Invention title: Adsorbent
Technical field
[0001]
　The present invention relates to an adsorbent for removing carbonyl sulfide.
Background technology
[0002]
　Carbonyl sulfide (chemical formula: COS) is a kind of sulfur compound and is known to be a toxic substance of various catalysts. For example, propylene, whose demand has been increasing in recent years, contains carbonyl sulfide as a trace impurity, and if such propylene is sent to the polymerization process without purification, the catalyst for propylene polymerization is poisoned by carbonyl sulfide. It is known that it ends up (Patent Document 1).
[0003]
　As a method for removing such impurities, for example, a distillation method for separating an object and impurities by utilizing a boiling point difference is industrially used. However, it is also known that carbonyl sulfide contained in propylene is difficult to completely separate by a distillation method because the boiling points of propylene and carbonyl sulfide are close to each other. Further, it is known that not only the case of propylene but also carbonyl sulfide contained in a hydrocarbon having 2 to 6 carbon atoms having a boiling point close to that of carbonyl sulfide is also difficult to completely separate by a distillation method (patented). Document 2).
[0004]
　As described above, as a method for removing carbonyl sulfide, which is difficult to separate by the distillation method, a method for removing carbonyl sulfide by contacting with an adsorbent, a method for removing by contacting with an absorbing liquid, a method for removing by hydrolysis, and the like are known. ing.
[0005]
　For example, Patent Document 3 discloses a method for removing carbonyl sulfide by contacting an adsorbent in which lead oxide or the like is supported on an alumina carrier with a fluid containing carbonyl sulfide. At this time, carbonyl sulfide is removed by contacting with lead oxide contained in the adsorbent.
[0006]
　Patent Document 4 discloses an absorbent (adsorbent) for a sulfur compound containing at least one selected from copper carbonate, basic copper carbonate, copper hydroxide and a mixture thereof. Further, when the sulfur compound is carbonyl sulfide, a method is disclosed in which carbonyl sulfide is hydrolyzed by γ-alumina used as a carrier and the generated hydrogen sulfide is removed by basic copper carbonate.
[0007]
　Patent Document 5 discloses that alumina can be used as a catalyst for hydrolyzing carbonyl sulfide, and that alumina may be acidic. However, it is also disclosed to promote unwanted polymerization side reactions when used in hydrocarbon streams containing sulfur compounds containing olefins. It is also disclosed that this side reaction is minimized by using an alkali such as sodium oxide or potassium oxide as a dopant. Such a hydrolysis catalyst in which an alkali is added to alumina is also reported in Patent Document 6, for example.
Prior art literature
Patent documents
[0008]
Patent Document 1: Japanese Patent Application Laid-Open No. 2012-206944
Patent Document 2: Japanese Patent Application Laid-Open No. 5-070375
Patent Document 3: Japanese Patent Application Laid-Open No. 5-293366
Patent Document 4: Japanese Patent Application Laid-Open No. 9-510141
Patent Document 5: Special Publication No. Table 2008-524377
Patent Document 6: Japanese Patent Application Laid-Open No. 2-276891
Outline of the invention
Problems to be solved by the invention
[0009]
　In the adsorbent that removes carbonyl sulfide after hydrolysis as in Patent Document 4, the removal rate of carbonyl sulfide is greatly affected by the hydrolysis reaction activity of carbonyl sulfide. Therefore, an object of the present invention is to provide an adsorbent containing a component having excellent hydrolysis reaction activity of carbonyl sulfide.
Means to solve problems
[0010]
　As a result of examining the hydrolysis reaction activity of carbonyl sulfide for various substances, the present inventors have found that the above-mentioned hydrolysis reaction activity is enhanced by using a weakly acidic aluminum compound. The present inventors have completed the present invention by finding that the adsorbent containing an aluminum compound and copper oxide can efficiently remove carbonyl sulfide contained in a fluid containing an olefin.
　That is, the adsorbent of the present invention is an adsorbent for removing carbonyl sulfide contained in a fluid containing an olefin, contains copper oxide, contains an aluminum compound, and the content of the aluminum compound is converted to Al. in ranges from 10 wt% to 50 wt%, ammonia temperature desorption measurement (hereinafter, NH 3 also called -TPD measurement.) NH in the temperature range of below 200 ° C. 100 ° C. or more, which is calculated by the 3 de The separation amount is in the range of more than 0.001 mmol / g and 1 mmol / g or less.
