CN111250048B - Copper-zinc-aluminum hydrotalcite desulfurization adsorbent and preparation method and application thereof - Google Patents

Copper-zinc-aluminum hydrotalcite desulfurization adsorbent and preparation method and application thereof Download PDF

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CN111250048B
CN111250048B CN202010134231.7A CN202010134231A CN111250048B CN 111250048 B CN111250048 B CN 111250048B CN 202010134231 A CN202010134231 A CN 202010134231A CN 111250048 B CN111250048 B CN 111250048B
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zinc
copper
aluminum
hydrotalcite
salt
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CN111250048A (en
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吴全贵
张钊
万鹏辉
李晓霞
王明先
许明艳
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Dongying Colt New Material Co ltd
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Abstract

The invention provides a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, and a preparation method and application thereof. The preparation method comprises the following steps: preparing a copper-zinc-aluminum ternary hydrotalcite-like compound by adopting a coprecipitation method; carrying out a first ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound and an anionic surfactant to obtain an anionic intercalated copper-zinc-aluminum ternary hydrotalcite-like compound of the anionic surfactant; and carrying out secondary ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound intercalated by the anions of the anionic surfactant and the salt solution containing the iron anions to obtain the copper-zinc-aluminum hydrotalcite desulfurizer intercalated by the anions of the anionic surfactant and the iron anions. The desulfurizer of the invention has small particle size and large interlayer spacing, and simultaneously has the advantages of uniform distribution of three elements of copper, zinc and aluminum, full exposure of active components, high desulfurization rate and stable desulfurization effect aiming at thioether compounds.

Description

Copper-zinc-aluminum hydrotalcite desulfurization adsorbent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of desulfurization, and relates to a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, a preparation method and application thereof, in particular to application of the desulfurization adsorbent in removing thioether impurities of a low-carbon hydrocarbon raw material.
Background
The tetraolefins can be isomerized to produce isobutene and further MTBE, and can also be separated to produce butene-1 and further to produce polybutene-1. The tetracarbon can be used for producing isobutene through dehydrogenation and further producing butyl rubber so as to improve the utilization value of the tetracarbon. The remaining C4 contains sulfides, such as carbonyl sulfide, dimethyl disulfide, etc., which are harmful impurities for further utilization of olefin and alkane, and can cause catalyst poisoning of downstream process and affect normal production of downstream equipment; generally, the control indexes are as follows: the total sulfur is less than or equal to 1 mg/g. Therefore, the content of sulfide in the unreacted lower hydrocarbon component must be strictly controlled, and thus the sulfur compounds must be removed before the lower hydrocarbon is used.
At present, the main methods for removing sulfides in low-carbon hydrocarbons comprise an alkaline washing method, a Merox method and a fiber membrane reactor method, but the methods have unsatisfactory removal effects of thioether compounds.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent; the invention also aims to provide the copper-zinc-aluminum hydrotalcite desulfurization adsorbent prepared by the preparation method; the invention also aims to provide the application of the copper-zinc-aluminum hydrotalcite desulfurization adsorbent in removing thioether impurities of low-carbon hydrocarbon raw materials.
The purpose of the invention is realized by the following technical means:
on one hand, the invention provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
preparing a copper-zinc-aluminum ternary hydrotalcite-like compound by adopting a coprecipitation method;
carrying out a first ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound and an anionic surfactant to obtain an anionic intercalated copper-zinc-aluminum ternary hydrotalcite-like compound of the anionic surfactant;
and carrying out secondary ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound intercalated by the anions of the anionic surfactant and the salt containing the iron anions to obtain the copper-zinc-aluminum hydrotalcite desulfurizer intercalated by the anions of the anionic surfactant and the iron anions.
