CN104741071A - Preparation method of attapulgite-based nano compound desulfurizer - Google Patents

Abstract

The invention belongs to the field of gasoline deep desulfurization, relates to deep adsorption desulfurization technology, in particular to a preparation method of an attapulgite nano-composite desulfurization adsorbent with high selectivity, large sulfur capacity and deep desulfurization effect. Load nano-scale manganese dioxide and titanium dioxide on the surface of attapulgite to prepare titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier, and then load nano-nickel oxide and nano-silver to prepare attapulgite-based nanocomposite gasoline desulfurizer Finally, under the action of hydrogen, the nickel oxide and manganese dioxide in the precursor are respectively reduced to nano-nickel and nano-manganese monoxide to obtain Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer.

Description

Preparation method of attapulgite-based nanocomposite desulfurizer

technical field

The invention belongs to the field of gasoline deep desulfurization, relates to deep adsorption desulfurization technology, in particular to a preparation method of an attapulgite nano-composite desulfurization adsorbent with high selectivity, large sulfur capacity and deep desulfurization effect.

Background technique

In the 21st century, people pay more and more attention to environmental protection. SO _x produced by the combustion of sulfur-containing gasoline is one of the main pollutants that pollute the air, especially SO ₂ in the atmosphere can cause a variety of respiratory organ diseases and induce cardiovascular diseases, and SO _x is the main cause of acid rain. At present, countries around the world strictly control the sulfur content in fuel oil, so the production of low-sulfur gasoline or even sulfur-free gasoline is a hot spot in the refining industry today.

Gasoline desulfurization technology can be simply divided into hydrodesulfurization (HDS) and non-hydrodesulfurization. HDS must be carried out under the conditions of high temperature and high pressure, not only the device investment and operating costs are huge, but also the octane number of gasoline will be greatly lost. Non-hydrogenation desulfurization technologies include adsorption desulfurization, biological desulfurization, oxidation desulfurization and extraction desulfurization. Among them, adsorption desulfurization has the advantages of mild operating conditions, low investment and operating costs, simple process flow, and selective adsorption of organic sulfides to reduce the loss of octane number. It is known as the most promising desulfurization technology for the production of sulfur-free gasoline in the future.

Contents of the invention

Purpose of the invention: In order to overcome the problems existing in the desulfurization adsorbents in the prior art, the present invention provides an attapulgite-based nanocomposite desulfurizer with controllable active component size, high selectivity, large sulfur capacity, and deep desulfurization effect (attapulgite nanocomposite desulfurization adsorbent) and its preparation method.

The technical scheme adopted in the present invention is:

First, nano-scale manganese dioxide and titanium dioxide are loaded on the surface of attapulgite to prepare titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier, and then nano-nickel oxide and nano-silver are loaded to prepare attapulgite-based nanocomposite gasoline desulfurizer The precursor, and finally under the action of hydrogen, the nickel oxide and manganese dioxide in the precursor are respectively reduced to nano-nickel and nano-manganese monoxide to obtain Ni-Ag/TiO ₂ /MnO/attapulgite, which is an efficient attapulgite The rod stone nanocomposite desulfurization adsorbent can produce deep removal effect on sulfides in gasoline, especially thiophenes. The adsorbent has the characteristics of controllable active component size, high selectivity, and large sulfur capacity, and has deep desulfurization effect. The attapulgite nanocomposite desulfurization adsorbent provided by the present invention, based on the total mass of the desulfurizer, comprises the following composition: 5.5-28% of nickel and silver, 1-5.5% of titanium dioxide, 30-60% of manganese monoxide, and attapulgite Stone 20-50%, wherein the molar ratio of nickel and silver is 40-10:1.

The specific steps of the preparation method of the above-mentioned attapulgite-based nanocomposite desulfurizer are:

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite support

First, mix the potassium permanganate solution and the attapulgite slurry evenly to obtain a mixed slurry, then add a mixed solution of titanium tetrachloride and manganese sulfate to the mixed slurry, and then heat up to 80-150°C for 2- 5h, add alkali solution, adjust pH=6～8, filter, wash, dry to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier,

Wherein, the molar ratio of potassium permanganate to manganese sulfate is 2-5:1, and in the attapulgite slurry, the attapulgite concentration is 50-150g/L,

In the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:6.1～68, wherein, the concentration of titanium tetrachloride is 0.01～0.1mol/L,

The alkaline solution is one of ammonium bicarbonate solution, potassium carbonate solution, sodium carbonate solution or ammonia water, with a concentration of 0.5-3mol/L;

