NL1029418C2 - Hydrocarbon treatment. - Google Patents

Description

NL7469-Me / td

Hydrocarbon treatment

FIELD OF THE INVENTION

The invention relates to the hydrothermal treatment of hydrocarbons prior to further processing. In particular, the invention provides a pre-treatment regime for Fischer-Tropsch (F-T) hydrocarbons prior to downstream processing. The invention also relates to a chemical treatment of hydrocarbons prior to further processing.

BACKGROUND OF THE INVENTION

The inventors have identified an area for process optimization in the processing of hydrocarbons. In particular, the inventors have identified an area for process optimization in the processing of F-T synthesis products by hydroconversion in general.

Product streams from F-T contain oxygenates and, to a certain extent, metals and / or metal species. Ketones, aldehydes, alcohols, esters and carboxylic acids are the most important components of the oxygenate fraction. Carboxylic acids and alcohols are capable of forming carboxylate and / or alkoxide complexes and / or metalloxanes under suitable conditions with the metals and / or metal species contained therein. These metal carboxylates and / or alkoxides and / or metalloxanes can form deposits in processing equipment and catalyst beds. Ultimately, the deposits in the catalyst beds can increase such that switching off reactors is inevitable.

The identified problem can be summarized as the clogging of catalyst beds or bed for downstream processing, by a component of said product streams or by a reaction product of a component of said product streams.

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SUMMARY OF THE INVENTION

Without being bound by theory, the inventors believe that the clogging is caused by organo-language material and / or fine particles. The organometallic material and / or the fine particles are in all likelihood rich in aluminum, and / or silicon, and / or titanium, and / or zirconium, and / or cobalt, and / or iron, and / or alkaline earth. alkali elements such as calcium and barium etc.

The synthesis products of the F-T method were analyzed and it was found that the condensate fraction was devoid of metal impurities (1 ppm or less), but that the wax contained metal impurities of the order of 10 - 100 ppm. This indicates that the F-T process and / or the filtration system and / or the refractory materials and / or the chemically leached metals or metal species may be the source of the metal impurities.

There may be two forms of metal oxygenate species that contribute to clogging the bed and one or both may be important: a) Fine particles: for example fine particles with a diameter of less than 1 micron that can be stabilized by surfactants (such as oxyge -naten) allowing them to stay in suspension. However, when this surface layer is disturbed, the particles precipitate and form deposits on collector media.

b) Organometallic type compounds: for example, when aluminum is the metal source, the formation of organoaluminum compounds is of the Al-OR type, such as alkoxy-aluminum, aluminum carboxylates and alumoxanes, or of the Al-30 R type, such as alkylaluminum, or combinations thereof, possible.

Bed clogging has been observed with various catalysts and occurs as a local clogging or as dispersed particulate matter.

The hypothesis is that the FT synthesis product stream has low concentrations of organometallic material and / or solubilized fine catalyst particles, and / or filter aid and / or refractory material and / or chemically leached metals or metal species of the reactor system contains. The wax contains oxygenates such as acids and alcohols that help to keep the fine particles in the wax in solubilized form.

It is thought that during hydroconversion, these oxygenates which keep the particles in suspension and / or the ligands of the organometallic constituents are hydrogenated and / or protonated and that the modified metal species are then deposited on the hydroconversion reactor catalyst bed, it does not lead to what is called "bed" "clogging".

Therefore, after careful consideration and experimentation, the inventors propose the following solution, which can at least partially alleviate the problem described above. According to a first aspect of the invention, a method is provided for treating hydrocarbons, which method also comprises hydrothermally treating metal oxygenate components in FT-derived hydrocarbons at a temperature of above 100 ° C, the hydrothermal treatment being carried out with water with a temperature between 100 ° C and 400 ° C and the hydro-thermal treatment is achieved after a primary filtration zone for sufficient time to allow particle growth and / or adsorption on a filterable particle, and at a pressure that is higher then select the water vapor pressure at the prevailing temperature.

In the process, water can be added for the purpose of the hydrothermal treatment.

The process may include chemical treatment of the metal oxygenate components in the F-T derived hydrocarbons to modify the metal oxygenates.

