CN109092241B - Magnesium-aluminum-zinc hydrotalcite adsorbent, preparation method and application thereof in refined desulfurization of liquefied gas - Google Patents
Magnesium-aluminum-zinc hydrotalcite adsorbent, preparation method and application thereof in refined desulfurization of liquefied gas Download PDFInfo
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Abstract
The invention provides a magnesium-aluminum-zinc hydrotalcite adsorbent, a preparation method and application thereof in fine desulfurization of liquefied gas. The preparation method comprises the following steps: dissolving metal salts of magnesium, aluminum and zinc elements in water to obtain a solution A, dissolving a precipitator in water to obtain a solution B, and mixing the solution A and the solution B to obtain a magnesium-aluminum-zinc ternary hydrotalcite-like precipitation solution; filtering and washing the magnesium-aluminum-zinc ternary hydrotalcite-like precipitation solution and drying at low temperature in vacuum to obtain magnesium-aluminum-zinc ternary hydrotalcite-like; dissolving a molybdovate heteropoly acid precursor and/or a tungstoate heteropoly acid precursor in water to obtain a solution C; and adding the magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C for ion exchange, filtering and drying in vacuum at low temperature to obtain the magnesium-aluminum-zinc hydrotalcite-like compound adsorbent. The magnesium-aluminum-zinc hydrotalcite adsorbent has high desulfurization stability and high desulfurization activity as a liquefied gas fine desulfurization adsorbent, and the removal rate is up to more than 98.6%.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to a magnesium-aluminum-zinc hydrotalcite adsorbent, a preparation method thereof and application thereof in fine desulfurization of liquefied gas.
Background
Liquefied petroleum gases produced by different processes contain a certain amount of sulfur-containing compounds, which can adversely affect downstream processing equipment such as catalyst deactivation, pipeline corrosion, and the like, and thus need to be removed. At present, many mature desulfurization methods and process technologies exist for liquefied petroleum gas desulfurization, and the methods mainly include rectification method, extraction method, oxidation method, adsorption method and the like. The rectification method mainly utilizes the boiling point difference of the sulfur-containing compound and the liquefied petroleum gas component to realize the separation of the sulfur-containing compound and the liquefied petroleum gas component, has the advantage of simple flow, but has higher energy consumption in the desulfurization process and is difficult to achieve the aim of fine desulfurization. The desulfurization by the extraction method has the advantages of simple process and less investment, but a specific extracting agent only has obvious effect of removing a certain type of sulfide, so that a general high-efficiency extracting agent is not found so far, and the expected effect is difficult to achieve aiming at the fine desulfurization. The oxidation desulfurization method is to oxidize sulfide into sulfone or sulfonic acid compound and then remove the sulfone or sulfonic acid compound, and a certain amount of olefin is inevitably lost in the oxidation process, so that the oxidation desulfurization method is not used in the desulfurization process of the liquefied gas raw material with high olefin content. Compared with other methods, the adsorption method is a method which is researched more at present, has the advantages of low energy consumption and simple and convenient operation, but the removal selectivity of the existing adsorbent to sulfide still needs to be further improved.
With the continuous development and progress of the technology, the limit of the total amount of sulfur-containing compounds in the liquefied petroleum gas is increasingly strict in a chemical process partially using a noble metal catalyst, a fuel cell using a noble metal electrode and the like, and the noble metal catalyst or the electrode loses activity rapidly due to excessively high sulfur content, and the regeneration difficulty is extremely high. Therefore, in order to reduce the total sulfur content of the lpg raw material to an extremely low level, it is necessary to find a suitable method for the chemical process using the noble metal catalyst and the fuel cell using the noble metal electrode.
Disclosure of Invention
Based on the problems of the desulfurization adsorbent in the prior art, the invention aims to provide the preparation method of the magnesium-aluminum-zinc-based hydrotalcite adsorbent, the preparation process is simple, and the prepared magnesium-aluminum-zinc-based hydrotalcite adsorbent can reduce the sulfide content in liquefied gas to an extremely low level at normal temperature; the invention also aims to provide the application of the magnesium-aluminum-zinc hydrotalcite adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas.
