技术领域technical field
本发明涉及一种含贵金属分子筛及其制备方法和应用，更具体地说涉及一种利用失活的钛硅分子筛催化剂制备含贵金属分子筛的方法，本发明还涉及一种烯烃直接氧化的方法。The present invention relates to a molecular sieve containing noble metal and its preparation method and application, more specifically to a method for preparing molecular sieve containing noble metal by using deactivated titanium silicon molecular sieve catalyst, and also relates to a method for direct oxidation of olefins.
背景技术Background technique
钛硅分子筛，是骨架由硅、钛、氧元素所组成的分子筛，在石油炼制和石油化工中应用前景广阔。其中，TS-1分子筛是将过渡金属元素钛引入具有ZSM-5结构的分子筛骨架中所形成的一种具有优良催化选择性氧化性能的新型钛硅分子筛。Titanium-silicon molecular sieve is a molecular sieve whose skeleton is composed of silicon, titanium and oxygen elements, and has broad application prospects in petroleum refining and petrochemical industry. Among them, TS-1 molecular sieve is a new type of titanium-silicon molecular sieve with excellent catalytic selective oxidation performance formed by introducing transition metal element titanium into the molecular sieve framework with ZSM-5 structure.
TS-1不但具有钛的催化氧化作用，而且还具有ZSM-5分子筛的择形作用和优良的稳定性，在环己酮催化氨氧化制备环己酮肟的工艺中成功地实现了工业应用。然而，通常在运行一段时间后催化剂催化性能会变差，催化剂出现失活现象。失活又分为暂时性失活和永久性失活。暂时性失活的催化剂可以经过再生使之恢复部分或全部活性，而永久性失活则无法通过再生恢复活性(再生后的活性低于初始活性的50％)。碱性环境下钛硅分子筛失活特别是氨肟化催化剂TS-1发生永久失活后，目前无法回收利用，主要采用堆积填埋的方式处理。这样，占用了宝贵的土地资源和库存空间，急需失活的氨肟化催化剂的回收利用技术开发。TS-1 not only has the catalytic oxidation of titanium, but also has the shape-selective effect and excellent stability of ZSM-5 molecular sieve, and has successfully realized industrial application in the process of preparing cyclohexanone oxime by catalytic ammoxidation of cyclohexanone. However, usually after a period of operation, the catalytic performance of the catalyst will deteriorate, and the catalyst will be deactivated. Inactivation is divided into temporary inactivation and permanent inactivation. Temporarily deactivated catalysts can be regenerated to restore some or all of their activity, while permanently deactivated catalysts cannot be regenerated (the regenerated activity is less than 50% of the initial activity). Titanium-silicon molecular sieve deactivation in alkaline environment, especially the permanent deactivation of ammonia oximation catalyst TS-1, cannot be recycled at present, and it is mainly disposed of by stacking and landfilling. In this way, precious land resources and storage space are occupied, and the development of recycling technology for deactivated ammoximation catalysts is urgently needed.
虽然过氧化氢(H2O2)是公认的绿色氧化剂，其氧化副产物只有水。但由于H2O2极不稳定，遇热、光，粗糙表面、重金属及其它杂质会分解，且具有腐蚀性，在包装、储存、运输中要采取特别的安全措施。因此，将H2O2就地应用，或将H2O2生产工艺与使用H2O2下游工艺相结合，才可更有效的利用这一化工产品。利用H2和O2可以直接合成H2O2，且原子利用率达100％，进而人们想利用H2和O2来原位合成H2O2再氧化有机原料以解决直接利用H2O2的成本和安全问题。由于Pt、Pd、Au等是H2和O2合成H2O2的有效组分，有许多文献专利报道将其负载在钛硅材料上原位生成H2O2用于有机物选择性氧化反应的研究。如，Meiers R.等(J.Catal.，1998，176：376-386)以Pt-Pd/TS-1为催化剂对丙烯气相环氧化进行了研究；US6867312B1以及US6884898B1等也都进行了这方面的研究。将贵金属负载在钛硅材料上原位生成H2O2用于有机物选择性氧化的方法虽然条件温和、选择性好(可达到95％以上)，但负载贵金属的钛硅材料催化剂活性较低，稳定性差。Although hydrogen peroxide (H2 O2 ) is recognized as a green oxidant, its oxidation by-product is only water. However, because H2 O2 is extremely unstable, rough surfaces, heavy metals and other impurities will decompose when exposed to heat and light, and it is corrosive, so special safety measures must be taken during packaging, storage and transportation. Therefore, the application ofH2O2on site, or the combination ofH2O2production process anddownstream process usingH2O2 , can make more efficient use of this chemical product. Using H2 and O2 can directly synthesize H2 O2 , and the atomic utilization rate is 100%, and then people want to use H2 and O2 to synthesize H2 O2 in situ and then oxidize organic raw materials to solve the problem of direct utilization of H2 O2 cost and safety issues. Since Pt, Pd, Au, etc. are effective components for the synthesis of H2 O2 from H2 and O2 , there are many literature and patent reports that they can be supported on titanium-silicon materials to generate H2 O2 in situ for the selective oxidation of organic matter. Research. For example, Meiers R. et al. (J.Catal., 1998, 176:376-386) used Pt-Pd/TS-1 as a catalyst to study the gas-phase epoxidation of propylene; US6867312B1 and US6884898B1 etc. have also carried out this aspect Research. Although the method of loading noble metals on titanium-silicon materials to generate H2 O2 in situ for selective oxidation of organic matter has mild conditions and good selectivity (up to 95%), the catalytic activity of titanium-silicon materials loaded with noble metals is low. Poor stability.
