WO2016000664A1 - 一种香兰素的制备方法 - Google Patents

一种香兰素的制备方法 Download PDF

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WO2016000664A1
WO2016000664A1 PCT/CN2015/085408 CN2015085408W WO2016000664A1 WO 2016000664 A1 WO2016000664 A1 WO 2016000664A1 CN 2015085408 W CN2015085408 W CN 2015085408W WO 2016000664 A1 WO2016000664 A1 WO 2016000664A1
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vanillin
salt
eugenol
organic solvent
reaction
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PCT/CN2015/085408
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English (en)
French (fr)
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毛海舫
王立志
刘振江
姚跃良
王朝阳
吴建新
赵飞飞
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嘉兴市中华化工有限责任公司
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Priority to EP15750614.8A priority Critical patent/EP3045444B1/en
Publication of WO2016000664A1 publication Critical patent/WO2016000664A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C07C47/58—Vanillin

Definitions

  • the invention belongs to the field of chemical industry, in particular to an eugenol, in particular to a preparation method of vanillin.
  • Vanillin commonly known as vanillin and vanillin, chemically known as 4-hydroxy-3-methoxybenzaldehyde, is a spectral fragrance with a strong milky aroma. Used in food, daily necessities, medical, brewing and tobacco industries. It can be obtained by plant extraction, biotransformation and chemical synthesis.
  • the plant extraction method is the most direct method for obtaining natural vanillin.
  • Vanillin is found in many essential oils and plants and has the highest content in vanilla beans.
  • the vanillin obtained by this method is a natural product with a strong aroma.
  • artificial pollination of flowers is required, which requires high labor intensity and is difficult to plant on a large scale. Therefore, the method is far from meeting market demand.
  • the biotransformation method has the advantages of cleanness, less pollution, safe production, and close to natural products.
  • the reaction system is too complicated.
  • the product vanillin has certain toxicity to the enzyme or microorganism, and the yield and conversion rate are low.
  • the separation of vanillin The process is complicated, the cost is high, and the residue of metabolites in the biotransformation process also reduces product quality and safety.
  • the vanillin in the market comes from chemical synthesis methods, including baicalein method, lignin method, p-cresol method, 4-methylguaiacol method, p-hydroxybenzaldehyde method, guaiacol method.
  • the chemical synthesis method generally uses the glyoxylic acid method, that is, guaiacol and glyoxylic acid are condensed under alkaline conditions to form 3-methoxy-4-hydroxymandelic acid, which is oxidized to 3 under the action of a catalyst.
  • -Methoxy-4-hydroxyacetophenone acid decarboxylated to vanillin, and then extracted, rectified, and dilute ethanol to obtain pure vanillin.
  • the natural grade vanillin made from eugenol is attractive, safe to eat and has high practical value, which has attracted extensive attention and in-depth research.
  • the Chinese patent CN1289836A published on April 4, 2001 reported the method of preparing vanillin from clove oil by Shanghai Tianxiang Fine Chemical Co., Ltd.: adding sodium hydroxide to clove oil, then adding oxidant and carbonyl mixed catalyst at 100 Oxidation is carried out at -300 ° C, and the final vanillin yield is 50% or more.
  • the oxidizing agents used are potassium permanganate, p-aminobenzenesulfonic acid and nitrobenzene, and the reaction temperatures are all above 100 °C.
  • the oxidizing agent used in the invention, such as potassium permanganate is an oxidant commonly used in the past, and the waste liquid produced by the reaction is difficult to handle, and the pollution to the environment is severely eliminated.
  • the method for synthesizing vanillin from eugenol is traditionally known as isomerization and reoxidation of eugenol, that is, eugenol is firstly isomeric to isoeugenol under the action of sodium hydroxide or potassium hydroxide, and then Oxidation to vanillin by the action of an oxidizing agent.
