0.2 0.5 0.9 200 15 1000 0 , 2 1.5 5.0 10.0 235 30 1300 1.1 4.5 11.0 40.0 Oxides such as yellow-red V205 or blacker V203 have significant solubility in water. which helps to extract them in our extractor.

Vanadiun-sodium compounds such as NaV04 or Na3V04 are also soluble in water; it is the same for NiS04 yellow on NiCL2 and FeCL2 green.

The water thus extracting the various oxides thwarts the formation of the eutectics mentioned above and also reduces the rate of their deposits in the reactor.

The presence of water and oxygenation of the hydrocarbons in our reactor contributes to the formation of compounds such as: C6H5SO3) 2Fe, 3H20 (brown) or C6H5SO3> 2Ni, 6H20 or C2H3O6> 2Ni (Green) also having a partial but significant solubility in water.

 All this explains the color of the water collected after separation WATER / HYDROCARBONS as well as the appearance of FLOCKS of density higher than that of the water.

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After avoiding the metal deposits in the reactor, it was found that they were concentrated in the heavy polyaromatic hydrocarbons tending to form "cages" as clearly shown by vacuum residue analysis.

Composés PM Tf Téb d n H5C2)3,Si,C6H5 192 149 230 ................... The table below gives some compounds of Si and Fe leaving essentially in DsV and RSV ******************************* *************************************

Compounds PM Tf Teb dn H5C2) 3, Si, C6H5 192 149 230 ...................

H2CeCH, Si, (δC6H5) 3334 ... 210 / 7mmHg .... 1,130 1,5617 C6H56> 4, Si 400 47 417 / 7mmHg ...............

C5H5) 2, Si, (C6H4C6H5) 2 488 170 570 ........ 1,140 ......

C6H5) 3, Si, C6H4C6H5 412 174 580 ........ 1,100 ......

C6H5> - <C6H4 4, Si 640 283 600 ...................

H3C) 3, Si, C5H4> 2, Fe 330 16 88 / 0.06 ..... 1.5454 H3C) 3, Si, C5H4> FeC5H5 258 23 65 / 0.5 ........ .. 1,5696 ********************************************* *********************** We take advantage of this property to extract them at point 13. 4 of our process, which is a new feature of our invention .

Composé Tf Téb D n H3C)4,C -17 +9 0,613 1,3476 H3C)4,Si .. +26 0,652 ...... It has also been observed that even the light elements that could be formed remained attached preferentially to silica or free carbon to give liquids which have a boiling point PI-150 C as shown in the table below:

Compound Tf Teb D H3C) 4, C -17 +9 0.613 1.3476 H3C) 4, Si .. +26 0.652 ......

H3CCH2) 4, C -33 146 0.754 1.4206 H3CCH2) 4, Si ... 152 0.762 1.4246 ************************* ************************************************ H3CCH2) 4, Pb -136 200 1,660 1,5195 Tetra-Ethyl lead for Essences (for memory we recall the remarkable physical properties of tetraethyl lead) Here are some more iron organometallic compounds which are: FER Compound PM Tf C Teb n Color C4H6Fe (CO) 193 19 .................. Yellow C6H4SFe (CO) 2 220 51 Subi .............. Light red C5H9C5H4) FeC5H5 254 16 ................... Red Liq H3COC5H4) FeC5H5 228 85 87 .................... .

H3CC02C5H4) 2, Fe 302 ... 114 ............... Red C6H5C5H5> FeC5H5 263 110 .................. Yellow Gold OHCC5H4> FeC5H5 214 121 .................. Red brown H80CH2C5H4> 2Fe 302 140 .................. Yellow C6H5C5H4> 2, Fe 338 154 ................... Yellow Gold H8C6H4C5H4> FeC5H5 278 165 ................. Jaiine-Vert, Fliiorescent.

C6H5> 2, C593> 2, Fe 490 220 .................. Ronge, Yellow They are normally liquid and extracted by our processes at 100 or 200 C

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 All these explanations are given only as an indication and not limiting in order to get an idea of the phenomena observed.

It has been found that the highly polyaromatic molecules that can form cages, which results in a very high refractive index, have a strong solvent power extracting undesirable molecules.

Hence our technique of maintaining in 13.4 a strong stationary liquid phase whose activity is increased by temperature, this phase also coming from components of vacuum residues.

Composé PH Tf Téb d n couleur H3COC5H4)FeC5H5 228 85 87 ..................... NOTES ON FINAL STABILIZATION OF SHAPED PRODUCTS It always passes a residue of low boiling products in useful products such as:

Compound PH Tf Teb dn color H3COC5H4) FeC5H5 228 85 87 .....................

H3CC02C5H4) 2, Fe 302 ... 114 ............... Red To these compounds are added the alcohols which react according to the scheme: -CéC- + H20 ≤ ==> Alcohol AS = -32 AH = -15 Teq 200 C. It follows that the final separation can not be a simple distillation as a result of Solid-dissolved phase / gas phase changes when it is subsequent to dehydration. Indeed it can happen then, what the refiners call "a shot of water" which destroys the packing of a conventional distillation unit.

In our control distillations we observed these effects at the mentioned temperatures, in the form of violent regurgitations, sudden dehydration, crackling accompanied by releases of white vapors etc ...

 That's why we adopt our extractor equipment to achieve this final stabilization operation safely.

This equipment allowed us to separate all of our products, about a hundred kg without any difficulty.

DESCRIPTION AND REALIZATION OF THE INJECTION ASSOCIATED WITH THE REACTOR We have seen that the injector had to transfer the maximum usable energy contained in the vapor or the gases, to the load to be converted on the one hand, and on the other hand, to put intimate contact steam and load, preferably without material contact with the metal walls.

These results are obtained as follows:
The charge which is a heavy phase with respect to gases or vapors, is divided into pairs of mechanically sprayed jets, opposite, obliquely, arranged as shown in the figure below, flowing up and down and meeting each other. on the axis of the injector.

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By mutual deviation they then flow axially at moderate speed, without any material contact.

 The purpose of mechanical spraying is to create fine droplets, preferably a mist, which thus develops a maximum surface area of the hydrocarbon feedstock.

Dans cet écoulement , on vient placer le jet de vapeur ou de gaz en cours de détente, son énergie étant essentiellement transformée en énergie cinétique dans toute la mesure du possible ,doncà très grande vitesse.

En injectant le jet de vapeur à grande vitesse dans le jet pulvérisé de la charge,on obtient un cisaillement mécanique de ce jet avec transfert d'énergie qui contribue à fournir l'activation des réactions,toutes ces opérations se faisantà très grande vitesse sans contact avec des parois matérielles et pratiquement à la température désirée du réacteur . The spraying can advantageously be assisted by about 5% of superheated HP vapor which contributes to nebulize the charge (as is well known in the injector heads of the burners of boilers and ovens)

In this flow, it comes to place the jet of vapor or gas during relaxation, its energy is essentially converted into kinetic energy to the extent possible, so at very high speed.

By injecting the jet of steam at high speed into the spray jet of the charge, we obtain a mechanical shear of this jet with energy transfer which contributes to provide the activation of the reactions, all these operations being done at very high speed without contact. with material walls and substantially at the desired reactor temperature.

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Le calcul des buses et tuyères se fait facilement selon les techniques propres aux turbines à vapeur ou aux turbines hydrauliques, en tenant compte pour la charge de son état polyphasique .

The calculation of the nozzles and nozzles is easily done according to the techniques specific to steam turbines or hydraulic turbines, taking into account the charge of its multiphase state.

DISPOSITION OF INJECTORS ON THE REACTOR FACILITATING ITS MECHANICAL CURING The reactor is empty. The majority of the solid carbon formed is driven by the effluents leaving the reactor, which is a great advantage of our process.

However a small part settles on the walls and accumulates there.

It is therefore necessary to remove at a suitable frequency these carbonaceous deposits or compounds of metal oxides contained in the charge. The presence of incombustible oxides requires the use of a mechanical means such as scratching sanding or otherwise.

For this you must open the reactor and avoid any interior part or projection.

