CN114917865A - Aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw material - Google Patents

Aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw material Download PDF

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Publication number
CN114917865A
CN114917865A CN202210620248.2A CN202210620248A CN114917865A CN 114917865 A CN114917865 A CN 114917865A CN 202210620248 A CN202210620248 A CN 202210620248A CN 114917865 A CN114917865 A CN 114917865A
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aromatic hydrocarbon
metal oxide
adsorbent
active
polyhydric alcohol
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CN114917865B (en
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李滨
武鲁明
李犇
陈自浩
赵训志
王银斌
张耀日
王相坤
王梦迪
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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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • 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
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/12—Recovery of used adsorbent
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention relates to an aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw materials. The aromatic hydrocarbon adsorbent comprises an active carrier, an active metal oxide and a binder, wherein the toluene vapor saturated adsorption capacity of the aromatic hydrocarbon adsorbent is more than 300mg/g, and the pore volume range is 0.2-0.6cm 3 (ii)/g; the preparation method comprises mixing active carrier, active metal oxide and binderMechanically mixing, granulating and molding the caking agent, and screening to obtain an adsorbent precursor with the particle size range of 0.3-2 mm; and (3) placing the adsorbent precursor into a high-pressure kettle for aromatic hydrocarbon solvent treatment at the temperature of 120-. The aromatic hydrocarbon adsorbent is applied to the production increase of ethylene cracking raw materials, and the purity of aromatic hydrocarbon components is more than 99%, the purity of non-aromatic hydrocarbon components is more than 99%, and the BMCI value is less than or equal to 12.

Description

Aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw material
Technical Field
The invention belongs to the technical field of materials, relates to an adsorbent, and particularly relates to an aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw materials.
Background
Petrochemical industry is an important pillar industry in national economy, provides a large amount of chemical raw materials for departments such as industry, agriculture, traffic, national defense and the like, and is one of industry departments with strong relevance and driving performance in national economy. Ethylene is one of the most important basic raw materials for modern petrochemical industry.
The ethylene cracking raw material in China goes through three stages of light diesel oil, naphtha and hydrogenation tail oil. And future world ethylene cracking feedstocks will substantially maintain the trend towards light feedstocks. The ethylene yield is directly influenced by the proportion of normal alkane and aromatic hydrocarbon in naphtha, and the ethylene yield can be improved by taking raffinate oil as an ethylene cracking raw material after the naphtha is subjected to aromatic extraction. After the naphtha is dearomatized and modified, the cracking olefin rate can be improved to a greater extent. However, in the process of cracking reaction, olefins are generated mainly by cracking normal paraffins, the thermal stability of aromatic rings is very strong, side chains are easy to break, benzene rings are difficult to open, and olefins are difficult to crack.
The currently common technologies comprise methods such as solvent extraction, crystallization separation, adsorption separation and the like.
The PTX deep cooling crystallization process which is industrialized is mainly common in European and American countries. The procedures of various cryogenic crystallization processes are largely the same and slightly different, and the essential difference lies in the difference of refrigerant and refrigeration mode and crystallizer type. However, the reliability of a plurality of large-scale devices in the cryogenic crystallization process is poor, the industrialization is difficult, and the cost of the operation and maintenance process is high, so the application is limited; the condensation point of partial alkane in naphtha is close to that of some aromatic hydrocarbon, so that the method not only reduces the purity of the aromatic hydrocarbon, but also increases the loss of ethylene cracking raw material.
The solvent extraction method developed by the company AUG, germany, and the Arosolvan process using N-methylpyrrolidone as a solvent and the Distapex process developed by the company IFP, france, and using dimethyl sulfoxide as a solvent are also being developed, but the application is limited due to complicated procedures and complicated operations.
The solvent extraction and crystallization separation method has the defects of complex operation, higher cost, low efficiency and the like, and the adsorption separation method is a method for improving the yield of ethylene in the cracking raw material based on a molecular concept.
