[0001]The present invention relates to an adsorbent for adsorbing and removing sulfur compounds contained in various processes.
BACKGROUND
[0002]Sulfur compounds in petroleum refining process or petrochemical process, etc., deteriorates the equipment and catalyst used in the process, or sulfur oxide generated upon combustion are problematic since they produce problems such as causing acid rain ing. In particular, and sulfur compounds contained in the raw materials used in these processes are problematic, various methods to remove this has been studied.
[0003]
　Method of removing sulfur compounds contained in the raw material used in the petroleum refining process and petrochemical process, etc., it is mainly a method of recovering as sulfur decomposing sulfur compounds with a catalyst, to adsorb the sulfur compounds on the adsorbent How to remove Te, etc. there is.
[0004]
　As a method for decomposing sulfur compounds using a catalyst, for example, a hydrodesulfurization process. Hydrodesulfurization process in the presence of a high temperature and a catalyst, a method of decomposing sulfur compounds with hydrogen, is useful as a method of treating a raw material containing a high concentration of sulfur compounds. However, this method is the use of equipment for supplying hydrogen, the need for a high temperature of 300 ~ 400 ° C., the handling of the catalyst due to the catalytic reaction has been pointed out problems such as becoming complicated ( Patent Document 1). Further, the reaction raw material and hydrogen another compound (by-product) is also likely to produce, in the process dislike such reactions is a problem that can not be used. For this reason, the hydrodesulfurization method is generally widely used in petroleum refining processes.
[0005]
　Meanwhile, a method of removing by adsorbing sulfur compounds the adsorbent is a simple way to say circulating feedstock containing sulfur compounds under the conditions of room temperature ~ 400 ° C. in a column which the adsorbent is filled, hydrogen supply equipment required, it has characteristics that can be removed to the order of less than ppm. The adsorbent of sulfur compounds, and those which physically adsorb sulfur compounds, those chemically adsorbed are known, as the physical adsorbents are known alumina, as a chemical adsorbent , those used in high temperature adsorbent comprising zinc oxide, what can be used at room temperature are known adsorbents containing copper oxide.
　However, when processing a raw material containing a high concentration of sulfur compounds, and that the greater the frequency of replacement of the adsorbents, there are also problems such as adsorption force varies depending on the type of sulfur compounds. How this reason, use of the adsorbent is generally widely used in petrochemical process (Patent Document 2).
[0006]
　Adsorbent of sulfur compounds is generally possible adsorption rate of sulfur compounds is large, it is required that the amount of adsorption of sulfur compounds in many cases. Further, the adsorbent of sulfur compounds used as an industrial, in addition to the above chemical properties, for example, physical properties such as mechanical strength are also required. Mechanical strength is low sulfur compound adsorbent is generally known that powdering and collapse easily occurs. For example, Patent Document 3, the adsorbent of sulfur compounds used in the liquid phase, the adsorbent for easily collapse, it is disclosed that is required high compressive strength of more than 4 kg.
CITATION
Patent Document
[0007]
Patent Document 1: Laid-Open Publication No. 7-118668
Patent Document 2: Laid-Open Publication No. 3-213115
Patent Document 3: Japanese Patent Publication No. 5-293366
Summary of the Invention
Problems that the Invention is to Solve
[0008]
　However, the conventional sulfur compound adsorbent, even such high crush strength, for example, a year using a long period of 2 years, leading to pulverization or disintegration gradually crushing strength is lowered problems was there.
[0009]
　The present inventors have results of investigation of decrease causes crushing strength of the sulfur sorbent, I have found that a trace amount of water contained in the raw material used in the various processes are responsible for lowering the crushing strength. The present invention has solved this new problem, by imparting water resistance to increase the consolidation strength of the particles each other constituting the adsorbent by including a certain amount of cellulose derivative in the adsorbent, moisture crush strength hardly reduced in a process comprising, providing a water resistance of sulfur compounds adsorbent to allow long-term use.