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il reste la virole nue du réacteur qu'on peut facilement nettoyer par n'importe quel moyen mécanique.

it remains the bare ferrule of the reactor which can be easily cleaned by any mechanical means.

This device is particularly advantageous especially when compared to the problems posed by packed reactors (Soaker Visbreaker) or filled with circulating catalysts or not.

 INJECTOR AND MATURATOR REACTOR A major problem is to know how to define the conditions of injection of products promoting a good initiation of useful reactions and then to define the equilibrium requirements for leaving stable products in the maturing reactor.

This practical definition which is an originality of our invention essentially consists in practically defining the key parameters governing these processes.

An example will be given dealing with the conversion of a vacuum residue with the objective of a light Gas-Oil production, Kerozene.

So we first take the Residue under vacuum.

Its density and its refractive index give us valuable information about its structure thanks to our know-how.

An extraction of asphalts with C3, C4, C5, specifies this structure in terms of molecules to be treated.

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 Preferably we take a global sample and conduct a thermal resistance test (or conversion by thermal cracking) that is moderate and easy to perform.

-{ !tus d(RsV) /dt = RsV e Ts étant une unité de temps Par exemple pour le résidu dont on va donner ensuite tous les résultats de conversion ,on a trouvé:

Température T C : 430 460 490 Ts secondes : 700 140 40 Notre expérience nous a conduits à penser que cette vitesse de réaction était liée au déséquilibre entre la composition des produits et celle qui existerait si on laissait faire les choses sans limitation de temps. If RsV is the quantity of the committed residue, and operating at the temperature T, it has been observed that RsV disappears forming other products according to a relation of the form:

For example, for the residue which will be given all the conversion results, we have found:

TC temperature: 430 460 490 Ts seconds: 700 140 40 Our experience has led us to think that this speed of reaction was related to the imbalance between the composition of products and that which would exist if we let things happen without time limitation.

To étant une unité de temps propre à chaque produit. If RsVéq is the residue that would remain in equilibrium with all the products generated, we would in fact:

To being a unit of time specific to each product.

Moreover, the conditions of mechanical failure of the molecules that we have already largely exposed, are related to the inter-atomic forces of cohesion of the component molecules and with exceeding a maximum deformation acceptable by the material considered.

This results in a WORK E equal to: E = Force x Deformation We think that there is a general relation between Ts and the temperature T, with R universal constant of perfect gases, of the form: -T (R / E)
Ts = To e So we have a simple way to evaluate the E value we give to our Vacuumed Vacuum.

Dans notre cas, avec Tl =430 C Ts(l) =700s T2=490 C Ts(2)=40s , on trouve que E vaut environ 42kcal/mol Ceci veut dire que si l'on n 'est pas capable d'engager cette énergie ,il ne se passera instantanément rien dans l'injecteur (ceci vent dire aussi que si on transfère une énergie très supérieure à la molécule celle-ci va être pulvérisée ) Indeed, according to our hypotheses and taking two pairs of measurements at temperature Ts (l), Tl; Ts (2), T2, we have:

In our case, with Tl = 430 C Ts (l) = 700s T2 = 490 C Ts (2) = 40s, we find that E is about 42kcal / mol This means that if we are not able to to engage this energy, nothing will happen instantaneously in the injector (this also means that if we transfer a much higher energy to the molecule it will be pulverized)

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 Now let's look at the preheating of the load and the temperature of the reactor.

Having provided a work of 42 kcal / mol without thermalizing it in heat, the average molecule of the RSV is broken in 2 parts and no more, for lack of energy.

First of all, it must be avoided that the double fragments produced can not be repaired immediately.

It is still the role of the injector that interposes gas molecules during relaxation between the fragments formed. This interposition is all the easier as the H20 vapor or C02 gas can react chemically with the broken ends of the molecules.

 According to our invention for this to be almost certainly achieved, it is necessary to have as many gaseous molecules as carbon couples for this situation to occur. If one only works with steam the ratio WATER (18g / mol) on Hydrocarbons (CHx 13 to 14) should be ideally of the order of 18 / (2x13) by weight is about 0.7.

As the RSV molecules are fragmented, it is necessary to put them in stable thermodynamic equilibrium. For this it is necessary to have a duration of time Ts which depends essentially on the temperature.

Referring to experimental data Ts, we see that it would be advantageous to adopt the highest possible temperature to reduce the duration of operations, but we have seen that this is not done without risks.

Thus, from 460 ° C., the polyaromatics polymerize towards said solid carbon.

Thanks to the reagents used, essentially the water vapor, these parasitic reactions can be partly blocked, but never completely.

The final choice is therefore a compromise based in particular on the accepted solid carbon.

 Practically it is negligible at 440 C.

 At 520 C, its accumulation in the reactor requires frequent scraping to eliminate it otherwise it becomes annoying and if nothing is done, it would go to completely fill the reactor.

We adopted a temperature of 460-470 C which gives us good results.

It was found that the pressure had a very beneficial effect on the speed of reaction. Very important, going from 1 to 20 or 30b, this effect then attenuates to cap around 150b and to decrease beyond 200 bars.

That is why we adopt pressures of 20 to 30 bar which allow us to divide by 2 approximately the times Ts which one would have under 1 bar.

At 470 C, we will need approximately 25 seconds to achieve equilibrium in the reactor.

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Our goal to control reactions is to cut a molecule in half at each pass. This requires 20 kcal / mol net as we have already seen.

If we bring 40kcal / mol for activation, it is enough to start from a preheated charge below 470 C to obtain the desired result.

Indeed, starting from this temperature slightly lower than the desired temperature of the reactor-maturator, by adding the energy of activation, the molecule would have a higher thermal temperature if it remained in the state, but it breaks by absorbing 20kcal / mol which ultimately leaves it at the target temperature for subsequent equilibrium operations.

 This is well understood, given the flow of steam (or gas) required already defined to heal certainly broken ends, it is deduced what must be the enthalpy of the steam sent to the injector.

To obtain 470 C in the reactor-maturator taking into account recycling, various energy transfer efficiencies, it is necessary to consider steam superheat temperatures of the order of 600 to 650 C for the RSV.

Advantageously, any energy balance and recycling material made, it is good to adopt a steam pressure of the order of 60b overheated to 600 C.

Our injection nozzle adiabatically relaxes the steam from 60 bar to 30 bar 470 C, and places 60 kcal / kg mechanically available in kinetic energy in the steam jet of the order of 700m / s.

 There is thus a vapor at the desired temperature of the reactor.

 At this temperature, there is absolutely no risk of "grilling" hydrocarbons, which receive usable energy in kinetic form that will "shear" mechanically.

Typically, the preheating will be approximately 20 ° C. to 25 ° C. lower than the temperature of the reactor-maturator, ie approximately 445-450 ° C.

This is particularly advantageous for the operation of the residue preheating furnace and avoids any problem of coking. Indeed it is known that visbraekers ovens are forced to heat the same type of residue to 460 C, and that beyond appear risks of coking.

With these operating conditions, we have never coked our oven.

Nevertheless, having fixed the steam flow rate and the speed of the unit, the overheating of the steam and the preheating of the charge are regulated in order to balance the thermal balance defined by the temperature of the maturator.

In practice having set the preheating of the charge 20 or 25 C below the outlet temperature of the reactor, the heating oil flow rate of the steam oven is adjusted by the outlet temperature of the reactor.

The example we have just given for the vacuum residue is generalized to any load.

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The main key parameter is the reactor temperature which rises if the products are lighter.

 For example, with very heavy vacuum distillates, temperatures will be of the order of 500.degree. C. and will be increased to 520.degree. C. for distillates under light vacuum or very heavy atmospheric gas oils.

 EXAMPLES OF ACHIEVEMENTS Figure 1 shows the process flow diagram of a unit according to our method of steam conversion of hydrocarbon products in a non-arid country.

Figure 2 shows the same scheme implemented in a desert region poor in water resources.

FIG. 3 represents the same process used to fix the surplus gases of a wellbore or a refinery in liquids.

FIG. 4 represents an industrial pilot, working at 5 kg / h of total feed, ie 2 kg / h of atmospheric residue or 1.5 kg / h of vacuum residue. This pilot also converted heavy distillates and oils into light distillates.

