EA039870B1 - Demetallization of hydrocarbons - Google Patents

Abstract

The invention refers to a process and a process plant for extraction of metals from a hydrocarbon mixture obtained from a gasification or pyrolysis process, the process comprising the steps of combining said hydrocarbon mixture with an aqueous acid forming a mixture, mixing said mixture, separating said mixture in a contaminated aqueous phase and a purified hydrocarbon phase, with the associated benefit of said aqueous acid being able to release metals bound in such gasification or pyrolysis processes.

Description

(57) The present invention relates to a method and apparatus for extracting metals from a hydrocarbon mixture obtained during a gasification or pyrolysis process, said method comprising the steps of combining said hydrocarbon mixture with an aqueous acid solution to form a mixture, mixing said mixture, separating said mixture onto an aqueous phase containing impurities and a purified hydrocarbon phase, whereby said aqueous acid solution preferentially releases the metals bound during said gasification or pyrolysis processes.

During the processing of mixtures of hydrocarbons, an important step is the removal of heteroatoms to ensure compliance with the necessary technical characteristics, to prevent harm to the environment and to achieve operational objectives. A common way to remove heteroatoms, such as sulfur, nitrogen and oxygen, from a mixture of hydrocarbons is hydrotreating, when such atoms are reacted with hydrogen. However, if metal impurities are present in the mixture, even at relatively low concentrations, the activity of the catalysts can be significantly reduced. The presence of metallic impurities can lead to the formation of solids on the surface of the catalyst, such as coke or tar, which deactivates the hydrotreating catalyst. Thus, when hydrotreating raw materials containing metals, a so-called protective layer is necessary before the hydrotreating step. Such a protective layer is characterized by a high ability to retain metals, so that the separated metals are simply trapped on the catalytic surfaces. Despite this high metal holding capacity, it is necessary to replace the catalytic particles at certain intervals, which is associated with significant costs due to the need to stop the operation of the plant and reduce productivity and replace the catalytically active material. Also costly is the configuration of the protective layers operating alternately, when one protective layer is blocked to replace the catalytically active material, while the other is included in the operation of the installation so that its operation does not stop.

The content of metals in the hydrocarbon mixture can vary from a few parts per million to thousands of ppm. Particularly high metal levels are obtained in the presence of recoverable oils and fats, pyrolysis oil and coke tar. Raw materials containing such substances are also characterized by the content of oxygen-containing compounds such as phenols, naphthenols, cresols and naphthenic acids. Surprisingly, it has been found that when metals are bound by such structures, significant amounts of metals can be released by contacting hydrocarbon mixtures with aqueous acids. In addition, it has been found that it is possible to obtain a plant configuration that provides a combined process, in which during the stages of the gas cleaning process, sulfuric acid is produced from by-products, which can be used for the demetallization process by acid washing.

The acid number is a measure of the content of organic acids in the stream. ASTM D664 provides a method for determining the acid number as the amount of a specified base, expressed as milligrams of potassium hydroxide per gram of sample, required to titrate a sample in a specified solvent to a specified critical point using a specified detection system.

As used in the purification process art, the term hydrocarbon mixture includes any streams in which hydrocarbons are the main component, but which also contain elements other than hydrogen and carbon, such as oxygen, sulfur, nitrogen, halides and metals.

As used throughout this document, the term two-phase mixture includes mixtures that separate into two phases, as well as emulsions and other mixtures consisting of two (or more) components that are dispersed at the microscopic level, even if such a mixture is stable at the macroscopic level .

When two phases are mentioned, this can mean one polar phase and one non-polar phase, however, this definition can also be interpreted as at least two phases, for example, a heavy non-polar phase with a density greater than that of an aqueous phase, an aqueous phase and a light non-polar phase with a density less than the density of the aqueous phase.

As used herein, the terms pyrolysis and gasification refer to a process in which a carbonaceous feedstock such as coal or biomass is heated in the absence of oxygen or in the presence of substoichiometric amounts of oxygen to oxidize CO2.

Pyrolysis and gasification products consist of a solid phase, a gas phase and a liquid phase, i.e. resins.

When used throughout this document, in accordance with the use in the field of cleaning processes, the term resin means a heavy hydrocarbon liquid. Terms such as pyrolysis oil, coal tar, and coke tar can be used to refer to the source of the tars. For the purposes of this application, tar is generally understood to mean the product of pyrolysis, coke production or coal gasification. The resin is characterized by the presence of a large number of heteroatoms (especially nitrogen, sulfur and oxygen), as well as a high content of aromatic compounds. Typical resin characteristics: hydrocarbon liquid containing from 0.5 or 1% to 5, 6 or 10% oxygen, with a density of more than 0.90 g/ml, more than 0.96 g/ml, more than 1.05 g/ml, with a ratio between nitrogen atoms and sulfur atoms (N:S) of more than 1:1, 2:1, 5:1 or 10:1, with a hydrogen content of less than 10% (wt./wt.) and with an acid number of more than 2 or 4 and less than 7 or 8 mg KOH/g.

The present invention does not apply exclusively to tar, but also to other hydrocarbon liquids with a high oxygen content, such as solid fats of animal origin, liquid vegetable fat and tall oils, containing up to 25% oxygen and having a high acidity.

- 1 039870

In a broad sense, the present invention relates to a method for extracting metals from a hydrocarbon mixture obtained during a gasification or pyrolysis process, while such a method includes the steps of mixing said hydrocarbon mixture with aqueous acid to form a mixture, mixing said mixture, separating said mixture into an aqueous mixture containing impurities a phase and a purified hydrocarbon phase, whereby the metals bound during said gasification or pyrolysis process are predominantly released by contact with an aqueous acid.

In accordance with one of the embodiments, the present invention relates to a method for producing a hydroprocessed hydrocarbon from a hydrocarbon mixture obtained during the gasification or pyrolysis process, or from a mixture of oxygen-containing compounds of biological origin, while the acid number of the specified hydrocarbon mixture is more than 1.5 mg KOH/ g, 2 mg KOH/g or 4 mg KOH/g, including the following steps:

a) combining said hydrocarbon mixture with an aqueous acid to form a mixture;

b) mixing said mixture;

c) separating said mixture into an aqueous phase containing impurities and a purified hydrocarbon phase;

d) mixing said purified hydrocarbon phase with a hydrogen rich gas to form a hydrotreating stream;

e) feeding said hydrotreating stream to the hydrotreating step to form a hydrotreated hydrocarbon, resulting in a predominantly high acid number hydrocarbon mixture during the treatment, such as more than 1.5 mg KOH/g, 2 mg KOH/g or 4 mg KOH/g , the materials used for the equipment must be particularly resistant to corrosion.

