WO2021109530A1 - 一种金属有机产物水解制备醇类物质的工艺 - Google Patents

一种金属有机产物水解制备醇类物质的工艺 Download PDF

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WO2021109530A1
WO2021109530A1 PCT/CN2020/095633 CN2020095633W WO2021109530A1 WO 2021109530 A1 WO2021109530 A1 WO 2021109530A1 CN 2020095633 W CN2020095633 W CN 2020095633W WO 2021109530 A1 WO2021109530 A1 WO 2021109530A1
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metal organic
hydrolysis
bicarbonate
organic products
product
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French (fr)
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吕国锋
郑兆祥
田金金
王徐斌
汤先亮
段晨彬
刘丽丽
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上虞新和成生物化工有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • the invention relates to a metal organic product post-treatment process, in particular to a process for preparing alcohols by hydrolyzing the metal organic product.
  • Grignard reagents are an important class of intermediates in organic synthesis, with the general formula RMgX.
  • the Grignard reagent and various types of ketones, aldehydes, esters and other substances can undergo Grignard reaction to obtain corresponding alcohol metal organic compounds, and then various alcohol substances can be obtained after acid hydrolysis reaction.
  • the hydrolysis method for obtaining alcohol metal organics by Grignard reaction is generally an acidic aqueous solution hydrolysis process.
  • Chinese patent CN 106748943 A discloses a method and device for continuous hydrolysis and neutralization of vitamin A intermediate double Grignard condensate, that is, continuous feed hydrolysis of an ether solution of acid water and vitamin A intermediate double Grignard condensate ,
  • the acid water is sulfuric acid, hydrochloric acid, phosphoric acid or ammonium chloride aqueous solution
  • the volume ratio of the acid water and the ether solution of the vitamin A intermediate double Grignard condensate is preferably (1.4 ⁇ 1.5):1
  • the vitamin A intermediate double The highest concentration of Grignard condensate in ether solution is only 1.6mol/L.
  • metal calcium or lithium organic compounds are generally hydrolyzed with acidic aqueous solutions such as hydrochloric acid or ammonium chloride.
  • the side reaction is particularly obvious when HX is HBr or HI.
  • R 1 , R 2 , and R 3 are all carbon-containing groups, that is, when the hydrolyzed product is a tertiary carbon alcohol, the above halogenation side reaction is also very easy to occur. The existence of this side reaction often leads to a decrease in the yield of the above-mentioned hydrolysis process or a decrease in the purity of the product.
  • the present invention provides a process for preparing alcohols by the hydrolysis of metal organic products.
  • the process can realize the effective recycling of wastewater, and at the same time, can avoid the occurrence of halogenation side reactions in the hydrolysis process and improve Product content.
  • a process for preparing alcohols by hydrolysis of metal organic products includes the following steps:
  • step 2) subjecting the hydrolyzed solid-liquid mixture obtained in step 1) to solid-liquid separation to obtain carbonate solids and oil-water mixtures;
  • step 2) The layering of the oil-water mixture in step 2) obtains a water layer and an oil layer in which the alcohols are dissolved;
  • step 3 After recovering the solvent from the oil layer in step 3), the alcohol substance is obtained.
  • the metal organic product has the following structure:
  • the alcohol substance has the following structure:
  • the hydrolysis principle of the metal organic product of the present invention is:
  • R 1 and R 2 are selected from alkyl, alkenyl or alkynyl;
  • R 3 is selected from two C or more alkylene groups
  • M is calcium or lithium
  • X is chlorine, bromine or iodine.
  • the metal organic product is selected from one of the following specific compounds:
  • the metal salt obtained by hydrolysis in the process of the present invention is in a solid form, which is beneficial to the recovery and reuse of the metal salt product.
  • the bicarbonate is magnesium bicarbonate, calcium bicarbonate or lithium bicarbonate consistent with the metal in the metal organic product.
  • the solid-liquid separation method of the hydrolyzed solid-liquid mixture can be vacuum filtration, pressure filtration or centrifugal separation.
  • the obtained carbonate solid is magnesium carbonate, calcium carbonate or lithium carbonate solid.
  • the reaction temperature is 0-50°C.
  • the molar equivalent ratio of bicarbonate to metal organic product is (1-2):1.
