• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals and product obtained. The procedure provides for the participation of any industrial mixer (8) to which an aqueous solution (1) of an oxo acid of the amphiphiles is added with an oxo acid of the nitrogen and an aromatic sulfonic acid or mixtures (2) of these and which are mixed with the heavy fraction (3) or hydrocarbon residue to be treated, so that this mixture is heated through any conventional heating system (9), at a temperature comprised between 20 and 100ºC and once the reaction has been carried out, the resulting product is passed to a decanter or centrifuge machine, where the separation step (4) of the organic phase (5) of the aqueous phase (6) takes place. In this way an organic phase directly used as fuel (7) containing less than 0.5% by weight of polymer solids is obtained and its viscosity is below 100 mm2/s at 50ºC.
    公开号:ES2696986A1
    申请号:ES201730953
    申请日:2017-07-21
    公开日:2019-01-21
    发明作者:Pedro De Urquiza Alvaro San
    申请人:Grupo Tradebe Medioambiente S L；
    IPC主号:
    专利说明:

    [0001] PROCESS FOR THE TREATMENT OF HEAVY HYDROCARBONS RESIDUES CONTAINING CALCIUM AND OTHER HEAVY METALS AND PRODUCT OBTAINED OBJECT OF THE INVENTION
    [0002] The present invention relates to a process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, such as rejections associated with the consumption of fuel oil in engines, in order to purify said waste and obtain a fuel such as result of the application of said procedure.
    [0003] BACKGROUND OF THE INVENTION
    [0004] Heavy fuel oil is a complex combination of hydrocarbons, sulfur compounds and organometallic compounds obtained as the residue of cracking processes in refineries. This finished fuel consists of saturated hydrocarbons with carbon numbers predominantly in the C15-C50 range.
    [0005] In the previous preparation of this fuel for use in fuel oil engines and since it usually has the presence of water and sediments, it is essential to carry out a preparation stage before injecting it into the engine.
    [0006] This preparation is made by vertical separators of plates. The fuel is fed to the separators that continuously generate a fuel already purified and also a waste constituted by the water and the sediments that are to be eliminated from the fuel oil and that appear mixed with abundant remains of fuel.
    [0007] Apart from this main waste stream, it is necessary to add the one coming from the purging and cleaning of the preparation circuit, including the pre-injection filters as well as the detergents and other cleaning products used in the engine room. Sometimes the used oil generated in the periodic oil changes of the engine is added to this waste. A possible use of this fuel is as fuel. However, the high content of metals and other impurities makes it difficult to use due to the high level of emissions (in an increasingly restrictive environment), high wear in injection systems as well as the high solid residue after combustion. The fuel obtained through this process presents serious stability problems as reflected in the accelerated aging tests.
    [0008] The technique for treating hydrocarbon residues is described, for example, in patents no. WO201421368, WO2007149292, WO2011014686, WO2011143770, US20050234284, WO2014121368, WO2011143770, GB299925, US2434528. Some of these describe a process for the reduction of water and sediment content through a decanting treatment and subsequent centrifugation. The separation method is similar to separation by gravity. The driving force is greater when it is the result of the rotation of the liquid: in the case of sedimentation, where the motive power is the result between the differences in density of solid and liquid particles, the separation is achieved with a force of the order of 1000 to 20000 times greater than gravity. The residue separates into an aqueous phase, a solid phase containing the heaviest impurities and a phase with little water and sediments. This is further subjected to a centrifugation treatment and a subsequent filtering before it can be used as a fuel.
    [0009] The aforementioned process has the disadvantage of not eliminating polluting compounds whose densities are not sufficiently differentiated by not reaching the terminal velocity of sedimentation of the particle in the centrifugal field.
    [0010] There is also a large bibliography in the patents named for the decontamination of used lubricating oils and their recycling to recover the lubricant bases obtaining as by-products or residues (depending on the treatment) of the fuel fractions process. In some of these processes, the use of sulfuric or phosphoric acid to reduce the metal content is mentioned as part of the oil pretreatment. These treatments are effective as a previous step to a thermal treatment and do not solve by themselves neither the problems of stability nor the acidity of the resulting flow, parameters, both critical for compliance with any fuel quality regulations. These thermal treatments on the other hand, although very effective for the decontamination of used lubricating oils and residues of similar characteristics, are not effective for the residues of fuel oil purification. Product obtained from the bottoms of the distillation columns of the refineries and that could only be thermally "treated" in greater depth by means of coke units to produce light distillates and coke.
