CN114870793B - Aromatic hydrocarbon adsorbent for high-sulfur nitrogen raw oil and preparation method thereof - Google Patents

Aromatic hydrocarbon adsorbent for high-sulfur nitrogen raw oil and preparation method thereof Download PDF

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CN114870793B
CN114870793B CN202210626848.XA CN202210626848A CN114870793B CN 114870793 B CN114870793 B CN 114870793B CN 202210626848 A CN202210626848 A CN 202210626848A CN 114870793 B CN114870793 B CN 114870793B
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adsorbent
aromatic hydrocarbon
sulfur
nitrogen
aromatic
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CN114870793A (en
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于海斌
臧甲忠
李滨
孙振海
李犇
洪美花
姜雪丹
隋芝宇
李佳
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0248—Compounds of B, Al, Ga, In, Tl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0251—Compounds of Si, Ge, Sn, Pb
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/08—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil according to the "moving bed" method
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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

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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a high-sulfur nitrogen raw oil aromatic adsorbent and a preparation method thereof. The adsorbent is applied to a simulated moving bed adsorption separation process, has a selective adsorption effect on aromatic hydrocarbon in high-sulfur nitrogen raw oil, and can be repeatedly used after desorption and regeneration by a desorbing agent, so that the purity of aromatic hydrocarbon components is higher than 99%, and the purity of non-aromatic hydrocarbon components is higher than 99%.

Description

Aromatic hydrocarbon adsorbent for high-sulfur nitrogen raw oil and preparation method thereof
Technical Field
The invention relates to an aromatic hydrocarbon adsorbent for high-sulfur nitrogen raw oil and a preparation method thereof.
Background
At present, china is still in a medium and high-speed development stage, and the refining industry still has great development potential as one of the pillar industries for guaranteeing the national economy development. The refining industry is based on the processing and utilization of fossil energy, has large industrial scale, large energy consumption and large total carbon emission, and focuses on realizing the aim of double carbon, and needs to implement a new development concept and explore a new development mode so as to realize low-carbon transformation development. Under the policies of 'double carbon' and 'double control', the oil refining chemical industry of China faces a severe development situation, and the whole situation is that a large amount of basic products are excessive and high-end chemicals are in shortage. And the diesel oil can be further subdivided into excessive finished oil, shortage of new materials and special chemicals, saturation of diesel consumption, small increase of gasoline market, and larger space for aviation kerosene and high-quality ship combustion.
The high sulfur nitrogen feedstock generally comprises straight run distillate and coker feedstock, and because of the relatively high sulfur nitrogen compounds therein, pretreatment to remove sulfur nitrogen compounds is typically required during processing, and then to enter the subsequent processing steps. The straight-run gasoline is gasoline obtained by directly fractionating crude oil, mainly contains saturated hydrocarbon of C4-C12, less unsaturated hydrocarbon and a small amount of sulfur compounds, has low octane number, and is usually used as a blending component of the gasoline or is subjected to catalytic reforming, wherein the catalytic reforming refers to a series of reactions such as aromatization, cyclization, isomerization, cracking, superposition and the like of the gasoline component under the action of a certain reaction condition and a catalyst, so that the octane number of the gasoline is improved. The straight-run diesel oil refers to a diesel oil component directly obtained by distillation of crude oil, the component of the straight-run diesel oil takes saturated hydrocarbon as a main component, single-ring aromatic hydrocarbon as a main component in aromatic hydrocarbon, the straight-run diesel oil is generally used as a secondary processing raw material or a blending raw material, and the straight-run diesel oil is rarely directly used and can be used for producing jet fuel, olefin, high-aromatic hydrocarbon reforming raw material and light aromatic hydrocarbon raw material.
The high-sulfur nitrogen raw oil is adsorbed and separated through a Simulated Moving Bed (SMB) process to obtain high-purity aromatic hydrocarbon and high-purity non-aromatic hydrocarbon components, molecular management of the corresponding raw oil components can be realized, market demand change can be more targeted and dealt with, and the subsequent conversion process of aromatic hydrocarbon and non-aromatic hydrocarbon can be coupled, so that the directional conversion of the high-sulfur nitrogen raw oil into chemicals can be realized, the processing flow is shortened, and the economic benefit is improved.
