1273133 ，仿谷易後結陰極上，因此在水溶液與陰極界面上製造金屬奈米 t廿^在—翻雜，故本發明之較佳實施例為以聲波電化學法來製 ； 造黃金奈米粒，並可降低(解決）金屬離子易於覆蓋在陰極上之現象， : 峨製得比—般電化學法還要更小之黃金奈米粒。 【發明内容】 …本發明所述含奈米金之黃金減其製造方法，該黃金酒包含··以 耳波包化學法製造之奈米級黃金，該黃金具有輸大小範圍約在u • 奈米，調配濃度約在隨至誦_之間，本發明之含奈米金 朴、…可藉由所έ之奈米級黃金而對一般酒類中所含之不欲成份-乙 , 轉去除個，而可增加酒品飲用時之Π感以及對身體健康有益之功 效二相當具有產業價值，以t化學法製造之奈米級黃金，較佳為以聲 波私化學法製造之奈米級黃金。關於本發明所彻聲波電化學製造奈 ；米級黃金之方法，如本發明人在台灣之申請案號93121450之以聲波電 化學法從貴金屬塊材製造可控制大小之貴金屬奈錄内容併入本案參 本^月之耳波私化學法製造奈米級黃金，可在無需添加任何穩定 h况下彳Ϊ巾在含有可與黃金形成安定錯合物之化合物的水溶液 巾’製造顆粒大小範圍約在Q1至3()奈米之安定黃金奈米粒，其中可 與金屬軸安定錯合物之化合物，雛為—般可食狀電解質，例如： 氯化鈉，氣化鉀，尤其以氯化鈉為佳。 本1明於此4化合物之水溶液（或含、;g水溶液）巾，以電化學之氧 化m原循環（oxldati〇n-reducti〇n cycies; 〇RC)程序粗化黃金基 材，以製造含有黃金的錯合物，織鱗波·學_法，配合使用 3之陰極過電位，在無f添加任何穩定劑之情況下，製造不同大小 而求之安定黃金奈米粒水溶液，再應用於酒類製品中。 6 1273133 本發明之含奈米金之黃金酒，其黃金含量可由〇· 〇1至3〇〇〇ppm， 依據不同之酒類，因其乙醛之含量不同，故所需之添加金之濃度亦有 所差異；又黃金對6醛之去除是一慢速率的反應，故添加量亦與添加 後酒存放的時間有關，若欲在短時間内即飲用者，可添加較高濃度之 黃金，以加速對酒中乙醛之去除率，若欲在很長時間後才飲用者，可 添加較低濃度之黃金，以降低成本，並且仍能保持對酒^乙醛之去除 V 率，黃金之功能除了對乙醛之去除外，並對身體具有鎮靜、堅固骨骼、 、 順暢五臟内腑等保㈣效，故可添加比去除乙_需要的量還多之黃 '金，以兼具保健效果，又黃金之添加量亦不宜太多，1多一者成本增 加，-者因黃金屬重金屬，過多的黃金仍會對健康有害，故含量不^ 超過又若濃度低於〇·〇1_則效用不大，故以〇〇1至__ 含量較為適當，其中，以1至為佳，又以1至300_最佳， 亚依不同之鋪製品而有不同，本發明之另—優點躺製得之黃金顆 粒極為細緻，為具有顆粒大小約在〇· i至3〇奈米範圍之内，甚至平均 大J在10奈米以下，除對乙盤之去除率高以外，更易為人體所吸收， 且具極加安定性，相當具有產業價值。 /本發明之奈米級黃金酒之製造，係以聲波電化學法於無添加任何 穩定劑之含有可與黃麵成蚊錯合物德合物的水紐或酒中 ^粒大小補約在〇·丨至3G奈米之安定黃金奈米粒。首先將黃金基 ^ ^騎氧氣之含討與黃金職安定錯合物德合物的水溶液或 電^化學之氧㈣原循環處理約_圈，使用之陰極與陽極端 ^ 28 V ^ 22 v v, Ag/AgC1, 5〇〇 ^ 陽極端電位時分別停留數十至數秒；之後，於溶液中會存在 =1"之錯合物。接著將黃金工作電極以白金電極取代，在約100 W σ曰波振盈下，待系統之開路電位穩定後（約為〇· 82 V vs. 7 1273133 g、，gci) 77犯㈣不同之陰極過電位，來製造顆粒大小不同之黃金 不米粒，Ik著使用之陰極過電位增加，所製造出之貴金屬奈米粒的顆 粒大】’亦由〇·；[增加至30奈米。同時，水溶液中黃金奈米粒與含有 K金之奈米錯合物的比值，亦可經_整聲波電化學還原法的使用時 間來控制。 本舍明之可與讀形成安定錯合物之化合物的濃度，濃度範圍依 化合物種類岐，以能與貴金屬形成敎錯合物為主，以食鹽為例， ：!又係於0· 0001-12N，較佳為〇· 0005—3N，更佳為〇·謝_1N，最佳為 0.001-0.3N。 # 本發明之陰闕餘可為ooh v，較料m v，更佳為 0· 2-0· 8 V。 本舍明之貝金屬奈米粒，可額外加入其他食用穩定劑，如糖球 (sugar ball) ’或一些穩定的技術等。 【實施方式】 黃金奈米粒之製造 實施例一 所有電化學實驗均於三槽式之玻璃反應器中進行，且由一怪電位 電流儀控·〇del PGSTAT3G，Eto Cheinie)，實驗溫度為室溫2沈， 以裸露面積為W之黃w、8 ▲自糾與飽和氯化狀銀/氯化 銀y分別為工作、相對與參考電極；電極於已去除氧氣之Q· Μ之食鹽 水洛液中以電化學之·程序粗化黃金紐，掃描之陰極與陽極端電 位刀別為〇. 28 V與+1. 22 V vs Ag/AgCl，掃描速率為500 mV/s， 陰極與陽極端電位分別停留1G與5秒，共㈣圈；在此粗化程序後， 且存在含有金與氯之錯合物，接著黃金卫作電極立刻以具有相同露面 1273133 積為4 cm2之白金片取代，而原電解液繼續使用，待系統之開路電位 (open circuit potential; OCP)穩定後，約為 〇·78 v vs Ag/Agn 立 以0· 6 V的陰極過電位，在超音波與輕微之攪拌下，進行5⑼秒，上、 製造黃金奈米粒。超音波產生器（m〇del χ·〇, Micr〇sQn)操作在如 kHz，以直徑為3· 2 mm之鈦化鋇振動器釋出100 w的功率。由圖上中 之TEM圖觀察所製造黃金奈米粒，圓球形顆粒之平均直徑小於川 nm，無聚集現象且分散情形良好。一'—一 黃金奈米粒之乙醛去除 實施例二 將不同濃度之黃金奈米粒，分別添加於人工調配酒精濃度為4〇^ (v/v %)、含有2000 ppm乙醛之水溶液中，而乙醛之去除實驗是在密 封、遮光，且輕微攪拌的試樣瓶中進行。 實施例三 對酒精濃度為42%(v/v%)、含有6〇ppm乙醛之商業用琴酒(Gin wine)，比照實施例二之方式，進行乙醛去除實驗。 乙醛去除的檢測： 以氣相層析-質譜儀（gas chromatography-mass spectr〇meter， GC-MS; Micromass TRIO-2000)，分析酒中乙醛之去除情形；每次實驗 樣品注入量為1 pL，實驗用之分析毛細管為DB—WAX 3〇 ^ length χ 〇· 25 mm i.d· χ 0· 25 μπι film thickness，攜行氣體為氦氣。 乙醛去除實驗測定前，先調配乙醛、乙酸與乙醇混合之標準溶液， 以確認個別成份於GC-MS圖譜中出現的位置；由圖2之實驗結果顯 9 1273133 =’出現在滞留時間為h63,道與3·8〇分鐘處之峰分別為乙駿、乙 酉夂^醇。、此特徵峰之指定，可進_步由質量/電荷圖譜得到證實。 圖3為未添加黃金奈米粒之空白實驗，乙·之濃度由乙駿之峰面 積〜乙駿與乙醇之峰面積的比值蚊，其值近似雇〇ppm。 ° 厂、4、加卯m之黃金奈米粒於2000 ppm乙酸之水溶液中， 1〇天後㈣之含量可下降至l_ppm。 人^圖5中可知’當添加1 PPm之黃金奈米粒於酒中，10天後乙酸 ▲ 3里可由2000 ppm下降至15〇〇卯㈤，黃金奈米粒之濃度增加至$ /、25 ppm ’乙駿之含量更可分別由2_卯爪下降至聽pp^ 1〇〇〇 ppm。