Thus, by adding aqueous acid and then removing the aqueous phase, there will be no additional requirements for downstream equipment, since the remaining amount of acid will be negligible compared to the acidity of the hydrocarbon mixture.

In accordance with another embodiment of the invention, the hydrocarbon mixture contains from 0.5 or 1% to 5, 6 or 10% oxygen, as a result of which said aqueous acid is predominantly particularly suitable for the release of metals associated with oxygen-containing compounds, such as phenols, naphthenol , naphthenic acids and cresols.

In accordance with another embodiment of the invention, the aqueous acid is selected from the group consisting of concentrated inorganic acids or organic acids, preferably citric acid, oxalic acid, hydrochloric acid, phosphoric acid or sulfuric acid, whereby predominantly acids provide a strong chelating effect for extracting metals from said hydrocarbon phase, in particular citric acid, oxalic acid and sulfuric acid, and these acids are easily removed further during purification processes.

In accordance with another embodiment of the invention, the process does not include the addition of an aqueous liquid containing elements other than C, H, O, N and S at a concentration of more than 0.1%, resulting in advantageous addition of elements that cannot be extracted. during normal cleaning processes.

In accordance with another embodiment of the invention, the concentration of aqueous acid is from 1 or 2% to 5, 10 or 30%, whereby advantageously such an acid concentration has both moderate corrosiveness against process equipment and high reactivity against associated metals.

In accordance with another embodiment of the invention, the ratio of the hydrocarbon mixture is from 20:1, 10:1, 50:1 to 2:1, 1:1 or 1:2, as a result of which this ratio advantageously provides both a high ability to remove metals, and a moderate increase in technological volume.

In accordance with another embodiment of the invention, the temperature in step b is 20-150°C, as a result of which the viscosity of the hydrocarbon mixture decreases at elevated temperatures, and the stability of the emulsion is disturbed, thus allowing separation into a purified hydrocarbon phase and an aqueous phase.

In accordance with another embodiment of the invention, the acid number in the mixture is greater than 2 or 4 and less than 7 or 8 mg KOH/g, whereby such acidity preferably corresponds to the normal acidity of the hydrocarbon mixture.

In accordance with another embodiment of the invention, the acid value in the hydrocarbon mixture is less than 7, 8, 25, or 150 mg KOH/g, whereby the processing of the hydrocarbon mixture with an acid value of 7, 8, 25, or 150 mg KOH/g can be advantageously conventional cleaning methods using equipment made from appropriate materials. Typically, the acidity of resins is 2-8 mg KOH/g, the acidity of biological oils and fats is 615 mg KOH/g, and fatty acids such as crude tall oil can be 100-150 mg KOH/g.

According to yet another embodiment of the invention, said hydrotreating step (e) comprises contacting the hydrotreating stream with one or more catalytically active materials.

- 2 039870 rials having activity in relation to one or more reactions selected from the group including hydrogenation of heteroatomic hydrocarbons, hydrogenation of diolefins and hydrogenation of metallic heteroatomic hydrocarbons, each of these one or more materials may be present in one or more reactors, and may any sequence of said one or more materials is used, and the pressure, temperature, and space velocity are such that the catalytically active material has activity for the respective reactions, thereby advantageously providing a device known in the purification industry for reducing the acidity of the hydrotreating stream, while meeting other requirements in regarding the treatment of the hydrotreating stream. Typically, the use of a material having catalytic activity in the hydrogenation of diolefins will occur at an average operating temperature in the range of 150-200°C, and the use of a material having catalytic activity in the hydrogenation of metals and other heteroatoms will occur at an average operating temperature in the range of 280 -400°C, preferably 300-360°C, the pressure may be in the range of 2.5-20 MPa, preferably 6-10 MPa, the liquid hourly space velocity may be 0.2-5 h' ¹ and the hydrogen/hydrocarbon ratio may be in the range of 100-2000 nm. ³ /m ³ , however, the specialist will understand that these conditions are interdependent and may vary depending on the choice of specific materials.

In accordance with another embodiment of the invention, some of said hydrotreated hydrocarbon is withdrawn and fed back as a recycle stream to a point located upstream of the point of withdrawal, while the ratio of hydrocarbon mixture: recycle stream is from 1:1/2 to 1: 3, whereby the predominantly hydrotreating stream or derivative stream is diluted, thereby reducing the temperature shock due to exothermic hydrogenation and reducing the corrosivity of the hydrotreating stream.

In accordance with yet another embodiment of the invention, the process further comprises a hydrocracking step (f), optionally including an additional hydrotreating step, and a separation step (g) to produce a vapor product and one or more liquid hydrocarbon products, wherein the operating temperature in step ( f) hydrocracking is 330-420°C, and the pressure is from 1.5, 6 or 10 MPa to 20 MPa, the liquid hourly space velocity is from 0.2 to 5 h ^-1 , and the hydrogen/hydrocarbon ratio is 100-2000 n .m ³ /m ³ , resulting in the conversion of hydrotreated hydrocarbons from high to low boiling point mainly during this hydrocracking step, while the commercial value of hydrocarbons, such as naphtha or middle distillate, which can be obtained after the separation step, increases. In addition, the recycle stream is preferably withdrawn at a point before the hydrocracking stage, which is carried out under high pressure, as a result of this, the volume of the stream in the equipment operating under high pressure will decrease. Typically, the use of a material having catalytic activity in the hydrogenation of diolefins will occur at an average operating temperature in the range of 150-200°C, and the use of a material having catalytic activity in the hydrogenation of metals and other heteroatoms will occur at an average operating temperature in the range of 280 -400°C, preferably 300-360°C, the pressure may be in the range of 2.5-20 MPa, preferably 6-10 MPa.

In accordance with yet another embodiment of the invention, prior to step (a), the method further comprises the step of gasifying the carbonaceous material, producing said hydrocarbon with an acid number greater than 1.5 mg KOH/g, thereby advantageously providing a process for converting the carbonaceous material to produce several useful products, including hydroprocessed hydrocarbons.

In accordance with yet another embodiment of the invention, the method further comprises the step of transporting an intermediate product from one geographic location to another, wherein said intermediate product is either said hydrocarbon with an acid number greater than 1.5 mg KOH/g, or said hydroprocessed hydrocarbon, resulting in which advantageously provides a method in which a stabilized intermediate product is obtained in the vicinity of a coke oven and then transported to a processing plant for subsequent conversion to obtain a commercially valuable product.

Another aspect of the present invention relates to a process plant for the production of purified hydrocarbon from tarry feed, comprising: an acid wash reactor having one or more inlets hydraulically connected to the tar feed inlet and to the acid feed inlet, and having an outlet hole; means for separating phases with an inlet, an outlet for withdrawing an aqueous phase and an outlet for withdrawing a purified hydrocarbon phase, wherein the outlet of said acid washing reactor is hydraulically connected to the inlet of said means for phase separating, as a result of which such a technological installation can advantageously be used to extract metals from hydrocarbon mixtures derived from resins.