The purpose of the invention is realized by the following technical scheme:
on one hand, the invention provides a preparation method of a magnesium-aluminum-zinc hydrotalcite adsorbent, which comprises the following steps:
dissolving metal salts of magnesium, aluminum and zinc elements in water to obtain a solution A, dissolving a precipitator in water to obtain a solution B, and mixing the solution A and the solution B to obtain a mother solution of a magnesium-aluminum-zinc ternary hydrotalcite compound;
filtering and washing mother liquor of the magnesium-aluminum-zinc ternary hydrotalcite-like compound and drying the mother liquor at low temperature in vacuum to obtain magnesium-aluminum-zinc ternary hydrotalcite-like compound;
dissolving the molybdenum heteropoly acid precursor and/or the tungstic heteropoly acid precursor in water to obtain a solution C;
and step four, adding the magnesium-aluminum-zinc ternary hydrotalcite into the solution C for ion exchange, filtering and drying in vacuum at low temperature to obtain the magnesium-aluminum-zinc hydrotalcite adsorbent.
In the above preparation method, preferably, the metal salt includes a nitrate and/or a sulfate of magnesium, aluminum, and zinc.
In the above preparation method, preferably, in the metal salt, the molar ratio of the magnesium salt to the aluminum salt to the zinc salt is 1: (0.2-4.0): (0.2-6.0).
In the above preparation method, preferably, the total concentration of the metal salts in the solution a is 0.1 to 3 mol/L.
In the above preparation method, preferably, the precipitant comprises a mixed solution of sodium hydroxide and sodium carbonate, or a mixed solution of potassium hydroxide and potassium carbonate; wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1: 2; the molar ratio of the potassium hydroxide to the potassium carbonate is 1:2.
In the above preparation method, preferably, the concentration of sodium ions or potassium ions in the solution B is 0.1 to 3 mol/L.
In the above-mentioned preparation method, preferably, the solution a and the solution B are mixed in equal proportion.
In the above preparation method, preferably, the molybdic heteropoly acid precursor comprises ammonium molybdate; the tungstic heteropoly acid precursor comprises ammonium tungstate;
in the above preparation method, preferably, the total concentration of the molybdic heteropoly acid precursor and/or tungstic heteropoly acid precursor in the solution C is 0.01-1.5 mol/L.
In the above preparation method, preferably, the mass ratio of the magnesium-aluminum-zinc ternary hydrotalcite to the solution C is 1: (5-20).
In the preparation method, the total mass fraction of molybdenum and/or tungsten in the magnesium-aluminum-zinc-based hydrotalcite adsorbent is preferably 5 to 15 percent based on metal oxide.
In the preparation method, preferably, in the second step, the low-temperature vacuum drying temperature is 10-50 ℃, the drying time is 5-50h, and the pressure under vacuum is not higher than 0.01 MPa.
In the above preparation method, preferably, in the fourth step, the ion exchange temperature is 40-80 ℃, and the ion exchange time is 10-50 h; the low-temperature vacuum drying after ion exchange is carried out at the temperature of 10-50 ℃, the drying time is 5-50h, and the pressure under vacuum is not higher than 0.01 MPa.
On the other hand, the invention also provides a magnesium-aluminum-zinc hydrotalcite adsorbent which is prepared by the preparation method.
On the other hand, the invention also provides the application of the magnesium-aluminum-zinc hydrotalcite adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas.
In the application, the desulfurization operation temperature is preferably 10-50 ℃, and the space velocity of the liquefied gas raw material is 0.1-1.5h-1The desulfurization pressure is 0.5-2.0MPa, and the total sulfur content in the liquefied gas raw material is not higher than 50 ppm.
The adsorbent provided by the invention has a regular hydrotalcite-like compound structure, namely, a cation layer which is regularly arranged is formed by magnesium, aluminum and zinc, molybdenum and tungsten heteropoly acid radical anions which enter the layers through ion exchange are contained between the cation layers, and the whole structure can still be kept stable at a higher temperature. The magnesium-aluminum-zinc cation layer of the adsorbent, and the interlaminar molybdenum and tungstopoly heteropoly acid and anion can play a role of desulfurization, so that the prepared adsorbent has extremely high desulfurization activity and desulfurization stability, can be applied to the fine desulfurization process of liquefied gas, and is particularly suitable for being used as a processing working section which takes the liquefied gas as a raw material and has strict requirements on the content of sulfide in the liquefied gas.
The magnesium-aluminum-zinc hydrotalcite adsorbent has extremely high desulfurization activity as a liquefied gas fine desulfurization adsorbent, and the removal rate is as high as more than 98.6%.