The method can include one or more of the following treatment steps: (i) extracting modified metal oxygenates using one or more polar solvents; (ii) filtering the modified metal oxygenates after sufficient time has been given for particle growth and / or adsorption on an filterable particle; (iii) adsorbing the modified metal oxygenate on an adsorbent; (Iv) allowing the modified metal oxygenates to settle after sufficient time has been given for particle green; (v) centrifuging off the modified metal oxygenates after sufficient time has been given for particle growth; (vi) distilling off the hydrocarbons from the treated streams; (vii) flocculation of the modified metal oxygenates; (Viii) magnetic precipitation; (ix) electrostatic precipitation / settling; and (x) flotation of the modified metal oxygenates and fine particles; or (xi) any combination of one or more of the treatments mentioned above.

F-T hydrocarbons contain oxygenates and to some extent metals and / or metal species.

Ketones, aldehydes, alcohols, esters and carboxylic acids are the most important components of the oxygenate fraction.

Carboxylic acids are capable of forming metal-carboxylate complexes under suitable conditions with the metal species present.

Alcohols are capable of forming metal alkoxide complexes with the metal species present under suitable conditions.

The metal oxygenate may be a metal carboxylate, a metal alkoxide or a combination thereof or a metalloxane.

The metal oxygenate can be a carboxy-substituted metalloxane. i

The hydrothermal treatment is preferably used Performed with water at a temperature between 120 ° C and 370 ° C, and even up to 400 ° C, typically 160 ° C to 250 ° C and at a pressure of 1 to 100 bar, preferably 5 to 50 bar.

The water for the hydrothermal treatment can

are selected from water already in the van of the F-T

reaction water from hydrocarbons is present, or a combination of the reaction water and water added for the purpose of hydrotreating.

| The hydrothermal treatment can be carried out! 10 in a substantially single liquid phase system in which both the hydrocarbons and water are present, said water being present in such proportions that it is ensured that substantially one liquid phase is present during the process conditions.

! The hydrothermal treatment can be carried out in the presence of an adsorbent such as silica. Adsorption of the modified metal oxygenates takes place on the silica particles and these can then be removed by filtration or other treatment methods.

The hydrothermal treatment can also be achieved by maintaining the product stream at the temperature and pressure used in the FT reactor after a primary filtration zone for sufficient time to allow particle green and / or adsorption on a filterable particle, ie the hydrothermal treatment can be carried out by maintaining the reactor conditions between primary and secondary filtration zones for sufficient time to allow particle green or adsorption on a filterable particle. More in particular, a pressure can be selected that is higher than the water vapor pressure at the prevailing temperature. Sufficient time will be between 1 to 60 minutes, preferably between 1 to 30 minutes and more preferably between 5 to 10 minutes.

The optional chemical treatment may include transesterification to exchange longer chain carboxylic acids or alcohols with shorter chain carboxylic acids.

The chemicals that can be used in the transesterification or ligand replacement step include methanol, ethanol, oxalic acid, acetic acid, propanoic acid, salicylic acid, succinic acid, tartaric acid, lactic acid, malonic acid, glycic acid, citric acid, carbonic acid, maleic acid, fumaric acid, phthalic acid, the anhydrides of these acids (e.g., maleic anhydride) and thermal decomposition products of these acids. Also included are solid acids such as silica-alumina and / or other mixed oxide systems that possess Bransted acid. The interaction between these listed chemicals and the metal oxygenates can be accelerated by the thermal treatments.

Hydrothermal treatment can result in hydroxylation and formation of metal hydroxides and / or metal oxyhydroxides and / or metalloxanes.

The hydrothermal treatment can be carried out before, during or after the optional chemical treatment.

According to a second aspect of the invention, there is provided a process for treating hydrocarbons, which process comprises chemically treating with one or more single-stage chemical treatment agents of metal oxygenate components in F-T derived hydrocarbons to modify the metal oxygenates.

The chemical treatment can be followed by one or more of the following treatment steps: (i) extracting the modified metal oxygenates using one or more polar solvents; (ii) filtering the modified metal oxyenates after sufficient time has been given for particle growth and / or adsorption on an filterable particle; (iii) adsorbing the modified metal oxygenate on an adsorbent; (iv) allowing the modified metal oxygenates to settle after sufficient time has been given for particle green;

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7 (v) centrifuging off the modified metal oxygenates after sufficient time has been given for particle growth; (vi) distilling off the hydrocarbons from the treated streams; (vii) flocculation of the modified metal oxygenates; (viii) magnetic precipitation; (Ix) electrostatic precipitation / settling; and (x) flotation of the modified metal oxygenates and fine particles; or (xi) any combination of one or more of the treatments mentioned above.