Means for Solving the Problems
[0010]
　Water resistant sulfur compound adsorbent of the present invention (hereinafter, also referred to as the adsorbent of the present invention.) Is characterized by containing a cellulose derivative with a copper component which adsorbs a sulfur compound.
　Adsorbents of the present invention have by comprising a cellulose derivative with a copper component, which has excellent water resistance, crush strength even when used in a process comprising the moisture is hard to decrease, dusting or disintegrating hard nature .
The invention's effect
[0011]
　Adsorbents of the present invention, conventional industrial gas, natural gas, various gases such as petroleum fractions and oils like (hereinafter, also referred to as process feed.) In the process of removing sulfur compounds contained in, particularly a significant effect on the process material containing trace amounts of moisture. Adsorbents of the present invention, the crush strength of the adsorbent be used in a process comprising the water is unlikely to decrease, powdering and collapse can be suppressed, increase or drift etc. of the differential pressure is less likely to occur. Therefore, the adsorbent of the present invention may be used in a process containing water, it can be used for a long time.
DESCRIPTION OF THE INVENTION
[0012]
　It will be specifically described based on an embodiment of the present invention.
[Adsorbent of the present invention]
　adsorbent of the present invention is a sulfur compound adsorbent characterized by containing a cellulose derivative with a copper component which adsorbs a sulfur compound. Cellulose derivatives fixing a copper component to each other, or since the copper ingredient with the carrier and fixed to each other increase the overall strength of the adsorbent, the adsorbent of the present invention may be used to process raw material containing moisture, crushing strength There hardly decreased, hardly powdered or disintegrating. The cellulose derivatives are not only increasing the crush strength of the adsorbent of the present invention, the effect of moisture in the interior of the adsorbent (bonding surface of the interior of the particle of the molded body) to block the penetration of the present invention It is considered to be one. Therefore, the adsorbent of the present invention crushing strength was immersed in a certain time the water is less likely to decrease. Specifically, for example, in Examples described below, while the retention rate of crushing strength after immersion in a certain time the water in the first embodiment of the present invention is 86%, Comparative Example 1 containing no cellulose derivative in retention rate crushing strength is 20% adsorbent of the present invention is much higher retention ratio of the crushing strength have been shown to have excellent water resistance.
[0013]
　It cellulose derivative contained in the adsorbent of the present invention are hydroxyethyl cellulose by substituting a part of the hydrogen atom of the hydroxyl group in the cellulose methyl cellulose substituted with a methyl group, hydroxypropyl cellulose or hydroxyethyl group substituted with hydroxypropyl groups preferably, and more preferably hydroxypropylmethylcellulose.
[0014]
　The content of the methoxy group contained in hydroxypropyl methylcellulose as the average number of hydroxyl groups substituted by methoxy groups per glucose ring unit of cellulose, preferably in the range of 1-2. Adsorbents of the present invention in which the content of methoxy groups comprises hydroxypropyl methylcellulose in this range, the water resistance becomes higher. The content of hydroxypropoxy groups in the hydroxypropylmethylcellulose has an average number of moles of hydroxypropoxy groups added per glucose ring unit of cellulose, 0.15 or more, in the range of 0.25 or less It is preferred.
[0015]
　Whether it contains a cellulose derivative on the adsorbent can be confirmed using the structural analysis method of common organic compounds. For example, in terms of eluted organic substances contained in the adsorbent in the solvent, H-NMR, IR, using conventional structural analysis methods such mass spectrum, specific that it contains the organic substance having the structure of cellulose derivatives if possible, it can be determined that contain cellulose derivatives.
[0016]
　The content of cellulose derivatives contained in the adsorbent of the present invention, the total weight of the adsorbent to 0.5% by weight or more, preferably in the range of 5 wt% or less, 1% by weight or more, 3% by weight it is particularly preferred in the range of. When the content of the cellulose derivative contained in the adsorbent of the present invention is too small, unpreferably water resistance is low, even if too much Conversely, copper component contained in the adsorbent of the present invention is excessively coated put away, because it may interfere with the adsorption of sulfur compounds is not preferable.