Drawings
Fig. 1 is an XRD spectrum of the molybdophosphoric acid doped magnesium aluminum zinc ternary hydrotalcite-like adsorbent prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The implementation provides a preparation method of a molybdenum-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite adsorbent, which comprises the following steps:
step one, dissolving magnesium nitrate, aluminum nitrate and zinc nitrate in deionized water according to the molar ratio of 1:3:6 to prepare a solution with the total concentration of metal ions of 0.5mol/L, and marking as a solution A1; sodium hydroxide and sodium carbonate are dissolved in deionized water according to the molar ratio of 1:2 to prepare a solution with the sodium ion concentration of 1.2mol/L, which is marked as solution B1. 1L of the solution A1 is quickly poured into the equal amount of the solution B1 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 20 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step three, dissolving a certain amount of ammonium molybdate into 200mL of deionized water to prepare an ammonium molybdate solution C1 with the concentration of 0.05 mol/L.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C1, performing ion exchange for 30 hours at 50 ℃, filtering and washing the solution after the ion exchange is finished, and drying the solution in a vacuum drying oven at 40 ℃ (the vacuum cavity pressure is 0.005MPa) for 30 hours to obtain the molybdenum-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass content of molybdenum oxide on the adsorbent is 6.3%.
The XRD spectrogram of the mo-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent prepared in this embodiment is shown in fig. 1. As can be seen from FIG. 1, the prepared hydrotalcite adsorbent has a clear XRD spectrogram of hydrotalcite compounds, and has good symmetry of diffraction peak shapes and high diffraction intensity, which indicates that the synthesized hydrotalcite adsorbent has a regular structure. Meanwhile, no diffraction peak of the molybdovanadate appears, which shows that the molybdovanadate has high dispersity in the adsorbent and is not aggregated.
The implementation also provides the application of the molybdic heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas, wherein in the fine desulfurization process, the desulfurization operation condition is 40 ℃, and the airspeed of a liquefied gas raw material is 0.5h-11.0MPa, the total sulfur content in the liquefied gas raw material is 37.1ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Example 2
The implementation provides a preparation method of a molybdenum-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite adsorbent, which comprises the following steps:
step one, dissolving magnesium nitrate, aluminum nitrate and zinc nitrate in deionized water according to the molar ratio of 1:2.5:5 to prepare a solution with the total concentration of metal ions of 1.0mol/L, and marking as a solution A2; dissolving potassium hydroxide and potassium carbonate in deionized water according to the molar ratio of 1:2 to prepare a solution with the potassium ion concentration of 2.0mol/L, and marking as a solution B2. 1L of the solution A2 is quickly poured into the equal amount of the solution B2 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 25 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 30 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step three, dissolving a certain amount of ammonium molybdate into 100mL of deionized water to prepare an ammonium molybdate solution C2 with the concentration of 0.2 mol/L.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C2, carrying out ion exchange for 50 hours at the temperature of 60 ℃, filtering and washing the solution after the ion exchange is finished, and then drying the solution in a vacuum drying oven at the temperature of 40 ℃ (the vacuum cavity pressure is 0.005MPa) for 40 hours to obtain the molybdenum-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass content of molybdenum oxide on the adsorbent is 8.6%.
The implementation also provides the application of the molybdic heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas, wherein in the fine desulfurization process, the desulfurization operation condition is 35 ℃, and the airspeed of a liquefied gas raw material is 0.8h-11.5MPa, the total sulfur content in the liquefied gas raw material is 22.8ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Example 3
The implementation provides a preparation method of a tungstoperous acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, which comprises the following steps:
step one, dissolving magnesium nitrate, aluminum nitrate and zinc nitrate in deionized water according to the molar ratio of 1:0.5:0.5 to prepare a solution with the total concentration of metal ions of 0.8mol/L, and marking as a solution A3; sodium hydroxide and sodium carbonate are dissolved in deionized water according to the molar ratio of 1:2 to prepare a solution with the sodium ion concentration of 2.5mol/L, which is marked as solution B3. 1L of the solution A3 is quickly poured into the equal amount of the solution B3 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 20 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 50 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step three, dissolving a certain amount of ammonium tungstate in 200mL of deionized water to prepare an ammonium tungstate solution C3 with the concentration of 0.05 mol/L.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C3, performing ion exchange for 30 hours at 50 ℃, filtering and washing the solution after the ion exchange is finished, and drying the solution in a vacuum drying oven at 40 ℃ (the vacuum cavity pressure is 0.005MPa) for 30 hours to obtain the tungsten-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass content of tungsten oxide on the adsorbent is 9.6%.