    [0011] There is also a bibliography on the use of carboxylic acids for the extraction of Na, being very effective in reducing Na but not so much in the rest of the pollutants that remain in the treated product at levels higher than those allowed despite repeated iterations of the treatment. .
    [0012] Thus, there remains a need for an effective process for the removal of calcium and other contaminants from heavy fractions containing calcium and other contaminants and fuel production that meets international standard ISO 8217 Table 2 and avoids the aforementioned drawbacks.
    [0013]
    [0014] DESCRIPTION OF THE INVENTION
    [0015] The object of the present invention is a process for the removal of calcium and other contaminants from heavy fractions containing them, resulting from the purification of heavy fuel oil used as fuel in ship engines and cogeneration, the method comprising:
    [0016] The mixture of an aqueous solution of an oxo acid of the amphiphiles with an oxo acid of the nitrogen and an aromatic sulfonic acid or mixtures thereof; with the heavy fraction at a temperature between 20 and 100 ° C, and the separation of the organic phase from the aqueous phase.
    [0017] Obtaining an organic phase directly used as fuel containing 2 less than 0.5% by weight of polymer solids and its viscosity is below 100 mm / s at 50 ° C.
    [0018] The main origin of the waste to be treated are the overhead centrifuges of heavy fuel systems of ship engines. In order to protect the engine and lengthen its useful life as well as to avoid failures in them and due to the particularities of the fuel used, it is necessary to use this purification prior to the injection of fuel into the engine. The fuels used mostly are listed in Table 2 of the ISO 8217 standard, although fuels in cogeneration engines, where the same casuistry exists, are governed by national regulations.
    [0019] The use of amphiphiles is very effective in the elimination of metals, the use of nitrogenoids and aromatics avoids side effects such as the polymerization of unsaturated compounds that solidify and make their subsequent treatment difficult. The process of the present invention results in a heavy fraction with low viscosity. The solid material removed by separation is less than 0.5% by weight of the total heavy oil fraction.
    [0020] The mixture of acids is also advantageous since it allows great flexibility and reliability, necessary due to the great variability of the original waste by its nature.
    [0021] The low metal heavy fraction obtained is characterized by a low viscosity and by the absence of a relevant amount of polymer solids (below 0.5% by weight). The absence of metals is a very important achievement since it allows the direct use of the fuel without subjecting the heavy fraction to other treatments, for example, passing through a fuel reduction unit or coke unit.
    [0022] The low viscosity of the product obtained allows a lower need for calories to take the fuel to the optimum injection viscosity range, with the energy saving that this entails and the consequent positive impact for the environment.
    [0023] The amphiphilic acids used according to the present invention are acids from period 3 and 4. Those from period 3 are those having between 1-2 sulfur atoms or mixtures thereof. In one embodiment, the acid is selected from the list: hydroxyhydruro dioxide sulfur acid, dihydroxy dioxide sulfur acid, heptaoxodisulfuric or pyrosulfuric acid, trioxosenic acid, heptaoxodiselnic acid and hydroxyhydroxyoxazulfuric acid or mixtures thereof.
    [0024] The nitrogenoid acids used are those of period 2 and 3. They contain between 1-2 nitrogen or phosphorus atoms or mixtures of these.
    [0025] Preferably the acid is selected from the list: hydroxy dioxide dioxide, hydroxy oxido nitrogen, trihydroxy oxido phosphorus acid, dihydroxyhydroxy diophophorous acid, trihydroxydiphosphoric acid, dihydroxy hydrurophosphoric acid and hydroxydihydroxy diophophorous acid or mixtures thereof.
    [0026] The importance of the use of aromatics in the acid mixture is to avoid the aggregation of asphaltenes, constituted mainly by aromatic rings linked with alkyl chains and cycloalkanes, in addition to heterocyclic compounds that possess N, S and O and their subsequent deposition. The aromatic acids used according to the present invention are the acids sulphonic Aromatics, preferably the acid is selected from the list: phenylsulfonic acid or benzenesulfonic acid, 1-phenanthrene sulfonic acid, p-methylbenzenesulfonic acid, pfenolsulfonic acid, 2-hydroxybenzenesulfonic acid and o-phenolsulfonic acid or mixtures thereof. The aqueous solution of the acid mixture as well as the proportion of each will vary, depending on the composition of the waste to guarantee the final result, in a large concentration range. However, it is preferable to use a solution in which the concentration of the acid is between 1% and 20% by weight.
