CN109092241A - It magnalium zinc-base houghite adsorbent and preparation method and is applied in liquefied gas fine de-sulfur - Google Patents
It magnalium zinc-base houghite adsorbent and preparation method and is applied in liquefied gas fine de-sulfur Download PDFInfo
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Abstract
It is applied the present invention provides magnalium zinc-base houghite adsorbent and preparation method and in liquefied gas fine de-sulfur.Preparation method obtains solution B the following steps are included: obtain solution A for the metal salt of magnesium, aluminum and zinc element is soluble in water, by precipitating reagent is soluble in water, and solution A and solution B are mixed to get magnalium zinc ternary houghite precipitation solution；By magnalium zinc ternary houghite precipitation solution filtration washing and low-temperature vacuum drying, magnalium zinc ternary houghite is obtained；By molybdenum heteropolyacid predecessor and/or heteropoly tungstic acid predecessor is soluble in water obtains solution C；Magnalium zinc ternary houghite is added in solution C and carries out ion exchange, simultaneously low-temperature vacuum drying is filtered, obtains magnalium zinc-base houghite adsorbent.The magnalium zinc-base houghite adsorbent has desulfurization stability and high desulphurizing activated as liquefied gas fine de-sulfur adsorbent, and removal efficiency is up to 98.6% or more.
Description
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of magnalium zinc-base houghite adsorbent and preparation method and
It is applied in liquefied gas fine de-sulfur.
Background technique
All contain a certain amount of sulfur-containing compound, these sulfur-containing compounds in the liquefied petroleum gas prepared by distinct methods
Catalyst inactivation, corrosive pipeline can be caused to the processing unit in downstream and wait adverse effect, it is therefore desirable to which it is removed.It is existing
In the stage, for LPG Desulfurization, there are many more mature sulfur methods and technology, mainly include rectification method, extraction
It follows the example of, oxidizing process and absorption method etc..Rectification method mainly utilizes the boiling point difference of sulfur-containing compound and liquefied petroleum gas components to realize
The separation of the two has the simple advantage of process, but its sweetening process energy consumption is higher while being difficult to reach the target of fine de-sulfur.Extraction
Following the example of desulfurization has the advantages that simple process, investment are lesser, but specific extractant only to certain a kind of sulfide removal effect compared with
To be obvious, a kind of general efficient extractant is not yet found so far, is difficult to achieve the desired results for fine de-sulfur.Oxidation sweetening method
It is to be oxidation of the sulfide into sulfone first or sulfonic compound removes again, is inevitably lost in oxidation process a certain amount of
Alkene, therefore without using in the sweetening process of high olefin content liquefied gas raw material.It is compared with other methods, absorption method is current
A kind of more method is studied, has that low energy consumption, advantage easy to operate, but existing adsorbent is to the removing of sulfide selectivity
It still needs to further increase.
It is with the continuous development of technology and progressive, partially using the chemical process of noble metal catalyst and using noble metal
Fuel cell of electrode etc. is increasingly strict to the limitation of the sulfur-containing compound total amount of liquefied petroleum gas, and excessive sulfur content can be rapid
Make noble metal catalyst or electrode loss of activity, and it is very big to regenerate difficulty.Therefore for the chemical industry mistake using noble metal catalyst
The fuel cell etc. of journey and use noble metal electrode needs to find suitable method for the total sulfur content of raw liquefied petroleum gas
It is reduced to extremely low level.
Summary of the invention
Based on the problems of desulfuration adsorbent in the prior art, the purpose of the present invention is to provide a kind of magnalium zinc-bases
The preparation method of houghite adsorbent, this method preparation process is simple, the magnalium zinc-base houghite adsorbent being prepared
The sulfide content in liquefied gas can be down to extremely low level at normal temperature；The object of the invention is also to provide the magnalium zinc
Application of the base class hydrotalcite adsorbent as fine de-sulfur adsorbent in liquefied gas fine de-sulfur.
The purpose of the present invention is achieved by the following technical programs:
On the one hand, the present invention provides a kind of preparation method of magnalium zinc-base houghite adsorbent, comprising the following steps:
Step 1 obtains solution A for the metal salt of magnesium, aluminum and zinc element is soluble in water, obtains precipitating reagent is soluble in water
Solution A and solution B are mixed to get the mother liquor of magnalium zinc ternary houghite compound by solution B；
The mother liquor filtration washing of magnalium zinc ternary houghite compound and low-temperature vacuum drying are obtained magnesium by step 2
Aluminium zinc ternary houghite；
Step 3, by molybdenum heteropolyacid predecessor and/or heteropoly tungstic acid predecessor is soluble in water obtains solution C；
Magnalium zinc ternary houghite is added in solution C and carries out ion exchange by step 4, filters and cryogenic vacuum is dry
It is dry, obtain magnalium zinc-base houghite adsorbent.