The inventor assembles the hydrotalcite-like compound through two times of ion exchange intercalation, when the first time of ion exchange is carried out, the anion (mainly OH) in the copper-zinc-aluminum ternary hydrotalcite-like compound is intercalated by using the anion in the anion surfactant - ) Exchanging, namely, assembling anion intercalation in the anionic surfactant into an anion layer of the copper-zinc-aluminum ternary hydrotalcite-like compound to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound with the anionic surfactant intercalation; during the second ion exchange, the salt solution containing iron anions is intercalated, and part of anions of the surfactant are replaced by the iron anions, so that the copper-zinc-aluminum hydrotalcite desulfurizer with the mixed intercalation of the anions of the anionic surfactant and the iron anions is obtained, the desulfurization effect (especially thioether compounds) of the adsorbent is gradually improved by the method, the desulfurizer prepared by the method has the advantages of small particle size, large distance between cation layers and high specific surface area, and meanwhile, the copper-zinc-aluminum elements are uniformly distributed, and active components are fully exposed, so that the desulfurizer has the advantages of high desulfurization rate and stable desulfurization effect aiming at the thioether compounds, can effectively remove sulfur compounds such as thioether, mercaptan, carbonyl sulfide and the like in the low-carbon alkane raw material, and especially can remove the thioether compounds to below 1ppm, and has good purification effect; can be widely applied to the chemical process of removing thioether from low-carbon hydrocarbon.
In the above method, preferably, the method for preparing the copper-zinc-aluminum ternary hydrotalcite-like compound by using the coprecipitation method comprises:
dissolving copper salt, zinc salt and aluminum salt in alcohol to obtain solution A, and reacting the solution A with a precipitator to obtain the copper-zinc-aluminum ternary hydrotalcite compound. In the invention, the crystal grain of the hydrotalcite-like compound synthesized by adding the alcohol is smaller.
In the above method, preferably, the precipitant comprises a mixed solution prepared by mixing any one of potassium hydroxide and sodium hydroxide with any one of sodium carbonate and potassium carbonate according to a molar ratio of 1 (0.5-4) and adding water.
In the above method, preferably, the total concentration of the metal ions in the precipitant is 0.1 to 5.0 mol/L.
In the above method, preferably, the copper salt, the zinc salt, and the aluminum salt include respective nitrate, sulfate, or chloride.
In the above method, preferably, the molar ratio of the copper salt, the zinc salt and the aluminum salt is 1: (0.2-1.5): (0.2 to 1.5).
In the above method, preferably, the alcohol comprises a combination of one or more of methanol, ethanol, propanol and butanol.
In the above method, the alcohol in the coprecipitation reaction is preferably in the form of an aqueous solution thereof, (an aqueous solution prepared by dissolving the alcohol in water, that is, an aqueous solution of the alcohol), and the volume fraction of the aqueous solution of the alcohol is preferably 10% to 60%.
In the above method, the total concentration of the copper salt, the zinc salt, and the aluminum salt in the aqueous alcohol solution is preferably 0.1 to 5.0 mol/L.
In the above method, preferably, the volume ratio of the solution a to the precipitant is 1: (1-3).
In the above method, preferably, the anionic surfactant comprises a long-chain alkyl benzene sulfonate and/or a long-chain alkyl sulfonate.
In the above method, preferably, the long-chain alkylbenzene sulfonate has a molecular formula of C n H 2n+1 -C 6 H 4 -SO 3 M; the molecular general formula of the long-chain alkyl sulfonate is C n H 2n+1 -SO 3 M；
Wherein n is 10, 12, 14, 16 or 18; m is Na and/or K.
In the above method, preferably, the first ion exchange is performed in an aqueous solution of an anionic surfactant, and the concentration of the anionic surfactant in the aqueous solution is 0.01 to 0.5 mol/L; the mass ratio of the aqueous solution of the anionic surfactant to the copper-zinc-aluminum ternary hydrotalcite-like compound is (5-50): 1.
in the above method, the temperature of the first ion exchange reaction is preferably 30 to 80 ℃, and the ion exchange time is preferably 10 to 50 hours.