WATER VAPOR CONVERSION In this version, see fig 1, the water is introduced in [0] by the pump [1] in a monotubular furnace [2] heated by a burner [3], the superheated steam is sent to the injector [4]
The fresh feed [5] which is stored in the tank [6] which receives the recycling [14] to which it is mixed, is pumped by the pump [17] which sends it to the oven [8] which preheats the whole and the sends to the inlet of the injector [4] The injector [4] working as has already been said, injects all into the reactor [10].

Under the control of the pressure measurement [20] the valve [12] discharges the effluents from the reactor by relaxing them in the extractor system [13] operating at a pressure close to atmospheric pressure.

This extraction system which has been described elsewhere comprises a series of extractions {13.1 to 13.5) set from room temperature to 360 C.

[13. 1] is at local ambient temperature, [13.2] is set to 100 C [13.3] to separate useful products (usually atmospheric distillates) from imperfectly converted atmospheric residues.

Output [13.4] can also be used for this purpose and in any case decreases the final separation of [13.3].

Output [13.5] extracts the heaviest products heavily loaded with polyaromatics and solid carbon precursor metals.

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 Part [13. 52] is extracted to prevent its accumulation in the installation and is sent to form heavy fuels while they are still acceptable in this fuel, while the rest [13. 51] is recycled to [14] for further conversion.

Useful products [13.2] and [13. 1] are in the form of very stable emulsions. They are advantageously combined (but can be separated if one is interested in light products) and sent to the system [15] which breaks the emulsions mechanically.

These broken emulsions are sent to a conventional decanter which separates Hydrocarbons [16.1] from water [16.2] and extracted heavier phases (sludge and sediments) [16.3] The Hydrocarbons fraction [16.1] is sent to the extractor [ 18] which separates the hydrocarbons which can be oxygenated or hydrated (a classic distillation risks to have dangerous "shots of water") 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) You can change the cutting points at will by changing the temperature of the extractors as this has been developed elsewhere.

Heavy fuels are made with the products released [18.6] (Atmospheric Residue) and extracts [13.52]. The carbon-bearing residues (loaded with metals) [15] are used as fuel to feed the burner [9] of the furnace [8], the incondensable gases are sent as priority fuel to the various furnace burners, the remainder being taken from the furnace. heavy fuel.

Finally, the little incondensable gas and the small carbon deposits produced by the unit's own consumption are reabsorbed, leaving the maximum number of liquid products required by the users.

This installation presents no danger of principle.

All dominant reactions are endothermic, therefore stable.

The presence of water vapor-process can stifle any potential fire hazard.

The low gas production does not give a link, in case of any incident, to heavy outgassing.

The Hold-UP (amount of material retained in the reactors is relatively modest), which facilitates the quick starts and stops of the unit.

The unit is freestanding and self-regulating due to the adopted operating technique, in particular extractors which work by natural overflow of the extracts. All these qualities allow its exploitation and its driving with an extreme facility (especially compared with the units to which it It can be substituted, such as an FCC with its catalyst coking problems between the RISER Reactor and its Regenerator supplied with pressurized air of about 3 bar, with its Hydrocyclone problems to remove the catalyst fines etc. .)

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INSTALLATION FOR ARID ZONES See Fig 2 If water is not available, it can be dispensed with using hot gases from a simple combustion containing CO 2 + H 2 O + N 2.

In this case the oven [2] of Figure 1 is replaced by the oven [68] of Figure 2. This furnace receives the liquid fuel (or gas) [61] which is pumped or compressed by [60] sent to the burner [64] which further receives the air [63] compressed by the compressor [62], then is sent as an oxidizer to the burner [64].

The temperature of the gases produced (fumes) is adjusted to the required value by bypassing more or less the convection zone which cools these gases mixed with the gases leaving the radiation to 900 C, if it is suitably thermally charged.

 In fact, the fuel flow rate is set according to the desired amount of gas.

An oxygen meter sets the oxidizer-Air necessary not to have excess, while the set temperature [54] of the gases to be supplied, drives the bypass valve [67] regulating this temperature.

In this version, the amount of water used is reduced compared to the case fig 1 operating entirely with steam.

The equipment [15] and [16] are reduced, but in return it is necessary to be equipped with a more complex air compressor and more expensive in power consumed than a food pump of oven with water.

All the rest of the installation is identical to the previous one.

This achievement is very simple and very safe.

 It requires the current monitoring of the combustion of the furnaces (flame detector), to avoid in case of flame extinguished any uncontrolled uncontrolled combustion which could happen to melt the reactor.

(It should be noted that the reactor can be removed from time to time by controlled air burning of the carbonaceous deposits, the solid deposits then falling by hammering or sanding).
RESORPTION OF EXCESSIVE LIGHT GAS IN REFINERY OR ON A PETROLEUM FIELD or
FOR MAXIMUM PRODUCTION OF SPECIES This case is shown schematically fig 3.

As we have already seen, we go through favorable Oxygenating and Moisturizing phases to 200 in the extractor.

qui à 200 C redonne à basse température:

Comme à haute température la nature des gaz importe moins que 1 énergie qu'ils transportent, ce mélange convient pour les conversions envisagées des lourds et comme on l'a déjà dit, leurs squelettes insaturés sont une bonne souche de fixation des-CH2- qui se forment favorablement vers 200 C sous une pression de 20 à 30 bars dans des réacteurs contenant déjà des hydrocarbures. Instead of grafting H 2 O onto the unsaturated bonds of the conversion products, it is possible to graft under the same conditions -CH 2 - resulting from the starting reaction at high temperature:

which at 200 C restores at low temperature:

Since at high temperature the nature of the gases is less important than the energy they carry, this mixture is suitable for the conversions envisaged for heavy metals and, as has already been said, their unsaturated skeletons are a good strain for fixing CH2- which are favorably formed at about 200 ° C. under a pressure of 20 to 30 bars in reactors already containing hydrocarbons.

An installation of this type is shown schematically fig 3.

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 The generation of the gases is schematically the same as in the case of fig 2. Only the adjustment of the combustion changes.

 At the Oxygen meter, we add a CO2 measuring device that will finally adjust the oxygen (or air) supplied to the burner.

The installation remains identical to the previous ones and differs only at the reactor outlet [10]. The effluents that come out are not relaxed and are stored under a pressure of about 25 bar. They are cooled by an exchanger [82] and then pass into an extractor [84] which works in the manner of [23] and [24].

[84] is under optimal conditions of temperature and pressure to perform useful reactions and will be dimensioned accordingly. Under the control of the pressure [74], the valve [85] which discharges the reactor [84] is piloted and partially returned to the initial process [13] here at [83] at atmospheric pressure and equipped with the outlets [13.3] [13.2 ] [13.1] who work as previously in the case Fig 1.

Partial autothermal Oxidation of the gases requires a constant monitoring of this combustion, as well as quick degassing means in the event of an incident (hydraulic guard and large flare to face any eventuality). Our experience in this area makes us think that this technique will be reserved for large units where all the necessary safety and precautions can be fully and effectively taken.

In the case OBJECTIF ESSENCES we can adopt a further OXIDATION of GAS or FUEL to obtain a mixture CO2 + H20 (total oxidation) or CO2 + H20 + CO + H2 (partial oxidation) which are favorable to us to improve the conversion rates in as well as the octane number of the species. In this case the safety of the installations becomes again total with the usual techniques of the refining.

These three variants show the possible adaptability of our process and the equipment it implements as a function of the needs to be satisfied and the constraints imposed.

EXAMPLES OF RESULTS OBTAINED WITH OUR INDUSTRIAL PILOT
Description of our pilot Our pilot whose diagram is given fig 4 allows to realize all the operations which we envisaged.

For reasons of space and cost, Hydrocarbon emulsion separation and extrusion operations [15] and [16] were not carried out continuously, but at the end of a controlled run according to the schematicprocess fig 5.

In the same way the stabilization (sort of reactive distillation) giving the final products, was done in recovery and continuously in our installation according to the diagram fig 7.