    [0027] The oxo acid formulation is made in an amount that is usually at least stoichiometric with respect to metal content. On the other hand that of aromatics is with the content of heteroatoms.
    [0028] The treatment temperature is generally between 60 ° C and 85 ° C.
    [0029] The heavy fraction and the aqueous solution of the acidic formulation are mixed intensively for a period of time preferably comprised between a few minutes and a few hours, depending on the mixing device. Normally, a contact time of between 30 minutes and 6 hours is sufficient to obtain an efficient metal removal. The mixing can be carried out using any industrial mixer, for example a static mixer or a stirred tank. After contact with the acid mixture, the water and the organic phase are separated, according to procedures known in the art, for example using a decanter or a centrifugal machine.
    [0030] The organic phase obtained after treatment with the acid mixture is characterized not only by a very low level of solids, but also by a small amount of ash and by a low viscosity.
    [0031] Preferably the amount of ash is less than 0.1% w / w.
    [0032] The viscosity at 50 ° C of the organic phase after the treatment is preferably less than 100 mm2 / s, more preferably less than 80 mm2 / s.
    [0033] In an aspect of the invention it is advantageous if the viscosity at 50 ° C of the organic phase is below 100 mm2 / s.
    [0034] DESCRIPTION OF THE DRAWINGS
    [0035] To complement the description that will be made next and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical realization thereof, a flat game is attached as an integral part of said description. where, with illustrative and non-limiting character, the following has been represented:
    [0036] Figure 1 shows a schematic diagram of an installation for the implementation of the process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals object of the invention.
    [0037] PREFERRED EMBODIMENT OF THE INVENTION
    [0038] In view of the figure outlined, it can be seen how in the process of the invention the participation of any industrial mixer (8), for example a static mixer or a stirred tank, has been envisaged.
    [0039] In said industrial tank or mixer (8), an aqueous solution (1) of an oxo acid of the amphigens is added with an oxo acid of the nitrogenoids and an aromatic sulfonic acid or mixtures (2) of these and which are mixed with the heavy fraction ( 3).
    [0040] This mixture is heated through any conventional heating system (9), at a temperature comprised between 20 and 100 ° C.
    [0041] Once the reaction is carried out, the resulting product is passed to a decanter or centrifugal machine, where the separation stage (4) of the organic phase (5) of the aqueous phase (6) takes place.
    [0042] In this way an organic phase directly used as fuel (7) is obtained which contains less than 0.5% by weight of polymeric solids and its viscosity is below 100 mm2 / s at 50 ° C.
    [0043] For its part, the aqueous phase (6) will be subjected to a physical-chemical treatment process, in order to separate the water (11) from the sludge (12) present in said mixture.
    [0044] As stated above, the oxo acids of the amphiphiles are selected from the group consisting of: hydroxyhydruro dioxide sulfur acid, dihydroxy dioxide sulfur acid, heptaoxodisulfuric acid or pyrosulphuric acid, trioxoselénico acid, heptaoxodiselénico acid and acid hidroxido hydrurooxidoazufre or mixtures of these.
    [0045] On the other hand, the nitrogenoid acids are selected from the group consisting of: hydroxy dioxide dioxide, hydroxy oxido nitrogen, trihydroxy oxido phosphorus acid, dihydroxy hydridooxidophosphorus acid, trihydroxydiphosphoric acid, dihydroxy hydrurophosphoric acid and hydroxy dihydroxy dioxide phosphorus or mixtures of these.
    [0046] As for the aromatic acids, they are selected from the group consisting of: phenylsulfonic acid or benzenesulfonic acid, 1-phenanthrene sulfonic acid, p-methylbenzenesulfonic acid, pfenolsulfonic acid, 2-hydroxybenzenesulfonic acid and o-phenolsulfonic acid or mixtures thereof. As for the organic phase, after the mixing stage in the industrial mixer (8), said phase constitutes the upper phase, the acid concentration in water being between 1 and 20% by weight, while its temperature will be between 60 ° C and 90 ° C.