发明内容Contents of the invention
本发明的目的在于提供一种使用卸出剂制备具有特别物化特征的含贵金属分子筛的方法。The purpose of the present invention is to provide a method for preparing a precious metal-containing molecular sieve with special physical and chemical characteristics by using a discharge agent.
发明人经过对失活的钛硅分子筛特别是碱性环境下失活的钛硅分子筛例如氨肟化催化剂发生永久失活后的物化性质进行表征，发现其晶体骨架基本保持完整，可以加以利用。发明人经过大量的研究进一步发现，在钛硅分子筛的制备过程中，可以采用失活的钛硅分子筛催化剂(特别是碱性条件下永久失活的钛硅分子筛催化剂例如失活的环己酮肟化催化剂作为主要原料)，经过特定的制备步骤(使用酸、碱依次处理结合热处理和焙烧等步骤)，可以重新得到催化氧化性能优异的分子筛，且制备出的分子筛具有特别的物化特征。The inventors have characterized the physical and chemical properties of deactivated titanium-silicon molecular sieves, especially titanium-silicon molecular sieves deactivated in alkaline environments such as ammoximation catalysts after permanent deactivation, and found that their crystal skeletons remain basically intact and can be used. The inventor has further found through a large amount of research that in the preparation process of titanium-silicon molecular sieves, deactivated titanium-silicon molecular sieve catalysts (especially permanently deactivated titanium-silicon molecular sieve catalysts such as deactivated cyclohexanone oxime under alkaline conditions can be used) Catalyst as the main raw material), after specific preparation steps (acid, alkali sequential treatment combined with heat treatment and roasting steps), molecular sieves with excellent catalytic oxidation performance can be obtained again, and the prepared molecular sieves have special physical and chemical characteristics.
为实现前述目的，本发明的第一方面，本发明提供了一种含贵金属分子筛，该含贵金属分子筛包括：贵金属元素、硅元素和氧元素，所述含贵金属分子筛的孔容在0.3cm3/g以上，总比表面积在200m2/g以上，外表面积在30m2/g以上，且外表面积占总比表面积的比例为7-55％；所述含贵金属分子筛在25℃、P/P0＝0.10以及吸附时间为1小时的条件下测得的苯吸附量为至少65mg/g分子筛，N2静态吸附测试下具有1.0-1.8nm范围的微孔孔径分布；所述贵金属为Ru、Rh、Pd、Re、Os、Ir、Pt、Ag和Au中的一种或多种。In order to achieve the aforementioned purpose, the first aspect of the present invention provides a noble metal-containing molecular sieve, which includes noble metal elements, silicon elements and oxygen elements, and the pore volume of the noble metal-containing molecular sieves is 0.3 cm3 / More than g, the total specific surface area is more than 200m2 /g, the outer surface area is more than 30m2 /g, and the ratio of the outer surface area to the total specific surface area is 7-55%; =0.10 and the adsorption time is 1 hour under the condition that the benzene adsorption measured is at least 65 mg/g molecular sieve, and theN2 static adsorption test has a micropore pore size distribution in the range of 1.0-1.8 nm; the noble metal is Ru, Rh, One or more of Pd, Re, Os, Ir, Pt, Ag and Au.
本发明的第二方面，本发明提供了一种本发明所述的含贵金属分子筛的制备方法，该方法包括：In a second aspect of the present invention, the present invention provides a method for preparing the noble metal-containing molecular sieve of the present invention, the method comprising:
(1)将卸出剂与酸溶液混合打浆，将得到的浆液进行第一热处理，分离得到第一固体，其中，所述卸出剂为以钛硅分子筛作为催化剂的反应装置的卸出剂；(1) mixing the unloading agent with the acid solution for beating, carrying out the first heat treatment on the obtained slurry, and separating and obtaining the first solid, wherein the unloading agent is the unloading agent of a reaction device using titanium-silicon molecular sieve as a catalyst;
(2)将所述第一固体、贵金属源与碱源在含水溶剂存在下混合后进行第二热处理。(2) The second heat treatment is performed after mixing the first solid, the noble metal source and the alkali source in the presence of an aqueous solvent.
