技术领域technical field
本发明是关于一种烯丙醇氧化制备环氧丙醇的方法。The invention relates to a method for preparing glycidyl alcohol by oxidation of allyl alcohol.
背景技术Background technique
环氧丙醇又称缩水甘油，是无色并近于无臭的液体。与水、低碳醇、乙醚、苯、甲苯、氯仿等混溶，部分溶于二甲苯、四氯乙烯、三氯乙烷，几乎不溶于脂肪族和脂环族烃类。是一种重要的精细化工原料，用来做天然油和乙烯基聚合物、破乳剂、染色分层剂的稳定剂，也用来合成甘油、缩水甘油醚(胺等)的中间体。可用于表面涂料、化学合成、医药、医药化工、杀菌剂和固体燃料的凝胶剂。Glycidol, also known as glycidol, is a colorless and nearly odorless liquid. Miscible with water, low-carbon alcohol, ether, benzene, toluene, chloroform, etc., partially soluble in xylene, tetrachloroethylene, trichloroethane, almost insoluble in aliphatic and alicyclic hydrocarbons. It is an important fine chemical raw material. It is used as a stabilizer for natural oil and vinyl polymers, demulsifiers, and dyeing layering agents. It is also used as an intermediate for the synthesis of glycerin and glycidyl ether (amines, etc.). It can be used in surface coatings, chemical synthesis, pharmaceuticals, pharmaceutical chemicals, fungicides and gels for solid fuels.
工业上生产环氧丙醇主要有以下两种方法：1、甘油氯醇法，由氯丙二醇在碱存在下反应而得。反应通常在0℃左右进行，反应产物分离出盐类后用减压蒸馏精制，即得纯缩水甘油。2、醇丙烯法，用过氧化氢或过乙酸对烯丙醇环氧化可获得缩水甘油。采用过乙酸为环氧化剂时，反应速度较快，产物中缩水甘油极易与乙酸反应生成缩水甘油乙酸酯，使蒸馏分离困难，而且缩水甘油和乙酸的混合物在室温下能发生强烈放热反应引起爆炸，因此该法在工业上应用困难很大。还可以采用六价钨酸盐为催化剂将烯丙醇与氧化剂(如次氯酸或高氯酸)进行环氧化反应制得，但该过程对环境污染大，而且所用催化剂活性低、不可再生。Industrial production of glycidol mainly has the following two methods: 1. Glycerol chlorohydrin method, which is obtained by reacting 3-propylene glycol in the presence of alkali. The reaction is usually carried out at about 0°C. After the salts are separated from the reaction product, it is purified by vacuum distillation to obtain pure glycidol. 2. Alcohol propylene method, using hydrogen peroxide or peracetic acid to epoxidize allyl alcohol to obtain glycidol. When peracetic acid is used as the epoxide, the reaction speed is fast, and the glycidol in the product is very easy to react with acetic acid to form glycidyl acetate, which makes distillation and separation difficult, and the mixture of glycidol and acetic acid can undergo a strong exothermic reaction at room temperature Cause an explosion, so the method is very difficult to apply in industry. It can also be prepared by epoxidizing allyl alcohol with an oxidizing agent (such as hypochlorous acid or perchloric acid) by using hexavalent tungstate as a catalyst, but this process is very polluting to the environment, and the catalyst used is low in activity and non-renewable .
发明内容Contents of the invention
本发明的目的是提供一种工艺简单，成本低廉、环氧丙醇选择性好的烯丙醇氧化方法。The purpose of the present invention is to provide a kind of technique simple, with low cost, the allyl alcohol oxidation method that glycidol selectivity is good.
为了克服现有技术制备环氧丙醇方法存在的上述问题，本发明的发明人进行了深入的研究，发现采用臭氧作为氧化剂来氧化烯丙醇，一方面能够克服现有技术存在的操作条件苛刻、设备腐蚀严重且污染环境的缺陷，并且还能够获得令人满意的环氧丙醇选择性，由此完成了本发明。In order to overcome the above-mentioned problems existing in the method for preparing glycidyl alcohol in the prior art, the inventor of the present invention has carried out in-depth research and found that using ozone as an oxidizing agent to oxidize allyl alcohol can overcome the harsh operating conditions in the prior art on the one hand. , serious corrosion of equipment and the defects of polluting the environment, and satisfactory glycidyl alcohol selectivity can also be obtained, thus completing the present invention.
本发明提供了一种烯丙醇氧化的方法，该方法包括，在氧化反应条件下，将烯丙醇与氧化剂接触，其特征在于，所述氧化剂为含有臭氧的气体。The invention provides a method for oxidizing allyl alcohol, which comprises, under oxidation reaction conditions, contacting allyl alcohol with an oxidizing agent, characterized in that the oxidizing agent is a gas containing ozone.
