CN107779224B - Gasoline processing method - Google Patents
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- CN107779224B CN107779224B CN201710240434.2A CN201710240434A CN107779224B CN 107779224 B CN107779224 B CN 107779224B CN 201710240434 A CN201710240434 A CN 201710240434A CN 107779224 B CN107779224 B CN 107779224B
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Abstract
The invention relates to the field of hydrogenation, and particularly discloses a gasoline processing method, which comprises the following steps: cutting gasoline into a light gasoline fraction, a medium gasoline fraction and a heavy gasoline fraction, performing etherification treatment on the light gasoline fraction, performing extractive distillation treatment on the medium gasoline fraction, and performing selective hydrogenation treatment on the heavy gasoline fraction, wherein the initial boiling point of the medium gasoline fraction is above 40 ℃, and the final boiling point is below 170 ℃; and the extraction distillation treatment is carried out to obtain a rich solvent and refined medium gasoline, and aromatic hydrocarbon and sulfide in the medium gasoline fraction are dissolved in the extraction distillation solvent to form the rich solvent. The gasoline processing method has the advantages of low energy consumption, high desulfurization efficiency and low octane value loss.
Description
Technical Field
The invention relates to the field of hydrogenation, in particular to a gasoline processing method.
Background
With the increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing the sulfur content of gasoline is considered to be one of the most important measures for improving air quality. Most of the sulfur in our country's gasoline products comes from thermally processed gasoline blending components, such as catalytically cracked gasoline. Therefore, the catalytic gasoline must be deeply desulfurized, and the pure catalytic gasoline desulfurization technology causes a problem: the octane number of the catalytic gasoline is reduced.
In order to saturate as little olefin as possible on the premise of ensuring a certain desulfurization depth, currently, the process technologies developed by researchers mainly include: the S-zorb technology developed by the medium petrochemical industry, the RSDS technology developed by the medium petrochemical industry science research institute, and the Prime-G + technology in France.
The S-zorb technology developed by medium petrochemical industry is used for desulfurizing full-range catalytic gasoline, the sulfur content after desulfurization can be controlled below 10ppm, and the octane number loss of the full-range catalytic gasoline is 1-2 units. The RSDS technology developed by the research institute of petrochemical and petrochemical engineering science firstly cuts catalytic gasoline into light and heavy fractions, the light fraction is extracted to remove mercaptan, the heavy fraction is subjected to selective hydrodesulfurization, when the sulfur content of a product of the technology is less than 10ppm, the yield of the light fraction is about 20 percent, most of the light fraction needs hydrogenation, and the octane number loss of full-fraction gasoline is about 3-4 units. The Prime-G + technique in france prehydrogenates gasoline before it is cut, where the lighter sulfides react with diolefins to form high-boiling sulfides without saturating the olefins, which technique also has an octane number loss of about 3-4 units.
Therefore, a gasoline processing method capable of realizing deep desulfurization of gasoline and reducing octane number loss is needed.
Disclosure of Invention
The invention aims to overcome the defect of serious octane number loss in the desulfurization process of the prior art and provides a gasoline processing method. The gasoline processing method has the advantages of low energy consumption, high desulfurization efficiency and low octane value loss.
The inventor of the invention finds that in the process of gasoline processing, gasoline is firstly cut into light gasoline fraction, medium gasoline fraction and heavy gasoline fraction, then the medium gasoline fraction is subjected to extractive distillation treatment, aromatic hydrocarbon and sulfide in the medium gasoline fraction are dissolved in an extractive distillation solvent to form a rich solvent, refined medium gasoline is distilled out, the sulfide and olefin components can be effectively separated, octane number loss caused by olefin saturation in the desulfurization process is partially avoided, further, the rich solvent is subjected to stripping treatment, the solvent and aromatic hydrocarbon containing sulfide can be separated, and the aromatic hydrocarbon containing sulfide and the heavy gasoline fraction can enter a selective hydrodesulfurization device together for desulfurization treatment.
Based on this, the invention provides a gasoline processing method, which comprises the following steps: cutting gasoline into a light gasoline fraction, a medium gasoline fraction and a heavy gasoline fraction, performing etherification treatment on the light gasoline fraction, performing extractive distillation treatment on the medium gasoline fraction, and performing selective hydrogenation treatment on the heavy gasoline fraction, wherein the initial boiling point of the medium gasoline fraction is above 40 ℃, and the final boiling point is below 170 ℃; and the extraction distillation treatment is carried out to obtain a rich solvent and refined medium gasoline, and aromatic hydrocarbon and sulfide in the medium gasoline fraction are dissolved in the extraction distillation solvent to form the rich solvent.
The liquid-liquid extraction process in the prior art is generally applicable to extraction of raw materials with relatively simple raw material components, such as aromatic extraction of reformate (raw materials basically only contain aromatic hydrocarbon and alkane, almost do not contain sulfide, nitride and oxide, and only contain a small amount of cyclane and olefin), and when the raw materials are complex in composition, the requirements on yield can be hardly met. The catalytic gasoline component is a feedstock with extremely complex composition, and the polarity competition of aromatics, olefins and sulfides (mercaptan, thioether and thiophene) is very strong if the liquid-liquid extraction of the prior art is used. According to the principle of superposition of solvent classification selectivity and light-heavy selectivity, light polar is carried away by the solvent, and heavy polar is lost. Therefore, the catalytic gasoline after liquid-liquid extraction contains heavy sulfides, and the oil dissolved by the solvent carries light olefins. The extraction distillation of the invention simultaneously carries out polar extraction and light and heavy distillation separation, and the whole process has the polar competition process of aromatic hydrocarbon, olefin and sulfide (mercaptan, thioether and thiophene) and also has the distillation separation process of light and heavy materials. Therefore, the polar extraction characteristic of the solvent can be exerted to the maximum extent, and the light and heavy separation characteristic of the components can also be reflected, so that the aromatic hydrocarbon component carried by the solvent and the sulfide in the medium gasoline form a rich solvent, the refined medium gasoline is distilled out, the olefin is difficult to see in the rich solvent, the sulfide is difficult to find in the refined medium gasoline, and further the deep desulfurization of the gasoline can be realized, and the octane number loss can be reduced.
