Patent Grant
11802249
This application claims the benefit of and priority to IN Provisional Patent Application No. 202111036981, filed 13 Aug. 2021, the entire disclosure of which is hereby incorporated by reference as if set forth in its entirety herein
The present application relates generally to a method for desulfurization of crude oil and sulfur rich petroleum refinery fractions, more in particular to a method that simultaneously generates polythiophene and other polymers along with desulfurizing the crude oil.
Refinery petroleum fractions, such as naphtha, gasoline, kerosene, diesel, Light cycle oil (LCO), vacuum gas oil (VGO), heavy residue oil (HRO), foots oil, fuel oil, and visbreaking tar (VisTar) streams, often have high content of Sulfur-Containing Heterocyclic Aromatic compounds (SCHAC). Bulky SCHACs are problematic when present in petroleum refinery fractions, as they cause corrosion of assets and are responsible for low fuel quality, health, and environmental problems. SCHAC are difficult to remove from petroleum fractions by conventional techniques such as hydrodesulfurization (HDS). Severe conditions of temperature and pressure are required for the deep desulfurization of SCHAC derivatives and their alkylated/alicyclic derivatives. Such sulfur residues thus either typically remain in the petroleum crude or product streams, causing these streams to be sold at a lower price or significant capital assets/cost, operating expenses and use of processes related to the generation of greenhouse gas (GHG) emissions to produce saleable products amenable to market needs.
Due to air quality concerns, sulfur content limits in petroleum-derived transportation fuels like diesel and gasoline have been falling steadily across the world since the beginning of the 21st century. More recently, the International Maritime Organization (IMO) has mandated a steep reduction in the sulfur content of marine fuels. As a consequence of this, high-sulfur crudes (referred to in the trade as “sour” crudes) trade at a significant discount to low-sulfur “sweet” crudes. Further, due to the higher tendency of sour crudes to induce corrosion, the high additional cost is incurred from tankage, process equipment, and pipeline maintenance point of view in handling, storage, and transportation of sour crudes and other petroleum-derived fractions and streams compared to the corresponding sweet crude counterparts.
Many efforts have also been made to reduce sulfur content in crude oil and in various derived petroleum refinery fractions. Such reduction of sulfur is essential for regulatory compliance, for suitability in fuel using equipment such as vehicles and furnaces, and for reducing corrosion of assets—but typically requires considerable additional equipment and processing effort at elevated temperatures and pressures. Approaches to desulfurization are broadly categorized into two types. (a) HDS; and (b) non-HDS techniques; HDS is the most used desulfurization technique used in the petroleum industry. HDS is performed with the help of a catalyst or by the conventional HDS with hydrogen. The non-HDS approach is further sub-classified into various techniques. (i) extractive desulfurization, (ii) adsorptive desulfurization, (iii) oxidative desulfurization (iv) chemical oxidation (v) photochemical oxidation (vi) ultrasound oxidation, (vii) biodesulfurization, (viii) anaerobic biodesulfurization.
The sulfur compounds present in petroleum crude oil and refinery fractions typically occur in three major categories of molecules: light sour gases (hydrogen sulfide and carbon oxysulfide), mercaptans (also referred to as thiols), and thiophenes, including thiophene derivatives such as benzothiophenes, dibenzothiophenes and various alkylated/alicyclic compounds of SCHAC. The SCHAC contain alkyl/alicyclic chains, whose length may vary from 1 to 30 carbons, which may be linear, branched, or in some cases may also contain cyclic structures. SCHACs such as thiophenes, benzothiophenes, and dibenzothiophenes are used to produce various agrochemicals and pharmaceuticals.
In a further study, it was found that the polymers obtained from SCHACs exhibit conductive and optical properties that are desirable for various commercial and industrial applications. Specifically, polythiophene and its derivatives are currently used in chemical sensors, solar cells, and batteries. Polythiophene can be chemically synthesized using oxidation catalyst or cross-coupling catalysts.
Yet another study discloses apparatus and processes for manufacturing polymers of thiophene, benzothiophene, and their alkylated/alicyclic derivatives. Additionally, a process was described for manufacturing polymers that includes isolating a SCHAC from cracked naphtha (the lightest fraction of crude oil that may be liquid under ambient conditions) and reacting the SCHAC to produce a polymer thereby in presence of a superacid (CF3SO3H) catalyst.
In another study, polythiophene-based polymers were prepared using FeCl3 catalyst at room temperature using the commercially obtained monomers. Such chemical synthesis typically results in a reaction mixture from which the polythiophene can be separated.