The implementation also provides the application of the tungstic heteropoly acid doped Mg-Al-Zn ternary hydrotalcite-like adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas, wherein in the fine desulfurization process, the desulfurization operation temperature is 30 ℃, and the airspeed of liquefied gas raw materials is 0.8h-11.0MPa, the total sulfur content in the liquefied gas raw material is 15ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Example 4
The implementation provides a preparation method of a tungstoperous acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, which comprises the following steps:
step one, dissolving magnesium nitrate, aluminum nitrate and zinc nitrate in deionized water according to the molar ratio of 1:1:2 to prepare a solution with the total concentration of metal ions of 0.2mol/L, and marking as a solution A4; sodium hydroxide and sodium carbonate are dissolved in deionized water according to the molar ratio of 1:2 to prepare a solution with the sodium ion concentration of 0.8mol/L, which is marked as solution B4. 1L of the solution A4 is quickly poured into the equal amount of the solution B4 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 20 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 40 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step three, dissolving a certain amount of ammonium tungstate in 400mL of deionized water to prepare an ammonium tungstate solution C4 with the concentration of 1.0 mol/L.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C4, performing ion exchange for 40 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, and drying the solution in a vacuum drying oven at 30 ℃ (the vacuum cavity pressure is 0.005MPa) for 40 hours to obtain the tungsten-containing heteropoly acid doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass content of molybdenum oxide on the adsorbent is 11.9%.
The implementation also provides the application of the tungstic heteropoly acid doped Mg-Al-Zn ternary hydrotalcite-like adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas, wherein in the fine desulfurization process, the desulfurization operation condition is 50 ℃, and the airspeed of liquefied gas raw materials is 1.5h-12.0MPa, the total sulfur content in the liquefied gas raw material is 22.8ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Example 5
The implementation provides a preparation method of molybdenum-and-tungstophosphoric acid-doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, which comprises the following steps:
step one, magnesium sulfate, aluminum sulfate and zinc sulfate are dissolved in deionized water according to the molar ratio of 1:2:4 to prepare a solution with the total concentration of metal ions of 0.6mol/L, and the solution is marked as solution A5; dissolving potassium hydroxide and potassium carbonate in deionized water according to the molar ratio of 1:2 to prepare a solution with the potassium ion concentration of 1.8mol/L, and marking as a solution B5. 1L of the solution A5 is quickly poured into the equal amount of the solution B5 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 50 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
Step three, the molar ratio of the raw materials is 3: 2 certain amount of ammonium molybdate and ammonium tungstate are dissolved in 100mL of deionized water to prepare 0.05mol/L ammonium molybdate solution C5.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C1, carrying out ion exchange for 50 hours at 50 ℃, filtering and washing the solution after the ion exchange is finished, and then drying the solution in a vacuum drying oven at 40 ℃ (the vacuum cavity pressure is 0.005MPa) for 30 hours to obtain a molybdenum-and tungsten-heteropoly acid-doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass contents of molybdenum and tungsten oxides on the adsorbent are respectively 6.2% and 4.8%.
The implementation also provides the application of the molybdenum-and-tungstopolyacid-doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas, wherein in the fine desulfurization process, the desulfurization operation condition is 40 ℃, and the airspeed of a liquefied gas raw material is 0.5h-11.0MPa, the total sulfur content in the liquefied gas raw material is 15ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Example 6
The implementation provides a preparation method of molybdenum-and-tungstophosphoric acid-doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, which comprises the following steps:
step one, magnesium sulfate, aluminum sulfate and zinc sulfate are dissolved in deionized water according to the molar ratio of 1:3:6 to prepare a solution with the total concentration of metal ions of 1.0mol/L, and the solution is marked as solution A6; sodium hydroxide and sodium carbonate are dissolved in deionized water according to the molar ratio of 1:2 to prepare a solution with the sodium ion concentration of 2.7mol/L, which is marked as solution B6. 1L of the solution A6 is quickly poured into the equal amount of the solution B6 to obtain mother liquor containing the magnesium-aluminum-zinc ternary hydrotalcite compound.
And step two, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 15 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 10 hours to obtain the magnesium-aluminum-zinc ternary hydrotalcite compound.
Step three, the molar ratio of the raw materials is 1: 4, certain amounts of ammonium molybdate and ammonium tungstate are dissolved in 300mL of deionized water to prepare an ammonium molybdate solution C6 with the concentration of 1.5 mol/L.