The chemical treatment agents that can be used in the transesterification or ligand replacement step include methanol, ethanol, oxalic acid, acetic acid, propanoic acid, salicylic acid, succinic acid, tartaric acid, lactic acid, malonic acid, glycic acid, citric acid, carbonic acid, maleic acid, furnaric acid , phthalic acid, the anhydrides of these acids (e.g.

maleic anhydride) and thermal decomposition products of these acids. Also included are solid acids such as silica-alumina and / or other mixed oxide systems that have Bronsted acid. The interaction between these listed chemicals and the metal oxygenates can be accelerated by the thermal treatments.

The chemical treatment can be carried out in a single liquid phase in which both the hydrocarbons and one or more chemical treatment agents are present, said chemical treatment agents or agents being present in levels below their saturation level in the hydrocarbons, for example.

In the chemical treatment, the amounts of chemical treatment agents added may be such that they yield a single liquid phase, i.e., the chemical treatment agents are completely dissolved in the hydrocarbons under the processing conditions.

The chemical treatment may include transesterification for the exchange of carboxylic acids or longer-chain alcohols against shorter-chain carboxylic acids.

The polar solvents include, inter alia, water, molten organic acids, ethylene glycol, ionic liquids, and combinations thereof.

Filter materials used in the filtration include clays, silica, silica-aluminas, silicate-containing aluminas, cellulose, activated carbon, sintered metals, and material flashes such as nylons and polycarbonates.

The adsorbents and / or filterable particles include clays, silica, silica-aluminas, silicate comprising aluminas, cellulose, activated carbon, sintered metals, titanium oxide and material filters such as nylons and polycarbonates.

The adsorbents can also be used as a filter material.

The adsorbents can be added during the chemical and / or hydrothermal treatment, or during one of the downstream processing processes.

The growth of filterable particles is influenced by the thermal and / or hydrothermal treatment conditions and optionally, depending on the acid used as the chemical treatment agent as well as on the processing conditions, reversible or irreversible particle growth can be obtained which in turn removes of the modified metal species by filtration.

EXAMPLES OF APPLYING THE METHOD OF THE INVENTION

Reactor wax of a Low Temperature F-T (LTFT) in-! The plant was analyzed and found to contain metal carboxylates (Mx [02CR] y), carboxy-substituted metalloxanes 9 ([Μ (0) χ (OH) y (O2CR) z] n), alkoxides and combinations thereof derived from the catalyst, and / or carrier, and / or reactor, and / or filter clays, and / or refractory materials were leached.

The longer the metal-bonded hydrocarbon chain (-CR) of the carboxylate or alkoxide ligands, the better the component is soluble in the wax.

It is thought that when adding the shorter chain and / or water carboxylic acids or anhydrides to the wax, the long chain oxygenates bound to the metal species and / or particles are exchanged with the carboxylic acids and / or hydroxides with shorter chain, if water is present by transesterification and / or ligand exchange and / or hydroxylation: - The modified metal oxygenates obtained by the exchange of the carboxylic acids with a longer hydrocarbon chain against carboxylic acids with a shorter chain or hydroxylation with water, the modified metal oxygenates are more soluble in polar solvents such as water or ethylene glycol and can be extracted from the wax by these polar solvents.

The modified metal oxygenates obtained by exchanging the carboxylic acids with longer hydrocarbon chain with shorter chain carboxylic acids or hydroxylation with water result in the growth of the particles which can then be filtered off.

The modified metal oxygenates, obtained by exchanging the carboxylic acid with a longer hydrocarbon chain for carboxylic acids or alcohols with a shorter chain or hydroxylation with water, result in the formation of extractable / adsorbable particles on an adsorbent.

EXPERIMENTAL

A) Demonstration of the removal of the metal 35 species from the wax using hydrothermal treatment 10

The experimental setup used for this study is shown in Figure 1. It is a continuous process in downstream mode. Application of pressure is optional.