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 In this case, the reactor (at amospheric pressure) is only a transfer line between the furnace [8] and the extractor [13] which replaces the assembly [18] of a totally in-line installation fig [ 1], [2] and [3] The pilot has a manifol for charging gases H2, CO2, N2, AIR or CH4.

In its most stripped form and closest to industrial applications the pilot is given fig 8.

 It converts the charges only to steam.

 [2] is the monotubular furnace for water.

 [1] is its charge pump drawing from a reservoir whose level is measured to know the injected water.

 [3] is the monotubular furnace heating the charge injected by the pump [7] [6] is the fresh charge tank and recycling (which must be carefully traced in order to maintain the liquid products so that they are pumpable). This tank is gauged by oiling which gives the weight of treated load.

 [4] is the injector that we described and defined previously.

 [10] is the reactor sized according to the method described in the patent.

 [12] is the reactor discharge valve that sets its pressure.

 [13] is a set of extractors as we defined them. Their temperature is regulated extractor by extractor as needed.

 [28] is a Volumetric Meter of the outgoing GAS placed behind a demister.

 [39] is another condensate recuperator.

 [13.1 to 13.5] are the outputs of the extracts.

 Temperatures are measured by mercury thermometers placed in deep wells.

 The pressures are measured by conventional gauges.

Processing and measurement of formed conversion products
Outgoing gases: The gases leaving [13] after being stripped and cooled to room temperature pass through a precise volumetric meter followed by a gas sampling system in flexible skins of 11.2 liters (previously emptied by a pump). pallet giving a very good vacuum).

By simple pipsée de l'outre (taking into account the taring) one has the density of the gases, which, taking into account the volume of the gases produced, gives directly the mass of the outgoing gases.

The composition of the gases collected is obtained by any appropriate technique.

In our case, considering that one can have several skins of great capacity, one can leave the gases, cool them by liquefying them with the liquid nitrogen and proceed to their natural distillation during their warming. If we had liberated hydrogen in our reactions, we would find it easily because it would not be trapped by liquid nitrogen and give permanent gases of molecular weight 2.

This industrial procedure allows an indisputable quantitative analysis of the outgoing gases.

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From a practical point of view, the flow of the gas makes it possible to control the good adjustment of the energy working conditions of the injector and of the reactor which follows it, because we know that the production of hydrocarbon gases must be minimal (objective; ). The gases are then essentially composed of SH2, CO2, CO that can be easily metered with simple means.

Liquid products formed:
These products are presented after a brief decantation, in the form of: a mobile light phase which we call "Claire" of a stable emulsion which we call "Mayonnaise" of a free water phase, which sometimes floats on sediments or Flocculent sludge we call "FLOCKS".

 The proportion of these various phases or emulsions is variable depending on the load and the operating conditions. It often happens that the emulsion phase is dominant and even unique.

In all cases the emulsion is extruded by the means already described, gives a "clear" phase (resulting from the mayonnaise) and "dirty" water (colored and acidic).

The direct light phase and the clear phase of mayonnaise are the products coming out in [16.11] which contain the useful conversion products (which can be hydrated or oxygenated as already indicated).

These products are then separated continuously in accordance with the process diagram FIG.

They are heated in the furnace [8] up to 3600 under approximately 1 bar, passed in [10] which serves as a transfer line to then give in: [13.5 - 18.5] the Atmospheric Residue [13. 4 - 18.4] section 300-360 [13.3 - 18.3] section 200-300 [13.2 - 18.2] section 100-200 [13.1 - 18.1] section PI-100 Section points can be changed by changing the temperature extractors. We deliberately limited the slices to 5 because they were sufficient in the first conversion phase of Fig 4.

This results in large quantities of products on which all desirable evaluations and measurements can be made.

The detailed characteristics of the products formed are obtained by conventional distillation, without stirring or packing so as to observe the phenomena of dehydration of these products which may release water.

The measurement of the refractive index and the density gives us information on the structure of the products formed and consequently on the smooth progress of the conversion.

This is particularly important for recycling, by monitoring that we do not polymerize polyaromatics that degenerate into massive coke

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[5] Charge RSV,charge 100.0 d=1.01 SOLIDE n=1.594 ************************************************************************** [15] Csol : 3.0 fuel-solide 3% [41] Cgaz : 4.0 2 fuel gaz 2% [16.3] +Divers 4.0 ********** [13.52] Purges 3.5 \ FUEL [18.5 ] 8.5 / Lourd 12% **************************************************************************** [18.1 à 18.4] Dat: 77.0 0.839 DISTILLATS Atmosph. EXAMPLES OF RESULTS OBTAINED 1 VACUUM RESIDUE CONVERSION. RSV

[5] RSV load, load 100.0 d = 1.01 SOLID n = 1.594 *********************************** *************************************** [15] Csol: 3.0 fuel-solid 3% [41] Cgaz: 4.0 2 gas oil 2% [16.3] + Other 4.0 ********** [13.52] Purges 3.5 \ FUEL [18.5] 8.5 / Heavy 12% ******** ************************************************** ****************** [18.1 to 18.4] Dat: 77.0 0.839 DISTILLATES Atmosp.

CONVERSION Cutting Atm% Wt Dp / V n [-18.1] PI -150 2.57 0.687 1.43112 [-18.2] 150-200 3.77 0.772 1.45504 [200-250 4.61 0.825 1.46368 -18.3 ] 250-300 46.68 0.8536 1.47443 [-18.4] 300-360 19.37 0.8535 1.48936 Dp / v is the quotient density of the Weight / Volume, da is the same density read on a hydrometer .

Repères Procédé Nature d: densité n: réfraction [0] H20 naturelle 1.00 Charge: [5] Charge RSV 1.01 1.594 SOLIDE [13.1 -13.2] [50].,~~~ Dv/P da n [16.1] Clair 0.893 0.906 1.51671 [16.2] Mayonnaise 0.977 1.51252 Clair Extrudé 0.925 0.933 1.51567 ************************************************************************** [16.11: Clair +Clair Extrudé de [13.1-13.2] % dans la coupe CONVERSION Coupe Atm %Pds Dp/V n [ 18.1] PI -150 3,03 0,687 1,43112 [ 18.2] 150-200 4,44 0,772 1,45504 [ 200-250 5,43 0,825 1,46368 18.3] 250-300 55,00 0,8536 1,47443 [ 18.4] 300-360 22,82 0,8535 1,48936 [ 18.5] Résidu Atm: 9,28 ******************************************************************** RECYCLAGE:DEBIT PRINCIPAL % dans la coupe [13.3] 200 C Coupe DSV % Pds Dp/v n PI -200 8,24 0,831 1,50099 200-250 29,21 0,903 1,50835 250-330 52,18 0,932 1,51879 RSV.3 10,37 1.595 The key points of this conversion are given below:

Benchmarks Process Nature d: density n: refraction [0] Natural H20 1.00 Charge: [5] Load RSV 1.01 1.594 SOLID [13.1 -13.2] [50]., ~~~ Dv / P da n [16.1] Light 0.893 0.906 1.51671 [16.2] Mayonnaise 0.977 1.51252 Clear Extruded 0.925 0.933 1.51567 *************************************** *********************************** [16.11: Clear + Clear Extrude of [13.1-13.2]% in the cut CONVERSION Cut Atm% Wt Dp / V n [18.1] PI -150 3.03 0.687 1.43112 [18.2] 150-200 4.44 0.772 1.45504 [200-250 5.43 0.825 1.46368 18.3] 250-300 55.00 0.8536 1.47443 [18.4] 300-360 22.82 0.8535 1.48936 [18.5] Atm Residue: 9.28 ************** ************************************************** **** RECYCLING: MAIN FLOW% in section [13.3] 200 C Section DSV% Wt Dp / ft PI -200 8.24 0.831 1.50099 200-250 29.21 0.903 1.50835 250-330 52.18 0.932 1.51879 RSV.3 10.37 1.595

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DEBIT TRES FAIBLE:RECYCLAGE+PURGE % dans la Coupe [13.4] 360 C Coupe DSV % Pds Dp/v n PI -195 Rien............................

VERY LOW FLOW: RECYCLING + PURGE% in Cup [13.4] 360 C Cup DSV% Wt Dp / vn PI -195 Nothing ....................... .....