Patent CN1600836 discloses a method for preparing low-olefin gasoline by modifying straight-run gasoline, which comprises mixing straight-run gasoline with carbon tetraolefin fraction, contacting with catalyst containing HZSM-5 at 0.2-0.6MPa and 300-500 ℃, and separating dry gas, liquefied gas and gasoline components in the product. Patent CN111303940a discloses a treatment method of straight-run diesel oil, which is to perform dearomatization treatment on the straight-run diesel oil by a solvent extraction method or an adsorption separation method to obtain an aromatic-rich component and a dearomatization component, wherein the adsorbent is a metal modified Y molecular sieve, but the straight-run gasoline needs hydrogenation reformation or hydrogenation light treatment before adsorption separation to remove sulfur and nitrogen compounds. Patent CN111718751a discloses a method for preparing aromatic hydrocarbon and light oil by catalytic conversion of straight-run diesel, which comprises the steps of performing pretreatment for removing alkaline nitride on straight-run diesel to obtain straight-run diesel with alkaline nitride removed, and then performing catalytic conversion reaction on the straight-run diesel with alkaline nitride removed by using a transition metal ion modified nano ZSM-5 molecular sieve catalyst as a reaction catalyst to obtain aromatic hydrocarbon and light oil.
The patent mainly processes high-sulfur nitrogen raw oil such as straight-run gasoline and diesel oil in a catalytic reaction and adsorption separation mode, wherein the adsorption separation technology processes the straight-run gasoline and diesel oil, and pretreatment is still needed to remove sulfur and nitrogen compounds so as to prevent the sulfur and nitrogen compounds from causing the deactivation of the adsorbent, and no adsorbent can not be influenced by the sulfur and nitrogen compounds in the raw oil, but also can realize the adsorption separation of high-purity aromatic hydrocarbon.
Disclosure of Invention
One of the technical problems to be solved by the invention is to overcome the defects in the prior art, and the aromatic adsorbent can directly adsorb and separate the raw oil containing sulfur-nitrogen compounds by carrying out stability modification on the surface of the adsorbent, and the separation performance is not influenced by the sulfur-nitrogen compounds; and the high-sulfur nitrogen raw oil is adsorbed and separated to obtain high-purity aromatic hydrocarbon and non-aromatic hydrocarbon components, and the high-sulfur nitrogen raw oil can stably run.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention provides a preparation method of a high-sulfur nitrogen raw oil aromatic adsorbent, which comprises the following steps:
(1) Modification of pore channels: mixing the silicon-aluminum adsorbent with a nonionic surfactant solution, and filtering to obtain a filter cake with a micelle filled pore structure formed by water and the nonionic surfactant.
(2) Metal activation: and (2) mixing and peptizing the stable metal compound and the organic amine solution of the dihydric alcohol to obtain metal sol, mixing the metal sol with the filter cake obtained in the step (1), and filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) in an autoclave for sulfur-nitrogen compound solvent treatment, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
wherein the silicon-aluminum adsorbent is at least one of silicon oxide, amorphous silicon aluminum, aluminum oxide, an X molecular sieve and a Y molecular sieve; the metal is at least one of Al, ti, zr, sn, and the mass content of the silicon-aluminum adsorbent in the aromatic hydrocarbon adsorbent is 80-99%.
In the preparation method of the aromatic hydrocarbon adsorbent of the high-sulfur nitrogen raw oil, the solid-liquid mass ratio in the step (1) is 1: (5-10), wherein the nonionic surfactant is at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether TX-10, the concentration of the nonionic surfactant is 0.5-1.5%, and the treatment condition is 40-100 ℃ for 2-12h.