Using an HPLC pump, water is pumped from a reservoir placed on a balance through a 140 ° C hot pipe. The water (2% by weight relative to the wax) joins the molten wax, which has been heated to 140 ° C. The combined streams then seep over a sand bed that has been heated to a temperature of 350 ° C. The inert material is used for a better distribution or mixing between the water and washing phases and for increasing the residence time, which provides growth possibilities for the modified aluminum oxygenates and improves the efficiency of the separation process. The product after the sand bed 15 is passed through a 1 micron filter (or smaller) to collect the modified aluminum oxygenate agglomerates. After the filter, the wax product has an aluminum content of ^ 1 ppm Al as determined in, for example, ICP. Optionally, filters larger than 1 micron in size can be used in combination with a filter aid.

B) Examples demonstrating the removal of the metal species from the wax by chemical treatment followed by filtration: B. Citric acid as chemical treatment agent.

For experiments CH1, CH3 and CH5, 250 grams of F-T reactor wax containing oxygenated aluminum species (carboxylates and / or alkoxides) was added to a 600 ml autoclave. Before the citric acid was added to the autoclave (time zero) and the stirrer started, the wax was heated to the treatment temperature. Wax samples were taken on-line over time and passed through a 0.85 micron filter. The filtered wax samples were then analyzed for aluminum using ICP (see Table BI for a summary of the results).

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Table BI____ ppm Al in wax after x minutes of stirring

Wt. %

Exp. lemon-

Nr. acid Temp x = 0 X = 5 x = 10 X = 15 ° C ____ CH1 0.1__165 50____1_CH3 0.05__165 50 39 13__1_ CH5 1 0.02 165 50 _ 43 | B.2.1 - Maleic anhydride as a chemical treatment agent with different water contents in the hydrothermal treatment.

For experiments B2 a to c: wax (200 g) containing 50 ppm of aluminum such as aluminum oxygenates was first melted in an oven at 140 ° C, and then placed in the Parr autoclave, and heated to 230 ° C with stirring (700 rpm) . Maleic acid anhydride (0.1 wt.% With respect to charged wax) was dissolved in water (4 g in exp B2 a, 6 g in exp B2 b and 16 g in exp B2 c) and placed in a metal tube which then connected to the Parr reactor. After the desired temperature was reached, the pressure of the vessel via the metal tube was increased to 10 bar. This ensured that the complete aqueous solution was forced into the Parr autoclave. The first sample was taken 5 minutes after this addition. Samples were also taken at 10 minutes. After samples were taken from the wax, the sample bottle was placed in the 140 ° C oven. This wax was then filtered hot (140 ° C) through 0.45 μπι filter paper. The wax was then analyzed for aluminum using ICP. As can be seen in Table B2A, adding water (hydrothermal treatment) improves the particle growth and thereby the filterability of the modified metal oxygenates from the wax.

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Table B2A____

Experiment Wt% ma- Wt% Al (ppm) Al (ppm) number of leic acid-water left after after 10 minutes anhydride_2 a__O ^ JL__2__5__1_ B2 b__ΌΛ__3__2__ B2 c__O ^ JL__8 __ <1 __ <1_ B.2.2 Maleic anhydride treatment at different concentration levels and different hydro thermal treatment temperatures.

In experiments B2 d to g: wax (200 g) containing 45 ppm of aluminum was first melted in an oven at 140 ° C, and then placed in the Parr autoclave and heated with stirring (700 rpm) to 230 ° C for experiments B2 d to f, or 170 ° C for experiment B2 g. Maleic anhydride (see Table B2B for added weight%) was dissolved in 4 g of water and placed in a metal tube which was then connected to the Parr reactor. After the desired temperature was reached, the pressure of the vessel via the metal tube was increased to 300 psi. This ensured that the complete aqueous solution was forced into the Parr autoclave. The first sample was taken 5 minutes after this addition. Samples were also taken at 10 minutes.

After samples were taken from the wax, the sample bottle was placed in the oven at 140 ° C. This wax was then filtered hot (140 ° C) through 0.8 µm filter paper. The wax was then analyzed for aluminum using ICP. As seen from the results listed in Table B2B, maleic acid contents of up to 0.01% by weight were sufficient to promote particle growth and thereby filterability on the modified metal oxygenates from the wax at 230 ° C, but more time was needed at 170 ° C. Since these temperatures are above the maleic acid decomposition temperature, it is speculated that the maleic acid decomposition product, i.e., fumaric acid, is the active chemical agent.