  • eugenol is firstly isomeric to isoeugenol under the action of sodium hydroxide or potassium hydroxide, and then Oxidation to vanillin by the action of an oxidizing agent.
  • Chinese Patent No. CN102206146A published on October 5, 2011, and Chinese Patent No. CN103641698A, published on March 19, 2014, disclose a process for the isomerization of eugenol to isoeugenol to prepare natural vanillin.
  • the technical problem to be solved by the present invention is to provide a preparation method of vanillin, which solves the complicated process of synthesizing vanillin by eugenol in the prior art.
  • the invention provides a preparation method of vanillin, comprising:
  • the method comprises the steps of separately weighing eugenol, a strong base, a catalyst, and a first organic solvent, wherein the molar ratio of the strong base to the eugenol is 1:2-15, and the amount of the catalyst is eugenol. 0.1% to 2.0% by weight, the volume of the first organic solvent is 3 to 10 times the volume of eugenol, and the above substances are separately added to a reaction vessel at a reaction pressure of 0.01 to 0.30 MPa, and heated under stirring. 60 ⁇ 120 ° C, then start to pass oxygen, control The partial pressure of oxygen is 0.01 to 1 MPa, and the oxidation reaction is carried out.
  • the reaction is terminated, cooled to room temperature, water is added, the volume ratio of the water to the first solvent is 0.5 to 2, and the solution is adjusted to neutral with an acid solution.
  • the aqueous phase is extracted with a second organic solvent, and then distilled under reduced pressure, and crystallized by a mixed solvent of ethanol and water to obtain vanillin.
  • the second organic solvent is toluene or ethylbenzene.
  • the first organic solvent is methanol or ethanol.
  • the catalyst is a cobalt salt, or a mixed salt of a cobalt salt and a copper salt, or a mixed salt of a cobalt salt and a nickel salt.
  • the volume ratio of ethanol to water is 0.3 to 5:1.
  • the weight ratio of the cobalt salt to the copper salt is an arbitrary ratio.
  • the weight ratio of the cobalt salt to the nickel salt is an arbitrary ratio.
  • the strong base is sodium hydroxide or potassium hydroxide.
  • the acid solution is hydrochloric acid or a sulfuric acid solution
  • the hydrochloric acid or sulfuric acid solution has a molar concentration of 1 to 3 mol/L.
  • reaction equation of the present invention is as follows:
  • the invention takes eugenol as a raw material, in the presence of a strong base, a cobalt salt, or a mixed salt of a cobalt salt and a copper salt, or a mixed salt of a cobalt salt and a nickel salt as a catalyst, and the reaction pressure is 0.01 to 0.30 MPa, and the reaction temperature is It is a method of synthesizing vanillin by introducing oxygen into a temperature of 60 to 120 ° C and controlling the partial pressure of oxygen to be 0.01 to 1 MPa.
  • the technical progress of the present invention is remarkable compared to the prior art.
  • the invention adopts eugenol as a raw material, and synthesizes vanillin in one step, without phenolic hydroxyl group protection, isomerization, etc. of eugenol
  • the process directly synthesizes vanillin, the process is simple, the post-treatment is convenient, the yield is high, the product has good aroma, and is suitable for industrial production.
  • the invention is simple in operation, low in cost and less in pollution.
  • the invention provides a preparation method of vanillin, comprising:
  • the present invention reacts eugenol with oxygen in the presence of a strong base and a catalyst to obtain a vanillin salt
  • the strong base is preferably sodium hydroxide or potassium hydroxide
  • the solvent of the reaction is preferably Methanol or ethanol, more preferably methanol
  • the catalyst is preferably a cobalt salt, a mixed salt of a cobalt salt and a copper salt or a mixed salt of a cobalt salt and a nickel salt
  • the present invention The ratio of the two in the mixed salt is not particularly required, and any ratio may be preferably a mass ratio of the cobalt salt to the copper salt of 1: (0.1 to 1); for the mixed salt of the cobalt salt and the nickel salt, the present invention
  • the ratio of the two in the mixed salt is not particularly limited, and the mass ratio of the cobalt salt to the nickel salt is preferably 1: (0.1 to 1).