The gasoline processing method provided by the invention can be matched with an optimal extractive distillation solvent to more effectively separate sulfide and olefin and reduce the loss of olefin in the desulfurization process.
Compared with the prior art, the gasoline processing method provided by the invention has the following advantages:
(1) the gasoline fraction is treated by adopting the extractive distillation technology, so that the problem of solvent carrying of the gasoline during refining is solved, and the washing of the gasoline during refining is cancelled, so that the running energy consumption of the device is reduced, the discharge of sulfur-containing sewage is avoided, and meanwhile, the refining problem of washing water does not exist;
(2) by adopting the extraction distillation technology, the problem of competition between the polarity of olefin and the polarity of sulfide and a solvent is solved, and the problem that the olefin component with high octane number is lost into the sulfur-rich aromatic hydrocarbon component does not exist, so that the return wash oil circulation is not needed, and the energy consumption is low;
(3) the invention has no problem that the olefin component with high octane number is lost into the sulfur-rich aromatic component, so the pentane component of the light olefin on the top is not needed to be added, and the material consumption of the device is low;
(4) because no light component back washing liquid circulation exists, a back washing liquid tower is cancelled, so that the device has no problems of tower flushing, foaming and the like, and the running stability of the device is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a gasoline processing method, which comprises the following steps: cutting gasoline into a light gasoline fraction, a medium gasoline fraction and a heavy gasoline fraction, performing etherification treatment on the light gasoline fraction, performing extractive distillation treatment on the medium gasoline fraction, and performing selective hydrogenation treatment on the heavy gasoline fraction, wherein the initial boiling point of the medium gasoline fraction is above 40 ℃, and the final boiling point is below 170 ℃; and the extraction distillation treatment is carried out to obtain a rich solvent and refined medium gasoline, and aromatic hydrocarbon and sulfide in the medium gasoline fraction are dissolved in the extraction distillation solvent to form the rich solvent.
In the present invention, the distillation range of the medium gasoline fraction is defined, and it will be appreciated by those skilled in the art that the distillation range of the medium gasoline fraction is lower than that of the light gasoline fraction, and the distillation range of the medium gasoline fraction is higher than that of the heavy gasoline fraction. For example, a medium gasoline fraction has a distillation range of 40 to 170 ℃, a light gasoline fraction having a distillation range of less than 40 ℃ (excluding 40 ℃), and a heavy gasoline fraction having a distillation range of more than 170 ℃ (excluding 170 ℃).
In the invention, the gasoline has complex composition and contains diolefin, olefin, cycloolefin, alkane, cyclane, arene and trace sulfide, nitride, oxide, colloid and the like, and preferably contains arene, olefin, diolefin, alkane and sulfide.
The sulfide of the present invention is at least one selected from the group consisting of thiol, thioether, disulfide, and thiophene.
The cutting in the present invention is carried out by cutting techniques conventionally used in the art, and the cutting conditions can be generally selected according to the nature of the specific cut material, and the end point of the cutting is determined so as to separate the light fraction, the middle fraction and the heavy fraction as much as possible.
The purpose of the invention can be achieved when the initial boiling point of the medium gasoline fraction is above 40 ℃ and the final boiling point is below 170 ℃, and when the initial boiling point of the medium gasoline fraction is above 65 ℃ and the final boiling point is below 150 ℃, the loss of the gasoline octane number is more favorably reduced.
According to a preferred embodiment of the invention, subjecting said medium gasoline fraction to extractive distillation comprises: gasoline is contacted with an extractive distillation solvent under extractive distillation conditions.
The manner in which the medium gasoline fraction is contacted with the extractive distillation solvent in the present invention is not particularly limited and may be carried out according to the conventional means in the art, and preferably, the medium gasoline fraction is introduced from the middle part of the extractive distillation column and the extractive distillation solvent is introduced from the upper part of the extractive distillation column.
The selection range of the extractive distillation conditions is wide, so long as the aromatic hydrocarbon and sulfide in the medium gasoline fraction are dissolved in the extractive distillation solvent, and preferably, the extractive distillation conditions comprise: the temperature of the mixture entering the tower is 60-100 ℃, and the preferred temperature is 80-90 ℃; the temperature at the top of the tower is 70-90 ℃, preferably 75-85 ℃; the bottom temperature is 140-180 ℃, preferably 155-170 ℃; the pressure at the top of the tower is 0.05-0.1 MPa.
The extraction distillation of the invention simultaneously carries out polar extraction and light and heavy distillation separation, and the whole process has the polar competition process of aromatic hydrocarbon, olefin and sulfide (mercaptan, thioether and thiophene) and also has the distillation separation process of light and heavy materials. Therefore, the polar extraction characteristic of the solvent can be exerted to the maximum extent, and the light and heavy separation characteristic of the components can also be reflected, so that the aromatic hydrocarbon component carried by the solvent and the sulfide in the medium gasoline form a rich solvent, the refined medium gasoline is distilled out, the olefin is difficult to see in the rich solvent, the sulfide is difficult to find in the refined medium gasoline, and further the deep desulfurization of the gasoline can be realized, and the octane number loss can be reduced.
The selection range of the feeding weight ratio of the extractive distillation solvent to the medium gasoline fraction is wide, and preferably, the feeding weight ratio of the extractive distillation solvent to the medium gasoline fraction is 1-4: 1, more preferably 2 to 3: 1.
according to a preferred embodiment of the present invention, the extractive distillation solvent includes at least one of sulfone compound, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 2-pyrrolidone, N-formylmorpholine, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, propylene carbonate, and ethylene carbonate.
