KR20130008806A - An adsorbent for adsorptive removal of sulfur compounds and purification method of the adsorbent - Google Patents

Abstract

PURPOSE: An adsorbent for adsorption desulfurization and a manufacturing method of the adsorbent are provided to facilitate a manufacturing process since a sintering process at a high temperature is not necessary when an acidic salt is dissolved in an appropriate solvent and then supported by a solid support such as a metal-organic skeletal material. CONSTITUTION: An adsorbent for adsorption desulfurization is manufactured by supporting an acidic salt on a porous solid support. The porous solid support is a metal-organic skeletal material. An anion of the acidic salt is at least one selected from the group consisting of chloride(Cl^-), nitrate(NO_3^-), sulfate(SO_4^2-), iodide(I^-), fluoride(F^-), and perchlorate(ClO_4^-), and a cation of the acidic salt is a metal cation excluding alkali metals and alkali earth metals.

Description

An adsorbent for adsorptive removal of sulfur compounds and purification method of the adsorbent}

The present invention relates to an adsorbent for adsorption desulfurization and a method for producing the same, and more particularly, to an adsorbent supporting an acid salt having an acid in a porous support and an easy method for producing the same.

The importance of the environment is increasing day by day, and the use of coal, bitumen, and oil sands, which can replace them, is becoming more important due to the depletion of high quality petroleum resources. These low quality raw materials have a very high content of impurities such as sulfur, nitrogen, and metals, so that these impurities must be removed in order to be used as an energy source, particularly as a fuel for transportation. Sulfur compounds remaining in transport fuels such as diesel oil, kerosene and gasoline include benzothiophene (BT), dibenzothiophene (DBT), methyldibenzothiophene (MDBT), dimethyldibezothiophene (DMDBT), and especially thiophene compounds with complex structures such as DMDBT. It is a hard sulfur compound that is difficult to do.

Recent environmental regulations allow less than 15 ppm of sulfur on the basis of sulfur for diesel fuels for transportation, and in particular for fuel cells, the sulfur content should be less than 1 ppm (preferably less than 60 ppb) (Catal. Sci. Technol. , 1, 23-42, 2011) Various desulfurization techniques have been developed and studied for them. Most notably, hydrogen is used in addition to HDS (hydrodesulfurization) technology or operation at high temperature and high pressure, and is particularly ineffective in removing the sulfur compounds. In addition to HDS, technologies such as oxidative desulfurization using oxidative reaction and adsorption desulfurization, precipitation and extraction using adsorption are being studied. Adsorption desulfurization using adsorption technology is not only favorable for mild operating conditions and removal of chronic sulfur compounds but also for small-scale operation without generating harmful hydrogen sulfide (Catal. Sci. Technol., 1, 23-42, 2011). Technology (Catal. Rev. Sci. Eng. 52, 381-410, 2010).

Various adsorbents that can be used for adsorptive desulfurization have been studied (Catal. Rev. Sci. Eng. 52, 381-410, 2010). First, silver (Ag) was the most widely used and solid adsorbents supported or ion exchanged such as Ag / titania, Ag / Al ₂ O ₃ , AgSO ₃ -SBA-15, AgY (USP 7625429) were studied. Adsorbents supported or ion exchanged with copper ions such as Cu / Al ₂ O ₃ , Cu (I) -Y (Catal. Today, 2006, 116, 530; Science, 301, 79, 2003; USP 7053256) have also been studied. As a result, the active site of adsorption was found to be monovalent silver or copper. Molecular sieves composed of WP / TiO ₂ -ZrO ₂ and NiP / TiO ₂ -ZrO ₂ (USP 7935248), Ti, Si, etc. (USP 7842645), Ni-based amorphous alloys (USP 6875340), etc. It is proposed as an adsorbent.

Korean Patent Publication No. 2007-0044979 discloses a desulfurization adsorbent for fuel cells using a basic metal salt and a desulfurization method using the same, and Korean Patent Publication No. 2005-0033351 discloses an adsorbent for desulfurization prepared by supporting a transition metal in zeolite. Known.