A13-X molecular sieve is adopted on a continuous flow adsorption device by a Chinese petroleum university (east China) team, naphtha refined by Shenghua refinery is taken as a raw material, the adsorption condition of naphtha liquid phase adsorption dearomatization is optimized by an orthogonal experiment method, and the regeneration method of an adsorbent after inactivation is explored. The research finds that: the 13-X molecular sieve has relatively stable adsorption activity and excellent desulfurization and denitrification effects when used for naphtha liquid phase adsorption dearomatization. However, this adsorbent can adsorb only light aromatic hydrocarbons having a narrow carbon number range, and has industrial limitations.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an aromatic hydrocarbon adsorbent and application thereof in increasing the yield of ethylene cracking raw materials, wherein the toluene vapor saturated adsorption quantity of the aromatic hydrocarbon adsorbent is more than 300mg/g, and the pore volume range is 0.2-0.6cm 3 And/g, when the aromatic hydrocarbon adsorption separation method is used for adsorbing and separating aromatic hydrocarbon from naphtha to a diesel oil fraction section, the purity of the aromatic hydrocarbon component obtained by separation is more than 99 percent, the purity of the non-aromatic hydrocarbon component is more than 99 percent, and the BMCI value is less than or equal to 12.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
in a first aspect, the present invention provides an aromatic hydrocarbon adsorbent, which consists of 80 to 99 mass percent of an active carrier, 0.2 to 10 mass percent of an active metal oxide and 0.8 to 10 mass percent of a binder;
the aromatic hydrocarbon adsorbent has toluene vapor saturated adsorption amount greater than 300mg/g and pore volume in the range of 0.2-0.6cm 3 /g；
The active carrier is active silicon oxide and/or an active silicon-based molecular sieve;
the active metal oxide is at least one of magnesia, alumina, titania, zirconia, ceria, or lanthana, typical but non-limiting combinations include a combination of magnesia and alumina, titania and zirconia, ceria and lanthana, magnesia, alumina and titania, zirconia and ceria, zirconia, ceria and lanthana, or magnesia, alumina, titania, zirconia, ceria and lanthana;
the aromatic hydrocarbon adsorbent is prepared by the following preparation method:
(1) activation of carrier adsorption performance: preparing the porous material with pore volume range of 0.2-0.6cm by a sol-gel method 3 The preparation method comprises the following steps of (1) uniformly mixing silicon oxide and/or a silicon-based molecular sieve parent substance per gram with an ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12 hours, filtering, washing and drying to obtain an active carrier;
(2) activation of adsorption property of metal oxide: weakly reducing metal oxide in reducing gas atmosphere, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12h, filtering, washing, drying, and then crushing until the particle size D90 is less than or equal to 10 μm to obtain active metal oxide;
(3) granulating and molding: mechanically mixing, granulating and molding an active carrier, an active metal oxide and a binder, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) the adsorption capacity is improved: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at the temperature of 120-;
the step (1) and the step (2) are not in sequence.
The total mass fraction of the active carrier, the active metal oxide and the binder in the aromatic hydrocarbon adsorbent provided by the invention is 100%.
The mass fraction of active carrier based on the total mass of the aromatic hydrocarbon adsorbent is from 80 to 99%, and may be, for example, 80%, 85%, 90%, 95%, or 99%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
The mass fraction of the active metal oxide is 0.2 to 10% based on the total mass of the aromatic hydrocarbon adsorbent, and may be, for example, 0.2%, 1%, 3%, 5%, 6%, 8%, or 10%, but is not limited to the enumerated values, and other values not enumerated within the range of values are also applicable.
The mass fraction of the binder is 0.8 to 10% based on the total mass of the aromatic hydrocarbon adsorbent, and may be, for example, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
The pore volume range of the aromatic hydrocarbon adsorbent provided by the invention is 0.2-0.6cm 3 Per g, may be, for example, 0.2cm 3 /g、0.3cm 3 /g、 0.4cm 3 /g、0.5cm 3 In g or 0.6cm 3 In terms of/g, but not limited to the values recited, other values not recited in the range of values are equally applicable.
