CN112007606A - Reversible enrichment material for aromatic hydrocarbon component in hydrocarbon fuel and preparation method thereof - Google Patents

Reversible enrichment material for aromatic hydrocarbon component in hydrocarbon fuel and preparation method thereof Download PDF

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Publication number
CN112007606A
CN112007606A CN201910472985.0A CN201910472985A CN112007606A CN 112007606 A CN112007606 A CN 112007606A CN 201910472985 A CN201910472985 A CN 201910472985A CN 112007606 A CN112007606 A CN 112007606A
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metal salt
mass
enrichment material
reversible
soluble
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CN201910472985.0A
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CN112007606B (en
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史延强
徐广通
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201910472985.0A priority Critical patent/CN112007606B/en
Priority to US17/615,353 priority patent/US20220219136A1/en
Priority to EP20812766.2A priority patent/EP3978110A4/en
Priority to PCT/CN2020/092590 priority patent/WO2020238953A1/en
Priority to JP2021571355A priority patent/JP2022534312A/en
Publication of CN112007606A publication Critical patent/CN112007606A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract

The invention relates to a reversible enrichment material of aromatic hydrocarbon components in hydrocarbon fuel and a preparation method thereof, wherein the reversible enrichment material comprises an inorganic carrier, and active metal salt and auxiliary agent metal salt loaded on the inorganic carrier; wherein the active metal salt is soluble silver salt and/or soluble copper salt, and the assistant metal salt is one or more selected from IA-IIIA group soluble metal salt and soluble transition metal salt except IB group; the preparation steps of the inorganic carrier comprise: the inorganic raw material is sequentially subjected to roasting treatment, acid washing treatment and/or alkali washing treatment and drying treatment. The reversible enrichment material provided by the invention can realize the separation of aromatic hydrocarbon and saturated hydrocarbon in hydrocarbon fuel, and has good reversibility.

Description

Reversible enrichment material for aromatic hydrocarbon component in hydrocarbon fuel and preparation method thereof
Technical Field
The invention relates to a reversible enrichment material of aromatic hydrocarbon components in hydrocarbon fuel and a preparation method thereof.
Background
The content of aromatic hydrocarbon in petroleum products is an important quality index, and the content of aromatic hydrocarbon in petroleum products such as gasoline, aviation fuel, diesel oil and the like is definitely specified. As a power source of an aircraft engine, aviation fuel is closely related to the safety performance and the economical efficiency of an aircraft, and aromatic hydrocarbon components in the aviation fuel have clear limit requirements in aviation fuel quality control standards due to relatively poor combustion performance and swelling property on rubber parts. In the process research and product quality control of aviation fuel, the rapid and accurate determination of the composition of aviation fuel is of great significance.
Regarding the determination of the content of aromatic hydrocarbons in aviation fuel, the specified method in the product standard is the fluorescence indicator method (GB/T11132-2008). The essence of the method is classical liquid-solid chromatography, the analysis process relates to preparation of silica gel for an adsorption column, filling of the adsorption column, addition of a color developing agent, leaching in the separation process, measurement after leaching and the like, the analysis period is long, the result reproducibility allowable range is wide, the performance of the silica gel, the filling and leaching speeds of the adsorption column, observation of a color developing point and the like can influence the analysis result, and the precision of the method is poor. In order to improve the analysis speed and the precision and accuracy of the analysis results, various methods for analyzing the aromatic hydrocarbon content of aviation fuel by High Performance Liquid Chromatography (HPLC) have been proposed abroad, such as ASTM D6591 and ASTM D6379. Compared with a fluorescence indicator method, the HPLC has higher separation efficiency and higher analysis speed, but the main problem is that a universal, convenient and reasonable detector is not used together, so that the application of the HPLC technology in medium and heavy petroleum fraction analysis is limited. For example, the main error source of the ASTM D6379 method is the use of its differential detector, which determines the correction factor of aromatic hydrocarbons and establishes a correction curve for the aromatic hydrocarbon component in aviation fuel using ortho-xylene as a model compound, but the refractive index of typical aromatic compounds in aviation fuel differs greatly from that of ortho-xylene, thereby also entailing a large analytical error (estimated deviation of about 10-15%).
With the rapid development of gas chromatography technology, it has been widely used in the field of petroleum product analysis. However, when gas chromatography is used for aviation fuel analysis, due to the lack of proper separation materials, the capacity of chromatographic peaks is insufficient, and the complete separation and analysis of saturated hydrocarbon and aromatic hydrocarbon components in aviation fuel cannot be realized.
Disclosure of Invention
The invention aims to provide a reversible enrichment material of aromatic hydrocarbon components in hydrocarbon fuel and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a reversible enrichment material for aromatic hydrocarbon components in hydrocarbon fuels, comprising:
a mineral support; and
an active metal salt, a first promoter metal salt and a second promoter metal salt supported on the inorganic support;
the active metal salt is soluble silver salt and/or soluble copper salt, the first assistant metal salt is selected from one or more of IA-IIIA group soluble metal salts, and the second assistant metal salt is selected from one or more of soluble transition metal salts except IB group soluble transition metal salts;
the preparation steps of the inorganic carrier comprise: the inorganic raw material is sequentially subjected to roasting treatment, acid washing treatment and/or alkali washing treatment and drying treatment.
Optionally, the conditions of the roasting treatment include: the temperature is 500 ℃ and 950 ℃ and the time is 4-16 hours.
Optionally, the acid washing treatment conditions include: the temperature is 100-: (1-20), wherein the acid solution used for the acid washing treatment is one or more selected from nitric acid, hydrochloric acid and sulfuric acid, and the concentration of the acid solution used for the acid washing treatment is 1-90 mass%;
the alkaline washing treatment conditions comprise: the temperature is 100-: (1-20), the alkali liquor used for alkali washing treatment is selected from one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the concentration of the alkali liquor used for alkali washing treatment is 1-90% by mass.