In the above method, preferably, the second ion exchange is performed in an aqueous solution of a salt containing iron anions, wherein the concentration of the salt containing iron anions in the aqueous solution is 0.01-0.1 mol/L; the mass ratio of the aqueous solution containing the iron anion salt to the copper-zinc-aluminum ternary hydrotalcite-like compound intercalated with the anions of the anionic surfactant is (5-50): 1.
in the above method, the temperature of the second ion exchange reaction is preferably 30 to 80 ℃, and the ion exchange time is preferably 10 to 50 hours.
In the above method, preferably, the iron-containing anion comprises a ferrous cyanide ion.
In the above method, preferably, filtration and drying are further performed after each ion exchange; the drying is low-temperature vacuum drying, the drying temperature is 10-50 ℃, the drying time is 10-50 h, and the pressure during drying is not higher than 0.01 MPa.
On the other hand, the invention also provides the copper-zinc-aluminum hydrotalcite desulfurization adsorbent prepared by the preparation method, wherein the particle size of the copper-zinc-aluminum hydrotalcite desulfurization adsorbent is 10-500 nm, and the interlayer spacing is 0.8-1.8 nm.
On the other hand, the invention also provides the application of the copper-zinc-aluminum hydrotalcite desulfurization adsorbent in removing thioether impurities of the low-carbon hydrocarbon raw material. The desulfurization adsorbent can effectively purify the thioether compounds of the low-carbon hydrocarbon, and provides protection for downstream catalysts and processes.
In the application, the temperature for desulfurization by using the copper-zinc-aluminum hydrotalcite desulfurization adsorbent is preferably 0-50 ℃, and the space velocity of the low-carbon hydrocarbon raw material is preferably 0.1-1.0 h -1 And the reaction pressure of desulfurization is 0.5-2.0 MPa.
The invention has the beneficial effects that:
the copper-zinc-aluminum hydrotalcite desulfurization adsorbent prepared by the invention has small particle size and large interlayer spacing, and meanwhile, three elements of copper, zinc and aluminum are uniformly distributed, active components are fully exposed, so that the adsorbent has the advantages of high desulfurization rate and stable desulfurization effect aiming at thioether compounds, can effectively remove sulfur-containing compounds such as thioether, mercaptan, carbonyl sulfide and the like in low-carbon alkane raw materials, and particularly can remove the sulfur-containing compounds to below 1ppm aiming at the thioether compounds, and has good purification effect; can be widely applied to the chemical process of removing thioether from low-carbon hydrocarbon.
Drawings
Fig. 1 is an SEM spectrum of the cu-zn-al based hydrotalcite desulfurization adsorbent prepared in example 1 of the present invention.
FIG. 2 is a SEM chromatogram of the Cu-Zn-Al based hydrotalcite desulfurization adsorbent prepared in comparative example 3 of the present invention.
Fig. 3 is an XRD spectrum of the adsorbents in example 1, comparative example 2 and comparative example 3 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 embodiment provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
200ml of methanol was mixed with 200ml of deionized water, and 25.0g of copper nitrate, 39.6g of zinc nitrate hexahydrate and 50.0g of aluminum nitrate nonahydrate were dissolved in the alcohol-water mixture and recorded as solution A.