  • the metal organic product solution is added to the reaction system by dripping, and the dripping time is 20-100 min; after the dripping, the reaction time for continuing the temperature keeping is 10-60 min.
  • step 2) a part of the carbonate solid is added with water and carbon dioxide is introduced to prepare an aqueous bicarbonate solution for use in the hydrolysis reaction of step 1); the other part is washed and dried to obtain a solid carbonate product.
  • the water layer of the metal organic product hydrolyzed by the Grignard reaction in the step 3) is cooled and crystallized, and centrifuged to obtain a MgX 2 solid product, and the separated wastewater can be used as water for the preparation of bicarbonate;
  • the aqueous layer of the hydrolyzed metal calcium or lithium organic product in the step 3) is directly used as the water used for the preparation of calcium bicarbonate or lithium bicarbonate.
  • the solvent and unreacted raw materials in the step 4) can be recovered by distillation or rectification process, and can be operated under normal pressure or reduced pressure.
  • the hydrolysis process of the present invention is suitable for the reaction solution obtained by the reaction of various metal organic reagents (such as Grignard reagents, metal calcium organic reagents or lithium organic reagents) with aldehydes, ketones or esters. All these Grignard reagents, alkyl calcium or alkane
  • the reaction solution obtained by the condensation reaction of base lithium with aldehyde, ketone or ester can be directly processed by the method of the present invention.
  • the specific reaction process of metal organic reagent and aldehyde, ketone or ester can refer to reports in the prior art, for example: Various Grignard reactions reported in CN 107513006 A, CN 106588958 A and other patents.
  • the invention effectively solves the problem of waste water discharge and realizes the recycling of waste water in the Grignard reaction hydrolysis process.
  • the present invention also provides a new method for preparing alcohols by alkaline hydrolysis of metal organic products. There is no formation of halogen acid during the hydrolysis process, thereby avoiding the side reaction of halogenation of hydrolyzed alcohols under acidic conditions and improving Calculate the hydrolysis yield and product content.
  • the solution containing the metal organic product used in the embodiment of the present invention can be a reaction solution directly obtained by an existing method (for example, CN 107513006 A, CN 106588958 A, etc.); it is also possible to perform simple concentration or dilution operations on the obtained reaction solution If the operation of this embodiment is performed again, the effect of the technical solution of the present invention will not be affected.
  • an existing method for example, CN 107513006 A, CN 106588958 A, etc.
  • dichloromagnesium condensate The metal-organic product obtained by the Grignard reaction is referred to as dichloromagnesium condensate, with the following structure:
  • the ether solution of alcohol products first recover the ether at 30 ⁇ 50°C under normal pressure, and then heat up to 50 ⁇ 70°C under reduced pressure (1 ⁇ 2mmHg) to recover the unreacted raw material C6 alcohol, obtain 89.1g alcohol products, the HPLC content is 99.5% (chlorine content is 0), and the yield is 99.4%.
  • the obtained magnesium salt aqueous solution was cooled to between 0-5° C., kept for 24 hours, and filtered to obtain 25.5 g of magnesium chloride solid.
  • 25.2 g (0.3 mol) of solid magnesium carbonate was added to the remaining brine obtained by filtration, and carbon dioxide was introduced while stirring until the solid magnesium carbonate disappeared completely, and a magnesium bicarbonate solution was obtained for use until the next hydrolysis.
  • This process achieves zero discharge of wastewater.
  • the ether layer was distilled and recovered at 30 ⁇ 50°C to obtain ether, and then heated to 50 ⁇ 70°C under reduced pressure (1 ⁇ 2mmHg) to recover the unreacted raw material C6 alcohol, 90.5g crude condensate product was obtained, and the HPLC content was 97.5% (6 -The content of chloro condensate is 0.34%, the content of 6-chloro condensate is 0.08%, and the content of 1,6-dichloro condensate is 0.16%), and the yield is 98.9%.
  • the metal-organic product obtained by the Grignard reaction is referred to as bis-bromomagnesium condensate, and the structure is as follows:
  • the methyl tetrahydrofuran solution of the diol was firstly reduced in pressure (76 mmHg) at 30 to 50°C to recover methyl tetrahydrofuran, and then the temperature was raised to 50 to 70°C under reduced pressure (1 to 2 mmHg) to recover the unreacted raw material C6 alcohol, to obtain 89.08g of bis
  • the HPLC content of the monohydric alcohol product is 99.7% (the bromine content is 0), and the yield is 99.5%.