Despite the above-described processes and methods, significant removal of sulfur from petroleum crude oil and its refinery fractions by polymerization is a challenging task, and complete removal is arduous and expensive. This is because the derivatives present in the petroleum refinery fractions are highly complex and derivatized with many substituents, complex molecular structures of the aromatic sulfur moieties.
It would, therefore, be beneficial to develop a synthesis method that could not only remove thiophene, benzothiophene, and their alkylated/alicyclic derivatives either from crude oil directly or at some stage of the crude oil (petroleum) refining process, while simultaneously generating useful products from the SCHAC contained in petroleum crude oil or its refinery fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams.
Therefore, developing an efficient methodology to significantly reduce or eliminate sulfur monomers present in petroleum crude oil itself or in refinery fractions including, but not limited to naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams and different crude oils, etc. is needed.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description section. This summary is not intended to identify or exclude key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
According to one aspect, embodiments relate to a method for desulfurizing crude oil and sulfur rich petroleum refinery fractions. The method includes feeding the crude oil and sulfur rich petroleum refinery fractions to a reactor. An oxidation catalyst is added to the crude oil and sulfur rich petroleum refinery fractions. The crude oil and sulfur rich petroleum refinery fractions and the oxidation catalyst are stirred to form co-polymers of sulfur-containing heterocyclic compounds. The co-polymers of sulfur-containing heterocyclic compounds are separated by filtration or by centrifugation.
Non-limiting and non-exhaustive embodiments of the invention are described with reference to the following figures, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified.
Further, persons skilled in the art to which this disclosure belongs will appreciate that elements in the figures are illustrated for simplicity and may not have necessarily been drawn to scale. Furthermore, in terms of the construction of the device, one or more components of the device may have been represented in the figures by conventional symbols, and the figures may show only those specific details that are pertinent to understanding the embodiments of the present disclosure so as not to obscure the figures with details that will be readily apparent to those of ordinary skill in the art having the benefit of the description herein.
For the purpose of promoting an understanding of the principles of the disclosure, reference will now be made to the embodiment(s) illustrated in the figures and specific language will be used to describe them. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended. Such alterations and further modifications to the disclosure, and such further applications of the principles of the disclosure as described herein being contemplated as would normally occur to one skilled in the art to which the disclosure relates are deemed to be a part of this disclosure.
It will also be understood by those skilled in the art that the foregoing general description and the following detailed description are exemplary and explanatory of the disclosure and are not intended to be restrictive thereof.
The terms “comprises,” “comprising,” or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such a process or a method. Similarly, one or more devices or sub-systems or elements or structures or components preceded by “comprises . . . a” does not, without more constraints, preclude the existence of other devices, other sub-systems, other elements, other structures, other components, additional devices, additional sub-systems, additional elements, additional structures, or additional components. Appearances of the phrase “in an embodiment,” “in another embodiment” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The system, methods, and examples provided herein are illustrative only and not intended to be limiting.
Embodiments of the present disclosure will be described below in detail with reference to the accompanying figures.
According to the specification, sulfur is removed from petroleum crude oil and refinery fractions and is effectively utilized in situ to synthesize a new family of copolymers, namely poly (thiophene-co-benzothiophene-co-dibenzothiophene) with or without alkyl/alicyclic substituted derivatives via oxidative polymerization of thiophene, benzothiophene, dibenzothiophene, and other alkylated/alicyclic derivative of SCHAC monomers present in petroleum refinery fractions. The petroleum refinery fractions may be naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams.
The petroleum crude oil and refinery fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams containing at least 0.005 wt % sulfur are processed to reduce the sulfur content by at least 1% with respect to what is present in the untreated crude. The removal process simultaneously synthesizes poly (thiophene-co-benzothiophene-co-dibenzothiophene) and copolymers of their alkyl/alicyclic derivatives. The copolymers thus developed have UV absorbing capabilities, low electrical resistivity, fluorescence, thermochromism, electrochromism, and photochromism depending on the sulfur species present in the starting feedstock used.
A synthetic method to reduce sulfur monomers from petroleum crude oil and refinery fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams by polymerization of SCHAC using oxidation catalyst is disclosed. The synthesized conducting copolymers poly(thiophene-co-benzothiophene-co-dibenzothiophene) have a formula
In another embodiment, conjugated copolymers of thiophene, benzothiophene, dibenzothiophene, and higher analogues of sulfur monomers functionalized with alkyl/alicyclic side-chain substituents of formula (I) are disclosed. SCHAC monomers appended with alkyl/alicyclic chain substituents may also be copolymerized using the same synthesis methodology.