(2) Preparation of attapulgite nanocomposite desulfurization adsorbent precursor

Mix the aqueous solution of nickel nitrate and silver nitrate with the titanium dioxide/manganese dioxide/attapulgite nano-composite carrier obtained in step (1), stir for 3-10 hours, dry, and roast at 350-550°C for 1-5 hours to obtain attapulgite Stone nanocomposite desulfurization adsorbent precursor, namely NiO-Ag/TiO ₂ /MnO ₂ /attapulgite nanocomposite material,

In the mixed aqueous solution of nickel nitrate and silver nitrate, the molar ratio of nickel and silver is 40-10:1, and the amount of mixed aqueous solution of nickel nitrate and silver nitrate meets the total mass fraction of nickel and silver in the attapulgite nanocomposite desulfurization adsorbent. 28%, and the solvent in the mixed aqueous solution is deionized water, and the consumption is calculated by equal volume impregnation method, and the consumption of deionized water is the pore volume of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier;

(3) Reducing the attapulgite nanocomposite desulfurization adsorbent precursor obtained in step (2) in a hydrogen atmosphere with a pressure of 0.5 to 1.0 Mpa at 350 to 600° C. to obtain an attapulgite based nanocomposite desulfurizer , namely Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer,

The above-mentioned Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer, based on the total mass of the desulfurizer, includes the following composition: 5.5-28% of nickel and silver, 1-5.5% of titanium dioxide, and 30-60% of manganese monoxide , attapulgite 20-50%, wherein the molar ratio of nickel and silver is 40-10:1,

The attapulgite nano-composite desulfurization adsorbent precursor is reduced in a hydrogen atmosphere at 350-600°C (preferably, the reduction temperature is 450-550°C), and NiO and _MnO2 are respectively reduced to Ni and MnO to obtain the desired unevenness Palladium nanocomposite desulfurization adsorbent,

Wherein, the hydrogen-facing atmosphere is a hydrogen atmosphere, a mixed atmosphere of "hydrogen and nitrogen" or "hydrogen and helium", wherein in the mixed atmosphere of "hydrogen and nitrogen" or "hydrogen and helium", the hydrogen content is 10- 99vol%.

The present invention also provides a kind of method of gasoline desulfurization, and its concrete steps are:

Fully contact the sulfur-containing raw material with the attapulgite-based nanocomposite desulfurizer at a temperature of 320-500°C, a pressure of 0.5-2.0Mpa, a mass space velocity of 20-30 ^-h , and a hydrogen-oil ratio of 200-400, In this process, the attapulgite-based nano-composite desulfurizer fully absorbs the sulfur components in the raw material to obtain gasoline with a sulfur content of less than 10ppm, achieving the purpose of deep desulfurization.

Specifically, the hydrogen atmosphere is a hydrogen atmosphere or a mixed atmosphere of "hydrogen and nitrogen". In the mixed atmosphere, the hydrogen content is 10-99vol%.

The above pressure is the air pressure of the hydrogen atmosphere; the hydrogen-oil ratio is the volume hydrogen-oil ratio, that is, the ratio of the hydrogen flow rate after hydrogen mixing to the volume flow rate of the sulfur-containing raw material.

The attapulgite nano-composite desulfurization adsorbent provided by the present invention can be regenerated after use and inactivation, the regeneration condition is: temperature 300-550°C, and then the regenerated attapulgite-based nano-composite desulfurization agent is obtained according to the above step (3) .

The beneficial effects of the present invention are:

(1) The hydrochloric acid produced by the hydrolysis of titanium tetrachloride and the sulfuric acid produced by the reaction of potassium permanganate and manganese sulfate form a self-generated mixed acid, which can acidify the attapulgite and increase the acid center of the attapulgite bar without adding additional acid And adsorption active centers, improve the specific surface and pore volume of attapulgite, which is beneficial to the number of silicon hydroxyl groups of attapulgite crystal rods, and is conducive to the deposition of MnO ₂ nanosheets and TiO ₂ particles on the surface of attapulgite; at the same time, SO in mixed acid is self-generated ₄ ^2- It is conducive to the production of anatase phase TiO ₂ nanocrystals with smaller particle size, which improves the specific surface of titanium dioxide/manganese dioxide/attapulgite nanocomposite support;

(2) The present invention uses attapulgite as the basic carrier to prepare titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier, and grow _δMnO2 crystal form nanosheets in situ on the surface of one-dimensional rod-shaped attapulgite to effectively inhibit MnO The agglomeration of ₂ improves the dispersion state of MnO ₂ in the composite carrier and the specific surface of the composite carrier, enriches the pores of the composite carrier, and facilitates the impregnation of active components;

(3) the present invention adopts nickel nitrate and silver nitrate to impregnate in proportion, can influence the dispersed state of nickel and silver on composite carrier mutually, is conducive to forming the nickel and silver that particle is smaller;

