CN114917865B - Aromatic hydrocarbon adsorbent and application thereof in yield-increasing ethylene cracking raw material - Google Patents

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

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CN114917865B
CN114917865B CN202210620248.2A CN202210620248A CN114917865B CN 114917865 B CN114917865 B CN 114917865B CN 202210620248 A CN202210620248 A CN 202210620248A CN 114917865 B CN114917865 B CN 114917865B
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aromatic hydrocarbon
adsorbent
metal oxide
active
polyol
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CN114917865A (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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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 saturated adsorption capacity of toluene vapor of the aromatic hydrocarbon adsorbent is more than 300mg/g, and the pore volume range is 0.2-0.6cm 3 /g; the preparation method comprises mechanically mixing active carrier, active metal oxide and binder, granulating, and sieving to obtain adsorbent precursor with particle diameter of 0.3-2 mm; and (3) placing the adsorbent precursor into an autoclave for aromatic hydrocarbon solvent treatment, treating at 120-200 ℃ for 12-24 hours, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent. The aromatic hydrocarbon adsorbent is applied to increasing yield of ethylene cracking raw materials, and realizes that 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 yield-increasing ethylene cracking raw material
Technical Field
The invention belongs to the technical field of materials, and relates to an adsorbent, in particular to an aromatic hydrocarbon adsorbent and application thereof in yield-increasing ethylene cracking raw materials.
Background
Petrochemical industry is an important pillar industry in national economy, provides a large amount of industrial raw materials for departments such as industry, agriculture, traffic, national defense and the like, and is one of industrial departments with strong association and drivability in national economy. Ethylene is one of the most important basic raw materials for modern petrochemical industry.
The ethylene cracking raw material in China undergoes three stages of light diesel oil, naphtha and hydrogenated tail oil. And future world ethylene cracking feedstocks will substantially maintain a trend toward light weight feedstocks. The ratio of normal alkane to aromatic hydrocarbon in the naphtha directly influences the ethylene yield, and the raffinate oil can be used as an ethylene cracking raw material after aromatic hydrocarbon extraction of the naphtha, so that the ethylene yield can be improved. After the naphtha is dearomatized and modified, the cracking olefin rate is improved to a greater extent. However, in the process of the cracking reaction, the normal alkane is mainly cracked to generate olefin, the aromatic ring has strong thermal stability, the side chain is easy to break, the benzene ring is difficult to open, and the olefin is difficult to crack.
The techniques commonly used at present comprise solvent extraction, crystallization separation, adsorption separation and other methods.
The industrialized PTX deep-cooling crystallization process is mainly common in European and American countries. The flow of the various cryogenic crystallization processes are different in size, and the essential difference is the difference between the refrigerant and the refrigeration mode and the type of the crystallizer. However, many large-scale equipment in the deep cooling crystallization process have poor reliability, difficult industrialization and high cost in the operation and maintenance process, so the application is limited; the condensation point of partial alkane in the naphtha is close to that of some aromatic hydrocarbon, and the method not only reduces the purity of the aromatic hydrocarbon, but also increases the loss of ethylene cracking raw materials.
The solvent extraction method is developed by the German AUG company, the Arosolvan process using N-methylpyrrolidone as a solvent and the Distapex process using dimethyl sulfoxide as a solvent, which are developed by the French IFP company, are also continuously developed, but the application is limited due to complicated flow, complicated operation and the like.
The solvent extraction and crystallization separation method has the defects of complicated 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.