And step four, adding 20g of dried magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C6, carrying out ion exchange for 45 hours at 50 ℃, filtering and washing the solution after the ion exchange is finished, and then placing the solution in a vacuum drying oven at 20 ℃ (the vacuum cavity pressure is 0.005MPa) to be dried for 50 hours to obtain a molybdenum-and tungsten heteropoly acid-doped magnesium-aluminum-zinc ternary hydrotalcite-like adsorbent, wherein the mass contents of molybdenum and tungsten oxides on the adsorbent are respectively 2.8% and 8.4%.
The implementation also provides the molybdenum-and tungsten-containing heteropoly acid-doped magnesium-aluminum-zinc ternary hydrotalcite adsorbent as a fine powderThe application of the desulfurization adsorbent in the fine desulfurization of liquefied gas is characterized in that in the fine desulfurization process, the desulfurization operation condition is 40 ℃, and the airspeed of the liquefied gas raw material is 0.2h-11.0MPa, the total sulfur content in the liquefied gas raw material is 42.2ppm, the detailed content of the sulfur-containing compounds is shown in Table 1, and the total sulfur content and the distribution of the sulfur-containing compounds in the product after 100 hours of desulfurization reaction are shown in Table 2.
Table 1 is a statistical table of the distribution of sulfur compounds in the liquefied petroleum gas feedstocks of examples 1 to 6; table 2 is a statistical table of the distribution of total sulfur and sulfur compounds in the liquefied petroleum gas products of examples 1 to 6 after 100 hours of desulfurization.
Table 1:
| sulfur-containing compounds | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 2.1 | 0 | 2.1 | 0 | 0 |
| Ethanethiol | 2.4 | 4.1 | 0 | 4.1 | 0 | 5.9 |
| Dimethyl sulfide | 5.1 | 3.3 | 2.0 | 3.3 | 2 | 5.1 |
| Thiophene(s) | 7.2 | 4.5 | 3.5 | 4.5 | 4 | 7.3 |
| Dimethyl disulfide | 15.5 | 6.2 | 6.7 | 6.2 | 6 | 11.6 |
| Ethanethione | 6.9 | 2.6 | 2.8 | 2.6 | 3 | 12.3 |
| Total of | 37.1 | 22.8 | 15.0 | 22.8 | 15.0 | 42.2 |
Table 2:
| sulfur-containing compounds | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| |
0 | 0 | 0 | 0 | 0 | 0 |
| Thiophene(s) | 0.2 | 0.1 | 0.1 | 0.1 | 0 | 0 |
| Dimethyl disulfide | 0.1 | 0 | 0.1 | 0 | 0.1 | 0.1 |
| Ethanethione | 0.2 | 0.1 | 0 | 0.2 | 0 | 0.1 |
| Total of | 0.5 | 0.2 | 0.2 | 0.3 | 0.1 | 0.2 |
| Removal rate | 98.65％ | 99.12％ | 98.67％ | 98.68％ | 99.33％ | 99.53％ |
From the experimental results of table 1 and table 2, it can be seen that: the magnesium-aluminum-zinc hydrotalcite adsorbent used as a liquefied gas fine desulfurization adsorbent has extremely high desulfurization activity, and the removal rate is as high as more than 98.6%.
Claims (10)
1. A preparation method of a magnesium-aluminum-zinc hydrotalcite adsorbent for refined desulfurization of liquefied gas is characterized by comprising the following steps:
dissolving metal salts of magnesium, aluminum and zinc elements in water to obtain a solution A, dissolving a precipitator in water to obtain a solution B, and mixing the solution A and the solution B to obtain a mother solution of a magnesium-aluminum-zinc ternary hydrotalcite compound;
filtering and washing mother liquor of the magnesium-aluminum-zinc ternary hydrotalcite-like compound and drying the mother liquor at low temperature in vacuum to obtain magnesium-aluminum-zinc ternary hydrotalcite-like compound; the low-temperature vacuum drying temperature is 10-50 ℃, the drying time is 5-50h, and the pressure under vacuum is not higher than 0.01 MPa;
dissolving ammonium molybdate and/or ammonium tungstate in water to obtain a solution C; in the solution C, the total concentration of ammonium molybdate and/or ammonium tungstate is 0.01-1.5 mol/L;
step four, adding the magnesium-aluminum-zinc ternary hydrotalcite-like compound into the solution C for ion exchange, filtering and carrying out low-temperature vacuum drying to obtain a magnesium-aluminum-zinc hydrotalcite-based hydrotalcite adsorbent; the temperature of ion exchange is 40-80 ℃, and the ion exchange time is 10-50 h; the low-temperature vacuum drying after ion exchange is carried out at the temperature of 10-50 ℃, the drying time is 5-50h, and the pressure under vacuum is not higher than 0.01 MPa; the mass ratio of the magnesium-aluminum-zinc ternary hydrotalcite to the solution C is 1: (5-20);
the total mass fraction of molybdenum and/or tungsten in the magnesium-aluminum-zinc hydrotalcite adsorbent is 5-15% calculated by metal oxide.
