CN106278854B - A kind of preparation method by α-isophorone isomery β-isophorone - Google Patents
A kind of preparation method by α-isophorone isomery β-isophorone Download PDFInfo
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Abstract
本发明公开了一种由α‑异佛尔酮异构β‑异佛尔酮的制备方法，以含钒化合物为催化剂、α‑异佛尔酮为原料进行液相反应，原料与催化剂的质量比为1000：1～100，常压、190℃～240℃下进行精馏操作，连续采出馏出液，将β‑异佛尔酮从反应体系中不断移出，所得馏出液中50％～90％重量为β‑异佛尔酮。与传统方法相比，本发明所使用的催化剂是十分新颖的，具有催化剂用量少，反应速度快，反应转化率高，反应选择性好等优点，反应转化率达到90％以上。且反应结束后使用真空蒸馏可以将反应物与反应副产物分离。
The invention discloses a preparation method for isomerizing β-isophorone from α-isophorone. The vanadium-containing compound is used as a catalyst and α-isophorone is used as a raw material for a liquid phase reaction. The quality of the raw material and the catalyst The ratio is 1000:1~100, the rectification operation is carried out at normal pressure, 190°C~240°C, the distillate is continuously extracted, and the β-isophorone is continuously removed from the reaction system, and 50% of the obtained distillate ~90% by weight is β-isophorone. Compared with the traditional method, the catalyst used in the present invention is very novel, and has the advantages of less catalyst consumption, fast reaction speed, high reaction conversion rate, good reaction selectivity, etc., and the reaction conversion rate reaches more than 90%. And vacuum distillation can be used to separate the reactants from the reaction by-products after the reaction.
Description
技术领域technical field
本发明涉及一种异佛尔酮异构方法，具体涉及一种由α-异佛尔酮异构β-异佛尔酮的制备方法。The invention relates to an isophorone isomerization method, in particular to a preparation method for isophorone isomerization from α-isophorone to β-isophorone.
背景技术Background technique
β-异佛尔酮是一种合成维生素和香料的重要中间体，同时也是制备类胡萝卜素和医药产品的重要合成结构单元。目前β-异佛尔酮是由α-异佛尔酮在一定的催化剂条件下异构化反应而得到。常用的催化剂主要有格氏试剂，高沸点固体酸，过渡金属的乙酰丙酮化合物，酸性陶瓷等。β-isophorone is an important intermediate for the synthesis of vitamins and spices, and also an important synthetic structural unit for the preparation of carotenoids and pharmaceutical products. At present, β-isophorone is obtained by the isomerization reaction of α-isophorone under certain catalyst conditions. Commonly used catalysts mainly include Grignard reagents, high-boiling solid acids, acetylacetonates of transition metals, and acidic ceramics.
该异构反应是一个去双碳与羰基共轭的平衡反应，由于α-异佛尔酮较为稳定，β-异佛尔酮的平衡浓度较低，异构化温度决定了该反应的平衡浓度，温度越高β-异佛尔酮的平衡浓度越大，由于β-异佛尔酮的沸点低于α-异佛尔酮，通过反应精馏可以移动上述平衡。The isomerization reaction is an equilibrium reaction in which the double carbon is removed and the carbonyl is conjugated. Since α-isophorone is relatively stable, the equilibrium concentration of β-isophorone is low, and the isomerization temperature determines the equilibrium concentration of the reaction. , the higher the temperature, the greater the equilibrium concentration of β-isophorone. Since the boiling point of β-isophorone is lower than that of α-isophorone, the above equilibrium can be shifted by reactive distillation.
目前为止，该反应大致可分为液相反应和气相反应两种。EP0488045B1指出了在多相催化剂上于气相中进行异构化反应的方法，使用Mg、Al、Si、Ni的氧化物和混合氧化物作为催化剂，反应中间体溶液β-异佛尔酮浓度不超过9％，最后通过真空蒸馏得到97％的β-异佛尔酮。但气相反应存在明显缺点，即反应副产物较多，时空产率(β-异佛尔酮绝对量/小时/公斤催化剂)较低。So far, the reaction can be roughly divided into liquid phase reaction and gas phase reaction. EP0488045B1 has pointed out the method that carries out isomerization reaction in gas phase on heterogeneous catalyst, uses oxide and mixed oxide of Mg, Al, Si, Ni as catalyst, and the concentration of reaction intermediate solution β-isophorone does not exceed 9%, and finally obtained 97% β-isophorone by vacuum distillation. However, there are obvious disadvantages in the gas phase reaction, that is, there are many reaction by-products, and the space-time yield (absolute amount of β-isophorone/hour/kg catalyst) is low.