Optionally, the conditions of the drying treatment include: the temperature is 100 ℃ and 200 ℃, and the time is 3-6 hours.
Optionally, the inorganic support has a specific surface area of 1 to 600m2The pore diameter range is 1-1000nm, and the particle size range is 80-800 μm.
Optionally, the inorganic carrier includes one or more of a diatomite carrier, an alumina carrier, a titania carrier, a zirconia carrier, a mesoporous molecular sieve carrier, an amorphous silica-alumina carrier, a silica gel carrier, and a controlled pore glass carrier.
Optionally, the content of the active metal salt in the reversible enrichment material is 0.1-80 mass%, preferably 0.5-50 mass%; the content of the first auxiliary metal salt is 0.1 to 80 mass%, preferably 0.2 to 40 mass%; the content of the second auxiliary metal salt is 0.5 to 80% by mass, preferably 0.5 to 30% by mass.
Optionally, the mass content ratio of the first promoter metal salt to the second promoter metal salt is 1: (0.05-0.15) or 1: (0.5 to 50).
Optionally, the soluble silver salt is silver nitrate and the soluble copper salt is copper nitrate and/or copper sulfate.
Optionally, in the first promoter metal salt, the group IA metal is selected from one or more of lithium, sodium and potassium, the group IIA metal is selected from one or more of beryllium, magnesium, calcium and barium, and the group IIIA metal is aluminum and/or gallium; in the second auxiliary agent metal salt, the transition metal is selected from one or more of zinc, cadmium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, platinum, rhodium and palladium.
Optionally, the second promoter metal salt is selected from two of a group VIII soluble transition metal salt and a group IIB soluble transition metal salt; the weight content ratio of the first auxiliary metal salt to the second auxiliary metal salt is 1: (0.05-0.15) or 1: (0.5 to 40).
A second aspect of the present disclosure provides a method for preparing a reversible enrichment material according to the first aspect of the present disclosure, the method comprising: and loading the active metal salt, the first auxiliary agent metal salt and the second auxiliary agent metal salt on the inorganic carrier, and then carrying out drying treatment.
The enrichment material has reversible enrichment performance on aromatic hydrocarbon, can realize effective separation of saturated hydrocarbon and aromatic hydrocarbon, has good saturated hydrocarbon passing performance and stronger aromatic hydrocarbon enrichment capacity, and can realize reversible absorption and enrichment of aromatic hydrocarbon components in hydrocarbon fuel. The enrichment material can be used for hydrocarbon composition analysis in petroleum products, particularly hydrocarbon composition analysis in aviation fuel, and accurate hydrocarbon composition data of the petroleum products can be conveniently and quickly obtained.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a reversible enrichment material of aromatic hydrocarbon components in hydrocarbon fuel, which comprises an inorganic carrier, and active metal salt, first auxiliary agent metal salt and second auxiliary agent metal salt which are loaded on the inorganic carrier; the active metal salt is soluble silver salt and/or soluble copper salt, the first assistant metal salt is selected from one or more of IA-IIIA group soluble metal salts, and the second assistant metal salt is selected from one or more of soluble transition metal salts except IB group soluble transition metal salts; the preparation steps of the inorganic carrier comprise: the inorganic raw material is sequentially subjected to roasting treatment, acid washing treatment and/or alkali washing treatment and drying treatment.
The enrichment material provided by the invention has the advantages that the active metal salt and two specific types of auxiliary metal salts are loaded on the inorganic carrier prepared in the specific preparation step, the enrichment performance of a single active metal salt on aromatic hydrocarbon components is effectively improved through the synergistic effect of the auxiliary metals, and the enrichment material is suitable for enriching the separation column of saturated hydrocarbon and aromatic hydrocarbon components in gas chromatography or gas chromatography/mass spectrometry for testing the content of aromatic hydrocarbon in hydrocarbon fuel; the reversible aromatic hydrocarbon enrichment material provided by the invention has obvious advantages in the aspects of saturated hydrocarbon passing performance and low-carbon-number aromatic hydrocarbon enrichment in aviation fuel, can stably enrich low-carbon-number aromatic hydrocarbon components (such as ethylbenzene) at the temperature of 170 ℃, does not retain long-chain alkane (such as n-hexadecane) in the saturated hydrocarbon, realizes the complete separation of the saturated hydrocarbon and the low-carbon-number aromatic hydrocarbon in the aviation fuel, and can realize the complete desorption of the aromatic hydrocarbon (such as 1-methylnaphthalene) adsorbed by the enrichment material at the temperature of 208 ℃. Therefore, the method can be well used for composition analysis in the aviation fuel, and the accuracy and the repeatability of the composition analysis in the aviation fuel are improved.
In accordance with the present disclosure, the inorganic support may be a porous inorganic known to those skilled in the art for use as a support, for example, the inorganic support may include one or more of a diatomaceous earth support, an alumina support, a titania support, a zirconia support, a mesoporous molecular sieve support, an amorphous silica-alumina support, a silica gel support, and a controlled pore glass support, preferably a diatomaceous earth support.
