TW201235097A - Method for removing sulfur compounds from an alcohol - Google Patents

Abstract

The present invention provides a method of removing sulfur compounds from alcohol which is able to reduce environmental load by performing reuse of adsorbents with saturated absorption of sulfur compounds. The method of removing sulfur compounds from alcohol of the present invention is characterized that alcohol containing sulfur compounds and adsorbents supporting silver are brought into contact with each other, sulfur compounds in alcohol is adsorptively removed, thereafter, eluent and/or gas is flowed while adsorbents are warmed up, sulfur compounds adsorbed in adsorbents are removed from adsorbents by desorption so as to reuse said adsorbents.

Description

201235097 VI. Description of the invention: [Technical field to which the invention pertains] + 1 yin system Prior art: Alcohols, in particular, ethanol obtained by fermentation derived from the like. In addition, the example of the use of the raw materials for the global environmental protection is high, and the production of the butadiene is used, and the problem of using bioethanol is 'because' It is an organic sulfur compound which has trace impurities in the day, especially thioether, and some cases. In particular, a method of supplying a trace amount of DMS by distillation and re-supplying it with a catalyst has been proposed. For example, in Patent Document 1, there is a method in which an adsorbent is exposed to an alcohol. Further, it is in contact with an adsorbent such as silver or silver oxide-activated alumina. The obstacles of the method, especially regarding the premise that the silver is a metal sorbent, as a sorbent, the saccharide, starch, cellulose, bioethanol of the plant is used as a renewable fuel or as a chemical raw material. Important chemical substances. Production of a chemical carboxylic acid ethyl ester, production of acetaldehyde, production of ethylamine, and the like. In particular, as a chemical raw material, it is inevitable to contain (hereinafter referred to as DMS), dithio-dimethyl used in the reaction of the catalyst after the inactivation of bioethanol still contains some to avoid catalyst loss. Live the way to react. Therefore, as a solution for this. It is proposed to make a Buddha stone containing silver or copper in Patent Document 2, and it is proposed to make alcohol carbon, aluminum oxide, lanthanum aluminum oxide (silica, however, as an adsorbent which practically provides such silver as an active ingredient, one-time sulfur Compound saturation adsorption is a difficult point to establish.

