CN110559994A - Load type adsorbent for adsorbing thiophene sulfides in oil and preparation method thereof - Google Patents

Abstract

The invention discloses a load type adsorbent for adsorbing thiophene sulfides in oil and a preparation method thereof, wherein the load type adsorbent consists of a carrier and an active component, and the carrier is 15 wt% of H₂O₂Or 15 wt% of HNO₃The active component of the modified active carbon is NiCl₂And mixing the carrier and the active component according to the mass ratio of 2:1, and preparing the load type adsorbent by a dry-mixing roasting method. The invention has the advantages that: (1) the pore structure and pore shape of the adsorbent have great influence on the adsorption performance, and the active carbon is treated with 15 wt% of H₂O₂Or HNO₃After modification, the modified porous material has huge specific surface area and dense pore structureAnd more surface functional groups, developed pores and large adsorption capacity, so the supported adsorbent provided by the invention has larger adsorption capacity to thiophene sulfides in diesel oil, and the removal rate to thiophene-n-octane reaches 65.58% and 70.54% respectively; (2) the production cost is reduced, and the requirement of industrial production operation cost can be met.

Description

Load type adsorbent for adsorbing thiophene sulfides in oil and preparation method thereof

Technical Field

The invention relates to an adsorbent and a preparation method thereof, in particular to a load type adsorbent for adsorbing thiophene sulfides in oil products and a preparation method thereof, belonging to the technical field of petrochemical industry.

Background

In recent years, with the development of diesel engine technology, especially the application of electronic fuel injection technology, and the advantages of large volumetric heating value, durability, high efficiency and the like of diesel oil, diesel oil has been widely used as fuel for vehicles, ships and internal combustion engine equipment. This makes the total demand for diesel oil more and more worldwide, and the production of diesel oil is greatly increased in all countries in the world. The demand of China for diesel oil is also strongly desired. In recent years, the demand for diesel fuel in the domestic market has increased considerably over gasoline.

SO is generated when sulfur in diesel oil is burnt at high temperature_x，SO_xNot only corrodes and damages engine parts, but also forms acid rain when being discharged into the air, and destroys the ecological environment. In addition, SO_xCan also poison the catalyst for treating the tail gas of the motor vehicle, reduce the catalytic performance of the catalyst and increase SO_xAnd the emission of particulate pollutants, thereby aggravating the pollution of urban environment. In addition, the high-content sulfur-containing polycyclic aromatic hydrocarbon has certain mutagenesis and carcinogenic effects on human bodies. Therefore, low sulfur reduction of diesel is a common concern in countries around the world. Strict diesel fuel sulfur standards are promulgated successively in developed countries and regions.

With the increasing demand of major industrialized countries in the world for diesel oil and the stricter standards of sulfur content in diesel oil, deep desulfurization of diesel oil is receiving wide attention.

The sulfur-containing compounds in the oil can be classified into two types according to chemical properties: active sulfides, and inactive sulfides.

1. Active sulfur compounds

the active sulfides mainly comprise: hydrogen sulfide, carbon disulfide, mercaptan, thioether, etc., which have the common feature of being chemically active and easily removable, four methods for removing active sulfides are listed in table 1.

TABLE 1 removal of active sulfides

Active sulfur compounds	Removal method
		Hydrogen sulfide	And (3) dry method: absorption and adsorption; and (2) wet method: absorption and liquid phase redox
Carbon disulfide	liquid phase catalytic oxidation method, amine method, adsorption method
		Thiols	Alkali washing, catalytic oxidation, physical adsorption and hydrorefining
Thioethers	Physical adsorption method of activated carbon and complexing and removing method of acid refining method

Experiments prove that the method can obtain better desulfurization effect.