The petroleum fractions such as naphtha, gasoline, kerosene, diesel, LCO, VGO, HRO, foots oil, fuel oil, and VisTar streams have different weight percentages of sulfur monomers, and different types of sulfur monomers. Such sulfur monomers are polymerized using Fe(III)chloride and other oxidation catalysts. In some embodiments, the oxidation occurs in presence of solvents, such as toluene, chloroform, hexane, tetrahydrofuran, 1,4-dioxane, or methylene chloride.
In yet another embodiment, a method of desulfurizing the petroleum crude oils and refinery fractions via copolymerization of the SCHAC using an oxidation catalyst is disclosed. The method comprises synthesizing conducting copolymers, i.e., poly(thiophene-co-benzothiophene-co-dibenzothiophene), with or without aliphatic and/or alicyclic side chains. The copolymers are separated from the crude samples by filtration/centrifugation. The filtrate is analyzed for the sulfur content, which is compared with the actual crude used. The highest desulfurization percentage of 91% for LCO is achieved, whereas crude oil with API-26 showed the desulfurization of 20%. This result clearly indicates the nature and composition of crude affect the polymerization and desulfurization efficiency. The polymerization reaction was performed under solvent-free conditions, which directly uses the actual crude samples and underscores the potential and wide applicability of the method. In some embodiments, with the petroleum crude oil with high viscosity, polymerization reaction was performed in presence of solvents such as toluene, hexane, chloroform, THF, and DCM for increasing the rate of polymerization reaction. The number average molecular weight of the copolymers was found to be in the range of 500-5000 with a yield ranging from 5 to 40%.
The polymerization reaction was performed under different experimental conditions to realize the efficacy of the method. The reaction time of the polymerization was varied from minutes to hours to days. The results demonstrated that 24 h of reaction time was optimum for the desulfurization of the crude oil and 12 h for petroleum refinery fractions. The amount of catalyst played a crucial role in the polymerization reaction, and the results showed that increasing the catalyst amount increased the yield of the polymerization reaction and also increased the degree of desulfurization. The potential oxidation catalyst used in the polymerization reactions were Fe(III)chloride, Fe(III)nitrate, Fe(III) sulfate, Fe(III)Phthalocyanine, Cu(II)acetate, Pd(II)acetate, Zn(II)acetate, Ni(II)phthalocyanine, Zn(II)phthalocyanine, Zn(II)chloride, Ni(II)acetate, Ni(II)chloride, Ni(II)nitrate, HAuCl4, vanadyl acetyl acetonate, and molybdenum acetyl acetonate and also mixed metal catalysts which are listed in Table-3.
From the sulfur analysis, FeCl3 is found to be the most efficient catalyst for polymerization reactions and effective desulfurization of petroleum crude oils and refinery fractions. The process tolerates and may operate over a wide range of FeCl3 catalyst concentration. FeCl3 was varied from 10 wt % to as low as 0.01 wt %. The NMR, and FT-IR characterizations of the polymers confirm the increase in aromatic content in polymers and confirm the basic SCHAC core. The absorption measurements show a broad absorption of the polymers compared to their crude counterparts with red-shifted absorptions. The absorption spectra of the copolymers show a bathochromic shift with peaks at 325 and 370 nm. Similarly, emission spectra of the copolymers show broad emission bands up to 700 nm with a maximum at 470 nm and also red-shifted emission due to increased conjugation. The copolymers produced exhibit improved chemical and physical properties in comparison to the existing polymers. These polymers find applications in anticorrosion. The polymers possess UV absorbing capabilities, low electrical resistivity, fluorescence, thermochromism, electrochromism, and photochromism, depending on the sulfur species present in the starting feedstock used.
Sulfur-based conjugated copolymers of formula (I) are synthesized from crude oil of API 15-40 using oxidation catalyst including FeCl3 and other transition metal salts including their nitrates, acetates, phthalocyanines, halides, carbonates, acetyl acetonates, sulphates, and other salts as catalyst. The sulfur monomers are polymerized using the oxidation catalyst and the resulting polymers are separated by filtration/centrifugation. The separated polymers and the remaining crude have been analyzed for the sulfur content in the samples, and the results are summarized in Table 1.
From Table 1, it is clear that sulfur content in the various crude oils has been reduced by 1% depending on the type of crude oil used. This indicates the successful removal of SCHAC monomers from the crude oils. The obtained polymers have been tested for the analysis of sulfur content, and the results are given in Table 1. This indicates the successful removal of sulfur monomers from the petroleum refinery fractions. The variation in the removal of sulfur monomers from petroleum refinery fractions are different because the weight percentage, nature, and composition of sulfur monomers present in each refinery fractions are different. The variation in the removal of SCHAC monomers from crude is different because the weight percentage, nature, and composition of sulfur monomers present in each petroleum crude oil are different. For the model studies, thiophene, benzothiophenes, and dibenzothiophenes from commercial sources are polymerized separately to obtain polythiophenes, polybenzothiophenes and polydibenzothiophenes are shown in Scheme 1.