公开号为CN 104311407A的中国发明专利申请文献公开了一种3,5,5-三甲基-3-环己烯-1-酮的合成工艺：以3,5,5-三甲基-2-环己烯-1-酮(α-IP)为原料，以碱性离子液体为催化剂，采用反应精馏技术来进行异构反应，制备一种3,5,5-三甲基-3-环己烯-1-酮(β-IP)，反应绝对压力为0.2–2Bar，反应温度150-230℃，产品β-IP的纯度可达到99.5wt％-99.8wt％，反应选择性可达到99.2％-99.9％。采用离子液体作为催化剂得到的产品纯度和反应选择性都能达到较高的水平，但是离子液体的制作过程繁琐，且成本较高，不利于工业化生产。The Chinese invention patent application document with publication number CN 104311407A discloses a synthesis process of 3,5,5-trimethyl-3-cyclohexen-1-one: 3,5,5-trimethyl-2 -Cyclohexen-1-one (α-IP) as raw material, using alkaline ionic liquid as catalyst, adopts reactive distillation technology to carry out isomerization reaction, and prepares a kind of 3,5,5-trimethyl-3- Cyclohexen-1-one (β-IP), the reaction absolute pressure is 0.2–2 Bar, the reaction temperature is 150-230°C, the purity of the product β-IP can reach 99.5wt%-99.8wt%, and the reaction selectivity can reach 99.2 % - 99.9%. The product purity and reaction selectivity obtained by using ionic liquid as a catalyst can reach a higher level, but the production process of ionic liquid is cumbersome and the cost is high, which is not conducive to industrial production.
公开号为CN1235954A的中国发明专利申请文献提出利用钠或钾的氢氧化物或碳酸盐作为催化剂，液相中催化异构化反应，催化剂选择性达到90％。公开号为CN1292374A的中国发明专利申请文献公开一种用均相的催化剂对α-异佛尔酮进行异构化连续制备β-异佛尔酮的方法：向反应区中加入α-异佛尔酮和碱性氢氧化物溶液,使反应混合物的温度达到150-216℃，通过蒸馏从该反应混合物中提取含有30-90％(重量)β-异佛尔酮的馏分，同时泄流出重质产物，然后通过蒸馏对上述从反应混合物提取的馏分进行精馏。该专利文献利用碱性氢氧化物溶液均相催化剂催化异构化反应，通过蒸馏方式从反应混合液中提取30％～90％(质量)的β-异佛尔酮。但均相反应中不容易将催化剂和蒸馏残留物分开，另用碱性氢氧化物溶液时空产率较低，副产物较多。The Chinese invention patent application document with publication number CN1235954A proposes to use sodium or potassium hydroxide or carbonate as a catalyst to catalyze the isomerization reaction in the liquid phase, and the catalyst selectivity reaches 90%. The Chinese invention patent application document with the publication number CN1292374A discloses a method for continuously preparing β-isophorone by isomerizing α-isophorone with a homogeneous catalyst: adding α-isophorone to the reaction zone Ketone and alkaline hydroxide solution, make the temperature of reaction mixture reach 150-216 ℃, extract the cut that contains 30-90% (weight) β-isophorone from this reaction mixture by distillation, let out heavy weight simultaneously product, and then rectify the above-mentioned fraction extracted from the reaction mixture by distillation. This patent document utilizes an alkaline hydroxide solution homogeneous catalyst to catalyze the isomerization reaction, and extracts 30% to 90% (mass) of β-isophorone from the reaction mixture by distillation. However, it is not easy to separate the catalyst and the distillation residue in the homogeneous reaction, and the space-time yield of alkaline hydroxide solution is low and there are many by-products.
发明内容Contents of the invention
本发明提供一种由α-异佛尔酮异构β-异佛尔酮的制备方法，提供一种转化率高且选择性好的新催化剂，即使用氧化钒及含钒类的化合物为催化剂，催化α-异佛尔酮异构化生产β-异佛尔酮。The invention provides a method for preparing isomerized β-isophorone from α-isophorone, and provides a new catalyst with high conversion rate and good selectivity, that is, vanadium oxide and vanadium-containing compounds are used as catalysts , to catalyze the isomerization of α-isophorone to produce β-isophorone.