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B2B Table ____

Experimental% male-Tempe-Al (ppm) Al (ppm) ment number acidity left after 5 left after 10 mer anhydride___minutes__minutes_ B 2 d__0Λ__230 ° C 1__1_ B 2 e__0.05__230 ° C 1__1_ B 2 f__0.01__230 ° C 1__1_

B 2 g 1 0.1 170 ° C 16

B. 3 - Polyacrylic acid (PAA)

The wax (200 g) containing 50 ppm aluminum was first melted in an oven at 14 ° C, and then placed in the Parr autoclave, and heated to 165 ° C with stirring (700 rpm). 0.1 wt.% PAA was added to 2 wt.% Water and placed in a metal tube which was then connected to the Parr reactor. After the desired temperature was reached, the pressure of the vessel was increased to 10 bar via the metal tube. This ensured that the complete aqueous solution was forced into the Parr autoclave. The first sample was taken 5 minutes after this addition. Samples were also taken at 10 minutes. After sampling the wax, the sample bottle was placed in the oven at 140 ° C. This wax was then filtered hot (140 ° C) through 0.45 µm filter paper. The wax was then analyzed for aluminum using ICP. As seen from the results, PAA was effective in removing modified metal oxygenates at 165 ° C.

Table B3 ___

Weight% PAA Weight% water Al (ppm) over Al (ppm) over __ after 5 minutes__ after 10 minutes 0.1__2 __ <1 __ <1_ B.4: The use of hydrothermal conditions and an filterable particle / adsorbent for modifying and adsorbing of modified metal oxygenates.

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The wax (200 g) containing soluble metal oxygenates was first melted in an oven at 140 ° C. 0.1 - 0.01% by weight of Aerosil 380 (Degussa) was added to the molten wax. The wax was then heated to 170 ° C with stirring (200 rpm).

Water (4 ml) was introduced into a metal tube connected to the Parr reactor. After the desired temperature was reached, a sample was taken. The water was then added to the reaction mixture and samples were taken at 5 and 10 minutes (Table B4) and passed through a 2.5 micron filter.

The water modified the metal complex so that it could adsorb onto the filterable particle.

Table B4 ppm Al in% by weight of silica Time Al% Al reference starting wax added_ (min) _ (ppm) dering_ 45 0.1 5 1 98 10 <1> 98 27 0.05 5 3 91 10 <1> 98 66 0.01 5 25 62 _10_22_67_ 15 B.5 The influence of the acid used on the stability of grown particles.

For experiments B5 a to e, wax (250 g) containing the soluble metal complexes was first melted in an oven at 165 ° C. 0.1 wt% citric acid was added to the molten wax. After the desired temperature was reached as indicated in Table B5, a sample was taken and treated after 5 minutes.

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Table B5______

Al ppm after filtering

Experiment Treatment for filtration__tration B5a Filter immediately _7_

Keep melted in oven (130 ° C) for B5b__45 minutes______2_

Cool (wax solidifies), hold for 45 minutes before melting again B5c and filter_30_

Cool (wax solidifies), hold B5d__ for 2 days before melting again and filter at 140 ° C.

Cool (wax solidifies), hold B5e__ for 2 days before melting again and filter at 200 ° C.

In experiment B5f, wax (200 g) containing 45 ppm of aluminum-5 min was first melted in an oven at 140 ° C, and then placed in the Parr autoclave, and heated to 170 ° C with stirring (700 rpm). Maleic anhydride (0.1 wt%) dissolved in water (2 wt%) was introduced into a metal tube which was then connected to the Parr reactor. After the desired temperature was reached, the pressure of the vessel via the metal tube was increased to 300 psi. This ensured that the complete aqueous solution was forced into the Parr autoclave. Two minutes were taken 15 minutes after this addition. After samples were taken from the wax, a sample was placed in the oven at 140 ° C. This wax was then filtered hot (140 ° C) through 0.8 µm filter paper. Sample 2 was cooled before being reheated to 140 ° C and filtered. The aluminum content of the wax was determined using ICP analysis. In contrast to the wax treated with citric acid, the filterability of the wax treated with maleic acid remained the same, while the reaction conditions determined the 16 filterability of the wax treated with citric acid.

Table B5B: experiment B5 f.