本发明提供的烯丙醇氧化的方法，以臭氧作氧化剂，在原料气中无需添加任何引发剂的情况下即可得到高的环氧丙醇选择性和较高臭氧有效利用率，而且在含钛催化剂存在下，可以进一步提高环氧丙醇选择性和臭氧有效利用率。该方法过程简单易控制，利于工业化生产和应用。The method for oxidation of allyl alcohol provided by the present invention uses ozone as an oxidizing agent, and can obtain high glycidyl alcohol selectivity and higher effective utilization rate of ozone without adding any initiator in the raw material gas, and in the presence of In the presence of a titanium catalyst, the selectivity of glycidol and the effective utilization rate of ozone can be further improved. The process of the method is simple and easy to control, and is beneficial to industrial production and application.
具体实施方式Detailed ways
本发明提供的烯丙醇氧化的方法，该方法包括，在氧化反应条件下，将烯丙醇与氧化剂接触，其特征在于，所述氧化剂为含有臭氧的气体。The method for oxidizing allyl alcohol provided by the present invention comprises, under oxidation reaction conditions, contacting allyl alcohol with an oxidizing agent, characterized in that the oxidizing agent is a gas containing ozone.
根据本发明的方法，采用含有臭氧的气体作为氧化剂。臭氧(分子式为O3，又名三原子氧，俗称“福氧、超氧、活氧”)在常温常压下，为呈淡蓝色的气体。本发明的发明人在研究过程中发现，采用含有臭氧的气体作为氧化剂来氧化烯丙醇，对于环氧丙醇具有较高的选择性，其工艺简便易行，操作条件温和。并且，臭氧在常温下能够自行分解为氧气，不会产生例如使用过氧化氢作为氧化剂时面临的需要对含有过氧化氢的溶液进行处理等缺点。因此，根据本发明方法环境友好。According to the method of the present invention, an ozone-containing gas is used as an oxidizing agent. Ozone (molecular formula is O3 , also known as triatomic oxygen, commonly known as "Fu oxygen, super oxygen, active oxygen") is a light blue gas at normal temperature and pressure. The inventors of the present invention found in the course of research that using ozone-containing gas as an oxidant to oxidize allyl alcohol has a higher selectivity for glycidol, and the process is simple and easy, and the operating conditions are mild. Moreover, ozone can be decomposed into oxygen by itself at room temperature, and there will be no disadvantages such as the need to process a solution containing hydrogen peroxide, which is faced when hydrogen peroxide is used as an oxidant. Therefore, the method according to the invention is environmentally friendly.
根据本发明的方法，所述含有臭氧的气体可以为臭氧，还可以为臭氧与稀释气体的混合气体。根据本发明的方法，所述含有臭氧的气体优选为臭氧与稀释气体的混合气体，这样可以方便地对臭氧的浓度进行调节，从而更好地控制反应速率。According to the method of the present invention, the ozone-containing gas may be ozone, or a mixed gas of ozone and diluent gas. According to the method of the present invention, the gas containing ozone is preferably a mixed gas of ozone and diluent gas, so that the concentration of ozone can be adjusted conveniently, so as to better control the reaction rate.
本发明中，在所述含有臭氧的气体为臭氧与稀释气体的混合气体时，所述混合气体中臭氧的浓度可以根据具体的氧化反应条件进行适当的选择。优选地，以所述混合气体的总体积为基准，所述混合气体中臭氧的含量为1体积％以上。更优选地，以所述混合气体的总体积为基准，所述混合气体中臭氧的含量为5体积％以上。一般地，以所述混合气体的总体积为基准，所述混合气体中臭氧的含量可以为5-80体积％，优选为5-50体积％，更优选为5-20体积％。In the present invention, when the ozone-containing gas is a mixed gas of ozone and a diluent gas, the concentration of ozone in the mixed gas can be properly selected according to specific oxidation reaction conditions. Preferably, based on the total volume of the mixed gas, the content of ozone in the mixed gas is more than 1% by volume. More preferably, based on the total volume of the mixed gas, the content of ozone in the mixed gas is more than 5% by volume. Generally, based on the total volume of the mixed gas, the content of ozone in the mixed gas may be 5-80% by volume, preferably 5-50% by volume, more preferably 5-20% by volume.