2. Non-reactive sulfides

Non-reactive sulfides, especially thiophenic organosulfurs, are difficult to remove because of their complex structure compared to reactive sulfides. In addition, the mass fraction of the inactive sulfide is generally high, and is up to 80% in the catalytic cracking gasoline and about 50% in the diesel oil, so the key to controlling the sulfide emission is to solve the problem of removing the thiophene organic sulfur.

hydrodesulfurization is a widely used and well developed desulfurization process in industrial production today. Hydrodesulfurization is to convert organic sulfur difficult to remove into H easy to remove by adding hydrogen under certain conditions and carrying out a series of reactions₂S or other sulfides. It can effectively remove inorganic sulfur and simple organic sulfur compounds, and the removal efficiency of the condensed ring thiophene sulfur-containing compounds and the derivatives thereof is not high. At the same time, since the wholeThe reaction has high requirements on temperature and pressure, increases the difficulty and investment of the reaction, is also a main problem existing in the prior hydrodesulfurization, and restricts the application range of the hydrodesulfurization.

conventional hydrodesulfurization techniques have not been adapted to the deep desulfurization requirements. Therefore, effective and economical alternative deep desulfurization techniques, i.e., adsorption desulfurization, oxidative desulfurization, biological desulfurization, and the like, are actively developed in various countries throughout the world. Table 2 compares the advantages and disadvantages of these desulfurization methods applied to gasoline desulfurization.

TABLE 2 comparison of the different desulfurization methods applied to oil desulfurization

Compared comprehensively, the adsorption desulfurization has good industrial application prospect with great economic benefit.

The adsorption desulfurization is an effective desulfurization technology for selectively adsorbing sulfur-containing compounds by using selected adsorbents to separate the sulfur-containing compounds. The process is attractive because of low hydrogen consumption, low pressure operation, low investment and operating costs. Meanwhile, many adsorbents have the capability of removing polar compounds containing sulfur, oxygen or nitrogen, and have a wide selection range, and a considerable part of the adsorbents can be regenerated through desorption.

The adsorption desulfurization is roughly classified into: physical adsorption desulfurization and chemical adsorption desulfurization.

1. Physical adsorption desulfurization

The physical adsorption desulfurization is to select a proper adsorbent to combine with sulfide by utilizing the physical properties of the sulfide so as to achieve the aim of desulfurization. Van der waals forces are the primary forces for physisorption, with no electron transfer, and therefore no activation energy (if any) is required. The physical adsorption desulfurization can be multilayer adsorption, and the adsorption speed is high and reversible. The adsorbed molecules can be desorbed by increasing the temperature or reducing the partial pressure of the adsorbate. Therefore, the used adsorbent can be regenerated by flushing the desorption agent, and the organic sulfur compounds with high concentration are removed and recycled.

2. chemical adsorption desulfurization

The chemical adsorption desulfurization is to fix sulfur on an adsorbent by utilizing the chemical reaction between organic sulfide and the adsorbent so as to achieve the aim of desulfurization. The chemical adsorption desulfurization mainly takes the action of molecules on the surface caused by heteropolar or homopolar force, and simultaneously generates electron transfer or enables the adsorbed molecules to be split into atoms and free radicals, and certain activation energy is required. The chemical adsorption desulfurization is only single-layer adsorption, has certain selectivity and low adsorption speed. Since sulfur is usually fixed on the adsorbent in the form of sulfide, desorption and regeneration are difficult and recycling is difficult.

In actual production, in order to ensure the desulfurization rate, a chemical adsorbent with relatively large adsorption capacity needs to be selected. The physical properties of thiophene compounds are similar to those of oil products and coking benzene raw materials, and the thiophene compounds can be effectively removed by chemical adsorption, but the cost of industrial application is too high. In practical operation, physical adsorption can be performed by using an adsorbent with high selectivity, and the adsorbent with high selectivity is one of the main research directions of adsorption desulfurization.

currently, the most representative foreign adsorption desulfurization processes are IRVAD process, S-Zorb process and SARS process.

1. IRVAD process

the IRVAD process uses the polarity of sulfur atom, uses alumina base as adsorbent, and in moving bed, the raw material is adsorbed and recovered at the top of the tower, and the adsorbent is counter-currently contacted with sulfur-containing liquid, discharged from the bottom of the tower, and reacted with hot gas flow for regeneration.

The process does not need hydrogenation, has low requirements on temperature and pressure, and has mild operation conditions.

However, the adsorptive desulfurization performance of this process is limited by the capacity of the adsorbent, which adsorbs Dibenzothiophene (DBT) through the aromatic ring pi electron cloud, and the affinity of the adsorbent for organic sulfides, and thus the adsorption capacity of the adsorbent is small, and therefore, in order to effectively remove sulfides from diesel fractions, a large amount of adsorbent and multiple regenerations are required. In addition, the removed sulfur still exists in the form of sulfide, and if emission is needed, the sulfide must be further decomposed.