  • the molar ratio of the eugenol to the strong base is 1: (2-15), more preferably 1: (3-10); the mass ratio of the eugenol to the catalyst is preferably 100: (0.1 ⁇ 3), more preferably 100: (0.2 to 2); the ratio of the eugenol to the solvent is 1 g: (3 to 10) mL, more preferably 1 g: (4 to 8) mL; in the reaction system
  • the oxygen partial pressure is preferably 0.01 to 1 MPa, more preferably 0.05 to 0.5 MPa, most preferably 0.1 to 0.3 MPa; and the reaction temperature is preferably 60 to 120 ° C, more preferably 80 to 110 ° C, and most preferably 85 to 100 ° C.
  • the present invention also reacts the obtained vanillin salt with an acid to obtain vanillin;
  • the present invention has no particular requirement for the acid, and any acid known in the art, preferably hydrochloric acid or sulfuric acid; the molar concentration of the acid is preferably 1 to 3 mol / L.
  • the preparation method provided by the invention introduces a specific catalyst in the process of preparing vanillin in eugenol, so that the isomerization and oxidation of eugenol can be completed by one-step reaction, and the process is simple, the post-treatment is convenient, and the yield is high.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

一种香兰素的制备方法，包括一个分别称取丁香酚、强碱、催化剂、第一有机溶剂的步骤，所述的强碱与丁香酚的摩尔比为1:2～15，所述的催化剂的用量是丁香酚重量的0.1％～2.0％，所述第一有机溶剂的体积为丁香酚体积的3～10倍，将上述的物质分别加入一个反应容器中，反应压力为0.01～0.30MPa，搅拌条件下加热至60～120℃，然后开始通入氧气，控制氧气分压为0.01～1MPa，进行氧化反应，4～30小时后结束反应，冷却至室温，加入水，所述的水和第一溶剂的体积比为0.5～2，并用酸溶液调节至中性，回收第一有机溶剂后，水相用第二有机溶剂萃取，再进行减压蒸馏，采用乙醇水混合溶剂结晶，干燥后得到香兰素。本发明无需对丁香酚进行酚羟基保护、异构化等过程直接合成香兰素，工艺简单、后处理方便。

Description