- 3 039870

In accordance with another embodiment of the invention, the process unit further comprises a gasification or pyrolysis section with an inlet for supplying solid carbon fuel, an inlet for supplying water and an inlet for supplying an oxidizer, an outlet for removing synthesis gas and an outlet for removing resin wherein said resin outlet is hydraulically connected to said feed inlet, whereby advantageously such a process unit provides a means for efficiently converting solid carbon fuel to refined hydrocarbons.

In accordance with another embodiment of the invention, the process plant further comprises a gas purification section, where gas containing CO, H2 and SO2 enters, with an inlet, an outlet for removing desulphurized synthesis gas and an outlet for removing sulfuric gas, a section for producing sulfuric acid with an inlet for supplying a source of sulfur and an outlet for removing sulfuric acid, while the specified outlet for removing sulfuric gas is hydraulically connected to the specified inlet for supplying a source of sulfur, the specified outlet for removing sulfuric acid is hydraulically connected to the specified inlet acid, and the resin outlet is hydraulically connected to said feed inlet, as a result of which, advantageously, such a process plant requires the supply of minimal amounts of raw material for demetallization from external sources, since it is necessary the required amount of acid is provided during the operation of the process plant itself.

In accordance with another embodiment of the invention, the phase separating means is selected from the group consisting of centrifuges, electrostatic separators, gravity separators, while centrifuges advantageously have a high separation efficiency, and gravity separators advantageously do not require high costs.

In accordance with another embodiment of the invention, the process unit includes a hydrotreating section with an inlet and an outlet, while the inlet of said hydrotreating section is hydraulically connected to the outlet to remove said purified hydrocarbon phase, as a result of which, advantageously, said process unit is compatible with conventional processes. at a processing plant.

In accordance with another embodiment of the invention, said process unit includes a hydrocracking section with inlet and outlet, wherein the inlet of said hydrocracking section is hydraulically connected to the outlet of said hydrotreating section, as a result of which, advantageously, such a process unit allows the production of a wide range of hydrocarbons, having commercial value, from a hydrocarbon mixture containing a large amount of impurities.

The recovery of metals from a hydrocarbon mixture is an important technological step, since the presence of metals can cause serious problems in the processing plant. In particular, providing protective layers for recovering metals can be costly, and the protective layers can cause significant pressure drops when the metals are held by such materials. Thus, it is desirable to provide a process in which metals are not retained in the process, but in which they are removed from the process.

Known methods of adding acids to extract metals from hydrocarbon mixtures, however, it was found that the highest extraction efficiency is usually achieved under neutral or near neutral conditions, while avoiding an increase in the acidity of the product, as this will increase the risk of equipment corrosion, in addition, for most processed products, there are acid number restrictions. However, coke tar, pyrolysis oils and reduced fats and oils generally have high acid numbers (2-8 mg KOH/g), so these products are processed using equipment made of corrosion resistant materials. Thus, the pre-treatment stage, which is contacted with aqueous acids to extract metal impurities, will not significantly change the suitability of the product for processing and will not affect the choice of material for the manufacture of reactors, vessels and other equipment, since the use of raw materials is envisaged in the field of processing plants. with an acid number of more than 0.5 mg KOH/g, while types of raw materials with an acid number of more than 1.0, 1.5 or 2.0 mg KOH/g are considered as aggressive substances, when using them, special attention should be paid to the development of the design and /or choice of materials.

During hydrotreating, the acid number/acidity decreases/decreases as acidic compounds are converted, eg naphthenic acids, phenols, naphthalenols.

In coke tar and pyrolysis oil, the amount of metals will typically be 200-500 ppm wt, and in reconstituted fats and oils, such amounts can reach hundreds of ppm wt. Most of these metals are in the form of soluble compounds that cannot be removed by mechanical filtration.

Without being bound by theory, it is believed that the addition of acid to the hydrocarbon mixture will result in the release of metals present as complexes with phenol and other organic groups (eg naphthenic acids), followed by recovery of the metals by chelation with the acid.

In order to prepare the product for further processing, the aqueous phase must be removed. This can be done using a variety of means, such as mixer-precipitators, centrifuges, electrostatic precipitators and gravity precipitators.

An advantage associated with the acid washing demetallization process is that the content of total and basic nitrogen compounds in the hydrocarbon mixture is reduced, thereby reducing the inhibition of NH ₃ and organic nitrogen during hydrotreating, in particular the inhibition of hydrocracking catalysts. This means that the volume of catalyst required as well as hydrogen consumption can be reduced.

The choice of acids for acid washing depends on several aspects. Obviously, an important aspect is the ability to remove metals, which is related to the ability of the acid to chelate and the concentration of the acid. In addition, acid compatibility with downstream cleaning processes is important. In this aspect, sulfuric acid has the advantage that any amounts of sulfuric acid entrained by hydrocarbons, as well as bisulfate and sulfate anions, will be easily removed further during the hydrodesulfurization process along with the removal of organic sulfur and hydrogen sulfide. Likewise, organic acids also need to be compatible with downstream processes, and when phosphoric or hydrochloric acid is used, a strong poisoning effect of phosphorus and chloride can occur, or they can enter downstream stages and introduce elements that would otherwise would not be present in the hydrocarbon feedstock.

In the case of resin processing, the viscosity of the resin is also important. Some resins are highly viscous and are preferably processed at about 80° C., while other resins may be less viscous and may therefore be processed at lower temperatures.

The method can be developed taking into account the properties of the raw material. If the resin is obtained directly from a previous pyrolysis or gasification process, the resin may need to be cooled for processing with an aqueous acid liquid phase, while if the resin enters the process after storage, the resin may need to be heated.

figures

In FIG. 1 shows the general scheme of the method according to the present invention.

In FIG. 2 is a diagram of the method of the present invention.

In FIG. 3 is a conceptual diagram of a combined process unit for processing coke tar according to the present invention.

In FIG. 4 is a diagram of a combined process plant according to the present invention.

In FIG. 5 describes a demetallization process by hydrotreating according to the prior art.