In the present invention, the inorganic raw material is well known to those skilled in the art, and may be commercially available, for example, as one or more of a diatomaceous earth raw material, alumina, titania, zirconia, a mesoporous molecular sieve, amorphous silica-alumina, silica gel, and controlled pore glass. The invention modifies inorganic raw materials to improve the passing capacity of the inorganic raw materials to long-chain alkane. The conditions of the calcination treatment may include: the temperature is 500-950 ℃, preferably 850-950 ℃, and the time is 4-16 hours, and the acid washing treatment conditions can include: the temperature is 100-: (1-20), wherein the acid solution used for the acid washing treatment is one or more selected from nitric acid, hydrochloric acid and sulfuric acid, and the concentration of the acid solution used for the acid washing treatment is 1-90 mass%; the conditions of the alkaline washing treatment may include: the temperature is 100-: (1-20), wherein the alkali liquor used for the alkali washing treatment is one or more of a sodium hydroxide solution, a potassium hydroxide solution and ammonia water, and the concentration of the alkali liquor used for the alkali washing treatment is 1-90 mass%, preferably 10-50 mass%; the conditions of the drying process may include: the temperature is 100-200 ℃, preferably 150-180 ℃ and the time is 3-6 hours.
According to the invention, the specific surface area of the mineral support may be between 1 and 600m2A/g, preferably from 1 to 100m2A/g, more preferably 2 to 50m2The pore size may be in the range from 1 to 1000nm and the particle size may be in the range from 80 to 800. mu.m, preferably 100 to 600. mu.m.
According to the present invention, the content of the active metal salt in the reversible enrichment material may be 0.1 to 80 mass%, preferably 0.5 to 50 mass%, more preferably 1 to 30 mass% or 0.8 to 15 mass%; the content of the first auxiliary metal salt may be 0.1 to 80 mass%, preferably 0.2 to 40 mass%; the content of the second auxiliary metal salt may be 0.5 to 80% by mass, preferably 0.5 to 30% by mass or 0.7 to 12% by mass. Further, the weight content ratio of the first promoter metal salt and the second promoter metal salt may be 1: (0.05 to 0.15) or (0.5 to 50), preferably 1: (0.5 to 40).
According to the invention, the soluble silver salt may be silver nitrate and the soluble copper salt may be copper nitrate and/or copper sulphate, preferably copper nitrate. The assistant metal salt is preferably soluble nitrate or sulfate of assistant metal, in the first assistant metal salt, the IA group metal can be one or more selected from lithium, sodium and potassium, the IIA group metal can be one or more selected from beryllium, magnesium, calcium and barium, the IIIA group metal can be aluminum and/or gallium, and in the second assistant metal salt, the transition metal can be one or more selected from zinc (IIB), cadmium (IIB), vanadium, chromium (VIB), molybdenum (VIB), tungsten (VIB), manganese (VIII), iron (VIII), cobalt (VIII), nickel (VIII), ruthenium (VIII), platinum (VIII), rhodium (VIII) and palladium (VIII).
According to the present invention, the reversible enrichment material preferably comprises three promoter metal salts, namely one first promoter metal salt and two second promoter metal salts, the first promoter metal salt may be selected from group IA-IIIA soluble metal salts, preferably from group IA-IIA soluble metal salts, the two second promoter metal salts may be selected from soluble transition metal salts other than group IB, preferably in one embodiment, the second promoter metal salts may comprise two selected from group IIB soluble metal salts and group VIII soluble metal salts. Wherein the content of the first auxiliary metal salt may be 0.1 to 80% by mass, preferably 0.2 to 40% by mass, for example, 0.5 to 20% by mass or 0.3 to 18% by mass; the contents of the two second auxiliary metal salts may be 0.5 to 80 mass% (preferably 0.5 to 30 mass%, for example, 1.5 to 22 mass% or 0.8 to 16 mass%) and 0.5 to 80 mass% (preferably 0.5 to 30 mass%, for example, 1.2 to 25 mass% or 0.75 to 20 mass%), respectively. Further, the weight content ratio of the first second aid metal salt and the second aid metal salt may be 1: (0.05-0.15) or 1: (0.5 to 40), preferably 1: (0.5 to 30). For example, in a more preferred embodiment, the first second promoter metal salt may be selected from group VIII soluble metal salts, the second promoter metal salt may be selected from group IIB soluble metal salts, and the ratio of the weight content of the first second promoter metal salt to the weight content of the second promoter metal salt may be 1: (0.5 to 30), preferably 1: (1.5-25) or 1: (3-20).
The invention also provides a preparation method of the reversible enrichment material, which comprises the following steps: the active metal salt and the auxiliary metal salt are loaded on an inorganic carrier and then dried. The conditions of the drying treatment may be the same as or different from those of the drying treatment in the step of preparing the inorganic support, and may be selected by those skilled in the art as needed.
The reversible enrichment material is particularly suitable for a separation column filler in aromatic hydrocarbon content analysis in gas chromatography analysis of aviation fuel and detailed hydrocarbon group composition analysis of aviation fuel in gas chromatography/mass spectrometry. During testing, the enrichment material is loaded into a chromatographic column to prepare a separation chromatographic column required for gas chromatographic analysis or gas chromatography/mass spectrometry combined analysis of aviation fuel composition so as to separate saturated hydrocarbon and aromatic hydrocarbon components in the aviation fuel, and the separation process comprises the following steps: saturated hydrocarbon in the aviation fuel enters a gas chromatography detector or a gas chromatography/mass spectrometry combined detector for component and content determination after passing through a separation column at a lower temperature, and then a column box is heated and the separation column is subjected to back flushing, so that aromatic hydrocarbon components enter a gas chromatography or gas chromatography/mass spectrometry combined instrument for analyzing the components and the content of aromatic hydrocarbon, and thus hydrocarbon composition or detailed hydrocarbon group composition analysis data of the aviation fuel is conveniently and quickly obtained.
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
The following examples are provided to illustrate the use effect of the reversible enrichment material provided by the present invention in the separation of saturated hydrocarbon and aromatic hydrocarbon components of aviation fuel, and the reversible enrichment material prepared by the present invention is filled in a chromatographic column of a gas chromatograph. The time of ethylbenzene peak and n-hexadecane passing through the separation column at the measured temperature is taken as an evaluation standard, namely the time of ethylbenzene peak is greater than that of n-hexadecane peak at the measured temperature, so that the reversible enrichment material has a good use effect. In the following examples and comparative examples, diatomaceous earth was obtained from Kagaku, Suzhou, under the trade name diatomaceous earth, and the remaining inorganic materials were obtained from Kagaku, chemical Co.