The aromatic hydrocarbon adsorbent provided by the invention has toluene vapor saturated adsorption capacity of more than 300mg/g and pore volume range of 0.2-0.6cm 3 /g。
In a second aspect, the present invention provides a method for producing the aromatic hydrocarbon adsorbent as described in the first aspect, the method comprising the steps of:
(1) activation of carrier adsorption performance: preparing the pore volume range of 0.2-0.6cm by a sol-gel method 3 A matrix of silica and/or silica-based molecular sieves per gram, and then oxidizingUniformly mixing the silicon and/or silicon-based molecular sieve matrix with an ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12h, filtering, washing and drying to obtain an activated carrier;
(2) activation of adsorption property of metal oxide: weakly reducing metal oxide in reducing gas atmosphere, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12h, filtering, washing, drying, and then crushing until the particle size D90 is less than or equal to 10 μm to obtain active metal oxide;
(3) granulating and molding: mechanically mixing an active carrier, an active metal oxide and a binder, granulating and molding, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic solvent treatment at the temperature of 120-200 ℃, wherein the aromatic solvent is at least one of toluene, o-xylene, p-xylene and m-xylene, and filtering, drying and roasting after the treatment is finished to obtain the aromatic adsorbent;
the step (1) and the step (2) are not in sequence.
The temperature of the treatment in step (1) is 80 to 150 ℃, and may be, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The treatment time in the step (1) is 2-12h, for example, 2h, 3h, 5h, 6h, 8h, 10h or 12h, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
The temperature of the weak reduction in the step (2) is 200-400 ℃, and may be, for example, 200 ℃, 210 ℃, 240 ℃, 250 ℃, 270 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 360 ℃ or 400 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
The temperature of the weak reduction in the step (2) is controlled to be 200-400 ℃, at this time, the metal oxide is not reduced into a metal simple substance, an oxygen vacancy is generated, the surface of the metal oxide is not coordinated and is unsaturated, and the metal oxide is easy to be activated by an ethanol solution of polyhydric alcohol.
The temperature of the treatment in step (2) is 80 to 150 ℃, and may be, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The treatment time of the step (2) is 2-12h, for example, 2h, 3h, 5h, 6h, 8h, 10h or 12h, but is not limited to the recited values, and other values in the range of values are also applicable.
The temperature of the treatment in step (4) is 120-.
The treatment time of the step (4) is 12-24h, for example, 12h, 15h, 16h, 18h, 20h, 21h or 24h, but is not limited to the recited values, and other values in the range of values are also applicable.
According to the preparation method provided by the invention, the metal oxide is subjected to weak reduction through reducing gas to generate oxygen vacancies, and active alcoholic hydroxyl groups are generated after the metal oxide is activated by alcohol. The silicon-based material generates active alcoholic hydroxyl through alcohol activation, the active alcoholic hydroxyl is compounded with metal oxide after the alcohol activation, mechanical mixing granulation molding is carried out under the action of a binder, an adsorbent precursor is obtained, and the aromatic adsorbent is obtained after the activation of an aromatic solvent.
The mass fraction of the ethanol solution of the polyol in the step (1) is 10 to 50%, for example, 10%, 20%, 30%, 40% or 50%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
The polyhydric alcohol in the ethanol solution of polyhydric alcohol of step (1) comprises at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol or trimethylolpropane, and typical but non-limiting combinations include combinations of ethylene glycol and 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, or ethylene glycol, 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
The mass fraction of the ethanol solution of the polyol in the step (2) is 10 to 50%, for example, 10%, 20%, 30%, 40% or 50%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
The polyhydric alcohol in the ethanol solution of polyhydric alcohol of step (2) comprises at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol or trimethylolpropane, and typical but non-limiting combinations include combinations of ethylene glycol and 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, or ethylene glycol, 2-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
The crushing method in the step (2) comprises at least one of ball milling, sand milling, air flow milling or colloid milling.