  • magnesium salt aqueous solution was cooled to between 0-5° C., kept for 24 hours, and filtered to obtain 49.3 g of magnesium bromide solid.
  • 25.2 g (0.3 mol) of solid magnesium carbonate was added to the remaining magnesium salt aqueous solution obtained by filtration, and carbon dioxide was introduced while stirring until the solid magnesium carbonate disappeared completely, and a magnesium bicarbonate solution was obtained for use until the next hydrolysis.
  • This process achieves zero discharge of wastewater.
  • the ether layer is obtained by static layering and 180mL. Neutralize with 100mL of 1.1mol/L sodium carbonate aqueous solution for 5-10min. After the water layer is separated, the methyltetrahydrofuran in the water is evaporated under reduced pressure at 30 ⁇ 50°C, and the COD of wastewater is 65000ppm. . After extracting the organic matter in the wastewater layer with 200 mL of dichloromethane, the COD of the wastewater was again detected to be 1500 ppm. The wastewater still needs to be sent to the sewage station for further biochemical treatment, and can be discharged after reaching the national standard.
  • the ether layer was distilled and recovered under reduced pressure at 30 ⁇ 50°C to obtain 145mL of methyltetrahydrofuran, and then heated to 50 ⁇ 70°C under reduced pressure (1 ⁇ 2mmHg) to recover the unreacted raw material C6 alcohol, 91.5g condensate product was obtained, and the HPLC content was 96.7 % (The content of the 6-bromo compound is 0.54%, the 1-bromo condensate is 0.14%, and the 1,6-dibromo condensate is 0.32%), and the yield is 99.2%.
  • the metal organic product obtained by the acetylation reaction of methyl ketene is bis(3-methyl-4-yne-1-penten-3-ol) calcium, and the structure is as follows:
  • the isopropyl ether solution of 3-methyl-4-yne-1-penten-3-ol was recovered at 60 ⁇ 80°C under normal pressure to recover the isopropyl ether, and then rectified to obtain 57.4g product, the content of which was 99.8% by gas chromatography. The yield was 99.6%.
  • This process achieves zero discharge of wastewater.
  • the metal organic product obtained by the Grignard reaction is 3-methyl-5-hexen-3-ol magnesium chloride, the structure is as follows:
  • the obtained magnesium salt aqueous solution was cooled to between 0-5° C., kept for 20 hours, and filtered to obtain 26.4 g of magnesium chloride solid.
  • 25.2 g (0.3 mol) of solid magnesium carbonate was added to the remaining magnesium salt aqueous solution obtained by filtration, and carbon dioxide was introduced while stirring until the solid magnesium carbonate disappeared completely, and a magnesium bicarbonate solution was obtained for use until the next hydrolysis.
  • This process achieves zero discharge of wastewater.
  • the metal organic product obtained by the acetylation reaction of methyl ketene is 3-methyl-4-yne-1-penten-3-ol lithium, the structure is as follows:
  • the ether solution of 3-methyl-4-yne-1-penten-3-ol was recovered at 30-50°C and then rectified to obtain 28.85g of product.
  • the content detected by gas chromatography was 99.5%, and the yield was 99.9%.
  • This process achieves zero discharge of wastewater.
  • the metal-organic product obtained by the Grignard reaction is referred to as bis-bromomagnesium condensate, and the structure is as follows:
  • the methyl tetrahydrofuran solution of diols was first reduced in pressure (76 mmHg) at 30-50°C to recover methyl tetrahydrofuran, and then the temperature was raised to 50-70°C under reduced pressure (1-2 mmHg) to recover unreacted raw material C6 alcohol, to obtain 75.8g of dihydric alcohol.
  • the HPLC content of the monohydric alcohol product is 99.4% (the bromine content is 0), and the yield is 99.6%.
  • magnesium salt aqueous solution was cooled to between 0-5° C., kept for 24 hours, and filtered to obtain 44.8 g of magnesium bromide solid.