In above-mentioned preparation method, it is preferable that the metal salt includes the nitrate and/or sulfate of magnesium, aluminium, zinc.
In above-mentioned preparation method, it is preferable that in the metal salt, the molar ratio of magnesium salts, aluminium salt and zinc salt is 1:(0.2-
4.0): (0.2-6.0).
In above-mentioned preparation method, it is preferable that in the solution A, the total concentration of the metal salt is 0.1-3mol/L.
In above-mentioned preparation method, it is preferable that the precipitating reagent includes the mixed solution or hydrogen of sodium hydroxide and sodium carbonate
The mixed solution of potassium oxide and potassium carbonate；Wherein, the molar ratio of the sodium hydroxide and the sodium carbonate is 1:2；The hydrogen-oxygen
The molar ratio for changing potassium and the potassium carbonate is 1:2.
In above-mentioned preparation method, it is preferable that in the solution B, the concentration of sodium ion or potassium ion is 0.1-3mol/L.
In above-mentioned preparation method, it is preferable that the solution A is mixed with the solution B equal proportion.
In above-mentioned preparation method, it is preferable that the molybdenum heteropolyacid predecessor includes ammonium molybdate；The heteropoly tungstic acid forerunner
Object includes ammonium tungstate；
In above-mentioned preparation method, it is preferable that in the solution C, molybdenum heteropolyacid predecessor and/or heteropoly tungstic acid predecessor
Total concentration be 0.01-1.5mol/L.
In above-mentioned preparation method, it is preferable that the mass ratio of the magnalium zinc ternary houghite and the solution C is 1:
(5-20)。
In above-mentioned preparation method, it is preferable that in terms of metal oxide, molybdenum and/or tungsten are in the magnalium zinc-base class neatly
Total mass fraction in stone adsorbent is 5%-15%.
In above-mentioned preparation method, it is preferable that in step 2, the temperature of low-temperature vacuum drying is 10-50 DEG C, when dry
Between be 5-50h, the pressure under vacuum is not higher than 0.01MPa.
In above-mentioned preparation method, it is preferable that in step 4, the temperature of ion exchange is 40-80 DEG C, when ion exchange
Between be 10-50h；The temperature of low-temperature vacuum drying is 10-50 DEG C, drying time 5-50h after ion exchange, the pressure under vacuum
Not higher than 0.01MPa.
It on the other hand, is using above-mentioned preparation side the present invention also provides a kind of magnalium zinc-base houghite adsorbent
What method prepared.
It is liquefying in another aspect, the present invention also provides above-mentioned magnalium zinc-base houghite adsorbents as fine de-sulfur adsorbent
Application in gas fine de-sulfur.
In above-mentioned application, it is preferable that desulfurization operations temperature is 10-50 DEG C, and the air speed of liquefied gas raw material is 0.1-1.5h-1, desulfurization pressure is 0.5-2.0MPa, and total sulfur content is not higher than 50ppm in liquefied gas raw material.
Adsorbent provided by the invention has regular houghite compound structure, i.e., first by magnalium zinc composition rule
The cationic layer of arrangement contains molybdenum, the heteropoly tungstic acid root anion for entering interlayer by ion exchange, Neng Gou between cationic layer
The stable structure of whole holding still is able at higher temperature.The magnalium zinc cation layer of adsorbent and molybdenum, the tungsten of interlayer are miscellaneous
Polyacid can play desulfidation with anion, therefore there is the adsorbent prepared high desulphurizing activated and desulfurization to stablize
Property, it can be applied to liquefied gas fine de-sulfur process, be particularly useful as simultaneously wanting wherein sulfide content using liquefied gas as raw material
Ask more stringent processing workshop section.
Magnalium zinc-base houghite adsorbent of the invention has high desulfurization living as liquefied gas fine de-sulfur adsorbent
Property, removal efficiency is up to 98.6% or more.