5 ____

Wt% Male Temperature Sample 1 (ppm Sample 2 (ppm Neic Acid Al) Al) anhydride 1 0.1 1 170 ° C 1 1 <1 1 1 1 1.

In these experiments, contaminated wax was pumped at a set temperature through a 10 mm diameter tube containing adsorbent or filter material. The pressure mentioned in the table is caused by the flow rate and the adsorbent characteristics of the wax.

In experiment C1, contaminated wax containing 14 ppm of aluminum and other metals such as cobalt was pumped through a cellulose Arbocel BVB40 as a filter / absorbent, without adding water or acid (see Table C1). No removal of aluminum was observed.

In experiment C2, experiment C1 was repeated but 2% by weight of water was added to the wax (see Table C2). The addition of water led to complete removal with continuous filtration for 2.5 hours.

In experiment C3, experiment C2 was repeated but with Vitacel L00 as filter material / adsorbent.

In experiment C4, experiment C2 was repeated but with Celpure S1000 as filter material / adsorbent.

In experiment C5, experiment C2 was repeated but with spray-dried Degussa silica (Aerosil 380) as filter material / adsorbent.

In experiment C6 a to j, the wash and water mixture was pumped through a packed bed with a residence time of 19 minutes, before being pumped through a Fitracel 9001 filter material. For experiments C6 a to e only water was added. This was done at different temperatures.

For experiments C6 f to j, a 0.1 M maleic acid in water solution at different temperatures was also added.

C.

Table Cl. Treatment of contaminated wax containing around 14 ppm of aluminum 18

Mon- Filter / Tempe- Pressure, bar Average - Time in be Result star-absorbing rature __ -Delivery float (minutes) __

material ° C Start End flow period cumulative Al C

m3 / m2 / h ___ latief___

Arbocel F96 BVB 40__170__0__0__5 ^ 1__15__L5__13 1

Arbocel F97 BVB 40__Γ70__0__0__4J3__15__30__19 2

Arbocel F98 BVB 40__170__0__0__5 ^ 0__15__45__17 1

Arbocel F100 BVB 40__170__0__0__5JL0__15__76__16 1

Arbocel F102 BVB 4 0__170__0__0 __ ^ 0__15__120__16 1

Working conditions F104 BVB 40__ITO__0__0__5JL2__15__180 14 1

Arbocel F106 BVB 40__170__0__0 __ ^ 0__15__225 16 2

Arbocel F108 BVB 40_ 170 0] 0 | 5.2 17_ [272 16 2

Table C2. Treatment of contaminated wax containing around 14 ppm of aluminum 19

Mon-Fiter / Temperature, bar Average Time in Result star-absorbing structure _ direct float (minutes) __ medium ° C Start End of flow, period cumul Al Cc m3 / m2 / h ___ latief___

Arbocel F115 BVB 40__170 0__0__3 ^ 8__15__15__1 __ <!

Arbocel F116 BVB 40__170 0__0__4 ^ 7__15__30 __ <1 <

Arbocel

Fl 17 BVB 40__170 0__1__5κ_0__15__45 __ <1 C

Arbocel F119 BVB 4 0__170 1__1__5Λ__30__90 __ <1 <

Arbocel F121 BVB 40__170 8__5__5 ^ _0__30__150 <1 <

Arbocel F123 BVB 4 0__170 1__1__5Λ__30__210 4 __ <

Arbocel F125 BVB 40__170 1__1__5 ^ 0__30__270 7__1_

Arbocel F127 BVB 40_ 170 1 6 5.0 30 [300 [6 1 20

Table C3: Treatment of contaminated wax that is approximately 14 ppm aluminum

Mon-Filter / Temperature, bar Average Time in absorbent medium _ float (minutes) medium ° C Start End flow, cumulative period m3 / m2 / h F127 Vitacel 170 1 10 5.2 18 18 __L00________ F128 Vitacel 170 10 25 5.0 15 33 __L00________ F129 Vitacel 170 25 75 5.0 30 63: __L00________ F130 Vitacel 170 75 87 4.8 21 84 _ L00________

Table C4: Treatment of contaminated wax containing about 16 ppm aluminum.