一种由α-异佛尔酮异构β-异佛尔酮的制备方法，包括如下步骤：A preparation method for isomerizing β-isophorone by α-isophorone, comprising the steps of:
以含钒化合物为催化剂、α-异佛尔酮为原料进行液相反应，常压下进行精馏操作，连续采出馏出液，所得馏出液中50％～90％重量为β-异佛尔酮。The vanadium-containing compound is used as a catalyst and α-isophorone is used as a raw material for liquid-phase reaction, rectification operation is carried out under normal pressure, and the distillate is continuously extracted. 50% to 90% of the obtained distillate by weight is β-isophorone Pholone.
α-异佛尔酮异构成β-异佛尔酮的反应如下：The reaction of α-isophorone isomerization to β-isophorone is as follows:
本发明为液相反应，α-异佛尔酮在催化剂存在下发生异构化反应生成β-异佛尔酮，反应在常压下进行，利用反应精馏技术将生成的β-异佛尔酮移出反应体系，反应连续进行。反应结束后使用真空蒸馏将反应残余物与催化剂分离，本发明的工艺简化了反应流程。The present invention is a liquid phase reaction, α-isophorone undergoes isomerization reaction in the presence of a catalyst to generate β-isophorone, the reaction is carried out under normal pressure, and the generated β-isophorone is purified by reactive distillation technology The ketone is removed from the reaction system, and the reaction continues. After the reaction is finished, vacuum distillation is used to separate the reaction residue from the catalyst, and the process of the invention simplifies the reaction process.
本发明所用催化剂为含钒化合物，特别优选氧化钒(V2O5)，相对于过渡金属的乙酰丙酮化合物和氢氧化物来说，氧化钒等含钒类的化合物催化剂的选择性更高，反应副产物占比更低，是一种较好的新型催化剂。The catalyst used in the present invention is a vanadium-containing compound, particularly preferably vanadium oxide (V 2 O 5 ). Compared with acetylacetonate compounds and hydroxides of transition metals, the selectivity of vanadium-containing compound catalysts such as vanadium oxide is higher. The proportion of reaction by-products is lower, and it is a better new catalyst.
本发明中，α-异佛尔酮与催化剂的质量比优选为1000：1～100；进一步优选，α-异佛尔酮与催化剂的质量比为1000：1～20；更进一步优选，α-异佛尔酮与催化剂的质量比在1000：1～10；更进一步优选，α-异佛尔酮与催化剂的质量比为1000：1～3。In the present invention, the mass ratio of α-isophorone to the catalyst is preferably 1000:1-100; more preferably, the mass ratio of α-isophorone to the catalyst is 1000:1-20; more preferably, α- The mass ratio of isophorone to catalyst is 1000:1-10; more preferably, the mass ratio of α-isophorone to catalyst is 1000:1-3.
通过实验发现，本发明催化剂的用量占α-异佛尔酮质量0.1％～10％范围内，制备得到的馏出液中β-异佛尔酮含量在60％以上，选择性85％以上；进一步发现，当催化剂的用量占α-异佛尔酮质量0.1％～0.3％范围内，尤其是0.15％时制备得到的馏出液中β-异佛尔酮含量在60％以上，选择性90％以上。本发明的催化剂在大大降低用量的同时确保高的反应转化率和高的反应选择性。It is found through experiments that the amount of the catalyst of the present invention accounts for 0.1% to 10% of the mass of α-isophorone, the content of β-isophorone in the prepared distillate is more than 60%, and the selectivity is more than 85%; It was further found that when the amount of the catalyst accounts for 0.1% to 0.3% of the mass of α-isophorone, especially 0.15%, the content of β-isophorone in the prepared distillate is more than 60%, and the selectivity is 90%. %above. The catalyst of the invention ensures high reaction conversion rate and high reaction selectivity while greatly reducing the dosage.
本发明的反应温度为190℃～240℃；进一步优选为200℃～230℃。在该温度范围内，有利于反应的平衡向β-异佛尔酮方向移动，增加β-异佛尔酮的产出量。The reaction temperature of the present invention is 190°C to 240°C; more preferably 200°C to 230°C. In this temperature range, the balance in favor of the reaction moves to the direction of β-isophorone, increasing the output of β-isophorone.