本发明的第三方面，本发明提供了本发明的含贵金属分子筛在催化烃直接氧化反应中的应用。In the third aspect of the present invention, the present invention provides the application of the noble metal-containing molecular sieve of the present invention in catalytic hydrocarbon direct oxidation reaction.
根据本发明的第四方面，本发明提供了一种烯烃直接氧化的方法，该方法包括：以甲醇为溶剂，将烯烃、含氧气体和催化剂接触，其特征在于，所述催化剂含有本发明所述的含贵金属分子筛和本发明所述的制备方法制备得到的含贵金属分子筛。According to the fourth aspect of the present invention, the present invention provides a method for direct oxidation of olefins, the method comprising: using methanol as a solvent, contacting olefins, oxygen-containing gas and a catalyst, characterized in that the catalyst contains The above-mentioned precious metal-containing molecular sieve and the precious metal-containing molecular sieve prepared by the preparation method of the present invention.
本发明的具有特殊的物化特征结构的含贵金属分子筛其苯吸附量较高且具有1.0-1.8nm范围的微孔孔径分布的优势，例如将其用于环状分子、烯烃分子参与或生成的反应，能够取得更好的催化效果。即由于本发明的材料其苯吸附量较高且具有1.0-1.8nm范围的微孔孔径分布，在催化反应中有利于反应物和产物分子(如芳香族化合物)，烯烃分子的扩散，对芳香族烃化合物、环类烃化合物等分子以及烯烃分子参与的催化氧化反应特别有利。The precious metal-containing molecular sieve with special physical and chemical characteristic structure of the present invention has the advantages of high benzene adsorption capacity and micropore pore size distribution in the range of 1.0-1.8nm, for example, it can be used in reactions involving or forming cyclic molecules and olefin molecules , can achieve better catalytic effect. Namely because its benzene adsorption capacity of the material of the present invention is higher and has the pore diameter distribution of 1.0-1.8nm scope, is conducive to the diffusion of reactant and product molecule (as aromatic compound), olefin molecule in catalytic reaction, to aromatic Catalytic oxidation reactions involving molecules such as alkene compounds, cyclic hydrocarbon compounds, and olefin molecules are particularly advantageous.
本发明的制备含贵金属分子筛的方法，能够制备得到具有本发明的特殊特征结构的含贵金属分子筛，例如苯吸附量较高且具有1.0-1.8nm范围的微孔孔径分布。并且本发明的方法使得失活的钛硅分子筛催化剂得到利用，变废为宝。The method for preparing noble metal-containing molecular sieves of the present invention can prepare noble metal-containing molecular sieves with special characteristic structures of the present invention, such as high benzene adsorption and micropore size distribution in the range of 1.0-1.8nm. And the method of the present invention enables the deactivated titanium-silicon molecular sieve catalyst to be utilized, turning waste into treasure.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the following detailed description.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
如前所述，本发明提供了一种含贵金属分子筛，该含贵金属分子筛包括：贵金属元素、硅元素和氧元素，所述含贵金属分子筛的孔容在0.3cm3/g以上，总比表面积在200m2/g以上，外表面积在30m2/g以上，且外表面积占总比表面积的比例为7-55％；所述含贵金属分子筛在25℃、P/P0＝0.10以及吸附时间为1小时的条件下测得的苯吸附量为至少65mg/g分子筛，N2静态吸附测试下具有1.0-1.8nm范围的微孔孔径分布；所述贵金属为Ru、Rh、Pd、Re、Os、Ir、Pt、Ag和Au中的一种或多种。As mentioned above, the present invention provides a noble metal-containing molecular sieve, the noble metal-containing molecular sieve includes: noble metal elements, silicon elements and oxygen elements, the pore volume of the noble metal-containing molecular sieve is above 0.3 cm3 /g, and the total specific surface area is More than 200m2 /g, the outer surface area is more than 30m2 /g, and the ratio of the outer surface area to the total specific surface area is7-55 %. The benzene adsorption measured under the condition of 1 hour is at least 65mg/g molecular sieve, and the micropore pore size distribution with the range of 1.0-1.8nm underN2 static adsorption test; the noble metal is Ru, Rh, Pd, Re, Os, Ir , one or more of Pt, Ag and Au.
本发明中，含贵金属分子筛的总比表面积指的是BET比表面积，而外比表面积指的是含贵金属分子筛的外表面的表面积，也可简称为外表面积，均可以按照ASTM D4222-98标准方法测得。In the present invention, the total specific surface area of the molecular sieve containing noble metal refers to the BET specific surface area, and the external specific surface area refers to the surface area of the outer surface of the molecular sieve containing noble metal, which can also be referred to as the outer surface area for short, and can be used according to the ASTM D4222-98 standard method Measured.