In the preparation method of the aromatic hydrocarbon adsorbent of the high-sulfur nitrogen raw oil, the stable metal compound in the step (2) is at least one of aluminum isopropoxide, tetrabutyl titanate, tetraethyl titanate, tetrabutyl zirconate, zirconium acetate and trimethyltin chloride, the dihydric alcohol is at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, the mass concentration of the dihydric alcohol is 30-60%, the organic amine is at least one of ethylenediamine, n-butylamine and triethylamine, the mass concentration of the organic amine is 5-20%, and the treatment condition is 60-120 ℃ for 4-24 hours.
In the preparation method of the high-sulfur nitrogen raw oil aromatic adsorbent, the sulfur compound in the step (3) is at least one of benzothiophene, benzyl mercaptan and phenyl sulfide, the nitrogen compound is at least one of pyridine, quinoline and acridine, the mass ratio of the sulfur compound to the nitrogen compound is 5-30, the treatment condition is 120-200 ℃, the roasting temperature is 500-700 ℃, and the roasting time is 2-12h.
The invention also provides a forming method of the high-sulfur nitrogen raw oil aromatic hydrocarbon adsorbent, the adsorbent and the binder are mixed, granulated and formed, and the granules with the grain size range of 0.3-2mm are screened, dried and roasted to obtain the formed adsorbent; the binder is at least one of silica sol, alumina sol, kaolin and attapulgite, the roasting temperature is 500-700 ℃ and the roasting time is 2-12.
The invention also provides the high-sulfur nitrogen raw oil aromatic adsorbent prepared by the preparation method.
The invention further provides application of the high-sulfur nitrogen feed oil aromatic hydrocarbon adsorbent in adsorption separation of aromatic hydrocarbon in high-sulfur nitrogen feed oil, wherein the adsorption separation process of aromatic hydrocarbon in high-sulfur nitrogen feed oil is a simulated moving bed process, and the purity of aromatic hydrocarbon components is higher than 99% and the purity of non-aromatic hydrocarbon components is higher than 99%.
In the above application technical scheme of the invention, the high-sulfur nitrogen raw oil preferably comprises at least one of straight-run gasoline, straight-run kerosene, straight-run diesel oil, coker gasoline, coker kerosene and coker diesel oil according to the processing mode.
In the application technical scheme of the invention, the high-sulfur nitrogen raw oil is prepared into a raw material between C4 and C22 according to hydrocarbon carbon groups, S is less than or equal to 10000ppm, and N is less than or equal to 1000ppm.
The aromatic hydrocarbon adsorbent for the high-sulfur nitrogen raw oil and the preparation method thereof have the beneficial effects that: according to the method, the metal salt and the silicon-aluminum adsorbent are respectively pretreated, so that the cooperative adsorption capacity between the metal salt and the silicon-aluminum adsorbent is enhanced, and the performance of the adsorbent in adsorption separation of aromatic hydrocarbon is improved; meanwhile, the adsorbent is insensitive to sulfur nitrogen compounds in the raw oil through stability treatment, is applied to adsorption separation of aromatic hydrocarbon in the high sulfur nitrogen raw oil, realizes that the purity of aromatic hydrocarbon components is more than 99 percent and the purity of non-aromatic hydrocarbon components is more than 99 percent, can stably operate, and has no attenuation on adsorption separation performance.
Detailed Description
The following describes the technical scheme of the invention in conjunction with examples, but is not limited to these examples.
The evaluation performance data of the adsorbents in examples were measured by: the straight-run gasoline/diesel oil is used as raw material, and the aromatic hydrocarbon content of the fraction section is 10-50%. Loading the adsorbent into a simulated moving bed, and carrying out adsorption separation on aromatic hydrocarbon into a countercurrent simulated moving bed adsorption separation process, wherein the adsorption bed layer is 8-24 layers, preferably 8-16 layers, the adsorption separation temperature is 40-150 ℃, preferably 50-10 ℃, the desorbant is a mixture of alkane and aromatic hydrocarbon, preferably methylcyclohexane and toluene, and the mass fraction of toluene is 10% -50%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed.