Detailed description of the invention
Fig. 1 is the magnalium zinc ternary houghite adsorbent of the doping containing molybdenum heteropolyacid prepared in the embodiment of the present invention 1
XRD spectra.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
This implementation provides a kind of preparation method of the magnalium zinc ternary houghite adsorbent of doping containing molybdenum heteropolyacid, including
Following steps:
Step 1, the ratio of 1:3:6 takes magnesium nitrate, aluminum nitrate, zinc nitrate to be dissolved in deionized water and is made into gold in molar ratio
The total concentration for belonging to ion is the solution of 0.5mol/L, is denoted as solution A 1；The ratio of 1:2 takes sodium hydroxide, sodium carbonate in molar ratio
It is dissolved in the solution for being made into that Na ion concentration is 1.2mol/L in deionized water, is denoted as solution B 1.1L solution A 1 is taken to pour into rapidly
In the solution B 1 of amount, the mother liquor containing magnalium zinc ternary houghite compound is obtained.
Step 2 takes out filter cake and is placed in 40 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 20 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3 takes a certain amount of ammonium molybdate to be dissolved in the ammonium molybdate for preparing that concentration is 0.05mol/L in 200mL deionized water
Solution C 1.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 1, in 50 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 40 DEG C of vacuum ovens after the completion by ion exchange 30 hours under part, ion exchange
Pressure is 0.005MPa) it is 30 hours dry, obtain the magnalium zinc ternary houghite adsorbent adulterated containing molybdenum heteropolyacid, the absorption
The mass content of the oxide of molybdenum is 6.3% in agent.
XRD spectra such as Fig. 1 institute of the magnalium zinc ternary houghite adsorbent of the doping containing molybdenum heteropolyacid of this implementation preparation
Show.As shown in Figure 1, the hydrotalcite adsorbent of preparation has clearly hydrotalcite-based compound XRD spectra, diffraction maximum peak shape pair
Title property is good, diffracted intensity is high, illustrates that the structure of the Study on Hydrotalcite like Sorbents of synthesis is more regular.Do not occur molybdenum heteropolyacid simultaneously
Diffraction maximum, illustrate that its dispersion degree in adsorbent is higher, do not assemble.
The magnalium zinc ternary houghite adsorbent that this implementation also provides the doping containing molybdenum heteropolyacid is adsorbed as fine de-sulfur
Application of the agent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations condition is 40 DEG C, liquefied gas feed space velocity
0.5h-1, 1.0MPa, total sulfur content is 37.1ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after 100 hours.
Embodiment 2
This implementation provides a kind of preparation method of the magnalium zinc ternary houghite adsorbent of doping containing molybdenum heteropolyacid, including
Following steps:
Step 1, the ratio of 1:2.5:5 takes magnesium nitrate, aluminum nitrate, zinc nitrate to be dissolved in deionized water and is made into molar ratio
The total concentration of metal ion is the solution of 1.0mol/L, is denoted as solution A 2；The ratio of 1:2 takes potassium hydroxide, carbonic acid in molar ratio
Potassium is dissolved in the solution for being made into that potassium concentration is 2.0mol/L in deionized water, is denoted as solution B 2.1L solution A 2 is taken to pour into rapidly
In the solution B 2 of equivalent, the mother liquor containing magnalium zinc ternary houghite compound is obtained.
Step 2 takes out filter cake and is placed in 25 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 30 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3 takes a certain amount of ammonium molybdate to be dissolved in the ammonium molybdate for preparing that concentration is 0.2mol/L in 100mL deionized water
Solution C 2.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 2, in 60 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 40 DEG C of vacuum ovens after the completion by ion exchange 50 hours under part, ion exchange
Pressure is 0.005MPa) it is 40 hours dry, obtain the magnalium zinc ternary houghite adsorbent adulterated containing molybdenum heteropolyacid, the absorption
The mass content of the oxide of molybdenum is 8.6% in agent.
The magnalium zinc ternary houghite adsorbent that this implementation also provides the doping containing molybdenum heteropolyacid is adsorbed as fine de-sulfur
Application of the agent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations condition is 35 DEG C, liquefied gas feed space velocity
0.8h-1, 1.5MPa, total sulfur content is 22.8ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after 100 hours.
Embodiment 3
This implementation provides a kind of preparation method of the magnalium zinc ternary houghite adsorbent of heteropoly acid containing tungsten doping, including
Following steps:
Step 1, the ratio of 1:0.5:0.5 takes magnesium nitrate, aluminum nitrate, zinc nitrate to be dissolved in deionized water and matches in molar ratio
The solution that total concentration at metal ion is 0.8mol/L, is denoted as solution A 3；The ratio of 1:2 takes sodium hydroxide, carbon in molar ratio
Sour sodium is dissolved in the solution for being made into that Na ion concentration is 2.5mol/L in deionized water, is denoted as solution B 3.1L solution A 3 is taken to fall rapidly
Enter in the solution B 3 of equivalent, obtains the mother liquor containing magnalium zinc ternary houghite compound.