本发明中，含贵金属分子筛的孔容和孔径分别指分子筛内的孔体积和孔直径，这为本领域技术人员所熟知，此处不赘述。In the present invention, the pore volume and pore diameter of the noble metal-containing molecular sieve respectively refer to the pore volume and pore diameter in the molecular sieve, which are well known to those skilled in the art and will not be described in detail here.
根据本发明的含贵金属分子筛，优选所述含贵金属分子筛的孔容为0.3-0.7cm3/g，优选为0.31-0.42cm3/g；总比表面积为200-450m2/g，优选为300-410m2/g；外表面积为30-150m2/g，优选为40-80m2/g；外表面积占总比表面积的比例为10-35％，优选为13-30％，更优选为17-25％；所述含贵金属分子筛在25℃、P/P0＝0.10以及吸附时间为1h的条件下测得的苯吸附量为至少75mg/g分子筛，更优选为80-130mg/g分子筛；1.0-1.8nm范围的微孔孔径占总微孔孔径分布量的比例≥5％；优选所述贵金属为Pd、Ag、Au和/或Pt。According to the noble metal-containing molecular sieve of the present invention, preferably the pore volume of the noble metal-containing molecular sieve is 0.3-0.7 cm3 /g, preferably 0.31-0.42 cm3 /g; the total specific surface area is 200-450 m2 /g, preferably 300 -410m2 /g; the external area is 30-150m2 /g, preferably 40-80m2 /g; the ratio of the external area to the total specific surface area is 10-35%, preferably 13-30%, more preferably 17 -25%; the benzene adsorption measured by the noble metal-containing molecular sieve under the conditions of 25°C, P/P0 =0.10 and an adsorption time of 1 hour is at least 75 mg/g molecular sieve, more preferably 80-130 mg/g molecular sieve; The proportion of micropore diameters in the range of 1.0-1.8nm to the total micropore diameter distribution is ≥5%; preferably, the noble metal is Pd, Ag, Au and/or Pt.
根据本发明的前述含贵金属分子筛，所述含贵金属分子筛的微孔孔径除了在0.4-0.7nm范围内有典型的微孔分子筛(如MFI拓扑结构分子筛的孔径在0.55nm附近)所特有的孔径分布外，在1.0-1.8nm范围内也有分布。这里需要特别说明的是，若在1.0-1.8nm范围内微孔孔径分布占总微孔孔径分布量的比例<1％时，则这部分微孔的孔分布忽略不计，即认为在1.0-1.8nm范围内没有微孔分布，此为本领域技术人员所公知。因此，本发明所述的在N2静态吸附测试下具有1.0-1.8nm范围的微孔孔径是指在1.0-1.8nm范围内的微孔孔径分布占总微孔孔径分布量的比例>1％。According to the aforementioned noble metal-containing molecular sieve of the present invention, the micropore diameter of the noble metal-containing molecular sieve has a characteristic pore size distribution of typical microporous molecular sieves (such as the pore diameter of the molecular sieve with MFI topological structure around 0.55nm) in the range of 0.4-0.7nm. In addition, there are also distributions in the range of 1.0-1.8nm. What needs to be specially explained here is that if the pore size distribution of micropores accounts for less than 1% of the total pore size distribution in the range of 1.0-1.8nm, the pore distribution of this part of the micropores is ignored, that is, it is considered to be between 1.0-1.8nm There is no micropore distribution in the nm range, which is well known to those skilled in the art. Therefore, the present invention has a micropore diameter in the range of 1.0-1.8nm under theN2 static adsorption test, which means that the ratio of the micropore diameter distribution in the range of 1.0-1.8nm to the total micropore diameter distribution is >1%. .
根据本发明，优选在0.4-0.7nm范围内的微孔孔径分布占总微孔孔径分布量的比例≤95％，在1.0-1.8nm范围内的微孔孔径分布占总微孔孔径分布量的比例≥5％；更优选的，在0.4-0.7nm范围内的微孔孔径分布占总微孔孔径分布量的比例≤90％，在1.0-1.8nm范围内的微孔孔径分布占总微孔孔径分布量的比例≥10％；最优选的，在0.4-0.7nm范围内的微孔孔径分布占总微孔孔径分布量的比例≤85％，在1.0-1.8nm范围内的微孔孔径分布占总微孔孔径分布量的比例≥15％，优选15-30％。本发明中，微孔孔径的测试方法为本领域技术人员所熟知，如采用N2静态吸附等方法测试。According to the present invention, it is preferred that the micropore size distribution in the range of 0.4-0.7nm accounts for the ratio of the total micropore size distribution less than or equal to 95%, and the micropore size distribution in the range of 1.0-1.8nm accounts for the proportion of the total micropore size distribution. Proportion ≥ 5%; more preferably, the proportion of micropore pore size distribution in the range of 0.4-0.7nm to the total micropore pore size distribution is ≤ 90%, and the proportion of micropore pore size distribution in the range of 1.0-1.8nm to the total micropore The proportion of the pore size distribution is ≥10%; most preferably, the proportion of the micropore pore size distribution in the range of 0.4-0.7nm to the total micropore pore size distribution is ≤85%, and the micropore size distribution in the range of 1.0-1.8nm The proportion of the total micropore size distribution is ≥15%, preferably 15-30%. In the present invention, the test method of micropore diameter is well known to those skilled in the art, such as usingN2 static adsorption and other methods for testing.