[0017]
　The content of the cellulose derivative can be measured by a known method. For example, high frequency induction heating combustion - measuring the carbon content by infrared absorption spectroscopy apparatus, can be calculated from the carbon content. Further, when containing an organic substance other than the cellulose derivative, it is possible to identify the organic type and proportions contained with a structural analysis method of the organic compound described above, is calculated using the carbon content of above this ratio . Furthermore, it may be calculated back from the charged amount of the organic material used as the raw material.
[0018]
　Adsorbents of the present invention preferably contains an inorganic binder with cellulose derivatives. Inorganic binder contained in the adsorbent of the present invention, for example, bentonite, alumina is preferably an inorganic compound having a large number of OH groups on the surface of the silica. In particular, preferably contains silica derived from a silica sol. Derived silica sol has a large number of silanol groups on its surface, since these silanol groups easily tied by the interaction between OH groups contained in the cellulose derivative, the crushing strength of the adsorbent of the present invention cellulose derivatives with a higher is hardly eluted in the process feed or water. Thus, when a state in which the cellulose derivative contained in the adsorbent of the present invention is linked by the interaction with the inorganic binder, compressive strength and water resistance is increased.
[0019]
　The content of the inorganic binder contained in the adsorbent of the present invention, 1 wt% or more in terms of oxide relative to the total weight of the adsorbent is preferably in the range of 10 wt% or less, 3 wt% or more, 7 and more preferably in the weight percent range. By the content of the inorganic binder is within this range, effects of the above is maximize. The content of the inorganic binder, for example, can be quantitatively ICP emission spectrometry, atomic absorption spectrometry, by a general quantitative analysis, such as X-ray fluorescence analysis.
[0020]
　Adsorbents of the present invention includes a copper component which adsorbs a sulfur compound. Copper components copper compound having a property of adsorbing the metal copper or copper oxide or sulfur compounds, or may be any form which they are mixed. Since metal copper is a risk of fire when handling in air, copper is used in the adsorbent of the present invention is copper oxide is preferable.
[0021]
　The content of the copper component contained in the adsorbent of the present invention, CuO converted at 30 wt% or more, preferably in the range of 70 wt% or less, 40 wt% or more, in the range of 60 wt% or less more preferable. When the content of copper component is too small, the adsorption of sulfur compounds is reduced not preferable, even if the content of the copper component is too large, the amount of adsorption of sulfur compounds expensive price of the adsorbent without too much increase since, it is preferable that the content of copper is in the range described above.
[0022]
　Adsorbents of the present invention preferably comprises a carrier. Adsorbents of the present invention, necessarily, has the advantages of the present invention be free carriers, preferred because it caused to disperse carrying copper component to a carrier adsorption amount and adsorption rate of the sulfur compounds is increased. Carrier contained in the adsorbent of the present invention is preferably inorganic, for example, can be used silica, alumina, titania, diatomaceous earth, an inorganic material such as zinc oxide. Note that the carrier used in the adsorbent of the present invention, boehmite alumina is particularly preferred. Boehmite alumina has a large number of OH groups on the surface thereof, so easier to combine with OH groups of the cellulose derivatives, adsorbents containing boehmite alumina and cellulose derivatives, compressive strength and water resistance is increased. The specific surface area of the support is at least 50 m 2 is preferably / g or more, 100 m 2 and particularly preferably / g or more. If the specific surface area of the carrier is too low, dispersibility of the supported copper component is poor, since the adsorption of the sulfur compounds may be lowered undesirably.
[0023]
　The specific surface area of the adsorbent of the present invention, 30 m 2 preferably at / g or more, 100 m 2 / g or more, 250 meters 2 and more preferably in the following range / g. If the specific surface area of the adsorbent of the present invention is too small, since the amount of adsorption of the sulfur compounds may be reduced, which is undesirable. The specific surface area is, for example, can be measured by a known measurement method such as BET multipoint method or 1-point method.