Recently, desulfurization using metal-organic frameworks with high surface areas has also been reported (J. Am. Chem. Soc., 131, 14538, 2009; J. Am. Chem. Soc. , 130, 6938; Chem. Eng. Technol. 33, 275, 2010; Chem. Commun. 47, 1306, 2011). The metal-organic framework material may be defined as a porous organic-inorganic polymer compound formed by combining a central metal ion with an organic ligand, and a crystalline compound including both organic and inorganic materials in a skeleton structure and having molecular or nano-sized pore structure. Means. Metal-organic frameworks have broader meanings of porous organic inorganic hybrid materials (Chem. Commun., 4780, 2006) and porous coordination polymers (Angew. Chem. Intl. Ed., 43, 2334. 2004) and many others have been used recently (Chem. Soc. Rev., 37, 191, 2008).

However, any adsorbent did not have sufficient adsorption capacity and used very expensive raw materials such as silver and palladium.

The present inventors completed the present invention by discovering that the adsorption agent containing both porous materials and acid salts can greatly increase the adsorption capacity of sulfur while trying to obtain an adsorbent for adsorption desulfurization having excellent adsorption capacity. Could. In addition, it was possible to complete the present invention by developing a simple manufacturing method for producing such an adsorbent.

Accordingly, the present invention provides a novel adsorbent for desulfurization and an easy method for preparing the adsorbent and a method for preparing the adsorbent containing both a metal-organic framework and an acid salt having a high surface area. As the metal-organic framework, for example, porous metal-terephthalate or metal-benzenetricarboxylate or the like is particularly excellent in physical properties and effects.

Accordingly, the present invention provides an adsorbent for adsorption desulfurization and an easy method for preparing the same, but particularly to provide a desulfurization adsorbent having a large adsorption removal capacity and an easy method for producing the adsorbent.

Accordingly, an object of the present invention is to develop an adsorbent having a high adsorption capacity and a method for easily preparing the same, which can be used for adsorption desulfurization.

Another object of the present invention is to provide an adsorbent having a large deactivation effect in a simple process.

In order to achieve the above object, the present invention relates to an efficient and method for producing the adsorbent for adsorption desulfurization, the adsorbent for adsorption desulfurization used in the present invention is composed of two kinds of components.

One of the components of the present invention is a support, mainly a porous solid material having a large surface area such as metal-organic frameworks, and another component is a metal salt having an acid.

The metal-organic framework material may be defined as a porous organic-inorganic polymer compound formed by combining metal ions in the center with an organic ligand, and include both organic and inorganic materials in the skeleton structure and have a molecular or nano-sized pore structure. It means a crystalline compound. Metal-organic frameworks have broader meanings of porous organic inorganic hybrid materials (Chem. Commun., 4780, 2006) and porous coordination polymers (Angew. Chem. Intl. Ed., 43, 2334. 2004).

The metal-organic framework material of the present invention is applicable to any structure or composition. That is, the metal material which is one member may be any metal, and Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, etc. This is a representative metal material. In particular, transition metals that make coordination compounds are suitable, and chromium, vanadium, iron, nickel, cobalt, copper, zinc, titanium, and manganese are suitable among transition metals. In addition to transition metals, metals such as lanthanum may be used as well as typical elements for making coordination compounds. Among the typical elements, aluminum and silicon are suitable, and among lanthanum metals, cerium and lanthanum are suitable. As the metal source, any compound of the metal may be used as well as the metal itself.