因此，根据本发明的含贵金属分子筛，优选1.0-1.8nm范围的微孔孔径占总微孔孔径分布量的比例≥10％，更优选≥15％，更优选1.0-1.8nm范围的微孔孔径分布占总微孔孔径分布量的比例15-30％。Therefore, according to the noble metal-containing molecular sieve of the present invention, the ratio of the micropore diameter in the range of 1.0-1.8nm to the total micropore diameter distribution is preferably ≥10%, more preferably ≥15%, and more preferably the micropore diameter in the range of 1.0-1.8nm The distribution accounts for 15-30% of the total micropore size distribution.
本发明中1.0-1.8nm范围的微孔孔径占总微孔孔径分布量的比例按如下公式计算：[1.0-1.8nm范围的微孔孔径的数量/(1.0-1.8nm范围的微孔孔径的数量)+(0.4-0.7nm范围内的微孔孔径的数量)]×100％。Among the present invention, the ratio of the micropore aperture in the 1.0-1.8nm range to the total micropore aperture distribution is calculated by the following formula: number)+(number of micropore diameters in the range of 0.4-0.7nm)]×100%.
根据本发明的含贵金属分子筛，优选硅元素：贵金属元素的摩尔比为100：(0.01-5)，更优选硅元素：贵金属元素的摩尔比为100：(0.02-2)，进一步优选硅元素：贵金属元素的摩尔比为100：(0.05-1)。According to the noble metal-containing molecular sieve of the present invention, the molar ratio of silicon element: noble metal element is preferably 100: (0.01-5), more preferably silicon element: the molar ratio of noble metal element is 100: (0.02-2), and further preferably silicon element: The molar ratio of noble metal elements is 100:(0.05-1).
根据本发明的含贵金属分子筛，还可以含有钛元素。优选以含贵金属分子筛的总重计，所述含贵金属分子筛中，钛元素的含量为0.01-5重量％，进一步优选为0.1-3重量％。The noble metal-containing molecular sieve according to the present invention may further contain titanium element. Preferably, based on the total weight of the noble metal-containing molecular sieve, the content of titanium element in the noble metal-containing molecular sieve is 0.01-5 wt%, more preferably 0.1-3 wt%.
本发明的前述含贵金属分子筛具有苯吸附量较高且具有1.0-1.8nm范围的微孔孔径分布等优势，本发明对前述含贵金属分子筛的制备方法无特殊要求，只要能够制备得到具有上述结构的含贵金属分子筛即可，根据本发明的一种优选的实施方式，本发明采用卸出剂制备前述含贵金属分子筛。The aforementioned noble metal-containing molecular sieve of the present invention has the advantages of high benzene adsorption capacity and micropore pore size distribution in the range of 1.0-1.8nm. Noble metal-containing molecular sieves are sufficient. According to a preferred embodiment of the present invention, the present invention uses a discharge agent to prepare the aforementioned noble metal-containing molecular sieves.
因此，如前所述，本发明提供了一种本发明所述的含贵金属分子筛的制备方法，该方法包括：Therefore, as previously mentioned, the present invention provides a preparation method of the noble metal-containing molecular sieve of the present invention, the method comprising:
(1)将卸出剂与酸溶液混合打浆，将得到的浆液进行第一热处理，分离得到第一固体，其中，所述卸出剂为以钛硅分子筛作为催化剂的反应装置的卸出剂；(1) mixing the unloading agent with the acid solution for beating, carrying out the first heat treatment on the obtained slurry, and separating and obtaining the first solid, wherein the unloading agent is the unloading agent of a reaction device using titanium-silicon molecular sieve as a catalyst;
(2)将所述第一固体、贵金属源与碱源在含水溶剂存在下混合后进行第二热处理。(2) The second heat treatment is performed after mixing the first solid, the noble metal source and the alkali source in the presence of an aqueous solvent.