According to a preferred embodiment of the present invention, the extractive distillation solvent comprises a main solvent, a cosolvent and an olefin polymerization inhibitor, wherein the main solvent is 70-99 wt%, the cosolvent is 0.999-29.9 wt%, and the olefin polymerization inhibitor is 10-1000 μ g/g, based on the total weight of the extractive distillation solvent; the main solvent is selected from sulfone compounds; the cosolvent is selected from at least one of N-methyl pyrrolidone, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, furfural and dimethylacetamide; the olefin polymerization inhibitor is at least one selected from p-tert-butyl catechol, diethylhydroxylamine, dipropylhydroxylamine, 2-sec-butyl-4, 6-dinitrophenol and sodium nitrite. The preferable extractive distillation solvent has higher solubility and selectivity, can ensure the selectivity to sulfide, and further reduces the selectivity to olefin, and the olefin polymerization inhibitor in the extractive distillation solvent has the function of inhibiting olefin polymerization, so that the extractive distillation solvent has more excellent performance.
In the research process, the inventor finds that the sulfone compound is used as a main solvent, and the selectivity of the solvent to aromatic hydrocarbon can be improved by matching the cosolvent and the olefin polymerization inhibitor, and the defect that the solvent and the aromatic hydrocarbon are not easy to separate is overcome. In addition, the co-use of the main solvent, the co-solvent and the olefin polymerization inhibitor does not cause the function of the single component to be resolved.
In order to further improve the selectivity of the extractive distillation solvent to aromatics and sulfides and reduce the selectivity to olefins, the content of the main solvent is preferably 80-95 wt%, the content of the cosolvent is 4.99-19.9 wt%, and the content of the olefin polymerization inhibitor is 1000 μ g/g, based on the total weight of the extractive distillation solvent, and the content of the main solvent is more preferably 85-90 wt%, the content of the cosolvent is more preferably 9.95-14.9 wt%, and the content of the olefin polymerization inhibitor is 500-.
According to the present invention, the content of the olefin polymerization inhibitor means the amount of the olefin polymerization inhibitor per g of the extractive distillation solvent.
According to a preferred embodiment of the invention, the co-solvent is a mixture of N-methylpyrrolidone and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether. The adoption of the preferred embodiment is more beneficial to the synergistic effect of the main solvent and the cosolvent, and the selectivity to the sulfide is ensured, and the selectivity to the olefin is further reduced.
In the present invention, the triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is used in an amount of preferably 10 to 200 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of N-methylpyrrolidone. By adopting the preferred embodiment, the N-methyl pyrrolidone and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether can be more favorably exerted, and the selectivity to sulfide is ensured, and the selectivity to olefin is further reduced.
When the co-solvent contains both N-methylpyrrolidone and triethylene glycol monomethyl ether and tetraethylene glycol monomethyl ether, the amount of triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is the total amount of triethylene glycol monomethyl ether and tetraethylene glycol monomethyl ether.
According to a preferred embodiment of the present invention, the olefin polymerization inhibitor is t-butylcatechol and/or 2-sec-butyl-4, 6-dinitrophenol, and when the preferred olefin polymerization inhibitor is used in combination with a main solvent and a cosolvent in an extractive distillation solvent, the inhibitor has a better olefin polymerization inhibition effect, and the extractive distillation solvent has more excellent performance.
The selection range of the sulfone compounds in the invention is wide, and the sulfone compounds can be various sulfone compounds commonly used in the field, for example, the sulfone compounds can be at least one selected from sulfolane, 3-methyl sulfolane, dimethyl sulfone and di-n-propyl sulfone, and are preferably sulfolane. Sulfolane has good solubility in hydrocarbon and good selectivity to aromatic hydrocarbon.
During the operation of the extractive distillation solvent mainly containing sulfone compounds, because of O in the system2And the extractive distillation solvent also comprises a corrosion inhibitor, wherein the corrosion inhibitor is preferably used for controlling the acidity of the system so that the pH value in the system is kept at about 6.0.
The corrosion inhibitor is not particularly limited in the present invention as long as it can control the system acidity while ensuring that the added corrosion inhibitor does not affect the performance of the extractive distillation solvent, and preferably, the corrosion inhibitor is selected from at least one of monoethanolamine, diethanolamine, N-methyl monoethanolamine and N-methyl diethanolamine, and most preferably, monoethanolamine.
In the invention, preferably, the corrosion inhibitor is used together with other substances in the extractive distillation solvent, so that the acidity of the system can be effectively controlled, the stability of the acidity of the whole system is ensured, and the effect of inhibiting olefin polymerization is also achieved to a certain extent.
The selection range of the dosage of the corrosion inhibitor is wide, preferably, the content of the corrosion inhibitor is 10-1000 mu g/g based on the total weight of the extractive distillation solvent, more preferably 100-1000 mu g/g, and still more preferably 500-1000 mu g/g.
According to a preferred embodiment of the present invention, the rich solvent may be subjected to a stripping treatment to yield a solvent and a sulfide-containing aromatic hydrocarbon. The solvent can be recycled.
The stripping conditions in the present invention are not particularly limited, and those skilled in the art can appropriately select the stripping conditions according to the actual situation, for example, the stripping conditions may include: the temperature at the top of the tower is 80-90 ℃, and the temperature at the bottom of the tower is 170-178 ℃; the pressure at the top of the tower is-40 to-60 KPa, and the reflux/feeding mass ratio is 0.5 to 1: 1.