Preferably, the binder in step (3) is at least one of silica sol, aluminum sol or kaolin, and typical but non-limiting combinations include a combination of silica sol and aluminum sol, a combination of aluminum sol and kaolin, a combination of silica sol and kaolin, or a combination of silica sol, aluminum sol and kaolin.
Preferably, the aromatic hydrocarbon solvent of step (4) comprises at least one of toluene, ortho-xylene, para-xylene or meta-xylene, and typical but non-limiting combinations include a combination of toluene and ortho-xylene, a combination of ortho-xylene and para-xylene, a combination of para-xylene and meta-xylene, a combination of ortho-xylene, para-xylene and meta-xylene, or a combination of toluene, ortho-xylene, para-xylene and meta-xylene.
Preferably, the calcination temperature in step (4) is 500-600 ℃, and may be, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃ or 600 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the silica-based molecular sieve comprises at least one of MCM-41, MCM-48, SBA-15, KIT-6, type X or type Y, typical but non-limiting combinations include combinations of MCM-41 with MCM-48, SBA-15 with KIT-6, type X with type Y, MCM-41, MCM-48 with SBA-15, KIT-6, combinations of type X with type Y, or MCM-41, MCM-48, SBA-15, KIT-6, combinations of type X with type Y.
In a third aspect, the invention provides an application of an aromatic hydrocarbon adsorbent in increasing the yield of an ethylene cracking raw material, wherein a non-aromatic hydrocarbon component is used as the ethylene cracking raw material, and the aromatic hydrocarbon adsorbent is used in a simulated moving bed adsorption separation process to realize that the purity of the aromatic hydrocarbon component is more than 99%, the purity of the non-aromatic hydrocarbon component is more than 99%, and the BMCI value is less than or equal to 12.
Preferably, the adsorption temperature of the simulated moving bed adsorption separation process is 120-180 ℃, such as 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
The adsorption pressure is from 0.1 to 2.0MPa, and may be, for example, 0.1MPa, 0.3MPa, 0.5MPa, 0.8MPa, 1MPa, 1.2MPa, 1.5MPa, 1.8MPa or 2MPa, but is not limited to the values recited, and other values not recited within the numerical range are also applicable.
The aromatic hydrocarbon resolving agent of the simulated moving bed adsorption separation process is one or more of benzene, toluene, ethanol and methanol.
The desorption temperature of the simulated moving bed adsorption separation process is 100-150 ℃, and can be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the active carrier and the metal oxide are treated by adopting the ethanol solution of the polyhydric alcohol, so that the coupling of the active carrier and the metal oxide is facilitated, the pore volume of the aromatic hydrocarbon adsorbent is improved, and the aromatic hydrocarbon adsorption quantity of the aromatic hydrocarbon adsorbent is improved;
(2) the aromatic hydrocarbon solvent is adopted to treat the coupling product of the active carrier and the active metal oxide, so that the aromatic hydrocarbon adsorption capacity is improved, and the toluene vapor saturated adsorption capacity is more than 300 mg/g;
(3) the production process of the aromatic hydrocarbon adsorbent is green and environment-friendly, the organic solvent can be recycled, and no waste is discharged;
(4) the aromatic hydrocarbon adsorbent provided by the invention is applied to the production increase of ethylene cracking raw materials, and the purity of aromatic hydrocarbon components is more than 99%, the purity of non-aromatic hydrocarbon components is more than 99%, and the BMCI value is less than or equal to 12.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments.