本发明中，所述以钛硅分子筛作为催化剂的反应装置的卸出剂可以为从各种使用钛硅分子筛作为催化剂的装置中卸出的卸出剂，例如可以为从以钛硅分子筛作为催化剂的氧化反应装置中卸出的卸出剂。所述氧化反应可以为各种氧化反应，例如所述以钛硅分子筛作为催化剂的反应装置的卸出剂可以为氨肟化反应装置的卸出剂、羟基化反应装置的卸出剂和环氧化反应装置的卸出剂中的一种或多种，具体可以为环己酮氨肟化反应装置的卸出剂、苯酚羟基化反应装置的卸出剂和丙烯环氧化反应装置的卸出剂中的一种或多种，优选所述卸出剂为碱性环境下反应失活的催化剂，因此，针对本发明优选所述卸出剂为环己酮氨肟化反应装置的卸出剂(如失活的钛硅分子筛TS-1，粉状，粒径在100-500nm)。In the present invention, the unloading agent of the reaction device using titanium-silicon molecular sieve as the catalyst can be the unloading agent unloaded from various devices using titanium-silicon molecular sieve as the catalyst, for example, it can be from the catalyst using titanium-silicon molecular sieve The unloading agent discharged from the oxidation reaction device. The oxidation reaction can be various oxidation reactions, for example, the unloading agent of the reaction device using titanium silicon molecular sieve as a catalyst can be the unloading agent of the ammoximation reaction device, the unloading agent of the hydroxylation reaction device and epoxy One or more of the unloading agents of the reaction device for cyclohexanone ammoximation, specifically the discharge agent for the cyclohexanone ammoximation reaction device, the discharge agent for the phenol hydroxylation reaction device and the discharge agent for the propylene epoxidation reaction device One or more in the agent, preferably described unloading agent is the catalyzer of reaction deactivation under alkaline environment, therefore, preferably described unloading agent is the unloading agent of cyclohexanone ammoximation reaction device for the present invention (such as deactivated titanium-silicon molecular sieve TS-1, in powder form, with a particle size of 100-500nm).
本发明中，所述卸出剂是指采用溶剂洗涤或焙烧等常规再生方法无法使之活性恢复到初始活性50％的情况下的失活的催化剂(初始活性是指在相同的反应条件下，催化剂在1h之内的平均活性。如在实际环己酮肟化反应中，一般催化剂的初始活性要达到95％以上)。In the present invention, described unloading agent refers to the deactivated catalyst (initial activity refers to under the same reaction conditions, The average activity of the catalyst within 1 hour. As in the actual cyclohexanone oximation reaction, the initial activity of the general catalyst should reach more than 95%).
卸出剂的活性根据其来源而有所不同。一般地，卸出剂的活性可以为该钛硅分子筛在新鲜时的活性(即，新鲜剂的活性)的5-95％。优选地，卸出剂的活性可以为该钛硅分子筛在新鲜时的活性的50％以下，进一步优选卸出剂的活性可以为该钛硅分子筛在新鲜时的活性的10-40％。所述钛硅分子筛新鲜剂的活性一般为90％以上，通常为95％以上。The activity of the unloading agent varies according to its source. Generally, the activity of the unloading agent may be 5-95% of the activity of the titanium silicate molecular sieve when fresh (ie, the activity of the fresh agent). Preferably, the activity of the unloading agent can be less than 50% of the activity of the titanium-silicon molecular sieve when it is fresh, and more preferably, the activity of the unloading agent can be 10-40% of the activity of the titanium-silicon molecular sieve when it is fresh. The activity of the titanium-silicon molecular sieve fresh agent is generally above 90%, usually above 95%.
本发明中，所述卸出剂可以来源于工业失活剂或者在实验室中进行反应后的失活催化剂。In the present invention, the unloading agent may be derived from an industrial deactivator or a deactivated catalyst after a reaction in a laboratory.
当然，从制备效果的角度，本发明的方法也可以采用新鲜的钛硅分子筛作为原料，只是从成本控制等角度来说不会合适，本发明提供的方法，主要以失活的钛硅分子筛作为原料，变废为宝，从而节约了成本。Of course, from the perspective of preparation effect, the method of the present invention can also use fresh titanium-silicon molecular sieves as raw materials, but it will not be suitable from the perspectives of cost control and the like. The method provided by the invention mainly uses deactivated titanium-silicon molecular sieves as raw materials. Raw materials, turning waste into treasure, thus saving costs.
本发明中，各个装置的卸出剂采用各个装置的反应进行各自测定，只要保证，在相同的装置中，相同的反应条件下，卸出剂的活性低于新鲜催化剂的活性，即为本发明的卸出剂。如前所述，优选的情况下，卸出剂的活性低于新鲜催化剂的活性的50％。In the present invention, the unloading agent of each device adopts the reaction of each device to measure separately, as long as it is ensured that, in the same device, under the same reaction conditions, the activity of the unloading agent is lower than that of the fresh catalyst, which is the method of the present invention. unloading agent. As previously mentioned, it is preferred that the activity of the unloading agent is less than 50% of the activity of the fresh catalyst.