16.0g of sodium hydroxide and 84.8g of sodium carbonate were weighed out and dissolved in 400ml of deionized water, and the solution B was recorded.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 40 ℃ for 20 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
Weighing 4.2g of sodium dodecyl benzene sulfonate, dissolving in 600ml of deionized water to prepare a sodium dodecyl benzene sulfonate solution, and adding 20g of copper-zinc-aluminum ternary hydrotalcite compound into the sodium dodecyl benzene sulfonate solution; ion exchange is carried out for 50h at the temperature of 40 ℃, after reaction, filtration and washing are carried out, and the mixture is placed in a vacuum drying oven at the temperature of 40 ℃ and dried for 30h (the pressure of a vacuum cavity is 0.005MPa), so as to obtain the benzene sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound;
weighing 6.76g of potassium ferrocyanide, dissolving in 800ml of deionized water, adding 20g of copper-zinc-aluminum ternary hydrotalcite-like compound powder intercalated by benzene sulfonate, carrying out ion exchange for 50 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, placing the solution in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for drying for 30 hours to obtain a copper-zinc-aluminum hydrotalcite desulfurization adsorbent formed by mixing, intercalating and assembling dodecyl benzene sulfonate ions and ferricyanide ions, tabletting and crushing the mixture to 20-30-mesh particles, and then using the adsorbent for desulfurization reaction.
The desulfurization adsorbent particles are applied to the process of removing ether from isobutane raw material, the desulfurization operation condition is 40 ℃, and the airspeed of liquefied gas raw material is 0.5h -1 1.0MPa, the total sulfur content in the isobutane raw material is 31ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
The SEM spectrum of the cu-zn-al hydrotalcite-based desulfurization adsorbent prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the morphology of the prepared desulfurization adsorbent is small particles with a particle size of about 50 nm.
Comparative example 1:
the comparative example provides a preparation method of a copper-zinc-aluminum hydrotalcite-based desulfurization adsorbent obtained without secondary ion exchange, which comprises the following steps:
200ml of methanol was mixed with 200mlg g of deionized water, and 25.0g of copper nitrate, 39.6g of zinc nitrate hexahydrate and 50.0g of aluminum nitrate nonahydrate were dissolved in the alcohol-water mixture and recorded as solution A.
16.0g of sodium hydroxide and 84.8g of sodium carbonate were weighed out and dissolved in 400ml of deionized water, and the solution B was recorded.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 40 ℃ for 20 hours to obtain a copper-zinc-aluminum ternary hydrotalcite-like compound desulfurization adsorbent, tabletting and crushing the adsorbent to 20-30-mesh particles, and then using the adsorbent in desulfurization reaction.
The desulfurization adsorbent particles are applied to the process of removing ether from isobutane raw material, the desulfurization operation condition is 40 ℃, and the airspeed of liquefied gas raw material is 0.5h -1 1.0MPa, the total sulfur content in the isobutane raw material is 31ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
Comparative example 2:
the comparative example provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent obtained by one-time ion exchange, which comprises the following steps:
200ml of methanol was mixed with 200mlg g of deionized water, and 25.0g of copper nitrate, 39.6g of zinc nitrate hexahydrate and 50.0g of aluminum nitrate nonahydrate were dissolved in the alcohol-water mixture and recorded as solution A.
16.0g of sodium hydroxide and 84.8g of sodium carbonate were weighed out and dissolved in 400ml of deionized water, and the solution B was recorded.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 40 ℃ for 20 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
Weighing 4.2g of sodium dodecyl benzene sulfonate, dissolving in 600ml of deionized water to prepare a sodium dodecyl benzene sulfonate solution, and adding 20g of copper-zinc-aluminum ternary hydrotalcite compound into the sodium dodecyl benzene sulfonate solution; ion exchange is carried out for 50h at the temperature of 40 ℃, after reaction, filtration and washing are carried out, and the mixture is placed in a vacuum drying oven at the temperature of 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for drying for 30h to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound desulfurization adsorbent with benzene sulfonate intercalation, and the desulfurization adsorbent can be used for desulfurization reaction after being pressed and crushed into particles of 20-30 meshes.
The desulfurization adsorbent particles are applied to the process of removing ether from isobutane raw material, the desulfurization operation condition is 40 ℃, and the airspeed of liquefied gas raw material is 0.5h -1 1.0MPa, the total sulfur content in the isobutane raw material is 31ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
Comparative example 3:
the comparative example provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
25.0g of copper nitrate, 39.6g of zinc nitrate hexahydrate and 50.0g of aluminum nitrate nonahydrate were weighed into 400ml of deionized water and identified as solution A.