The 13-X molecular sieve is adopted on a continuous flowing adsorption device by China petroleum university (Huadong) team, naphtha is refined from Shenghua refinery as raw material, the adsorption condition of naphtha liquid phase adsorption dearomatization is optimized by an orthogonal experiment method, and a regeneration method after the deactivation of the adsorbent is explored. The research finds that: the 13-X molecular sieve has relatively stable adsorption activity and excellent desulfurization and denitrification effects when being used for naphtha liquid phase adsorption dearomatization. However, the adsorbent can only adsorb light aromatic hydrocarbons with a narrow carbon number range distribution, and has industrial limitations.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an aromatic hydrocarbon adsorbent and application thereof in increasing yield of ethylene cracking raw materials, wherein the saturated adsorption capacity of toluene vapor 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 catalyst is used for adsorption separation of aromatic hydrocarbon in naphtha-diesel fraction, the purity of the separated aromatic hydrocarbon component is more than 99%, the purity of non-aromatic hydrocarbon component is more than 99%, and the BMCI value is less than or equal to 12.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an aromatic hydrocarbon adsorbent comprising 80-99% by mass of an active carrier, 0.2-10% by mass of an active metal oxide, and 0.8-10% by mass of a binder;
the saturated adsorption capacity of toluene vapor of the aromatic hydrocarbon adsorbent is more than 300mg/g, and the pore volume range is 0.2-0.6cm 3 /g；
The active carrier is active silicon oxide and/or active silicon-based molecular sieve;
the active metal oxide is at least one of magnesia, alumina, titania, zirconia, ceria or lanthana, and typical but non-limiting combinations include magnesia and alumina combinations, titania and zirconia combinations, ceria and lanthana combinations, magnesia, alumina and titania combinations, titania, zirconia and ceria combinations, zirconia, ceria and lanthana combinations, or magnesia, alumina, titania, zirconia, ceria and lanthana combinations;
the aromatic hydrocarbon adsorbent is prepared by the following preparation method:
(1) Activation of the adsorption performance of the carrier: the pore volume is 0.2-0.6cm by sol-gel method 3 And (2) uniformly mixing the silicon oxide and/or silicon-based molecular sieve matrix with an ethanol solution of polyalcohol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying to obtain an active carrier;
(2) Metal oxide adsorption performance activation: weakly reducing metal oxide in a reducing gas atmosphere, uniformly mixing the metal oxide with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying, and then crushing to a granularity D90 of less than or equal to 10 mu m to obtain active metal oxide;
(3) Granulating and forming: mechanically mixing an active carrier, an active metal oxide and a binder, granulating and forming, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) And (3) improving the adsorption quantity: placing the adsorbent precursor in an autoclave for aromatic hydrocarbon solvent treatment at 120-200 ℃ for 12-24 hours, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
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 the active carrier is 80-99% by total mass of the aromatic hydrocarbon adsorbent, and may be, for example, 80%, 85%, 90%, 95% or 99%, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The mass fraction of active metal oxide is 0.2-10%, for example 0.2%, 1%, 3%, 5%, 6%, 8% or 10% based on the total mass of the aromatic hydrocarbon adsorbent, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
The binder may be present in an amount of 0.8 to 10% by mass, based on the total mass of the aromatic hydrocarbon adsorbent, for example, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The pore volume of the aromatic hydrocarbon adsorbent provided by the invention is in the range of 0.2-0.6cm 3 Per g, for example, may be 0.2cm 3 /g、0.3cm 3 /g、0.4cm 3 /g、0.5cm 3 /g or 0.6cm 3 The values of/g are not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The aromatic hydrocarbon adsorbent provided by the invention has the saturated adsorption capacity of toluene vapor of more than 300mg/g and the pore volume range of 0.2-0.6cm 3 /g。
In a second aspect, the present invention provides a process for the preparation of an aromatic adsorbent according to the first aspect, the process comprising the steps of:
(1) Activation of the adsorption performance of the carrier: the pore volume is 0.2-0.6cm by sol-gel method 3 Uniformly mixing/g of silicon oxide and/or silicon-based molecular sieve matrix and ethanol solution of polyalcohol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying to obtain an activated carrier;
(2) Metal oxide adsorption performance activation: weakly reducing metal oxide in a reducing gas atmosphere, uniformly mixing the metal oxide with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying, and then crushing to a granularity D90 of less than or equal to 10 mu m to obtain active metal oxide;
(3) Granulating and forming: mechanically mixing an active carrier, an active metal oxide and a binder, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 120-200 ℃, wherein the aromatic hydrocarbon 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 hydrocarbon adsorbent;
the step (1) and the step (2) are not in sequence.
The temperature of the treatment in the 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 values recited, and other values not recited in the numerical range are equally applicable.
The treatment in step (1) is carried out for a period of time ranging from 2 to 12 hours, for example, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, 10 hours or 12 hours, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The temperature of the weak reduction in the step (2) is 200 to 400 ℃, and may be, for example, 200 ℃, 210 ℃, 240 ℃, 250 ℃, 270 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 360 ℃, or 400 ℃, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Controlling the weak reduction temperature in the step (2) to be 200-400 ℃, wherein the metal oxide is not reduced into a metal simple substance at the moment, oxygen vacancies are generated, and the surface coordination of the metal oxide is unsaturated and is easy to be activated by ethanol solution of polyalcohol.