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Mon - Filter Temperature - Pressure, bar Average - Time in Resultate star type rature (floating) (min ° C__ flow rate) _______

Start End m3 / m2 / h periodically cumulated Al Co C

the Latief F143 Celpure S1000 170__4__6__5 ^ 0__15__15__3__J .__ f F144 Celpure S1000 170 6__6__5 ^ JL__15__30__5__1 __ <F145 Celpure S1000 170 6__6__5_10__15__45__9__1__i F146 Celpure S1000 170 6__6__5_10__30__75__14__1 __ <F147 Celpure S1000 170 6__6__5 ^ 2__45__120 17 2__6 F148 Celpure S1000 170 6 12 5.0 30 150 19 2 < F149 Celpure S1000 170 12 30 4.8__15__165 7 1 __ <F150 Celpure S1000 170 30 40 4.9__40__205 2 <1 <F151 Celpure S1000 170 [40 41 5.0 15 220 1 <1 | <22

Table C5: Treatment of contaminated wax which is approximately 22 ppm of aluminum

Mon-Filter Tem-Pressure, bar Average-Time in Result star / absorbent float ture _ flow, (minutes) __ ° C Start End m3 / m2 / h perio-cumul Al C <lative F153 S102 sprayed.

dried Degussa Aerosil 380 F154 SiO 2 sprayed 170 5 5 5.0 15 30 1.

dried Degussa

Aerosil 380 __ F155 S1O2 spray 170 5 5 5.0 30 60 1 <1 dried Degussa __Aerosil 380_ F156 S1O2 spray 170 8 7 5.2 15 75 1 <dried Degussa __Aerosil 380__ ___ 23

F157 SiO 2 sprayed 170 7 7 5.0 30 105 1 C

dried Degussa __Aerosil 380 _ _____ F158 SiC> 2 sprayed 170 10 7 5.0 40 145 1 <dried Degussa ___Aerosil 380___________ F159 Si02 sprayed 170 7 7 5.1 60 205 1 <dried Degussa ___Aerosil 380__________ F160 Si02 sprayed 170 7 7 5.1 40 245 4 <'dried Degussa __Aerosil 380__________ 24

Sample Temp Pressure over Water% Filter / Stay #. ° C filter, bar added absorbent for fil. + 0.1M Maleic D71__170 41__ic acid__Filtracel EFC 9001 19_ 2 + 0.1M Maleic D72__150 8__ic acid__Filtracel EFC 9001 19_ 2 + 0.1M Maleï- D73__160 8__neic acid__Filtracel EFC 9001 19_ 2 + 0.1M Malex- D74__170 12tracelic acid EFC 9001 EFF 900C

Claims (24)