In the figures, the position numbers correspond to the following elements:

- hydrocarbon mixture;

- heater;

- aqueous acid;

- mixing reactor;

- means for phase separation;

- water phase with impurities;

- purified hydrocarbon phase;

- stream rich in hydrogen;

- hydrotreating reactor;

- protective layer for extraction of metals;

- material with catalytic activity in hydrotreating;

- hydroprocessed product flow;

- gas and liquid separator;

- hydroprocessed hydrocarbons;

- steam flow;

- acid gas removal section;

- a stream rich in hydrogen sulfide;

- flow of recirculated gas;

- make-up hydrogen;

- stream rich in sulfur dioxide;

- sulfur dioxide converter;

- oxidation of sulfur dioxide;

- stream rich in sulfur trioxide;

- 5 039870

- sulfuric acid production unit;

- concentrated sulfuric acid;

- water;

100 - carbon raw materials;

102 - solid product;

104 - gaseous outlet stream;

106 - resin;

108 - exhaust gas;

110 - gas rich in SO ₂ ;

112 - resin;

114 - sulfuric acid;

116 - demetallized resin;

118 - hydroprocessed hydrocarbons;

120 - furnace;

122 - gas cleaner;

124 - resin condensation;

126 - section of sulfuric acid;

128 - demetallization section;

130 - hydrotreating section;

132 - gas cleaning (not shown);

600, 700 - carbon raw materials;

602, 702 - solid carbonaceous coke;

604, 704 - gaseous outlet stream;

606, 706 - liquid resin;

610, 710 - aqueous phase with impurities;

612, 712 - sulfuric acid;

614, 714 - purified hydrocarbon phase;

616, 716 - heavy residue;

618, 718 - refined hydrocarbons for processing;

620, 720 - stream for hydroprocessing;

624, 724 - stream rich in hydrogen;

648, 748 - gas stream rich in hydrogen;

634, 734 - hydrotreated recycle product;

622, 722 - conditioned stream;

626, 726 - demetallized hydrocarbon;

628, 728 - hydroprocessed product stream;

632, 732 - hydroprocessed hydrocarbons;

630 - steam flow;

638, 738—hydrotreated hydrocracking feedstock;

640, 739 - hydrocracked product;

642, 742 - grease;

644, 744 - middle distillate;

646, 746 - naphtha;

660, 760 - coke oven;

668, 768 - protective layer for the extraction of metals;

670, 770 - hydroprocessing reactor;

662, 762 - demetallization section;

672, 772 - gas and liquid separator;

674, 774 - pump;

676, 678, 778 - hydrotreating reactors;

680, 780 - hydrocracking reactor;

682, 782 - installation for fractionation;

730 - flow of the heavy part of the raw material;

740 - hydrocracked hydrocarbons;

770, 788 - compressor.

In FIG. 1 shows a simplified diagram of the method of the present invention. Hydrocarbon mixture 2, containing oxygen-containing compounds and metals, if necessary, is heated in 3, and together with aqueous acid 4 is fed into a mixing reactor 6, in which mixing takes place. The mixture is fed into a phase separator 8, from which an aqueous phase 12 containing impurities and a purified hydrocarbon phase 10 are withdrawn.

The specific design of the mixing reactor 6 may be selected from a wide range of options; similarly, separation can be done using gravity

- 6 039870 devices, centrifuges, electrostatic separators or other means for separation. The centrifuge is more expensive and has a higher production cost, but the higher efficiency it provides may be a factor that outweighs these drawbacks.

Shown in FIG. 2, the method is carried out in a combined mixing and separating device of the mixer-precipitator type, in which phase separation occurs by simple gravitational settling.

The hydrocarbon mixture 2, containing oxygen-containing compounds and metals, is optionally heated in 3, and together with aqueous acid 4 is fed into a device such as a mixer-precipitator with a mixing reactor 6, in which mixing takes place. The mixture is fed into a separating means 8, which in this case is a precipitator, in which the phase separation is carried out by simple gravitational settling. An aqueous phase 12 containing impurities and a purified hydrocarbon phase 14 are removed from the precipitator.

In FIG. 3 is a schematic diagram of the integrated process unit for processing coke tar according to the present invention, without specific details (side streams not shown). In the production of coke tar, the carbonaceous feedstock 100 is fed into the coke oven 120, and the solid carbonaceous coke 102 and the gaseous effluent 104 _are removed from there. Resin 106 is cooled and fed to a resin condensation step 124 where liquid resin 112 is withdrawn. SO2 rich gas 110 is treated in sulfuric acid section 126 (which may be dry or wet type) to produce sulfuric acid 114. Liquid resin 112 and sulfuric acid 114 is fed to a demetallization section 128 from where demetallized resin 116 is removed and fed to a hydrotreating section 130 from which hydrotreated hydrocarbons 118 are removed.

A similar process scheme can also be applied in the production of pyrolysis oil from biomass as a carbonaceous feedstock. In this case, the solid product 102 from the pyrolysis oven 120 will typically be waste, and the specific gas scrubbing 132 (not shown) in the pyrolysis process may differ from that in the coke oven process, but the overall configuration will be very similar.

In FIG. 4 is a more detailed specific diagram of the combined process plant of the present invention. In the demetallization section 128, the hydrocarbon mixture 2 containing oxygen-containing compounds and metals, such as resin, together with aqueous acid 4 is fed into a mixing reactor 6, in which mixing occurs for a certain time. The mixture is fed to a phase separator 8 from which an aqueous phase 10 containing impurities and a purified hydrocarbon phase 12 are withdrawn. a material 20 having hydrotreating catalytic activity known to those skilled in the art is disposed. A hydrotreated product stream 22 is withdrawn from the hydrotreating reactor. The hydroprocessed product stream 22 is subjected to separation in a gas/liquid separator 24, or optionally in a separator cascade, and separated into hydrotreated (and thereby desulfurized) hydrocarbons 26 and a vapor stream 28. The vapor stream 28 is fed to an acid gas removal section 30, in which the for example, an amine scrubber that separates vapor stream 28 into hydrogen sulfide-rich stream 32 and recycle gas stream 34. Make-up hydrogen 36 is added to recycle gas stream 34 to form hydrogen-rich stream 14. In the sulfuric acid production section 126, sulfur dioxide from the coke oven, optionally together with combusted H2S and reclaimed waste acid, is produced as a sulfur dioxide rich stream 42. This stream is fed to a sulfur dioxide converter 44, which contains a material 46 with catalytic activity in the oxidation of sulfur dioxide, where sulfur dioxide is oxidized to sulfur trioxide to form a stream 48 rich in sulfur trioxide, which is fed to a sulfuric acid production unit 50, which may be a condenser where hydrated sulfur trioxide is condensed to form concentrated sulfuric acid 52, or which may be an absorber where sulfur trioxide is absorbed to form sulfuric acid to form concentrated sulfuric acid 52. Generally, to concentrated sulfuric acid obtained 52 water 54 is added, however this step can be omitted if the sulfuric acid is at the desired concentration.

As will be known to those skilled in the art, there are various configurations of hydrotreating section 130 in which separation occurs in different ways, in which more reactors are present, or in which make-up hydrogen is added at different points in the process.