Effect of the invention
[0011]
　According to the present invention, it is possible to provide an adsorbent containing a component having excellent hydrolysis reaction activity of carbonyl sulfide.
Mode for carrying out the invention
[0012]
　Hereinafter, the present invention will be specifically described based on the embodiments.
[0013]
[Adsorbent of the
　present invention ] The adsorbent of the present invention is an adsorbent for removing carbonyl sulfide contained in a fluid containing an olefin, and contains copper oxide, an aluminum compound, and the aluminum compound. The amount is in the range of 10% by mass or more and 50% by mass or less in terms of Al, and the amount of NH 3 desorbed in the temperature range of 100 ° C. or more and 200 ° C. or less calculated by NH 3- TPD measurement is 0.001 mmol / g. It is in the range of more than 1 mmol / g or less. 　The adsorbent of the present invention contains a component that hydrolyzes carbonyl sulfide to hydrogen sulfide and a component that adsorbs hydrogen sulfide, and exhibits weak acidity. Since the adsorbent of the present invention contains a weakly acidic compound as a component that hydrolyzes carbonyl sulfide to hydrogen sulfide, it also exhibits weak acidity as an adsorbent. For example, it contains a weakly acidic aluminum compound. The adsorbent of the present invention contains copper oxide as a component that adsorbs hydrogen sulfide. Copper oxide also has a function of adsorbing carbonyl sulfide. Comparing the case where hydrogen sulfide is adsorbed on copper oxide and the case where carbonyl sulfide is adsorbed, the adsorption rate is faster when hydrogen sulfide is adsorbed. Therefore, when comparing an adsorbent containing a component that hydrolyzes copper oxide and carbonyl sulfide with an adsorbent containing copper oxide but not a component that hydrolyzes carbonyl sulfide, the former has a higher removal rate of carbonyl sulfide. It will be faster.
[0014]
　Since the adsorbent of the present invention contains a weakly acidic compound, it exhibits weakly acidic properties. In the present invention, the amount of NH 3 elimination in the temperature range of 100 ° C. or higher and 200 ° C. or lower calculated by NH 3- TPD measurement was used as an index indicating weak acidity . NH 3 and -TPD measurement, a one way to evaluate the solid acidity of the substance, NH is a basic compound 3 was adsorbed to acid sites of the substance as a probe, followed heating to desorb This is a method for measuring the amount of NH 3 . By using this method, the amount of acid in the substance can be determined from the amount of NH 3 eliminated. Furthermore, it is also known that the desorption temperature of NH 3 changes depending on the acid strength. For example, when the acid strength is low , the interaction between NH 3 and the acid point becomes small, so that the desorption temperature of NH 3 Will be low. In the present invention, the weak acidity of the aluminum compound contained in the adsorbent of the present invention is defined by utilizing such an evaluation method. In the adsorbent of the present invention, the amount of NH 3 desorbed in the temperature range of 100 ° C. or higher and 200 ° C. or lower calculated by the NH 3- TPD measurement is in the range of more than 0.001 mmol / g and 1 mmol / g or less. This NH 3When the desorption amount is 0.001 mmol / g or less, the hydrolysis activity of carbonyl sulfide becomes low, and the removal rate thereof also becomes slow, which is not preferable. The amount of NH 3 desorbed may be in the range of 0.005 mmol / g or more and 0.1 mmol / g or less, or may be in the range of 0.005 mmol / g or more and 0.05 mmol / g or less. In the adsorbent of the present invention, the NH 3 it is to be easily imagined that hydrolysis activity of carbonyl sulfide The more the desorption amount increases. However, for example, NH, such as the aforementioned range 3 even when desorption amount is relatively small, the hydrolysis reaction activity is high, and increases the removal rate.
[0015]
　The adsorbent of the present invention preferably contains, as a weakly acidic compound, a weakly acidic aluminum compound instead of the alkali-supported alumina disclosed in Patent Documents 5 and 6.