本发明对于所述稀释气体的种类没有特别限定，所述稀释气体例如可以为氧气、二氧化碳、氮气、氩气、氦气、氖气和空气中的至少一种。优选地，所述稀释气体为氧气、二氧化碳、氦气和空气中的至少一种。根据本发明，可以将臭氧与上述稀释气体混合，从而制备所述含有臭氧的混合气体；由于空气含有氧气、二氧化碳和氮气，也可以将臭氧与空气混合，从而制备所述含有臭氧的混合气体。根据本发明的方法，采用臭氧发生器来现场生成臭氧时，可以采用氧气作为所述臭氧发生器的氧气源，也可以采用空气来向所述臭氧发生器提供氧气。采用氧气作为所述臭氧发生器的氧气源得到的臭氧的纯度较高，能够获得更高的烯丙醇转化率和环氧丙醇选择性；采用空气作为所述臭氧发生器的氧气源，则能够进一步降低运行成本。The present invention has no particular limitation on the type of the diluent gas, for example, the diluent gas may be at least one of oxygen, carbon dioxide, nitrogen, argon, helium, neon and air. Preferably, the diluent gas is at least one of oxygen, carbon dioxide, helium and air. According to the present invention, ozone can be mixed with the above diluent gas to prepare the ozone-containing mixed gas; since air contains oxygen, carbon dioxide and nitrogen, ozone can also be mixed with air to prepare the ozone-containing mixed gas. According to the method of the present invention, when an ozone generator is used to generate ozone on site, oxygen can be used as the oxygen source of the ozone generator, and air can also be used to provide oxygen to the ozone generator. The purity of the ozone that adopts oxygen as the oxygen source that described ozone generator obtains is higher, can obtain higher allyl alcohol conversion rate and glycidyl alcohol selectivity; Adopt air as the oxygen source of described ozone generator, then The running cost can be further reduced.
根据本发明的方法，在所述氧化剂为臭氧与稀释气体的混合气体，且所述稀释气体为两种以上时，本发明对于每一种稀释气体的含量没有特别限定，只要最终的含有臭氧的气体中，臭氧的含量能够将烯丙醇氧化即可，例如：所述臭氧的含量可以为上文所述的臭氧含量。According to the method of the present invention, when the oxidizing agent is a mixed gas of ozone and diluent gas, and there are two or more kinds of diluent gases, the present invention does not specifically limit the content of each diluent gas, as long as the final ozone-containing In the gas, the content of ozone can oxidize allyl alcohol. For example, the content of ozone can be the above-mentioned ozone content.
在根据本发明的一种优选的实施方式中，所述含有臭氧的气体为臭氧、或者臭氧与稀释气体的混合气体，且以所述混合气体的总体积为基准，所述混合气体中臭氧的含量为1体积％以上，所述稀释气体为氧气、二氧化碳、氮气、氩气、氦气、氖气和空气中的至少一种。在根据本发明的一种更为优选的实施方式中，以所述混合气体的总体积为基准，所述混合气体中臭氧的含量为5体积％以上，所述稀释气体为氧气、二氧化碳、氦气和空气中的至少一种。In a preferred embodiment of the present invention, the ozone-containing gas is ozone or a mixed gas of ozone and diluent gas, and based on the total volume of the mixed gas, the amount of ozone in the mixed gas The content is more than 1% by volume, and the diluent gas is at least one of oxygen, carbon dioxide, nitrogen, argon, helium, neon and air. In a more preferred embodiment according to the present invention, based on the total volume of the mixed gas, the content of ozone in the mixed gas is more than 5% by volume, and the diluent gas is oxygen, carbon dioxide, helium At least one of gas and air.
根据本发明的方法是通过采用含有臭氧的气体作为氧化剂来实现以温和的操作条件和较高的选择性来制备环氧丙醇，同时还不会对设备产生严重的腐蚀的目的。本发明对于烯丙醇与氧化剂中的臭氧的摩尔比无特殊要求，可以根据具体的应用场合进行适当的选择。在确保烯丙醇的转化率以及环氧丙醇的选择性的条件下，从进一步降低臭氧的用量，进而进一步降低根据本发明的方法的成本的角度出发，所述烯丙醇与氧化剂中的臭氧的摩尔比优选为1∶0.1-10，更优选为1∶0.1-5，进一步优选为1∶0.5-5。The method according to the present invention is to realize the preparation of glycidol with mild operating conditions and higher selectivity by using the gas containing ozone as the oxidant, and meanwhile the purpose of not causing severe corrosion to the equipment. The present invention has no special requirements on the molar ratio of allyl alcohol to ozone in the oxidizing agent, and can be properly selected according to specific application occasions. Under the condition of ensuring the conversion rate of allyl alcohol and the selectivity of glycidyl alcohol, from the perspective of further reducing the amount of ozone, and then further reducing the cost of the method according to the present invention, the allyl alcohol and the oxidizing agent The molar ratio of ozone is preferably 1:0.1-10, more preferably 1:0.1-5, even more preferably 1:0.5-5.