The temperature of the treatment in the 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 values recited, and other values not recited in the numerical range are equally applicable.
The treatment in step (2) is performed for a period of time ranging from 2 to 12 hours, and may be, for example, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, 10 hours or 12 hours, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The temperature of the treatment in the step (4) is 120 to 200 ℃, and may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, or 200 ℃, for example, but the treatment is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
The treatment in step (4) is performed for 12-24 hours, for example, 12 hours, 15 hours, 16 hours, 18 hours, 20 hours, 21 hours or 24 hours, but the treatment is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
According to the preparation method provided by the invention, the metal oxide is subjected to weak reduction by the reducing gas to generate oxygen vacancies, and the active alcohol hydroxyl is generated after alcohol activation. The silicon-based material is subjected to alcohol activation to generate active alcohol hydroxyl, so that the active alcohol hydroxyl is compounded with the metal oxide after the alcohol activation, and the metal oxide is mechanically mixed, granulated and molded under the action of a binder to obtain an adsorbent precursor, and the adsorbent precursor is activated by an aromatic hydrocarbon solvent to obtain the aromatic hydrocarbon adsorbent.
The mass fraction of the ethanol solution of the polyol described in step (1) is 10-50%, for example 10%, 20%, 30%, 40% or 50%, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The polyol in the alcoholic solution of the polyol 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-propanediol, 1, 4-butanediol and 1, 6-hexanediol, combinations of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, or combinations of ethylene glycol, 2-propanediol, 1, 4-butanediol and 1, 6-hexanediol.
The mass fraction of the ethanol solution of the polyol in step (2) is 10-50%, for example 10%, 20%, 30%, 40% or 50%, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The polyol in the alcoholic solution of the polyol 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-propanediol, 1, 4-butanediol and 1, 6-hexanediol, combinations of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol, or combinations of ethylene glycol, 2-propanediol, 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 of step (3) is at least one of silica sol, alumina sol or kaolin, and typical but non-limiting combinations include a combination of silica sol and alumina sol, a combination of alumina sol and kaolin, a combination of silica sol and kaolin, or a combination of silica sol, alumina 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 combinations of toluene and ortho-xylene, combinations of ortho-xylene and para-xylene, combinations of para-xylene and meta-xylene, combinations of ortho-xylene, para-xylene and meta-xylene, or combinations of toluene, ortho-xylene, para-xylene and meta-xylene.
Preferably, the baking temperature in the step (4) is 500 to 600 ℃, and may be 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, or 600 ℃, for example, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the silicon-based molecular sieve comprises at least one of MCM-41, MCM-48, SBA-15, KIT-6, X-type or Y-type, and typical but non-limiting combinations include combinations of MCM-41 and MCM-48, combinations of SBA-15 and KIT-6, combinations of X-type and Y-type, combinations of MCM-41, MCM-48 and SBA-15, KIT-6, combinations of X-type and Y-type, or combinations of MCM-41, MCM-48, SBA-15, KIT-6, X-type and Y-type.