本发明中，以环己酮氨肟化反应装置的卸出剂为例，所述活性通过以下方法测定：Among the present invention, taking the unloading agent of cyclohexanone ammoximation reaction device as an example, the activity is measured by the following method:
取TS-1分子筛(按“Zeolites，1992，Vol.12：943～950”中所描述的方法制备，TiO2的质量百分含量为2.1％)置于100mL带连续进料和膜分离装置的淤浆床反应器内，在搅拌状态下以5.7mL/h的速度加入水和30wt％的过氧化氢的混合物(水与过氧化氢的体积比为10：9)，以10.5mL/h的速度加入环己酮和叔丁醇的混合物(环己酮和叔丁醇的体积比为1：2.5)，以5.7mL/h的速度加入36wt％氨水，上述三股物料流为同时加入，同时以相应的速度连续出料，反应温度维持在80℃，反应稳定后每隔1小时对产物取样用气相色谱法对液相的组成进行分析，采用以下公式计算环己酮的转化率并将其作为钛硅分子筛的活性。环己酮的转化率＝[(加入的环己酮的摩尔量-未反应的环己酮的摩尔量)/加入的环己酮的摩尔量]×100％。其中，以第1h的结果作为初始活性。Take TS-1 molecular sieve (prepared according to the method described in "Zeolites, 1992, Vol.12: 943-950", the mass percentage ofTiO2 is 2.1%) and place it in a 100mL tank with continuous feeding and membrane separation device. In the slurry bed reactor, a mixture of water and 30wt% hydrogen peroxide was added at a rate of 5.7mL/h under stirring (the volume ratio of water to hydrogen peroxide was 10:9), and at a rate of 10.5mL/h Speed adds the mixture of cyclohexanone and tert-butanol (the volume ratio of cyclohexanone and tert-butanol is 1:2.5), adds 36wt% ammoniacal liquor with the speed of 5.7mL/h, and above-mentioned three streams of material flow are to add simultaneously, simultaneously with The corresponding speed is continuously discharged, and the reaction temperature is maintained at 80 ° C. After the reaction is stable, the product is sampled every 1 hour and the composition of the liquid phase is analyzed by gas chromatography. The conversion rate of cyclohexanone is calculated by the following formula and used as Activity of titanium silicate molecular sieves. The conversion rate of cyclohexanone=[(the molar amount of cyclohexanone added-the molar amount of unreacted cyclohexanone)/the molar amount of cyclohexanone added]×100%. Among them, the result at 1h was taken as the initial activity.
根据本发明的方法，优选，步骤(2)按如下步骤进行：将贵金属源与碱源在含水溶剂存在下混合得到混合溶液，将所述混合溶液与所述第一固体混合后进行所述第二热处理。According to the method of the present invention, preferably, step (2) is carried out as follows: the noble metal source and the alkali source are mixed in the presence of an aqueous solvent to obtain a mixed solution, and the mixed solution is mixed with the first solid to perform the second step. Second heat treatment.
根据本发明的方法，优选所述打浆在常温常压下进行。According to the method of the present invention, preferably, the beating is carried out at normal temperature and pressure.
根据本发明的方法，无特殊说明的情况下，热处理一般是在密封的情况下在自生压力下进行。According to the method of the present invention, unless otherwise specified, heat treatment is generally carried out under autogenous pressure under the condition of sealing.
根据本发明的方法，优选第一热处理的温度为10-200℃，更优选为50-180℃，进一步优选为60-180℃。According to the method of the present invention, the temperature of the first heat treatment is preferably 10-200°C, more preferably 50-180°C, and even more preferably 60-180°C.
根据本发明的方法，所述第一热处理的时间可以依据需要进行确定，针对本发明，优选第一热处理的时间为0.5-36h，优选为1-24h，更优选为1-12h。According to the method of the present invention, the time of the first heat treatment can be determined according to needs. For the present invention, the time of the first heat treatment is preferably 0.5-36h, preferably 1-24h, more preferably 1-12h.
根据本发明的方法，优选第二热处理的温度为100-200℃，更优选为120-180℃，进一步优选为140-170℃。According to the method of the present invention, preferably the temperature of the second heat treatment is 100-200°C, more preferably 120-180°C, further preferably 140-170°C.
根据本发明的方法，优选所述第二热处理的时间可以依据需要进行确定，针对本发明，优选第二热处理的时间为0.5-24h，优选为2-24h，更优选为6-24h。According to the method of the present invention, preferably, the time of the second heat treatment can be determined according to needs. For the present invention, the time of the second heat treatment is preferably 0.5-24h, preferably 2-24h, more preferably 6-24h.