Step 2 takes out filter cake and is placed in 20 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 50 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3 takes a certain amount of ammonium tungstate to be dissolved in the ammonium tungstate for preparing that concentration is 0.05mol/L in 200mL deionized water
Solution C 3.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 3, in 50 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 40 DEG C of vacuum ovens after the completion by ion exchange 30 hours under part, ion exchange
Pressure is 0.005MPa) it is 30 hours dry, obtain the magnalium zinc ternary houghite adsorbent of heteropoly acid containing tungsten doping, the absorption
The mass content of the oxide of tungsten is 9.6% in agent.
The magnalium zinc ternary houghite adsorbent that this implementation also provides heteropoly acid containing tungsten doping is adsorbed as fine de-sulfur
Application of the agent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations temperature is 30 DEG C, liquefied gas feed space velocity
0.8h-1, 1.0MPa, total sulfur content is 15ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction 100
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after hour.
Embodiment 4
This implementation provides a kind of preparation method of the magnalium zinc ternary houghite adsorbent of heteropoly acid containing tungsten doping, including
Following steps:
Step 1, the ratio of 1:1:2 takes magnesium nitrate, aluminum nitrate, zinc nitrate to be dissolved in deionized water and is made into gold in molar ratio
The total concentration for belonging to ion is the solution of 0.2mol/L, is denoted as solution A 4；The ratio of 1:2 takes sodium hydroxide, sodium carbonate in molar ratio
It is dissolved in the solution for being made into that Na ion concentration is 0.8mol/L in deionized water, is denoted as solution B 4.1L solution A 4 is taken to pour into rapidly
In the solution B 4 of amount, the mother liquor containing magnalium zinc ternary houghite compound is obtained.
Step 2 takes out filter cake and is placed in 20 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 40 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3 takes a certain amount of ammonium tungstate to be dissolved in the ammonium tungstate for preparing that concentration is 1.0mol/L in 400mL deionized water
Solution C 4.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 4, in 40 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 30 DEG C of vacuum ovens after the completion by ion exchange 40 hours under part, ion exchange
Pressure is 0.005MPa) it is 40 hours dry, obtain the magnalium zinc ternary houghite adsorbent of heteropoly acid containing tungsten doping, the absorption
The mass content of the oxide of molybdenum is 11.9% in agent.
The magnalium zinc ternary houghite adsorbent that this implementation also provides heteropoly acid containing tungsten doping is adsorbed as fine de-sulfur
Application of the agent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations condition is 50 DEG C, liquefied gas feed space velocity
1.5h-1, 2.0MPa, total sulfur content is 22.8ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after 100 hours.
Embodiment 5
This implementation provides a kind of preparation method of magnalium zinc ternary houghite adsorbent adulterated containing molybdenum and heteropoly tungstic acid,
The following steps are included:
Step 1, the ratio of 1:2:4 takes magnesium sulfate, aluminum sulfate, zinc sulfate to be dissolved in deionized water and is made into gold in molar ratio
The total concentration for belonging to ion is the solution of 0.6mol/L, is denoted as solution A 5；The ratio of 1:2 takes potassium hydroxide, potassium carbonate in molar ratio
It is dissolved in the solution for being made into that potassium concentration is 1.8mol/L in deionized water, is denoted as solution B 5.1L solution A 5 is taken to pour into rapidly
In the solution B 5 of amount, the mother liquor containing magnalium zinc ternary houghite compound is obtained.
Step 2 takes out filter cake and is placed in 40 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 50 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3, in molar ratio for 3:2 take a certain amount of ammonium molybdate and ammonium tungstate be dissolved in 100mL deionized water prepare it is dense
Degree is the ammonium molybdate solution C5 of 0.05mol/L.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 1, in 50 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 40 DEG C of vacuum ovens after the completion by ion exchange 50 hours under part, ion exchange
Pressure is 0.005MPa) it is 30 hours dry, the magnalium zinc ternary houghite adsorbent adulterated containing molybdenum and heteropoly tungstic acid is obtained, it should
Molybdenum on adsorbent, tungsten the mass content of oxide be respectively 6.2% and 4.8%.