  • 25.2 g (0.3 mol) of solid magnesium carbonate was added to the remaining magnesium salt aqueous solution obtained by filtration, and carbon dioxide was introduced while stirring until the solid magnesium carbonate disappeared completely, and a magnesium bicarbonate solution was obtained for use until the next hydrolysis.
  • This process achieves zero discharge of wastewater.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种金属有机产物水解制备醇类物质的工艺，具体包括步骤：1)含有金属有机产物的溶液与碳酸氢盐水溶液中进行水解反应，得到水解固液混合物；2)将步骤1)得到的水解固液混合物进行固液分离分别得到碳酸盐固体和油水混合物；3)步骤2)所述的油水混合物分层得到醇类产品溶液和水层；4)步骤3)所述的醇类产品溶液回收溶剂后得到醇类产品。该工艺能够实现废水的有效循环利用，同时，可避免水解过程卤代副反应的发生，能有效的改善产品含量。

Description

一种金属有机产物水解制备醇类物质的工艺 技术领域
本发明涉及金属有机产物后处理工艺，具体涉及一种金属有机产物水解制备醇类物质的工艺。
背景技术
格氏试剂是有机合成中的一类重要中间体，通式为RMgX。格氏试剂与各种类型的酮、醛、酯等物质可以进行格氏反应得到相应的醇类金属有机物，然后经酸性水解反应后得到各种醇类物质。
目前，格氏反应得到醇类金属有机物的水解方法一般为酸性水溶液水解工艺。中国专利CN 106748943 A中公开了一种维生素A中间体双格氏缩合物的连续水解中和的方法及装置，即酸水与维生素A中间体双格氏缩合物的醚类溶液连续进料水解，其中酸水为硫酸、盐酸、磷酸或氯化铵水溶液，酸水与维生素A中间体双格氏缩合物的醚类溶液体积比优选为(1.4～1.5)：1，而维生素A中间体双格氏缩合物在醚类溶液中的浓度最高只有1.6mol/L。
金属钙或锂的有机化合物在维生素A中间体C6醇合成中也有重要的应用：
Figure PCTCN2020095633-appb-000001
其中金属钙或锂有机化合物一般是用盐酸或氯化铵等酸性水溶液进行水解。
以上这些金属有机化合物按照传统工艺进行的水解过程会产生大量的酸性废水，产品还需进行中和，也会产生一定量的碱性废水，导致生产过程废水量较大。
另外，由于格氏反应产物大部分为醇类，在酸性水解时会存在低浓度 的氢卤酸，导致发生以下副反应：
Figure PCTCN2020095633-appb-000002
其中，HX为HBr或HI时副反应尤其明显。当R 1、R 2、R 3均为含碳基团，即水解产物为叔碳醇时，上述卤代副反应也是非常容易发生。这种副反应的存在往往会导致上述水解过程收率下降或产品纯度下降。
发明内容
针对上述传统工艺中存在的问题，本发明提供了一种金属有机产物水解制备醇类物质的工艺，该工艺能够实现废水的有效循环利用，同时，可避免水解过程卤代副反应的发生，改善产品含量。
一种金属有机产物水解制备醇类物质的工艺，包括如下步骤：
1)含有金属有机产物的溶液与碳酸氢盐水溶液进行水解反应，得到水解固液混合物；
2)将步骤1)得到的水解固液混合物进行固液分离分别得到碳酸盐固体和油水混合物；
3)步骤2)所述的油水混合物分层得到水层和溶有所述醇类物质的油层；
4)步骤3)所述的油层回收溶剂后得到所述的醇类物质。
所述的金属有机产物具有如下结构：
R 1OMgX、(R 2O) nM或XMgO-R 3-OMgX。
所述的醇类物质具有如下结构：
R 1OH、R 2OH或HO-R 3-OH。
本发明所述金属有机产物的水解原理为：
Figure PCTCN2020095633-appb-000003