16.0g of sodium hydroxide and 84.8g of sodium carbonate were weighed out and dissolved in 400ml of deionized water, and the solution B was recorded.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 40 ℃ for 20 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
Weighing 4.2g of sodium dodecyl benzene sulfonate, dissolving in 600ml of deionized water to prepare a sodium dodecyl benzene sulfonate solution, and adding 20g of copper-zinc-aluminum ternary hydrotalcite compound into the sodium dodecyl benzene sulfonate solution; ion exchange is carried out for 50h at the temperature of 40 ℃, after reaction, filtration and washing are carried out, and the mixture is placed in a vacuum drying oven at the temperature of 40 ℃ and dried for 30h (the pressure of a vacuum cavity is 0.005MPa), so as to obtain the benzene sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound;
weighing 6.76g of potassium ferrocyanide, dissolving in 800ml of deionized water, adding 20g of copper-zinc-aluminum ternary hydrotalcite-like compound powder intercalated by benzene sulfonate, carrying out ion exchange for 50 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, placing the solution in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for drying for 30 hours to obtain a copper-zinc-aluminum hydrotalcite desulfurization adsorbent formed by mixing, intercalating and assembling dodecyl benzene sulfonate ions and ferricyanide ions, tabletting and crushing the mixture to 20-30-mesh particles, and then using the adsorbent for desulfurization reaction.
The desulfurization adsorbent particles are applied to the process of removing ether from isobutane raw material, the desulfurization operation condition is 40 ℃, and the airspeed of liquefied gas raw material is 0.5h -1 1.0MPa, the total sulfur content in the isobutane raw material is 31ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
The SEM spectrogram of the copper zinc aluminum hydrotalcite-based desulfurization adsorbent prepared in the comparative example is shown in fig. 2, and it can be seen from fig. 2 that the prepared desulfurization adsorbent has a non-uniform morphology, and the particle size distribution is from 50 nm to 700 nm, which is much larger than the particle size of the adsorbent prepared in example 1.
The XRD comparison patterns of the copper zinc aluminum based hydrotalcite desulfurization adsorbents prepared in the above example 1, comparative example 2 and comparative example 3 are shown in fig. 3. As can be seen from fig. 3: the four adsorbents all have typical hydrotalcite-like structures, indicating two ion exchanges and causing damage to the hydrotalcite-like structures. The diffraction peaks of example 1, comparative example 1 and comparative example 2 were significantly broadened and the intensities thereof were significantly decreased compared to those of comparative example 3, which indicates that the adsorbents prepared in example 1, comparative example 1 and comparative example 2 had a slightly lower relative crystallinity and the sizes of the grains obtained by the preparation were smaller, which is consistent with the results obtained by comparing fig. 1 and fig. 2. In addition, example 1 and comparative example 2 have a significant difference in the position of the diffraction peak in the (003) plane, as compared with comparative example 1 and comparative example 3. Calculated from the positions of diffraction peaks corresponding to the (003) plane, the height between the cation layers in example 1 was 0.514 nm, that in comparative example 1 was 0.258 nm, that in comparative example 2 was 0.507 nm, and that in comparative example 3 was 0.254 nm. The above data indicate that the spacing between the cation layers of the adsorbent prepared after ion exchange is increased, indicating that intercalation assembly is successfully achieved by the organic anion and cation layers used.
Example 2:
the embodiment provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
160ml of ethanol is mixed with 240ml of deionized water, and 45.4g of copper chloride, 23.0g of zinc chloride and 50.6g of aluminum nitrate nonahydrate are weighed and dissolved in the alcohol-water mixed solution, and the solution is marked as solution A.