I 201235097 When we look at the conventional technology, in the method of the patent document, it is difficult to say that it is used in the re-use of the adsorbent for saturated adsorption of sulfur compounds. Practical, and in the special &quot; also offer 2, although there are proposed high-temperature sintering adsorbents above 4〇〇t, = text adsorption of sulfur regeneration method, but this method is too large in energy and loading and unloading 'There is a contradictory result for the purpose of using bioethanol, that is, reducing the purpose of the ring. [Patent Document] [Patent Document 1] Japanese Patent Publication No. 2007-5 15448 [Patent Document 2] Japanese Patent Laid-Open Publication No. No. No. No. Publication No. No. No. No. No. No. No. No. Removed Adsorbent The object of the present invention is to provide a method of vulcanization derived from alcohol which is used to reduce the environmental load by reusing saturated adsorbed sulfur compounds. Another object of the present invention is to provide a method for producing the above-mentioned alcohol, which comprises the method for removing a sulfur compound derived from the above-mentioned alcohol, and the step of removing the compound. [Means for Solving the Problem] In view of the above problems, the inventors repeatedly As a result of the review, a unexpectedly discovered that the adsorption of silver by organosulfur compounds such as DMS is a binary reaction, that is, the sulfur compound corresponds to the temperature change of the system, and the adsorption and desorption of the adsorbent can be reversibly repeated. . For example, if the pump is used, it will temporarily desorb the adsorption capacity due to the saturated adsorption of sulfur compounds. 'As long as it is cooled again, the 201235097 agent is heated with only a small amount of energy, so that the adsorption capacity of the adsorbed sulfur compound will be Recovery, semi-permanently repeated use as a method of providing a sulfur-derived compound derived from alcohols, characterized by the removal of the alcohol by adsorption of the alcohol having the sulfur compound and the carrier The sulfur compound in the medium is then passed through the liquid and/or the steroid, and the sulfur compound adsorbed to the adsorbent is desorbed from the adsorbent by the desorption of the adsorbent at the temperature of the adsorbent. The sulfur compound is preferably methyl sulfide. Further, the alcohol is preferably ethanol. Further, the adsorbent is preferably loaded with silver. Further, the temperature at which adsorption is removed from the adsorbent is preferably 200. (: the following., skin, . "(10) Keshen, IU, mouth-, 篁^ method's system includes the removal step of the sulfur compound based on the above-mentioned sulfur compound from the a person k / thick alcohol [Effects of the Invention] According to the present invention, the bioethanol derived from the alcohol and the sulfur-removing compound is removed by the bio-ethanol of the π 咱 避免 避免 触 7 7 7 7 7 7 7 失 失 失 失 制造 制造 制造 制造And raw materials for the production of butadiene, etc., and bio-ethylene: the raw material of ethylene or the versatility of chemical raw materials is an alcohol that can be regenerated and carbon, and the chemical substances, especially: the second ball environment Protection of the fermentation of powder, cellulose, etc. to obtain J B: from the sugar of the plant, the sulfur-containing agent is removed in addition to the side adsorption, and the cation exchange tree of the sub-agent is used in the vulcanization of the adsorbent The method for removing the sulfur-containing compound of the present invention is characterized in that the method for removing the sulfur compound derived from alcohol is characterized in that the method for removing the sulfur compound derived from alcohol is characterized in that the method for removing the sulfur compound derived from alcohol is characterized in that By causing the silver-loaded adsorbent to contain sulfuration When the alcohol is contacted, the sulfur compound in the alcohol is adsorbed and removed, and then the temperature of the adsorbent is raised while the elution liquid and/or the gas are passed, so that the sulfur compound adsorbed to the adsorbent is desorbed from the adsorption. When the agent is removed, the adsorbent is used in the same manner. <Alcohol> The alcohol which is supplied to the method for removing the sulfur compound derived from the alcohol of the present invention is as long as the alcohol which contains the sulfur compound such as an organic sulfur compound as an impurity Particularly, for example, one of an alcohol such as ethanol, yeast, n-propanol, isopropanol or n-butanol (for example, a carbon number of a monohydric alcohol is preferably a carbon number of 1 to 4). a polyterpene alcohol such as ethylene glycol, propylene glycol or glycerin (for example, a 2 to 6-membered alcohol having a carbon number of 1 to 10, preferably a carbon number of 2 to 3 3 of an alcohol), etc. The above alcohol may also be two kinds. The above mixture may also contain 〇% (by weight, /., the same below) to about 5% by weight of water, sulfur compound &gt; as a sulfur compound and I - compound. For Α ϋ ..., temple limit, However, in particular, organic sulfur is an organic sulfur compound, which can be listed as For the class, for example, the thioether-like symmetric or asymmetric alkane having a CS bond, an alkylthiodi-n-propyl sulfide, a methyl propyl sulfide, a thioether, or a isopropyl sulfide. 2, especially carbon number 2~丨0'--dimethym (Dimethy 201235097 disulfide), dithiodimethane (Dimethyi 卩 to (3) out of heart), 2,3_ thiobutane (2 , 3-Dithiabutane) and other disulfides; mercaptans such as methyl mercaptan and ethanethiol; dimethyl sulfoxide, diethyl sulfoxide, dipropylene arsenide, 3-methylthio]-propanol, etc. Sulfoxides (especially c2iq_dialkylarylene); or methionine, S-mercaptomethionine, sulfur-containing amino acid, and the like. Among them, as the sulfur compound, DMS and dithiodiethane which are commonly contained in the naturally fermented alcohol are exemplified as the organic sulfur compound. The content of the sulfur compound in the alcohol to be adsorbed is, for example, more than 0.1 ppm by weight to 6000 ppm, preferably more than 〇lppm 2〇〇〇ρρπ^, more preferably more than 〇·1 ppm of 500 ppm or less, further preferably More than O lppm 200ppm or less. &lt;Adsorbent&gt; The cation-exchange resin which is a silver-loaded adsorbent used in the present invention, which is ion-exchanged by silver ions, is exemplified by cerium oxide, aluminum oxide, zeolite, activated carbon, and the like. The carrier of the carrier carries silver = silver or silver oxide. Further, the cation exchange resin is not particularly limited, and a commercially available cation exchange resin can be used. The ion exchange of silver ions to the cationic parent resin (in the present case, the case where ion exchange is carried out), and the loading of silver ions or silver oxide on the carrier can be carried out by a conventional method. With respect to the loading amount (content) of silver ions, the weight of the metal of the silver element may be, for example, 50 parts by weight or less, preferably 〇丨 to "weight" with respect to 1 part by weight of the carrier (containing the ion exchange resin). Further, it may be 2 〇 weight injury. In addition, the loading amount of silver ions in the cation exchange resin is based on the dry weight. 201235097 Gentry as the adsorption #丨, especially the cation exchange tree 曰 曰 &amp; In terms of its neatness, there is no need for special equipment such as dryers and sintering furnaces. The machine 'has good reproducibility to load the desired amount of silver ions: the cation exchange resin itself is cheap, and the quality is good. The product of the woman is easy to obtain, so it is the best. &lt;Adsorption method&gt;: In the embodiment of the present invention, the so-called packed tower which continuously washes the alcohol through the adsorbent layer is the most practical and practical. Efficient either = bed or m - generally used in the conventional way of adsorption operation, but to improve the adsorption capacity, but also to the room: ~ the most convenient, alcohol in the dipping skills / 7 p to > phoenix below . After the treatment, the "compound content can be used as the "regeneration of the adsorbent" 〇.1ppm or less. The present invention is characterized in that the side is desorbed by the side of the liquid/dissociation liquid and/or the gas-flowing compound. ; 吏 temporarily adsorbed to the point of use of sulfur in the adsorbent. ° and the ability to recover 'and the adsorbent can be regenerated and re-washed or gas> as the adsorbent during the regeneration of the adsorbent for the adsorption treatment of the 兮e chase, the direct use of other uses: alcohol and not Sulfur compounds are the easiest, but they can also be solvents such as solvents or water. Examples of the other organic solvent include a solvent, an alcohol-based solvent, an ester-based solvent-based solvent, a solvent, a guanamine-based solvent, a pulverized solvent, a propylene glycol-methyl group, and an alcohol oxime solvent. For example: propyl glycol, propylene glycol monomethyl ether, etc. 201235097 solvent; ethylene glycol monomethyl ether, ethylene glycol-ethyl shout, ethylene glycol monoethyl: methyl ether acetate vinegar 'Ethylene glycol, ethylene glycol-butyl acetal vinegar, etc.... Ethylene glycol-butyl bond medium, such as lactic acid lactic acid, such as lactic acid vinegar, etc.::: a propionic vinegar-based solvent such as a second-line vinegar; acetic acid A, medium, 3_methoxypropionic acid, butyl acetate, etc., acetic acid vinegar, acetonitrile, acetic acid propyl ketone methyl ethyl ketone, methyl isobutyl hydrazine I solvent contains acetone, ketone, Cyclohexanone and the like. The test solvent comprises B:·2-pentanone)'methylpentylhydrofuran, dioxane and the like. The guanamine is soluble in the fourth. Azul-------------------------------------------------------------------------- The hydrocarbon-based solvent includes aromatic ketones such as benzene, dimethyl diformamide, and ethylbenzene; aliphatic hydrocarbons such as hexanone or octyl alcohol; and alicyclic hydrocarbons such as cyclohexane. Preferred solvents include alcohols such as methanol, ethanol, propanol and butanol; glycols such as water di-alcohol-methyl ether and propylene glycol-mercapto ether acetate; medium; vinegar-based solvent such as lactic acid and vinegar a ketone-based solvent such as methyl isobutyl hydrazine, methyl amyl ketone or cyclohexanone; and a mixed solvent thereof. &amp; regeneration of the adsorption y does not necessarily require the liquid to flow, and the same purpose can be achieved even if an inert gas such as nitrogen or nitrogen is used; water vapor; and a gas such as a mixed gas: claw passage. These gases can also be diluted with air or the like. The regeneration of the adsorbent may be performed in parallel with both the dissolving liquid circulation treatment and the gas circulation treatment. The temperature at which the adsorbent is regenerated may be more efficient in separating the sulfur compound at a high concentration, but considering the energy load, the heat resistance of the device and the adsorbent, it is preferably 2 〇〇 ° C or less, preferably From room temperature (for example: 25 ° C ± 2 ° c) to 200 ° C, more preferably from room temperature to 12 (TC -10- 201235097 circumference. In addition, 'when using the eluent' temperature at the time of regeneration of the adsorbent It can be set from room temperature to 100 ° C. When using gas, it can be set to 50~120 ° C. The flow rate of the eluent can be set to, for example, 1 to 10 mL per 2 mL of adsorbent. The minute ' is preferably 2 to 6 mL/min. Further, the amount of the eluent required for regeneration is also according to the treatment temperature, but is, for example, about 0.2 to 3 L, preferably 〇5 to 丨5, with respect to 20 mL of the adsorbent. The gas flow can be set at a treatment temperature of, for example, 100 to 10000 mL/min, preferably 2 to 5 〇〇〇mL/min, relative to 2 mL of the adsorbent. The time required for regeneration is also based on the treatment temperature, but is, for example, about 0.5 to 3 hours, preferably about 5 hours. In the above-described adsorbent to be regenerated, the content of the sulfur compound in the alcohol after the adsorption treatment can be, for example, 0.1 ppm or less by the adsorption method similar to the above. [Method for Producing Alcohol with Lower Sulfur Compound Content] The invention relates to a method for producing an alcohol having a reduced sulfur compound content, which comprises a step of removing a sulfur compound by the above-mentioned desulfurization method derived from an alcohol-based sulfur compound. Therefore, the catalyst is inactivated, and the pair can be reduced. environmental