Support preparation example 1
Selecting diatomite raw materials and water according to a mass ratio of 1: 0.8, mixing, preparing slurry, roasting at 850 ℃ for 8 hours, carrying out 3-time pickling treatment on the roasted diatomite, wherein the used acid is sulfuric acid, the mass concentration of the acid solution is 20%, the pickling temperature is 135 ℃ each time, the pickling time is 8 hours, and the mass ratio of the diatomite raw material to the acid solution is 1: 5, filtering the diatomite after acid washing treatment, and drying the diatomite for 3 hours at 150 ℃. The contents of the components of diatomaceous earth before and after pickling are shown in Table 1.
TABLE 1 diatomaceous earth composition Change before and after treatment
Before treatment After treatment
SiO2 73.1 81.4
Al2O3 9.7 8.7
Fe2O3 5.2 4.6
CaO 3.6 1.3
MgO 3.1 1.8
K2O 2.5 1.1
MnO 1.2 0.9
P2O5 1.6 0.2
Grinding the prepared diatomite carrier product, sieving for later use, marking as an inorganic carrier Z1, wherein the pore diameter is mainly 50nm-1000nm, and the specific surface area is 13m measured by a nitrogen physical adsorption method2/g。
Support preparation example 2
Selecting controllable-aperture glass, roasting at 600 ℃ for 10 hours, carrying out 1-time pickling treatment on the roasted controllable-aperture glass, wherein the acid is nitric acid, the mass concentration of acid liquor is 30%, the pickling temperature is 150 ℃, the pickling time is 10 hours, and the mass ratio of the diatomite raw material to the acid liquor is 1: 10, filtering the diatomite after acid washing treatment, and drying the diatomite for 3 hours at 150 ℃. Screening the prepared glass carrier product with controllable aperture for later use, marking as a glass carrier Z2 with controllable aperture, wherein the aperture diameter is mainly 2-50 nm, and the specific surface area is 367m measured by nitrogen physical adsorption method2/g。
Support preparation example 3
Selecting diatomite raw materials and water according to a mass ratio of 1: 1, mixing, preparing slurry, roasting at a high temperature of 950 ℃ for 15 hours, carrying out alkali washing treatment on the roasted diatomite for 2 times, wherein the alkali is sodium hydroxide, the mass concentration of the alkali is 15%, the alkali washing temperature is 105 ℃, and the alkali washing time is 9 hours each timeThe mass ratio of the diatomite raw material to the alkali liquor calculated on a dry basis is 1: 12, filtering the diatomite after alkali washing treatment, and drying the diatomite for 3 hours at 120 ℃. Grinding the prepared diatomite carrier product, sieving for later use, marking as diatomite carrier Z3 with pore diameter of 50-1000 nm, and specific surface area of 9m determined by nitrogen physical adsorption method2/g。
Support preparation example 4
Selecting diatomite raw materials and water according to a mass ratio of 1: 1.5, mixing, preparing slurry, roasting at a high temperature of 700 ℃ for 6 hours, carrying out acid washing treatment on roasted diatomite for 2 times, wherein the acid is hydrochloric acid, the mass concentration of acid liquor is 5%, the acid washing temperature is 110 ℃, the acid washing time is 3 hours each time, and the mass ratio of the diatomite raw material to the acid liquor on a dry basis is 1: 30, filtering the diatomite after acid washing treatment, and drying the diatomite for 1.5 hours at 110 ℃. Grinding the prepared diatomite carrier product, sieving for later use, marking as diatomite carrier Z4 with pore diameter of 50-1000 nm, and specific surface area of 4m determined by nitrogen physical adsorption method2/g。
Comparative support example 1
Selecting diatomite raw materials and water according to a mass ratio of 1: 0.8, preparing slurry, roasting at 850 ℃ for 8 hours at high temperature, grinding the roasted diatomite, screening for later use, marking as a diatomite carrier D1 with the pore diameter of mainly 50nm-1000nm, and the specific surface area of 2m measured by a nitrogen physical adsorption method2/g。
Comparative support example 2
Selecting a diatomite raw material, carrying out acid washing treatment for 3 times, wherein the used acid is sulfuric acid, the mass concentration of an acid solution is 20%, the temperature of each acid washing is 135 ℃, the time is 8 hours, and the mass ratio of the diatomite raw material to the acid solution is 1: 5, filtering the diatomite after acid washing treatment, and drying the diatomite for 3 hours at 150 ℃. Sieving the washed diatomaceous earth, and marking as diatomaceous earth carrier D2 with pore diameter of 50-1000 nm and specific surface area of 3m as determined by nitrogen physical adsorption method2/g。
Example 1
And (3) taking 150-400 mu m of the diatomite carrier Z15.2125 g, immersing in 10mL of silver nitrate with the mass fraction of 0.25%, a potassium nitrate solution with the mass fraction of 0.5% and cadmium nitrate with the mass fraction of 3%, evaporating to remove water, and drying in an oven at 150 ℃ for 1h to obtain the enrichment material with the mass fraction of 0.5% of silver nitrate, 1% of potassium nitrate and 6% of cadmium nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 5.336 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 2.537 minutes and the peak time of ethylbenzene was 3.824 minutes, measured at a column box temperature of 170 ℃.