2. The method of claim 1, wherein: the metal salt comprises nitrate and/or sulfate of magnesium, aluminum and zinc.
3. The method of claim 2, wherein: in the metal salt, the molar ratio of magnesium salt, aluminum salt and zinc salt is 1: (0.2-4.0): (0.2-6.0).
4. The method of claim 1, wherein: in the solution A, the total concentration of the metal salt is 0.1-3 mol/L.
5. The method of claim 1, wherein: the precipitator comprises a mixed solution of sodium hydroxide and sodium carbonate or a mixed solution of potassium hydroxide and potassium carbonate; wherein the molar ratio of the sodium hydroxide to the sodium carbonate is 1: 2; the molar ratio of the potassium hydroxide to the potassium carbonate is 1:2.
6. The method of claim 5, wherein: in the solution B, the concentration of sodium ions or potassium ions is 0.1-3 mol/L.
7. The method of claim 1, wherein: and mixing the solution A and the solution B in equal proportion.
8. A magnesium aluminum zinc based hydrotalcite adsorbent, which is prepared by the preparation method of any one of claims 1 to 7.
9. The use of the magnesium aluminum zinc based hydrotalcite adsorbent according to claim 8 as a fine desulfurization adsorbent in the fine desulfurization of liquefied gas.
10. Use according to claim 9, characterized in that: in the application, the desulfurization operation temperature is 10-50 ℃, and the airspeed of the liquefied gas raw material is 0.1-1.5h-1The desulfurization pressure is 0.5-2.0MPa, and the total sulfur content in the liquefied gas raw material is not higher than 50 ppm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951851A (en) * | 1997-10-31 | 1999-09-14 | Poirier; Marc-Andre | Sulfur removal from hydrocarbon fluids by contacting said fluids with hydrololcite-like adsorbent material |
| JP2005263596A (en) * | 2004-03-22 | 2005-09-29 | National Institute For Materials Science | Layered double hydroxide/zeolite composite and its producing method |
| CN1727052A (en) * | 2005-07-28 | 2006-02-01 | 华东师范大学 | Method for preparing high effective sulfur transfer agent for catalytic cracking fume |
| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
| CN101890329A (en) * | 2010-07-21 | 2010-11-24 | 北京化工大学 | Thiophene adsorbents and application thereof |
| CN103816929A (en) * | 2014-02-27 | 2014-05-28 | 南京工业大学 | Hydrotalcite like catalyst, preparation method and application thereof |
-
2018
- 2018-09-04 CN CN201811023773.6A patent/CN109092241B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951851A (en) * | 1997-10-31 | 1999-09-14 | Poirier; Marc-Andre | Sulfur removal from hydrocarbon fluids by contacting said fluids with hydrololcite-like adsorbent material |
| JP2005263596A (en) * | 2004-03-22 | 2005-09-29 | National Institute For Materials Science | Layered double hydroxide/zeolite composite and its producing method |
| CN1727052A (en) * | 2005-07-28 | 2006-02-01 | 华东师范大学 | Method for preparing high effective sulfur transfer agent for catalytic cracking fume |
| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
| CN101890329A (en) * | 2010-07-21 | 2010-11-24 | 北京化工大学 | Thiophene adsorbents and application thereof |
| CN103816929A (en) * | 2014-02-27 | 2014-05-28 | 南京工业大学 | Hydrotalcite like catalyst, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 倪哲明等.新型杂多酸阴离子层柱材料的合成、表征及性能的研究.《浙江大学学报（理学版）》.2003, * |
| 新型杂多酸阴离子层柱材料的合成、表征及性能的研究;倪哲明等;《浙江大学学报（理学版）》;20030531;第299页摘要、第300页第1.2-1.4节，第301页第2.3节 * |
| 环糊精和水滑石脱除噻吩和硫醇的研究;布劳里;《中国优秀硕士学位论文全文数据库工程科技I辑》;20120215;第29页第3.3.1节和表3.3 * |
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