(4) The attapulgite nano-composite desulfurization adsorbent provided by the present invention, that is, Ni-Ag/TiO ₂ /MnO/attapulgite, Ni, Ag and MnO have strong reducing properties, and can adsorb sulfide in gasoline with high selectivity , Ni-Ag/TiO ₂ /MnO components can produce synergistic adsorption effect on sulfide in gasoline. The adsorption principle is: Ni-Ag in the Ni-Ag/TiO _{2 /} MnO group can highly selectively adsorb sulfide in gasoline to form Ag ₂ S and NiS, and under the action of hydrogen, the sulfide in Ag ₂ S and Ni _x S Sulfur is transferred to MnO to form MnS, which restores Ni and Ag, and so on. At the same time, Ni-Ag/TiO ₂ has a certain hydrogenation catalytic activity, which can promote the hydrogenolysis reaction of sulfide to form H ₂ S, which is replaced by MnO Absorption to form MnS;

(5) In the present invention, the one-dimensional rod-shaped attapulgite is used as the basic carrier to grow in-situ δ MnO ₂ crystal-type nanosheet anatase phase TiO ₂ nanocrystals to form titanium dioxide/manganese dioxide with large specific surface area and abundant pores /Attapulgite nano-composite carrier, and then impregnate the active components with equal volume, so that the components of the obtained attapulgite nano-composite desulfurization adsorbent can be mixed evenly at the nanoscale;

(6) The attapulgite nanocomposite desulfurization adsorbent provided by the present invention has controllable active component size, high selectivity, low olefin saturation rate, large sulfur capacity and regenerability, and is suitable for deep desulfurization.

Detailed ways

In this experiment, the specific surface (S _BET ) and pore volume (V _Total ).

In this experiment, Japan Rigaku Company and D/max 2500PC X-ray diffractometer were used to analyze the structure and phase composition of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent.

In this experiment, a fixed-bed micro-reactor experimental device was used to evaluate the desulfurization performance of the attapulgite nanocomposite desulfurization adsorbent in the examples and comparative examples. The specific conditions are based on the gasoline desulfurization method provided by the present invention. And the RPP-2000S fluorescent sulfur analyzer was used to measure the sulfur content in gasoline.

This experiment refers to the national standard GB/T11132-2008 "Determination of Hydrocarbons in Liquid Petroleum Products (Fluorescent Indicator Adsorption Method)" to determine the olefin content in gasoline before and after desulfurization.

The calculation method of desulfurization rate is:

Desulfurization rate = (1 - sulfur content of desulfurized gasoline / sulfur content of raw gasoline) × 100%

Calculation method of olefin saturation rate:

Olefin saturation rate = (Olefin content in gasoline before desulfurization - Olefin content in gasoline after desulfurization) / Olefin content in gasoline before desulfurization

Gasoline yield:

Gasoline yield = (weight of gasoline before desulfurization - weight of gasoline after desulfurization) / weight of gasoline before desulfurization

The gasoline used in this experiment is self-prepared simulated gasoline, and the raw materials are ethanethiol, thiophene, benzothiophene, isopentene and cyclohexane. In the simulated gasoline, the sulfur provided by ethanethiol, thiophene and benzothiophene is 125ppm, of which ethanethiol is 10ppm, thiophene is 90ppm, and benzothiophene is 25ppm; the mass fraction of isopentene is 20% of the simulated gasoline, and the rest is cyclohexyl alkyl.

Example 1

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 2.5:1, take 33.4g potassium permanganate and add it to 160ml, 50g/L attapulgite rod In the stone clay slurry, mix evenly, then add 137.5ml of the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:6.1, and the concentration of titanium tetrachloride is 0.1mol/ L, then warming up to 80°C while keeping the temperature for 2 hours, adding 0.5mol/L ammonium bicarbonate solution, adjusting pH=6, filtering, washing, and drying to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier;

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 5ml deionized water according to the molar ratio of nickel and silver at 40:1, and stir evenly; The total mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 24.5% of the loading capacity and 6.85g of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1) are uniformly stirred for 3 hours, dried, and calcined at 350°C for 1 hour to obtain concavo-convex Palygorskite nanocomposite desulfurization adsorbent precursor;

(3) The attapulgite nano-composite desulfurization adsorbent precursor obtained in (2) is reduced for 10 hours in an atmosphere with a pressure of 0.5Mpa, 350°C, and a hydrogen volume content of 99% (the remaining 1% is nitrogen), to obtain The attapulgite nanocomposite desulfurization adsorbent, based on the total mass of the desulfurizer, includes the following composition: nickel and silver 24.5%, titanium dioxide 5.5%, manganese monoxide 30%, attapulgite 40%, wherein the molar ratio of nickel and silver is 40:1.