195-250 8.63 0.859 1.49888 250-300 43.33 0.904 1.53737 RSV.4 48.04 1.625 [13.5] 470 C NOTHING ................. ........................ We see that the section [13.4] contains a RSV part and (250-300) DSV which extracted metals and polyaromatics. Part of this is removed to purge the reactor. The 3.5% adopted gave us good results.

[5] Charge: Rat, charge 100.0 d=0,97 Figé n=1.5576 [15] Csol : 1.5 fuel sol [41] Cgaz 3.0 fuel gaz 1.5% [16.3] +Divers 3.0 ********** [13.52] Purges 2.0 \ FUEL [18.5 ] 9.5 Lourd 11.5%

total Dist.Atmosp: 81,0 sur charge [16.11: Clair +Clair Extrudé de [13.1-13.2] % sur Charge CONVERSION Coupe Atm %Pds Dp/V n [ -18.1] PI -150 2,7 0,69 1,432 [ -18.2] 150-200 10,6 0,77 1,452 [ 200-250 19,0 0,82 1,462 -18.3] 250-300 33,2 0,86 1,484 [ -18.4] 300-360 15,5 0,88 1,497

[ -18.5] Résidu Atm: 9,50 [5] Charge: Rat,charge 100.0 d=0,97 Figé n=1.5576 [5] Rat Coupe DSV % Pde Dp/v n PI -200 2,33 1.499 200-250 8,32 1,509 250/RSV 36,5 1,524 RSV 52,8 1,599

RECYCLAGE:DEBIT PRINCIPAL % dans la coupe [13.3] 200 C Coupe DSV % Pds Dp/v n PI -200 6,95 1,503 200-250 2R,14 0,867 1,509 250-330 49,45 0,923 1,530 RSV.3 15,46 1.599 ************************************************** ************************* 2 ATMOSPHERIC RESIDUE CONVERSION Reactor 470 C

[5] Charge: Rat, charge 100.0 d = 0.97 Fig. N = 1.5576 [15] Csol: 1.5 fuel oil sol [41] Cgaz 3.0 fuel gas 1.5% [16.3] + Miscellaneous 3.0 ********* * [13.52] Purges 2.0 \ FUEL [18.5] 9.5 Heavy 11.5%

total Dist.Atmosp: 81.0 on load [16.11: Clear + Clear Extruded of [13.1-13.2]% on Charge CONVERSION Cut Atm% Wt Dp / V n [-18.1] PI -150 2.7 0.69 1.432 [ -18.2] 150-200 10.6 0.77 1.452 [200-250 19.0 0.82 1.462 -18.3] 250-300 33.2 0.86 1.484 [-18.4] 300-360 15.5 0.88 1,497

[-18.5] Atm residue: 9.50 [5] Charge: Rat, charge 100.0 d = 0.97 Fig. N = 1.5576 [5] Rat DSV cut% Pde Dp / vn PI -200 2.33 1.499 200-250 8 , 32 1.509 250 / RSV 36.5 1.524 RSV 52.8 1.599

RECYCLING: MAIN FLOW% in section [13.3] 200 C Section DSV% Wt Dp / ft PI -200 6.95 1.503 200-250 2R, 14 0.867 1.509 250-330 49.45 0.923 1.530 RSV.3 15.46 1.599

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DEBIT TRES FAIBLE:RECYCLAGE+PURGE % dans la Coupe [13.4J 360 C Coupe DSV % Pds Dp/v n PI -195 0,0 .............................

VERY LOW FLOW: RECYCLING + PURGE% in the Cup [13.4J 360 C Cut DSV% Pds Dp / vn PI -195 0.0 ..................... ........

195-250 10.5 1.509 250-325 39.8 0.934 1.530 RSV.4 48.04 1.06 1.630 ************************* ******************************************* [13.5] 470 C NOTHING clearly sees that heavy metals and polyaromatics are concentrated in the RSV of the extract [13,4], which is why part of this extract is purged.

Recycling decreases compared to the case dealing only with RSV, the treatment capacity is then at its nominal value of 2kg / h of Atmospheric Residue.

3 PRODUCTION OF OXYGEN COMPOUNDS or HYDRATED EMULSION
By operating a first conversion pass of the Atmospheric Residue we obtain clear direct products + emulsions.

 We had the idea to return them in our pilot to oxygenate or hydrate during this new conversion.

Recettes-: Poids densité indice de réfraction Coupe V.t V.eau V.HC HC,sec Dp/V n PI - 120 3,25 0-9 2.25 1,54 0,684 1,43112 120 0,3 0,3 --.- -.-- 120 -200 5,6 -.- 5,6 4,18 0,746 1,44963 200 -250 9,1 1-0 8,1 6,38 0,790 1,46368 250 -300 26,1 -.- 26,1 22,27 0,853 1,48191 300 -360 53,0 -.- 53,0 46,06 0,869 1,49677 H20= 2.2 g pour:80,43 g d'HC,Sec ---------------------------~----- La distillation sans sable de la même charge a donné:
H20= 7,9g pour:85,86 g d'HC, Sec Ceci montre clairement que l'on a formé des produits oxygénés hydratés qui se dépolymérisent en premier lieuà des températures voisines comprises entre 120 et 250 C sous 1 bar. The sand distillation of the direct light phase and extruded after this second conversion gave the results below:

Recipes-: Weight density refractive index Cut Vt V.water HCV HC, dry Dp / V n PI - 120 3.25 0-9 2.25 1.54 0.684 1.43112 120 0.3 0.3 -. - -.-- 120 -200 5,6 -.- 5,6 4,18 0,746 1,44963 200 -250 9,1 1-0 8,1 6,38 0,790 1,46368 250 -300 26,1 - .- 26.1 22.27 0.853 1.48191 300 -360 53.0 -.- 53.0 46.06 0.869 1.49677 H20 = 2.2 g for: 80.43 g HC, Sec ---- ----------------------- ~ ----- The distillation without sand of the same load gave:
H20 = 7.9g for: 85.86 g of HC, Sec This clearly shows that hydrated oxygenated products have been formed which depolymerise firstly at temperatures of between 120 and 250 ° C at 1 bar.

Now it is well known that water binds to the ethylenic bonds according to the reactions of the type below:

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Exemples: AS AH Téq 1b C2H4 + H20 ===) H3C-CHÔH -29,96 /-10.9 900C C18H36 + H20 ===> Alcool C18 -32.15 /-15,03 194 C La température d'équilibre de ces réactions se fait précisément sous lb vers 200 C pour les alcools lourds et entre 90 et 200 C pour les alcools légers.

Examples: AS AH Teq 1b C2H4 + H20 ===) H3C-CH6H -29.96 /-10.9 900C C18H36 + H20 ===> Alcohol C18 -32.15 / -15.03 194 C The equilibrium temperature of these reactions It is precisely under 1 lb at 200 ° C. for the heavy alcohols and between 90 ° C. at 200 ° C. for the light alcohols.

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

The presence of hydrated oxygenated products is favorable for the quality of the products formed, in particular species.

This oxygenation or hydration further promotes combustion in both furnaces and diesel engines.

In addition, by their polar characteristics due to the OH function, these products serve as third solvents between the water on the one hand and the hydrocarbon skeleton of the hydrocarbons thus making it possible to obtain emulsions which are very stable over time (Our samples of more than 8 years have not moved) 4 CONVERSION OF THE LAST VOLTAGE DISTALLAT UNDER VACUUM says 80, Kuwait Oil Plant BP Dunkerque
Reactor 500 C These controlled run conditions were chosen to verify the increase in productivity and to test the speed control of deposits in the reactor.

In addition, the liquid-liquid extraction techniques at the furfural of the feedstock and the effluents allow us to analyze the structure of the products formed and to confirm our practice of driving and dimensioning the units designed according to our process.