Figure PCTCN2020095633-appb-000004
Figure PCTCN2020095633-appb-000005
Figure PCTCN2020095633-appb-000006
其中，R 1、R 2选自烷基、烯基或炔基；
R 3选自两个C以上的亚烃基；
M为钙或锂，X为氯、溴或碘。
从工业应用的角度考虑，所述的金属有机产物选自以下具体化合物中的一种：
Figure PCTCN2020095633-appb-000007
用碳酸氢盐代替氯化铵或稀硫酸等酸性水溶液进行上述金属有机反应产物的水解，实现了水解废水的循环利用，从工艺本质上杜绝了含有机物废水的排放问题。该方法在弱碱性条件下进行，还解决了水解产物醇类物质与氢卤酸发生醇的卤代副反应的问题，减少了副产物的生成。同时，本发明的工艺中水解得到金属盐为固体形式，有利于金属盐产品的回收再利用。
作为优选，所述的碳酸氢盐为与金属有机产物中金属相一致的碳酸氢镁、碳酸氢钙或碳酸氢锂。
作为优选，所述的水解固液混合物的固液分离方式可以为减压抽滤、加压过滤或离心分离。得到的碳酸盐固体为碳酸镁、碳酸钙或碳酸锂固体。
作为优选，所述的步骤1)中，反应温度为0～50℃。
作为优选，所述的步骤1)中，碳酸氢盐与金属有机产物的摩尔当量比为(1～2)：:1。
作为优选，所述的步骤1)中，金属有机产物溶液通过滴加的方式加入反应体系，滴加时间为20～100min；滴加完继续保温反应时间为10～60min。
作为优选，所述的步骤2)中，碳酸盐固体一部分加水并通入二氧化碳重新制备得到碳酸氢盐水溶液，用于步骤1)水解反应；另一部分经洗涤干燥得到固体碳酸盐产品。
作为优选，所述的步骤3)中的格氏反应金属有机产物水解的水层经过冷却结晶，离心过滤得到MgX 2固体产品，分离得到的废水可作为碳酸氢盐制备所用的水；
作为优选，所述的步骤3)中的金属钙或锂有机产物水解的水层，直接作为碳酸氢钙或碳酸氢锂制备所用的水。
作为优选，所述的步骤4)中的溶剂和未反应原料的回收可采用蒸馏或精馏工艺，可以采用常压或减压操作。
本发明的水解工艺适应于各种金属有机试剂(例如格氏试剂、金属钙有机试剂或锂有机试剂)与醛、酮或酯反应得到的反应液，所有这些格氏试剂、烷基钙或烷基锂与醛、酮或酯进行缩合反应得到的反应液都可以尝试采用本发明的方法直接进行处理，金属有机试剂与醛、酮或酯的具体反应过程可以参考现有技术的报道，例如：CN 107513006 A、CN 106588958 A等专利中所报道的各种格氏反应。
同现有技术相比，本发明的有益效果体现在：
本发明有效地解决了废水排放的问题，实现了格氏反应水解过程废水循环利用。本发明还提供了一种金属有机产物碱性水解制备醇类物质的新方法，水解过程中没有氢卤酸的形成，从而避免了水解产物醇类物质在酸性条件下进行卤代副反应，提高了水解收率和产品含量。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
本发明实施例中所用的含有金属有机产物的溶液可以为现有的方法(例如CN 107513006 A、CN 106588958 A等)直接获得的反应液；也可以对得到的反应液做简单的浓缩或者稀释操作，再进行本实施例的操作，并不影响本发明技术方案的效果。
实施例1
格氏反应得到的金属有机产物简称为双氯镁缩合物，结构如下：
Figure PCTCN2020095633-appb-000008
将含0.3mol碳酸氢镁的水溶液500mL加入至四口反应器中，然后滴加含0.295mol双氯镁缩合物的乙醚溶液300mL(该溶液还含有4％的3-甲基-2-烯-4-炔戊醇(简称C6醇，下同))，20min左右滴完，继续搅拌60min后停止水解反应，水解过程温度控制在0～20℃之间。过滤得到固体碳酸镁49.5g，油水混合物分层得到醇类产品的乙醚溶液295mL和镁盐水溶液490mL。
醇类产品的乙醚溶液先在30～50℃常压回收乙醚，然后再升温至50～70℃减压(1～2mmHg)回收未反应的原料C6醇，得到89.1g醇类产品，HPLC含量为99.5％(氯代物含量为0)，收率为99.4％。