According to a preferred embodiment of the invention, the aromatics containing sulphides are subjected to selective hydrogenation, preferably after mixing them with the heavy gasoline fraction. The gasoline processing method provided by the invention enables almost all sulfides in the gasoline to be dissolved into aromatic hydrocarbons (almost no olefin), applies the extraction process to the gasoline desulfurization process, efficiently separates the olefin and the sulfides, and mixes the aromatic hydrocarbons (almost no olefin) containing the sulfides with the heavy gasoline fraction and then jointly carries out selective hydrogenation treatment, thereby ensuring deep desulfurization and reducing octane number loss.
The invention carries out selective hydrogenation treatment on the heavy gasoline fraction and the aromatic hydrocarbon containing sulfide, removes the sulfide in the heavy gasoline fraction, and simultaneously reserves the olefin in the heavy gasoline to the maximum extent so as to avoid excessive octane number loss.
The conditions for the selective hydrogenation are not particularly limited in the present invention, and all the selective hydrogenation methods of the prior art can be applied to the present invention.
In the present invention, the process for selective hydrotreating comprises: under selective hydrogenation conditions, the sulfide-containing aromatic hydrocarbon, the heavy gasoline fraction and hydrogen are contacted with a selective hydrodesulfurization catalyst.
According to a preferred embodiment of the present invention, the selective hydrogenation conditions comprise: the temperature is 250 ℃ and 600 ℃, and the liquid hourly space velocity is 1-10h-1The volume ratio of hydrogen to oil is 200-700, and the pressure is 2-8 MPa; further preferably, the temperature is 260--1The volume ratio of hydrogen to oil is 250-400 and the pressure is 2-6 MPa.
According to the present invention, the selective hydrodesulfurization catalyst may be any of various selective hydrodesulfurization catalysts conventionally used in the art, and generally comprises a carrier and a selective hydrodesulfurization active component, wherein the selective hydrodesulfurization active component is contained in an amount of 1 to 40 wt% and the carrier is contained in an amount of 60 to 99 wt%, based on the total amount of the selective hydrodesulfurization catalyst. The selective hydrodesulfurization active component can be one or more elements selected from VIB group and VIII group, preferably, the selective hydrodesulfurization active component is one or more elements selected from tungsten, nickel, molybdenum and cobalt. The carrier may be various carriers conventionally used, that is, various heat-resistant porous materials commonly used in the art, and specifically, the heat-resistant porous materials may be heat-resistant inorganic oxides and/or silicates.
According to the gasoline processing method, the light gasoline fraction is 15-30 parts by weight, the medium gasoline fraction is 30-50 parts by weight, the heavy gasoline fraction is 20-50 parts by weight, the light gasoline fraction is 20-25 parts by weight, the medium gasoline fraction is 35-45 parts by weight, and the heavy gasoline fraction is 30-45 parts by weight based on 100 parts by weight of the total gasoline.
According to a preferred embodiment of the invention, the method further comprises, before cutting the gasoline, subjecting the gasoline to a pre-hydrogenation treatment which saturates the diolefins in the gasoline and converts the small molecule sulphides to large molecule sulphides. Before the gasoline is cut, the gasoline is subjected to pre-hydrogenation treatment, so that light gasoline fraction with lower sulfur content can be obtained more favorably, and octane number loss is avoided to the maximum extent.
According to a preferred embodiment of the present invention, a method for pre-hydrotreating gasoline comprises: under the condition of prehydrogenation, contacting gasoline and hydrogen with a prehydrogenation catalyst, wherein the prehydrogenation catalyst comprises a carrier and a metal active component, the metal active component comprises molybdenum and/or tungsten and nickel, the content of the carrier is 66-86%, the content of the molybdenum and/or tungsten is 2-9% and the content of the nickel is 12-25% by weight based on the total weight of the catalyst, and the weight ratio of the molybdenum and/or tungsten to the nickel is 0.1-0.5: 1.
In the present invention, the content of molybdenum and/or tungsten refers to the total content of molybdenum and tungsten, that is, when the metal active component contains both molybdenum and tungsten, the content represents the total content of molybdenum and tungsten; when the metal active component contains molybdenum but does not contain tungsten, the content represents the content of molybdenum; when the metal active component contains tungsten but does not contain molybdenum, the content indicates the content of tungsten.
The inventors of the present invention have found in the course of their studies that the object of the present invention can be achieved as long as the prehydrogenation catalyst contains molybdenum and/or tungsten and nickel in such proportions as described above, but preferably, the prehydrogenation catalyst has a higher desulfurization activity when the carrier is contained in an amount of 66 to 86% by weight, the molybdenum and/or tungsten is contained in an amount of 2 to 9% by weight and the nickel is contained in an amount of 12 to 25% by weight based on the total weight of the prehydrogenation catalyst.
More preferably, the weight ratio of molybdenum and/or tungsten to nickel is 0.1-0.5: 1. The inventors of the present invention have considered that, although the object of the present invention can be achieved by blending at least one of molybdenum and tungsten with nickel as the metal active component, the desulfurization activity of the prehydrogenation catalyst can be further improved when molybdenum and tungsten are contained in the metal active component, particularly when the weight ratio of molybdenum to tungsten is 0.1 to 0.9:1, preferably 0.1 to 0.6: 1.
According to the invention, the total pore volume of the prehydrogenation catalyst may be from 0.3 to 1.2cm3Per g, preferably 0.5-1.0cm3/g。
According to the invention, the specific surface area of the prehydrogenation catalyst may be from 30 to 150m2A/g, preferably from 70 to 150m2(ii) in terms of/g. The specific surface area in the present invention is a BET specific surface area.
The carrier may be any of various heat-resistant porous materials commonly used in the art. In particular, the heat-resistant porous material may be a heat-resistant inorganic oxide and/or silicate.
Preferably, the support is one or more of alumina, silica, titania, magnesia, zirconia, thoria, beryllia, clay and molecular sieves. More preferably, the support is one or more of alumina, silica and molecular sieves.