Due to the existence of these technical problems, the IRVAD process has not been able to meet the increasingly strict environmental requirements and has been gradually eliminated.

2. S-Zorb process

The adsorbent adopted by the S-Zorb process is formed by immobilizing zinc and other metal oxides on a suitable carrier, and can retain the structure of residual hydrocarbon while adsorbing sulfur atoms, which is the main idea of the S-Zorb gasoline desulfurization process design. The used adsorbent is oxidized by air and further treated in hydrogen for reuse.

The process utilizes a bubbling bed adsorption reactor and an on-line regeneration system, allows much longer run lengths than a typical fixed bed, and does not place very high requirements on reactor size and wall thickness. Practice proves that the process can remove about 98 percent of sulfur in gasoline, so that the process has good effect of removing the thiophene organic sulfur.

However, the process is operated at conditions which are more severe than those of the IRVAD process, and if the desulfurization criteria are to be met, the temperature must be controlled at 340-410 deg.C and the hydrogen pressure at 2-20 bar. Therefore, although the process is applied to the industrial stage, the process is only suitable for refining oil products, and has limitations for operations requiring normal temperature and pressure (such as desulfurization of fuel cells).

3. SARS technology

The SARS process is a selective adsorption desulfurization which can be operated at normal temperature and pressure. It is important to design an adsorbent that can selectively react with the low sulfur content components. The process utilizes the fixed-point adsorption of sulfur and an adsorbent to replace the original complexation, so that the adsorbent can separate thiophene sulfides and can retain aromatic compounds.

The process does not need hydrogenation, has low operation requirement and adopts a fixed bed reactor. Aiming at the condition of lower content of thiophene in the feed, the method has good treatment effect. At present, the process has been successful in the laboratory range, and the research focus will also focus on the scale-up of the experiment and the development of high efficiency adsorbents.

The 3 processes are relatively representative adsorption desulfurization processes in recent foreign countries and have respective characteristics. The IRVAD process is a fluidized bed adsorption desulfurization process, and has the disadvantages of complex process, high desulfurization efficiency and low processing cost. The S-Zorb process is a fluidized bed adsorption desulfurization process in a hydrogen state, and the process is more complicated than the IRVAD process, but the desulfurization efficiency is higher, and the raw material application range is wide. The SARS process is a fixed bed adsorption desulfurization process, and has the advantages of simple process, easy operation, low investment and operation cost, but requires the adsorbent to have higher sulfur capacity and easy regeneration, so as to prolong the adsorption-regeneration operation period.

In China, the research on the deep desulfurization of diesel oil is still in the stage of just starting, and most of the research is still in the small test or pilot test stage. However, gasoline low-cure to no-cure will be a necessary trend to develop, and efforts are therefore made to achieve gasoline low-cure to no-cure industrial applications.

In the research process of the catalytic cracking gasoline adsorption desulfurization process, A refining research institute of Luoyang petrochemical engineering company develops an LADS-A type adsorbent, the feasibility of the adsorbent is verified through A gas-liquid phase fixed bed test, the adsorbent can be regenerated by matching with the use of an LADS-D desorption agent, and in A pilot test experiment of A service life prolonging port, the refined catalytic cracking gasoline can reach the national standard through the circulation of an adsorption stage, A purging intermediate oil stage and A desorption stage. However, compared with foreign technologies, the technology has a certain gap in the sulfide removal capacity.

The key of the adsorption desulfurization technology is the selective adsorption performance, adsorption capacity and effective regeneration method of the adsorbent to sulfide in diesel oil.

Adsorbents are solid substances that can effectively adsorb one or more components from a gas or liquid phase. Adsorbents generally have the following characteristics:

1. The surface groups have large specific surface, rich pores and proper pore structure, and are beneficial to adsorption;

2. Does not react with adsorbate and medium, and does not evaporate, sublimate and dissolve under adsorption condition;

3. Has good thermal stability and mechanical strength, and is easy to manufacture and recycle.

Adsorbents can be broadly classified into two broad categories, non-polar and polar, depending on the surface properties. The former mainly comprises carbonaceous materials such as activated carbon, activated carbon fibers and carbon molecular sieves, and the latter mainly comprises silica gel, molecular sieves, activated alumina and the like.