得到的镁盐水溶液降温至0～5℃之间，保温24h，过滤得到25.5g氯化镁固体。将25.2g(0.3mol)固体碳酸镁加入过滤得到的剩余盐水中，边搅拌边通入二氧化碳直至固体碳酸镁完全消失，得到碳酸氢镁溶液待用至下一次水解。
本工艺废水实现零排放。
对比试验1：
含0.295mol双氯镁缩合物的乙醚溶液300mL(与实施例1的双氯镁缩合物的溶液组成相同)加入至四口反应器中，控制温度在30℃，边搅拌边滴加1.45mol/L氯化铵水溶液450mL，50min左右滴完，然后继续搅拌10min后停止水解反应。
静止分层得到水解废水501mL，30～50℃蒸除水中的氨气和乙醚后检测废水COD为110000ppm。再用200mL二氯甲烷萃取废水层中的有机物后，再次检测废水COD为4500ppm。该废水仍需送至污水站进一步进行生物化学处理，达到国家规定的标准后才能排放。
静止分层得到醚层280mL用1.1mol/L的碳酸钠水溶液100ml进行中 和反应5～10min。静止分层得到的中和水层102mL，30～50℃蒸除水中的氨气和乙醚后检测废水COD为50000ppm。再用200mL二氯甲烷萃取废水层中的有机物后，再次检测废水COD为2500ppm。该废水仍需送至污水站进一步进行生物化学处理，达到国家规定的标准后才能排放。
醚层在30～50℃蒸馏回收得到乙醚，然后再升温至50～70℃减压(1～2mmHg)回收未反应的原料C6醇，得到90.5g缩合物粗产品，HPLC含量为97.5％(6-氯代缩合物含量0.34％，6-氯代缩合物含量0.08％，1,6-二氯代缩合物含量0.16％)，收率为98.9％。
实施例2
格氏反应得到的金属有机产物简称为双溴镁缩合物，结构如下：
Figure PCTCN2020095633-appb-000009
将含0.3mol碳酸氢镁的水溶液500mL加入至四口反应器中，然后滴加含0.295mol双溴镁缩合物的甲基四氢呋喃溶液300mL(含有3％的3-甲基-2-烯-4-炔戊醇(简称C6醇，下同))，100min左右滴完，然后继续搅拌10min后停止水解反应，水解过程温度控制在5～25℃之间。然后过滤得到固体碳酸镁49.4g。油水混合物分层得到二元醇的甲基四氢呋喃溶液290mL和镁盐水溶液520mL。
二元醇的甲基四氢呋喃溶液先在30～50℃减压(76mmHg)回收甲基四氢呋喃，然后升温至50～70℃减压(1～2mmHg)回收未反应的原料C6醇，得到89.08g二元醇产品，HPLC含量为99.7％(溴代物含量为0)，收率为99.5％。
得到的镁盐水溶液降温至0～5℃之间，保温24h，过滤得到49.3g溴化镁固体。将25.2g(0.3mol)固体碳酸镁加入过滤得到的剩余镁盐水溶液中，边搅拌边通入二氧化碳直至固体碳酸镁完全消失，得到碳酸氢镁溶液待用至下一次水解。
本工艺废水实现零排放。
对比试验2：
含0.295mol双溴镁缩合物的甲基四氢呋喃溶液300mL(与实施例2的双溴镁缩合物的溶液组成相同)加入至四口反应器中，控制温度在20℃，边搅拌边滴加1.15mol/L稀硫酸270mL，35min左右滴完，然后继续搅拌10min后停止水解反应。
静止分层得到水解废水304mL，30～50℃减压蒸除水中的甲基四氢呋喃后检测废水COD为85000ppm。再用200mL二氯甲烷萃取废水层中的有机物后，再次检测废水COD为4500ppm。该废水仍需送至污水站进一步进行生物化学处理，达到国家规定的标准后才能排放。
静止分层得到醚层180mL用1.1mol/L的碳酸钠水溶液100mL进行中和反应5～10min，分去水层后，30～50℃减压蒸除水中的甲基四氢呋喃后检测废水COD为65000ppm。再用200mL二氯甲烷萃取废水层中的有机物后，再次检测废水COD为1500ppm。该废水仍需送至污水站进一步进行生物化学处理，达到国家规定的标准后才能排放。
醚层在30～50℃减压蒸馏回收得到甲基四氢呋喃145mL，然后升温至50～70℃减压(1～2mmHg)回收未反应的原料C6醇，得到91.5g缩合物产品，HPLC含量为96.7％(6-溴代物含量为0.54％，1-溴代缩合物为0.14％，1，6-二溴代缩合物为0.32％)，收率为99.2％。
实施例3
甲基乙烯酮进行乙炔化反应得到的金属有机产物为双(3-甲基-4-炔-1-戊烯-3-醇基)钙，结构如下：