Similarly, the sulfuric acid section 126 can be configured in various configurations: the hydrogen sulfide-rich stream can be preconcentrated by removing water, CO2 and other components, the hydrogen sulfide oxidation can be carried out by high temperature combustion or medium temperature catalytic oxidation, the production of sulfuric acid can be carried out by the so-called dry process, in which from stream 42,

- 7 039870 rich in sulfur dioxide, water is removed. This process is typically associated with the use of an absorber as a block 50 for the production of sulfuric acid. If a condenser-type sulfuric acid production unit 50 is used, water may be added before the condenser to hydrate sulfur trioxide to produce sulfuric acid. As a rule, water is added to the resulting concentrated sulfuric acid 54.

In accordance with alternative embodiments of the invention, the collected impurity-containing aqueous phase 10 can, together with the stream 32 rich in hydrogen sulfide, be fed to a combustion plant (not shown) with the necessary quantities of auxiliary fuel, an oxidizer, and combusted to form, among other things, SO ₂ that can be combined with stream 42.

The impure aqueous phase 10 can also be recycled and combined with aqueous sulfuric acid 4 (sulfuric acid make-up). In this case, the wash stream can be withdrawn and fed to the regeneration stage, where the spent acid is combusted.

In FIG. 5 shows an embodiment in accordance with the prior art, where the demetallization is carried out in a hydrotreating section. Here, the purified hydrocarbon phase 12 is mixed with a hydrogen rich stream 14 and fed into a hydrotreating reactor 16 containing a metal recovery guard 18 and a hydrotreating catalytic material 20 known to those skilled in the art. A hydrotreated product stream 22 is withdrawn from the hydrotreating reactor. The hydrotreated product stream 22 is separated in a gas/liquid separator 24 and separated into a hydrotreated (desulphurized and demetallized) hydrocarbon 26 and a vapor stream 28. which separates vapor stream 28 into hydrogen sulfide-rich stream 32 and recycle gas stream 34. Make-up hydrogen 36 is added to recycle gas stream 34 to form hydrogen-rich stream 14. Compared to the hydrotreating section shown in FIG. 2, a separate protective layer 18 is required here to extract the metal. This can be realized by using two guard bed reactors operating alternately located upstream of the main reactor.

In FIG. 6 is a diagram of a process plant for processing coke tar according to the present invention. The carbonaceous feedstock 600 is fed into the coke oven 660 and solid carbonaceous coke 602 is withdrawn from there, optionally together with the oven feed air, the gaseous effluent 604, and the liquid mixture 606 of tar and hydrocarbons. The liquid mixture of resin and hydrocarbons 606 and sulfuric acid 612 are fed into the demetallization section 662, from which an aqueous phase 610 containing impurities and a purified hydrocarbon phase 614 are removed. 618 for recycling.

Refined hydrocarbons for processing 618 are combined with hydrogen rich gas stream 648, heated, and optionally combined with hydrotreated recycle stream 634 to form hydroprocessing stream 620. The hydroprocessing stream 620 is sent to an optionally used diolefin saturation guard reactor 666 in which the diolefins are saturated using a material having catalytic activity in the saturation of the diolefins. In the diolefin saturation reactor 666, hydrogen-rich stop stream 624 is added. The stop stream is hydrogen make-up gas, but can also be recycled and purified hydrogen rich gas. The total acid number of all streams prior to the addition of recycled hydrotreated product 634 will be high (greater than 1.5 mg KOH/g), thus such streams will be highly corrosive, so the equipment must be made of corrosion resistant materials. In the case of a recycle stream, the equipment located after the addition of the recycle hydroprocessed product 634 may have less corrosion resistance as the stream is diluted with the recycle stream. In addition, the use of a recirculated stream has the advantage that such a stream provides thermal mass, thus the temperature rise in the process is reduced. The saturation of the diolefins occurs with the release of a large amount of heat, so the conditioned stream 622 will have a higher temperature, however, it may be necessary to heat this stream by heat exchange (heat exchange step not shown). The conditioned stream 622 is fed to an optionally used metal recovery reactor 668 containing a hydrogenation catalytic material with a high metal retention capacity to remove remaining metal heteroatoms from the conditioned stream 622 to form a demetallized hydrocarbon stream 626. Next, in the hydroprocessing reactor 670, the demetallized hydrocarbon stream 626 is mixed with a hydrogen-rich stream 624 and a hydroprocessed product stream 628 is withdrawn. ) hydrocarbons 632 and vapor stream 630, which includes hydrogen, water, ammonia and hydrogen sulfide. A portion of the hydroprocessed hydrocarbon stream 632 may be provided as an optional recycle stream 634, which is combined with the treated stream.

618 hydrocarbons for processing.

The remainder of the hydrotreated hydrocarbon stream is pressurized by pump 674 prior to the hydrotreating step by contacting the hydrotreating catalytic material in hydrotreating reactors 676 and 678 to produce a hydrotreated hydrocracking feed stream 638. The hydrotreated hydrocracking feedstock 638 is fed into hydrocracking reactor 680 for contact with material having catalytic activity in hydrocracking.

The boiling point range of the hydrocracked product 640 will be wider than the hydrocracked feed stream 638, thus the feed stream will be fed to a fractionator 682 from which a lubricant 642 with a boiling point of more than 350° C., middle distillate can be withdrawn. 644 with a boiling point in the range of 150-350°C, naphtha 646 with a boiling point of less than 150°C, and a hydrogen-rich vapor stream 648 with a boiling point of 30°C. Purification of the vapor phase, if necessary, can be carried out using means known in the art, it can be compressed, supplied as a gas stream 648 rich in hydrogen, and combined with the purified hydrocarbon 618.

According to other embodiments, the separation process can be carried out in various ways known to those skilled in the art, by simply separating gas and liquid, or by adding a cascade hot high pressure separator and a hot low pressure separator before the fractionator.

According to other embodiments, the hydrotreated stream 638 may be fed to a fractionator 682, for example, only a heavy stream similar to stream 644 with a middle distillate boiling point may be removed from it and fed to a reactor 680 containing material having a catalytic hydrocracking activity. This configuration can be especially attractive if middle distillates are not the main product.

According to alternative embodiments, pump 674 may be omitted and the hydrotreating section (reactors 666, 668 and 670) and the hydrocracking section (reactors 676, 678 and 680) may be operated at the same pressure.

According to other alternative embodiments, the number of reactors may be different and the material having catalytic activity may be in one reactor.

In alternative embodiments, the intermediate product is transported from one plant to another, in accordance with FIG. 6, such a product can be a liquid mixture of resin and hydrocarbons 606, a refined hydrocarbon mixture 614, a refined hydrocarbon mixture for hydroprocessing 618, conditioned hydrocarbons 622, demetallized hydrocarbons 626, or hydroprocessed hydrocarbons 628. Transportation can be by pipeline or by tank truck.