According to the invention, the pore volume of the support is not particularly critical, and is preferably from 0.8 to 1.4cm3/g。
The prehydrogenation catalyst according to the invention can be prepared by various methods known in the art, for example by conventional impregnation methods, such as dry impregnation (i.e. equivalent volume impregnation), for example by the following steps: contacting molybdenum and/or tungsten salt and nickel salt solution (such as deionized water solution) with the carrier to make the content of molybdenum and/or tungsten in the finally formed prehydrogenation catalyst less than 10% and the content of nickel in the finally formed prehydrogenation catalyst 10-30%, drying and roasting so as to obtain the prehydrogenation catalyst of the present invention. The method in which the molybdenum and/or tungsten salt and the nickel salt solution (e.g., deionized water solution) are contacted with the support can be carried out as follows: (1) the molybdenum salt and/or the tungsten salt and the nickel salt may be formed into a mixed aqueous solution and then the support may be immersed therein; (2) or preparing the molybdenum salt and/or the tungsten salt and the nickel salt into aqueous solutions respectively, and then sequentially contacting the carrier with the molybdenum salt and/or the tungsten salt and the nickel salt solution (the order of contacting with the three solutions is arbitrary).
According to the invention, the nickel salt can be various water-soluble nickel salts, such as one or more of various commonly used water-soluble nickel salts such as nickel nitrate, nickel chloride, nickel sulfate and the like; the tungsten salt can be various water-soluble tungsten salts, such as one or more of various commonly used water-soluble tungsten salts such as ammonium metatungstate, ammonium thiotungstate and the like; the molybdenum salt can be one or more of various water-soluble molybdenum salts, such as ammonium heptamolybdate, ammonium tetramolybdate, ammonium dimolybdate and the like.
The invention has no special requirements on the drying and roasting method and conditions, and can be carried out by referring to the prior art. For example, the temperature of drying may be 80 to 200 ℃ and the time of drying may be 1 to 10 hours. The roasting temperature can be 300-800 ℃, and the roasting time can be 1-8 h.
The conditions of the pre-hydrotreatment in the present invention are not particularly limited, and for example, the selective hydrotreatment conditions may include: the temperature is 120 ℃ and 350 ℃, and the liquid hourly space velocity is 0.5-10h-1The pressure is 1-10MPa, and the volume ratio of hydrogen to oil is 200-700: 1.
In the invention, the light gasoline fraction obtained by cutting gasoline is subjected to etherification treatment, wherein the etherification treatment condition is that C5 and C6 olefins in the light gasoline fraction are converted into corresponding ethers (high-octane gasoline components) as much as possible, so that the gasoline octane number is improved.
The conditions for the etherification in the present invention are not particularly limited, and those skilled in the art can select the conditions according to the actual circumstances.
Specifically, the etherification treatment method comprises the following steps: under the etherification condition, the light gasoline fraction and the etherification reagent are contacted with an etherification catalyst to obtain an etherification product.
According to the present invention, the etherification conditions of the present invention may be conventional etherification conditions, and the etherification conditions of the present invention generally include: the temperature is 30-200 deg.C, preferably 65-85 deg.C, the pressure is 0.1-5MPa, preferably 0.5-2MPa, and the liquid hourly space velocity is 0.1-5h-1And preferably 0.5-2.5h-1The volume ratio of the etherification agent to the light gasoline fraction is 0.1-10:1, preferably 0.5-5: 1.
In the present invention, the etherification reagent may be any of various conventionally used etherification reagents, and preferably methanol and/or ethanol.
In the present invention, the etherification catalyst may be any of various conventionally used etherification catalysts, for example, cation exchange resin and/or heteropoly acid, wherein the cation exchange resin is preferably a strongly acidic cation exchange resin, the heteropoly acid compound-containing catalyst may be the heteropoly acid compound itself, preferably, the heteropoly acid compound-containing catalyst is an immobilized heteropoly acid catalyst, and the immobilized heteropoly acid catalyst may be a conventional immobilized heteropoly acid catalyst, for example, an immobilized heteropoly acid catalyst in which a heteropoly acid compound is immobilized on activated carbon (see the literature: research on light gasoline etherification reaction performance of an immobilized heteropoly acid catalyst, xu Hai, etc., research center on petroleum refining engineering technology at the university of Western-Ann Petroleum).
In the invention, the etherified product obtained by etherifying the light gasoline fraction can be directly used as required, or the desulfurized product obtained by selectively hydrodesulfurizing the sulfur-rich aromatic hydrocarbon and the heavy gasoline fraction obtained from the middle gasoline fraction can be directly used as required, generally speaking, because the sulfur content of the product obtained by selectively hydrodesulfurizing the sulfur-rich aromatic hydrocarbon and the heavy gasoline fraction is relatively low (generally below 10 mug/g), while the etherified product obtained by etherifying the light gasoline fraction can have relatively high sulfur content (generally 20-60 mug/g) because of no desulfurization, therefore, the etherified product obtained by etherifying the light gasoline fraction, the desulfurized product obtained by selectively hydrodesulfurizing the sulfur-rich aromatic hydrocarbon and the heavy gasoline fraction and the raffinate oil obtained by extracting and distilling the middle gasoline fraction are preferably mixed and then used, so that the sulfur content of the blended product is proper, after combustion, the fuel can meet the current emission standard and can not cause energy waste. That is, preferably, the gasoline processing method of the present invention further comprises mixing an etherification product obtained by etherification of the light gasoline fraction, raffinate oil obtained by extractive distillation of the medium gasoline fraction, and a product obtained by selective hydrogenation of the sulfur-rich aromatic hydrocarbon and the heavy gasoline fraction.