根据本发明的方法，烯丙醇与氧化剂的接触优选在含钛催化剂存在下进行。本发明的发明人在研究过程中发现，在烯丙醇与氧化剂的接触在含钛催化剂的存在下进行时，能够提高本发明方法的烯丙醇的转化率，特别是能够大幅度提高臭氧的有效利用率和环氧丙醇的选择性。According to the method of the present invention, the contacting of allyl alcohol with an oxidizing agent is preferably carried out in the presence of a titanium-containing catalyst. The inventors of the present invention found in the research process that when the contact of allyl alcohol and the oxidant was carried out in the presence of a titanium-containing catalyst, the conversion rate of the allyl alcohol of the method of the present invention could be improved, especially the ozone yield could be greatly improved. Effective utilization and selectivity of glycidol.
根据本发明的方法，所述含钛催化剂的用量可以根据具体的应用场合进行适当的选择。优选地，以二氧化钛计，所述含钛催化剂与烯丙醇的摩尔比为1∶0.1-100。更优选地，以二氧化钛计，所述含钛催化剂与烯丙醇的摩尔比为1∶1-50。According to the method of the present invention, the amount of the titanium-containing catalyst can be properly selected according to specific application occasions. Preferably, based on titanium dioxide, the molar ratio of the titanium-containing catalyst to allyl alcohol is 1:0.1-100. More preferably, based on titanium dioxide, the molar ratio of the titanium-containing catalyst to allyl alcohol is 1:1-50.
根据本发明的方法，所述含钛催化剂可以为各种形式的含钛催化剂。优选地，所述含钛催化剂为含钛分子筛、含钛分子筛的成型催化剂、无定形硅钛和二氧化钛中的至少一种。更优选地，所述含钛催化剂为MFI结构的钛硅分子筛(如TS-1)、MEL结构的钛硅分子筛(如TS-2)、BEA结构的钛硅分子筛(如Ti-Beta)、MWW结构的钛硅分子筛(如Ti-MCM-22)、六方结构的钛硅分子筛(如Ti-MCM-41、Ti-SBA-15)、MOR结构的钛硅分子筛(如Ti-MOR)、TUN结构的钛硅分子筛(如Ti-TUN)、其他结构的钛硅分子筛(如Ti-ZSM-48)和二氧化钛中的至少一种。更优选地，所述含钛催化剂为MFI结构的钛硅分子筛(如TS-1)。上述分子筛可以商购得到，或者采用本领域公知的方法合成，本文不再赘述。According to the method of the present invention, the titanium-containing catalyst may be various forms of titanium-containing catalysts. Preferably, the titanium-containing catalyst is at least one of titanium-containing molecular sieves, shaped catalysts containing titanium molecular sieves, amorphous silicon titanium and titanium dioxide. More preferably, the titanium-containing catalyst is titanium-silicon molecular sieve with MFI structure (such as TS-1), titanium-silicon molecular sieve with MEL structure (such as TS-2), titanium-silicon molecular sieve with BEA structure (such as Ti-Beta), MWW Structured titanium-silicon molecular sieve (such as Ti-MCM-22), hexagonal structure titanium-silicon molecular sieve (such as Ti-MCM-41, Ti-SBA-15), MOR structure titanium-silicon molecular sieve (such as Ti-MOR), TUN structure At least one of titanium-silicon molecular sieves (such as Ti-TUN), titanium-silicon molecular sieves of other structures (such as Ti-ZSM-48) and titanium dioxide. More preferably, the titanium-containing catalyst is a titanium-silicon molecular sieve with an MFI structure (such as TS-1). The above-mentioned molecular sieves can be obtained commercially, or synthesized by methods known in the art, and will not be described in detail herein.
根据本发明的方法，所述含钛催化剂最优选为空心结构晶粒的MFI结构的钛硅分子筛，该空心结构的空腔部分的径向长度为5-300纳米，且所述钛硅分子筛在25℃、P/P0＝0.10、吸附时间为1小时的条件下测得的苯吸附量为至少70毫克/克，该钛硅分子筛的低温氮吸附的吸附等温线和脱附等温线之间存在滞后环。下文中，将该类型的钛硅分子筛称为空心钛硅分子筛。According to the method of the present invention, the titanium-containing catalyst is most preferably a titanium-silicon molecular sieve with an MFI structure of hollow structure crystal grains, the radial length of the cavity part of the hollow structure is 5-300 nanometers, and the titanium-silicon molecular sieve is The benzene adsorption measured under the conditions of 25°C, P/P0 =0.10, and adsorption time of 1 hour is at least 70 mg/g, and the low-temperature nitrogen adsorption of the titanium-silicon molecular sieve is between the adsorption isotherm and the desorption isotherm There is a hysteresis loop. Hereinafter, this type of titanium-silicon molecular sieve is called hollow titanium-silicon molecular sieve.