1. Activated carbon

The active carbon has large specific surface area, good pore structure, abundant surface groups, high-efficiency desulfurization capability and the performance of loading other active ingredients. Can be used as carrier to prepare high-dispersion adsorbent, and has low cost and abundant resources.

Velu et al adsorbed to remove diesel fuel simulated by 220ppm 4, 6-dimethyldibenzothiophene, n-heptane and hexadecane using activated carbon loaded with transition metal oxides. The result shows that the 4, 6-dimethyldibenzothiophene can be completely removed when the adsorption temperature of the fixed bed is 60 ℃. Calculation of the adsorption breakthrough curve shows that 12.6mg of sulfur can be adsorbed per gram of adsorbent. Subsequently, Velu et al examined the performance of the adsorbent regenerated by washing with a 1:1 mixture of methanol and toluene at 70 ℃. From the desorption curve, only 20ml of solution was required to remove most of the sulfur per gram of adsorbent. However, to completely remove all sulfides from this adsorbent under the experimental conditions, 50-80ml of solution was required for washing. The washed adsorbent was further purged with nitrogen at 300 ℃ for 1 hour at a flow rate of 40ml/min to remove adsorbed solution molecules. The regenerated adsorbent is used for desulfurization again under the same experimental conditions, and the penetration curve of the regenerated adsorbent is consistent with that before regeneration, which shows that the solution washing regeneration effect is good.

Arturo J and the like use a Cu (I) -Y type molecular sieve to adsorb and remove sulfides in fuel oil, and a section of activated carbon bed layer is added in front of a Cu (I) -Y type molecular sieve bed layer to serve as a protective layer of the Cu (I) -Y type molecular sieve. Experimental results show that the adsorption desulfurization performance of the Cu (I) -Y type molecular sieve can be greatly improved by adopting the activated carbon bed layer as a protective layer. For example, IJ treats 14.7ml of gasoline with an initial sulfur concentration of 335ppm down to "zero sulfur" per gram of Cu (I) -Y type molecular sieve adsorbent. When activated carbon was used as the protective layer, 1g of a bed of activated carbon in combination with a Cu (I) -Y molecular sieve I gave 19.6ml of "zero sulfur" gasoline, and 1g of an adsorbent bed of the same combination was able to treat 34.3ml of diesel.

These research works show that the activated carbon has a certain adsorption and removal capacity for sulfides in diesel oil, but the adsorption capacity of the activated carbon for thiophene sulfides in diesel oil is not very large, and the requirement of industrial production operation cost cannot be met. Current research is focused primarily on the adsorption of inorganic sulfur, mercaptans and thioethers.

2. Molecular sieves

The zeolite molecular sieve is a crystal of a three-dimensional aluminosilicate metal structure formed by a silicon-aluminum tetrahedron, and is a strong polar adsorbent with uniform pore size. It is one of the most commonly used thiophene adsorbents, and has very high selective adsorption and separation capacity after being exchanged by different metal cations or modified by other methods by utilizing the physical and chemical characteristics of the thiophene adsorbent, such as specific surface area, pore size, acidity and alkalinity, polarity and the like. The polarity of the molecular sieve gradually decreases with increasing Si/Al ratio. The most commonly used synthetic molecular sieves in industry are type A, X, Y, L, mordenite, ZSM series molecular sieves, and the like.

The composition of the molecular sieve is a non-stoichiometric compound, the framework elements and the cationic elements of which can be replaced by adjacent elements in the same period, for example: molecular sieves of the aluminum silicate type use phosphorus instead of silicon to form molecular sieves of the aluminum phosphate type, others are: li⁺、Mg²⁺、Mn²⁺、Fe²⁺、Zn²⁺、Co²⁺、Be²⁺、B³⁺、Al³⁺、Fe³⁺、Ga³⁺and tetravalent Si, Ge, Ti and As⁵⁺、P⁵⁺Introducing 13 elements into the molecular sieve skeleton can form various structures with different performances to meet various special requirements.

The molecular sieve is mainly used for removing thiophene compounds with lower content, such as deep desulfurization of gasoline, and has higher requirement on feeding, so that the molecular sieve has certain limitation in application.

The thiophene organic sulfur is removed based on the complex generated by the metal ions and the thiophenic compounds, so that the proper metal ions are selected to modify the molecular sieve or change the acidity of the adsorbent, and the adsorption efficiency of the adsorbent can be really improved.