Example 2
Soaking 150-400 mu m of glass carrier Z25.0525g with controllable aperture in 10mL of silver nitrate with the mass fraction of 0.5%, gallium nitrate with the mass fraction of 0.5% and palladium nitrate solution with the mass fraction of 10%, naturally evaporating to remove water, and drying in an oven at 150 ℃ for 1h to obtain the enrichment material with the mass fraction of 1% of silver nitrate, the mass fraction of 1% of gallium nitrate and the mass fraction of 20% of palladium nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 4.215 minutes and the peak flowing-out time of the ethylbenzene to be 5.725 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 3.284 minutes and the peak time of ethylbenzene was 4.307 minutes, measured at a column box temperature of 170 ℃.
Example 3
And (2) soaking 150-400 mu m of diatomite carrier Z35.0210 g in 10mL of silver nitrate with the mass fraction of 0.5%, beryllium nitrate with the mass fraction of 5% and zinc nitrate solution with the mass fraction of 1%, naturally evaporating to remove water, and drying in an oven at 150 ℃ for 1h to obtain the enrichment material with the mass fraction of 1% of silver nitrate, the mass fraction of 10% of beryllium nitrate and the mass fraction of 2% of zinc nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 5.674 minutes under the condition that the temperature of a column box is 150 ℃.
Example 4
Taking 150-400 mu m of diatomite carrier Z45.2100g, except that the carrier is soaked in 10mL of 0.5 mass percent copper nitrate, 3 mass percent sodium chloride and 1 mass percent nickel nitrate solution, naturally evaporating to remove water, and then placing in a 100 ℃ oven for drying for 1h to obtain an enrichment material with the mass percent of copper nitrate of 1%, the mass percent of sodium chloride of 6% and the mass percent of nickel nitrate of 2%.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.602 minutes and the peak flowing-out time of the ethylbenzene to be 6.025 minutes under the condition that the temperature of a column box is 150 ℃.
Example 5
150 mu m-400 mu m of diatomite carrier Z16.2564g is taken, except that the carrier is soaked in 20mL of copper sulfate with the mass fraction of 1.25%, magnesium nitrate with the mass fraction of 1% and platinum nitrate solution with the mass fraction of 5%, after the water is removed by natural evaporation, the carrier is placed in an oven at 150 ℃ for drying for 1h, and the enrichment material with the mass fraction of copper sulfate of 4%, the mass fraction of magnesium nitrate of 3.2% and the mass fraction of platinum nitrate of 16% is obtained.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.602 minutes and the peak flowing-out time of the ethylbenzene to be 6.323 minutes under the condition that the temperature of a column box is 150 ℃.
Example 6
Taking 150-400 mu m of diatomite carrier Z15.5587g, except that the carrier is placed in 20mL of 0.125 mass percent of copper nitrate, 2.5 mass percent of magnesium nitrate and 0.25 mass percent of ferric nitrate solution, evaporating to remove water, and then placing in a 100 ℃ oven for drying for 1h to obtain the enrichment material with 0.5 mass percent of copper nitrate, 10 mass percent of magnesium nitrate and 1 mass percent of ferric nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.602 minutes and the peak flowing-out time of the ethylbenzene to be 6.284 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 2.163 minutes and the peak time of ethylbenzene was 4.821 minutes, as measured at a column box temperature of 170 ℃.
Example 7
Taking 150-400 mu m diatomite carrier Z14.9532g, except that the carrier is placed in 10mL of copper nitrate solution with the mass fraction of 5%, potassium nitrate with the mass fraction of 10% and cobalt nitrate solution with the mass fraction of 2.5%, evaporating to remove water, and then placing in an oven at 150 ℃ for drying for 1h to obtain the enrichment material with the mass fraction of copper nitrate of 10%, the mass fraction of potassium nitrate of 20% and the mass fraction of cobalt nitrate of 5%.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.602 minutes and the peak flowing-out time of the ethylbenzene to be 6.886 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow time of n-hexadecane was 2.205 minutes and the peak time of ethylbenzene was 4.974 minutes, as measured at a column box temperature of 170 ℃.
Example 8
Taking 150-400 mu m diatomite carrier Z14.9865g, except that the carrier is placed in 15mL of 5 mass percent copper nitrate, 4 mass percent potassium nitrate, 1 mass percent ferric nitrate and 0.5 mass percent rhodium nitrate solution, after evaporating to remove moisture, placing in an oven at 150 ℃ for drying for 1h to obtain the enrichment material with the mass percent of copper nitrate of 15 percent, potassium nitrate of 12 percent, ferric nitrate of 3 percent and rhodium nitrate of 1.5 percent.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.602 minutes and the peak flowing-out time of the ethylbenzene to be 8.897 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 2.163 minutes and the peak time of ethylbenzene was 5.462 minutes, as measured at a column box temperature of 170 ℃.
Example 9
Taking 150-400 mu m diatomite carrier Z14.8765g, except that the carrier is placed in 15mL of silver nitrate with the mass fraction of 10%, aluminum nitrate with the mass fraction of 2%, cadmium nitrate with the mass fraction of 5% and ferric nitrate solution with the mass fraction of 0.5%, after evaporating and removing water, placing in a 150 ℃ oven for drying for 1h, and obtaining the enrichment material with the mass fraction of 30% of silver nitrate, 6% of aluminum nitrate, 15% of cadmium nitrate and 1.5% of ferric nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 9.215 minutes under the condition that the temperature of a column box is 150 ℃; the complete efflux time of n-hexadecane was 2.257 minutes and the peak time of ethylbenzene was 5.847 minutes, measured at a column box temperature of 170 ℃.