Table 1: Pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 1

Table 2: Phase composition and structure of each active component of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 1

Titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier is reduced by impregnation and roasting. The attapulgite nanocomposite desulfurization adsorbent TiO ₂ has little change in grain size. The grain size of Ni is within 20nm and that of Ag is within 10nm. within.

Example 2

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 2:1, take 34.8g potassium permanganate and add it to 67ml, 50g/L attapulgite rod In the stone clay slurry, mix evenly, then add 140.63ml of a mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:10, and the concentration of titanium tetrachloride is 0.08mol/ L, then heated up to 100°C and kept for 3h reaction, added 1.5mol/L potassium carbonate solution, adjusted pH=6.5, filtered, washed, dried to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier.

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 5ml deionized water according to the molar ratio of nickel and silver at 20:1, and stir evenly; The total mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 5.5% of the loading capacity and 6.67g of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1) are uniformly stirred for 5 hours, dried, and calcined at 400°C for 3 hours to obtain the concavo-convex The precursor of the nano-composite desulfurization adsorbent of the rod stone.

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 5 hours in a hydrogen-argon mixed atmosphere with a pressure of 0.75Mpa, 400°C, and a hydrogen content of 10% vol to obtain attapulgite nanocomposites. Composite desulfurization adsorbent, based on the total mass of desulfurizer, includes the following composition: nickel and silver 5.5%, titanium dioxide 4.5%, manganese monoxide 40%, attapulgite 50%, wherein the molar ratio of nickel and silver is 20:1 .

Table 3: Pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 2

Table 4: Phase composition and structure of each active component of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 2

Since the content of Ag in the attapulgite nanocomposite desulfurization adsorbent in Example 2 is very small, less than 3%, the Ag component cannot be detected by XRD.

Example 3

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 5:1, take 108.75g potassium permanganate and add it to 40ml, 100g/L attapulgite rod In the stone clay slurry, mix evenly, then add 100ml of the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:28.2, and the concentration of titanium tetrachloride is 0.05mol/L , and then heated up to 150° C. for 5 hours of heat preservation, added 3 mol/L ammonia solution, adjusted to pH=7.5, filtered, washed, and dried to obtain a titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier.

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 5ml deionized water according to the molar ratio of nickel and silver at 10:1, and stir evenly; The total mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 28% and the 7.04g titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1) is evenly stirred for 8 hours, dried, and calcined at 550°C for 4 hours to obtain the concavo-convex The precursor of the nano-composite desulfurization adsorbent of the rod stone.

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 3 hours in a hydrogen-helium mixed atmosphere with a pressure of 1.0Mpa, 600°C, and a hydrogen content of 50% vol to obtain attapulgite nanocomposites. Composite desulfurization adsorbent, based on the total mass of desulfurizer, includes the following composition: nickel and silver 28%, titanium dioxide 2%, manganese monoxide 50%, attapulgite 20%, wherein the molar ratio of nickel and silver is 10:1 .

Table 5: Pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 3

Table 6: Phase composition and structure of each active component of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 3

Since the content of TiO ₂ in the titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 3 is very small, less than 3%, XRD fails to detect the TiO ₂ component.

Example 4

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 3.5:1, take 93.5g potassium permanganate and add it to 42ml, 120g/L attapulgite rod In the stone clay slurry, mix evenly, then add 250ml of the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:68, and the concentration of titanium tetrachloride is 0.01mol/L , then raise the temperature to 90° C. and keep it warm for 4 hours, add 2.0 mol/L sodium carbonate solution, adjust the pH to 8.0, filter, wash, and dry to obtain a titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier.

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 6ml deionized water according to the molar ratio of nickel and silver at 25:1, and stir evenly; The common mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 14% of the loading capacity and 8.57g of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1) are uniformly stirred for 8 hours, dried, and calcined at 380°C for 5 hours to obtain concavo-convex The precursor of the nano-composite desulfurization adsorbent of the rod stone.

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours in a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain attapulgite nanocomposites. Composite desulfurization adsorbent, based on the total mass of desulfurizer, includes the following composition: nickel and silver 14%, titanium dioxide 1%, manganese monoxide 60%, attapulgite 25%, wherein the molar ratio of nickel and silver is 25:1 .

Table 7: Pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 4

Table 8: Phase composition and structure of each active component of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 4

Since the content of TiO ₂ in the titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Example 4 is very small, less than 3%, XRD fails to detect the TiO ₂ component.