This implementation also provides the magnalium zinc ternary houghite adsorbent containing molybdenum and heteropoly tungstic acid doping as fine de-sulfur
Application of the adsorbent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations condition is 40 DEG C, liquefied gas feed space velocity
0.5h-1, 1.0MPa, total sulfur content is 15ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction 100
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after hour.
Embodiment 6
This implementation provides a kind of preparation method of magnalium zinc ternary houghite adsorbent adulterated containing molybdenum and heteropoly tungstic acid,
The following steps are included:
Step 1, the ratio of 1:3:6 takes magnesium sulfate, aluminum sulfate, zinc sulfate to be dissolved in deionized water and is made into gold in molar ratio
The total concentration for belonging to ion is the solution of 1.0mol/L, is denoted as solution A 6；The ratio of 1:2 takes sodium hydroxide, sodium carbonate in molar ratio
It is dissolved in the solution for being made into that Na ion concentration is 2.7mol/L in deionized water, is denoted as solution B 6.1L solution A 6 is taken to pour into rapidly
In the solution B 6 of amount, the mother liquor containing magnalium zinc ternary houghite compound is obtained.
Step 2 takes out filter cake and is placed in 15 DEG C of vacuum ovens that (vacuum chamber pressure is after being filtered, washed mother liquor
It is 0.005MPa) 10 hours dry, obtain magnalium zinc ternary houghite compound.
Step 3, in molar ratio for 1:4 take a certain amount of ammonium molybdate and ammonium tungstate be dissolved in 300mL deionized water prepare it is dense
Degree is the ammonium molybdate solution C6 of 1.5mol/L.
Step 4, the magnalium zinc ternary houghite compound after taking 20g dry is added in above-mentioned solution C 6, in 50 DEG C of items
Solution is filtered, washed is placed on (vacuum chamber in 20 DEG C of vacuum ovens after the completion by ion exchange 45 hours under part, ion exchange
Pressure is 0.005MPa) it is 50 hours dry, the magnalium zinc ternary houghite adsorbent adulterated containing molybdenum and heteropoly tungstic acid is obtained, it should
Molybdenum on adsorbent, tungsten the mass content of oxide be respectively 2.8% and 8.4%.
This implementation also provides the magnalium zinc ternary houghite adsorbent containing molybdenum and heteropoly tungstic acid doping as fine de-sulfur
Application of the adsorbent in liquefied gas fine de-sulfur, during the fine de-sulfur, desulfurization operations condition is 40 DEG C, liquefied gas feed space velocity
0.2h-1, 1.0MPa, total sulfur content is 42.2ppm in liquefied gas raw material, and the detailed content of sulfur-containing compound is shown in Table 1, desulphurization reaction
Total sulfur content and sulfur-containing compound distribution are shown in Table 2 in product after 100 hours.
Table 1 is embodiment 1-6 raw liquefied petroleum gas sulfur-containing compound distribution statistics table；Table 2 is desulphurization reaction 100 hours
Embodiment 1-6 liquefied petroleum gas product total sulfur and sulfur-containing compound distribution statistics table afterwards.
Table 1:
| Sulfur-containing compound | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Carbonyl sulfur | 0 | 0 | 0 | 0 | 0 | 0 |
| Hydrogen sulfide | 0 | 0 | 0 | 0 | 0 | 0 |
| Carbon disulfide | 0 | 0 | 0 | 0 | 0 | 0 |
| Methyl mercaptan | 0 | 2.1 | 0 | 2.1 | 0 | 0 |
| Ethyl mercaptan | 2.4 | 4.1 | 0 | 4.1 | 0 | 5.9 |
| Methyl sulfide | 5.1 | 3.3 | 2.0 | 3.3 | 2 | 5.1 |
| Thiophene | 7.2 | 4.5 | 3.5 | 4.5 | 4 | 7.3 |
| Dimethyl disulfide | 15.5 | 6.2 | 6.7 | 6.2 | 6 | 11.6 |
| Ethyl sulfide | 6.9 | 2.6 | 2.8 | 2.6 | 3 | 12.3 |
| It amounts to | 37.1 | 22.8 | 15.0 | 22.8 | 15.0 | 42.2 |
Table 2:
| Sulfur-containing compound | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Carbonyl sulfur | 0 | 0 | 0 | 0 | 0 | 0 |
| Hydrogen sulfide | 0 | 0 | 0 | 0 | 0 | 0 |
| Carbon disulfide | 0 | 0 | 0 | 0 | 0 | 0 |
| Methyl mercaptan | 0 | 0 | 0 | 0 | 0 | 0 |
| Ethyl mercaptan | 0 | 0 | 0 | 0 | 0 | 0 |
| Methyl sulfide | 0 | 0 | 0 | 0 | 0 | 0 |
| Thiophene | 0.2 | 0.1 | 0.1 | 0.1 | 0 | 0 |
| Dimethyl disulfide | 0.1 | 0 | 0.1 | 0 | 0.1 | 0.1 |
| Ethyl sulfide | 0.2 | 0.1 | 0 | 0.2 | 0 | 0.1 |
| It amounts to | 0.5 | 0.2 | 0.2 | 0.3 | 0.1 | 0.2 |
| Removal efficiency | 98.65% | 99.12% | 98.67% | 98.68% | 99.33% | 99.53% |
From Tables 1 and 2 experimental result: using magnalium zinc-base houghite adsorbent of the invention as liquefied gas essence
Desulfuration adsorbent has high desulphurizing activated, and removal efficiency is up to 98.6% or more.