Example 10
Taking 150-400 mu m of diatomite carrier Z15.0615g, except that the carrier is placed in 20mL of silver nitrate with the mass fraction of 2%, lithium nitrate with the mass fraction of 1%, ammonium tungstate with the mass fraction of 3% and ruthenium nitrate solution with the mass fraction of 0.2%, after evaporating and removing moisture, placing in an oven at 150 ℃ for drying for 1h, and obtaining the enrichment material with the mass fraction of 8% of silver nitrate, 4% of lithium nitrate, 12% of ammonium tungstate and 0.8% of ruthenium nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 8.867 minutes under the condition that the temperature of a column box is 150 ℃; the complete efflux time of n-hexadecane was 2.313 minutes and the peak time of ethylbenzene was 4.885 minutes, measured at a column box temperature of 170 ℃.
Example 11
Taking 150-400 mu m diatomite carrier Z110.2684g, placing the diatomite carrier Z110.2684g into 20mL of solution containing 2 mass percent of silver nitrate, 1 mass percent of ferric nitrate, 0.5 mass percent of tungsten nitrate and 1 mass percent of potassium nitrate, evaporating to remove water, and placing the solution in an oven at 150 ℃ for drying for 1h to obtain the enrichment material with 3.9 mass percent of silver nitrate, 1.9 mass percent of ferric nitrate, 1 mass percent of tungsten nitrate and 1.9 mass percent of potassium nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.467 minutes and the peak flowing-out time of the ethylbenzene to be 5.844 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 2.445 minutes and the peak time of ethylbenzene was 4.157 minutes, measured at a column box temperature of 170 ℃.
Example 12
Taking 150-400 mu m diatomite carrier Z14.8765g, except that the carrier is placed in 15mL of silver nitrate with the mass fraction of 10%, aluminum nitrate with the mass fraction of 2%, cadmium nitrate with the mass fraction of 20% and ferric nitrate solution with the mass fraction of 0.1%, after evaporating and removing water, placing in a 150 ℃ oven for drying for 1h, and obtaining the enrichment material with the mass fraction of 30% of silver nitrate, 6% of aluminum nitrate, 60% of cadmium nitrate and 0.3% of ferric nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.341 minutes and the peak flowing-out time of the ethylbenzene to be 6.535 minutes under the condition that the temperature of a column box is 150 ℃; the complete outflow time of n-hexadecane was 2.363 minutes and the peak outflow time of ethylbenzene was 4.031 minutes, measured at a column box temperature of 170 ℃.
Example 13
Substantially the same as in example 9, except that the diatomaceous earth carrier Z1 was replaced with a diatomaceous earth carrier Z4.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.704 minutes and the peak flowing-out time of the ethylbenzene to be 7.657 minutes under the condition that the temperature of a column box is 150 ℃; the total outflow time of the n-hexadecane measured at the column box temperature of 170 ℃ was 2.481 minutes, and the peak outflow time of the ethylbenzene was 4.882 minutes
Comparative example 1
Substantially the same as in example 9 except that the diatomaceous earth carrier Z1 was replaced with silica gel. The silica gel (produced by Qingdao ocean chemical Co., Ltd.) has a particle diameter of 150-400 μm and a specific surface area of 418m2In g, the average pore diameter was 20.8 nm.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 5.932 minutes and the peak flowing-out time of the ethylbenzene to be 6.948 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 4.128 minutes and the peak time of ethylbenzene was 4.815 minutes, measured at a column box temperature of 170 ℃.
Comparative example 2
Substantially the same as in example 9, except that the diatomaceous earth carrier Z1 was replaced with γ -Al2O3，γ-Al2O3Has a particle diameter of 150 to 400 μm and a specific surface area of 270m2In g, the average pore diameter is 12.1 nm.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the total outflow time of the n-hexadecane to be 5.027 minutes and the peak outflow time of the ethylbenzene to be 6.316 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 3.894 minutes and the peak time of ethylbenzene was 4.128 minutes, measured at a column box temperature of 170 ℃.
Comparative example 3
Basically the same as example 9, except that the diatomaceous earth carrier Z1 was replaced with SBA-15 mesoporous molecular sieve, the particle size of the SBA-15 mesoporous molecular sieve was 150 μm to 400 μm, and the specific surface area was 582m2Per g, average pore diameterThe diameter is 9.8 nm.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 5.276 minutes and the peak flowing-out time of the ethylbenzene to be 6.371 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 4.628 min and the peak time of ethylbenzene was 5.312 min, measured at a column box temperature of 170 ℃.
Comparative example 4
Substantially the same as in example 9 except that the diatomaceous earth support Z1 was replaced with zirconia having a particle diameter of 150 μm to 400 μm and a specific surface area of 92m2In g, the average pore diameter was 7.8 nm.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 5.034 minutes and the peak flowing-out time of the ethylbenzene to be 6.211 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 4.314 minutes and the peak time of ethylbenzene was 4.689 minutes, measured at a column box temperature of 170 ℃.
Comparative example 5
Essentially the same as in example 9, except that the diatomaceous earth starting material was loaded directly without treatment.
Filling the prepared trapping material into a chromatographic column of a packed column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 5.926 minutes and the peak flowing-out time of the ethylbenzene to be 6.323 minutes at the temperature of a column box of 150 ℃; when the n-hexadecane is not completely discharged under the condition of column box temperature of 170 deg.C, ethylbenzene already begins to produce peak, and the n-hexadecane and ethylbenzene can not be separated.
Comparative example 6
5.5362g of the diatomite carrier prepared in example 1 is taken, the carrier is placed in 30mL of silver nitrate with the mass fraction of 4% and calcium nitrate solution with the mass fraction of 12%, after water is removed through evaporation, the carrier is placed in an oven at 150 ℃ for drying for 1h, and an enrichment material with the mass fraction of 20% of silver nitrate and the mass fraction of 60% of calcium nitrate is obtained.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 3.827 minutes under the condition that the temperature of a column box is 150 ℃; the normal hexadecane and the ethylbenzene can not be separated under the condition that the temperature of the column box is 170 ℃.