In FIG. 7 is a diagram of a process plant for processing coke tar according to the present invention. The carbonaceous feedstock 700 is fed into the coke oven 760 and solid carbonaceous coke 702 is withdrawn from there, optionally together with the oven air flow, the gaseous effluent 704, and the liquid mixture 706 of tar and hydrocarbons. Liquid resin-hydrocarbon mixture 706 and sulfuric acid 712 are fed to a demetallization section 762, from which an aqueous phase 710 containing impurities and a purified hydrocarbon phase 714 are removed. If desired, a heavy residue 716 can be removed from the purified hydrocarbon stream 714, resulting in refined hydrocarbons. 718 for recycling.

Refined hydrocarbons for processing 718 are combined with hydrogen rich gas stream 722, heated, and optionally combined with recycle hydroprocessed product stream 734 to form hydroprocessing stream 720. The hydroprocessing stream 720 is sent to an optionally used diolefin saturation guard reactor 766, in which the diolefins are saturated using a material having catalytic activity in the saturation of the diolefins. In the diolefin saturation reactor 766, hydrogen rich stream 724 is added at a point upstream of the reactor, possibly as a stop stream (not shown). The stop stream may be a hydrogen make-up gas or a hydrogen-rich recycle gas. The total acid number of all streams prior to the addition of recycled hydrotreated product 734 will be high (greater than 1.5 mg KOH/g), thus such streams will be highly corrosive, so equipment must be constructed from corrosion resistant materials. In the case of a recycle stream, the equipment located after the addition of the recycle hydroprocessed product 734 may have less corrosion resistance as the stream is diluted with the recycle stream. In addition, the use of a recycle stream has the advantage that such a stream provides thermal mass, thus the temperature rise in the process is reduced. The saturation of the diolefins occurs with the release of a large amount of heat, so the conditioned stream 722 will have a higher temperature, however, additional heating of this stream may be necessary with the optional fired heater 784 and/or by heat exchange. The conditioned stream 722 is fed to an optionally used metal recovery reactor 768 containing a material having hydrogenation catalytic activity with a high metal retention capacity to remove remaining metal heteroatoms from the conditioned stream 722 to form a demetallized hydrocarbon stream 726. Next, in the hydroprocessing reactor 770, the demetallized hydrocarbon stream 726 is mixed with a hydrogen rich stream 724 and a hydrotreated product stream 728 with a reduced amount of organic nitrogen is withdrawn. The hydrotreated product stream 728 is separated in a gas-liquid separator 772 or, if necessary, in a cascade of separators and separated into hydrotreated (denitrogenated and desulphurized) hydrocarbons 732, a sour water stream 730, and a vapor stream 722, which includes hydrogen and hydrogen sulfide. A portion of the hydroprocessed hydrocarbon stream 732 may be supplied as an optionally used recycle stream 734, which is combined with the purified hydrocarbon stream 718 for processing.

The remaining hydrotreated hydrocarbon stream 732 is pressurized with a pump 774 prior to the hydrotreating step by contacting a material having hydrotreating catalytic activity in a hydrotreating reactor 778 to produce a hydrotreated hydrocracking feed stream 738. The hydrotreated hydrocracking feed stream 738 is fed into hydrocracking reactor 780 for contact with material having catalytic activity in hydrocracking.

The hydrocracked product 739 will contain two phases, and a gas-liquid separator 786 is used to separate the vapor phase 750 for recycle (after removal of sour gas, if necessary) from the liquid phase 740. The boiling point range of the liquid phase 740 will be wider than with the hydrocracking feed stream 738, thus the feed stream will be fed to the fractionator 782, from which fractions such as lubricant 742 with a boiling point of more than 350 ° C, middle distillate 744 with a boiling point in the range of 150-350 ° C can be removed , naphtha 746 with a boiling point less than 150°C and a vapor phase stream rich in hydrogen 748 with a boiling point of 30°C.

According to other embodiments, the separation process can be carried out in various ways known to those skilled in the art, by simply separating gas and liquid, or by adding a cascade hot high pressure separator and a hot low pressure separator before the fractionator.

In accordance with other embodiments, the hydrotreated stream 738 may be fed to a fractionator 782, for example, only a heavy stream similar to stream 744 with a boiling point in the middle distillate range may be removed from it and fed to the reactor 780, which contains the material , which has catalytic activity in hydrocracking. This configuration can be especially attractive if middle distillates are not the main product.

According to alternative embodiments, pump 774 may be omitted and the hydrotreating section (reactors 766, 768 and 770) and the hydrocracking section (reactors 778 and 780) may be operated at the same pressure. As those skilled in the art will appreciate, operating at the same pressure will simplify the design as only one gas loop is needed, however hydrotreating and hydrocracking can also be problematic to set up.

According to other alternative embodiments, the number of reactors may be different and the material having catalytic activity may be in one reactor.

In alternative embodiments, the intermediate product is transported from one plant to another, in accordance with FIG. 7, such a product can be a liquid mixture of resin and hydrocarbons 706, a refined hydrocarbon mixture 714, a purified hydroprocessing hydrocarbon mixture 718, a hydrogen rich stream 724, demetallized hydrocarbons 726, or hydroprocessed hydrocarbons 728. Transportation can be by pipeline or by a tanker truck.

Fig. 6 and 7 are for purposes of explanation and illustration only, and show some of the process elements that are not described above, such as heat exchangers, pumps, and the addition of hydrogen rich gas to stop the reaction, as well as additional means of separating and gas purification. In the practice of the present invention, fewer or more such elements or additional elements may be required, thus the drawings are given by way of illustration only and are not construed as limiting the present invention.

- 10 039870

Examples

In table. 1 shows two examples of the composition of coke tar. Both compositions are characterized by the presence of large amounts of oxygen, sulfur and nitrogen, as well as a high content of metals (Ca, Fe, Mg).

Example 1

The ability to remove Fe, Mg and Ca from coke tar was evaluated experimentally for several treatments, including the use of the following acids: citric acid, oxalic acid, hydrochloric acid, phosphoric acid and sulfuric acid.

In table. 2 summarizes the data on the order of the experiment and the results. In all experiments, coke tar was heated to 80°C and either directly filtered or combined with water or acid (the concentration is indicated in the column Acid, wt.%) in a certain mass ratio of water / tar or acid / tar (Water / tar (w/w)). The metal recovery efficiency varied considerably. While 60-95% of Ca was removed by filtration, 60% of Mg was removed by water washing, significant Fe removal was achieved only by acid washing, while the removal efficiency of Ca and Mg was also significantly improved by using acid washing.