一种香兰素的制备方法
本申请要求于2014年6月30日提交中国专利局、申请号为201410304472.6、发明名称为“一种香兰素的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于化工领域，尤其涉及一种丁香酚，具体来说是一种香兰素的制备方法。
背景技术
香兰素，俗名香草醛和香兰醛，化学名称为4-羟基-3-甲氧基苯甲醛，为一种光谱型香料，具有浓郁奶香气息。多用于食品、日常用品、医疗、酿酒和烟草等行业。可通过植物提取法、生物转化法和化学合成法得到。
植物提取法是获取天然香兰素最直接的方法，香兰素在许多精油及植物中均有发现，在香荚兰豆中含量最高。该法获得的香兰素属于天然产品，香气浓郁。但在香荚兰豆种植过程中需要对花朵进行人工授粉，劳动强度要求高、难以大规模栽种，故该法远远不能满足市场需求。
生物转化法具有清洁、污染少、生产安全、产品接近天然等优点，但是反应体系过于复杂，产物香兰素对酶或微生物具有一定毒性，收率和转化率都较低，香兰素的分离工艺复杂，所用成本高，生物转化过程中代谢产物的残留还会降低产品品质和安全性。
市场上的香兰素多来自于化学合成法，包括黄樟素法、木质素法、对甲酚法、4-甲基愈创木酚法、对羟基苯甲醛法、愈创木酚法等。目前，化学合成法普遍采用的是乙醛酸法，即愈创木酚和乙醛酸在碱性条件下缩合生成3-甲氧基-4-羟基扁桃酸，在催化剂作用下被氧化为3-甲氧基-4-羟基苯乙酮酸，脱羧成为香兰素，再经过萃取、精馏、稀乙醇结晶得到香兰素纯品。但该法在工业化生产上易产生大量的含酚废水，从而导致环境污染。其余制备香兰素的方法国内外都有所涉及，但以上方法不是工艺路线长， 对设备要求高，环境污染严重，就是反应效率低、产品分离复杂、香气质量差。
以丁香酚为原料制得的天然级香兰素香气诱人、食用安全、实用价值高，从而受到人们广泛的关注和深入的研究。2001年4月4日公开的中国专利CN1289836A报道了上海天香精细化工有限公司以丁香油为原料制备香兰素的方法：在丁香油中加入氢氧化钠，然后加入氧化剂、羰基类混合催化剂在100～300℃进行氧化，最终香兰素收率50％以上。其中，所用的氧化剂为高锰酸钾、对氨基苯磺酸和硝基苯，并且反应温度均在100℃以上。该发明使用的氧化剂如高锰酸钾等都是传统上人们普遍使用的氧化剂，反应产生的废液难以处理，对环境的污染严重，正在逐步被淘汰。
以丁香酚为原料合成香兰素的方法，传统上普遍先将丁香酚异构化，再氧化，即丁香酚首先在氢氧化钠或氢氧化钾的作用下异构为异丁香酚，然后在氧化剂的作用下氧化为香兰素。如2011年10月5日公开的中国专利CN102206146A，与2014年3月19日公开的中国专利CN103641698A，均公开了由丁香酚异构化成异丁香酚再制备天然香兰素的方法。
发明内容
针对上述现有技术中存在的缺陷，本发明所要解决的技术问题是提供一种香兰素的制备方法，所述的这种方法要解决现有技术中通过丁香酚合成香兰素的工艺复杂、成本高、污染大的技术问题。
本发明提供了一种香兰素的制备方法，包括：
1)将丁香酚在强碱和催化剂存在条件下与氧气反应，得到香兰素盐，
2)将香兰素盐与酸反应，得到香兰素。
进一步的，包括一个分别称取丁香酚、强碱、催化剂、第一有机溶剂的步骤，所述的强碱与丁香酚的摩尔比为1:2～15，所述的催化剂的用量是丁香酚重量的0.1％～2.0％，所述第一有机溶剂的体积为丁香酚体积的3～10倍，将上述的物质分别加入一个反应容器中，反应压力为0.01～0.30MPa，搅拌条件下加热至60～120℃，然后开始通入氧气，控制 氧气分压为0.01～1MPa，进行氧化反应，4～30小时后结束反应，冷却至室温，加入水，所述的水和第一溶剂的体积比为0.5～2，并用酸溶液调节至中性，回收第一有机溶剂后，水相用第二有机溶剂萃取，再进行减压蒸馏，采用乙醇水混合溶剂结晶，干燥后得到香兰素。