In a third aspect, the invention provides an application of an aromatic hydrocarbon adsorbent in increasing yield of ethylene cracking raw materials, 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, so 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 ℃, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, but the adsorption temperature is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The adsorption pressure is 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 in the numerical range are equally 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 to 150 ℃, and may be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
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 polyalcohol, so that the coupling of the active carrier and the metal oxide is facilitated, the pore volume of the aromatic adsorbent is increased, and the aromatic adsorption capacity of the aromatic adsorbent is increased;
(2) According to the invention, the coupling product of the active carrier and the active metal oxide is treated by adopting an aromatic hydrocarbon solvent, so that the aromatic hydrocarbon adsorption capacity is improved, and the saturated adsorption capacity of toluene vapor is more than 300mg/g;
(3) The aromatic adsorbent provided by the discovery is green and environment-friendly in the production process, and the organic solvent can be recycled without waste emission;
(4) The aromatic hydrocarbon adsorbent provided by the invention is applied to the ethylene cracking raw material for increasing yield, and realizes that 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 scheme of the invention is further described by the following 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 the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.4cm 3 SBA-15 of/g, then uniformly mixing SBA-15 with ethanol solution of polyalcohol, heating to 120 ℃ for 8 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is 30 percent, and the polyol is glycol;
(2) Metal oxide adsorption performance activation: reducing aluminum oxide in a hydrogen atmosphere at 350 ℃ for 2 hours, uniformly mixing the aluminum oxide with an ethanol solution of polyol, heating to 120 ℃ for 8 hours, filtering, washing, drying, and then grinding and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active aluminum oxide; the mass fraction of the ethanol solution of the polyol is 30 percent, and the polyol is glycol;
(3) Granulating and forming: mechanically mixing an active carrier, active magnesium oxide and silica sol, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 160 ℃ for 18 hours, wherein the aromatic hydrocarbon solvent is toluene, filtering, drying and roasting at 550 ℃ after the treatment is finished, so as to obtain the aromatic hydrocarbon adsorbent;
example 2
The embodiment provides an aromatic hydrocarbon adsorbent, which consists of 85% of active carrier, 8% of active metal oxide and 7% of binder by mass fraction;
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) Metal oxide adsorption performance activation: reducing zirconium oxide in hydrogen atmosphere at 300 ℃ for 2 hours, uniformly mixing the zirconium oxide with ethanol solution of polyalcohol, heating to 100 ℃ for 10 hours, filtering, washing, drying, and then ball-milling and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active zirconium oxide; the mass fraction of the ethanol solution of the polyol is 20%, and the polyol is 2-propylene glycol;
(2) Activation of the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.3cm 3 Uniformly mixing MCM-48 with an ethanol solution of polyalcohol, heating to 100 ℃ for 10 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is 20%, and the polyol is 2-propylene glycol;
(3) Granulating and forming: mechanically mixing an active carrier, active zirconia and silica sol, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 140 ℃ for 20 hours, wherein the aromatic hydrocarbon solvent is o-xylene, filtering, drying and roasting at 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% of active carrier, 2% of active metal oxide and 3% of binder by mass fraction;
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 the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.5cm 3 Uniformly mixing MCM-41 with an ethanol solution of polyalcohol, heating to 140 ℃ for 5 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is as follows40% of a polyol which is 1, 4-butanediol;
(2) Metal oxide adsorption performance activation: reducing titanium oxide in carbon monoxide atmosphere at 300 ℃ for 2 hours, uniformly mixing the titanium oxide with ethanol solution of polyalcohol, heating to 140 ℃ for 5 hours, filtering, washing, drying, and then ball-milling and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active titanium oxide; the mass fraction of the ethanol solution of the polyol is 40%, and the polyol is 1, 4-butanediol;
(3) Granulating and forming: mechanically mixing an active carrier, active titanium oxide and silica sol, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 180 ℃ for 15 hours, wherein the aromatic hydrocarbon solvent is paraxylene, 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% of active carrier, 10% of active metal oxide and 10% of binder by mass fraction;
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 the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.2cm 3 Uniformly mixing/g of KIT-6 with an ethanol solution of polyol, heating to 80 ℃ for 12 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is 10%, and the polyol is 1, 6-hexanediol;
(2) Metal oxide adsorption performance activation: reducing zirconium oxide in carbon monoxide atmosphere at 300 ℃ for 2 hours, uniformly mixing the zirconium oxide with ethanol solution of polyalcohol, heating to 80 ℃ for 12 hours, filtering, washing, drying, and then ball-milling and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active zirconium oxide; the mass fraction of the ethanol solution of the polyol is 10%, and the polyol is 1, 6-hexanediol;