[0016]
　It is not clear why such a weakly acidic aluminum compound is effective in the hydrolysis reaction of carbonyl sulfide, but the present inventors speculate that the reason is as follows. That is, the acid point has a positive charge, the carbonyl sulfide has a structure of O = C = S, and the negative charge is biased to the O atom due to the difference in electronegativity between the O atom and the S atom. Considering that it is a polar molecule, the following reasons can be considered. First, the negatively charged O atom contained in carbonyl sulfide is adsorbed on the acid point having a positive charge, and this reacts with the surface OH group existing on the surface of the aluminum compound to promote the hydrolysis reaction. It is considered to be. Further, since the water molecule is also a polar molecule like carbonyl sulfide, it is considered that the hydrolysis reaction is promoted even if the water molecule adsorbed on the acid point reacts with carbonyl sulfide. When an adsorbent containing an aluminum compound having a strong acid strength is used in a fluid containing an olefin, the adsorbent may be coated with a polymer produced by the polymerization reaction of the olefin. This may reduce the adsorption amount and removal rate of carbonyl sulfide. However, since the adsorbent containing a weakly acidic aluminum compound has a weak acid strength, it is considered that such a reaction is unlikely to occur even when used in a fluid containing an olefin.
[0017]
　Aluminum compound contained in the adsorbent of the present invention, NH 3 -TPD NH at a temperature range of below 200 ° C. 100 ° C. or more, which is calculated by measuring 3 desorption amount is in the range of less than 0.01 mmol / g or more 10 mmol / g It is preferable to be in. An adsorbent containing such a weakly acidic aluminum compound has a high hydrolysis activity of carbonyl sulfide and a high removal rate thereof. Aluminum compound contained in the adsorbent of the present invention, the NH 3 desorption amount may be in the range of 0.01 mmol / g or more 1mmol / g, 0.01mmol / g or more 0.05 mmol / g or less It may be in the range of. In the aluminum compound contained in the adsorbent of the present invention, the NH 3 is that the hydrolysis activity of the carbonyl sulfide The more the desorption amount increases is intended to be easily imagined, for example, as described above in the range Even when the amount of NH 3 desorbed is relatively small, its hydrolytic activity is high.
[0018]
　The aluminum compound contained in the adsorbent of the present invention is preferably aluminum hydroxide, aluminum oxide (alumina) or a mixture thereof. When aluminum hydroxide is contained, its crystal structure is more preferably pseudoboehmite. The crystal structure of aluminum hydroxide can be determined from the X-ray diffraction pattern. However, since boehmite and pseudo-boehmite have similar crystal structures, it is difficult to clearly distinguish them from the X-ray diffraction pattern. However, it is known that the X-ray diffraction pattern of pseudo-boehmite is broader than that of boehmite. Therefore, in the present invention, if the half-value width (half-value total width) of the peak attributed to the (020) plane derived from the crystal structure of boehmite is 1.0 ° or more, it has a pseudo-boehmite structure. Judge as a thing. When aluminum oxide is contained, the crystal structure thereof is more preferably one or more selected from χ (chi), ρ (low), and θ (theta), and chi is particularly preferable. The crystal structure of aluminum oxide can be determined from the X-ray diffraction pattern.
[0019]
　The content of the aluminum compound contained in the adsorbent of the present invention (hereinafter, also referred to as Al content) is in the range of 10% by mass or more and 50% by mass or less in terms of Al. If this content is too large, the content of copper oxide is relatively reduced, so that hydrogen sulfide generated by hydrolysis of carbonyl sulfide cannot be completely removed. Further, if this content is too small, the hydrolysis of carbonyl sulfide is difficult to proceed, so that the carbonyl sulfide removal rate of the adsorbent becomes slow. When this content is in the range of 10% by mass or more and 30% by mass or less, the removal rate of carbonyl sulfide becomes faster, which is preferable.
[0020]
　The adsorbent of the present invention preferably has an alkali content of less than 0.5% by mass in terms of metal, and particularly preferably less than 0.1% by mass. The adsorbent of the present invention has a plurality of acid points exhibiting weak acid properties, and these acid points may be inactivated when an alkali is adsorbed. Therefore, it is preferable that the alkali content of the adsorbent of the present invention is as low as possible.
[0021]
　In the adsorbent of the present invention, the content of the transition metal component other than copper may be less than 1% by mass, respectively, in terms of metal, and in particular, less than 0.1% by mass. There are various hydrolysis catalysts for carbonyl sulfide in which a transition metal component such as Cr or Zn is supported on an aluminum compound, but the adsorbent of the present invention contains carbonyl sulfide even when these transition metals are extremely small or absent. Can be hydrolyzed and the removal rate of carbonyl sulfide is fast.