根据本发明的方法，烯丙醇与氧化剂的接触优选在溶剂存在下进行，这样可以使烯丙醇与氧化剂的接触更为均匀，从而更好的控制反应速度。本发明对于所述溶剂的种类没有特别限定，所述溶剂可以为本领域常用的各种溶剂。优选地，所述溶剂为水、C1-C10的醇、C3-C10的酮、C2-C8的腈和C1-C6的羧酸中的至少一种。例如，所述溶剂可以为水、甲醇、乙醇、正丙醇、异丙醇、叔丁醇、异丁醇、丙酮、丁酮、乙腈和乙酸中的至少一种。本发明的发明人在研究过程中意外的发现，在所述溶剂为水、C1-C4的醇和/或C3-C8的酮时，能够进一步提高烯丙醇的转化率以及环氧丙醇的选择性。进一步优选地，所述溶剂为水、甲醇和/或丙酮。According to the method of the present invention, the contact between allyl alcohol and oxidant is preferably carried out in the presence of a solvent, which can make the contact between allyl alcohol and oxidant more uniform, thereby better controlling the reaction rate. The present invention does not specifically limit the type of the solvent, and the solvent may be various solvents commonly used in the art. Preferably, the solvent is at least one of water, C1 -C10 alcohol, C3 -C10 ketone, C2 -C8 nitrile and C1 -C6 carboxylic acid. For example, the solvent may be at least one of water, methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone, acetonitrile and acetic acid. The inventors of the present invention unexpectedly found in the research process that when the solvent is water, C1 -C4 alcohol and/or C3 -C8 ketone, the conversion rate of allyl alcohol and epoxy Propanol selectivity. Further preferably, the solvent is water, methanol and/or acetone.
根据本发明的方法，所述溶剂的量可以为本领域的常规选择。从进一步降低本发明的方法的成本的角度出发，所述烯丙醇与溶剂的摩尔比优选为1∶1-150，更优选为1∶1-100，进一步优选为1∶1-50。According to the method of the present invention, the amount of the solvent can be conventionally selected in the art. From the perspective of further reducing the cost of the method of the present invention, the molar ratio of the allyl alcohol to the solvent is preferably 1:1-150, more preferably 1:1-100, and even more preferably 1:1-50.
根据本发明的方法，对于所述氧化反应条件无特殊要求，可以为常规的氧化反应条件。优选情况下，所述氧化反应条件包括：温度可以为0-180℃，优选为20-160℃，进一步优选为20-120℃；压力可以为0.1-3MPa，优选为0.1-2.5MPa，进一步优选为0.1-2MPa。According to the method of the present invention, there is no special requirement for the oxidation reaction conditions, which may be conventional oxidation reaction conditions. Preferably, the oxidation reaction conditions include: the temperature can be 0-180°C, preferably 20-160°C, more preferably 20-120°C; the pressure can be 0.1-3MPa, preferably 0.1-2.5MPa, more preferably 0.1-2MPa.
根据本发明的方法，烯丙醇与氧化剂的接触时间可以进行适当的选择。一般地，所述接触的时间可以为0.1-10小时，优选为1-5小时。需要说明的是，当在所述温度下，可以产生所需的压力时，所述压力可以为自生压力，当在所述温度下，所述温度产生的压力达不到所需的压力时，所述压力可以通过外界施加压力来实现，此为本领域熟知的技术，本文不再进行详述。According to the method of the present invention, the contact time of allyl alcohol and the oxidizing agent can be properly selected. Generally, the contacting time may be 0.1-10 hours, preferably 1-5 hours. It should be noted that, when the required pressure can be generated at the temperature, the pressure can be an autogenous pressure; when the pressure generated by the temperature cannot reach the required pressure at the temperature, The pressure can be achieved by external pressure, which is a well-known technique in the art, and will not be described in detail herein.
根据本发明的方法，可以采用常规方法将环氧丙醇从烯丙醇与氧化剂的接触产物中分离出来。例如：可以通过将所述接触产物进行分馏，从而分离出环氧丙醇。所述分馏的方法和条件是本领域所公知的，本文不再赘述。According to the method of the present invention, conventional methods can be used to separate glycidyl alcohol from the contact product of allyl alcohol and oxidizing agent. For example: Glycidyl alcohol can be isolated by fractional distillation of the contact product. The methods and conditions of the fractionation are well known in the art, and will not be repeated here.
根据本发明的方法，可以采用间歇操作，也可以采用连续操作等，加料方式也可以是本领域技术人员已知的任何适宜的方式，本发明对此均无特殊要求，在此不一一赘述。连续操作时，在含钛催化剂存在下，在臭氧空速为10-10000h-1条件下进行反应，臭氧空速优选为10-5000h-1。According to the method of the present invention, batch operation can be adopted, continuous operation can also be adopted, and the feeding method can also be any suitable mode known to those skilled in the art. The present invention has no special requirements to this, and will not go into details here. . During continuous operation, the reaction is carried out under the condition that the ozone space velocity is 10-10000h-1 in the presence of a titanium-containing catalyst, and the ozone space velocity is preferably 10-5000h-1 .