15.6g of sodium hydroxide and 163.2 g of sodium carbonate were weighed into 1000ml of deionized water and recorded as solution B.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 40 ℃ for 20 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
4.5g of sodium tetradecyl sulfonate is dissolved in 300ml of deionized water to prepare a sodium tetradecyl sulfonate solution, and 20g of copper-zinc-aluminum ternary hydrotalcite compound is added into the sodium tetradecyl sulfonate solution; ion exchange is carried out for 40h at the temperature of 50 ℃, after reaction, filtration and washing are carried out, and the mixture is placed in a vacuum drying oven at the temperature of 20 ℃ (the pressure of a vacuum cavity is 0.005MPa) to be dried for 50h, so as to obtain the sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound;
weighing 16.8g of potassium ferrocyanide, dissolving in 800ml of deionized water, adding 20g of a sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound after complete dissolution, carrying out ion exchange for 50 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, placing the solution in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for drying for 30 hours to obtain a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, mixing tetradecyl sulfonate ions and ferricyanide ions, intercalating and assembling to obtain the copper-zinc-aluminum hydrotalcite desulfurization adsorbent, tabletting and crushing the adsorbent to 20-30-mesh particles, and then using the adsorbent for desulfurization reaction.
The adsorbent for removing sulfur from copper-zinc-aluminum hydrotalcite obtained in the embodiment is applied to the process of removing sulfur and ether from n-butane raw material, wherein the desulfurization operation condition is 30 ℃, and the airspeed of liquefied gas raw material is 0.2h -1 2.0MPa, the total sulfur content in the n-butane raw material is 18ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
Example 3:
the embodiment provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
160ml of ethanol is mixed with 240ml of deionized water, 63.8g of copper sulfate, 38.8g of zinc sulfate and 54.7g of aluminum sulfate are weighed and dissolved in the alcohol-water mixed solution, and the solution A is marked.
16.8g of potassium hydroxide and 82.9g of potassium carbonate are weighed out and dissolved in 600ml of deionized water and identified as solution B.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven (the pressure of a vacuum cavity is 0.005MPa) at 20 ℃ for 20 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
Dissolving 6.9g of sodium dodecyl benzene sulfonate in 200ml of deionized water to prepare a sodium eicosyl benzene sulfonate solution, adding 20g of copper-zinc-aluminum ternary hydrotalcite-like compound into the sodium eicosyl benzene sulfonate solution, carrying out ion exchange for 30 hours at 50 ℃, filtering after reaction, washing, and drying in a vacuum drying oven at 30 ℃ (the vacuum cavity pressure is 0.005MPa) for 50 hours to obtain a benzene sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound;
weighing 22.1g of potassium ferrocyanide, dissolving in 900ml of deionized water, adding 20g of benzene sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound into the solution after complete dissolution, carrying out ion exchange for 50 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, drying the solution in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 30 hours to obtain a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, mixing and intercalating dodecyl benzene sulfonate ions and ferrous cyanide ions, and crushing the mixture into 20-30-mesh particles, wherein the particles can be used for desulfurization reaction.
The adsorbent for removing sulfur from copper-zinc-aluminum hydrotalcite obtained in the embodiment is applied to the process of removing sulfur and ether from propane raw materials, wherein the desulfurization operation condition is 30 ℃, and the airspeed of liquefied gas raw materials is 1.5h -1 2.0MPa, the total sulfur content in the propane raw material is 27ppm, 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 50 hours of desulfurization reaction are shown in Table 2.
Example 4:
the embodiment provides a preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent, which comprises the following steps:
190ml of methanol, 10ml of butanol and 200ml of deionized water are mixed, 54.3g of copper sulfate, 70.1g of zinc chloride and 117.3g of aluminum sulfate are dissolved in an alcohol-water mixed solution, and the solution is marked as solution A.
12.0g of sodium hydroxide and 63.6g of sodium carbonate were dissolved in 800ml of deionized water and the solution was designated as solution B.