Example 1
(1) Modification of pore channels: 10kg of silica gel is weighed, 50kg of aqueous solution containing 250g of dodecylphenol polyoxyethylene ether OP-10 is added, the mixture is treated for 12 hours at 40 ℃, and then the mixture is filtered, so that a filter cake with a micelle filled pore structure formed by water and OP-10 is obtained.
(2) Metal activation: and (2) weighing 405g of aluminum isopropoxide and 20kg of n-butylamine solution of ethylene glycol for peptizing, wherein the mass concentration of the ethylene glycol is 30% and the mass concentration of the n-butylamine is 5%, then mixing with the filter cake obtained in the step (1), treating for 24 hours at 60 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of benzothiophene and pyridine with a mass ratio of 5, treating for 12 hours at 120 ℃, and then filtering, drying and roasting for 12 hours at 500 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: straight-run gasoline is used as a raw material, the sulfur and nitrogen content is shown in table 1, the mass fraction of aromatic hydrocarbon component is 13%, an adsorbent is filled into a simulated moving bed, the aromatic hydrocarbon adsorption separation is a countercurrent simulated moving bed adsorption separation process, the adsorption bed layer is 12 layers, the adsorption separation temperature is 60 ℃, and the desorbent is methylcyclohexane and toluene, wherein the mass fraction of toluene is 20%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed after continuous operation for 30 days. The evaluation results are shown in Table 2.
Example 2
(1) Modification of pore channels: 10kg of amorphous silica-alumina is weighed, 100kg of aqueous solution containing 1500g of polyoxyethylene nonylphenol ether TX-10 is added, the mixture is treated for 2 hours at 100 ℃, and then the mixture is filtered to obtain a filter cake with a micelle filled pore structure formed by water and TX-10.
(2) Metal activation: and (2) weighing 10635g of tetrabutyl titanate and 20kg of ethylene glycol triethylamine solution for peptizing, wherein the mass concentration of the ethylene glycol is 60% and the mass concentration of the triethylamine is 20%, then mixing with the filter cake obtained in the step (1), treating for 4 hours at 120 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of benzyl mercaptan and quinoline with the mass ratio of 30, treating for 2 hours at 200 ℃, and then filtering, drying and roasting for 2 hours at 700 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: the evaluation results are shown in Table 2, in the same manner as in example 1.
Example 3
(1) Modification of pore channels: 10kg of alumina is weighed, 80kg of aqueous solution containing 800g of polyoxyethylene nonylphenol ether TX-10 is added, the mixture is treated for 8 hours at 60 ℃, and then the mixture is filtered, so that a filter cake with a micelle filled pore structure formed by water and TX-10 is obtained.
(2) Metal activation: weighing 1500g of tetraethyl titanate and 20kg of ethylene diamine solution of 2-propylene glycol for peptization, wherein the mass concentration of the 2-propylene glycol is 40% and the mass concentration of the ethylene diamine is 10%, then mixing with the filter cake obtained in the step (1), treating for 6 hours at 100 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of phenyl sulfide and acridine with the mass ratio of 10, treating for 8 hours at 150 ℃, and then filtering, drying and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: example 1 was the same and the evaluation results are shown in Table 2.
Example 4
(1) Modification of pore channels: weighing 10 and kgX molecular sieves, adding 80kg of an aqueous solution containing 800g of dodecylphenol polyoxyethylene ether OP-10, treating at 60 ℃ for 8 hours, and then filtering to obtain a filter cake with a micelle filled pore structure formed by water and OP-10.
(2) Metal activation: weighing 1639g of tetrabutyl zirconate and 20kg of 1, 4-butanediol triethylamine solution for peptizing, wherein the mass concentration of the 4-butanediol is 40% and the mass concentration of the triethylamine is 10%, then mixing with the filter cake obtained in the step (1), treating for 16h at 80 ℃, filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of phenyl sulfide and acridine with the mass ratio of 10, treating for 8 hours at 150 ℃, and then filtering, drying and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: straight-run diesel oil is used as a raw material, the sulfur and nitrogen content is shown in table 1, the mass fraction of aromatic hydrocarbon component is 21%, an adsorbent is filled into a simulated moving bed, the aromatic hydrocarbon adsorption separation is a countercurrent simulated moving bed adsorption separation process, the adsorption bed layer is 12 layers, the adsorption separation temperature is 60 ℃, and the desorbent is methylcyclohexane and toluene, wherein the mass fraction of toluene is 20%. Two materials are extracted from the simulated moving bed, one material is rich in aromatic hydrocarbon components, the other material is rich in non-aromatic hydrocarbon components, and the purity of the two materials is analyzed after continuous operation for 30 days. The evaluation results are shown in Table 2.