此結果顯示鱗波電化學方法製造之黃金奈米粒，制中的乙酸 去除，有其特有之催化活性；而此催化特性，亦可成功地應用在商業 酒類’由實施例二之實驗結果顯示，在含有6Qppm乙狀琴酒中，僅 添加1 ppm之黃金奈練，2G天後乙狀含餅可下降至無法檢出之 程度。 以上為本發明之實施例，非用以限制本發明，本發明之奈米級黃 金酒確實可去除酒中之乙盤，增加酒品飲用時之口感，以及對身體健 康有益之功效，可廣泛應用於各種酒類之產業領域，並具極佳之效果， 相當具有產業利用性。 1273133 【圖式簡平說明】 圖1· 奈米金之TEM圖，_糊粒大小與分散情形； V的陰極過，切音麟機之授掉下， 錯合物的水麵中製造黃金奈米粒。 製備條件為以0.6 於含有金與氯之 圖2· 圖3. 圖4·1273133, the imitation valley is easy to be attached to the cathode, so that the metal nano-tano is formed on the interface between the aqueous solution and the cathode, so the preferred embodiment of the present invention is made by sonic electrochemical method; And can reduce (solve) the phenomenon that metal ions are easily covered on the cathode: 峨 Made of gold nanoparticles smaller than the general electrochemical method. SUMMARY OF THE INVENTION The gold-containing wine of the present invention is reduced in its manufacturing method, and the gold wine comprises nano-grade gold manufactured by the ear wave package chemical method, and the gold has a size range of about • Rice, the concentration of the blending is about 随 , 、, the nano-golden syrup of the present invention, ... can be removed from the undesired ingredients contained in the general liquor by the glutinous rice-grade gold. It can increase the sensation of drinking and the beneficial effects on the health of the wine. It is quite industrially valuable. The nano-grade gold produced by the t-chemical method is preferably the nano-grade gold produced by the sonic private chemical method. Regarding the method of the invention, the method of the invention of the present invention, in the case of the inventor's application in the Taiwan Patent Application No. 93112450, the sonic electrochemical method for the manufacture of a controllable precious metal from the precious metal block is incorporated into the present case. The nano-gold is made by the ear-wave private chemical method of the moon. It can be manufactured in an aqueous solution containing a compound which can form a stable complex with gold without any added stability. Q1 to 3 () nano-diamond gold nanoparticles, which can be compounded with a metal axis, a compound that is a kind of edible electrolyte, such as: sodium chloride, potassium carbonate, especially sodium chloride good. The present invention discloses an aqueous solution (or an aqueous solution containing the same) of the above-mentioned 4 compounds, and roughens the gold substrate by an electrochemical oxidation m-origin cycle (oxldati〇n-reducti〇n cycies; 〇RC) to produce Gold complex, weaving scale wave · learning _ method, in conjunction with the use of 3 cathode overpotential, in the absence of any stabilizer added to the f, the production of different sizes of aqueous solution of gold nanoparticles, and then applied to alcohol products in. 6 1273133 The gold content of the nano-gold-containing wine of the present invention can be from 1 to 3 ppm by weight of 〇·〇, and according to different alcohols, the concentration of the added gold required is also different