进一步的，所述的第二有机溶剂为甲苯或者乙苯。
进一步的，所述的第一有机溶剂为甲醇或乙醇。
进一步的，所述的催化剂为钴盐、或者钴盐与铜盐的混合盐、或者钴盐与镍盐的混合盐。
进一步的，所述乙醇水混合溶剂中，乙醇和水的体积比为0.3～5:1。
进一步的，在所述的钴盐与铜盐的混合盐中，所述钴盐与铜盐的重量比为任意比。
进一步的，在所述的钴盐与镍盐的混合盐中，所述钴盐与镍盐的重量比为任意比。
进一步的，所述的强碱为氢氧化钠或者氢氧化钾。
进一步的，所述的酸溶液为盐酸或者硫酸溶液，所述的盐酸或者硫酸溶液的摩尔浓度为1～3mol/L。
本发明的反应方程式如下所示：
Figure PCTCN2015085408-appb-000001
本发明是以丁香酚为原料，在强碱存在下，钴盐、或者钴盐与铜盐的混合盐、或者钴盐与镍盐的混合盐为催化剂，反应压力为0.01～0.30MPa，反应温度为60～120℃，通入氧气，控制氧气分压为0.01～1MPa进行氧化反应合成香兰素的方法。
本发明和已有技术相比，其技术进步是显著的。本发明采用丁香酚为原料，一步催化合成香兰素，无需对丁香酚进行酚羟基的保护、异构化等 过程直接合成香兰素，工艺简单、后处理方便、收率较高，产品香气佳，适合工业化生产。而且本发明操作简单、成本低、污染少。
具体实施方式
本发明提供了一种香兰素的制备方法，包括：
1)将丁香酚在强碱和催化剂存在条件下与氧气反应，得到香兰素盐，
2)将香兰素盐与酸反应，得到香兰素。
按照本发明，本发明将丁香酚在强碱和催化剂存在条件下与氧气反应，得到香兰素盐，其中，所述强碱优选为氢氧化钠或氢氧化钾；所述反应的溶剂优选为甲醇或乙醇，更优选为甲醇；所述催化剂优选为钴盐、钴盐与铜盐的混合盐或者钴盐与镍盐的混合盐；其中，对于钴盐与铜盐的混合盐，本发明对该混合盐中二者的比例没有特殊要求，任何比例均可，优选为钴盐与铜盐的质量比为1：(0.1～1)；对于钴盐和镍盐的混合盐，本发明对该混合盐中二者的比例没有特殊要求，优选为钴盐与镍盐的质量比为1：(0.1～1)。
所述丁香酚与所述强碱的摩尔比为1：(2～15)，更优选为1：(3～10)；所述丁香酚与所述催化剂的质量比优选为100：(0.1～3)，更优选为100：(0.2～2)；所述丁香酚与溶剂的用量比为1g：(3～10)mL，更优选为1g：(4～8)mL；所述反应体系中氧气分压优选为0.01～1MPa，更优选为0.05～0.5MPa，最优选为0.1～0.3MPa；所述反应的温度优选为60～120℃，更优选为80～110℃，最优选为85～100℃。
本发明还将得到的香兰素盐与酸进行反应，得到香兰素；本发明对酸没有特殊要求，本领域公知的酸均可，优选为盐酸或硫酸；所述酸的摩尔浓度优选为1～3mol/L。
本发明提供的制备方法，通过在丁香酚制备香兰素的过程中引入特定的催化剂，使得丁香酚的异构化和氧化可以通过一步反应完成，且工艺简单，后处理方便，收率高。
本发明实施例仅供说明具体方法，但并不限制本发明。
实施例1
在体积为1000ml高压釜中，加入73.8g丁香酚、90g氢氧化钠、0.075g 醋酸钴和0.075g醋酸镍，然后加入450ml甲醇，保持高压釜良好的密封性，搅拌条件下加热至60～65℃，然后开始通入氧气，控制氧气分压为0.3MPa进行氧化反应。反应结束后，冷却至室温，加入300ml水，并用盐酸中和至中性。回收甲醇后，水相用甲苯萃取。萃取液回收甲苯，再进行减压蒸馏，乙醇水混合溶剂结晶，干燥后得到白色针状晶体香兰素36.0克，收率为52.68％，纯度为99.8％。
实施例2