Example 1
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 90% of active carrier, 5% of active metal oxide and 5% of binder by mass fraction;
the active carrier is an active silicon-based molecular sieve, the active metal oxide is active alumina, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of carrier adsorption performance: the pore volume range of 0.4cm is prepared by a sol-gel method 3 SBA-15 per gram, then evenly mixing the SBA-15 with an ethanol solution of polyhydric alcohol, heating to 120 ℃, treating for 8 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyhydric alcohol is 30%, and the polyhydric alcohol is ethylene glycol;
(2) activation of adsorption property of metal oxide: reducing alumina in hydrogen atmosphere at 350 ℃ for 2h, then uniformly mixing with ethanol solution of polyhydric alcohol, heating to 120 ℃ for processing for 8h, filtering, washing, drying, and then grinding and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active alumina; the mass fraction of the ethanol solution of the polyhydric alcohol is 30%, and the polyhydric alcohol is ethylene glycol;
(3) granulating and molding: mechanically mixing, granulating and molding the active carrier, the active magnesium oxide and the silica sol, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at 160 ℃ for 18h, wherein the aromatic hydrocarbon solvent is toluene, and filtering, drying and roasting at 550 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
example 2
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 85 mass percent of active carrier, 8 mass percent of active metal oxide and 7 mass percent of binder;
the active carrier is an active silicon-based molecular sieve, the active metal oxide is active zirconia, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of adsorption property of metal oxide: reducing zirconium oxide in hydrogen atmosphere at 300 ℃ for 2h, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 100 ℃ for treatment for 10h, filtering, washing, drying, and then ball-milling until the particle size D90 is less than or equal to 10 mu m to obtain active zirconium oxide; the mass fraction of the ethanol solution of the polyhydric alcohol is 20%, and the polyhydric alcohol is 2-propylene glycol;
(2) activation of carrier adsorption performance: the pore volume range of 0.3cm is prepared by a sol-gel method 3 MCM-48 of/g, then MCM-48 is evenly mixed with ethanol solution of polyhydric alcohol, the temperature is raised to 100 ℃ for treatment for 10 hours, and the activated carrier is obtained by filtration, washing and drying; the mass fraction of the ethanol solution of the polyhydric alcohol is 20%, and the polyhydric alcohol is 2-propylene glycol;
(3) and (3) granulation and forming: mechanically mixing, granulating and molding an active carrier, active zirconia and silica sol, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at the temperature of 140 ℃ for 20 hours, wherein the aromatic hydrocarbon solvent is o-xylene, and filtering, drying and roasting at the temperature of 520 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
example 3
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 95 mass percent of active carrier, 2 mass percent of active metal oxide and 3 mass percent of binder;
the active carrier is an active silicon-based molecular sieve, the active metal oxide is active titanium oxide, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of carrier adsorption performance: the pore volume range of 0.5cm is prepared by a sol-gel method 3 Then, uniformly mixing the MCM-41 with an ethanol solution of polyhydric alcohol, heating to 140 ℃, treating for 5 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyhydric alcohol is 40%, and the polyhydric alcohol is 1, 4-butanediol;
(2) activation of metal oxide adsorption performance: reducing titanium oxide in carbon monoxide atmosphere at 300 ℃ for 2h, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 140 ℃ for treatment for 5h, filtering, washing, drying, and then ball-milling and crushing until the particle size D90 is less than or equal to 10 mu m to obtain active titanium oxide; the mass fraction of the ethanol solution of the polyhydric alcohol is 40%, and the polyhydric alcohol is 1, 4-butanediol;
(3) and (3) granulation and forming: mechanically mixing, granulating and molding an active carrier, active titanium oxide and silica sol, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at 180 ℃ for 15h, wherein the aromatic hydrocarbon solvent is p-xylene, and filtering, drying and roasting at 580 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
example 4
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 80 mass percent of active carrier, 10 mass percent of active metal oxide and 10 mass percent of binder;
the active carrier is an active silicon-based molecular sieve, the active metal oxide is active zirconia, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of carrier adsorption performance: the pore volume range of 0.2cm is prepared by a sol-gel method 3 Per gram of KIT-6, then evenly mixing the KIT-6 with an ethanol solution of polyhydric alcohol, heating to 80 ℃, treating for 12 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyhydric alcohol is 10 percent, and the polyhydric alcohol is 1, 6-hexanediol;