Comparative example 1

The mixed solution of titanium tetrachloride and manganese sulfate in embodiment 4 is changed into manganese sulfate solution, prepares manganese dioxide/attapulgite nano-composite carrier, other operations are all the same as embodiment 4, and concrete operation steps are as follows:

(1) Preparation of manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 3.5:1, take 93.5g potassium permanganate and add it to 42ml, 120g/L attapulgite clay In the slurry, mix evenly, then add 250ml of 0.68mol/L manganese sulfate solution, then raise the temperature to 90°C and keep it warm for 4 hours, add 2.0mol/L sodium carbonate solution, adjust pH=8.0, filter, wash, and dry to obtain carbon dioxide Manganese/attapulgite nanocomposite carrier;

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 6ml deionized water according to the molar ratio of nickel and silver at 25:1, and stir evenly; The total mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 14% of the load, and the 8.70g manganese dioxide/attapulgite nanocomposite carrier in (1) is uniformly stirred for 8 hours, dried, and calcined at 380°C for 5 hours to obtain attapulgite Nanocomposite desulfurization adsorbent precursor;

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours in a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain attapulgite nanocomposites. The composite desulfurization adsorbent, based on the total mass of the desulfurizer, includes the following composition: nickel and silver 14%, manganese monoxide 60.6%, attapulgite 25.4%, wherein the molar ratio of nickel and silver is 25:1.

Table 9: Pore structure parameters of manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 1

Table 10: Phase composition and structure of active components of manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 1

Comparative example 2

Potassium permanganate is replaced by the potassium sulfate of equimolar amount in embodiment 4, prepares titanium dioxide/attapulgite nano-composite carrier, other operations are all the same as embodiment 4, and specific operation steps are as follows:

(1) Preparation of titanium dioxide/attapulgite nanocomposite carrier: According to the molar ratio of potassium sulfate and manganese sulfate of 3.5:1, take 102.97g of potassium sulfate and add it to 42ml, 120g/L attapulgite clay slurry, mix well , then add 250ml of mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:68, wherein the concentration of titanium tetrachloride is 0.01mol/L, and then heat up to 90°C for heat preservation reaction 4h, add 2.0mol/L sodium carbonate solution, adjust pH=8.0, filter, wash, and dry to obtain titanium dioxide/attapulgite nanocomposite carrier;

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 6ml deionized water according to the molar ratio of nickel and silver at 25:1, and stir evenly; The total mass fraction of the palygorskite nanocomposite desulfurization adsorbent is 14% and the 11.76g titanium dioxide/attapulgite nanocomposite carrier in (1) is uniformly stirred for 8 hours, dried, and calcined at 380°C for 5 hours to obtain the attapulgite nanocomposite Desulfurization adsorbent precursor;

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours in a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain attapulgite nanocomposites. Composite desulfurization adsorbent. Based on the total mass of the desulfurizer, it includes the following composition: nickel and silver 14%, titanium dioxide 3.3%, attapulgite 82.7%, wherein the molar ratio of nickel and silver is 25:1.

Table 11: Pore structure parameters of titanium dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 2

Table 12: Phase composition and structure of active components of titanium dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 2

Comparative example 3

The attapulgite slurry in Example 4 was replaced with an equal volume of deionized water to prepare a titanium dioxide/manganese dioxide nanocomposite carrier. Other operations were the same as in Example 4, and the specific steps were as follows:

(1) Preparation of titanium dioxide/manganese dioxide nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 3.5:1, take 93.5g potassium permanganate and add it to 42ml deionized water, mix well, then add tetrachloride The mixed solution of titanium and manganese sulfate is 250ml, the molar ratio of titanium tetrachloride and manganese sulfate is 1:68, the concentration of titanium tetrachloride is 0.01mol/L, and then the temperature is raised to 90°C and the reaction is kept for 4 hours, and 2.0mol /L sodium carbonate solution, adjust pH=8.0, filter, wash, and dry to obtain titanium dioxide/manganese dioxide nanocomposite carrier;

(2) Preparation of nanocomposite desulfurization adsorbent precursor: nickel nitrate and silver nitrate are dissolved in 6ml deionized water at a molar ratio of nickel and silver of 25:1, and stirred evenly; The mass fraction in is 14% and the 46.15g titanium dioxide/manganese dioxide nano-composite carrier in (1) is uniformly stirred for 8 hours, dried, and roasted at 380°C for 5 hours to obtain the precursor of the composite desulfurization adsorbent, wherein the If the titanium dioxide/manganese dioxide nanocomposite carrier has insufficient quality, it can be prepared according to (1);

(3) The composite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours under a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain a composite desulfurization adsorbent. Based on the total mass, it includes the following composition: nickel and silver 14%, titanium dioxide 1.4%, manganese monoxide 84.6%, wherein the molar ratio of nickel and silver is 25:1.