), 아미드기(-CONH₂), 술폰산기(-SO₃H), 술폰산 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산 음이온기(-CS₂ ^-), 피리딘기 또는 피라진기 등이 예시될 수 있다. 보다 안정한 금속-유기 골격물질을 유도하기 위해서는 배위할 수 있는 자리가 2개 이상인, 예를 들면 바이덴테이트 또는 트리덴테이트인 유기물이 유리하다. 유기물로는 배위할 자리가 있다면 비피리딘, 피라진 등의 중성 유기물, 테레프탈레이트, 나프탈렌디카복실레이트, 벤젠트리카복실레이트, 글루타레이트, 숙신네이트 등으로 예시될 수 있는 카본산 음이온 등의 음이온성 유기물은 물론 양이온 물질도 가능하다. 카본산 음이온의 경우 예를 들면 테레프탈레이트 같은 방향족 링을 갖는 것 외에 포르메이트 같은 선형의 카본산의 음이온은 물론이고 시클로헥실디카보네이트와 같이 비방향족 링을 갖는 음이온 등 어느 것이라도 가능하다. 배위할 수 있는 자리를 가진 유기물은 물론이고 잠재적으로 배위할 자리를 가져 반응 조건에서 배위할 수 있게 변화되는 것도 가능하다. 즉, 테레프탈산 같은 유기산을 사용하여도 반응 후에는 테레프탈레이트로 금속 성분과 결합할 수 있다. 사용할 수 있는 유기물의 대표적인 예로는 벤젠디카르복실산, 나프탈렌디카복실산, 벤젠트리카복실산, 나프탈렌트리카복실산, 피리딘디카복실산, 비피리딜디카복실산, 포름산, 옥살산, 말론산, 숙신산, 글루타르산, 헥산다이오익산, 헵탄다이오익산, 또는 시클로헥실디카복실산에서 선택되는 유기산 및 그들의 음이온, 피라진, 비피리딘 등이다. 또한, 하나 이상의 유기물을 혼합하여 사용할 수도 있다.Organics, which are another member of the metal-organic framework, are also called linkers and can be any organic with coordinating functional groups. The coordinating functional groups are carboxylic acid groups, carboxylic acid anion groups, amino groups (-NH). ₂ ), imino (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^- ), Pyridine group or pyrazine group and the like can be exemplified. In order to induce a more stable metal-organic framework, organic materials having two or more coordinating sites, for example, bidentate or tridentate, are advantageous. Organic materials include anionic organic materials such as carbonic anion, which can be exemplified by neutral organics such as bipyridine and pyrazine, terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, succinate, etc. Of course, cationic materials are also possible. In the case of the carbonic acid anion, for example, in addition to having an aromatic ring such as terephthalate, any of anions having a linear carbonic acid such as formate and an anion having a non-aromatic ring such as cyclohexyldicarbonate can be used. Organics with coordinating sites, as well as potentially coordinating sites, can also be changed to coordinate under reaction conditions. That is, even if an organic acid such as terephthalic acid is used, it can be combined with a metal component with terephthalate after the reaction. Representative examples of organic materials that can be used include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and hexanedioo Organic acids selected from Ixic acid, heptanedioic acid, or cyclohexyldicarboxylic acid and their anions, pyrazine, bipyridine and the like. It is also possible to mix and use one or more organics.

Representative examples of such metal-organic frameworks include chromium-terephthalate (called MIL-101; Science, 309, 2040, 2005), iron-benzenetricarboxylate (MIL-100 (Fe); Chem. Commun. , 2820, 2007), aluminum-benzenetricarboxylate (called MIL-100 (Al); Chem. Mater., 21, 5695, 2009), chromium-benzenetricarboxylate (MIL-100 (Cr)); Angew.Chem.Intl.Ed., 43, 6296, 2004), copper-benzenetricarboxylate (called Cu-BTC; Science, 283, 1148, 1999), vanadium-terephthalate (called MIL-47; Angew Chem. Intl. Ed., 41, 281, 2002; Phys. Chem. Chem. Phys., 10, 2979, 2008), aluminum-terephthalate (called MIL-53 (Al); Chem. Eur. J. , 10, 1373, 2004), and another chromium-terephthalate (called MIL-53 (Cr); J. Am. Chem. Soc., 124, 13519, 2002).

However, there are many metal-organic frameworks, and if the surface area is 100 m ² / g or more, it can be used as an adsorbent for adsorption desulfurization. Preferably, it is preferable to use an adsorbent having a surface area of 100 to 5000 m ² / g, but is not limited thereto. Other materials used for the support include surface area and pore volume, such as mesoporous materials such as SBA-15, SBA-16, MCM-41 and MCM-48 and zeolites such as ZSM-5, Na-Y, Beta and MCM-22. Is a large solid material.