However, modified adsorbents are still a few used industrially for various reasons, such as cost, equipment manufacturing and use techniques.

Meanwhile, due to modification, desorption conditions of the molecular sieve become harsh and are difficult to recycle.

3. Activated alumina

The metal oxide (mainly active alumina) has certain adsorption capacity to thiophene compounds. Thiophene organic sulfides and Ag⁺The metal ions can form pi complex, and the complex is adsorbed by alumina without hydrogen consumption or high temperature and high pressure.

The activated alumina is a polar adsorbent, is an amorphous porous structure substance of a partial hydrate, and not only contains amorphous gel, but also contains a rigid skeleton structure formed by hydroxide crystals. Jeevanadam et Al modify the surface of a nano alumina crystal as an adsorbent to form Ag-AP-Al₂O₃And carrying out adsorption test on the thiophene compound by using the product. Experiments prove that the modified Ag-AP-Al₂O₃The Ag in the material is in a Lewis acid position and plays a role of a thiophene adsorption center, so that the material has better adsorption capacity.

However, the activated alumina is commonly used in the production process of gas, oil products and petrochemical products, and after the activated alumina is recycled, the physicochemical property of the activated alumina is not changed greatly, so that the activated alumina is not used for removing thiophene sulfides in diesel oil.

Disclosure of Invention

The invention aims to provide a supported adsorbent with larger adsorption capacity to thiophene sulfides in diesel oil and a method for preparing the supported adsorbent, which can meet the requirement of industrial production and operation cost.

In order to achieve the above object, the present invention adopts the following technical solutions:

The load type adsorbent for adsorbing thiophene sulfides in oil products consists of a carrier and an active component, and is characterized in that the carrier is 15 wt% of H₂O₂Or 15 wt% of HNO₃Modified active carbon, wherein the active component is NiCl₂And mixing the carrier and the active component according to the mass ratio of 2:1, and preparing the load type adsorbent by a dry-mixing roasting method.

The load type adsorbent for adsorbing the thiophene sulfides in the oil product is characterized in that the activated carbon is coconut shell activated carbon or coal-made activated carbon.

The preparation method of the load type adsorbent for adsorbing the thiophene sulfides in the oil product is characterized by comprising the following steps of:

Step 1: grinding active carbon, weighing a certain amount of active carbon, and then respectively pouring 15 wt% of H into beakers filled with the active carbon₂O₂And 15 wt% HNO₃Fully mixing until no bubbles exist, heating to 80 ℃, keeping the temperature until the solution is completely volatilized, cleaning with distilled water until the pH value of the cleaning solution is basically consistent with that of the distilled water, and finally drying in an oven at 115 ℃ for later use;

Step 2: subjecting to 15 wt% of H₂O₂Or 15 wt% of HNO₃Modified active carbon and active component NiCl₂Mixing the materials according to the mass ratio of 2:1, and then preparing the supported adsorbent by a dry-mixing roasting method.

The method is characterized in that in Step1, the ground activated carbon is sieved by a 60-80 mesh sieve.

The method described above is characterized in that in Step2, the baking temperature is 400 ℃ and the baking time is 4 hours.

The invention has the advantages that:

(1) The pore structure and pore shape of the adsorbent have great influence on the adsorption performance, and the active carbon is treated with 15 wt% of H₂O₂or HNO₃After modification, the modified product has huge specific surface area, dense pore structure and more poresThe surface functional group has developed pores and large adsorption capacity, so the load-type adsorbent provided by the invention has large adsorption capacity on thiophene sulfides in diesel oil, and the removal rates of thiophene-n-octane respectively reach 65.58% and 70.54%;

(2) The production cost is reduced, and the requirement of industrial production operation cost can be met.

Detailed Description

The present invention will be described in detail with reference to the following embodiments.

The load type adsorbent consists of a carrier and an active component. The type of the carrier and the type of the active component both have great influence on the desulfurization effect of the adsorbent.

under the conditions of no need of high temperature and high pressure and no need of hydrogen consumption, the optimum adsorbent is prepared by taking the removal degree of thiophene in n-octane as a research target from the aspects of carrier type and active component type so as to achieve the aim of realizing deep desulfurization under mild conditions.