Table 13: Pore structure parameters of titanium dioxide/manganese dioxide nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 3

Table 14: Phase composition and structure of active components of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 3

Since the content of TiO ₂ in the titanium dioxide/manganese dioxide nanocomposite carrier and the composite desulfurization adsorbent in Comparative Example 3 is very small, less than 3%, the TiO ₂ component cannot be detected by XRD.

Comparative example 4

The mixed solution of nickel nitrate and silver nitrate is changed into nickel nitrate solution in embodiment 4, and other operations are all identical with embodiment 4, and concrete operation steps are as follows:

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 3.5:1, take 93.5g potassium permanganate and add it to 42ml, 120g/L attapulgite rod In the stone clay slurry, mix evenly, then add 250ml of the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:68, and the concentration of titanium tetrachloride is 0.01mol/L , then heat up to 90° C. and keep warm for 4 hours, add 2.0 mol/L sodium carbonate solution, adjust pH=8.0, filter, wash, and dry to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier;

(2) Prepare attapulgite nano-composite desulfurization adsorbent precursor: nickel nitrate is dissolved in 6ml deionized water, stir well; Stir evenly for 8 hours with the 8.57g titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1), dry, and roast at 380°C for 5 hours to obtain the attapulgite nanocomposite desulfurization adsorbent precursor;

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours in a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain attapulgite nanocomposites. The composite desulfurization adsorbent, based on the total mass of the desulfurizer, includes the following composition: 14% nickel, 1% titanium dioxide, 60% manganese monoxide, and 25% attapulgite.

Table 15: Pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 4

Table 16: Phase composition and structure of each active component of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 4

Since the content of TiO ₂ in the titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 4 was very small, less than 3%, XRD could not detect the TiO ₂ component.

Comparative Example 5

The mixed solution of nickel nitrate and silver nitrate in embodiment 5 is changed into silver nitrate solution, and other operations are all identical with embodiment 4, and concrete operation steps are as follows:

(1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier: according to the molar ratio of potassium permanganate and manganese sulfate as 3.5:1, take 93.5g potassium permanganate and add it to 42ml, 120g/L attapulgite rod In the stone clay slurry, mix evenly, then add 250ml of the mixed solution of titanium tetrachloride and manganese sulfate, the molar ratio of titanium tetrachloride and manganese sulfate is 1:68, and the concentration of titanium tetrachloride is 0.01mol/L , then heat up to 90° C. and keep warm for 4 hours, add 2.0 mol/L sodium carbonate solution, adjust pH=8.0, filter, wash, and dry to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier;

(2) Preparation of the attapulgite nanocomposite desulfurization adsorbent precursor: silver nitrate is dissolved in 6ml deionized water, and stirred evenly; the above solution is 14% according to the mass fraction of silver in the attapulgite nanocomposite desulfurization adsorbent Stir evenly for 8 hours with the 8.57g titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier in (1), dry, and roast at 380°C for 5 hours to obtain the attapulgite nanocomposite desulfurization adsorbent precursor;

(3) The attapulgite nanocomposite desulfurization adsorbent precursor obtained in (2) is reduced for 8 hours in a hydrogen-nitrogen mixed atmosphere with a pressure of 0.6Mpa, 500°C, and a hydrogen content of 60% vol to obtain attapulgite nanocomposites. The composite desulfurization adsorbent, based on the total mass of the desulfurizer, includes the following composition: 14% silver, 1% titanium dioxide, 60% manganese monoxide, and 25% attapulgite.

Table 17 shows the pore structure parameters of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 5

Table 18: Phase composition and structure of active components of titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 5

Since the content of TiO ₂ in the titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier and attapulgite nanocomposite desulfurization adsorbent in Comparative Example 5 was very small, less than 3%, XRD could not detect the TiO ₂ component.

Application example 1

The attapulgite nano-composite desulfurization adsorbent obtained in the above-mentioned Example 1 is evaluated on the fixed-bed micro-reaction device for desulfurization performance evaluation. The gasoline used is the simulated gasoline prepared in the experiment. The operating conditions are: at a temperature of 320 ° C, a pressure of 1.0 MPa, The mass space velocity is 30 ^-h (per gram of attapulgite nano-composite desulfurization adsorbent, the gasoline to be desulfurized per hour is 30g, and so on in the following application examples), and the pure hydrogen atmosphere with a hydrogen-to-oil ratio of 200 runs for 12 hours , using the RPP-2000S fluorescent sulfur analyzer to measure the sulfur content of simulated gasoline after desulfurization.