Example 5
(1) Modification of pore channels: weighing 10kgY molecular sieve, adding 70kg of aqueous solution containing 840g of dodecylphenol polyoxyethylene ether OP-10, treating at 80 ℃ for 10 hours, and then filtering to obtain a filter cake with a micelle filled pore structure formed by water and OP-10.
(2) Metal activation: weighing 1395g of zirconium acetate, peptizing with 20kg of 1, 6-hexanediol triethylamine solution, wherein the mass concentration of the 1, 6-hexanediol is 40% and the mass concentration of the triethylamine is 10%, mixing with the filter cake obtained in the step (1), treating at 80 ℃ for 20h, filtering, washing and drying to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of benzothiophene and pyridine with the mass ratio of 10, treating for 8 hours at 150 ℃, and then filtering, drying and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(4) Evaluation of adsorbent: example 4 was the same and the evaluation results are shown in Table 2.
Example 6
(1) Modification of pore channels: 10kg of silica gel is weighed, 60kg of aqueous solution containing 900g of polyoxyethylene nonylphenol ether TX-10 is added, the mixture is treated for 12 hours at 60 ℃, and then the mixture is filtered to obtain a filter cake with a micelle filled pore structure formed by water and TX-10.
(2) Metal activation: 696g of trimethyltin chloride and 20kg of ethylene glycol n-butylamine solution are weighed for peptizing, wherein the mass concentration of the ethylene glycol is 40% and the mass concentration of the n-butylamine is 10%, then the mixture is mixed with the filter cake obtained in the step (1), and the mixture is treated for 6 hours at 100 ℃, filtered, washed and dried to obtain the adsorbent precursor.
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) into an autoclave, adding a mixed solvent of benzothiophene and pyridine with the mass ratio of 10, treating for 8 hours at 150 ℃, and then filtering, drying and roasting for 6 hours at 550 ℃ to obtain the adsorbent.
(5) Evaluation of adsorbent: example 4 was the same and the evaluation results are shown in Table 2.
Comparative example 1
The synthesis procedure was carried out without adding the stable metal compound tetrabutyl titanate, the rest of the procedure was the same as in example 1, the adsorbent evaluation was the same as in example 1, and the evaluation results are shown in Table 2.
Comparative example 2
The synthesis procedure was carried out without adding the stable metal compound tetrabutylzirconate, the rest of the procedure was the same as in example 5, the adsorbent evaluation was the same as in example 4, and the evaluation results are shown in table 2.
TABLE 1 adsorption separation of feedstock impurity content
TABLE 2 evaluation results of adsorbents

Claims (8)

1. The preparation method of the aromatic hydrocarbon adsorbent for the high-sulfur nitrogen raw oil is characterized by comprising the following steps of:
(1) Modification of pore channels: mixing the silicon-aluminum adsorbent with a nonionic surfactant aqueous solution, and filtering to obtain a filter cake with a micelle filled pore structure formed by water and the nonionic surfactant; the nonionic surfactant is at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether TX-10, the mass concentration of the nonionic surfactant is 0.5% -1.5%, and the treatment condition is 40-100 ℃ for 2-12h;
(2) Metal activation: mixing and peptizing a stable metal compound and an organic amine solution of dihydric alcohol to obtain metal sol, mixing the metal sol with the filter cake obtained in the step (1), and filtering, washing and drying to obtain an adsorbent precursor; the stable metal compound is at least one of aluminum isopropoxide, tetrabutyl titanate, tetraethyl titanate, tetrabutyl zirconate, zirconium acetate and trimethyltin chloride;
(3) Stability adjustment: placing the adsorbent precursor obtained in the step (2) in an autoclave for sulfur-nitrogen compound solvent treatment, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent; the mass ratio of the sulfur compound to the nitrogen compound in the sulfur-nitrogen compound solvent is 5-30, the sulfur compound is at least one of benzothiophene, benzyl mercaptan and phenyl sulfide, and the nitrogen compound is at least one of pyridine, quinoline and acridine;
wherein the silicon-aluminum adsorbent is at least one of amorphous silicon-aluminum, an X molecular sieve and a Y molecular sieve; the metal is at least one of Al, ti, zr, sn, and the mass content of the silicon-aluminum adsorbent in the aromatic hydrocarbon adsorbent is 80-99%.