A carrier

1. Hollow alumina

the preparation method comprises the following steps:

(1) Taking 37.5gAl (NO)₃)₃·9H₂Dissolving O (0.1mol) in 50ml of deionized water, and after the O is completely dissolved, dropwise adding 127ml of 2.5mol/L ammonia water solution at the flow rate of 5ml/min to obtain sol;

(2) Filtering and separating the obtained sol, and repeatedly washing the sol with deionized water until the filtrate is neutral to obtain a filter cake;

(3) Transferring the obtained filter cake into a beaker, adding deionized water to make the mixed volume about 100ml, transferring the filter cake into a constant temperature tank, stirring at 80 ℃ under reflux, and adding 10ml of nitric acid solution with the concentration of 1mol/L to make H⁺/Al³⁺Stirring at 80 deg.c for over 6 hr to obtain 1mol/L boehmite sol with fresh pH 4.0;

(4) Weighing 11.6g P123, 9.1g CTABr, 25.2g F127, 17.2g sucrose, 30.0g polyethylene glycol 6000, 10.0g polyethylene glycol 10000, 21.04g citric acid, 20g polyacrylamide and 30g carboxymethyl cellulose, respectively dissolving in a small amount of water, stirring at 35 ℃ to completely dissolve, adding into boehmite sol, wherein the numbers of LJP123, LJCTABr, LJF127, LJZT, LJJYEC6000, LJJYEC10000, LJNMS, LJBXXA and LJJJJJJJJJXWS are respectively;

(5) and (3) aging the obtained product at room temperature for 3h, drying the product in a 110 ℃ oven, then transferring the product into a muffle furnace for roasting at the constant temperature of 500 ℃ for 4h, and then uniformly grinding the obtained product.

2. Modified activated carbon

The preparation method comprises the following steps:

Activated carbon (coconut shell activated carbon is noted as AC)₁And the coal-based activated carbon is noted as AC₂) Grinding, collecting 60-80 mesh granules, weighing a certain amount of 60-80 mesh active carbon, and adding 15 wt% of H into a beaker filled with active carbon₂O₂and 15 wt% HNO₃Fully mixing until no air bubble exists, heating to 80 ℃, keeping the temperature until the solution is completely volatilized, cleaning with distilled water until the pH value of the cleaning solution is basically consistent with that of the distilled water, and finally drying in an oven at 115 ℃ for later use. Respectively marking the modified coconut shell activated carbon as AC₁(H₂O₂) And AC₁(HNO₃) The modified coal-based activated carbon is respectively marked as AC₂(H₂O₂) And AC₂(HNO₃)。

3. ZSM-5 molecular sieve

ZSM-5(50) catalyst from Tianjin Nankai university.

ZSM-5(38) catalyst from Tianjin Nankai university.

ZSM-5(25) catalyst from Tianjin Nankai university.

II, active component

1. Cuprous chloride

Analytically pure (more than or equal to 97.0 percent) red rock reagent factory in Hedong district in Tianjin city.

2. Copper chloride

Analytically pure (more than or equal to 99.0 percent) in a chemical reagent factory of Xian.

3. Nickel chloride

Analytically pure (more than or equal to 98.0 percent) in a chemical reagent factory of Xian.

Thirdly, preparing the load type adsorbent

In the invention, a dry-mixing roasting method which is simple and simple in process is adopted to prepare the supported adsorbent.

1. Mechanism of dry mix roasting process

The active ingredient is dispersed on the surface of the carrier in a single layer, which is a quite common phenomenon and spontaneous process, when the active ingredient is dispersed on the carrier with high specific surface, the total free energy of the system (including both the active ingredient and the carrier) is reduced due to the dispersion, because the dispersion is a process that the salt or oxide is changed from an ordered crystalline phase to a two-dimensional single-layer dispersion state, the degree of disorder is greatly increased, and the entropy is greatly increased, and meanwhile, the salt or oxide is dispersed in a single layer, can form quite strong surface bonds (which can be regarded as surface ionic bonds) with the surface of the carrier, and has small difference with the original chemical bond strength in the crystal interior, so that the enthalpy is not greatly changed. The entropy increases and the enthalpy does not change much, resulting in a decrease in the total free energy of the system.