Application example 2

The attapulgite nano-composite desulfurization adsorbent obtained in the above-mentioned Example 2 is evaluated on the fixed-bed micro-reaction device for desulfurization performance. The gasoline used is the simulated gasoline prepared in the experiment. The operating conditions are: at a temperature of 500 ° C, a pressure of 2.0 MPa, Mass space velocity 20 ^-h , hydrogen-oil ratio 400 pure hydrogen atmosphere, run for 12 hours, use RPP-2000S fluorescence sulfur determination instrument to measure the sulfur content of simulated gasoline after desulfurization.

Application example 3

The attapulgite nano-composite desulfurization adsorbent obtained in the above-mentioned embodiment 3 is evaluated on the fixed-bed micro-reaction device for desulfurization performance. The gasoline used is the simulated gasoline prepared in the experiment. The operating conditions are: at a temperature of 450 ° C, a pressure of 1.5 MPa, Mass space velocity 25 ^-h , hydrogen-nitrogen mixture gas with hydrogen-oil ratio 250, hydrogen content 10%, run for 12 hours, use RPP-2000S fluorescence sulfur determination instrument to measure the sulfur content of simulated gasoline after desulfurization.

Application example 4

The attapulgite nano-composite desulfurization adsorbent obtained in the above-mentioned Example 4 is evaluated on the fixed bed micro-reaction device for desulfurization performance evaluation, the gasoline used is the simulated gasoline prepared in the experiment, and the operating conditions are: at a temperature of 400 ° C, a pressure of 1.2 MPa, Mass space velocity 25 ^-h , hydrogen-nitrogen mixture gas with hydrogen-oil ratio 300, hydrogen content 50%, run for 12 hours, use RPP-2000S fluorescence sulfur determination instrument to measure the sulfur content of simulated gasoline after desulfurization.

Application example 5

The attapulgite nano-composite desulfurization adsorbent after desulfurization in Application Example 4 (in Example 4) was reused, and the same process as in Application Example 4 was used for desulfurization again, and the number of repetitions was 3 times.

Application example 6

The attapulgite nano-composite desulfurization adsorbent after desulfurization in Application Example 3 (in Example 3) is reused, and the same process as in Application Example 3 is used for desulfurization again, repeating once.

Application example 7

The attapulgite nano-composite desulfurization adsorbent after desulfurization in Application Example 2 (in Example 2) is reused, and the same process as in Application Example 2 is used for desulfurization again, repeating once.

Application example 8

The attapulgite nano-composite desulfurization adsorbent after desulfurization in Application Example 1 (in Example 1) was reused, and the same process as in Application Example 1 was used for desulfurization again, and repeated once.

Application example 9

Same as Application Example 4, except that the attapulgite nanocomposite desulfurization adsorbent in Example 4 is replaced by the adsorbent in Comparative Example 1.

Application Example 10

Same as Application Example 4, except that the attapulgite nanocomposite desulfurization adsorbent in Example 4 is replaced by the adsorbent in Comparative Example 2.

The attapulgite nano-composite desulfurization adsorbent after desulfurization in this application example (in comparative example 2) is reused, and the same process as in application example 4 is used for desulfurization again, and the number of repetitions is 2 times.

Application Example 11

Same as Application Example 4, except that the attapulgite nanocomposite desulfurization adsorbent in Example 4 is replaced by the adsorbent in Comparative Example 3.

Application Example 12

Same as Application Example 4, except that the attapulgite nanocomposite desulfurization adsorbent in Example 4 is replaced by the adsorbent in Comparative Example 4.

Application Example 13

Same as Application Example 4, except that the attapulgite nanocomposite desulfurization adsorbent in Example 4 is replaced by the adsorbent in Comparative Example 5.

Calculate the desulfurization rate, olefin saturation rate and gasoline yield in application examples 1-13, as shown in Table 19:

Table 19

Claims (10)