[0024]
　Crush strength of the adsorbent of the present invention is preferably 1 at the pellet per 20N or more, and more preferably at least 30 N. When crushing strength of the adsorbent of the present invention is too low, so tends to occur powdering and collapse of the adsorbent, it is not preferred. Incidentally, crush strength, for example, can be measured by a method described later in the Examples. Adsorbents of the present invention by comprising a cellulose derivative, it is possible to easily achieve a crushing strength of more than 20N per pellet.
[0025]
　Adsorbents of the present invention, crush strength before immersion in water for crushing strength (I) after immersion in 900 hours water (I 0 ) retention of (I / I 0 ) is 50% or more, 100% it is preferably in the range of 75% or more, and particularly preferably in the range of 100% or less. In the present invention, the retention rate can be used as a measure for evaluating the water resistance described above. When the retention rate is too low, when used in the process, including water, crushing strength under the influence of moisture and significantly reduced, since lead to powdering and collapse undesirable.
[0026]
　The shape of the adsorbent of the present invention may be spherical, cylindrical, trilobal shape, it may have a known shape such as a quatrefoil shape, so that the outer surface area becomes larger while keeping the crushing strength, adjusting the shape and size it is preferable to. For example, the adsorbent of the present invention, in the shape of cylindrical shape, and a diameter of more than 1 mm in diameter, 3 mm.phi less, or more 1mmH height, if the following ranges 7MmH, large external surface area while maintaining the crushing strength The preferred since.
[0027]
　Adsorption rate constant of the sulfur compounds of the adsorbent of the present invention, at least 0.001Sec -1 if more is suitable as the adsorbent of sulfur compounds. Adsorption rate of sulfur compounds 0.001Sec -1 lower than is sometimes not possible to sufficiently remove the sulfur compounds contained in the process feed. Incidentally, the adsorption rate of sulfur compounds can be calculated by the method described in Examples to be described later.
[0028]
　Adsorbents of the present invention are adsorbent to remove sulfur compounds contained in various process feed, a significant effect on the process material, especially containing trace amounts of moisture. Conventional adsorbents, with the process feed comprising water such traces, gradually crushing strength under the influence of moisture is reduced, although powdering or collapse is likely to occur, the adsorbent of the present invention are cellulose includes a derivative, crushing strength becomes large particles constituting the adsorbent by the cellulose derivative is consolidated to one another, and because the water resistance is imparted, crushing also be used to process raw materials containing trace amounts of moisture decrease in strength is small. The content of water contained in the process feed using an adsorbent of the present invention is different depending on the type of material, generally 0.1ppm or more, in the range 1000 ppm.
[0029]
　Adsorbents of the present invention, among the above-mentioned process feed, can be used particularly suitably for process feed liquid. Process feed liquid, large resistance when in contact with the adsorbent, easily occur powdering and collapse of adsorbent than when contacting the adsorbent gaseous process feed. However, the adsorbent of the present invention is greater crush strength is consolidating mutually particles constituting the adsorbent, because it has a water resistance, be used to process feed liquid cause powdering or disintegration of the adsorbent hard. Adsorbents of the present invention, among the above-mentioned process feed, it is particularly preferable to use the process feed including in particular propylene.
[0030]
　Adsorbents of the present invention is a sorbent to remove sulfur compounds contained in the aforementioned process feed, if a general sulfur compound by the adsorbent of the present invention can be adsorbed and removed. For example, it is possible to adsorb hydrogen sulfide, alkyl thiophenes, sulfur compounds such as mercaptans and carbonyl sulfide (COS). Adsorbents of the present invention, among these general sulfur compounds, especially excellent adsorption ability of the carbonyl sulfide.
[0031]
　Adsorbents of the present invention contain cellulose derivatives, having a hard characteristic decreases even crush strength using the process feed, including trace amounts of moisture. Conventionally, adsorbents containing copper compound as a component for adsorbing the sulfur compounds are known, the conventional adsorbent, does not contain a cellulose derivative. Because such conventional sulfur compound adsorbent, generally, are manufactured by a method of sintering after how baking after impregnation of the copper compound or a copper compound and a carrier are mixed, molded into the carrier , if those also include cellulose derivatives as an organic binder and a lubricant with a copper compound, since the firing process these burning or decomposition and deterioration, ultimately resulting adsorbent containing no cellulose derivative it is to become.