depending on the content of acetaldehyde. There is a difference; gold removal of 6 aldehyde is a slow rate of reaction, so the amount of addition is also related to the storage time of the wine after the addition, if you want to drink in a short time, you can add a higher concentration of gold, In order to speed up the removal rate of acetaldehyde in wine, if you want to drink it after a long time, you can add a lower concentration of gold to reduce the cost, and still maintain the removal rate of wine acetaldehyde, gold In addition to the removal of acetaldehyde, the function of the body is calm, strong bones, and smooth internal organs, etc., so it can add more yellow gold than the amount needed to remove B. And the amount of gold added should not be too much, the cost of more than one is increased, and because of the heavy metal of yellow metal, too much gold will still be harmful to health, so the content is not more than if the concentration is lower than 〇·〇1_ The effect is not large, so the content of 〇〇1 to __ is more appropriate Among them, the preferred ones are preferably 1 to 300 _, and the other is different from the laid products. The other advantage of the present invention is that the gold particles are extremely fine, and have a particle size of about 〇. · Within the range of i to 3 nanometers, even the average large J is below 10 nanometers. In addition to the high removal rate of the ethylbenzene, it is more easily absorbed by the human body, and it has extremely stable stability and is quite industrially valuable. / The manufacture of the nano-grade gold wine of the present invention is carried out by sonic electrochemical method without adding any stabilizer, and the size of the water or the wine can be supplemented with the size of the yellow-faced adult mosquito complex. 〇·丨 to 3G nano-dating gold nanoparticles. First, the gold base ^ ^ riding oxygen is discussed with the gold solution or the chemical oxygen (4) original cycle treatment about _ circle, using the cathode and anode end ^ 28 V ^ 22 vv, Ag/AgC1, 5〇〇^ The anode terminal potential stays for tens to several seconds, respectively; after that, there will be a =1" complex in the solution. Then the gold working electrode is replaced by a platinum electrode, and after about 100 W σ曰 wave vibration, after the open circuit potential of the system is stabilized (about 〇·82 V vs. 7 1273133 g, gci), 77 (four) different cathodes Overpotentials are used to produce gold non-grain particles of different particle sizes. The cathode overpotential used by Ik is increased, and the particles of the noble metal nanoparticles produced by the large particles are also increased from '〇 to 30 nm. At the same time, the ratio of the gold nanoparticles in the aqueous solution to the nano-compound containing K gold can also be controlled by the use time of the oscillating wave electrochemical reduction method. The concentration of the compound which can form a stable complex with Benming, the concentration range depends on the type of the