The alcohol J# which reduces the sulfur compound content can be produced by load, which can be used as a raw material for the production of ethyl carboxylic acid, manufacture of acetaldehyde, manufacture of butyl sulphate, manufacture of ethylene, manufacture of ethylamine, and the like. Wait. </ RTI> The present invention is not limited by the following examples of the invention by way of examples. [Example 1] -11- 201235097 (1) Amberlyst 1 5 (manufactured by 〇rgano Co., Ltd.) of 20 mL of acidic ion exchange resin was filled in a glass tube with a cannula (the inner diameter of the glass tube was 12 mm, and the length was 200 mm). 'A 1 mL aqueous solution in which 5 g of silver nitrate was dissolved was passed through a tube at room temperature. After silver ions were supported on the resin, the resin layer was washed with pure water. At this time, the silver ion content of the resin layer was 7.6 wt%. (2) The resin layer was kept at room temperature (25 Å), and the fermentation ethanol (containing 14 ppm of dmS; ethanol content of 93% by weight) was flow-washed at a flow rate of 4 niL/min. The concentration of DMS in the liquid. The DMS concentration in the effluent was maintained at a detection limit of 0.1 ppm or less between 62 hours after the start of the flow washing. The flow wash rate after DMS penetration (breakthr〇ugh) was 14.9L. (3) Then, '8 will be on one side. (: The warm water flows through the casing, and the DMS-free ethanol (the ethanol content is 93% by weight) is flow-washed in the opposite direction to the flow-washing direction at a flow rate of 4 niL/min. (4) The amount of washing in the ethanol reaches 丨At the time of L, cold water is passed through the casing, and the resin layer is cooled to room temperature. (5) The fermentation ethanol is passed through the resin layer under the same conditions as in (2). The amount of ethanol flowing through the dms is 丨丨9 L. (6) Then, the same desorption operation as in (3) (4) and the same adsorption operation were repeated three times. The results are shown in Table 1.