[0032]
　On the other hand, the adsorbent of the present invention, since it is not calcined after which contains a cellulose derivative with a copper component which adsorbs a sulfur compound, comprises an amount of the cellulose derivative. Therefore, the adsorbent of the present invention, unlike the conventional sulfur compound adsorbent crushing strength is hardly reduced even with the process including a small amount of moisture, high water resistance. Incidentally, the water resistance is determined by the retention rate of crushing strength after immersion fixed time in water. Specific measuring method is shown in Example.
[0033]
Manufacturing Method
　The method for manufacturing the adsorbent of the present invention (hereinafter, the production method of the present invention) will be described in detail.
Production method of the present invention includes the steps of obtaining a raw material mixture by mixing the copper component and the cellulose derivatives, such as copper oxide, a step of molding the raw material mixture. The manufacturing method of the present invention does not include a step of firing a raw material mixture. Hereinafter, an example of using copper oxide as the copper component. Incidentally copper component is not limited to copper oxide.
[0034]
　Copper oxide used in the production method of the present invention may be those obtained by sintering the copper compound, or may be synthesized in an aqueous solution. When firing the copper compound, copper chloride, copper carbonate, copper compound such as copper nitrate 300 above, by firing in a temperature range below 500 ℃, it is possible to obtain copper oxide. Further, when synthesizing a copper oxide in an aqueous solution can be obtained by hydroxide in the aqueous solution of copper is heated to 50 ° C. or higher in a dispersed state.
[0035]
　In the production method of the present invention, in the step of mixing the copper oxide and cellulose derivatives, it may be mixed carrier. In the production method of the present invention, but not necessarily it has the advantages of the present invention be free of carrier, when dispersed and supported the copper component on the carrier, preferably the adsorption amount and adsorption rate of the sulfur compounds is increased. Carriers used in the method of the present invention is preferably inorganic, such as silica, alumina, silica - alumina, titania, diatomaceous earth, it may be used inorganic substances such as zinc oxide. Note that the carrier used in the adsorbent of the present invention, boehmite alumina is particularly preferred. Boehmite alumina has a large number of OH groups on the surface thereof, so easier to combine with OH groups of the cellulose derivatives, adsorbents containing boehmite alumina and cellulose derivatives, compressive strength and water resistance is increased. The specific surface area of the support is at least 50 m 2 is preferably / g or more, 100 m 2 and particularly preferably / g or more. If the specific surface area of the carrier is too small, dispersibility of the supported copper component is poor, since the adsorption of the sulfur compounds may be lowered undesirably.
[0036]
　In the production method of the present invention, by using inorganic binder with cellulose derivatives, water resistance is further improved. Inorganic binders used in the production method of the present invention, for example, bentonite, alumina is preferably an inorganic compound having a large number of OH groups on the surface of the silica. Particularly preferably contains silica derived from a silica sol.
[0037]
　In the production method of the present invention, a method for mixing the copper oxide and cellulose derivatives or a method of further mixing an inorganic binder or carrier in these may be any method in which these components can be uniformly mixed, a conventionally known method it can be used. For example, it can be mixed using a kneader or mixer. The raw material mixture obtained after mixing, may be in powder form, may be a block form, also water may be clay in addition to the time of mixing. Powdery raw material mixture may be molded into a desired shape by compression molding tabletting molding or the like, clay-like raw material mixture may be molded into a desired shape by extrusion molding. Further, in this molding step, it is possible to improve the moldability by using a lubricating material necessary. For example, if the compression molding, can be added to graphite as a powdery raw material mixture easily fed into the mold. When extruding a clay-like raw material mixture may also be added to lubricating material such as cellulose and oleic acid in order to reduce the resistance of the extrusion. By using such a lubricant, it is possible to improve the productivity of the molding process.