compound, and can form a ruthenium complex with the noble metal, taking the salt as an example, and is also based on 0·0001-12N. Preferably, it is 0005·0005-3N, more preferably 〇·谢_1N, and the best is 0.001-0.3N. # The yin of the present invention may be ooh v, more preferably m v, more preferably 0· 2-0· 8 V. Benbenming's shell metal nanoparticles can be additionally added with other food stabilizers, such as sugar balls or some stable techniques. [Embodiment] Production of Golden Nanoparticles Example 1 All electrochemical experiments were carried out in a three-tank glass reactor, controlled by a strange potential current meter, 〇del PGSTAT3G, Eto Cheinie), and the experimental temperature was room temperature. 2 sink, with bare area W, yellow w, 8 ▲ self-correcting and saturated chlorinated silver/silver chloride y respectively, working, relative and reference electrode; electrode in the oxygen-removed Q· Μ 食 盐水 salt In the electrochemical program, the gold is added, and the cathode and anode potentials of the scanning are 〇. 28 V and +1. 22 V vs Ag/AgCl, scanning rate is 500 mV/s, cathode and anode potential Stay 1G and 5 seconds respectively for a total of (four) cycles; after this roughening procedure, there is a complex containing gold and chlorine, and then the gold-powered electrode is immediately replaced by a white gold plate with the same exposed surface of 1273133 and 4 cm2. The original electrolyte continues to be used. After the open circuit potential (OCP) of the system is stabilized, it is about 78·78 v vs Ag/Agn with a cathode overpotential of 0·6 V. Under ultrasonic and slight agitation , for 5 (9) seconds, on, to make gold nanoparticles. The ultrasonic generator (m〇del χ·〇, Micr〇sQn) operates at, for example, kHz, releasing 100 watts of power from a titanic yttrium vibrator with a diameter of 3.2 mm. The gold nanoparticles produced by the TEM image in the figure were observed. The average diameter of the spherical particles was smaller than that of the Sichuan nm, and there was no aggregation and the dispersion was good. Example 1 of removing acetaldehyde from a gold nanoparticle. The gold nanoparticles of different concentrations were separately added to an artificially prepared aqueous solution containing 4 〇^ (v/v %) and containing 2000 ppm of acetaldehyde. The acetaldehyde removal test was carried out in a sealed, light-shielded, and slightly stirred sample vial. Example 3 An acetaldehyde removal test was carried out in the same manner as in Example 2 for a commercial gin (Gin wine) having an alcohol concentration of 42% (v/v%) and containing 6 〇 ppm of acetaldehyde. Detection of acetaldehyde removal: The gas chromatography-mass spectr〇meter (GC-MS; Micromass TRIO-2000) was used to analyze the removal of acetaldehyde in wine; the injection amount of each sample was 1 pL, the analytical capillary for the experiment is DB-WAX 3〇^ length χ 〇 · 25 mm id· χ 0· 25 μπι film thickness, carrying gas is helium. Before the acetaldehyde removal test, the standard solution of acetaldehyde, acetic