(2) activation of metal oxide adsorption performance: reducing zirconia at 300 ℃ in a carbon monoxide atmosphere for 2h, uniformly mixing the zirconia with an ethanol solution of polyhydric alcohol, heating to 80 ℃, treating for 12h, filtering, washing, drying, and then performing ball milling and crushing until the particle size D90 is less than or equal to 10 mu m to obtain active zirconia; the mass fraction of the ethanol solution of the polyhydric alcohol is 10%, and the polyhydric alcohol is 1, 6-hexanediol;
(3) granulating and molding: mechanically mixing, granulating and molding the active carrier, the active zirconia and the kaolin, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing an adsorbent precursor in a high-pressure kettle, treating at 120 ℃ for 24 hours by using an aromatic hydrocarbon solvent which is m-xylene, filtering, drying and roasting at 500 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
example 5
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 99 mass percent of active carrier, 0.2 mass percent of active metal oxide and 0.8 mass percent of binder;
the active carrier is an active silicon-based molecular sieve, the active metal oxide is active magnesium oxide, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of carrier adsorption performance: the pore volume range of 0.6cm is prepared by a sol-gel method 3 Uniformly mixing the X-type silicon-based molecular sieve with an ethanol solution of polyhydric alcohol, heating to 150 ℃, treating for 2 hours, filtering, washing and drying to obtain an activated carrier; the above-mentionedThe mass fraction of the ethanol solution of the polyhydric alcohol is 50 percent, and the polyhydric alcohol is glycol;
(2) activation of adsorption property of metal oxide: reducing magnesium oxide in hydrogen atmosphere at 400 ℃ for 2h, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 150 ℃ for treatment for 2h, filtering, washing, drying, and then ball-milling until the particle size D90 is less than or equal to 10 μm to obtain active magnesium oxide; the mass fraction of the ethanol solution of the polyhydric alcohol is 50%, and the polyhydric alcohol is glycol;
(3) and (3) granulation and forming: mechanically mixing, granulating and molding an active carrier, active magnesium oxide and kaolin, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at 200 ℃ for 12h, wherein the aromatic hydrocarbon solvent is toluene, and filtering, drying and roasting at 600 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
comparative example 1
This comparative example provides an aromatic hydrocarbon adsorbent consisting of 90 mass% of a carrier, 5 mass% of an active metal oxide, and 5 mass% of a binder;
the active carrier is the pore volume range of 0.4cm in the step (1) of example 1 3 SBA-15,/g, the active metal oxide is active magnesium oxide, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) the pore volume range of 0.4cm is prepared by a sol-gel method 3 SBA-15 per gram;
(2) activation of adsorption property of metal oxide: reducing magnesium oxide in hydrogen atmosphere at 400 ℃ for 2h, uniformly mixing with ethanol solution of polyhydric alcohol, heating to 120 ℃ for treating for 8h, filtering, washing, drying, and then grinding to obtain active magnesium oxide with the particle size D90 being less than or equal to 10 mu m; the mass fraction of the ethanol solution of the polyhydric alcohol is 30%, and the polyhydric alcohol is ethylene glycol;
(3) and (3) granulation and forming: mechanically mixing SBA-15, active magnesium oxide and silica sol, granulating and molding, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing an adsorbent precursor in a high-pressure kettle, treating at 160 ℃ for 18h by using an aromatic hydrocarbon solvent which is toluene, filtering, drying and roasting at 550 ℃ after the treatment is finished, so as to obtain the aromatic hydrocarbon adsorbent;
comparative example 2
The present comparative example provides an aromatic hydrocarbon adsorbent composed of 90 mass% of an active carrier, 5 mass% of a metal oxide and 5 mass% of a binder;
the active carrier is an active silicon-based molecular sieve, the metal oxide is magnesium oxide, and the binder is silica sol;
the preparation method of the aromatic hydrocarbon adsorbent comprises the following steps:
(1) activation of carrier adsorption performance: the pore volume range of 0.4cm is prepared by a sol-gel method 3 SBA-15 per gram, then evenly mixing the SBA-15 with an ethanol solution of polyhydric alcohol, heating to 120 ℃, treating for 8 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyhydric alcohol is 30 percent, and the polyhydric alcohol is glycol;
(2) the same magnesium oxide as in example 1 is provided;
(3) and (3) granulation and forming: mechanically mixing, granulating and molding the active carrier, the magnesium oxide and the silica sol, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing an adsorbent precursor in a high-pressure kettle, treating at 160 ℃ for 18h by using an aromatic hydrocarbon solvent which is toluene, filtering, drying and roasting at 550 ℃ after the treatment is finished, so as to obtain the aromatic hydrocarbon adsorbent;
comparative example 3
This comparative example provides an aromatic hydrocarbon adsorbent, which was the same as in example 1 except that the ethanol solution of the polyhydric alcohol in step (1) was replaced with an equal volume of anhydrous ethanol.