Sanseongyeom the anion is ^{chloride (Cl -), nitrate (} NO 3 -), sulfate (SO 4 2 -), iodide (I -), fluoride (F -), perchlorate (ClO 4 -) at least one ion selected from the group consisting of and Cations are salts composed of metal ions except alkali metals and alkaline earth metals. Examples include, but are not limited to, CuCl ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , NiCl ₂ , Ni (NO ₃ ) ₂ , NiSO _4, and the like.

The method for preparing the adsorbent according to the present invention includes the following steps, and particularly provides a method for easily preparing the adsorbent without a high temperature firing step.

1) dissolving the acid salt in a suitable solvent to form a solution; And

2) adding the solution to a solid support of a metal-organic framework; And

3) drying the suspension.

In the present invention, the solvent is not particularly limited, and for example, solvents such as ethanol, ketone, aldehyde, ether, and ester may be used. For example, ethanol, propanol or methanol is preferable. Although the temperature of the drying step is not particularly limited, it is usually good to dry at room temperature below 200 ℃, preferably below 150 ℃ in terms of effects.

As described above, in the preparation of the adsorbent for adsorption desulfurization according to the present invention, when the acid salt is dissolved in a suitable solvent and supported on a solid support such as a metal-organic framework, it may be an easy manufacturing method that does not require a high temperature baking process. have. In addition, an adsorbent including an acid salt supported on a solid support such as a metal-organic framework has a very high desulfurization capacity and thus can be used for adsorptive desulfurization of fuels such as gasoline, kerosene, diesel and jet fuels and transportation fuels.

Figure 1 shows the benzothiophene adsorption isotherm using the CuCl ₂ / MIL-47 adsorbent of the present invention.
Figure 2 shows the adsorption amount of benzothiophene by adsorption time using the acid salt / MIL-47 adsorbent of the present invention.
Figure 3 shows the adsorption amount of benzothiophene by adsorption time using the CuCl ₂ / Cu-BTC adsorbent of the present invention.

Hereinafter, the present invention is described in more detail in the following non-limiting examples.

Example  1 - 4

0.013 g of CuCl ₂ was dissolved in 2 mL of ethanol and 0.15 g of purified MIL-47 (vanadium-terephthalate) was added. After stirring well for 30 minutes, ethanol was evaporated at room temperature and dried at 100 ° C. for 6 hours. The adsorbent thus prepared was named CuCl ₂ (0.15) / MIL-47. 0.15 means Cu / V (copper / vanadium element) ratio (mol / mol).

In addition, the adsorbent was prepared in the same manner as in Example 1, but the amount of CuCl ₂ was decreased to prepare the adsorbents of Examples 2 to 4. Example 2 is CuCl ₂ (0.08) / MIL-4, Example 3 is CuCl ₂ (0.05) / MIL-47, and Example 4 is CuCl ₂ (0.02) / MIL-47.

The adsorption capacity experiment of the prepared adsorbent was performed as follows.

Benzothiophene was dissolved in n- octane to obtain a solution of benzothiophene at a constant concentration. 0.1 g of the adsorbent obtained in Examples 1-4 was added to 15.0 mL of benzothiophene solution, followed by stirring at 25 ° C. for 24 hours to allow benzothiophene to be adsorbed. The benzothiophene concentration was analyzed by GC and adsorption isotherms as shown in FIG. 1 were obtained. Against the MIL-47 CuCl ₂ did not exist CuCl ₂ is supported MIL-47 can all be seen having a remarkably enhanced absorption capacity. In FIG. 1, the x axis represents the concentration of benzothiophene and the y axis represents the adsorption amount adsorbed.

Figure 2 shows the adsorption capacity according to the type of acid salt in a fixed state of 1000ppm initial concentration of benzothiophene. It was found that the adsorption amount of benzothiophene at the same time was improved compared to MIL-47 of Comparative Example 1 in which no acid salt was present.

Example  5, 6

The same procedure as in Example 1 was carried out except that other acid salts (NiCl ₂ and Cu (NO ₃ ) ₂ ) were used instead of CuCl ₂ . Example 5 was prepared by adjusting the amount of the acid salt so that the Ni / V ratio is 0.05, and Example 6 is a mol / mol ratio of Cu / V to 0.05. The result is shown in FIG. 2, and it turned out that the adsorption amount of the benzothiophene improves at the same time compared with the comparative example 1 which did not use the acid salt.