2. Operation method of dry mixing roasting

The carrier and the active component are mixed according to the mass ratio of 2:1, and then baked for 4 hours in a muffle furnace at 400 ℃ in a nitrogen atmosphere.

In this embodiment, the carrier is used in an amount of 3g and the active ingredient in an amount of 1.5 g.

Fourthly, observing the effect of various load type adsorbents on adsorbing thiophene-n-octane

1. Preparing a standard solution of thiophene-n-octane

0.766g of thiophene is weighed into a 500ml volumetric flask, diluted to the scale by n-octane, 50ml of the solution is taken into a 250ml volumetric flask, and diluted to the scale by n-octane for later use.

2. Static adsorption

Accurately weighing 0.5g of prepared supported adsorbent, putting the adsorbent into a conical flask, adding 10ml of thiophene-n-octane standard solution, adsorbing for 12 hours at normal temperature and normal pressure, and filtering out the adsorbent for later use.

3. Adsorption results

TABLE 3 Supported adsorbents and their effect on the adsorption of thiophene-n-octane

4. Comparison of adsorption Effect

(1) Comparison between identical active Components

The thiophene-n-octane removal ratio in table 3 shows that:

(a) For the supported adsorbent with CuCl as the active component, four preferred adsorbents and their ordering are (expressed as carriers): AC₁(HNO₃)＞AC₁(H₂O₂)＞AC₂(H₂O₂)＞LJJYEC6000；

(b) For the active ingredient CuCl₂The four preferred adsorbents and their ordering are (expressed as carriers): AC₁(H₂O₂)＞AC₁(HNO₃)＞ZSM-5(50)＞LJCTABr；

(c) For the active component NiCl₂The four preferred adsorbents and their ordering are (expressed as carriers): AC₁(H₂O₂)＞AC₁(HNO₃)＞AC₂(HNO₃)＞AC₂(H₂O₂)。

It can be seen that under the same operation conditions, the adsorption desulfurization effects of the loaded adsorbents with the same active components but different carriers are greatly different, wherein the desulfurization performance of the loaded adsorbent using the modified activated carbon as the carrier is obviously higher than that of other adsorbents, and the desulfurization effect of the loaded adsorbent using the modified activated carbon as the carrier is the best in general terms, and then the loaded adsorbent using the ZSM-5 molecular sieve as the carrier and the loaded adsorbent using the hollow alumina as the carrier are the second.

Subsequently we modified the Activated Carbon (AC)₁(H₂O₂)、AC₁(HNO₃)、AC₂(H₂O₂)、AC₂(HNO₃) On the basis of the composition) for comparison of different active ingredients.

(2) Comparison between identical vectors

Based on the results of comparison between the same active components, the removal rate of thiophene-n-octane in table 3 is known as follows:

(a) For the carrier AC₁(H₂O₂) The three adsorbents are ordered as (expressed as active components): NiCl₂＞CuCl＞CuCl₂；

(b) For the carrier AC₁(HNO₃) The three adsorbents are ordered as (expressed as active components): NiCl₂＞CuCl＞CuCl₂；

(c) for the carrier AC₂(H₂O₂) The three adsorbents are ordered as (expressed as active components): CuCl > NiCl₂＞CuCl₂；

(d) For the carrier AC₂(HNO₃) The three adsorbents are ordered as (expressed as active components): NiCl₂＞CuCl＞CuCl₂。

It can be seen that under the same operation conditions, the difference of adsorption desulfurization effect is larger for the loaded adsorbents with the same carrier (all modified activated carbon) but different active components, wherein AC is used₁(H₂O₂) As carrier, NiCl₂Supported adsorbents as active component (product number: AC)₁(H₂O₂)-0.5NiCl₂) The adsorption desulfurization effect is the best, the removal rate of the thiophene-n-octane reaches 70.54 percent, and AC is used₁(HNO₃) As carrier, NiCl₂Supported adsorbents as active component (product number: AC)₁(HNO₃)-0.5NiCl₂) Has a secondary effect of adsorption desulfurization, but thiophene-n-octaneThe removal rate of the alkane also reaches 65.58 percent.