Comparative example 4
This comparative example provides an aromatic hydrocarbon adsorbent, which was the same as in example 1 except that the ethanol solution of the polyhydric alcohol in step (1) was replaced with an equal volume of ethylene glycol.
Comparative example 5
This comparative example provides an aromatic hydrocarbon adsorbent, which was the same as in example 1 except that the ethanol solution of a polyhydric alcohol in step (2) was replaced with an equal volume of anhydrous ethanol.
Comparative example 6
This comparative example provides an aromatic hydrocarbon adsorbent, which was the same as in example 1 except that the ethanol solution of the polyhydric alcohol in step (1) was replaced with an equal volume of ethylene glycol.
Performance testing
The aromatic hydrocarbon adsorbents provided in examples 1 to 5 and comparative examples 1 to 6 were subjected to performance tests,
a fixed bed pulse adsorption column is adopted, 100mL of adsorbent is filled, simulated oil is ethylene cracking raw oil, the analysis of raw material composition is shown in Table 1, the pulse sample injection amount is 7mL, the adsorption column is wetted by cyclohexane, cyclohexane is introduced at a constant pump speed of 1.2mL/min, the temperature of the adsorption column is kept at about 150 ℃, the pressure of the adsorption column is 0.1-2.0MPa, after the adsorption column is fully wetted, a six-way valve is switched to introduce simulated diesel pulses into the adsorption column, samples are collected every 5 minutes, the aromatic hydrocarbon content is detected, the samples collected at the stage are marked as clean diesel components from the beginning of introducing ethylene cracking raw oil to the detection of a large amount of aromatic hydrocarbons as an adsorption section, the samples collected at the stage are aromatic hydrocarbon components, and the aromatic hydrocarbon content is analyzed and calculated. The sorbent evaluation is shown in table 2.
TABLE 1 ethylene cracking feed oil composition
Aromatic content, wt.% Non-aromatic content, wt.%
34.3 65.7
Table 2 evaluation of the effects of the different adsorbents
Pore volume, cm, of adsorbent 3 /g Toluene adsorption amount of adsorbent, mg/g The removal rate of aromatic hydrocarbons,%
Example 1 0.48 360 99.4
Example 2 0.51 374 99.6
Example 3 0.55 391 99.8
Example 4 0.47 332 99.2
Example 5 0.45 327 99.0
Comparative example 1 0.36 268 89.6
Comparative example 2 0.39 284 91.5
Comparative example 3 0.38 296 94.3
Comparative example 4 0.41 307 96.3
Comparative example 5 0.39 298 95.1
Comparative example 6 0.40 301 93.6
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The aromatic hydrocarbon adsorbent is characterized by comprising 80-99% of active carrier, 0.2-10% of active metal oxide and 0.8-10% of binder by mass;
the aromatic hydrocarbon adsorbent has toluene vapor saturated adsorption amount greater than 300mg/g and pore volume in the range of 0.2-0.6cm 3 /g；
The active carrier is active silicon oxide and/or an active silicon-based molecular sieve;
the active metal oxide is at least one of magnesium oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide or lanthanum oxide;
the aromatic hydrocarbon adsorbent is prepared by the following preparation method:
(1) activation of carrier adsorption performance: preparing the pore volume range of 0.2-0.6cm by a sol-gel method 3 The preparation method comprises the following steps of (1) uniformly mixing silicon oxide and/or a silicon-based molecular sieve parent substance per gram with an ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12 hours, filtering, washing and drying to obtain an active carrier;
(2) activation of adsorption property of metal oxide: weakly reducing the metal oxide in the atmosphere of reducing gas, uniformly mixing the metal oxide with an ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12h, filtering, washing, drying, and then crushing until the granularity D90 is less than or equal to 10 mu m to obtain an active metal oxide;
(3) granulating and molding: mechanically mixing an active carrier, an active metal oxide and a binder, granulating and molding, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) the adsorption capacity is improved: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at the temperature of 120-;
the step (1) and the step (2) are not in sequence.