[0022]
　The adsorbent of the present invention contains copper oxide. As described above, the copper oxide contained in the adsorbent of the present invention is a component for removing hydrogen sulfide produced by hydrolyzing carbonyl sulfide. Further, since water is generated when hydrogen sulfide comes into contact with copper oxide and is removed (CuO + H 2 S → CuS + H 2 O), this water can be reused for the hydrolysis reaction of carbonyl sulfide. The copper oxide contained in the adsorbent of the present invention can be identified from the X-ray diffraction pattern. Further, the copper oxide contained in the adsorbent of the present invention has a half-value width (half-value total width) of the diffraction peak attributed to copper oxide appearing in the range of 2θ = 37 to 40 ° of 0.8 to 2 °. It is preferably in the range. If this half-value range includes copper oxide in the above range, the removal rate of carbonyl sulfide tends to be faster.
[0023]
　The content of copper oxide contained in the adsorbent of the present invention (hereinafter, also referred to as Cu content) is preferably in the range of 5% by mass or more and 50% by mass or less in terms of Cu, and is 30% by mass or more and 50% by mass or less. More preferably, it is in the range of% or less. If the content of copper oxide is too small, the hydrogen sulfide produced by the hydrolysis of carbonyl sulfide cannot be completely removed and flows out. Hydrogen sulfide is known as a toxic substance for various catalysts, and it is not preferable to let hydrogen sulfide flow out. Even if the content of copper oxide is too high, the content of the above-mentioned aluminum compound is relatively reduced, so that carbonyl sulfide cannot be hydrolyzed efficiently, and the removal rate of carbonyl sulfide tends to decrease. ..
[0024]
　In the adsorbent of the present invention, the molar ratio of copper to aluminum (Cu / Al) is preferably in the range of 0.1 or more and 2 or less, and more preferably in the range of 0.5 or more and less than 1. When this molar ratio is within the above range, the balance between the hydrolysis of carbonyl sulfide and the removal of hydrolyzed hydrogen sulfide is good, and as a result, the removal rate of carbonyl sulfide is increased.
[0025]
　The adsorbent of the present invention can be used as an adsorbent without any problem even if its specific surface area is less than 200 m 2 / g. In general, an adsorbent is required to have a high specific surface area because it adsorbs adsorbed species on its surface. However, since the adsorbent of the present invention removes carbonyl sulfide after a hydrolysis reaction, carbonyl sulfide can be efficiently removed even with a specific surface area that is not necessarily high as an adsorbent. This specific surface area may be 100 m 2 / g or more and less than 200 m 2 / g. If the specific surface area is less than 100 m 2 / g, the amount of carbonyl sulfide adsorbed by the adsorbent may be small, which is not preferable.
[0026]
　The shape of the adsorbent of the present invention may be any conventionally known shape, and may be, for example, spherical, columnar, or a shape similar thereto. The size (minimum distance among the sizes of the adsorbent) is preferably in the range of 0.5 mm or more and 6 mm or less. If the size of the adsorbent is too large, the contact area between the adsorbent and the olefin is reduced, which may reduce the removal rate of carbonyl sulfide, which is not preferable. On the other hand, if the size of the adsorbent is too small, the pressure loss becomes high when the fluid containing the olefin is circulated, and the fluid may not be circulated.
[0027]
　The adsorbent of the present invention is used as an adsorbent for removing carbonyl sulfide contained in a fluid containing an olefin. The adsorbent of the present invention is suitable as an adsorbent for removing carbonyl sulfide contained in a fluid containing C2 to C6 olefins, and particularly suitable as an adsorbent for removing carbonyl sulfide contained in a fluid containing propylene. is there. Further, the adsorbent of the present invention can efficiently remove carbonyl sulfide even in a fluid containing a liquid olefin that is difficult to diffuse inside the adsorbent.