Fifthly, determining the optimal supported adsorbent for adsorbing the thiophene sulfides in the diesel oil and the preparation method thereof

By comparing the effect of adsorbing thiophene-n-octane with each supported adsorbent, it can be seen that the activated carbon was modified (with 15 wt% of H, respectively)₂O₂Solution modified, 15 wt% HNO₃Solution modification) as carrier and NiCl₂Adsorbents as active components (individually denoted as Via H)₂O₂Modified supported adsorbents, HNO₃Modified supported sorbent) is optimal.

1. Preparation of warp H₂O₂modified supported adsorbents

Activated carbon (coconut shell activated carbon is noted as AC)₁And the coal-based activated carbon is noted as AC₂) Grinding, collecting 60-80 mesh granules, weighing a certain amount of 60-80 mesh active carbon, and adding 15 wt% of H into a beaker filled with active carbon₂O₂Fully mixing until no air bubble exists, heating to 80 ℃, keeping the temperature until the solution is completely volatilized, cleaning with distilled water until the pH value of the cleaning solution is basically consistent with that of the distilled water, and finally drying in an oven at 115 ℃ to obtain the modified activated carbon AC₁(H₂O₂) And AC₂(H₂O₂) (carrier) for use.

Mixing carrier with active component NiCl₂Mixing according to the mass ratio of 2:1, and then baking in a muffle furnace under the protection of nitrogen at the baking temperature of 400 ℃ for 4 h.

2. Preparation of HNO₃Modified supported adsorbents

Activated carbon (coconut shell activated carbon is noted as AC)₁And the coal-based activated carbon is noted as AC₂) Grinding, collecting 60-80 mesh granules, weighing a certain amount of 60-80 mesh active carbon, and adding 15 wt% of HNO into a beaker filled with active carbon₃Fully mixing until no air bubble exists, heating to 80 ℃, keeping the temperature until the solution is completely volatilized, cleaning with distilled water until the pH value of the cleaning solution is basically consistent with that of the distilled water, and finally drying in an oven at 115 ℃ to obtain the modified activated carbonAC₁(HNO₃) And AC₂(HNO₃) (carrier) for use.

Mixing carrier with active component NiCl₂Mixing according to the mass ratio of 2:1, and then baking in a muffle furnace under the protection of nitrogen at the baking temperature of 400 ℃ for 4 h.

the pore structure and pore shape of the adsorbent have great influence on the adsorption performance, and the active carbon is treated with 15 wt% of H₂O₂Or HNO₃After modification, the modified desulfurization adsorbent has a huge specific surface area, a dense pore structure and more surface functional groups, developed pores and large adsorption capacity, so that a good adsorption desulfurization effect is shown.

In addition, because the activated carbon has a special carbon structure, the pores of the supported adsorbent taking the activated carbon as the carrier have the characteristic of slit type, which is obviously different from the pores of other types of adsorbents, thereby showing better desulfurization effect.

It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.

Claims (5)

1. The load type adsorbent for adsorbing the thiophene sulfides in the oil product consists of a carrier and an active component, and is characterized in that the carrier is 15 wt% of H₂O₂Or 15 wt% of HNO₃The active component of the modified active carbon is NiCl₂And mixing the carrier and the active component according to the mass ratio of 2:1, and preparing the load type adsorbent by a dry-mixing roasting method.

2. The supported adsorbent for adsorbing thiophenic sulfides in oil according to claim 1, wherein said activated carbon is coconut shell activated carbon or coal-made activated carbon.

3. A process for preparing a supported adsorbent for adsorbing thiophenic sulfides in oils according to claim 1 or 2, comprising the steps of:

Step 1: grinding active carbon, weighing a certain amount of active carbon, and then respectively pouring 15 wt% of H into beakers filled with the active carbon₂O₂And 15 wt% HNO₃fully mixing until no bubbles exist, heating to 80 ℃, keeping the temperature until the solution is completely volatilized, cleaning with distilled water until the pH value of the cleaning solution is basically consistent with that of the distilled water, and finally drying in an oven at 115 ℃ for later use;

Step 2: subjecting to 15 wt% of H₂O₂Or 15 wt% of HNO₃Modified active carbon and active component NiCl₂Mixing the materials according to the mass ratio of 2:1, and then preparing the supported adsorbent by a dry-mixing roasting method.

4. The method of claim 3, wherein the milled activated carbon is passed through a 60-80 mesh screen in Step 1.

5. The method according to claim 3, wherein in Step2, the baking temperature is 400 ℃ and the baking time is 4 h.