In the invention, the desulfurization rate is defined as the ratio of the difference between the sulfur content in the gasoline before treatment and the sulfur content in the gasoline after treatment to the sulfur content in the gasoline before treatment, and the calculation method is (the sulfur content in the gasoline before treatment-the sulfur content in the gasoline after treatment)/the sulfur content in the gasoline before treatment.
In the invention, the octane number is a research octane number, and the determination method only needs to refer to a conventional method for determining the research octane number, and the method has no special requirements.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples, the properties of the catalytic gasoline used are shown in Table 1.
TABLE 1
| Properties of the raw materials | |
| Density (20 ℃), kg/m3 | 0.737 |
| Sulfur content, μ g/g | 1800 |
| Olefin, wt.% | 37.8 |
| Aromatic hydrocarbons, wt.% | 24.2 |
| Initial cut point, DEG C | 42 |
| End point of distillation,. degree.C | 203 |
| Research octane number RON | 92 |
Example 1
(1) Pre-hydrotreatment
Preparation of the prehydrogenation catalyst according to the dry impregnation method: the dry impregnation method involves dry impregnation with an aqueous solution of ammonium heptamolybdate and ammonium metatungstate and nickel nitrate. The concentrations of the three salt solutions in the precursor solution were adjusted to deposit the desired weight of metal oxide on the support, and the solid obtained after impregnation was aged at room temperature for 4h and dried at 120 ℃ for 6 h. Finally, the dried solid was calcined at 500 ℃ for two hours in air using an alumina support (pore volume 1.2 cm)3Per g), the prehydrogenation catalyst prepared according to the process described above contained 2.5% by weight of MoO35.5% by weight of WO318% by weight of NiO and a specific surface area (BET) of 70m2Per g, Total Pore Volume (TPV) 1.0cm3/g；
0.2 g of the prehydrogenated catalyst was taken and sulfided using a catalyst containing 5% by weight of CS2The normal hexane is vulcanized oil at a liquid hourly space velocity of 36h-1Sulfurizing for 3H at a feed rate of 0.3 ml/min, H2The flow rate is 180 ml/min, and the hydrogen partial pressure is 3.2 MPa;
the pre-hydrogenation catalyst after sulfuration and catalytic gasoline (properties are shown in table 1) are subjected to pre-hydrogenation reaction, and the reaction conditions comprise: the pressure is 3.2MPa, and the liquid hourly space velocity is 6h-1Feed rate of 0.2 ml/min and hydrogen to oil volume ratio of 300, to givePre-hydrotreating the product.
(2) Cutting the prehydrogenation treated product: distilling and cutting the prehydrogenation treated product to obtain heavy gasoline fraction (35 weight portions) with the distillation range of 150-203 ℃, medium gasoline fraction (40 weight portions) with the distillation range of 65-150 ℃ and light gasoline fraction (25 weight portions) with the distillation range of 42-65 ℃.
(3) And (3) carrying out etherification treatment on the light gasoline fraction: the light gasoline fraction with the distillation range of 42-65 ℃ obtained in the step (2) is processed at the temperature of 75 ℃, the pressure of 1MPa and the liquid hourly space velocity of 1h-1The etherification reagent is methanol, the etherification catalyst is strong acid cation resin which is commercially available from Shenzhen Meiheng environmental protection technology Limited company, and the volume ratio of the methanol to the light gasoline fraction is 1, so as to obtain an etherification product.
(4) And (3) medium gasoline fraction extraction distillation: introducing the medium gasoline fraction into the middle part of an extractive distillation tower, introducing an extractive distillation solvent F-1 (the specific composition is shown in Table 2) into the extractive distillation tower from the upper part (the mass ratio of the extractive distillation solvent to the medium gasoline fraction is 2:1), and performing extractive distillation under the conditions of: the temperature of the tower is 84 ℃, the temperature of the tower top is 76-77 ℃, the temperature of the tower bottom is 158-: the temperature at the top of the tower is 80-82 ℃, the temperature at the bottom of the tower is 177-179 ℃, and the reflux/feeding mass ratio is 1; the lean solvent is obtained at the bottom of the tower, the sulfur-rich aromatic hydrocarbon is obtained at the top of the tower, and the pH value of the obtained lean solvent is about 7 after the system operates for 6 months.
(5) Selective hydrodesulfurization treatment: carrying out selective hydrodesulfurization treatment on the sulfur-rich aromatic hydrocarbon obtained in the step (4) and the heavy gasoline fraction with the distillation range of 150-: the temperature is 280 ℃, and the liquid hourly space velocity is 2.5h-1The hydrogen-oil volume ratio was 250, the pressure was 2.5MPa, and the catalyst was purchased from the institute of petrochemical science and technology under the designation RSDS-31, to obtain a selective hydrodesulfurization product having a sulfur content of 10. mu.g/g.
(6) Mixing the etherification product, raffinate oil and the selective hydrogenation product: and (3) mixing the etherification product obtained in the step (3), the raffinate oil obtained in the step (4) and the selective hydrotreating product obtained in the step (5) to obtain the low-sulfur reaction oil, wherein the sulfur content and the research octane number of the low-sulfur reaction oil are shown in a table 3, and the desulfurization rate and the octane number loss are shown in a table 3.
TABLE 2 extractive distillation solvent composition
Note: the balance of the extractive distillation solvent is water
Example 2
The process of example 1 was followed except that:
step (1): the prehydrogenation catalyst prepared according to the preceding method contained 1% by weight of MoO33% by weight of WO320% by weight of NiO and a specific surface area (BET) of 90m2Per g, Total Pore Volume (TPV) 0.8cm3/g。
And (4): the extractive distillation solvent F-1 is replaced by the extractive distillation solvent F-2, the specific composition of the extractive distillation solvent F-2 is shown in Table 2, and the mass ratio of the extractive distillation solvent to the medium gasoline fraction is 3: 1.