[0028]
　The adsorbent of the present invention can be suitably used in a process in which the concentration of carbonyl sulfide contained in a fluid containing an olefin is in the range of 0.01 ppm or more and 30 ppm or less. Further, the adsorbent of the present invention can hydrolyze carbonyl sulfide by utilizing the surface OH groups of the aluminum compound contained in the adsorbent of the present invention even in a process in which the amount of water is smaller than that of carbonyl sulfide. Therefore, carbonyl sulfide can be removed efficiently. More specifically, carbonyl sulfide can be efficiently removed even in a process in which the molar ratio (H 2 O / COS) of carbonyl sulfide to water contained in the fluid containing olefin is less than 1. The water produced when hydrogen sulfide produced by the hydrolysis of carbonyl sulfide is removed by contact with copper oxide is also reused for the hydrolysis reaction of carbonyl sulfide.
[0029]
　The adsorbent of the present invention can efficiently remove carbonyl sulfide in a process in which the temperature of the fluid containing the olefin is in the range of −10 ° C. or higher and 70 ° C. or lower. If the temperature of the fluid containing the olefin is too low, the carbonyl sulfide is not efficiently hydrolyzed, and the removal rate of the carbonyl sulfide tends to decrease. Further, when the temperature of the fluid containing the olefin is too high, the polymerization reaction of the olefin tends to occur, so that it is preferable to use it in the above range.
[0030]
[Method for producing
　the adsorbent of the present invention ] The adsorbent of the present invention can be produced, for example, by the method for producing the adsorbent of the present invention described below.
　The method for producing an adsorbent of the present invention is a method for producing an adsorbent for removing carbonyl sulfide contained in a fluid containing an olefin, and is 100 ° C. or higher and 200 ° C. or lower calculated by ammonia temperature desorption measurement. of NH in the temperature range 3 desorption amount, and the aluminum compound in the range of 0.01 mmol / g or more 10 mmol / g, and a copper oxide, the content of the aluminum compound, calculated as Al, 10 wt% or more It is a method of mixing so as to be in the range of 50% by mass or less.
[0031]
　It is known that the acid properties of an aluminum compound change depending on its crystal structure, impurities (Si, alkali, etc.), production method, and the like. The aluminum compound contained in the adsorbent of the present invention can be obtained, for example, by surface-treating a conventionally known aluminum compound with a weak acid. When an aluminum compound surface-treated with a weak acid is fired, the acid properties of the surface change, so it is preferable to use the aluminum compound without firing. Specifically, it is preferable not to bake at a temperature of 300 ° C. or higher. In addition, the amount of NH 3 desorbed in the temperature range of 100 ° C. or higher and 200 ° C. or lower calculated by NH 3- TPD measurement from the aluminum compounds sold as industrial raw materials is 0.01 mmol / g or more and 10 mmol / g or less. Aluminum compounds in the range may be obtained and used. In addition, a component other than the above-mentioned aluminum compound, which is weakly acidic, may be added.
[0032]
　The copper oxide may be obtained by calcining a copper compound, or may be synthesized in an aqueous solution. When a copper compound is fired, it can be obtained by firing a copper compound such as copper acetate, basic copper carbonate, and copper nitrate at 300 ° C. or higher and 500 ° C. or lower. Further, when copper oxide is synthesized in an aqueous solution, it can be obtained by heating to 50 ° C. or higher with copper hydroxide dispersed in the aqueous solution.
[0033]
　In the present invention, the above-mentioned aluminum compound and copper oxide may be mixed and then molded into a desired shape. For example, it may be compression-molded and then crushed to form a desired shape, or may be molded into a desired shape by a method such as tableting or extrusion molding. At this time, a molding aid or the like may be added in order to improve the moldability. It is preferable not to fire after mixing the above-mentioned aluminum compound and copper oxide. When fired in such a state, the acid properties of the aluminum compound may change due to the formation of by-products such as CuAl 2 O 4 and the influence of heat.
Example
[0034]
　Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
　Further, the method for preparing copper oxide used in the examples and comparative examples of the present invention is shown below.
[0035]
　(Preparation Method of Copper Oxide) A
　mother liquor was prepared by dissolving 231 g of sodium hydroxide in 5.8 kg of ion-exchanged water.
Next, 676 g of copper sulfate pentahydrate was dissolved in 2.6 kg of ion-exchanged water to prepare an additive solution. The mother liquor and the additive liquor were mixed in a heated state to form a copper oxide precipitate. The slurry containing the copper oxide precipitate was filtered to separate the copper oxide precipitate, and then thoroughly washed to obtain a copper oxide precipitate cake. The precipitated cake was dispersed in 4.0 kg of ion-exchanged water to obtain a copper oxide slurry. The copper oxide slurry was dried to obtain powdered copper oxide.