    [0047] PRACTICAL EXAMPLES
    [0048] The fuel, after and before the treatment, was characterized using the following procedures: the metal content was measured using an atomic absorption spectrometer after dilution of the fuel in a mixture of light distillates, all metal contents were expressed as weight percentage /weight. The kinematic viscosity was measured using the suitable viscosity meter immersed in an oil bath at 50 ° C and expressed in mm2 / s. The ash content was determined by means of complete calcination of the sample at 800 ° C for a minimum of four hours and expressed as a percentage by weight / weight (w / w). The possible formation of polymer solid has been reviewed by filtering the mixture at 100 ° C using a 1.6 micron pore size filter.
    [0049] Comparative example 1
    [0050] A heavy metal-rich fraction obtained from a representative residue mixture was characterized obtaining an ash content (solid residue after calcination at 800 ° C) of 1.35% w / w and a viscosity of 90 mm2 / s at 50 °. C. The treatment procedure was as follows: the heavy fraction (100 g) was heated to a temperature of 90 ° C and a solution of hydroxyhydro-oxido-sulfuric acid in water (25 g, 8% w / w) was added and mixed at 90 °. C for fifteen minutes. Then, the mixture was centrifuged at 4500 rpm for 5 minutes and the two phases were separated (organic and aqueous). The organic phase was separated in the upper fraction and characterized by obtaining an ash value of 0.05% w / w and a viscosity value of 78 mm2 / s at 50 ° C. In this case, the presence of a polymeric solid phase was observed in the bottom of the centrifugal tube, well above 1%.
    [0051] Comparative example 2
    [0052] Example 1 was repeated using a solution of dihydroxyhydrurophosphorus acid (25 g, 10.5% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.16% w / w and the viscosity at 50 ° C of the final organic phase was 80 mm2 / s. In this case the presence of a polymeric solid phase was observed at the bottom of the centrifuge tube, well above 1%.
    [0053] Comparative example 3
    [0054] Example 1 was repeated using a solution of p-methylbenzenesulfonic acid (25 g, 7.5% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 1.1% w / w and the viscosity at 50 ° C of the final organic phase was 80 mm2 / s. The mixture was filtered without problems and the amount of the solid retained in the filter was less than 0.5% w / w Comparative Example 4
    [0055] Example 1 was repeated using a mixture of hydroxyhydro-oxido-sulfuric acid, dihydroxy-dihydroxyphosphide and p-methylbenzenesulfonic acid (25 g, 12% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.05% w / w and the viscosity at 50 ° C of the final organic phase was 75 mm2 / s. The mixture was filtered without problems and the amount of the solid retained in the filter was less than 0.5% w / w.
    [0056] Comparative example 4A
    [0057] Example 4 was repeated using 12.5 g of a mixture of hydroxyhydro-oxido-sulfur acid, dihydroxide hydrurophosphorus and p-methylbenzenesulfonic acid (21% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.02% and the viscosity at 50 ° C of the final organic phase was 78 mm2 / s. The mixture was filtered without problems and the amount of the solid retained in the filter was less than 0. , 5% p / p.
    [0058] Comparative example 4B
    [0059] Example 4 was repeated using 50 g of more dilute hydroxyhydro-oxidase-sulfur, dihydroxide hydrurophosphorus and p-methylbenzenesulfonic acid mixture (2.6% w / w) by heating the mixture to 60 ° C. The organic phase was separated in the upper fraction, the ash content of the final organic phase was 0.035% and the viscosity at 50 ° C of the final organic phase was 80 mm2 / s the mixture was filtered without problems and the amount of the solid retained in the filter was less than 0.5% w / w.
    [0060] Comparative example 4C
    [0061] Example 4 was repeated using a mixing temperature of 25 ° C. The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.6% and the viscosity at 50 ° C of the final organic phase was 85 mm2 / s. In this case, the presence of a polymeric solid phase was observed in the bottom of the centrifugal tube, well above 1%.
    [0062] Example 5
    [0063] Example 1 was repeated using a solution of 1-phenylarsulfonic acid, dihydroxy-oxido-sulfuric acid and dihydroxy-hydrurophosphoric acid and benzenesulfonic acid (25 g, 12.5% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.05% w / w and the viscosity at 50 ° C of the final organic phase 5 was 80 mm2 / s the mixture was filtered without problems and the amount of the solid retained in the filter was less than 0.5% p / p.