Example 3
The process of example 1 was followed except that:
step (1): the prehydrogenation catalyst prepared according to the preceding method contained 0.5% by weight of MoO34.5% by weight of WO325% by weight of NiO and a specific surface area (BET) of 100m2In terms of/g, Total Pore Volume (TPV) of 0.5cm3/g。
And (4): the extractive distillation solvent F-1 is replaced by the extractive distillation solvent F-3, the specific composition of the extractive distillation solvent F-3 is shown in Table 2, and the mass ratio of the extractive distillation solvent to the medium gasoline fraction is 2.5: 1.
Example 4
The procedure was as described in example 1, except that the same mass of N-methylpyrrolidone was used instead of triethylene glycol monomethyl ether in the extractive distillation solvent used in step (4). After the system had been in operation for 6 months, the resulting lean solvent had a pH of about 7 and was free of polymeric olefin suspension.
Example 5
The procedure was as described in example 1, except that the same mass of triethylene glycol monomethyl ether was used instead of N-methylpyrrolidone in the extractive distillation solvent used in step (4). After the system had been in operation for 6 months, the resulting lean solvent had a pH of about 7 and was free of polymeric olefin suspension.
Example 6
The procedure was as described in example 1, except that the same mass of diethylhydroxylamine was used instead of tert-butylcatechol in the extractive distillation solvent used in step (4). After the system had been operating for 6 months, the resulting lean solvent had a pH of about 7 and a small amount of polymerized olefin suspended in the lean solvent.
Example 1 in contrast, a small amount of polymeric olefin suspension in the lean solvent occurred after 6 months of operation of the system, i.e. a small amount of olefin polymerization had occurred.
Example 7
The procedure is as described in example 1, except that the extractive distillation solvent does not contain a corrosion inhibitor, which is replaced by the same mass of sulfolane. After the system is operated for 6 months, the pH value of the obtained lean solvent is reduced to 5.5, and the performance is reduced.
Example 8
The process is carried out as in example 1, except that the extractive distillation solvent is replaced by a composite solvent comprising sulfolane as main solvent and o-xylene as co-solvent as described in CN1262264A, wherein the sulfolane content is 94 wt% and the o-xylene content is 6 wt%, based on the total weight of the composite solvent.
Example 9
The procedure is as described in example 1, except that the preparation of the pre-hydrotreating catalyst is carried out as in example 1, with the difference that the concentrations of the three salt solutions in the precursor solution are adjusted to deposit the desired weight of metal oxide on the support, with the following properties: 15% by weight of MoO30% by weight of WO39% by weight of NiO and a specific surface area (BET) of 90m2Per g, Total Pore Volume (TPV) 0.8cm3/g。
Example 10
The procedure of example 1 was followed except that the catalytic gasoline was cut directly without the prehydrogenation treatment as described in step (1).
Comparative example 1
The procedure of example 1 was followed, except that the prehydrogenated product was cut in step (2): and (3) performing distillation cutting on the prehydrogenated product at 70 ℃ to obtain a heavy fraction with the distillation range of 70-203 ℃ and a light fraction with the distillation range of 42-70 ℃, and excluding the step (4).
TABLE 3
| Desulfurization degree (%) | Loss of octane number | |
| Example 1 | 94.3 | 0.9 |
| Example 2 | 93.6 | 0.9 |
| Example 3 | 93.3 | 0.9 |
| Example 4 | 90.5 | 1.3 |
| Example 5 | 88.2 | 1.4 |
| Example 6 | 86.1 | 1.6 |
| Example 7 | 93.8 | 1.2 |
| Example 8 | 84.3 | 1.8 |
| Example 9 | 83.2 | 1.7 |
| Example 10 | 80.0 | 2.0 |
| Comparative example 1 | 85.4 | 2.9 |
From the above, the gasoline processing method provided by the invention solves the problem of competition between the polarity of olefin and the polarity of sulfide and solvent, and has no problem that the olefin component with high octane number is lost into the sulfur-rich aromatic hydrocarbon component, so that the oil return circulation is not needed, and the energy consumption is low; the gasoline processing provided by the invention has no problem that the olefin component with high octane number is lost to the sulfur-rich aromatic hydrocarbon component, so that the pentane component of the light olefin on the top is not required to be added, and the material consumption of a device is low; because no light component back washing liquid circulation exists, a back washing liquid tower is cancelled, so that the device has no problems of tower flushing, foaming and the like, and the running stability of the system is improved. The gasoline processing method provided by the invention can be matched with an optimal extractive distillation solvent to more effectively separate sulfide and olefin and reduce the loss of olefin in the desulfurization process. Preferably, the gasoline processing method is matched with a specific prehydrogenation treatment catalyst, so that the desulfurization rate is improved, and the loss of octane number is further reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A gasoline processing method, characterized in that the method comprises: cutting gasoline into light gasoline fraction, medium gasoline fraction and heavy gasoline fraction, etherifying the light gasoline fraction, extracting and distilling the medium gasoline fraction, selectively hydrogenating the heavy gasoline fraction,
wherein the initial boiling point of the medium gasoline fraction is above 40 ℃ and the final boiling point is below 170 ℃; the extraction distillation treatment is carried out to obtain a rich solvent and refined medium gasoline, and aromatic hydrocarbon and sulfide in medium gasoline fraction are dissolved in the extraction distillation solvent to form the rich solvent;
the extraction distillation treatment of the medium gasoline fraction comprises the following steps: under the condition of extractive distillation, contacting the medium gasoline fraction with an extractive distillation solvent;
the extractive distillation solvent comprises a main solvent, a cosolvent and an olefin polymerization inhibitor, wherein the main solvent accounts for 70-99 wt%, the cosolvent accounts for 0.999-29.9 wt%, and the olefin polymerization inhibitor accounts for 10-1000 mug/g;
the main solvent is selected from sulfone compounds;
the cosolvent is a mixture of N-methyl pyrrolidone and triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether; the olefin polymerization inhibitor is p-tert-butyl catechol and/or 2-sec-butyl-4, 6-dinitrophenol.