在体积为1000ml高压釜中，加入73.8g丁香酚、30g氢氧化钠、0.22g醋酸钴和0.22g醋酸铜，然后加入300ml甲醇，保持高压釜良好的密封性，搅拌条件下加热至80～85℃，然后开始通入氧气，控制氧气分压为0.05M Pa进行氧化反应。反应结束后，冷却至室温，加入300ml水，并用盐酸中和至中性。回收甲醇后，水相用甲苯萃取。萃取液回收甲苯，再进行减压蒸馏，乙醇水混合溶剂结晶，干燥后得到白色针状晶体香兰素33.9克，收率为49.9％，纯度为99.9％。
实施例3
在体积为1000ml高压釜中，加入73.8g丁香酚、180g氢氧化钠、1.48g醋酸钴，然后加入540ml甲醇，保持高压釜良好的密封性，搅拌条件下加热至100～105℃，然后开始通入氧气，控制氧气分压为0.01MPa进行氧化反应。反应结束后，冷却至室温，加入450ml水，并用盐酸中和至中性。回收甲醇后，水相用甲苯萃取。萃取液回收甲苯，再进行减压蒸馏，乙醇水混合溶剂结晶，干燥后得到白色针状晶体香兰素41.4克，收率为60.5％，纯度为99.9％。
实施例4
在体积为1000ml高压釜中，加入73.8g丁香酚、90g氢氧化钾、0.22g醋酸钴和0.07g醋酸镍，然后加入375ml甲醇，保持高压釜良好的密封性，搅拌条件下加热至115～120℃，然后开始通入氧气，控制氧气分压为0.1MPa进行氧化反应。反应结束后，冷却至室温，加入360ml水，并用盐酸中和至中性。回收甲醇后，水相用甲苯萃取。萃取液回收甲苯，再进行减压蒸馏，乙醇水混合溶剂结晶，干燥后得到白色针状晶体香兰素 33.1克，收率为48.2％，纯度为99.7％。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 一种香兰素的制备方法，包括：
    1)将丁香酚在强碱和催化剂存在条件下与氧气反应，得到香兰素盐，
    2)将香兰素盐与酸反应，得到香兰素。
  2. 根据权利要求1所述的制备方法，其特征在于，所述香兰素的制备方法具体为：
    包括一个分别称取丁香酚、强碱、催化剂、第一有机溶剂的步骤，所述的强碱与丁香酚的摩尔比为1:2～15，所述的催化剂的用量是丁香酚重量的0.1％～2.0％，所述第一有机溶剂的体积为丁香酚体积的3～10倍，将上述的物质分别加入一个反应容器中，反应压力为0.01～0.30MPa，搅拌条件下加热至60～120℃，然后开始通入氧气，控制氧气分压为0.01～1MPa，进行氧化反应，4～30小时后结束反应，冷却至室温，加入水，所述的水和第一溶剂的体积比为0.5～2，并用酸溶液调节至中性，回收第一有机溶剂后，水相用第二有机溶剂萃取，再进行减压蒸馏，采用乙醇水混合溶剂结晶，干燥后得到香兰素。
  3. 如权利要求2所述的一种香兰素的制备方法，其特征在于，所述的第二有机溶剂为甲苯或者乙苯。
  4. 如权利要求2所述的一种香兰素的制备方法，其特征在于，所述的第一有机溶剂为甲醇或乙醇。
  5. 如权利要求1所述的一种香兰素的制备方法，其特征在于，所述的催化剂为钴盐、或者钴盐与铜盐的混合盐、或者钴盐与镍盐的混合盐。
  6. 如权利要求2所述的一种香兰素的制备方法，其特征在于，所述乙醇水混合溶剂中，乙醇和水的体积比为0.3～5:1。
  7. 如权利要求5所述的一种香兰素的制备方法，其特征在于，在所述的钴盐与铜盐的混合盐中，所述钴盐与铜盐的重量比为任意比。
  8. 如权利要求5所述的一种香兰素的制备方法，其特征在于，在所述的钴盐与镍盐的混合盐中，所述钴盐与镍盐的重量比为任意比。
  9. 如权利要求2所述的一种香兰素的制备方法，其特征在于，所述 的强碱为氢氧化钠或者氢氧化钾。
  10. 如权利要求2所述的一种香兰素的制备方法，其特征在于，所述的酸溶液为盐酸或者硫酸溶液。
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