2. The method according to claim 1, wherein the mass ratio of the silica-alumina-based adsorbent to the nonionic surfactant solution in the step (1) is 1: (5-10).
3. The preparation method of claim 1, wherein the dihydric alcohol in the step (2) is at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, the mass concentration of the dihydric alcohol is 30% -60%, the organic amine is at least one of ethylenediamine, n-butylamine and triethylamine, the mass concentration of the organic amine is 5-20%, and the treatment condition is 60-120 ℃ for 4-24h.
4. The method according to claim 1, wherein the treatment condition in the step (3) is 120-200 ℃, the roasting temperature is 500-700 ℃ and the roasting time is 2-12h.
5. A high sulfur nitrogen feedstock aromatic adsorbent prepared by the method of any one of claims 1 to 4.
6. The use of the high sulfur nitrogen feed oil aromatic adsorbent of claim 5 in adsorption separation of aromatic hydrocarbons in high sulfur nitrogen feed oil, wherein the adsorption separation process of aromatic hydrocarbons in high sulfur nitrogen feed oil is a simulated moving bed process, and the purity of aromatic components is higher than 99% and the purity of non-aromatic components is higher than 99%.
7. The use according to claim 6, wherein the high sulfur nitrogen feedstock comprises at least one of straight run gasoline, straight run kerosene, straight run diesel, coker gasoline, coker kerosene, coker diesel in a processing mode.
8. The use according to claim 6, wherein the high sulfur nitrogen feedstock oil is a feedstock between C4 and C22 in hydrocarbon carbon groups, S is less than or equal to 10000ppm, N is less than or equal to 1000ppm.
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Citations (5)

* Cited by examiner, † Cited by third party
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US5220099A (en) * 1988-08-31 1993-06-15 Exxon Chemical Patents Inc. Purification of a hydrocarbon feedstock using a zeolite adsorbent
US5925330A (en) * 1998-02-13 1999-07-20 Mobil Oil Corporation Method of m41s functionalization of potentially catalytic heteroatom centers into as-synthesized m41s with concomitant surfactant extraction
RU2010153767A (en) * 2010-12-28 2012-07-10 Светлана Борисовна Зуева (RU) WASTE WATER TREATMENT METHOD
CN104549423A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Metal modified Y zeolite and preparation method and application thereof
CN106187666A (en) * 2016-06-30 2016-12-07 中国海洋石油总公司 A kind of C10+the method that aromatics absorption separates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5220099A (en) * 1988-08-31 1993-06-15 Exxon Chemical Patents Inc. Purification of a hydrocarbon feedstock using a zeolite adsorbent
US5925330A (en) * 1998-02-13 1999-07-20 Mobil Oil Corporation Method of m41s functionalization of potentially catalytic heteroatom centers into as-synthesized m41s with concomitant surfactant extraction
RU2010153767A (en) * 2010-12-28 2012-07-10 Светлана Борисовна Зуева (RU) WASTE WATER TREATMENT METHOD
CN104549423A (en) * 2013-10-22 2015-04-29 中国石油化工股份有限公司 Metal modified Y zeolite and preparation method and application thereof
CN106187666A (en) * 2016-06-30 2016-12-07 中国海洋石油总公司 A kind of C10+the method that aromatics absorption separates

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