2. The gasoline processing method of claim 1 wherein the extractive distillation conditions comprise: the temperature of the mixture entering the tower is 60-100 ℃; the temperature of the tower top is 70-90 ℃; the temperature of the bottom of the tower is 140-180 ℃; the pressure at the top of the tower is 0.05-0.1 MPa.
3. The gasoline processing method of claim 1 wherein the feed weight ratio of the extractive distillation solvent to the medium gasoline fraction is 1-4: 1.
4. the gasoline processing method of claim 1 wherein the feed weight ratio of the extractive distillation solvent to the medium gasoline fraction is 2-3: 1.
5. the gasoline processing method of claim 1 wherein the extractive distillation conditions comprise: the temperature of the mixture entering the tower is 80-90 ℃; the temperature of the tower top is 75-85 ℃; the bottom temperature is 155-170 ℃.
6. The gasoline processing method as defined in claim 1, wherein the content of said main solvent is 80-95 wt%, the content of said co-solvent is 4.99-19.9 wt%, and the content of said olefin polymerization inhibitor is 100-1000 μ g/g.
7. The gasoline processing method as defined in claim 1, wherein the content of said main solvent is 85-90 wt%, the content of said co-solvent is 9.95-14.9 wt%, and the content of said olefin polymerization inhibitor is 500-1000 μ g/g.
8. The gasoline processing method according to claim 1, wherein the sulfone-based compound is selected from at least one of sulfolane, 3-methylsulfolane, dimethylsulfone, and di-n-propylsulfone.
9. The gasoline processing method according to claim 1, wherein the sulfone-based compound is sulfolane.
10. The gasoline processing method according to claim 1, wherein the triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is used in an amount of 10 to 200 parts by weight based on 100 parts by weight of the N-methylpyrrolidone.
11. The gasoline processing method according to claim 1, wherein the triethylene glycol monomethyl ether and/or tetraethylene glycol monomethyl ether is used in an amount of 50 to 100 parts by weight based on 100 parts by weight of the N-methylpyrrolidone.
12. The gasoline processing method of claim 1 wherein the extractive distillation solvent further comprises a corrosion inhibitor selected from at least one of monoethanolamine, diethanolamine, N-methyl monoethanolamine, and N-methyl diethanolamine.
13. The gasoline processing method according to claim 12, wherein the content of the corrosion inhibitor is 10 to 1000 μ g/g based on the total weight of the extractive distillation solvent.
14. The gasoline processing method of claim 12, wherein the corrosion inhibitor is contained in an amount of 100-1000 μ g/g based on the total weight of the extractive distillation solvent.
15. The gasoline processing method of claim 12, wherein the corrosion inhibitor is contained in an amount of 500-1000 μ g/g based on the total weight of the extractive distillation solvent.
16. The gasoline processing method of claim 1, wherein the rich solvent is subjected to a stripping treatment to yield a solvent and sulfide-containing aromatic hydrocarbons.
17. The gasoline processing method of claim 16, wherein the sulfide-containing aromatic hydrocarbons are selectively hydrotreated.
18. The gasoline processing method of claim 16, wherein the sulfide-containing aromatic hydrocarbons are mixed with the heavy gasoline fraction and then subjected to selective hydrotreating together.
19. The gasoline processing method of claim 18, wherein the selective hydrotreating process comprises: under selective hydrogenation conditions, the sulfide-containing aromatic hydrocarbon, the heavy gasoline fraction and hydrogen are contacted with a selective hydrodesulfurization catalyst.
20. The gasoline processing method according to any one of claims 1 to 19, wherein the initial boiling point of the medium gasoline fraction is 65 ℃ or higher and the final boiling point is 150 ℃ or lower.
21. The gasoline processing method according to any one of claims 1 to 19, wherein the light gasoline fraction is 20 to 25 parts by weight, the medium gasoline fraction is 35 to 45 parts by weight, and the heavy gasoline fraction is 30 to 45 parts by weight.
22. The gasoline processing method according to any one of claims 1 to 19, wherein the method further comprises subjecting the gasoline to a pre-hydrotreating treatment before the gasoline is cut, wherein the pre-hydrotreating treatment saturates diolefins in the gasoline and converts small molecule sulfides into large molecule sulfides.
23. The gasoline processing method of claim 22, wherein the method of pre-hydrotreating gasoline comprises: under the condition of prehydrogenation, contacting gasoline and hydrogen with a prehydrogenation catalyst, wherein the prehydrogenation catalyst comprises a carrier and a metal active component, the metal active component comprises molybdenum and/or tungsten and nickel, the content of the carrier is 66-86%, the content of the molybdenum and/or tungsten is 2-9% and the content of the nickel is 12-25% by weight based on the total weight of the catalyst, and the weight ratio of the molybdenum and/or tungsten to the nickel is 0.1-0.5: 1.
24. The gasoline processing method of claim 22 wherein the pre-hydrotreating conditions include a temperature of 120 ℃ and 350 ℃ and a liquid hourly space velocity of 0.5-10h-1The pressure is 1-10MPa, and the volume ratio of hydrogen to oil is 200-700: 1.
25. The gasoline processing method according to any one of claims 1 to 19, wherein the gasoline contains aromatic hydrocarbons, olefins, paraffins, and sulfides.
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| CN103360201A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Method for extracting, distilling and recovering styrene from hydrocarbon mixture |
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| CN105238441A (en) * | 2015-09-30 | 2016-01-13 | 中国石油大学(北京) | Method for carrying out advanced desulphurization on gasoline |
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