acid and ethanol was mixed to confirm the position of the individual components in the GC-MS spectrum; the experimental results shown in Fig. 2 were 9 1273133 = 'appeared in the residence time H63, the peaks at the road and 3·8〇 minutes are respectively B, 酉夂, and 醇. The designation of this characteristic peak can be confirmed by the mass/charge map. Fig. 3 is a blank experiment in which no gold nanoparticles are added, and the concentration of B. is the ratio of the peak area of the peak of the unit to the peak area of the tube and the ethanol, and the value is approximately ppm. ° Plant, 4, gold nanoparticles of 卯m in 2000 ppm acetic acid in water, after 1 day (four) content can be reduced to l_ppm. People ^ Figure 5 shows that when adding 1 PPm of gold nanoparticles in wine, after 10 days, acetic acid ▲ 3 can be reduced from 2000 ppm to 15 〇〇卯 (five), the concentration of gold nanoparticles increased to $ /, 25 ppm ' The content of Yijun can be reduced from 2_卯 claw to listening to pp^1〇〇〇ppm. This result shows that the gold nanoparticle produced by the scale wave electrochemical method, the acetic acid removal in the preparation has its own catalytic activity; and the catalytic property can also be successfully applied to commercial liquors, as shown by the experimental results of the second embodiment, In the 6Qppm sylvestre wine, only 1 ppm of gold nugget is added, and after 2G days, the sigmoid cake can be reduced to the extent that it cannot be detected. The above is an embodiment of the present invention, and is not intended to limit the present invention. The nano-grade gold wine of the present invention can remove the ethyl plate in the wine, increase the taste of the wine when drinking, and has beneficial effects on the health of the body. It is used in various industrial fields of alcohol, and has excellent effects, and is quite industrially useful. 1273133 [Illustration of the diagram] Figure 1 · TEM image of nano gold, _ paste size and dispersion; V cathode, over the cut-off machine, the gold nano-particles in the water surface of the complex . The preparation conditions are as follows: 0.6 for gold and chlorine. Figure 2· Figure 3. Figure 4·
圖5. 乙酸、乙酸與乙醇混合液之標準GC_MS圖譜。 酒精/辰度為4G % (v/v %)、含有2⑻Q ppm乙盤之水溶液中，未 添加κ金奈米教，經1G天測試後之GC_MS圖譜。 酒精濃度為4G % (v/v %)、含有2_ ppm乙社水溶液中，添 加25 ppm之黃金奈米粒，經1〇天測試後乙醛之殘留量。 酒精濃度為40 % (v/v %)、含有2000 ppm乙醛之水溶液中，添 加不同濃度之黃金奈米粒，經10天測試後乙醛之殘留量。Figure 5. Standard GC_MS spectrum of a mixture of acetic acid, acetic acid and ethanol. The alcohol/length is 4G % (v/v %), and the aqueous solution containing 2 (8) Q ppm is not added with κ Jinnai, and the GC_MS spectrum after 1G test. The alcohol concentration was 4 G % (v/v %), and the residual amount of acetaldehyde was measured after 1 day of testing by adding 25 ppm of gold nanoparticles to a 2 ppm aqueous solution. The residual amount of acetaldehyde was measured after 10 days of adding gold nanoparticles of different concentrations in an aqueous solution containing 40% (v/v %) of alcohol and containing 2000 ppm of acetaldehyde.