[0038]
　Incidentally, if the moisture molded body after molding is left can also be 200 ° C. and dried at a temperature below to remove moisture. At this time, heating the molded body after molding to a temperature above 200 ° C., and the combustion cellulose derivatives, or decomposed and altered will be sometimes effect can not be obtained according to the present invention. In particular, when fired at a temperature higher than 300 ° C., since the cellulose derivative is completely burned or decomposed and deteriorated, not fired at a temperature above 300 ° C. After the addition of the cellulose derivative.
Example
[0039]
　Examples of the present invention together with comparative examples are shown below. The present invention is not limited to these examples.
[0040]
Example 1
　was dissolved sodium hydroxide 231g of ion-exchanged water 5.8 kg, to prepare a mother liquor. Next, to prepare a poured liquid to dissolve the copper sulfate pentahydrate 676g of ion-exchanged water 2.6 kg. By mixing the mother liquor and poured liquid in each heated state, to produce a precipitate of copper oxide. The slurry containing the precipitate of the copper oxide was filtered, after separating the precipitate of copper oxide, to obtain a precipitate cake copper oxide washed thoroughly. The precipitate cake was obtained copper oxide slurry is dispersed in deionized water 4.0 kg. Drying the copper oxide slurry, to obtain a powdery copper oxide.
[0041]
　Next, the copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1 .4, cellulose hydroxypropoxy group content 0.2) 4g, as lubricant (Yuken industry Co., Ltd.: YB-154) to 4g, silica sol 100 g (JGC catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 125g in a mixer, to obtain a raw material mixture is uniformly mixed.
[0042]
　The raw material mixture was put into an extrusion molding machine to obtain a molded body by extrusion molding into a cylindrical height 3 ~ 5 mm in diameter 1.8Mmfai. Its molded and dried for 16 hours at a temperature of 120 ° C. in an electric dryer, to give a sulfur compound adsorbent. The composition of the sulfur compound adsorbent was analyzed by the following measurement methods. The results are shown in Table 1.

　After crushing a sulfur compound adsorbent powder, the sample is placed pressure molding ring, and 3min pressure molding at a molding pressure of 30 MPa. Molded sample X-ray fluorescence analyzer (Rigaku Corporation, ZSX100e) set in, was measured by the order (semi-quantitative) analysis.
[0043]
　The organic binder content of the resultant sulfur compound adsorbent using a value calculated back from the charged amount. The results are shown in Table 1. Incidentally, for example, analyzing the carbon content of the sulfur compound in the adsorbent in the following manner may be calculated back the content of the cellulose derivative from that value.

　After crushing a sulfur compound adsorbent powder, high frequency induction heating combustion - IR absorption analyzer (LECO Corp., CS230) is used to measure the amount of carbon. The calibration curve prepared using a standard steel sample is the average of three measurements and the carbon content of the sample.
[0044]
　It was analyzed sulfur compounds of the produced sulfur compound adsorbent adsorption rate constant (carbonyl sulfide) by the following measuring method. The results are shown in Table 1.

　First, was prepared simulant (COS concentration 10 ppm / 1-hexene). Then set in the reaction tube to a bed height of sulfur compound adsorption agent is 8 cm, it was attached and the reaction tube in COS adsorption test device. Then, after performing a 170 ° C. 1 hour pretreatment under a stream of nitrogen, and cooled to room temperature. It was then circulated at a feed rate of 5 g / min simulated solution previously prepared to the reaction tube. The inlet and outlet of the liquid of the reaction tube was sampled every predetermined time, a gas chromatograph equipped with a SCD detector (manufactured by Agilent Technologies, Model 7890B) were analyzed COS concentration using. From the difference between the inlet COS concentration and outlet COS concentration after circulation 2 hours was calculated adsorption rate constant COS.
[0045]
　It was evaluated water resistance of the produced sulfur compound adsorbent by the following measuring method. The results are shown in Table 1.