[5] Charge 80, R 100.0 d = 0.936 SOLID n = 1.530 Tf = 80 C ******************************* ********************************************* [15] Csol: 3.0 ffl soil 3% [41] Cgaz: 4.0 2 fuel gas 2% [16.3] + Miscellaneous 0.5 ********** [13.52] Purges 3.5 \ FUEL [18.5] 11.2 / Heavy 14.7 % ************************************************* *************************** total Dist.Atmosp: 77.8 on load [16.11: Clear + Clear Extruded from [13.1-13.2] % on Charge CONVERSION Cut Atm% Wt Dp / V n [-18.1] PI -150 10.49 0.692 1.429 [-18.2] 150-200 17.06 0.746 1.443 [200-250 17.26 0.786 1.465 -18.3] 250- 300 17.56 0.841 1.485 [-18.4] 300-360 15.43 0.878 1.509 -18.5] Atm Residue: 11.20

<Desc / Clms Page number 48>

[5] Charge: 80K,charae 100.0 d=0,936 SOLIDE n=1.530 Tf=80 C Séparation Extractive au Furfural *~ ------------------------ # -------------------A Coupe : P.AR : P.A A-N N-B Dp/V . 1.058 : 1.008 : 0.943 : 0.866 n 1.610 : 1.575 : 1.529 : 1.489 %pds 13 21 21 46 RECYCLAGE:DEBIT PRINCIPAL d n [13.3] 200 C 0.972 1.568 DEBIT TRES FAIBLE:RECYCLAGE+PURGE d n [13.4] 3600 1,02 1.591 Quelques Polyaromatiques: non extraits [13.5] 470 C ( renvoyés en [13.4] ) On voit clairement que les métaux et polyaromatiques lourds se concentrent dans l'extrait [13.4],c'est pourquoi on purge une partie de cet extrait.

[5] Load: 80K, charae 100.0 d = 0.936 SOLID n = 1.530 Tf = 80 C Furfural Extractive Separation * ~ ------------------------ # ------------------- A Cut: P.AR: PA AN NB Dp / V. 1.058: 1.008: 0.943: 0.866 n 1.610: 1.575: 1.529: 1.489% wt 13 21 21 46 RECYCLING: MAIN FLOW dn [13.3] 200 C 0.972 1.568 VERY LOW FLOW: RECYCLING + PURGE dn [13.4] 3600 1.02 1.591 Some Polyaromatic: not extracted [13.5] 470 C (referred to in [13.4]) It is clear that the heavy metals and polyaromatics are concentrated in the extract [13.4], which is why part of this extract is purged.

The conversion is done with low recycling, thanks to the operating conditions adopted in particular with a reactor to 500 C.

It should be noted that we have a very significant gasoline production (27.55% PI-200 C weight which compares very favorably to FCC species).

CONVERSION WITH MIXTURES OF. DIVERSE GAS
AND EFFECT of NATURE OF CHARGE on REACTOR TEMPERATURE
In order to be able to work in arid regions where water is scarce, or to improve the quality of the species, we have studied the ease with which our process can operate with various permanent gases or easily produced mixtures such as fumes. ovens for example.

Some units such as the decarbonation unit of the BENFIEL unit in a hydrogen production complex release large amounts of C02 that may be considered for possible use.

Another concern was to test our knowledge and experience by working on Light Vacuum Distillates or Heavy Atmospheric Diesel to go to lighter Diesel and Gasoline, in a nutshell to meet an unbalanced demand for fuel. these products by the market. Indeed our unit allows to promote at will the production of diesel or gasoline what can not do the existing conversion units that have a fixed distribution of the products they generate.

<Desc / Clms Page number 49>

 We therefore chose as a charge to convert an ELF brand MOTOR OIL, tracked and readily available in all large areas of density 0.885 and index n = 1.488 (average values).

We knew that C02 was a good candidate for conversions. that CO2 + H20 had potential advantages. that C02 + H2 could be beneficial, but H2 was likely to be unresponsive and would only participate in business by its physical qualities.

 That N2 could do the trick but, used alone, did not protect from coking.

All these combinations have been explored.

We were able to verify that we could very usefully adopt a reactor temperature of 520-530 C.

6 CONVERSION HUILE au C02 PUR SANS RECYCLAGE [5] Charge:Huile 100,00 d=0,885 n=1,488 [16.11] CONVERSION Coupe %Pds Dp/v n PI -150 6,74 0,700 1,432 150-200 8,62 0,750 1,448 200-250 8,99 0,807 1,464 250-300 9,35 0,824 1,476 300-360 9,49 0,836 1,487 Total Distil.Atm 43,10 Rat 3,11 0,860 [13.3] 52,79 0,878 [13.4] 0,91 0,861 [13.5] **********************************************************************

7 CONVERSION HUILE au C02 + H2 sans RECYCLAGE [5] Charge:Huile 100,00 0,885 1,488 [16.11] CONVERSION Coupe %Pds Dp/v n PI -150 8,53 0,727 1,433 150-200 8,93 0,760 1,447 200-250 11,56 0,798 1,463 250-300 8,34 0,816 1,474 300-360 7,70 0,832 1,487 45,06 Rat 1,74 0,848 [13. 3] 52,63 0,880 [13.4] 0,91 0,915 Without recycling, the Conversions observed were: ***************************************** ******************************

6 CONVERSION TO PURE CO 2 WITHOUT RECYCLING [5] Charge: Oil 100.00 d = 0.885 n = 1.488 [16.11] CONVERSION% Wt. -250 8.99 0.880 1.464 250-300 9.35 0.824 1.476 300-360 9.49 0.836 1.487 Total Dist.Atm 43.10 Rat 3.11 0.860 [13.3] 52.79 0.878 [13.4] 0.91 0.861 [ 13.5] ************************************************ **********************

7 OIL CONVERSION to C02 + H2 without RECYCLING [5] Charge: Oil 100.00 0.885 1.488 [16.11] CONVERSION% Wt% Dp / vn Wt -150 8.53 0.727 1.433 150-200 8.93 0.760 1.447 200-250 11 , 56 0.798 1.463 250-300 8.34 0.816 1.474 300-360 7.70 0.832 1.487 45.06 Rat 1.74 0.848 [13. 3] 52.63 0.880 [13.4] 0.91 0.915

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[13.5J ********************************************************************** 8 CONVERSION HUILE au C02 + H20 sans RECYCLAGE [5] Charge:Huile 100,00 0,885 1,488 [16.11J CONVERSION Coupe %Pds Dp/v n PI -150 3,91 0,762 1,441 150-200 7,54 0,732 1,450 200-250 10,14 0,789 1,464 250-300 9,58 0,812 1,475 300-360 14,56 0,828 1,484 45,73 Rat 13,67 0,848 [13.3J 38,30 0,880 [13.4J 1,40 0,868 [13.5J 0,9 0,885 ********************************************************************** H20 tend à freiner l'apparition des fractions légères comme prévu.

[13.5J *********************************************** *********************** 8 OIL CONVERSION to C02 + H20 without RECYCLING [5] Charge: Oil 100.00 0.885 1.488 [16.11J CONVERSION% WIP Dp / vn PI -150 3.91 0.762 1.441 150-200 7.54 0.732 1.450 200-250 10.14 0.789 1.464 250-300 9.58 0.812 1.475 300-360 14.56 0.828 1.484 45.73 Rat 13.67 0.848 [13.3D 38.30 0.880 [13.4J 1.40 0.868 [13.5D 0.9 0.885 **************************** ****************************************** H20 tends to slow down the appearance of light fractions as expected.

There are no very significant differences separating the performance of these gas mixtures.

From the octane point of view, the ranking is in ascending order CO2 CO 2 + H 2 O, CO 2 + H2, without this being very marked.