And (3) quickly pouring the solution A into the solution B to obtain mother liquor containing the copper-zinc-aluminum ternary hydrotalcite-like compound, filtering and washing the mother liquor, taking out a filter cake, and drying the filter cake in a vacuum drying oven at 50 ℃ (the pressure of a vacuum cavity is 0.005MPa) for 40 hours to obtain the copper-zinc-aluminum ternary hydrotalcite-like compound.
Dissolving 3.5g of sodium octadecyl sulfonate in 200ml of deionized water to prepare a sodium octadecyl sulfonate solution, and adding 20g of copper-zinc-aluminum ternary hydrotalcite-like compound into the sodium octadecyl sulfonate solution; ion exchange is carried out for 40h at the temperature of 40 ℃, after reaction, filtration and washing are carried out, and the mixture is placed in a vacuum drying oven at the temperature of 50 ℃ and dried for 35h (the pressure of a vacuum cavity is 0.005MPa), so as to obtain the sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound;
weighing 17.6g of potassium ferrocyanide, dissolving in 800ml of deionized water, adding 20g of sulfonate intercalated copper-zinc-aluminum ternary hydrotalcite-like compound powder into potassium ferrocyanide solution after complete dissolution, carrying out ion exchange for 50 hours at 40 ℃, filtering and washing the solution after the ion exchange is finished, placing the solution in a vacuum drying oven at 40 ℃ (the pressure of a vacuum cavity is 0.005MPa) for drying for 30 hours to obtain a copper-zinc-aluminum hydrotalcite-like desulfurization adsorbent, mixing and intercalating octadecylsulfonate ions and ferrocyanide ions, and crushing the copper-zinc-aluminum hydrotalcite-like desulfurization adsorbent into 20-30-mesh particles for desulfurization reaction.
The adsorbent for removing sulfur from copper-zinc-aluminum hydrotalcite obtained in the embodiment is applied to the process of removing sulfur and ether from n-butane raw material, wherein the desulfurization operation condition is 20 ℃, and the airspeed of liquefied gas raw material is 0.5h -1 0.5MPa, the total sulfur content in the n-butane raw material is 11ppm, the detailed content of sulfur-containing compounds is shown in Table 1, and the desulfurization reaction is carried out for 50hThe total sulfur content and the distribution of sulfur-containing compounds in the final product are shown in Table 2.
Table 1:
Figure BDA0002396764200000101
(Note: data in ppm in Table 1)
Table 2:
Figure BDA0002396764200000102
(Note: data units in Table 2 are ppm)
From the experimental results of table 2, it can be seen that: the two-time ion exchange can gradually improve the desulfurization effect of the adsorbent (especially thioether compounds), and the desulfurization adsorbent prepared by the method can effectively remove sulfur-containing compounds such as thioether, mercaptan, carbonyl sulfide and the like in the low-carbon alkane raw material, especially can remove the thioether compounds to below 1ppm, and has a good purification effect.

Claims (20)

1. A preparation method of a copper-zinc-aluminum hydrotalcite desulfurization adsorbent comprises the following steps:
preparing a copper-zinc-aluminum ternary hydrotalcite-like compound by adopting a coprecipitation method: dissolving copper salt, zinc salt and aluminum salt in alcohol to obtain a solution A, and reacting the solution A with a precipitator to obtain a copper-zinc-aluminum ternary hydrotalcite compound;
carrying out a first ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound and an anionic surfactant to obtain an anionic intercalated copper-zinc-aluminum ternary hydrotalcite-like compound of the anionic surfactant;
and carrying out secondary ion exchange reaction on the copper-zinc-aluminum ternary hydrotalcite-like compound intercalated by the anions of the anionic surfactant and the salt containing the iron anions to obtain the copper-zinc-aluminum hydrotalcite desulfurizer intercalated by the anions of the anionic surfactant and the iron anions.