[0036]
　[Example 1]
　Commercially available aluminum oxide (manufactured by UOP, product name: VERSAL R-3) and the above-mentioned copper oxide were physically mixed at a mass ratio of 1: 1. This was set in a tablet molding machine and pressed at a pressure of 60 MPa for 1 minute. After pulverizing the obtained molded product into granules, the granules were classified using sieves having a mesh size of 355 μm and 710 μm to obtain granules having a mesh size of 355 to 710 μm. These granules were designated as Adsorbent A. Information on raw materials (type of aluminum compound and alkali content) and information on adsorbent (Cu content, Al content and alkali content of adsorbent, and molar ratio of copper to aluminum in adsorbent (Cu /) Al)) is also shown in Table 1.
[0037]
　(NH 3- TPD measurement: NH 3 desorption amount in the temperature range of 100 ° C. or higher and 200 ° C. or lower )
　Regarding the aluminum compound used in Example 1 and the adsorbent obtained by the method of Example 1, NH 3- TPD Measurements were made. Specifically, 0.05 g of the above-mentioned aluminum compound was weighed as a sample and set in a sample tube of an NH 3- TPD measuring device (manufactured by Microtrack Bell, device name: BEL-CAT A) (the above-mentioned adsorption). When measuring the agent as a sample, 0.1 g of the sample was weighed.) Then, the inert gas (He) was heat-treated at 150 ° C. for 60 minutes while flowing through the sample tube at a flow rate of 30 ml / min. Thereafter, while maintaining the temperature of the sample tube at 100 ° C., NH 3 gas containing (NH 3 : 5%, the He: balance) was circulated for 60 minutes, NH sample 3 was adsorbed. Then, the inert gas was kept flowing in the sample tube at a flow rate of 30 ml / min for 60 minutes. Next, water vapor was introduced into the test tube for 30 minutes while maintaining the holding temperature of 100 ° C. and the flow rate of the inert gas of 30 ml / min, and NH 3 which was physically adsorbed was removed. The introduction of water vapor was stopped, and the mixture was maintained at a holding temperature of 100 ° C. and a flow rate of an inert gas of 30 ml / min for 30 minutes. Next, the temperature was raised to 700 ° C. at a heating rate of 10 ° C./min and held for 10 minutes. At this time, NH 3 detached from the sample Was measured using a quadrupole mass spectrometer (Q-Mass). From the data obtained by this measurement, the amount of NH 3 desorbed while the temperature of the sample tube was 100 ° C or higher and 200 ° C or lower was calculated, and this was divided by the charged amount of the sample to obtain 100 ° C or higher and 200 ° C or lower. NH at a temperature range 3 to calculate the desorption amount. The results are shown in Table 1.
[0038]
　(X-ray diffraction measurement: crystal structure of aluminum compound)
　X-ray diffraction measurement was performed on the aluminum compound and the adsorbent used in Example 1. Specifically, the sample was filled in a sample plate and set in an X-ray diffractometer (manufactured by Rigaku Corporation, device name: MultiFlex). Then, X-ray diffraction measurement was performed under the following conditions.

　Operation axis: 2θ / θ
　source: CuKα
　measurement method: Continuous
　voltage: 40 kV
　current: 20 mA
　Start angle: 2θ = 10 °
　End angle: 2θ = 80 °
　Sampling width: 0.020 °
　scan Velocity: 4.000 ° / min
　As a result of analyzing the X-ray diffraction pattern obtained by the X-ray diffraction measurement using the analysis software attached to the X-ray diffraction measuring device, it was assigned to the crystal structure shown in Table 1.
[0039]
　(Specific surface area measurement) The
　obtained adsorbent is pretreated under nitrogen flow, set in a fully automatic specific surface area measuring device (manufactured by Mountech, model: MacsorbHM model-1220), and the nitrogen adsorption method (BET method) is applied. The specific surface area was calculated by the BET 1-point method from the amount of nitrogen desorbed. Specifically, 0.1 g of a sample is filled in a measurement cell, pretreated at 250 ° C. to 40 min under nitrogen flow, and nitrogen mixed gas (nitrogen is 30% and helium is 70% in terms of body integration ratio). Nitrogen was equilibrium-adsorbed to the sample by keeping it at the liquid nitrogen temperature in the air stream of. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, and the amount of nitrogen desorbed during that time was detected by TCD. Finally, pure nitrogen was circulated in a 1 cc pulse, and the specific surface area was calculated from the ratio with the previous amount of nitrogen desorption.