_ 1st table adsorption-desorption operation cycle number - medium DMS concentration #through the flow wash amount first -~---_15Ppm 14.9L 1 time --------__l4ppm 11.9L 2 times---____25ppm 11.6L 3 times-----Hppm 12.0 L 4 times____Hppm 11.8L -12-201235097 [Example 2] (1) In the same manner as in Example 1, an acidic ion exchange resin Amberlyst 15 (20 mL) loaded with silver ions was filled. Stainless steel tube (inner diameter 6 mm, length 800 mm) 〇 (2) A fermented ethanol (93% by weight of ethanol) containing 15 ppm of DMS was flowed through the filled resin layer at a flow rate of 4 mL/min at room temperature until The concentration of DMS in the effluent exceeds 〇. 1 ppm. The total amount of flow washing ethanol was 1 1.2L. (3) In the resin layer, water vapor was ventilated at a flow rate of 100 mL/min for about 1 hour in the opposite direction to the flow direction of the ethanol. During this time, the temperature of the resin layer was maintained at about 100 °C. (4) After cooling the resin layer to room temperature, the fermentation ethanol containing 15 ppm of DMS was washed in the same manner as in (2). The amount of flow washing ethanol until DMS penetration (DMS concentration of 0.1 ppm or more) was 10.1 L. (5) Next, the same desorption operation as in (3) and the same adsorption operation were repeated three times. The results are integrated in Table 2. _ Initial 3-A ___4 times [Example 3] Table 2 _ - Flow wash &amp; DMS concentration in alcohol ISppm 15ppm 15ppm I5ppm 15ppm Flow wash rate after penetration