Figure PCTCN2020095633-appb-000010
将含0.3mol碳酸氢钙的水溶液500mL加入至四口反应器中，然后滴加含0.299mol3-甲基-4-炔-1-戊烯-3-醇基钙的异丙醚溶液300mL，60min左右滴完，然后继续搅拌30min后停止水解反应，水解过程温度控制在30～50℃之间。然后离心得到固体碳酸钙59.6g。油水混合物分层得到3-甲基-4-炔-1-戊烯-3-醇的异丙醚溶液289mL和钙盐水溶液504mL。
3-甲基-4-炔-1-戊烯-3-醇的异丙醚溶液在60～80℃常压回收异丙醚，然 后精馏得到57.4g产品，气相色谱检测含量为99.8％，收率为99.6％。
将30g(0.3mol)固体碳酸钙加入水解得到的钙盐水溶液中，边搅拌边通入二氧化碳直至固体碳酸钙完全消失，得到碳酸氢钙溶液待用至下一次水解。
本工艺废水实现零排放。
实施例4
格氏反应得到的金属有机产物为3-甲基-5-己烯-3-醇基氯化镁，结构如下：
Figure PCTCN2020095633-appb-000011
将含0.3mol碳酸氢镁的水溶液500mL加入至四口反应器中，然后滴加含0.58mol3-甲基-5-己烯-3-醇基氯化镁的乙醚溶液300mL，30min左右滴完，然后继续搅拌40min后停止水解反应，水解过程温度控制在15～30℃之间。过滤得到固体碳酸镁48.65g，油水混合物分层得到3-甲基-5-己烯-3-醇基氯化镁乙醚溶液296mL和镁盐水溶液498mL。
3-甲基-5-己烯-3-醇基氯化镁的乙醚溶液先在30～50℃常压回收乙醚，然后精馏得到65.54g3-甲基-5-己烯-3-醇产品，HPLC含量为99.6％(氯代物含量0)，收率为98.6％。
得到的镁盐水溶液降温至0～5℃之间，保温20h，过滤得到26.4g氯化镁固体。将25.2g(0.3mol)固体碳酸镁加入过滤得到的剩余镁盐水溶液中，边搅拌边通入二氧化碳直至固体碳酸镁完全消失，得到碳酸氢镁溶液待用至下一次水解。
本工艺废水实现零排放。
实施例5
甲基乙烯酮进行乙炔化反应得到的金属有机产物为3-甲基-4-炔-1-戊烯-3-醇基锂，结构如下：
Figure PCTCN2020095633-appb-000012
将含0.3mol碳酸氢锂的水溶液500mL加入至四口反应器中，然后滴 加含0.3mol3-甲基-4-炔-1-戊烯-3-醇基锂的乙醚溶液300mL，50min左右滴完，然后继续搅拌20min后停止水解反应，水解过程温度控制在10～20℃之间。然后离心得到固体碳酸锂22.1g。油水混合物分层得到3-甲基-4-炔-1-戊烯-3-醇乙醚溶液296mL和锂盐水溶液501mL。
3-甲基-4-炔-1-戊烯-3-醇乙醚溶液在30～50℃回收乙醚，然后精馏得到28.85g产品，气相色谱检测含量为99.5％，收率为99.9％。
将11.1g(0.15mol)固体碳酸锂加入水解得到的锂盐水溶液中，边搅拌边通入二氧化碳直至固体碳酸锂完全消失，得到碳酸氢锂(0.3mol)溶液待用至下一次水解。
本工艺废水实现零排放。
实施例6
格氏反应得到的金属有机产物简称为双溴镁缩合物，结构如下：
Figure PCTCN2020095633-appb-000013
将含0.3mol碳酸氢镁的水溶液500mL加入至四口反应器中，然后滴加含0.25mol双溴镁缩合物的甲基四氢呋喃溶液300mL(含有3％的3-甲基-2-烯-4-炔戊醇(简称C6醇，下同))，70min左右滴完，然后继续搅拌30min后停止水解反应，水解过程温度控制在10～30℃之间。然后过滤得到固体碳酸镁41.95g。油水混合物分层得到二元醇的甲基四氢呋喃溶液294mL和镁盐水溶液522mL。
二元醇的甲基四氢呋喃溶液先在30～50℃减压(76mmHg)回收甲基四氢呋喃，然后升温至50～70℃减压(1～2mmHg)回收未反应的原料C6醇，得到75.8g二元醇产品，HPLC含量为99.4％(溴代物含量为0)，收率为99.6％。
得到的镁盐水溶液降温至0～5℃之间，保温24h，过滤得到44.8g溴化镁固体。将25.2g(0.3mol)固体碳酸镁加入过滤得到的剩余镁盐水溶液中，边搅拌边通入二氧化碳直至固体碳酸镁完全消失，得到碳酸氢镁溶液待用至下一次水解。