本发明所采用的精馏操作本身可采用常规精馏设备和操作方法，控制回流时间为30～40小时，回流比为5～15:1。The rectification operation adopted in the present invention itself can adopt conventional rectification equipment and operation methods, and the reflux time is controlled to be 30-40 hours, and the reflux ratio is 5-15:1.
收集精馏液时采出量控制为5～15秒/滴。进一步优选为8秒/滴。When collecting the distillate, the output is controlled to be 5-15 seconds/drop. More preferably, it is 8 seconds/drop.
本发明的制备方法中，副反应多为高温下α-异佛尔酮的聚合反应，副反应的产物主要为异佛尔酮的高聚物，副反应过多，容易使得催化剂失活，反应效率下降；本发明通过筛选高选择性的催化剂氧化钒及合适的催化剂用量，减少副反应的发生，从而来降低副产物的生成，提高转化率。In the preparation method of the present invention, the side reaction is mostly the polymerization reaction of α-isophorone at high temperature, and the product of the side reaction is mainly a high polymer of isophorone. Too many side reactions easily make the catalyst deactivated. Decreased efficiency; the present invention reduces the occurrence of side reactions by screening highly selective catalyst vanadium oxide and appropriate catalyst dosage, thereby reducing the generation of by-products and increasing the conversion rate.
进一步优选地，本发明的制备方法包括如下步骤：Further preferably, the preparation method of the present invention comprises the following steps:
以含钒化合物为催化剂、α-异佛尔酮为原料进行液相反应，催化剂的用量为原料质量的0.1～0.3％，常压、200℃～230℃下进行精馏操作，反应时间为30～40小时，回流比为10～12，连续采出馏出液，所得馏出液中50％～90％重量即为β-异佛尔酮。The vanadium-containing compound is used as a catalyst and α-isophorone is used as a raw material for liquid phase reaction. The amount of catalyst used is 0.1-0.3% of the raw material mass. The rectification operation is carried out under normal pressure and 200°C-230°C. The reaction time is 30 ~ 40 hours, the reflux ratio is 10 ~ 12, continuous extraction of distillate, 50% ~ 90% by weight of the obtained distillate is β-isophorone.
最优选地，以含氧化钒为催化剂、α-异佛尔酮为原料进行液相反应，催化剂的用量为原料质量的0.15％，常压、230℃下进行精馏操作，反应时间为35小时，回流比为10:1，连续采出馏出液，所得馏出液中60％以上重量为β-异佛尔酮。该反应条件下催化剂的反应选择性在90％以上，其中的副产物比例占原料比例在5％以下。Most preferably, liquid phase reaction is carried out with vanadium oxide as catalyst and α-isophorone as raw material, the amount of catalyst used is 0.15% of the raw material mass, rectification operation is carried out under normal pressure and 230°C, and the reaction time is 35 hours , the reflux ratio is 10:1, and the distillate is continuously extracted, and more than 60% by weight of the distillate obtained is β-isophorone. Under the reaction conditions, the reaction selectivity of the catalyst is above 90%, and the ratio of the by-products to the raw materials is below 5%.
本发明在常压条件下，在190℃～240℃的反应温度下，α-异佛尔酮与氧化钒及含钒类的化合物的质量比为1000：1到10：1，利用反应精馏技术，将β-异佛尔酮从反应体系中不断移出。与传统方法相比。本发明所使用的催化剂十分新颖，反应选择性好，反应转化率达到90％以上，副产物较少。In the present invention, under normal pressure conditions, at a reaction temperature of 190°C to 240°C, the mass ratio of α-isophorone to vanadium oxide and vanadium-containing compounds is 1000:1 to 10:1, using reactive distillation Technology, β-isophorone is continuously removed from the reaction system. compared with traditional methods. The catalyst used in the invention is very novel, the reaction selectivity is good, the reaction conversion rate reaches more than 90%, and the by-product is less.
附图说明Description of drawings
图1是本发明实施例1所得产物的气相色谱图。Fig. 1 is the gas chromatogram of the product obtained in Example 1 of the present invention.
具体实施方式Detailed ways
以下的实施例将对本发明进行更为全面的描述。The following examples will more fully describe the present invention.