2. A method for producing the aromatic hydrocarbon adsorbent according to claim 1, comprising the steps of:
(1) activation of carrier adsorption performance: preparing the pore volume range of 0.2-0.6cm by a sol-gel method 3 The matrix per gram is uniformly mixed with the ethanol solution of the polyhydric alcohol, the mixture is heated to 80-150 ℃ for treatment for 2-12h, and the activated carrier is obtained after filtration, washing and drying;
(2) activation of metal oxide adsorption performance: weakly reducing the metal oxide in the atmosphere of reducing gas, uniformly mixing the metal oxide with an ethanol solution of polyhydric alcohol, heating to 80-150 ℃, treating for 2-12h, filtering, washing, drying, and then crushing until the granularity D90 is less than or equal to 10 mu m to obtain an active metal oxide;
(3) and (3) granulation and forming: mechanically mixing, granulating and molding an active carrier, an active metal oxide and a binder, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) controlling the adsorption quantity: placing the adsorbent precursor in a high-pressure kettle for aromatic hydrocarbon solvent treatment at the temperature of 120-; the aromatic hydrocarbon solvent is at least one of toluene, o-xylene, p-xylene and m-xylene;
the step (1) and the step (2) are not in sequence.
3. The method according to claim 2, wherein the mass fraction of the ethanol solution of the polyhydric alcohol in the step (1) is 10 to 50%, and the polyhydric alcohol comprises at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol, and trimethylolpropane.
4. The method according to claim 2, wherein the mass fraction of the ethanol solution of the polyhydric alcohol of step (2) is 10 to 50%, and the polyhydric alcohol comprises at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol, or trimethylolpropane;
the crushing method in the step (2) comprises at least one of ball milling, sand milling, air flow milling or colloid milling.
5. The method of claim 2, wherein the binder of step (3) comprises at least one of silica sol, aluminum sol, or kaolin.
6. The method as claimed in claim 2, wherein the temperature of the calcination in the step (4) is 500-600 ℃.
7. The method of claim 2, wherein the silica-based molecular sieve comprises at least one of MCM-41, MCM-48, SBA-15, KIT-6, type X, or type Y.
8. The application of the aromatic hydrocarbon adsorbent in increasing the yield of the ethylene cracking raw material according to claim 1, wherein the non-aromatic hydrocarbon component is used as the ethylene cracking raw material, and the aromatic hydrocarbon adsorbent is used in a simulated moving bed adsorption separation process to realize the purity of the aromatic hydrocarbon component of more than 99 percent, the purity of the non-aromatic hydrocarbon component of more than 99 percent and the BMCI value of less than or equal to 12.
9. The use as claimed in claim 8, wherein the simulated moving bed adsorption separation process has an adsorption temperature of 120-180 ℃ and an adsorption pressure of 0.1-2.0 MPa.
10. The application of the simulated moving bed adsorption separation process as claimed in claim 8, wherein the aromatic hydrocarbon resolving agent of the simulated moving bed adsorption separation process is one or more of benzene, toluene, ethanol and methanol; the desorption temperature of the simulated moving bed adsorption separation process is 100-150 ℃.
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