Table 1 provides a summary of petroleum crude oils, reaction parameters, polymer yields, and sulfur content analysis. The sulfur monomers are polymerized using the oxidation catalyst, and the resulting polymers are separated by simple filtration/centrifugation. The separated polymers and the crude have been analyzed for the sulfur content, and the results are summarized in Table 1. Table 2 provides a summary of petroleum refinery fractions, reaction parameters, polymer yields, and sulfur content analysis as shown below.
The metals and anions used as catalysts in the polymerization process are listed in Table 3.
The NMR spectrum of the synthesized polymer (P8) from LCO is given in
The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present disclosure.
20 g of the crude oil (API-40) was taken in a two-neck round bottom flask, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 60° C. for 12 h. The resultant polymer was separated by centrifugation. The polymer was dried under vacuum at room temperature. This polymer was designated as P1. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
The FeCl3 catalyst amount was varied from 0.5, 1, 2, and 3 wt % with respect to the 25 g of the crude oil (API-40). The polymerization process was performed at 60° C. as per the procedure explained in Example-1. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
20 g of the crude oil (API-40), 1 g of the FeCl3 catalyst, and the reaction temperature was varied from 25, and 70° C. The reaction time was maintained for 6 h. The effect of temperature on the polymerization reaction was studied, and the sulfur content analysis is shown in Table 1.
20 g of the crude oil (API-26) was taken in a two-neck round bottom flask, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 70° C. for 12 h. After 12 h, hexane was added to the reaction mixture, and the resultant polymer was separated by centrifugation. The polymer was dried under vacuum at room temperature. This polymer was designated as P2. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
The FeCl3 catalyst amount was varied from 0.002, 0.01, and 0.1, wt % with respect to the 20 g of the crude oil (API-26). The polymerization process was performed at 70° C. as per the procedure explained in Example 4. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
20 g of the crude oil (API-18) was taken in a two-neck round bottom flask, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 70° C. for 12 h. After 12 h, hexane was added to the reaction mixture, and the resultant polymer was separated by centrifugation. The polymer was dried under vacuum at room temperature. This polymer was designated as P3. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
20 g of the crude oil (API-15) was taken in a two-neck round bottom flask, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 70° C. for 12 h. After 12 h, hexane was added to the reaction mixture, and the resultant polymer was separated by centrifugation. The polymer was dried under vacuum at room temperature. This polymer was designated as P4. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 1.
20 g of the naphtha fraction was taken in a two-neck round bottom flask. The flask was filled with a nitrogen atmosphere and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 25° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P5. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the gasoline fraction was taken in the two-neck round bottom flask. The flask was filled with a nitrogen atmosphere and 1 g of the FeCl3 was added through a funnel. The resulting mixture was stirred at 25° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P6. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the kerosene fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 25° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P7. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the diesel fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 25° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P8. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the LCO fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 25° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P9. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the VGO fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through funnel. The resulting mixture was stirred at 70° C. for 12 h. The contents were cooled and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P10. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the HRO fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through funnel. The resulting mixture was stirred at 100° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P11. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the foots oil fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through funnel. The resulting mixture was stirred at 70° C. for 12 h. The contents were cooled and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P12. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the fuel oil fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 70° C. for 12 h. The contents were cooled and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P13. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
20 g of the VisTar fraction was taken in a two-neck round bottom flask. The flask was kept under a nitrogen atmosphere, and 1 g of FeCl3 catalyst was added through a funnel. The resulting mixture was stirred at 70° C. for 12 h. The contents were cooled, and the polymer was separated by centrifugation. The resultant polymer was dried under vacuum at room temperature. This polymer was designated as P14. The catalyst amount, and sulfur content analysis of the polymerization reactions are summarized in Table 2.
The figures and the foregoing description give examples of embodiments. Those skilled in the art will appreciate that one or more of the described elements may well be combined into a single functional element. Alternatively, certain elements may be split into multiple functional elements. Elements from one embodiment may be added to another embodiment. For example, orders of processes described herein may be changed and are not limited to the manner described herein. Moreover, the actions of any flow diagram need not be implemented in the order shown; nor do all of the acts necessarily need to be performed. Also, those acts that are not dependent on other acts may be performed in parallel with the other acts. The scope of embodiments is by no means limited by these specific examples. Numerous variations, whether explicitly given in the specification or not, such as differences in structure, dimension, and use of material, are possible. The scope of embodiments is at least as broad as given by the following claims.
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| Number | Date | Country | |
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| 20230091449 A1 | Mar 2023 | US |