　sulfur compounds adsorbent tens g filled in a glass bottle filled with pure water was immersed at room temperature 900 hours. Then removed sulfur compound adsorption agent, in an electric dryer and dried for 16 hours at a temperature of 120 ° C., to remove water contained in the sulfur compound sorbent.
　Next, pure water crushing strength before immersion sulfur compound adsorption agent (I 0 ) and pure water crushing strength of the sulfur compound adsorption agent after immersion (I) was measured, retention of the crushing strength (I / I 0 was to evaluate the water resistance). Incidentally, the crushing strength of the sulfur compounds adsorbent crushing strength meter (manufactured by Instron Corporation, Model 3365) was measured was used as the average value of the crushing strength of 10 pellets. Also, the cylindrical sulfur compound adsorbent was measured collapse strength in the transverse direction (the side surface of the cylinder).
[0046]
Example 2
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, cellulose hydroxypropoxy group content 0.2) 2 g, as a lubricant (Yuken industry Co., Ltd.: YB-154) to 4g, silica sol 100 g (JGC catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 125g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0047]
Example 3
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, cellulose hydroxypropoxy group content 0.2) 17 g, as a lubricant (Yuken industry Co., Ltd.: YB-154) to 4g, silica sol 100 g (JGC catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 125g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0048]
Example 4
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, hydroxypropoxy group content 0.2) 4g, silica sol 100g as an inorganic binder (JGC catalysts and Chemicals Ltd., trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and a mixer of ion-exchanged water 125g the charge to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0049]
Example 5
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 160 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 240 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, cellulose hydroxypropoxy group content 0.2) 4g, as lubricant (Yuken industry Co., Ltd.: YB-154) to 4g, silica sol 100 g (JGC catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 150g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0050]
Example 6
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 120 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 280 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, cellulose hydroxypropoxy group content 0.2) 4g, as lubricant (Yuken industry Co., Ltd.: YB-154) to 4g, silica sol 100 g (JGC catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 175g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0051]
Example 7
　by dissolving a 48 wt% aqueous solution of sodium hydroxide 1090g of ion-exchanged water 7.1 kg, to prepare a mother liquor by adding further zinc oxide 460 g. Then, ion-exchanged water 5.8kg of copper sulfate pentahydrate 1092G, to prepare a poured liquid by dissolving copper nitrate trihydrate 453 g. By mixing the mother liquor and poured liquid in each heated state, to produce a precipitate of copper oxide containing zinc oxide. The precipitate slurry was filtered by adding graphite 44 g, after separation of the precipitate containing graphite, to obtain a precipitate cake was thoroughly washed. The precipitate cake was slurried dispersed in ion-exchange water 12 kg. The slurry was dried to give copper oxide, zinc oxide, and a powder containing graphite.
　Then, the powder was 400 g, hydroxypropylmethyl cellulose as a cellulose derivative (manufactured by Shin-Etsu Chemical Co., product name; Metolose 90SH, methoxy group content 1.4, hydroxypropoxy group content 0.2) to 4g, as an inorganic binder g of bentonite 20g, and ion exchange water 152g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0052]
Comparative Example 1
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, silica sol 100 g (JGC Catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L, Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 125g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0053]
Comparative Example 2
　to obtain a powdery copper oxide in the same manner as in Example 1. The copper oxide 200 g, commercially available boehmite alumina as a carrier (specific surface area: 280 meters 2 / g) to 200 g, polyvinyl alcohol (molecular weight 1500) 4g, silica sol 100 g (JGC Catalysts and Chemicals Ltd. as an inorganic binder, trade name; S-20L , Si concentration: 20 wt% (SiO 2 equivalent)), and was charged with deionized water 125g in a mixer, to obtain a raw material mixture is uniformly mixed. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0054]
Comparative Example 3
　Example 7 In the same manner as in the copper oxide, to give zinc oxide, and a powder containing graphite. Next was charged with the powder was 400 g, the bentonite as an inorganic binder 20g, and deionized water 152g mixer to uniformly mixed to obtain a raw material mixture. The raw material mixture used to obtain a sulfur compound adsorbent in the same manner as in Example 1. Moreover, it was subjected to various analyzes in the same manner as in Example 1. The results are shown in Table 1.