[0040]
　(Test of Hydrolysis Reaction Activity of carbonyl Sulfide)
　The hydrolysis reaction activity of carbonyl sulfide was evaluated for the aluminum compound used in Example 1. Specifically, a reaction tube having an inner diameter of 0.53 cm is filled with an adsorbent A (granule shape: 355 to 710 μm) as a sample so that the layer height is 1.5 cm, and the reaction tube is filled with adsorbent A (granule shape: 355 to 710 μm) at 150 ° C. for 1 hour under nitrogen flow. Heat-treated. Then, while maintaining the temperature of the sample at 22 ° C., the raw material liquid (COS: 10 mass ppm, 1-hexene: balance) was circulated at a supply rate of 3.2 g / min. A gas chromatograph equipped with a chemiluminescent sulfur detector (SCD detector) for the inlet and outlet liquids 90 minutes after the flow of the raw material liquid, in which the inlet and outlet liquids of the reaction tube are sampled at predetermined time intervals. manufactured by Agilent technologies, Inc., apparatus name: 7890B GC) that COS concentration and H using 2 were measured S concentration. From the obtained results, the conversion rate of COS was calculated based on the following formula (1). The results are shown in Table 1.
Equation (1): COS conversion rate [%] = the exit of the H 2 S concentration / inlet of the COS concentration × 100
[0041]
　(Test for removal rate of carbonyl sulfide)
　The removal rate of carbonyl sulfide was evaluated for the adsorbent obtained in Example 1. Specifically, it is the same as the above-mentioned method for evaluating the hydrolysis reaction activity of carbonyl sulfide, except that the adsorbent is set in the reaction tube so that the layer thickness of the adsorbent is 8 cm. The COS removal rate constant was calculated from the difference in COS concentration between the inlet and outlet of the reaction tube 90 minutes after the flow of the raw material liquid. The results are shown in Table 1.
[0042]
　[Example 2]
　Adsorbent B was prepared in the same manner as Adsorbent A except that commercially available aluminum hydroxide (manufactured by UOP, product name: V-250) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0043]
　[Example 3]
　Adsorbent C was prepared in the same manner as Adsorbent A except that commercially available aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., product name: C10W) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0044]
　[Example 4]
　Commercially available aluminum hydroxide A (manufactured by UOP, product name: V-250) and the above-mentioned copper oxide are physically mixed at a mass ratio of 9: 1, set in a tablet molding machine, and 60 MPa. Pressure was pressed for 1 minute. After pulverizing the obtained molded product into granules, the granules were classified using sieves having a mesh size of 355 μm and 710 μm to obtain granules having a mesh size of 355 to 710 μm. These granules were designated as adsorbent D. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0045]
　[Example 5]
　Adsorbent E was prepared in the same manner as Adsorbent D except that commercially available aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., product name: C10W) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0046]
　[Example 6]
　Adsorbent F was prepared in the same manner as Adsorbent D except that commercially available aluminum oxide (manufactured by UOP, product name: VERSAL R-3) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0047]
　[Example 7]
　Using 200 g of copper oxide used in Example 1, commercially available χ (chi) -alumina (specific surface area: 210 m 2 / g) as a carrier, 8 g of an organic binder, and 100 g of silica sol as an inorganic binder (Si concentration). : 20% by mass (SiO 2 equivalent) and 125 g of ion-exchanged water were charged into a mixer and mixed uniformly to obtain a raw material mixture.