本工艺废水实现零排放。

Claims (13)

  1. 一种金属有机产物水解制备醇类物质的工艺，其特征在于，包括如下步骤：
    1)含有金属有机产物的溶液与碳酸氢盐水溶液进行水解反应，得到水解固液混合物；
    2)将步骤1)得到的水解固液混合物进行固液分离分别得到碳酸盐固体和油水混合物；
    3)将步骤2)所述的油水混合物进行分液得到水层和溶有所述醇类物质的油层；
    4)将步骤3)所述的油层回收溶剂后得到所述的醇类物质。
  2. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的金属有机产物由金属有机试剂与醛、酮或酯反应得到；
    所述含有金属有机产物的溶液的溶剂为醚类溶剂或烃类溶剂。
  3. 根据权利要求2所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的溶剂为甲基四氢呋喃、四氢呋喃、乙醚、异丙醚或甲苯。
  4. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的金属有机产物具有如下结构：
    R 1OMgX、(R 2O) nM或XMgO-R 3-OMgX
    其中，R 1、R 2选自烷基、烯基或炔基；
    R 3选自两个C以上的亚烃基；M为钙或锂，M为钙时，n＝2，M为锂时，n＝1；
    X为氯、溴或碘。
  5. 根据权利要求2所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的金属有机试剂为格氏试剂、金属钙或锂有机试剂。
  6. 根据权利要求5所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的金属有机试剂为格氏试剂、烷基钙或烷基锂。
  7. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述的碳酸氢盐为碳酸氢镁、碳酸氢钙或碳酸氢锂，并且所述的碳酸氢盐的金属阳离子与所述金属有机产物中的金属一致。
  8. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，步骤1)中，水解反应的反应温度为0～50℃；
    碳酸氢盐与金属有机产物的摩尔当量比为(1～2)：1。
  9. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，步骤1)中，所述的金属有机产物溶液通过滴加的方式加入所述的碳酸氢盐水溶液，滴加时间为20～100min；滴加完继续保温反应时间为10～60min。
  10. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，步骤2)所述的碳酸盐固体一部分加水并通入二氧化碳重新制备得到碳酸氢盐水溶液，用于步骤1)水解反应；另一部分经洗涤干燥得到固体碳酸盐产品。
  11. 根据权利要求4所述的金属有机产物水解制备醇类物质的工艺，其特征在于，当所述的金属有机产物为R 1OMgX或XMgO-R 3-OMgX时，步骤3)所述的水层降温至0～10℃冷却结晶，离心过滤得到MgX 2固体产品，分离得到的废水作为碳酸氢盐制备所用的水；
    当所述的金属有机产物为(R 2O) nM时，步骤3)所述的水层直接作为碳酸氢钙或碳酸氢锂制备所用的水。
  12. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，步骤4)中，还包括对未反应原料的回收；
    所述的溶剂和未反应原料的回收可采用蒸馏或精馏工艺，可以采用常压或减压操作。
  13. 根据权利要求1所述的金属有机产物水解制备醇类物质的工艺，其特征在于，所述金属有机产物选自以下具体化合物中的一种：
    Figure PCTCN2020095633-appb-100001
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