[0055]
[Table 1]

[0056]
　As shown in Table 1, while the retention rate of crushing strength after any adsorbents of Examples 1-7 was immersed in a predetermined time water (I / Io) is from 55 to 90% Comparative Example retention crushing strength of 1-2 adsorbent (I / Io), respectively 20% and 37%, moreover, the adsorbent of Comparative example 3 will collapse in the immersion. Thus, the adsorbent of the present invention as compared to the adsorbent of Comparative Example 1-3 water resistance is much better.
　Furthermore, the crushing strength of the adsorbent of Example 1-6 whereas a 42.0N ~ 47.8N, each crush strength of the adsorbent of Comparative Examples 1 and 2 the shape are the same 30.2N, a 40.8N, adsorbents of examples 1-6 in comparison with the adsorbent of Comparative example 1-2 crushing strength is greatly improved.
　Further, as in Example 7 using bentonite as an inorganic binder with cellulose derivatives, looking for Comparative Example 3 using bentonite as an inorganic binder without using cellulose derivatives, crushing strength of the adsorbent of Example 7 35.5N , whereas the in crushing strength of the adsorbent of Comparative example 3 is 13.8N, crushing strength of the adsorbent of example 7 is much larger than the adsorbent of Comparative example 3.
　Further, the adsorbent of Example 1-6, the adsorption rate constant of sulfur compounds 0.013Sec -1 ~ 0.021Sec -1 whereas it is, the adsorption rate constant of the adsorbent of Comparative Examples 1 and 2 the 0.018Sec -1 ~ 0.020Sec -1 is, for the adsorbent of Comparative example 3 the diameter of the cylinder is slightly thicker in example 7, both the adsorption rate constant 0.009Sec -1A is the adsorption rate constant of the sulfur compounds are almost the same level. Thus, the adsorbent of the present invention is the adsorption rate constant of the sulfur compounds also contain cellulose derivatives without much decrease, whereas, water resistance and crushing strength are remarkably improved.

WE CLAIM

It includes a copper component to adsorb sulfur compounds,
including cellulose derivatives,
water resistant sulfur compound adsorption agent, characterized in that.
[Requested item 2]
The cellulose derivative is hydroxypropyl methylcellulose, water resistant sulfur compound adsorption agent according to claim 1.
[Requested item 3]
The molar substitution of hydroxypropoxy groups in the hydroxypropylmethylcellulose, 0.15 or more, in the range of less than 0.25, water resistance sulfur compound adsorption agent according to claim 2.
[Requested item 4]
The content of the cellulose derivative, relative to the total weight of the adsorbent, 0.5% by weight or more, in the range of 5 wt% or less, water resistance of sulfur compound according to any one of claims 1 to 3 adsorbent.
[Requested item 5]
Crushing strength before immersion in water for crushing strength (I) after immersion in 900 hours water (I 0 ) retention of (I / I 0 ) is in the range of 50% or more, less 100%, wherein water resistant sulfur compound adsorption agent according to claim 4.
[Requested item 6]
Water resistant sulfur compound sorbent according to any one of claims 1 to 5 for use in the process feed comprising a sulfur compound and water.
[Requested item 7]
A method of manufacturing a water-resistant sulfur compound adsorbent,
a step of obtaining a raw material mixture by mixing a copper component and a cellulose derivative to adsorb sulfur compounds,
comprising the step of drying by molding the raw material mixture,
the raw material mixture without the step of firing,
manufacturing method characterized by the production of water-resistant sulfur compound sorbent.
[Requested item 8]
Drying temperature of the raw material mixture is at 200 ° C. or less, the production method of water-resistant sulfur compound adsorption agent according to claim 7, characterized in that no firing the raw material mixture after drying.