　This raw material mixture was put into an extrusion molding machine and extruded into a columnar shape having a diameter of 1.6 mmφ and a height of 3 to 5 mm to obtain a molded body. The molded product was dried in an electric dryer at a temperature of 120 ° C. for 16 hours to obtain a sulfur compound adsorbent. After pulverizing the obtained sulfur compound adsorbent into granules, the granules were classified using sieves having a mesh size of 355 μm and 710 μm to obtain granules having a mesh size of 355 to 710 μm. These granules were designated as the adsorbent G. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0048]
　[Comparative Example 1]
　Commercially available aluminum hydroxide (manufactured by Showa Denko Co., Ltd., product name: H-32) and the above-mentioned copper oxide are physically mixed at a mass ratio of 1: 9, set in a tablet molding machine, and 60 MPa. Pressure was pressed for 1 minute. After pulverizing the obtained molded product into granules, the granules were classified using sieves having a mesh size of 355 μm and 710 μm to obtain granules having a mesh size of 355 to 710 μm. These granules were designated as Adsorbent H. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0049]
　[Comparative Example 2]
　Adsorbent I was prepared in the same manner as Adsorbent G except that commercially available aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., product name: C10W) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0050]
　[Comparative Example 3]
　Adsorbent J was prepared in the same manner as Adsorbent G except that commercially available aluminum hydroxide (manufactured by UOP, product name: V-250) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0051]
　[Comparative Example 4]
　Adsorbent K was prepared in the same manner as Adsorbent G except that commercially available aluminum oxide (manufactured by UOP, product name: VERSAL R-3) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0052]
　[Comparative Example 5]
　Adsorbent L was prepared in the same manner as Adsorbent A except that commercially available aluminum hydroxide (manufactured by Showa Denko KK, product name: H-32) was used. Moreover, the same measurement as in Example 1 was performed. The results are shown in Table 1. Information on raw materials and adsorbents is also shown in Table 1.
[0053]
[table 1]

[0054]
　Table As is apparent from 1 to show the result, NH 3 desorption amount adsorbent in the range below 1 mmol / g greater than the 0.001 mmol / g (Examples 1-7) is, NH 3 desorption amount is Compared with Comparative Examples 1 to 5 which are adsorbents in the range of 0.001 mmol / g or less, the COS removal rate is significantly faster.
The scope of the claims
[Claim 1]
　An adsorbent for removing carbonyl sulfide contained in a fluid containing an olefin, which contains
　copper oxide and an
　aluminum compound, and
　the content of the aluminum compound is 10% by mass or more and 50% by mass in terms of Al. the following there of the range,
　NH at a temperature range of 100 ° C. or higher 200 ° C. or less, which is calculated by the ammonia temperature desorption measurements 3 desorption amount is in the range of 1 mmol / g greater than the 0.001 mmol / g,
　the adsorbent ..
[Claim 2]
　The aluminum compound, NH at a temperature range of 100 ° C. or higher 200 ° C. or less, which is calculated by the ammonia temperature desorption measurements 3 desorption amount is 0.01 mmol / g or more, an aluminum compound in the range of 10 mmol / g , The adsorbent according to claim 1.
[Claim 3]
　The adsorbent according to claim 2, wherein the aluminum compound is at least one selected from the group consisting of aluminum hydroxide and aluminum oxide.
[Claim 4]
　The adsorbent according to claim 3, wherein the crystal structure of the aluminum hydroxide is pseudo-bemite.
[Claim 5]
　The adsorbent according to claim 3, wherein the crystal structure of the aluminum oxide is at least one selected from the group consisting of χ, ρ, and θ.
[Claim 6]
The adsorbent according to any one of claims 1 to 5, wherein the 　specific surface area is in the range of less than 200 m 2 / g.
[Claim 7]
　The adsorbent according to any one of claims 1 to 6, wherein the content of the copper oxide is in the range of 5% by mass or more and 50% by mass or less in terms of Cu.
[Claim 8]
　The adsorbent according to claim 7, wherein the Cu / Al molar ratio is in the range of 0.1 or more and 2 or less.
[Claim 9]
　The adsorbent according to any one of claims 1 to 8, wherein the alkali content is in the range of less than 0.5% by mass.
[Claim 10]
　A method for producing an adsorbent for removing carbonyl sulfide contained in a fluid containing olefins,
　NH at a temperature range of 100 ° C. or higher 200 ° C. or less, which is calculated by the ammonia temperature desorption measurements 3 desorption amount is , 0.01 mmol / g or more and 10 mmol / g or less, and copper oxide so
　that the content of the aluminum compound is in the range of 10% by mass or more and 50% by mass or less in terms of Al. A
　method for producing an adsorbent to be mixed .