实施例1Example 1
称取0.45克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为230℃，待精馏柱顶温稳定后开始采出，回流比控制在10:1，采出量控制在8秒/滴，30小时后采出完毕。得馏出液用气相色谱标定，气象色谱图如图1所示(α-异佛尔酮/β-异佛尔酮＝64.06/31.56)，β-异佛尔酮含量在60％以上，选择性90％以上，其中的副产物占原料重量比例在5％以下。Weigh 0.45 g of vanadium oxide and 300 g of α-isophorone, and add them into a three-neck flask. Connected to the rectification column, the reaction temperature is 230°C, the extraction starts after the top temperature of the rectification column is stable, the reflux ratio is controlled at 10:1, the output is controlled at 8 seconds/drop, and the extraction is completed after 30 hours. Get distillate and calibrate with gas chromatography, gas chromatogram as shown in Figure 1 (alpha-isophorone/beta-isophorone=64.06/31.56), beta-isophorone content is more than 60%, select The property is more than 90%, and the proportion of by-products in raw materials is less than 5%.
实施例2Example 2
称取0.90克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为230℃，待精馏柱顶温稳定后开始采出，回流比控制在10:1；采出量控制在8秒/滴，30小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性85％以上，其中的副产物占原料重量比例在5％以下。Weigh 0.90 g of vanadium oxide and 300 g of α-isophorone, and add them into a three-neck flask. Connect to the rectification column, the reaction temperature is 230°C, and start to extract after the top temperature of the rectification column is stable, the reflux ratio is controlled at 10:1; the output is controlled at 8 seconds/drop, and the extraction is completed after 30 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 85%, and the weight ratio of by-products in raw materials is less than 5%.
实施例3Example 3
称取1.35克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为230℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1；30小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性85％以上，其中的副产物占原料重量比例在5％以下。Weigh 1.35 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-neck flask. Connected to the rectification column, the reaction temperature is 230°C, and the extraction starts after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, and the reflux ratio is controlled at 10:1; the extraction is completed after 30 hours, and the obtained The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 85%, and the weight ratio of by-products in raw materials is less than 5%.
实施例4Example 4
称取1.8克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为230℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，30小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性85％以上，其中的副产物占原料重量比例在5％以下。Weigh 1.8 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-neck flask. Connect to the rectification column, the reaction temperature is 230°C, start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 30 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 85%, and the weight ratio of by-products in raw materials is less than 5%.
实施例5Example 5
称取2.25克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为230℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，30小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性80％以上，其中的副产物占原料重量比例在8％以下。Weigh 2.25 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-necked flask. Connect to the rectification column, the reaction temperature is 230°C, start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 30 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 8%.
实施例6Example 6
称取2.7克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，30小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性80％以上，其中的副产物占原料重量比例在8％以下。Weigh 2.7 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-necked flask. Connected to the rectification column, the reaction temperature is 225°C, and the extraction starts after the top temperature of the rectification column is stable, the extraction volume is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 30 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 8%.
实施例7Example 7
称取3.6克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，35小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性80％以上，其中的副产物占原料重量比例在8％以下。Weigh 3.6 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-necked flask. Connect to the rectification column, the reaction temperature is 225°C, start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 35 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 8%.
实施例8Example 8
称取4.5克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，35小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性80％以上，其中的副产物占原料重量比例在8％以下。Weigh 4.5 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-neck flask. Connect to the rectification column, the reaction temperature is 225°C, start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 35 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 8%.
实施例9Example 9
称取8.1克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为220℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，35小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在60％以上，选择性80％以上，其中的副产物占原料重量比例在8％以下。Weigh 8.1 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-neck flask. Connect to the rectification column, the reaction temperature is 220°C, and start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 35 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 60%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 8%.
实施例10Example 10
称取9克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为220℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，35小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在50％以上，选择性80％以上，其中的副产物占原料重量比例在10％以下。Weigh 9 grams of vanadium oxide and 300 grams of α-isophorone into a three-neck flask. Connect to the rectification column, the reaction temperature is 220°C, and start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 35 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 50%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 10%.
实施例11Example 11
称取11.7克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为220℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，35小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在50％以上，选择性80％以上，其中的副产物占原料重量比例在10％以下。Weigh 11.7 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-neck flask. Connect to the rectification column, the reaction temperature is 220°C, and start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 35 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 50%, the selectivity is more than 80%, and the weight ratio of by-products in raw materials is less than 10%.