In experiments with concentrated acids (15-28 wt.%), effective extraction of metals was carried out using citric acid, oxalic acid, phosphoric and, to some extent, hydrochloric acid. At lower concentrations (1-5%), phosphoric and sulfuric acid showed sufficient efficiency, which, however, was reduced at an acid concentration of 1% compared to 5%.

In table. Figure 3 summarizes the performance of acid wash using phosphoric and sulfuric acid in the presence of nitrogen. It is clear that both acids remove nitrogen from the resin, however, the removal of the main nitrogen can be carried out using sulfuric acid.

In addition, measurements showed that the phosphorus level in the feedstock was less than 1 ppm, measurements showed that the phosphorus level in the resin treated with 5% phosphoric acid was 2390 ppm, and the phosphorus level in the resin treated with 5% sulfuric acid was lower. detection limits, while the detection limit was 1 ppm. This shows the value of using acids, such as sulfuric acid, containing only those elements whose use in refining processes is well known, since any residual sulfuric acid will be removed in the hydrotreating step downstream, while the presence of 2390 ppm phosphoric acids will poison the catalytically active materials.

Experiments show that a wide range of acids can be used for highly efficient demetallization of coke tar at moderate temperatures and moderate acid concentrations.

Example 2

In table. 4 shows the conditions of the hydroprocessing process according to FIG. 7. As a raw material in the process using coal tar 3 in accordance with the table. 1, a plant with a comparative configuration where demetallization is carried out by hydrotreating (the original version with no acid washing 762 and with a large amount of hydrodemetallization 768), or with a configuration in accordance with the present invention with active acid washing (acid washing with demetallization in 764) is used. and low volume of hydrodemetallization 768). In both embodiments, pilot tests were carried out using 706 coal tar, which was obtained from an external source, in a plant that did not include a 764 separator.

Example 2 is based on a combination of an experiment from Example 1 demonstrating acid washing and another experiment demonstrating hydrodemetallization and hydroprocessing of coal tar, as well as a chemical reaction simulation combining the results of these experiments with demonstrating the hydroprocessing efficiency of acid washed tar. The experiments were carried out in a pilot plant simulating the configuration according to FIG. 7 by performing hydrodemetallization in a first run using commercially available TK-743T and TK-49T catalysts from Haldor Tops0e A/S. In this example, temperature control was carried out using external means, there was no recirculation flow. In addition, the entire amount of hydrogen was supplied through the reactor inlet. The demetallization product was fed to a hydrotreatment/hydrocracking pilot reactor containing a commercially available hydrotreating catalyst TK-609T from Haldor Tops0e A/S and a commercially available hydrotreating catalyst TK-951T from Haldor Tops0e A/S.

From Table. 4 shows that only 20% by volume of the demetallization catalyst is required in the acid wash variant. The amount of demetallization catalyst was determined based on a two-year run time period. Since acid washing also removes nitrogen, the catalyst volume of the high pressure hydrotreating reactor - which is calculated from the volume of denitrogenation required - can be reduced to 25% of the original. In addition, further reducing the amount of ammonia (which is a poison to hydrocracking catalysts) released into the high pressure hydrotreating reactor allows a 33% reduction in hydrocracking catalyst volume while maintaining the same level of conversion in the hydrocracking reactor. The product boil curve shows a high amount of naphtha, however if more middle distillate is to be produced, the conditions in the hydrocracking reactor can be easily changed to produce less naphtha, or alternatively, the final hydrocracking reactor can be fed only part of the intermediate product 738, while the remainder is fed to the unit 782 for fractionation.

The example shows that the described acid washing process can recover metals as well as some of the initial nitrogen, and that there are various advantages to removing metals in a washing step located at the beginning of the process, since the volume required for metal recovery and hydrodenitrogenation, can be reduced.

Table 1

Sample name Method Coal tar 1 Coal tar 2 Coal tar 3 O, wt.% D.B. 8.1 7.1 7.11 S, wt.% D4294 0.1569 0.1709 0.2155 N, May. ppm D4629 6026 6075 5787 H, wt.% D7171 9.41 9.46 9.54 C, wt.% By Difference 82.3 83.3 82.5 SG60/60°F D4052 1.006 1.003 1.0002 Basic N, ppm May. titration 3573 4233 3764 Metals, ppm wt. Calcium ICP-OES 103 210 226 Iron ICP-OES 78 BUT 128 Magnesium ICP-MS 3.2 8.2 4.1 total acid number, mg KOH / g D664 6.3 4.5 5.4 Carbon residue, wt.% D4530 4.92 5.12 5.91 Simulated distillation D7213 0.5 wt.% (IBP), °C D7213 151 132 155 5 wt%, °C D7213 196 192 196 10 wt%, °C D7213 221 220 220 30 wt%, °C D7213 288 286 288 40 wt%, °C D7213 318 316 318 50 wt%, °C D7213 349 344 349 60 wt%, °C D7213 378 372 378 70 wt%,°C D7213 405 401 406 90 wt%, °C D7213 475 471 476 95 wt%. °C D7213 511 509 513 99.5 wt.% (FBP), °C D7213 590 588 588

- 12 039870

table 2

Removal Acid, wt.% Water/resin (w/w) Sa Fe mg Filtration 60-95% 0-11% 0-8% Washing with water 0 2:1 nineteen% 24% 60% Lemon acid 27.8 2:1 100% 82% 99% Oxalic acid 15.3 2:1 100% 76% 99% Hydrochloric acid 26.4 2:1 71% 75% 75% Phosphoric acid 23.1 2:1 100% 100% 100% Phosphoric acid 5.0 1:1 97% 94% >69% Phosphoric acid 1.0 1:1 75% 62% >69% Sulfuric acid 5.0 1:1 94% 92% >69% Sulfuric acid 1.0 1:1 78% 74% >69%

Table 3. Denitrogenation

N, ppm, wt. raw resin Resin treated with H3PO4, 1% wt. Resin treated with H3PO4, 5% wt. Resin treated with H2SO4, 1% wt. Resin treated with H2SO4, 5% wt. N, ppm, wt. 5970 4811 4213 3811 3157 Basic N, ppm, wt. 3682 2897 2463 2044 1326 Denitrogenation of total N nineteen% 29% 36% 47% Denitrogenation of basic N 21% 33% 44% 64%