(3) Granulating and forming: mechanically mixing an active carrier, active zirconia and kaolin, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 120 ℃ for 24 hours, wherein the aromatic hydrocarbon solvent 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% of active carrier, 0.2% of active metal oxide and 0.8% of binder by mass fraction;
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 the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.6cm 3 Uniformly mixing the X-type silicon-based molecular sieve with an ethanol solution of polyalcohol, heating to 150 ℃ for 2 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is 50%, and the polyol is glycol;
(2) Metal oxide adsorption performance activation: reducing magnesium oxide in hydrogen atmosphere at 400 ℃ for 2 hours, uniformly mixing the magnesium oxide with ethanol solution of polyalcohol, heating to 150 ℃ for 2 hours, filtering, washing, drying, and then ball-milling and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active magnesium oxide; the mass fraction of the ethanol solution of the polyol is 50%, and the polyol is glycol;
(3) Granulating and forming: mechanically mixing an active carrier, active magnesium oxide and kaolin, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 200 ℃ for 12 hours, wherein the aromatic hydrocarbon solvent is toluene, filtering, drying and roasting at 600 ℃ after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
comparative example 1
The present comparative example provides an aromatic hydrocarbon adsorbent consisting of 90% by mass of a support, 5% by mass of an active metal oxide, and 5% by mass of a binder;
the active carrier is the porous volume range of 0.4cm in the step (1) of the embodiment 1 3 SBA-15 of/g, wherein 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 prepared by a sol-gel method is 0.4cm 3 SBA-15 in/g;
(2) Metal oxide adsorption performance activation: reducing magnesium oxide in hydrogen atmosphere at 400 ℃ for 2 hours, uniformly mixing the magnesium oxide with ethanol solution of polyalcohol, heating to 120 ℃ for 8 hours, filtering, washing, drying, and then grinding and crushing until the granularity D90 is less than or equal to 10 mu m to obtain active magnesium oxide; the mass fraction of the ethanol solution of the polyol is 30 percent, and the polyol is glycol;
(3) Granulating 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 the adsorbent precursor in an autoclave for aromatic hydrocarbon solvent treatment at 160 ℃ for 18 hours, wherein the aromatic hydrocarbon solvent 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 consisting of 90% by mass of an active carrier, 5% by mass of a metal oxide, and 5% by 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 the adsorption performance of the carrier: the pore volume range prepared by a sol-gel method is 0.4cm 3 SBA-15 of/g, then uniformly mixing SBA-15 with ethanol solution of polyalcohol, heating to 120 ℃ for 8 hours, filtering, washing and drying to obtain an activated carrier; the mass fraction of the ethanol solution of the polyol is 30 percent, and the polyol is glycol;
(2) Providing the same magnesium oxide as in example 1;
(3) Granulating and forming: mechanically mixing an active carrier, magnesium oxide and silica sol, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 160 ℃ for 18 hours, wherein the aromatic hydrocarbon solvent 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 is the same as in example 1 except that the ethanol solution of the polyol in step (1) is replaced with an equal volume of absolute ethanol.
Comparative example 4
This comparative example provides an aromatic hydrocarbon adsorbent which is the same as example 1 except that the ethanol solution of the polyol in step (1) is replaced with an equal volume of ethylene glycol.
Comparative example 5
This comparative example provides an aromatic hydrocarbon adsorbent which is the same as in example 1 except that the ethanol solution of the polyol in step (2) is replaced with an equal volume of absolute ethanol.
Comparative example 6
This comparative example provides an aromatic hydrocarbon adsorbent which is the same as example 1 except that the ethanol solution of the polyol in step (1) is replaced with an equal volume of ethylene glycol.
Performance testing
Performance tests were performed on the aromatic hydrocarbon adsorbents provided in examples 1 to 5 and comparative examples 1 to 6,
a fixed bed pulse adsorption column is adopted, 100mL of adsorbent is filled, simulated oil is ethylene pyrolysis raw oil, the raw material composition analysis is shown in the attached table 1, the pulse sample feeding amount is 7mL, the adsorption column is wetted by cyclohexane, cyclohexane is fed in 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 completely wetted, a six-way valve is switched to pulse simulated diesel oil into the adsorption column, samples are collected every 5 minutes, the aromatic hydrocarbon content is detected, the samples collected at the stage from the beginning of feeding ethylene pyrolysis raw oil to the detection of a large amount of aromatic hydrocarbon are taken as adsorption sections, the samples collected at the stage are recorded as clean diesel oil components, the aromatic hydrocarbon content is gradually reduced to 0 from the detection of a large amount of aromatic hydrocarbon to be taken as desorption section, the samples collected at the stage are taken as aromatic hydrocarbon components, and the aromatic hydrocarbon content is analyzed and calculated. The adsorbent evaluation is shown in Table 2.