以下的实施例将对本发明作进一步说明，但并不因此限制本发明的内容。The following examples will further illustrate the present invention, but do not limit the content of the present invention.
实施例中，如未特别说明，所用到的试剂均为市售的分析纯试剂，所用到的反应器为通用型250mL不锈钢高压釜式反应器。In the examples, unless otherwise specified, the reagents used are commercially available analytical reagents, and the reactor used is a general-purpose 250mL stainless steel autoclave reactor.
实施例中，所用臭氧为由福建新大陆环保科技有限公司生产的NLO-15型臭氧发生器提供，臭氧浓度可调，最大体积浓度可达80％。以下实施例中如未特别说明，均使用氧气源来制备臭氧。In the embodiment, the ozone used is provided by the NLO-15 ozone generator produced by Fujian Newland Environmental Protection Technology Co., Ltd. The ozone concentration is adjustable, and the maximum volume concentration can reach 80%. In the following examples, unless otherwise specified, an oxygen source is used to prepare ozone.
实施例中，所用的钛硅分子筛(TS-1)催化剂是按文献[Zeolites，1992，Vol.12第943-950页]中所描述的方法制备出的TS-1分子筛样品，氧化钛含量为2.4重量％。In the embodiment, the titanium-silicon molecular sieve (TS-1) catalyst used is the TS-1 molecular sieve sample prepared by the method described in the literature [Zeolites, 1992, Vol.12 pages 943-950], and the titanium oxide content is 2.4% by weight.
实施例中，所用的空心钛硅分子筛HTS系CN1301599A所述钛硅分子筛的工业产品(湖南建长石化股份有限公司制造，经X-射线衍射分析为MFI结构的钛硅分子筛，该分子筛的低温氮吸附的吸附等温线和脱附等温线之间存在滞后环，晶粒为空心晶粒且空腔部分的径向长度为15-180纳米；该分子筛样品在25℃，P/P0＝0.10，吸附时间1小时的条件下测得的苯吸附量为78毫克/克)，氧化钛含量为2.5重量％。In the embodiment, the hollow titanium-silicon molecular sieve HTS used is an industrial product of the titanium-silicon molecular sieve described in CN1301599A (manufactured by Hunan Jianchang Petrochemical Co., Ltd., analyzed as a titanium-silicon molecular sieve of MFI structure by X-ray diffraction, and the low-temperature nitrogen of the molecular sieve There is a hysteresis loop between the adsorption isotherm and the desorption isotherm, the grains are hollow grains and the radial length of the cavity part is 15-180 nanometers; the molecular sieve sample is at 25°C, P/P0 =0.10, The benzene adsorption measured under the condition of an adsorption time of 1 hour was 78 mg/g), and the titanium oxide content was 2.5% by weight.
本发明中，采用气相色谱进行体系中各组成的分析，通过校正归一法进行定量，均可参照现有技术进行，在此基础上计算反应物的转化率和产物的选择性等评价指标。In the present invention, the analysis of each composition in the system is carried out by gas chromatography, and the quantification is carried out by the calibration and normalization method, both of which can be carried out with reference to the prior art. On this basis, evaluation indicators such as the conversion rate of the reactant and the selectivity of the product are calculated.
在实施例中：In the example:
实施例1Example 1
在温度为60℃和压力为0.5MPa下，以臭氧(15％体积比，其余为氧气)为氧化剂，将烯丙醇、臭氧和溶剂丙酮按照1∶1∶1的摩尔比下进行反应。反应2小时的结果如下：烯丙醇转化率为64％；臭氧有效利用率为41％；环氧丙醇选择性为53％。At a temperature of 60° C. and a pressure of 0.5 MPa, with ozone (15% by volume, the rest being oxygen) as an oxidant, allyl alcohol, ozone and solvent acetone were reacted in a molar ratio of 1:1:1. The results of the reaction for 2 hours are as follows: the conversion rate of allyl alcohol is 64%; the effective utilization rate of ozone is 41%; the selectivity of glycidyl alcohol is 53%.
实施例2Example 2
在温度为20℃和压力为1.5MPa下，以臭氧(30％体积比，其余为空气)为氧化剂，将烯丙醇、臭氧和溶剂乙酸按照1∶1∶5的摩尔比下进行反应。反应5小时的结果如下：烯丙醇转化率为25％；臭氧有效利用率为38％；环氧丙醇选择性为69％。At a temperature of 20° C. and a pressure of 1.5 MPa, with ozone (30% by volume, the rest being air) as an oxidant, allyl alcohol, ozone and solvent acetic acid were reacted in a molar ratio of 1:1:5. The result of reacting for 5 hours is as follows: the conversion rate of allyl alcohol is 25%; the effective utilization rate of ozone is 38%; the selectivity of glycidol is 69%.