1. A preparation method of attapulgite-based nanocomposite desulfurizer, characterized in that: the preparation method is, at first, nano-scale manganese dioxide and titanium dioxide are loaded on the surface of attapulgite to obtain titanium dioxide/manganese dioxide/ Attapulgite nano-composite carrier, and then loaded with nano-nickel oxide and nano-silver to prepare the attapulgite-based nano-composite gasoline desulfurizer precursor, and finally reduce the nickel oxide and manganese dioxide in the precursor to nano Nickel and nano-manganese monoxide to obtain Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer, The Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer, based on the total mass of the desulfurizer, includes the following composition: 5.5-28% of nickel and silver, 1-5.5% of titanium dioxide, and 30-60% of manganese monoxide %, attapulgite 20-50%, wherein the molar ratio of nickel and silver is 40-10:1. 2. A preparation method of attapulgite-based nanocomposite desulfurizer, characterized in that: the specific steps of the preparation method are, (1) Preparation of titanium dioxide/manganese dioxide/attapulgite nanocomposite support First, mix the potassium permanganate solution and the attapulgite slurry evenly to obtain a mixed slurry, then add a mixed solution of titanium tetrachloride and manganese sulfate to the mixed slurry, and then heat up to 80-150°C for 2- 5h, add alkali solution, adjust pH = 6-8, filter, wash and dry to obtain titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier; (2) Preparation of attapulgite nanocomposite desulfurization adsorbent precursor Mix the aqueous solution of nickel nitrate and silver nitrate with the titanium dioxide/manganese dioxide/attapulgite nano-composite carrier obtained in step (1), stir for 3-10 hours, dry, and roast at 350-550°C for 1-5 hours to obtain attapulgite Stone nanocomposite desulfurization adsorbent precursor, namely NiO-Ag/TiO ₂ /MnO ₂ /attapulgite nanocomposite; (3) Reducing the attapulgite nanocomposite desulfurization adsorbent precursor obtained in step (2) in a hydrogen atmosphere with a pressure of 0.5 to 1.0 Mpa at 350 to 600° C. to obtain an attapulgite based nanocomposite desulfurizer , namely Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer; The Ni-Ag/TiO ₂ /MnO/attapulgite composite desulfurizer, based on the total mass of the desulfurizer, includes the following composition: 5.5-28% of nickel and silver, 1-5.5% of titanium dioxide, and 30-60% of manganese monoxide %, attapulgite 20-50%, wherein the molar ratio of nickel and silver is 40-10:1. 3. The preparation method of attapulgite-based nano-composite desulfurizer according to claim 2, characterized in that the molar ratio of potassium permanganate to manganese sulfate in step (1) is 2-5:1. 4. The preparation method of attapulgite-based nano-composite desulfurizer according to claim 2, characterized in that: in the attapulgite slurry described in step (1), the attapulgite concentration is 50-150 g/L. 5. the preparation method of attapulgite-based nano-composite desulfurizer as claimed in claim 2, is characterized in that: in the mixed solution of titanium tetrachloride and manganese sulfate described in step (1), titanium tetrachloride and The molar ratio of manganese sulfate is 1:6.1-68, wherein the concentration of titanium tetrachloride is 0.01-0.1 mol/L. 6. the preparation method of attapulgite-based nano-composite desulfurizer as claimed in claim 2, is characterized in that: the alkali solution described in step (1) is ammonium bicarbonate solution, potassium carbonate solution, sodium carbonate solution or ammoniacal liquor One of them, the concentration is 0.5~3mol/L. 7. The preparation method of attapulgite-based nanocomposite desulfurizer as claimed in claim 2, characterized in that: in the mixed aqueous solution of nickel nitrate and silver nitrate described in step (2), the molar ratio of nickel to silver is 40-10 : 1; the amount of the mixed aqueous solution of nickel nitrate and silver nitrate satisfying that the total mass fraction of nickel and silver in the attapulgite nanocomposite desulfurization adsorbent is 5.5% to 28%; and the solvent in the mixed aqueous solution is deionized water , the amount of deionized water is calculated by the equal volume impregnation method, and the amount of deionized water is the pore volume of the titanium dioxide/manganese dioxide/attapulgite nanocomposite carrier. 8. The preparation method of attapulgite-based nanocomposite desulfurizer as claimed in claim 2, characterized in that: the hydrogen-facing atmosphere described in step (3) is a hydrogen atmosphere, "hydrogen and nitrogen" or "hydrogen and helium" Gas" mixed atmosphere, wherein in the mixed atmosphere of "hydrogen and nitrogen" or "hydrogen and helium", the hydrogen content is 10-99vol%. 9. The gasoline desulfurization method carried out by using the attapulgite-based nano-composite desulfurizer as claimed in any one of claims 1 and 2, characterized in that: the desulfurization method is to combine sulfur-containing raw materials with the attapulgite The stone-based nano-composite desulfurizer is fully contacted in a hydrogen atmosphere with a temperature of 320-500°C, a pressure of 0.5-2.0Mpa, a mass space velocity of 20-30 ^-h , and a hydrogen-oil ratio of 200-400. 10. The gasoline desulfurization method carried out by using attapulgite-based nano-composite desulfurizer as claimed in claim 9, characterized in that: the hydrogen-facing atmosphere is a hydrogen atmosphere or a mixed atmosphere of "hydrogen and nitrogen", and the In the mixed atmosphere, the hydrogen content is 10-99vol%.