Claims (10)
1. a kind of preparation method of magnalium zinc-base houghite adsorbent, which comprises the following steps:
Step 1 obtains solution A for the metal salt of magnesium, aluminum and zinc element is soluble in water, obtains solution for precipitating reagent is soluble in water
Solution A and solution B are mixed to get the mother liquor of magnalium zinc ternary houghite compound by B；
The mother liquor filtration washing of magnalium zinc ternary houghite compound and low-temperature vacuum drying are obtained magnalium zinc by step 2
Ternary houghite；
Step 3, by molybdenum heteropolyacid predecessor and/or heteropoly tungstic acid predecessor is soluble in water obtains solution C；
Magnalium zinc ternary houghite is added in solution C and carries out ion exchange by step 4, filters simultaneously low-temperature vacuum drying,
Obtain magnalium zinc-base houghite adsorbent.
2. preparation method according to claim 1, it is characterised in that: the metal salt includes the nitrate of magnesium, aluminium, zinc
And/or sulfate；
Preferably, in the metal salt, the molar ratio of magnesium salts, aluminium salt and zinc salt is 1:(0.2-4.0): (0.2-6.0)；
Preferably, in the solution A, the total concentration of the metal salt is 0.1-3mol/L.
3. preparation method according to claim 1, it is characterised in that: the precipitating reagent includes sodium hydroxide and sodium carbonate
The mixed solution of mixed solution or potassium hydroxide and potassium carbonate；Wherein, the molar ratio of the sodium hydroxide and the sodium carbonate is
1:2；The molar ratio of the potassium hydroxide and the potassium carbonate is 1:2；
Preferably, in the solution B, the concentration of sodium ion or potassium ion is 0.1-3mol/L.
4. preparation method according to claim 1, it is characterised in that: the solution A is mixed with the solution B equal proportion.
5. preparation method according to claim 1, it is characterised in that: the molybdenum heteropolyacid predecessor includes ammonium molybdate；Institute
Stating heteropoly tungstic acid predecessor includes ammonium tungstate；
Preferably, in the solution C, the total concentration of molybdenum heteropolyacid predecessor and/or heteropoly tungstic acid predecessor is 0.01-
1.5mol/L。
6. preparation method according to claim 1, it is characterised in that: the magnalium zinc ternary houghite and the solution
The mass ratio of C is 1:(5-20).
7. preparation method according to claim 6, it is characterised in that: in terms of metal oxide, molybdenum and/or tungsten are in the magnesium
Total mass fraction in aluminium zinc-base houghite adsorbent is 5%-15%.
8. preparation method according to claim 1, it is characterised in that: in step 2, the temperature of low-temperature vacuum drying is
10-50 DEG C, drying time 5-50h, the pressure under vacuum is not higher than 0.01MPa；
Preferably, in step 4, the temperature of ion exchange is 40-80 DEG C, ion-exchange time 10-50h；After ion exchange
The temperature of low-temperature vacuum drying is 10-50 DEG C, drying time 5-50h, and the pressure under vacuum is not higher than 0.01MPa.
9. a kind of magnalium zinc-base houghite adsorbent is obtained using any one of the claim 1-8 preparation method preparation
?.
10. magnalium zinc-base houghite adsorbent is as fine de-sulfur adsorbent in liquefied gas fine de-sulfur described in claim 9
Using；
Preferably, in the application, desulfurization operations temperature is 10-50 DEG C, and the air speed of liquefied gas raw material is 0.1-1.5h-1, desulfurization
Pressure is 0.5-2.0MPa, and total sulfur content is not higher than 50ppm in liquefied gas raw material.
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