实施例3Example 3
在温度为80℃和压力为0.2MPa下，以臭氧(5％体积比，其余为氧气)为氧化剂，将烯丙醇、臭氧和溶剂乙腈按照1∶2∶10的摩尔比下进行反应。反应1小时的结果如下：烯丙醇转化率为82％；臭氧有效利用率为43％；环氧丙醇选择性为47％。At a temperature of 80° C. and a pressure of 0.2 MPa, with ozone (5% by volume, the rest being oxygen) as an oxidant, allyl alcohol, ozone and solvent acetonitrile were reacted in a molar ratio of 1:2:10. The result of reacting for 1 hour is as follows: the conversion rate of allyl alcohol is 82%; the effective utilization rate of ozone is 43%; the selectivity of glycidyl alcohol is 47%.
实施例4Example 4
在温度为40℃和压力为0.1MPa下，以臭氧(15％体积比，其余为氧气)为氧化剂，将烯丙醇、臭氧和溶剂丙酮按照1∶4∶50的摩尔比下进行反应。反应2小时的结果如下：烯丙醇转化率为47％；臭氧有效利用率为39％；环氧丙醇选择性为52％。At a temperature of 40° C. and a pressure of 0.1 MPa, with ozone (15% by volume, the rest being oxygen) as an oxidant, allyl alcohol, ozone and solvent acetone were reacted in a molar ratio of 1:4:50. The results of the reaction for 2 hours are as follows: the conversion rate of allyl alcohol is 47%; the effective utilization rate of ozone is 39%; the selectivity of glycidyl alcohol is 52%.
实施例5Example 5
本实施例说明在催化剂存在下的反应过程和结果。This example illustrates the reaction procedure and results in the presence of a catalyst.
以TS-1为催化剂，催化剂与烯丙醇的摩尔比例为1∶50，臭氧体积空速为20h-1，其它反应条件同实施例4。反应2小时的结果如下：烯丙醇转化率为61％；臭氧有效利用率为68％；环氧丙醇选择性为61％。TS-1 was used as the catalyst, the molar ratio of catalyst to allyl alcohol was 1:50, the volume space velocity of ozone was 20h-1 , and other reaction conditions were the same as in Example 4. The results of the reaction for 2 hours are as follows: the conversion rate of allyl alcohol is 61%; the effective utilization rate of ozone is 68%; the selectivity of glycidyl alcohol is 61%.
实施例6Example 6
本实施例说明在催化剂存在下的反应过程和结果。This example illustrates the reaction procedure and results in the presence of a catalyst.
按照实施例5的反应条件进行反应，不同的是以HTS替代TS-1为催化剂。反应3小时的结果如下：烯丙醇转化率为66％；臭氧有效利用率为74％；环氧丙醇选择性为72％。The reaction was carried out according to the reaction conditions of Example 5, except that HTS was used instead of TS-1 as the catalyst. The results of the reaction for 3 hours are as follows: the conversion rate of allyl alcohol is 66%; the effective utilization rate of ozone is 74%; the selectivity of glycidyl alcohol is 72%.
实施例7Example 7
在温度为50℃和压力为1.0MPa下，以臭氧(10％体积比，其余为空气)为氧化剂，将烯丙醇、臭氧和溶剂水按照1∶0.3∶3的摩尔比下进行反应。反应4小时的结果如下：烯丙醇转化率为26％；臭氧有效利用率为72％；环氧丙醇选择性为53％。At a temperature of 50° C. and a pressure of 1.0 MPa, with ozone (10% by volume, the rest being air) as an oxidant, allyl alcohol, ozone and solvent water are reacted in a molar ratio of 1:0.3:3. The results of the reaction for 4 hours are as follows: the conversion rate of allyl alcohol is 26%; the effective utilization rate of ozone is 72%; the selectivity of glycidyl alcohol is 53%.
实施例8Example 8
在温度为120℃和压力为1.0MPa下，以臭氧(10％体积比，其余为等体积的二氧化碳和氧气)为氧化剂，将烯丙醇、臭氧和溶剂丙酮按照1∶0.7∶25的摩尔比下反应。反应3小时的结果如下：烯丙醇转化率为31％；臭氧有效利用率为46％；环氧丙醇选择性为56％。At a temperature of 120°C and a pressure of 1.0MPa, with ozone (10% by volume, the rest being equal volumes of carbon dioxide and oxygen) as an oxidant, allyl alcohol, ozone and solvent acetone are mixed in a molar ratio of 1:0.7:25 The next reaction. The results of the reaction for 3 hours are as follows: the conversion rate of allyl alcohol is 31%; the effective utilization rate of ozone is 46%; the selectivity of glycidol is 56%.
实施例9Example 9
本实施例说明在催化剂存在下的反应过程和结果。This example illustrates the reaction procedure and results in the presence of a catalyst.