Care must be taken not to have an excess of C02 + H20 gas flow which would reduce conversions in pure loss.

il il il le il fi es le et Il fi le te et fi fi le et 99 Il le le le es le il Il il le le le fi VI 91 le le et VI f 1 il il el il

[5] Charge HUILE MOTEUR 100.0 d=0,886 n=1,49148 [15] Csol : 0.5 feuil sol 0,5 % [41] Cgaz : 3.2 fuel gaz 1.6 % [16.3] +Divers 0.0 ********** [13.52] Purges 0.5 \ FUEL [18.5 ] 6.3 / Lourd 6,8 % **************************************************************************** [18.1 à 18.4] Dat: 89,5 DISTILLATS Atmosph. 9 OIL CONVERSION with C02 + H20 WITH RECYCLING

he he he he is he and He fi le you and fi fi and 99 He is it he He il the it fi fi 91 the it and VI f 1 il he il he

[5] Load ENGINE OIL 100.0 d = 0.886 n = 1.49148 [15] Csol: 0.5 foil 0.5% [41] Cgaz: 3.2 fuel gas 1.6% [16.3] + Other 0.0 ******* *** [13.52] Purges 0.5 \ FUEL [18.5] 6.3 / Heavy 6.8% ****************************** ********************************************** [18.1 to 18.4 ] Dat: 89.5 DISTILLATES Atmosph.

CONVERSION Cutting Atm% Wt Dp / V n [-18.1] PI -150 16.79 0.721 1.427 [-18.2] 150-200 13.24 0.763 1.445 [200-250 18.43 0.811 1.462 -18.3] 250-300 18.24 0.831 1.478 [-18.4] 300-360 21.80 0.868 1.489 [13.3] 0.882 1.507 [13.4] 0.897 1.511 [13.5]

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 ************************************************** ************************** This oil is converted to 30% PI-200 species. These various examples show that we can convert very varied with great security and with excellent yields.

(The tests with pure N2 showed that there was a strong tendency to coke) 10 DEPOSITS IN THE REACTOR We had chosen the ELF Motor Oils as test load in the examples 6, 7, 8, 9 especially in thinking that we would only be limited by chemical considerations for a conversion study of light cuts.

 We mainly made the conversions with permanent gases, in particular CO2 and hydrogen supplied by Air Liquide and the demineralized water of the trade, the oven temperature being 530 C.

We began to measure the controlled combustion deposits using the hydrocracker technique by carefully following the combustion front.

There remained unexplained problems of local pressure drops in the reactor.

So we decided after a long, controlled walk:
1 / to carry out a meticulous burning,
2 / to open the reactor and its injector.

The injector was clean.

We then extracted from the reactor by the well-known technique of hammering, scales of deposits, and by turbining with a long-tailed drill, a gray powder.

 Neither the scales nor the powder were combustible.

151.2 g of Solid were collected for 62300 g of load or a deposition rate, Solid / Charge = 0.24% These deposits can have as origin only the treated oil and have manifested themselves only by their accumulation.

 [In our residue conversion tests we adopted the mechanical scraping technique to extract carbon and solid residues from the reactor, a more laborious but more precise operation that gives the quantity of deposits formed by weight. These deposits can then be analyzed for any other purpose].

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 11 EXTRACTIVE DEMETALLIZATION of RESIDUES OR LOADS Here are the properties of a Kuwait RSV which served us as reference load in our conversions.

FRACTIONNEMENT du RSV par EXTRACTION C3-C5 6/1 ~~~~~~~~~~ ~~~~~ ~~~~~ RSV * POSITION * DAO C3 * ExC4 * Ex C5 * Asp C5 ! * % CHARGE RSV * 18,7 * 33,7 * 30,4 * 17,5 ! 100 % RSV * Densité 20 C * 0,896 * 1,000 *1,047 * 1,067 ! 1,010 * n réfrac 20 C *. 1,519 1 1,592 1,624 *. 1,641 1,59415 z Tf C * 50 * 60 * 100 * 146 ! + 41 C * Sédiments * * * * ! 0,096%Pds * Carb Rési %Rsv * 0,62 * 2,96 * 8,09 * 8,23 ! 19,9 * Soufre %Rsv * 0,53 * 1,62 * 1,62 * 1,23 ! 5,0 * Nickel ppmRsv* 0,2 * 10,2 * 14,4 * 17,2 42 * Vanadium ppmRsv* 1,0 * 32,3 * 47,2 * 55,5 I 136 NaCl % Pds * - * - * 0,0003* 0,0107 ! 0,0110 * VISCO Cst 100 C* * * * ! 1402 Cst * --------------- -------- ------- ------- -------j-----##------* H/C * 1,64 * 1,35 * 1,22 * 1,18 ! H/C=1,33 * II II II II II II II II II II II II II II II * II II II II II II II II * II II II II II II II * II II II II II II II * 11 II II M II II II M * II II II II II II II II II II M II II II On constate que les métaux (Nickel Vanadiun) se concentrent dans les produits les plus polyaromatiques à fort indice de réfraction n et ayant la densité la plus élevée. Il en est de même pour les sels et le soufre. An extractive fractionation with Propane C3, Butane C4 and Pentane C5 makes it possible to separate the constituents of this residue under vacuum according to their nature ranging from DAO (for deasphalted oils) to very hard asphalts (Asp C5).

FRACTIONING the RSV by EXTRACTION C3-C5 6/1 ~~~~~~~~~~~~~~~~~~~ RSV * POSITION * DAO C3 * ExC4 * Ex C5 * Asp C5! *% RSV LOAD * 18.7 * 33.7 * 30.4 * 17.5! 100% RSV * Density 20 C * 0.896 * 1,000 * 1,047 * 1,067! 1,010 * n refrac 20 C *. 1,519 1,592 1,624 *. 1.641 1.59415 z Tf C * 50 * 60 * 100 * 146! + 41 C * Sediments * * * *! 0.096% Wt * Carb Res.% Rsv * 0.62 * 2.96 * 8.09 * 8.23! 19.9 * Sulfur% Rsv * 0.53 * 1.62 * 1.62 * 1.23! 5.0 * Nickel ppmRsv * 0.2 * 10.2 * 14.4 * 17.2 42 * Vanadium ppmRsv * 1.0 * 32.3 * 47.2 * 55.5 I 136 NaCl% Pds * - * - * 0.0003 * 0.0107! 0.0110 * VISCO Cst 100 C * * * *! 1402 Cst * --------------- -------- ------- ------- ------- j-- --- ## ------ * H / C * 1.64 * 1.35 * 1.22 * 1.18! H / C = 1,33 * II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II III II II It is found that the metals (Nickel Vanadiun) are concentrated in the most polyaromatic products with a high refractive index n and having the specific gravity. higher. It is the same for salts and sulfur.

These constituents are very troublesome because they are poisons for subsequent catalytic refining treatments.

The polyaromatics that contain them are coking precursors on the one hand, and on the other hand, as a mixture, increase the viscosity of the products to make them impompables greatly deteriorating the quality of the fuels used for fuel applications.

For all these reasons it is advantageous to extract them separately.

DEBIT TRES FAIBLE:RECYCLAGE+PURGE % dans la Coupe [13.4] 360 C Coupe DSV % Pds Dp/v n PI -195 Rien............................. The CONVERSION of this RESIDUE IN VACUUM (RSV) reported in the example N 1, provided us on the extraction [13.4] the following extract:

VERY LOW FLOW: RECYCLING + PURGE% in Cup [13.4] 360 C Cup DSV% Wt Dp / vn PI -195 Nothing ....................... ......

195-250 8.63 0.859 1.49888 250-300 43.33 0.904 1.53737 RSV.4 48.04 1.625 *********************** ************************************************** Referring to the densities and indices of refraction, it can be seen that the extract [13. 4] is practically and exclusively composed of EXC4, EXC5 and AspC5 On the other hand the examination of the extract [13.3] shows us that it contains practically no more charged components in Metals, Salts, Sulfur etc .., its fraction the heavier being a DAO and the 10% of RV.3 neighbors of an EXC3.

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**************************************************************************** RECYCLAGE:DEBIT PRINCIPAL % dans la coupe [13.3] 200 C Coupe DSV % Pds Dp/v n PI -200 8,24 0,831 1,50099 200-250 29,21 0,903 1,50835 250-330 52,18 0,932 1,51879 RSV.3 10,37 1.595 [13.5] 470 C RIEN ( L'extracteur [13.5] fonctionne en mode de garde. ) **************************************************************************** A 360 C,et à pression atmosphérique, L'EXTRACTEUR [13.4] démétallise la charge d'une manière efficace et contrôlée en concentrant Métanx, Sels et Soufre dans un extrait [13.4] bien défini, ce qui est une nouvelle caractéristique de notre invention.