- 13 039870

Table 4

Thread No. Characteristic original version acid wash 706 Initial N 5970 5970 706 Metals >350ppm >350ppm 706 Total Acid Number 5.4 5.4 718 Initial N 5970 3157 718 Metals >350ppm <20ppm 718 Total Acid Number 5.4 5-6 718 Pace. bale product 718 1VR-150°C 0% 0% 718 150-260°C 21% 21% 718 260-390°C 44% 44% 718 >390°C 36% 36% Relative volume 768 catalyst 100% 20% Hourly volumetric 768 fluid velocity 0.80 4.0 726 By beam. N 5300 3083 726 Metals <20ppm <20ppm 726 Total Acid Number <5 <5 726 Pace. bale product 726 1VR-150°C 2% 2% 726 150-260°C nineteen% nineteen% 726 260-390°С 45% 45% 726 >390°С 34% 34% Relative volume 770 catalyst 100% 100% Hourly volumetric 770 fluid velocity 1.4 1.4 728 By beam. N 2905 1690 728 Pace. bale product 728 1VR-150°C 4% 4% 728 150-260°C 27% 27% 728 260-390°С 45% 45% 728 >390°C 23% 23% Relative volume 778 catalyst 100% 25% Hourly volumetric 778 fluid velocity 0.47 1.89 738 By beam. N 23 23 738 Product boiling point 738 1VR-150°С ten% ten% 738 150-260°С 35% 35% 738 260-390°C 40% 40% 738 >390°C sixteen% sixteen% 738 Rel. _NH3 100% 58% Relative volume 780 catalyst 100% 66.75% Hourly volumetric 780 fluid velocity 0.61 0.91 780 Temperature 390°C 390°С 740 1VR-150°С 22% 22% 740 150-260°С 24% 24% 740 260-390°С 39% 39% 740 >390°C fifteen% fifteen%

CLAIM

Claims (18)

1. A method for producing a hydroprocessed hydrocarbon from a hydrocarbon mixture, which is pyrolysis oil, coal tar or coke tar, obtained during a gasification or pyrolysis process, while the acid number of the specified hydrocarbon mixture is more than - 14 039870 1.5 mg KOH/g, including the following steps: a) combining said hydrocarbon mixture with an aqueous acid selected from the group consisting of strong inorganic acids or organic acids to form a mixture; b) mixing said mixture; c) separating said mixture into an aqueous phase containing impurities and a purified hydrocarbon phase; d) mixing said purified hydrocarbon phase with a hydrogen rich gas to form a hydrotreating stream; e) feeding said hydrotreating stream to a hydrotreating step to form a hydrotreated hydrocarbon; provided that the method does not include the step of adding an aqueous liquid containing elements other than C, H, O, N and S at a concentration greater than 0.1%. 2. The method according to claim 1, characterized in that the hydrocarbon mixture contains from 0.5 or from 1% to 5, 6 or 10% oxygen. 3. Process according to claim 1 or 2, characterized in that the aqueous acid is citric acid, oxalic acid or sulfuric acid. 4. Process according to any one of claims 1 to 3, characterized in that the hydrocarbon mixture has an acid number of more than 2 mg KOH/g, preferably more than 4 mg KOH/g. 5. Method according to any one of claims 1 to 4, characterized in that the concentration of aqueous acid is from 1 or 2% to 5, 10 or 30%. 6. The method according to any one of claims 1 to 5, characterized in that the ratio of hydrocarbon mixture to acid is from 20:1, 10:1, 50:1 to 2:1, 1:1 or 1:2. 7. Method according to any one of claims 1 to 6, characterized in that the temperature in step b) is in the range from 20 to 150°C. 8. Process according to any one of claims 1 to 7, characterized in that the hydrocarbon mixture has an acid number of less than 7 mg KOH/g, preferably less than 25 mg KOH/g, more preferably less than 150 mg KOH/g. 9. A process according to any one of claims 1 to 8, characterized in that said hydrotreating step (e) comprises contacting the hydrotreating stream with one or more catalytically active materials having activity with respect to one or more reactions selected from the group of hydrogenation of heteroatomic hydrocarbons, hydrogenation of diolefins and hydrogenation of metallic heteroatomic hydrocarbons, wherein each of said one or more materials may be present in one or more reactors, wherein any sequence of said one or more materials may be used, wherein the pressure, temperature, and space velocity are such that catalytically the active materials are active for the respective reactions. 10. The method according to claims 1 to 9, characterized in that a certain amount of said hydroprocessed hydrocarbon is withdrawn and fed back as a recycle stream at a position located upstream relative to the tapping point, while the ratio of hydrocarbon mixture:recycle stream is from 1: _1/2 to 1:3. 11. The process according to claims 1 to 10, further comprising a hydrocracking step (f), optionally including an additional hydrotreating step and a separation step (g), to produce a vapor product and one or more liquid hydrocarbon products, wherein the operating temperature of the step (f) hydrocracking is 330-420°C, and the pressure is from 1.5, 6 or 10 MPa to 20 MPa, the liquid hourly space velocity is from 0.2 to 5 h ^-1 and the hydrogen/hydrocarbon ratio is 100- 2000 nm ³ / m ³ . 12. The method according to claims 1 to 11 further comprising upstream of step (a) the step of gasifying the carbonaceous material to form said hydrocarbon with an acid value greater than 1.5 mg KOH/g. 13. The method of claim 12, further comprising the step of transporting an intermediate from one geographic location to another, wherein said intermediate is either said hydrocarbon with an acid number greater than 1.5 mg KOH/g or said hydroprocessed hydrocarbon. 14. Process plant for the production of purified hydrocarbon from solid carbon fuel by the method according to any one of claims 1-13, including: a) a gasification or pyrolysis section having a solid carbon fuel inlet, a water inlet, a synthesis gas outlet, and a tar outlet; b) an acid wash reactor having one or more inlets in fluid communication with said outlet for removing resin and with an outlet for removing a source of strong acid, and having an outlet; c) means for separating the phases having an inlet, an outlet for withdrawing an aqueous phase and an outlet for withdrawing a purified hydrocarbon phase, wherein the outlet of said acid wash reactor is hydraulically connected to the inlet of said - 15 039870 means for phase separation; d) a hydrotreating section having an inlet and an outlet, wherein the inlet of said hydrotreating section is hydraulically connected to the outlet to remove said purified hydrocarbon phase. 15. Process plant according to claim 14, characterized in that the phase separation device is selected from the group including centrifuges, electrostatic separators, gravity separators. 16. Process plant according to claim 14 or 15, wherein said gasification or pyrolysis section additionally has an oxidizer inlet. 17. Process plant according to any one of claims 14 to 16, further comprising a hydrocracking section having an inlet and an outlet, wherein the inlet of said hydrocracking section is hydraulically connected to the outlet of said hydrotreating section. 18. A process plant according to any one of claims 14 to 17, further comprising a gas purification section having an inlet, an outlet for removing desulphurized synthesis gas and an outlet for removing sulfuric gas, while said inlet of the gas purification section is hydraulically connected to said synthesis gas outlet, and a sulfuric acid production section having an inlet for supplying a sulfur source and an outlet for discharging sulfuric acid, wherein said outlet for discharging sulfuric gas is hydraulically connected to said inlet for supplying a sulfur source .