实施例12Example 12
称取14.4克氧化钒，300克α-异佛尔酮，加入到三口瓶中。接上精馏柱，反应温度为210℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，40小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在50％以上，选择性80％以上，其中的副产物比例占原料在10％以下。Weigh 14.4 grams of vanadium oxide and 300 grams of α-isophorone, and add them into a three-necked flask. Connect to the rectification column, the reaction temperature is 210°C, start to extract after the top temperature of the rectification column is stable, the output is controlled at 8 seconds/drop, the reflux ratio is controlled at 10:1, and the extraction is completed after 40 hours. The distillate is calibrated by gas chromatography, the content of β-isophorone is more than 50%, the selectivity is more than 80%, and the proportion of by-products in the raw material is less than 10%.
实施例13Example 13
称取5g氢氧化钠，300gα-异佛尔酮，加入三口瓶。接上精馏柱。反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，40小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在50％以上，选择性70％以上，其中副产物占原料重量比例比例在15％以上。Weigh 5g of sodium hydroxide and 300g of α-isophorone into a three-neck bottle. Connect the distillation column. The reaction temperature is 225°C, and the extraction starts after the top temperature of the rectification column is stable. The output is controlled at 8 seconds/drop, and the reflux ratio is controlled at 10:1. After 40 hours, the extraction is completed, and the distillate is obtained by gas chromatography. According to the calibration, the content of β-isophorone is more than 50%, the selectivity is more than 70%, and the weight ratio of by-products to raw materials is more than 15%.
实施例14Example 14
称取0.5g氢氧化钠，300gα-异佛尔酮，加入三口瓶。接上精馏柱。反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，40小时后采出完毕，得馏出液用气相色谱标定，β-异佛尔酮含量在50％以上，选择性70％以上，其中副产物占原料重量比例在10％以上。Weigh 0.5g of sodium hydroxide and 300g of α-isophorone into a three-necked flask. Connect the distillation column. The reaction temperature is 225°C, and the extraction starts after the top temperature of the rectification column is stable. The output is controlled at 8 seconds/drop, and the reflux ratio is controlled at 10:1. After 40 hours, the extraction is completed, and the distillate is obtained by gas chromatography. According to calibration, the content of β-isophorone is more than 50%, the selectivity is more than 70%, and the by-products account for more than 10% by weight of raw materials.
实施例15Example 15
称取5g乙酰丙酮铜，300gα-异佛尔酮，加入三口瓶。接上精馏柱。反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，40小时采出毕，得馏出液用气相色谱标定，β-异佛尔酮的含量在50％以上，选择性70％以上，其中副产物占原料重量比例在15％以上。Weigh 5g of copper acetylacetonate and 300g of α-isophorone into a three-necked flask. Connect the distillation column. The reaction temperature is 225°C, and the extraction starts after the top temperature of the rectification column is stable. The output is controlled at 8 seconds/drop, and the reflux ratio is controlled at 10:1. After 40 hours of extraction, the distillate is calibrated by gas chromatography , the content of β-isophorone is more than 50%, the selectivity is more than 70%, and the weight ratio of by-products to raw materials is more than 15%.
实施例16Example 16
称取0.5g乙酰丙酮铜，300gα-异佛尔酮，加入三口瓶。接上精馏柱。反应温度为225℃，待精馏柱顶温稳定后开始采出，采出量控制在8秒/滴，回流比控制在10:1，40小时采出毕，得馏出液用气相色谱标定，β-异佛尔酮的含量在50％以上，选择性70％以上，其中副产物占原料重量比例在10％以上。Weigh 0.5g of copper acetylacetonate and 300g of α-isophorone into a three-necked flask. Connect the distillation column. The reaction temperature is 225°C, and the extraction starts after the top temperature of the rectification column is stable. The output is controlled at 8 seconds/drop, and the reflux ratio is controlled at 10:1. After 40 hours of extraction, the distillate is calibrated by gas chromatography , the content of β-isophorone is more than 50%, the selectivity is more than 70%, and the weight ratio of by-products to raw materials is more than 10%.
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| CN115433067B (en) * | 2022-08-23 | 2023-12-19 | 万华化学集团股份有限公司 | Preparation method of beta-isophorone |
| CN116514643B (en) * | 2023-04-28 | 2025-02-28 | 山东新和成维生素有限公司 | Production method and production system of beta-isophorone |
| CN117024258B (en) * | 2023-10-08 | 2023-12-15 | 山东富宇石化有限公司 | Method for preparing beta-isophorone by catalysis of modified X-type molecular sieve |
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