A method for treating hydrocarbons, which method also comprises hydrothermally treating metal oxygenate components in FT-derived hydrocarbons at a temperature above 100 ° C, wherein the hydrothermal treatment is carried out with water with a temperature between 100 ° C and 400 ° C and the hydrothermal treatment is achieved after a primary filtration zone for sufficient time to allow particle growth and / or adsorption on a filterable particle, and at a pressure selected to be higher than the water vapor pressure at the prevailing temperature. The method of claim 1, wherein water is added for the purpose of the hydrothermal treatment. The method of claim 1 or 2, which method comprises chemically treating the metal oxygenate components in the F-T derived hydrocarbons to modify the metal oxygenates. The method of claim 1 or claim 2, wherein the treatment is followed by one or more of the following treatment steps: (i) extracting modified metal oxygenates using one or more polar solvents; (ii) filtering the modified metal oxygenates after sufficient time has been given for particle green and / or adsorption on an filterable particle; (iii) adsorbing the modified metal oxygenate on an adsorbent; (iv) allowing the modified metal oxygenates to settle after sufficient time has been given for particle growth; (v) centrifuging off the modified metal oxygenates after sufficient time has been given for particle green; (vi) distilling off the hydrocarbons from the treated streams; (vii) flocculation of the modified metal oxygenates; (viii) magnetic precipitation; (ix) electrostatic precipitation / settling; and (x) flotation of the modified metal oxygenates and fine particles; or any combination of one or more of the treatments mentioned above. The method of any one of the preceding claims, wherein the metal oxygenate is a metal carboxylate, a metal alkoxide, a metalloxane, or a combination of two or more thereof. The method of any one of claims 1 to 20, wherein the metal oxygenate is a carboxy-substituted metalloxane. The method according to any of the preceding claims, wherein the hydrothermal treatment is carried out with water between 120 ° C and 370 ° C. 8. A method according to any one of the preceding claims, wherein the water for the hydrothermal treatment is selected from water that is already present in the reaction water present from the hydrocarbons originating from the FT, or a combination of the reaction water and water for the purpose of the hydrotreatment has been added. 9. A method according to any one of the preceding claims, wherein the hydrothermal treatment is carried out in a substantially single liquid phase system in which both the hydrocarbons and water are present; 27 yy wherein the said water is present in such proportions! that it is ensured that substantially one liquid phase is present during the process conditions. A method according to any one of the preceding claims, wherein the hydrothermal treatment is carried out in the presence of an adsorbent. The method of claim 10, wherein the adsorbent comprises silica. The method of claim 11, wherein adsorption of the modified metal oxygenates on the silica particles takes place and these particles are then removed by filtration or other treatment methods. 13. A method according to any one of the preceding claims, wherein the chemical treatment comprises transesterification for exchanging carboxylic acids or alcohols with a longer hydrocarbon chain against a shorter chain carboxylic acids. 14. A method according to claim 13, wherein the chemicals used in the transesterification or ligand replacement step are selected from the group of methanol, ethanol, oxalic acid, acetic acid, propanoic acid, salicylic acid, succinic acid, tartaric acid, lactic acid, malonic acid, glycic acid, citric acid, carbonic acid, maleic acid, fumaric acid, phthalic acid, the anhydrides of these acids, and thermal decomposition products of these acids. The method of claim 16, wherein the chemicals used in the transesterification or ligand replacement step are selected from the group of silica-alumina and / or other mixed oxide systems that 30 have Bronsted acidity. The method of any one of the preceding claims, wherein the hydrothermal treatment results in hydroxylation and the formation of one or more metal hydroxides, metal oxyhydroxides, and metalloxanes. A method according to any one of the preceding claims, wherein the hydrothermal treatment is carried out before, during or after the chemical treatment. i 18. A process for treating hydrocarbons, which process comprises chemical treatment with one or more single-stage chemical treatment agents of metal oxygenate components in F-T derived hydrocarbons for modifying the metal oxygenates. 19. A method according to claim 18, wherein the chemical treatment is followed by one or more of the following treatment steps: (i) extracting the modified metal oxygenates using one or more polar solvents; (ii) filtering the modified metal oxygenates after sufficient time has been given for particle green and / or adsorption on an filterable particle; (iii) adsorbing the modified metal oxygenate on an adsorbent; (iv) allowing the modified metal oxygenates to settle after sufficient time has been given for particle green; (v) centrifuging off the modified metal oxygenates after sufficient time has been given for particle green; (vi) distilling off the hydrocarbons from the treated streams; (vii) flocculation of the modified metal oxygenates; (viii) magnetic precipitation; (ix) electrostatic precipitation / settling; and (x) flotation of the modified metal oxygenates and fine particles; or any combination of one or more of the treatments mentioned above. 20. Method according to claim 18, wherein the chemical treatment agents used in the transesterification or ligand replacement step are selected from the group of methanol, ethanol, oxalic acid, acetic acid, propanoic acid, salicylic acid, succinic acid, tartaric acid, lactic acid , malonic acid, glycic acid, citric acid, carbonic acid, maleic acid, fumaric acid, phthalic acid, the anhydrides of these acids, and thermal decomposition products of these acids, and solid acids including but not limited to silica-alumina and / or other mixed oxide systems that Bronsted acidity. 21. Method according to claim 18, wherein the chemical treatment is carried out in a single liquid phase in which both the hydrocarbons and one or more chemical treatment agents are present, said chemical treatment agents or agents having levels below their saturation level in the hydrocarbons present. The method of any one of claims 18 to 21, wherein the polar solvents are selected from the group consisting of at least water, molten organic acids, ethylene glycol, ionic liquids, and combinations thereof. The method of any one of claims 18 to 22, wherein one or more of the adsorbents, filter material, and filterable particles are selected from the group of at least clays, silica, silica-aluminas, silicate-containing aluminas, cellulose, activi 30 carbon, sintered metals, titanium oxide and material filters such as nylons and polycarbonates. The method of any one of claims 18 to 23, wherein the adsorbents are added during the chemical treatment, the hydrothermal treatment, during one of the downstream processes, or during two or more of the aforementioned steps.