2. The preparation method according to claim 1, wherein the precipitant comprises any one of potassium hydroxide and sodium hydroxide and any one of sodium carbonate and potassium carbonate in a molar ratio of 1: (0.5-4) mixing and adding water to prepare a mixed solution.
3. The method according to claim 2, wherein the total concentration of metal ions in the precipitant is 0.1 to 5.0 mol/L.
4. The production method according to claim 1, wherein the copper salt, the zinc salt, and the aluminum salt include respective nitrates, sulfates, or chlorides.
5. The production method according to claim 1 or 4, wherein the molar ratio of the copper salt, the zinc salt and the aluminum salt is 1: (0.2-1.5): (0.2 to 1.5).
6. The method of claim 1, wherein the alcohol comprises a combination of one or more of methanol, ethanol, propanol, and butanol.
7. The preparation method according to claim 1 or 6, wherein the alcohol in the coprecipitation reaction is in the form of an aqueous solution thereof, and the volume fraction of the aqueous solution of the alcohol is 10-60%.
8. The production method according to claim 1, wherein the total concentration of the copper salt, the zinc salt and the aluminum salt in the aqueous alcohol solution is 0.1 to 5.0 mol/L.
9. The production method according to claim 1, wherein the volume ratio of the solution a to the precipitant is 1: (1-3).
10. The production method according to claim 1, wherein the anionic surfactant comprises a long-chain alkylbenzene sulfonate and/or a long-chain alkyl sulfonate.
11. The process according to claim 10, wherein the long-chain alkylbenzene sulfonate has a molecular formula of C n H 2n+1 -C 6 H 4 -SO 3 M; the molecular general formula of the long-chain alkyl sulfonate is C n H 2n+1 -SO 3 M；
Wherein n is 10, 12, 14, 16 or 18; m is Na and/or K.
12. The method according to claim 1, wherein the first ion exchange is carried out in an aqueous solution of an anionic surfactant, and the concentration of the anionic surfactant in the aqueous solution is 0.01 to 0.5 mol/L; the mass ratio of the aqueous solution of the anionic surfactant to the copper-zinc-aluminum ternary hydrotalcite-like compound is (5-50): 1.
13. the method according to claim 1, wherein the temperature of the first ion exchange reaction is 30 to 80 ℃ and the ion exchange time is 10 to 50 hours.
14. The production method according to claim 1, wherein the second ion exchange is carried out in an aqueous solution of a salt containing iron anions, the concentration of the salt containing iron anions in the aqueous solution being 0.01 to 0.1 mol/L; the mass ratio of the aqueous solution containing the iron anion salt to the copper-zinc-aluminum ternary hydrotalcite-like compound intercalated with the anions of the anionic surfactant is (5-50): 1.
15. the preparation method according to claim 1, wherein the temperature of the second ion exchange reaction is 30 to 80 ℃ and the ion exchange time is 10 to 50 hours.
16. The method of claim 1, wherein the iron-containing anion comprises ferrous cyanide.
17. The method according to claim 1, wherein each ion exchange is followed by filtration and drying; the drying is low-temperature vacuum drying, the drying temperature is 10-50 ℃, the drying time is 10-50 h, and the pressure during drying is not higher than 0.01 MPa.
18. The copper-zinc-aluminum hydrotalcite desulfurization adsorbent prepared by the preparation method of any one of claims 1 to 17, wherein the particle size of the copper-zinc-aluminum hydrotalcite desulfurization adsorbent is 10 to 500nm, and the interlayer spacing is 0.8 to 1.8 nm.
19. Use of the adsorbent for desulfurization of copper zinc aluminum hydrotalcite according to claim 18 for removing thioether impurities from a low carbon hydrocarbon feedstock.
20. The application of the adsorbent of claim 19, wherein the temperature for desulfurization by the adsorbent is 0-50 ℃, and the space velocity of the low-carbon hydrocarbon raw material is 0.1-1.0 h -1 And the reaction pressure of desulfurization is 0.5-2.0 MPa.
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