Comparative example 7
5.7805g of the diatomite carrier prepared in example 1 was taken, except that the carrier was placed in 12mL of a solution containing 0.5 mass percent of silver nitrate and 15 mass percent of manganese nitrate, evaporated to remove water, and then dried in an oven at 150 ℃ for 1 hour to obtain an enriched material containing 1 mass percent of silver nitrate and 30 mass percent of manganese nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 3.758 minutes under the condition that the temperature of a column box is 150 ℃; the normal hexadecane and the ethylbenzene can not be separated under the condition that the temperature of the column box is 170 ℃.
Comparative example 8
5.0526g of the diatomite carrier prepared in example 1 was taken, except that the carrier was placed in 10mL of a solution of silver nitrate with a mass fraction of 0.25% and copper nitrate with a mass fraction of 1.25%, evaporated to remove water, and then dried in an oven at 150 ℃ for 1 hour to obtain an enriched material with a mass fraction of 0.5% for silver nitrate and a mass fraction of 2.5% for copper nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.618 minutes and the peak flowing-out time of the ethylbenzene to be 3.855 minutes under the condition that the temperature of a column box is 150 ℃; the normal hexadecane and the ethylbenzene can not be separated under the condition that the temperature of the column box is 170 ℃.
Comparative example 9
5.1527g of the diatomite carrier prepared in example 1 was taken, except that the carrier was placed in 10mL of a solution of silver nitrate with a mass fraction of 0.25%, chromium nitrate with a mass fraction of 1.25% and palladium nitrate with a mass fraction of 0.5%, evaporated to remove moisture, and then dried in an oven at 150 ℃ for 1 hour to obtain an enriched material with a mass fraction of 0.5% of silver nitrate, a mass fraction of 2.5% of chromium nitrate and a mass fraction of 1% of palladium nitrate.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.784 minutes and the peak flowing-out time of the ethylbenzene to be 5.223 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 2.645 minutes and the peak time of ethylbenzene was 3.144 minutes, measured at a column box temperature of 170 ℃.
Comparative example 10
Substantially the same as in example 9 except that the carrier D1 of comparative example 1 was used. Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 5.315 minutes and the peak flowing-out time of the ethylbenzene to be 6.427 minutes under the condition that the temperature of a column box is 150 ℃; the complete flow-out time of n-hexadecane was 4.612 minutes and the peak time of ethylbenzene was 4.871 minutes, measured at a column box temperature of 170 ℃.
Comparative example 11
Substantially the same as in example 9 except that the carrier D2 of comparative example 2 was used.
Filling the prepared enrichment material into a chromatographic column of a filling column with the inner diameter of 2mm and the length of 200mm, connecting the chromatographic column into a gas chromatograph, and measuring the complete flowing-out time of the n-hexadecane to be 3.364 minutes and the peak flowing-out time of the ethylbenzene to be 4.025 minutes under the condition that the temperature of a column box is 150 ℃; the normal hexadecane and the ethylbenzene can not be separated under the condition that the temperature of the column box is 170 ℃.
As can be seen from the above examples and comparative examples, the reversible enrichment material obtained after the interaction between the inorganic carrier prepared by the steps of roasting, acid washing and/or alkali washing and drying and the active metal and the auxiliary metal salt in the claims has better separation effect of saturated hydrocarbon and aromatic hydrocarbon.
Test example 1
This test example serves to illustrate the aromatic hydrocarbon desorption performance of the reversible enrichment material of the invention. Taking the enriched material prepared in example 8 as an example, the aromatic hydrocarbon desorption performance evaluation is carried out.
The enriched material prepared in example 8 was packed in a column of a packed column having an inner diameter of 2mm and a length of 200mm to prepare a desired column.
Preparing cyclohexane solutions of ethylbenzene, isopropylbenzene, n-butylbenzene, n-pentylbenzene, phenylhexane, n-heptylbenzene, p-di-tert-butylbenzene, 1,3, 5-triisopropylbenzene, tetrahydronaphthalene and 1-methylnaphthalene respectively as standard samples, wherein the mass fractions of the cyclohexane solutions are 1%, 2%, 5%, 10%, 8%, 5%, 3%, 2% and 2% respectively; and preparing a mixed standard sample containing decane, n-undecane, n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, pentylcyclohexane, hexylcyclohexane, decahydronaphthalene, cumene, butylbenzene, tetrahydronaphthalene and 1-methylnaphthalene, wherein the mass fraction of saturated hydrocarbons in the mixed standard sample is 82.9%, and the mass fraction of aromatic hydrocarbons is 17.1%. The prepared chromatographic column is connected into a chromatographic column box, and carrier gas N is set2The flow rate of (2) was 25mL/min and the initial column box temperature was 155 ℃. The amount of the sample was 0.02. mu.L, and the cyclohexane peak area (A) was measured after the cyclohexane completely flowed out of the columnMeasuring cyclohexane) Switching the six-way valve to reverse blow the carrier gas in the chromatographic column, raising the temperature of the column box to 208 ℃, and measuring the area (A) of the aromatic hydrocarbon peakAromatic hydrocarbon detection) (ii) a And for the mixed standard sample, after hexadecane completely passes through the chromatographic column, switching the six-way valve, carrying gas back flushing, simultaneously raising the temperature of the column box to 208 ℃, enabling mixed aromatic hydrocarbon to flow out of the chromatographic column, measuring the peak areas of saturated hydrocarbon and mixed aromatic hydrocarbon, calculating the mass fraction of aromatic hydrocarbon of each standard sample by adopting a normalization method, comparing the mass fraction with the prepared data, calculating the recovery rate, and obtaining the measurement result shown in table 2.