TABLE 1 ethylene pyrolysis feedstock composition
Aromatic hydrocarbon content, wt% Non-aromatic content, wt%
34.3 65.7
TABLE 2 evaluation effects of different adsorbents
Adsorbent pore volume, cm 3 /g Toluene adsorption capacity of adsorbent, mg/g Aromatic hydrocarbon removal rate, percent
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
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims (9)

1. An 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 fraction;
the saturated adsorption capacity of toluene vapor of the aromatic hydrocarbon adsorbent is more than 300mg/g, and the pore volume range is 0.2-0.6cm 3 /g；
The active carrier is 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 the adsorption performance of the carrier: the pore volume is 0.2-0.6cm by sol-gel method 3 Uniformly mixing the silicon-based molecular sieve with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying to obtain an active silicon-based molecular sieve; the silicon-based molecular sieve comprises at least one of MCM-41, MCM-48, SBA-15, KIT-6, X type or Y type; the mass fraction of the ethanol solution of the polyol is 10-50%;
(2) Metal oxide adsorption performance activation: weakly reducing metal oxide in a reducing gas atmosphere, uniformly mixing the metal oxide with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing, drying, and crushing to a granularity D90 of less than or equal to 10 mu m to obtain active metal oxide; the temperature of the weak reduction is 200-400 ℃; the mass fraction of the ethanol solution of the polyol is 10-50%;
(3) Granulating and forming: mechanically mixing an active silicon-based molecular sieve, an active metal oxide and a binder, granulating and forming, and screening particles with the particle size range of 0.3-2mm to obtain an adsorbent precursor;
(4) And (3) improving the adsorption quantity: placing the adsorbent precursor in an autoclave for aromatic hydrocarbon solvent treatment at 120-200 ℃ for 12-24 hours, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent;
the step (1) and the step (2) are not in sequence.
2. A process for the preparation of the aromatic hydrocarbon adsorbent of claim 1, comprising the steps of:
(1) Activation of the adsorption performance of the carrier: the pore volume is 0.2-0.6cm by sol-gel method 3 Silicon per gramThe method comprises the steps of (1) uniformly mixing a silicon-based molecular sieve with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing and drying to obtain an active silicon-based molecular sieve; the silicon-based molecular sieve matrix comprises at least one of MCM-41, MCM-48, SBA-15, KIT-6, X type or Y type; the mass fraction of the ethanol solution of the polyol is 10-50%;
(2) Metal oxide adsorption performance activation: weakly reducing metal oxide in a reducing gas atmosphere, uniformly mixing the metal oxide with an ethanol solution of polyol, heating to 80-150 ℃ for 2-12h, filtering, washing, drying, and crushing to a granularity D90 of less than or equal to 10 mu m to obtain active metal oxide; the temperature of the weak reduction is 200-400 ℃; the mass fraction of the ethanol solution of the polyol is 10-50%;
(3) Granulating and forming: mechanically mixing an active silicon-based molecular sieve, an active metal oxide and a binder, granulating and forming, 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 an autoclave for aromatic hydrocarbon solvent treatment at 120-200 ℃ for 12-24 hours, and filtering, drying and roasting after the treatment is finished to obtain the aromatic hydrocarbon adsorbent; 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 of claim 2, wherein the polyol of step (1) comprises at least one of ethylene glycol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, glycerol, or trimethylolpropane.
4. The method of claim 2, wherein the polyol of step (2) 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 a silica sol, an alumina sol, or kaolin.
6. The method of claim 2, wherein the firing in step (4) is at a temperature of 500-600 ℃.
7. The application of the aromatic hydrocarbon adsorbent in increasing yield of ethylene cracking raw materials, which is characterized in that the aromatic hydrocarbon adsorbent is used for a simulated moving bed adsorption separation process to treat ethylene cracking raw material oil, so that the purity of aromatic hydrocarbon components is more than 99%, the purity of non-aromatic hydrocarbon components is more than 99%, the BMCI value is less than or equal to 12, and the non-aromatic hydrocarbon components are used as ethylene cracking raw materials.
8. The use according to claim 7, wherein the adsorption temperature of the simulated moving bed adsorption separation process is 120-180 ℃ and the adsorption pressure is 0.1-2.0MPa.
9. The use according to claim 7, wherein the aromatic desorbent of the simulated moving bed adsorptive separation process is one or more of benzene, toluene, ethanol, methanol; the desorption temperature of the simulated moving bed adsorption separation process is 100-150 ℃.
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