Example  7, 8

Example 1 and prepared in the adsorbent in the same way MIL-47 Cu-BTC in place - was used (copper benzenetricarboxylic carboxylate) CuCl CuCl ₂ by changing the amount of _{2 (0.07) / Cu-BTC} ( Example 7 ) And CuCl ₂ (0.04) / Cu-BTC (Example 8) were prepared. 0.07 and 0.04 correspond to the mol / mol ratio of Cu (acid salt) / Cu (MOF). Also, in case of Cu-BTC CuCl ₂ did not exist CuCl Cu-BTC a _divalent support as described in 3, it can be seen that improvement in the amount of benzothiophene adsorbed at the same time.

Comparative example  One ( MIL -47)

Adsorption experiment was performed in the same manner as in Example 1 except that MIL-47 without CuCl ₂ was used as the adsorbent. As shown in FIG. 1, the equilibrium adsorption amount was very low.

Comparative example  2 ( Cu - BTC )

Adsorption experiment was performed in the same manner as in Example 7, but Cu-BTC without CuCl ₂ was used as the adsorbent. As shown in Figure 3, the adsorption amount at the same time was very low.

Comparative example  3 (high temperature firing effect)

Adsorption experiment was performed similarly to Example 1, but the adsorption experiment was performed after firing the adsorbent prepared in Example 3 at 750 ° C. for 5 hours. The adsorbent after firing was black and probably consisted of copper oxide and carbon. As a result, it showed that the adsorption capacity was very low (<5%) compared to the adsorbent of Example 3, which was not calcined, and thus, the adsorbent which did not undergo firing after supporting the acid salt in the adsorbent as in the present invention showed very excellent performance. there was.

As shown in the above Examples and Comparative Examples, it is understood from the results of the Examples and Comparative Examples that the adsorbent for adsorption desulfurization and the method for producing the adsorbent for desulfurization at low temperature are an economical and effective method for producing the adsorbent for adsorption desulfurization at low temperature. Can be. In addition, it can be seen that the prepared adsorbent has a very high adsorption capacity and can be effectively used for adsorption desulfurization.

Claims (10)

Adsorbent for adsorption desulfurization prepared by supporting acid salt on a porous solid support.
The method of claim 1, wherein
The porous solid support is an adsorbent for desulfurization, which is a metal-organic framework.
The method of claim 1, wherein
The sanseongyeom the anion is ^{chloride (Cl -), nitrate (} NO 3 -), sulfate (SO 4 2 -), iodide (I -), fluoride (F -), perchlorate (ClO 4 -) at least one anion selected from the group consisting of and Adsorbent, characterized in that the cation is a salt consisting of a metal cation except alkali metal and alkaline earth metal.
The method of claim 3, wherein
The acid salt is an adsorbent, characterized in that at least one salt selected from CuCl ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , NiCl ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ .
The method according to claim 2, wherein
The metal-organic skeletal porous solid support is an organic linker, and includes a carboxylic acid group, a carboxylic acid anion group, an amino group (-NH ₂ ), and an imino group (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^- ), A pyridine group or a pyrazine group acid salt is an adsorbent in which at least one linker selected from CuCl ₂ , Cu (NO ₃ ) ₂ , CuSO ₄ , NiCl ₂ , Ni (NO ₃ ) ₂ , and NiSO ₄ is combined with a metal. The method of claim 1, wherein
The porous solid support is vanadium-benzenedicarboxylate and the acid salt is copper chloride, characterized in that the adsorbent for desulfurization.
1) dissolving the acid salt in a solvent to make a solution; And
2) adding the solution to a metal-organic framework; And
3) drying the adsorbent. 8. The method of claim 7,
The manufacturing method of the adsorbent does not include a high temperature baking step.
8. The method of claim 7,
The solvent is an alcohol, ketone, ether, aldehyde or ester solvent manufacturing method of the adsorbent.
The method of claim 9,
The solvent is a method for producing an adsorbent, characterized in that ethanol, propanol or methanol.

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