以TiO2为催化剂(市售，锐钛矿型)，催化剂与烯丙醇的摩尔比例为1∶5，臭氧体积空速为3000h-1，其它反应条件同实施例8。TiO2 was used as catalyst (commercially available, anatase type), the molar ratio of catalyst to allyl alcohol was 1:5, the volume space velocity of ozone was 3000h-1 , and other reaction conditions were the same as in Example 8.
反应3小时的结果如下：烯丙醇转化率为52％；臭氧有效利用率为76％；环氧丙醇选择性为67％。The results of the reaction for 3 hours are as follows: the conversion rate of allyl alcohol is 52%; the effective utilization rate of ozone is 76%; the selectivity of glycidyl alcohol is 67%.
实施例10Example 10
在温度为100℃和压力为2.0MPa下，以臭氧(10％体积比，其余为体积比为7∶10的氦气和氧气)为氧化剂，将烯丙醇、臭氧和溶剂乙腈按照1∶2∶60的摩尔比下反应。反应1小时的结果如下：烯丙醇转化率为48％；臭氧有效利用率为42％；环氧丙醇选择性为55％。At a temperature of 100°C and a pressure of 2.0MPa, with ozone (10% volume ratio, the rest being helium and oxygen at a volume ratio of 7:10) as the oxidant, allyl alcohol, ozone and solvent acetonitrile were mixed in a ratio of 1:2 : 60 molar ratio to react. The result of reacting for 1 hour is as follows: the conversion rate of allyl alcohol is 48%; the effective utilization rate of ozone is 42%; the selectivity of glycidol is 55%.
实施例11Example 11
本实施例说明在溶剂为甲醇的情况下的反应过程和结果。This example illustrates the reaction procedure and results when the solvent is methanol.
按照实施例10的反应条件进行反应，不同的是利用甲醇替代乙腈为溶剂。反应1小时的结果如下：烯丙醇转化率为57％；臭氧有效利用率为64％；环氧丙醇选择性为61％。The reaction was carried out according to the reaction conditions of Example 10, except that methanol was used instead of acetonitrile as the solvent. The result of reacting for 1 hour is as follows: the conversion rate of allyl alcohol is 57%; the effective utilization rate of ozone is 64%; the selectivity of glycidol is 61%.
实施例12Example 12
本实施例说明在催化剂存在下的反应过程和结果。This example illustrates the reaction procedure and results in the presence of a catalyst.
以HTS为催化剂，催化剂与烯丙醇的摩尔比例为1∶10，臭氧体积空速为1000h-1，其它反应条件同实施例11。反应1小时的结果如下：烯丙醇转化率为81％；臭氧有效利用率为76％；环氧丙醇选择性为73％。HTS was used as the catalyst, the molar ratio of catalyst to allyl alcohol was 1:10, the volume space velocity of ozone was 1000h-1 , and other reaction conditions were the same as in Example 11. The result of reacting for 1 hour is as follows: the conversion rate of allyl alcohol is 81%; the effective utilization rate of ozone is 76%; the selectivity of glycidol is 73%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050626.4ACN103288779B (en) | 2012-02-29 | 2012-02-29 | Method for oxidizing allyl alcohol |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210050626.4ACN103288779B (en) | 2012-02-29 | 2012-02-29 | Method for oxidizing allyl alcohol |
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| CN103288779A CN103288779A (en) | 2013-09-11 |
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| CN201210050626.4AActiveCN103288779B (en) | 2012-02-29 | 2012-02-29 | Method for oxidizing allyl alcohol |
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| CN1452615A (en)* | 2000-09-05 | 2003-10-29 | 对流层研究协会研究所 | Method for producing epoxides by oxidising olefins |
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| CN101184740A (en)* | 2005-04-19 | 2008-05-21 | 西班牙高等科研理事会 | Process and catalyst for epoxidation of olefinic compounds in the presence of oxygen |
| CN101570523A (en)* | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol |
| CN101704802A (en)* | 2009-11-19 | 2010-05-12 | 浙江大学 | Preparation method of epoxy compound |
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| CN1452615A (en)* | 2000-09-05 | 2003-10-29 | 对流层研究协会研究所 | Method for producing epoxides by oxidising olefins |
| CN1507438A (en)* | 2001-05-01 | 2004-06-23 | ����̼����ѧ�����ϼ�����˾ | Synthesis of lower alkylene oxdies and lower alkylene glycols from lower alkanes and/or lower alkenes |
| CN101184740A (en)* | 2005-04-19 | 2008-05-21 | 西班牙高等科研理事会 | Process and catalyst for epoxidation of olefinic compounds in the presence of oxygen |
| CN101570523A (en)* | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol |
| CN101704802A (en)* | 2009-11-19 | 2010-05-12 | 浙江大学 | Preparation method of epoxy compound |
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| CN103288779A (en) | 2013-09-11 |
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