11.2LT0.1L &quot;10.2L ~ 9.9L 10.1L (1) In the same manner as in Example 1, an acidic ion exchange tree Amberlyst 15 (2 〇 mL) carrying silver ions was filled in a non-mineral steel pipe (inside) The diameter is 6mm and the length is 800mm). -13- 201235097 (2) The fermented ethanol (15% by weight of ethanol) containing 15卯111 (1% by weight) was washed at room temperature at a flow rate of 4 mL/min until the effluent was The DMS concentration exceeded 〇.lppm. The total amount of flow washing ethanol was 1 1.1L. "(3) In a resin layer, nitrogen (100 v〇1%) was ventilated at a flow rate of 1 OOOmL/min for about 1 hour in the opposite direction to the flow direction of ethanol. During this period, the stainless steel tube was heated by a heating belt. The temperature of the resin layer was maintained at about 10 〇C. (4) After cooling the resin layer to room temperature, the fermentation ethanol containing 15 ppm of DMS was washed in the same manner as (2). DMS penetration (DMS concentration 〇lppm or more The amount of the flow-washed ethanol was 10 4 L. (5) Then, the same desorption operation as in (3) and the adsorption operation similar to (4) were repeated three times. The results are shown in Table 3. Table 3

Adsorption-desorption operation cycle number DMS concentration in flow-washed ethanol Flow-through amount after penetration First time 15p〇m 11.1L 1 time 15ppm 10.4L 2 times 15ρρπι 10.5L 3 times 15ppm 10.4L 4 times 15〇t&gt;m 10.4L

[Example 4] (1) A silver nitrate aqueous solution (concentration: 16% by weight, 8 mL) was impregnated into 20 mL of a commercially available cerium oxide carrier (Q10 manufactured by ρυπ siLYSIA; average particle diameter: 3 mm) at 11 Torr. (: After drying, sinter is sintered in 50 TC air to prepare a adsorbent containing 1% by weight (as metal weight) of silver dioxide dioxide beads. -14- 201235097 (2) with casing The glass tube (glass tube inner diameter 12 mm, length 200 mm) was filled with the adsorbent of (1), and the fermentation ethanol (the ethanol content was 93% by weight) containing 15 ppm of DMS was washed at a flow rate of 4 mL/min at room temperature. Pass the adsorbent layer until the concentration of DMS in the effluent exceeds 〇. 1 ppm. The total amount of washed ethanol is 4.4L. (3) Then, while the warm water of 80 °C flows through the casing, it will not contain Ethanol of DMS (ethanol content: 93% by weight) was flow-washed at a flow rate of 4 mL/min in the opposite direction to the flow-washing direction. (4) When the amount of washing of the ethanol reached 〇·5 l, the cold water was flowed through the cannula to the resin. The layer was cooled to room temperature. (5) The fermentation process ethanol was washed through the resin layer under the same conditions as in (2). The amount of ethanol flow after DMS penetration was 36 l. (6) Then 'and (3), (4) The same desorption operation and the same adsorption operation as in (5) were further repeated three times. The results are shown in Table 4.

[Main component symbol description] None. -15-

Claims (1)

201235097 VII. Patent application scope: 1. A method for removing sulfur compounds derived from alcohol, characterized in that the sulfur compound in the alcohol is adsorbed and removed by contacting the alcohol containing sulfur compound with the adsorbent carrying silver. Thereafter, the temperature of the adsorbent is raised while the eluent and/or the gas are circulated, and the sulfur compound adsorbed to the adsorbent is desorbed from the adsorbent, and the adsorbent is repeatedly used. 2. A method of removing a sulfur compound derived from an alcohol as claimed in claim 1 wherein the sulfur compound is sulfonium sulfide. 3. A method of removing a sulfur compound derived from an alcohol as claimed in claim 1 or 2 wherein the alcohol is ethanol. 4. The method for removing an alcohol-derived sulfide according to any one of claims 1 to 3, wherein the adsorbent is a cation exchange resin carrying silver ions. 5. The method for removing an alcohol-derived sulfide according to any one of claims 1 to 4, wherein the temperature at which the sulfur compound adsorbed to the adsorbent is removed from the adsorbent is 200 ° C or lower. A method for producing an alcohol which lowers a sulfur compound content, which comprises a step of removing a sulfur compound by a method for removing a sulfide derived from an alcohol according to any one of claims 1 to 5. !; -16 - 201235097 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: