CN113322094B - Reactive extraction desulfurization and denitrification and high value-added product recovery process - Google Patents
Reactive extraction desulfurization and denitrification and high value-added product recovery process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
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- C—CHEMISTRY; METALLURGY
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
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- C—CHEMISTRY; METALLURGY
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention belongs to the field of petrochemical industry, and discloses a process for reactive extraction desulfurization and denitrification and high-added-value product recovery, wherein the reactive extraction process realizes removal of sulfur and nitride in diesel oil and recovery of high-added-value oxidation products. The active extractant is adopted to extract aromatic sulfide and nitride in the diesel oil, so as to realize ultra-deep desulfurization and denitrification of the diesel oil. Transferring the extracted active extraction phase into a reaction tower, and converting the aromatic sulfur and nitride into high-added-value oxidation products through catalytic oxidation. The separation of the active extractant and the recovery of the oxidation products with high added value are realized by a back extraction method; the separation and purification of oxidation products with different high added values are realized by fractionation, flash evaporation and other methods. The invention has good desulfurizing and denitrifying effects on diesel oil, can avoid oxidation of oil products, has simple operation flow, can obtain high added value products, and can recycle the extractant.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and relates to a process for removing sulfur and nitride in diesel oil and a process for recovering products, in particular to a process for removing sulfur and nitride in oil products and separating and recovering products with high added value through extraction, oxidation and other processes.
Background
Harmful components such as sulfur, nitrogen and the like in diesel oil can cause SO x And NO x And the emission is harmful to the ecological environment and the human health. The world clearly requires control of sulfur and nitrogen content in diesel to alleviate the increasingly serious environmental pollution phenomenon. Clean production of diesel is an effective solution to this problem. At present, the hydrodesulfurization method widely adopted in industry needs harsh reaction conditions such as high temperature, high pressure, hydrogen consumption and the like to remove sulfur and nitride in oil products. In addition, the basic nitrides in the oil product can easily react with the acid catalytic active sites of the catalyst, so that the catalyst is poisoned and deactivated. The non-hydrodesulfurization method has advantages of mild reaction conditions, low energy consumption and the like, and is therefore attracting attention of researchers, such as widely-developed extraction desulfurization and oxidation desulfurization technologies. However, the common direct extraction method has the problems of low single use efficiency, difficult regeneration of the extractant and the like; the traditional oxidation method can cause oxidation side reaction of the oil product, reduce the combustion value of the oil product, and has the defects of poor selectivity, more side reaction and the like. What is needed is a system that can be simultaneously resolvedThe technology for solving the problems is used for clean production of diesel oil. Various methods have been proposed to achieve higher desulfurization rates by coupling.
Patent [ CN101333457A ] provides a method for combining catalytic oxidation desulfurization and adsorption of gasoline for removing sulfide in the gasoline. Adding an oxidant into water, mixing to obtain an aqueous solution, mixing the aqueous solution with gasoline, and carrying out oxidation treatment by using oxygen without the oxidant; and then the sulfur compounds are adsorbed and removed to obtain the desulfurized gasoline.
The patent [ CN1718681A ] adopts a high shear dispersion emulsification technology to strengthen the reaction of petroleum products and an oxidant, oxidizes organic sulfur compounds in the petroleum products into sulfone, and then adopts an extraction or adsorption method to react with alkali metal or alkaline earth metal hydroxide so as to desulfurize.
The patent [ CN10826932A ] adopts fuel oil and water-soluble oxidant to carry out oxidation desulfurization reaction in an interface mass transfer strengthening reactor, so as to oxidize sulfide into sulfone products. The sulfone products are removed through selective adsorption after oil-water separation, thereby achieving the purpose of desulfurization.
The technology adopts a method of firstly oxidizing and then extracting or adsorbing to remove sulfides in the oil product, but if the oil product is directly mixed with the oxidizing agent by using strong oxidizing agents such as oxygen, hydrogen peroxide and the like, the oil product is possibly co-oxidized while desulfurizing and denitrifying, the oxygen content in the oil product is directly increased, and the combustion value is suddenly reduced. Therefore, there is a need to solve this problem in oxidative desulfurization.
Disclosure of Invention
Based on the common problems existing at present, the invention couples extraction and catalytic oxidation, develops a novel reaction type extraction ultra-deep desulfurization and denitrification method, and recycles and recovers high added value oxidation products.
The reaction process of the corresponding design is shown in fig. 1, and the unit operation is divided into three modules: (1) a reaction extraction module: realize extraction of sulfur and nitride; (2) an extractant regeneration module: the method is used for regenerating the extractant, and separating extracted sulfur and nitride selective catalytic oxidation and oxidation products; (3) a product separation module: and (3) separating and purifying oxidation products of sulfur and nitride with high added value.
Specifically, the process for reactive extraction desulfurization and denitrification and high value-added product recovery comprises the following steps:
(1) At normal temperature, the diesel oil is mixed with an extractant by an extraction tower, and sulfur and nitride in the diesel oil are removed by selective ultra-deep extraction;
(2) Separating the diesel oil from the extractant in the step (1) to obtain the extracted extractant and clean oil products after ultra-deep desulfurization and denitrification; wherein the extracted extractant can be recovered for cyclic utilization.
(3) Transferring the extracted extractant in the step (2) into a regeneration tower through continuous operation, selectively converting extracted sulfur and nitride into oxidation products under the action of an oxidant and a back-extraction agent, wherein the oxidation products are sulfone, isatin or indigo with high added value, and transferring the regenerated extractant into the extraction tower for continuous use;
(4) And (3) separating, namely, fractionating and flash evaporating according to the boiling point and polarity difference of the oxidation products to obtain the oxidation products with high added value.
In the step (1), the extractant is an active ionic liquid or a porous ionic liquid. The mass ratio of the diesel oil to the extractant is 20: 1-20: 20.
further, in step (1), the active ionic liquid includes, but is not limited to: an active ionic liquid is obtained by ion exchange of alkyl imidazole salt, pyridine salt, quaternary phosphonium salt or quaternary ammonium salt and the like with metal chloride salt. The method is characterized in that: not only has extraction effect on sulfur and nitride in oil products, but also contains high-efficiency selective catalytic active center.
Wherein the metal chloride salt is tungsten chloride, molybdenum chloride, vanadium chloride, titanium chloride or ferric chloride.
Further, in step (1), the porous ionic liquid includes, but is not limited to: forming an ionic liquid with steric hindrance through ion exchange by taking alkyl imidazole salt, pyridine salt, quaternary phosphonium salt or quaternary ammonium salt as cations and bis (trifluoromethyl sulfonimide) salt, tetrafluoroborate or hexafluorophosphate as anions; porous portions include, but are not limited to, reactive microporous boron nitride, titanium silicalite molecular sieves, metal organic frameworks; the sterically hindered ionic liquid and the porous portion form a porous ionic liquid by hydrogen bonding. The method is characterized in that: has extraction effect on sulfur and nitride in oil products, can effectively absorb gaseous oxidants such as oxygen, and also contains efficient selective catalytic active centers.
In the step (3), the oxidant is oxygen, hydrogen peroxide or tert-butyl hydroperoxide, and the amount of the oxygen is as follows: the dosage of hydrogen peroxide or tertiary butyl hydroperoxide is 10-120 mL/min: the oxygen/sulfur molar ratio is kept between 2 and 10.
In the step (3), the stripping agent is N, N-dimethylformamide, toluene or acetonitrile polar solvent, and the dosage is as follows: the mass ratio of the stripping agent to the ionic liquid is 20: 1-20: 20.
in step (3), the conditions for the selective conversion are: the temperature is 30-150deg.C, and the pressure is 1-2Mpa.
In the step (4), the fractionation temperature and the flash evaporation temperature are 100-500 ℃.
The beneficial effects of the invention are as follows:
the method provided by the invention can not only deeply remove aromatic sulfur and nitride in diesel under mild and low energy consumption conditions, but also selectively separate and recycle high added value oxidation products. Most importantly, a reaction type extractant with a catalytic function is developed, the catalytic oxidation process is transferred from the oil phase reaction to the extractant phase, the oxidation of the oil product can be directly avoided, the molecular oil refining concept is met, the value of each molecule in the oil is improved, the complementation is realized with the existing hydrogenation technology, and the ultra-deep desulfurization and denitrification technology with application prospect in the future is expected.
Drawings
FIG. 1 is a schematic flow chart of the process for desulfurizing and denitrifying by diesel oil reaction extraction and recovering products.
Detailed description of the preferred embodiments
The following describes a process for desulfurizing and denitrifying by diesel oil reaction and recovering products by combining examples, and the technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination among the specific embodiments.
The process for recycling the reaction type extraction desulfurization denitrification and high added value products comprises 3 unit operations: extraction unit operation, oxidation regeneration unit operation, and separation and purification unit operation. The 3 unit operations correspond to the extraction column apparatus, the oxidation regeneration column apparatus (including the elution column), and the separation column apparatus, and related associated apparatus and equipment, respectively, included in the process.
The invention provides a process for reactive extraction desulfurization and denitrification and high value-added product recovery, which comprises the following steps: firstly, the diesel oil is subjected to extraction to remove sulfur and nitride in the diesel oil to obtain the diesel oil with ultra-low content of pollutants; transferring the extractant to an oxidation regeneration tower, adding an oxidant such as air and oxygen or hydrogen peroxide, and oxidizing sulfur and nitride by a catalytic oxidation method; the extractant subjected to the oxidation process enters an elution process, the extractant and oxidation products are eluted and separated, and the extractant is regenerated; the oxidized products enter a separation tower and are subjected to flash distillation and fractionation to obtain different types of high-added-value sulfones, isatins, indigo and other products.
Example 1
Extractant TS-1@ [ C ] 16 mim][NTf 2 ]The preparation process includes mixing bis (trifluoromethyl sulfonyl imide) lithium salt and chlorohexadecyl methylimidazole in certain molar amount, dissolving in water, stirring for 30min, washing with deionized water for several times to eliminate inorganic lithium salt, and drying to obtain [ C ] 16 mim][NTf 2 ]And (3) an ionic liquid. Dispersing 5 parts by weight of titanium silicalite molecular sieve TS-1 in 100 parts by weight of methanol, and adding 50 parts by weight of [ C 16 mim][NTf 2 ]Heating to 100deg.C, stirring for 12 hr, vacuum drying to obtain extractant TS-1@ [ C ] 16 mim][NTf 2 ]. After successful preparation, the preparation is carried out in small batches by scaling up and applied to the process.
100 parts by weight of diesel oil (sulfur, nitrogen) and 20 parts by weight of TS-1@C 16 mim][NTf 2 ]Slowly feeding into extraction tower, controlling the temperature of the mixed solution at 60deg.C, mechanically stirring and mixing, stopping stirring after 20min, standing for 5-20min, separating the liquid into upper and lower layers, and extracting sulfur and nitride to obtain lower layer extractant TS-1@ [ C ] 16 mim][NTf 2 ]The upper layer is diesel oil with ultra-low pollutant content, and the extraction results of different sulfur and nitride are shown in tables 1 and 2. Transferring the extractant and the separated pollutant into an oxidation regeneration tower, reacting at 100 ℃ and blowing oxygen, TS-1@C 16 mim][NTf 2 ]The extractant has catalytic oxidation property, can oxidize sulfur and nitride into corresponding oxides, and different sulfur and nitride are converted into corresponding oxidation products as shown in tables 3 and 4. The oxidized extraction solution enters an elution process, the extractant and the oxidized product are eluted and separated, and the extractant TS-1@C is carried out 16 mim][NTf 2 ]Is regenerated by the regeneration of (a); the oxidation products eluted by the back extractant enter a fractionating tower to fractionate different kinds of high added value products.
TABLE 1 extraction results for different sulfides
TABLE 2 extraction results of nitrides
TABLE 3 conversion of different sulfides to corresponding oxidation products
TABLE 4 conversion of different nitrides to corresponding oxidation products
Example 2
Extractant BN-900@ Bpy][FeCl 4 ]The preparation process includes mixing chlorobutyl pyridinium salt and anhydrous ferric trichloride in certain molar amount, dissolving in water, stirring for 30min, washing with deionized water several times, and drying to obtain [ Bpy ]][FeCl 4 ]. Dispersing 5 parts by weight of microporous boron nitride BN-900 in 100 parts by weight of methanol, and adding 50 parts by weight of [ Bpy ]][FeCl 4 ]Heating to 100deg.C, stirring for 12 hr, vacuum drying to obtain extractant BN-900@ Bpy][FeCl 4 ]. After successful preparation, the preparation is carried out in small batches by scaling up and applied to the process.
100 parts by weight of diesel oil (sulfur, nitrogen) and 8 parts by weight of BN-900@ Bpy][FeCl 4 ]Slowly feeding into extraction tower, controlling the temperature of the mixed solution at 50deg.C, mechanically stirring and mixing, stopping stirring after 20min, standing for 20-50min at room temperature, separating into upper and lower layers, and extracting sulfur and nitride to obtain extractant BN-900@ Bpy][FeCl 4 ]The upper layer is diesel oil with ultra-low pollutant content, and the extraction results of different sulfur and nitride are shown in tables 5 and 6. Transferring the extractant and the separated pollutant to an oxidation regeneration tower, reacting at 50 ℃ and bubbling oxygen, BN-900@ Bpy][FeCl 4 ]The extractant has catalytic oxidation property, can oxidize sulfur and nitride into corresponding oxides, and different sulfur and nitride are converted into corresponding oxidation products as shown in tables 3 and 4. Eluting the oxidized extraction solution, separating the extractant from the oxidized product, and performing extractant BN-900@ Bpy][FeCl 4 ]Is regenerated by the regeneration of (a); the oxidation products eluted by the back extractant enter a fractionating tower to fractionate different kinds of high added value products.
TABLE 5 extraction results for different sulfides
TABLE 6 extraction results for different nitrides
Example 3
Extractant PMo-UIO-66@P 66614 ][Br]The preparation process comprises adding a certain amount of phosphomolybdic acid into the synthesis process of UIO-66, and performing ultrasonic treatmentAfter 30min, the solution was transferred to a stainless steel autoclave with internal polytetrafluoroethylene and reacted at 120 ℃ for 24h. After cooling to room temperature, centrifugation, washing and drying at 80 ℃. Precursor is put in N by using a tube electric furnace 2 Is activated for 2 hours at different temperatures. Obtaining the PMo-UIO-66 material. Dispersing 5 parts by weight of PMo-UIO-66 in methanol, adding 50 parts by weight of [ P ] 66614 ][Br]Heating to 100deg.C, stirring for 12 hr, vacuum drying to obtain extractant PMo-UIO-66@ [ P ] 66614 ][Br]. After successful preparation, the preparation is carried out in small batches by scaling up and applied to the process.
100 parts by weight of diesel oil (sulfur, nitrogen) and 8 parts by weight of PMo-UIO-66@ [ P 66614 ][Br]Slowly feeding into extraction tower, controlling the temperature of the mixed solution at 50deg.C, mechanically stirring and mixing, stopping stirring after 20min, standing for 20-50min at normal temperature, separating into upper and lower layers, and extracting sulfur and nitride to obtain lower layer of extractant PMo-UIO-66@ [ P ] 66614 ][Br]The upper layer is diesel oil with ultra-low pollutant content, and the extraction results of different sulfur and nitride are shown in tables 7 and 8. Transferring the extractant and the separated pollutant to an oxidation regeneration tower, reacting at 50 ℃ and blowing oxygen, and finally introducing PMo-UIO-66@P 66614 ][Br]The extractant has catalytic oxidation property, can oxidize sulfur and nitride into corresponding oxides, and different sulfur and nitride are converted into corresponding oxidation products as shown in tables 3 and 4. Eluting the oxidized extraction solution, eluting and separating the extractant from the oxidized product, and performing extractant PMo-UIO-66@ [ P ] 66614 ][Br]Is regenerated by the regeneration of (a); the oxidation products eluted by the back extractant enter a fractionating tower to fractionate different kinds of high added value products.
TABLE 7 extraction results for different sulfides
TABLE 8 extraction results for different nitrides
Claims (6)
1. A process for reactive extraction desulfurization and denitrification and high value-added product recovery is characterized by comprising the following steps:
(1) At normal temperature, the diesel oil is mixed with an extractant by an extraction tower, and sulfur and nitride in the diesel oil are removed by selective ultra-deep extraction; the extractant is active ionic liquid or porous ionic liquid;
the active ionic liquid is selected from the group consisting of: an active ionic liquid obtained by ion exchange of alkyl imidazole salt, pyridine salt, quaternary phosphonium salt or quaternary ammonium salt and metal chloride salt; the metal chloride salt is tungsten chloride, molybdenum chloride, vanadium chloride, titanium chloride or ferric chloride;
the porous ionic liquid is selected from: forming an ionic liquid with steric hindrance through ion exchange by taking alkyl imidazole salt, pyridine salt, quaternary phosphonium salt or quaternary ammonium salt as cations and bis (trifluoromethyl sulfonimide) salt, tetrafluoroborate or hexafluorophosphate as anions; the porous part is active microporous boron nitride, titanium silicon molecular sieve or metal organic framework; the ionic liquid with steric hindrance and the porous part form a porous ionic liquid through hydrogen bonding;
(2) Separating the diesel oil from the extractant in the step (1) to obtain the extracted extractant and clean oil products after ultra-deep desulfurization and denitrification;
(3) Transferring the extracted extractant in the step (2) into a regeneration tower through continuous operation, selectively converting extracted sulfur and nitride into oxidation products under the action of an oxidant and a back-extraction agent, wherein the oxidation products are sulfone, isatin or indigo with high added value, and transferring the regenerated extractant into the extraction tower for continuous use;
(4) And (3) separating, namely, fractionating and flash evaporating according to the boiling point and polarity difference of the oxidation products to obtain the oxidation products with high added value.
2. The process of claim 1, wherein in step (1), the mass ratio of diesel oil to extractant is 20: 1-20: 20.
3. the process of claim 1, wherein in step (3), the oxidant is oxygen, hydrogen peroxide or t-butyl hydroperoxide, and the amount of oxygen is: the dosage of hydrogen peroxide or tertiary butyl hydroperoxide is 10-120 mL/min: the molar ratio of oxygen/sulfur is kept to be 2-10.
4. The process of claim 1, wherein in step (3), the stripping agent is N, N-dimethylformamide, toluene or acetonitrile polar solvent in an amount of: the mass ratio of the stripping agent to the ionic liquid is 20: 1-20: 20.
5. the process of claim 1, wherein in step (3), the conditions for the selective conversion are: the temperature is 30-150deg.C, and the pressure is 1-2Mpa.
6. The process of claim 1 wherein in step (4), the fractionation, flash temperature is from 100 ℃ to 500 ℃.
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