The recovery rate was 100 mass% × (A)Aromatic hydrocarbon detection/AMeasuring cyclohexane)/(mAromatic hydrocarbons/mCyclohexane)
TABLE 2
Aromatic hydrocarbon species The recovery rate is mass%
Ethylbenzene production 100.2
Isopropyl benzene 100.6
N-butylbenzene 100.2
N-pentylbenzene 99.9
Phenylhexane 99.5
N-heptylbenzene 100.1
P-di-tert-butyl benzene 99.8
1,3, 5-triisopropylbenzene 99.9
Tetrahydronaphthalenes 99.3
1-methylnaphthalene 98.7
Mixed aromatic hydrocarbons 101.2
As can be seen from the data in Table 2, the aromatic hydrocarbon desorption performance of the enrichment material disclosed by the invention is good, the desorption recovery rate of the enrichment material after various aromatic hydrocarbons are adsorbed is more than 98%, and the reversible adsorption of the aromatic hydrocarbons can be realized.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.

Claims (12)

1. A reversible enrichment material for aromatic hydrocarbon components in hydrocarbon fuels, characterized in that the reversible enrichment material comprises:
a mineral support; and
an active metal salt, a first promoter metal salt and a second promoter metal salt supported on the inorganic support;
the active metal salt is soluble silver salt and/or soluble copper salt, the first assistant metal salt is selected from one or more of IA-IIIA group soluble metal salts, and the second assistant metal salt is selected from one or more of soluble transition metal salts except IB group soluble transition metal salts;
the preparation steps of the inorganic carrier comprise: the inorganic raw material is sequentially subjected to roasting treatment, acid washing treatment and/or alkali washing treatment and drying treatment.
2. The reversible enrichment material of claim 1, wherein the conditions of the firing treatment comprise: the temperature is 500 ℃ and 950 ℃ and the time is 4-16 hours.
3. The reversible enrichment material of claim 1, wherein the acid wash treatment conditions comprise: the temperature is 100-: (1-20), wherein the acid solution used for the acid washing treatment is one or more selected from nitric acid, hydrochloric acid and sulfuric acid, and the concentration of the acid solution used for the acid washing treatment is 1-90 mass%;
the alkaline washing treatment conditions comprise: the temperature is 100-: (1-20), the alkali liquor used for alkali washing treatment is selected from one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the concentration of the alkali liquor used for alkali washing treatment is 1-90% by mass.
4. The reversible enrichment material of claim 1, wherein the conditions of the drying process comprise: the temperature is 100 ℃ and 200 ℃, and the time is 3-6 hours.
5. The reversible enrichment material of claim 1, wherein the inorganic support has a specific surface area of 1-600m2The pore diameter range is 1-1000nm, and the particle size range is 80-800 μm.
6. The reversible enrichment material of claim 1 or 5, wherein the inorganic support comprises one or more of a diatomaceous earth support, an alumina support, a titania support, a zirconia support, a mesoporous molecular sieve support, an amorphous silica-alumina support, a silica gel support, and a controlled pore glass support.
7. The reversible enrichment material according to claim 1, wherein the content of the active metal salt in the reversible enrichment material is 0.1 to 80 mass%, preferably 0.5 to 50 mass%; the content of the first auxiliary metal salt is 0.1 to 80 mass%, preferably 0.2 to 40 mass%; the content of the second auxiliary metal salt is 0.5 to 80% by mass, preferably 0.5 to 30% by mass.
8. The reversible enrichment material of claim 1, wherein the mass content ratio of the first promoter metal salt to the second promoter metal salt, calculated as metal oxide, is 1: (0.05-0.15) or 1: (0.5 to 50).
9. The reversible enrichment material of claim 1, wherein the soluble silver salt is silver nitrate and the soluble copper salt is copper nitrate and/or copper sulfate.
10. The reversible enrichment material of claim 1, wherein in the first promoter metal salt, the group IA metal is selected from one or more of lithium, sodium and potassium, the group IIA metal is selected from one or more of beryllium, magnesium, calcium and barium, and the group IIIA metal is aluminum and/or gallium; in the second auxiliary agent metal salt, the transition metal is selected from one or more of zinc, cadmium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, platinum, rhodium and palladium.
11. The reversible enrichment material of claim 1, wherein the second promoter metal salt is selected from two of a group VIII soluble transition metal salt and a group IIB soluble transition metal salt; the weight content ratio of the first auxiliary metal salt to the second auxiliary metal salt is 1: (0.05-0.15) or 1: (0.5 to 40).
12. The method for preparing a reversible enrichment material of any of claims 1 to 11, comprising: and loading the active metal salt, the first auxiliary agent metal salt and the second auxiliary agent metal salt on the inorganic carrier, and then carrying out drying treatment.
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CN1485129A (en) * 2002-09-28 2004-03-31 中国石油化工股份有限公司 Adsorbing material and the application thereof
US20050127321A1 (en) * 2003-10-15 2005-06-16 Fagan Paul J. Compositions containing lactone compatibilizers
CN101519602A (en) * 2008-02-28 2009-09-02 中国石油化工股份有限公司 Material for trapping the unsaturated hydrocarbon in hydrocarbon raw materials
CN108102727A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 For the method for coke oven gas purification recycling aromatic hydrocarbons

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Publication number Priority date Publication date Assignee Title
CN1485129A (en) * 2002-09-28 2004-03-31 中国石油化工股份有限公司 Adsorbing material and the application thereof
US20050127321A1 (en) * 2003-10-15 2005-06-16 Fagan Paul J. Compositions containing lactone compatibilizers
CN101519602A (en) * 2008-02-28 2009-09-02 中国石油化工股份有限公司 Material for trapping the unsaturated hydrocarbon in hydrocarbon raw materials
CN108102727A (en) * 2017-07-19 2018-06-01 湖北申昙环保新材料有限公司 For the method for coke oven gas purification recycling aromatic hydrocarbons

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