    [0064] Example 6
    [0065] Example 1 was repeated using a solution of dihydroxy dioxide sulfur acid, trihydroxy oxido phosphorus acid and benzenesulfonic acid (25 g, 10% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.20% w / w and the viscosity at 50 ° C of the final organic phase was 85 mm2 / s. The mixture was filtered without problems and the amount of solid retained in the filter was less of 0.5% p / p.
    [0066] Example 7
    [0067] Example 1 was repeated using a solution of trihydroxydiphosphoric acid, hydroxyhydroxy-oxido-sulfuric acid and 1-phenanthrene sulfonic acid (25 g, 11.5% w / w). The organic phase was separated in the upper fraction. The ash content of the final organic phase was 0.06% w / w and the viscosity at 50 ° C of the final organic phase was 80 mm2 / s. The mixture was filtered without problems and the amount of the solid retained in the filter was less than 0.5% w / w.
    权利要求:
    Claims (7)
    [1]
    1. Procedure for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, which is designed to carry out the removal of calcium and other heavy fraction contaminants from a residue resulting from the purification of heavy fuel oil used as fuel in boat engines and cogeneration, characterized because in it the following operational phases are defined:
    • Mixing an aqueous solution (1) of an oxo acid of the amphiphiles with an oxo acid of the nitrogenoids and an aromatic sulfonic acid or mixtures (2) of these; with the heavy fraction (3) at a temperature between 20 and 100 ° C,
    • Separation (4) of the organic phase (5) of the aqueous phase (6).
    • Obtaining from said separation stage (4) an organic phase directly used as fuel (7).
    [2]
    2. Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, according to claim 1, characterized in that the oxo acids of the amphiphiles are selected from the group consisting of: hydroxyhydruro dioxide sulfur acid, dihydroxy dioxide sulfur acid, heptaoxodisulfuric acid or pyrosulfuric acid, acid trioxoselénico, heptaoxodiselénico acid and acid hidroxido hydrurooxidoazufre or mixtures of these.
    [3]
    3. Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, according to claim 1, characterized in that the nitrogenoid acids are selected from the group consisting of: hydroxy dioxide dioxide, hydroxy oxido nitrogen, trihydroxy oxido phosphorus acid, dihydroxyhydroxy diophophorous acid, trihydroxydisophobic acid , dihydroxyhydrurophosphoric acid and hydroxydihydroxyhydrophosphorus acid or mixtures thereof.
    [4]
    4. Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, according to claim 1, characterized in that the aromatic acids are selected from the group consisting of: phenylsulfonic acid or benzenesulfonic acid, 1-phenylarsulfonic acid, p-acid methylbenzenesulfonic acid, p-phenolsulfonic acid, 2-hydroxybenzenesulfonic acid and o-phenolsulfonic acid or mixtures thereof.
    [5]
    Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, according to claims 1 to 4, characterized in that after the mixing step, the organic phase is the upper phase and the concentration of acid in water is included between 1 and 20% by weight.
    [6]
    6. Process for the treatment of heavy hydrocarbon residues containing calcium and other heavy metals, according to claims 1 to 4, characterized in that after the mixing step, the organic phase is the upper phase maintained at a temperature comprised between 60 and 60. ° C and 90 ° C.
    [7]
    7. Product obtained by the process of claims 1 to 6, characterized in that it consists of an organic phase usable as fuel, containing less than 0.5% by weight of polymer solids and a viscosity below 100 mm2 / s at 50 °. C.
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    同族专利:
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    引用文献:
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    ES201730953A|ES2696986B2|2017-07-21|2017-07-21|PROCEDURE FOR THE TREATMENT OF HEAVY HYDROCARBONS RESIDUES CONTAINING CALCIUM AND OTHER HEAVY METALS AND PRODUCT OBTAINED|ES201730953A| ES2696986B2|2017-07-21|2017-07-21|PROCEDURE FOR THE TREATMENT OF HEAVY HYDROCARBONS RESIDUES CONTAINING CALCIUM AND OTHER HEAVY METALS AND PRODUCT OBTAINED|
    EP18000610.8A| EP3431571A1|2017-07-21|2018-07-18|Method for treating heavy hydrocarbon residues containing calcium and other heavy metals and product obtained|
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