************************************************** ************************** RECYCLING: MAIN FLOW% in section [13.3] 200 C DSV cut% Pds Dp / vn PI -200 8 , 24 0.831 1.50099 200-250 29.21 0.903 1.50835 250-330 52.18 0.932 1.51879 RSV.3 10.37 1.595 [13.5] 470 C NOTHING (The extractor [13.5] operates in keep. ) *********************************************** ***************************** At 360 C, and at atmospheric pressure, the EXTRACTOR [13.4] demetallizes the charge of a effective and controlled manner by concentrating Metanx, Salts and Sulfur in a well-defined extract [13.4], which is a new feature of our invention.

Claims (22)

1 Process for converting hydrocarbon residues or heavy distillates at high melting temperature which can be loaded with impurities such as metals, sediments, sulfur, nitrogen, etc., into light liquid clean products distilling at atmospheric pressure, these results being obtained without significant production of gas or carbonaceous solid residues by a new process which preferably comprises preheating the feed below the selected reactor temperature, treating the feed with a jet of gas or superheated steam, preferably during relaxation in such a way that the energy thus provided is of the order of the activation energy to share the molecules into lighter molecules, the excess of this energy over the required energy to carry out the reaction being used to pass the suitably preheated charge to the temperature chosen for the reactor, these operations are in a suitable injector which injects the finely sprayed charge and treated by the jet of gas or vapor in an empty reactor (without catalyst), this reactor allowing the previously activated products to stabilize at the chosen temperature, which requires a residence time the temperature is chosen to avoid the parasitic reactions forming solid deposits or gases, this duration being reduced by a suitable pressure which also reduces the volume required for the reactor, the products thus formed being then depressed at a pressure typically suitable for atmospheric pressure to pass through a series of extractors consisting of contactors-mixers surmounted by a zone of tranquillizer :! and one decantation separating the heavy phases of light liquid or gaseous phases, one of these extractors used in particular to demetallize the charge, the extracts obtained hate temperature can be recycled without stress until their total conversion, the raffinates obtained at low temperature constituting the conversion products which can be oxygenated and hydrated in a steam conversion, these conversion products being in the form of stable emulsions WATER / hydrocarbons easily broken by mechanical means then being stabilized in a distillation Extractive that supports the presence of water or hydrated and oxygenated compounds that can sometimes be depolymerized. 2 Conversion process using a gas mixture providing a portion of the energy required for the reaction, preferably oxygenated such as H2O, CO2, CO, which may be accompanied by H2 or neutral gas such as N2, this energy being preferably provided by a conventional thermal furnace or from a combustion of hydrocarbons under pressure and air. According to claim 2, the process using superheated steam with preferably an expansion ratio such that the energy to be supplied is in mechanical form known as adiabatic expansion with working, the steam being at the end of this relaxation at the desired temperature of the reactor. A process which preferably injects gases or steam into at least two pairs of convergent jets of the spray charge to increase the contact area of the gases with the vapor, the velocity of the gases or vapor involved in a transfer efficient movement energy to the finely divided load and thus helping to shear it. <Desc / Clms Page number 55>  5 apparatus consisting of an injector carrying out the operations of claim N 4 6 conversion process using a reactor allowing the charge treated as just said, to stay for a suitable period of time at a temperature of favorable reactor preferably under a pressure which is used to decrease this time and the volume of the reactor. 7 process in which the reactor contains only the feedstock, the gases or vapors and the products being formed, without using any catalyst. 8 procedure for defining the required energy level deduced from the measurement of at least two unit conversion times at at least two temperatures, which makes it possible to define the specific energy E, referred to as the activation of any load, which according to our experience for a vacuum residue is about 40kcal, of which only 20 are used by the cracking reaction, the difference of these two values setting the preheat temperature difference of the load to the operating temperature of the reactor. 9 process which allows to break in two equal parts on average 60% of the molecules at each passage in the injector, which schematically passed in a controlled way the RESIDUES under EMPTY (fathers products) to DISTILLATES under VACUUM (son products) then to ATMOSPHERIC DISTILLATES (grandson products) 10 A process which, according to 11, breaks only the molecules into two equal parts, does not produce large quantities of gas which otherwise would be due to too much fragmentation into many pieces as a result of the non-action. compliance with the rules defined in claim 8, this appearance of gas being a practical reference of a beginning of maladjustment leaving the optimal working conditions. It is a non-critical, non-critical process that tolerates imperfections in achieving optimal conditions, but at the cost of reduced performance that results in increased gas production or solid deposition. 12 process that uses OXYGENIC COMPOUNDS that stabilize the fresh breaks of the molecules, these compounds being in practice H20 and CO2, capable of giving respectively highly reactive OH and CO compounds, in particular on the unsaturated bonds, this being only an explanation a posteriori effects observed which result in a blocking production of solid carbonaceous deposits and production of gas, this effect blocking parasitic reactions having the effect of moderating the useful reaction rates. The method according to claim 10 preferably employs at least one H 2 O or CO 2 per pair of carbon, ie by weight, at least one WATER / Carbon ratio of 0.7 (H 2 O or CO 2 which can be approximately interchanged mole per mole). The process advantageously employs pure water vapor, which reduces the energy requirements for pumping. <Desc / Clms Page number 56>  A method according to claims 10 and 12 for creating oxygenated and hydrated compounds, particularly stable WATER / HYDROCARBON emulsions for producing improved fuels. 16 process which implements a series of extractors, each extractor operating at an adjustable temperature and consisting of a mixing chamber contacting the incoming products with the heavy phase it contains, surmounted by a plenum where the products heavy or liquid settling and down and then fall back into the mixing chamber which then overflows into an outlet provided for this purpose at its upper level, the contacting for the purpose of extracting the most miscible solid, liquid or gaseous products from the incoming phase , soluble or reactive with the heavy stationary phase, this mass transfer strongly depending on the temperature and the nature of the stationary phase. 17 according to the extractors designed according to claim 14 allows the choice of their operating temperature to define extracts of products not properly formed and useful raffinates, these extractors working at atmospheric pressure. 18 method that allows the extraction of atmospheric distillates useful by setting an extractor to 200 C to fix the ideas. 19 process that allows using an extractor maintained at 360 C and containing a heavy phase resembling a vacuum asphalt residue to extract an extract that trapped the metals thus demetallizing the load. Process which makes it possible to extract the incompletely converted but demetallized products in the extract of an extractor set towards 200 C to fix ideas and working at atmospheric pressure. 21 process using these same extractors to make a separation in conventional distillatory section in the presence of free water or bound to emulsions or chemically linked to oxygenated or hydrated hydrocarbons. A process for separating the formed products from water by breaking stable emulsions formed by mechanical means such as extrusion which consists of forcing the emulsions through several webs, or to pour dry sand on the emulsions or to roll steel balls in the emulsions, these methods being given as an indication and not limiting, followed by a settling system which separates the various phases, the lightest phase of hydrocarbons supernatant on a phase heavier residual hydrocarbon / water emulsion itself located above an acidic water that allows to precipitate various heavy elements and sludge that it extracted during the various contacts with the components of the load. It is a process that allows very deep conversions to be chained using the fact that the optimum temperature increases in the opposite direction to the density or boiling point of the products. A vacuum residue has an optimal reactor temperature around 470 C, while for a vacuum distillate it would be 500 C and for an oil or a heavy gas oil it is of the order of 530 C. Ansi starting from a vacuum residue to go to species it would be useful for large units to adopt three lines in series <Desc / Clms Page number 57>  each with a low recycle rate, the first converting the RsV to DsV at 370 C, with demetallization, the second converting the DsV to Rat at 500 C, then the heavy D-oils to light and gasoline at 530 C. This method limits at least the temperature of the reactor as a function of the impurities such as vanadium nickel, salt, etc., as a function of the glass eutectics which generate solid deposits on the walls of the reactor, the corresponding experimental data being usefully provided by the practice of the glass industry. A method of taking the smallest temperature as defined in claim N 24 compared with the maximum temperature that the heavier products can withstand without thermally polymerizing, the experiment showing that they are generally both bounded below 550 C to fix ideas.