根据本发明的方法，优选本发明的方法还包括：在将卸出剂与酸溶液混合打浆前，先将所述卸出剂进行焙烧。According to the method of the present invention, preferably, the method of the present invention further includes: before mixing the discharge agent with the acid solution for beating, first roasting the release agent.
本发明中，所述焙烧的条件的可选范围较宽，针对本发明优选所述焙烧的条件包括：焙烧的温度为300-800℃，优选为550-600℃；焙烧的时间为2-12h，优选为2-4h，焙烧的气氛包括空气气氛；更优选所述焙烧的条件包括：首先在350-600℃于氮气气氛中焙烧0.5-6h，然后在350-600℃于空气气氛中焙烧0.5-12h。In the present invention, the optional range of the roasting conditions is relatively wide, and the preferred roasting conditions for the present invention include: the roasting temperature is 300-800°C, preferably 550-600°C; the roasting time is 2-12h , preferably 2-4h, the roasting atmosphere includes an air atmosphere; more preferably the roasting conditions include: first roasting in a nitrogen atmosphere at 350-600°C for 0.5-6h, and then roasting in an air atmosphere at 350-600°C for 0.5 -12h.
根据本发明的方法，优选所述酸溶液的浓度>0.1mol/L，更优选≥1mol/L，进一步优选2-15mol/L。本发明中，所述酸溶液的主要溶剂为水，也可依据需要加入其他溶剂助剂。如此制备得到的含贵金属分子筛其孔容、比表面积、苯吸附量及在1.0-1.8nm的微孔孔分布等的特征更明显。According to the method of the present invention, the concentration of the acid solution is preferably >0.1 mol/L, more preferably ≥1 mol/L, further preferably 2-15 mol/L. In the present invention, the main solvent of the acid solution is water, and other solvent additives can also be added as required. The characteristics of the precious metal-containing molecular sieve prepared in this way are more obvious, such as pore volume, specific surface area, benzene adsorption capacity, and micropore distribution of 1.0-1.8 nm.
根据本发明的方法，优选卸出剂、贵金属源、酸、碱源与水的质量比为100：(0.1-10)：(0.005-50)：(0.5-50)：(20-1000)，优选卸出剂、贵金属源、酸、碱源与水的质量比为100：(0.5-2.0)：(1-15)：(1-20)：(100-800)，卸出剂以SiO2计，酸以H+计，碱源以N或OH-计，更优选卸出剂与酸的质量比为100：(10-15)。According to the method of the present invention, the mass ratio of preferably unloading agent, precious metal source, acid, alkali source and water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), Preferably, the mass ratio of unloading agent, precious metal source, acid, alkali source and water is 100: (0.5-2.0): (1-15): (1-20): (100-800), and the unloading agent is SiO2 In terms of acid, in terms of H+ , in terms of alkali source, in terms of N orOH- , the mass ratio of unloading agent to acid is more preferably 100: (10-15).
本发明中，所述钛硅分子筛可以为常见的具有各种拓扑结构的钛硅分子筛，例如：所述钛硅分子筛可以选自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)和其它结构的钛硅分子筛(如Ti-ZSM-48)。In the present invention, the titanium-silicon molecular sieve can be a common titanium-silicon molecular sieve with various topological structures, for example: the titanium-silicon molecular sieve can be selected from a titanium-silicon molecular sieve with an MFI structure (such as TS-1), a titanium-silicon molecular sieve with a MEL structure Silicon molecular sieve (such as TS-2), titanium silicon molecular sieve with BEA structure (such as Ti-Beta), titanium silicon molecular sieve with MWW structure (such as Ti-MCM-22), titanium silicon molecular sieve with hexagonal structure (such as Ti-MCM-41 , Ti-SBA-15), titanium-silicon molecular sieves with MOR structure (such as Ti-MOR), titanium-silicon molecular sieves with TUN structure (such as Ti-TUN) and titanium-silicon molecular sieves with other structures (such as Ti-ZSM-48).
优选地，所述钛硅分子筛选自MFI结构的钛硅分子筛、MEL结构的钛硅分子筛和BEA结构的钛硅分子筛。更优选地，所述钛硅分子筛为MFI结构的钛硅分子筛，如TS-1分子筛。Preferably, the titanium-silicon molecular sieve is selected from titanium-silicon molecular sieves with MFI structure, titanium-silicon molecular sieves with MEL structure and titanium-silicon molecular sieves with BEA structure. More preferably, the titanium-silicon molecular sieve is a titanium-silicon molecular sieve with an MFI structure, such as TS-1 molecular sieve.
根据本发明的方法，所述酸的种类的可选范围较宽，其可以为有机酸和/或无机酸，优选为无机酸；其中，无机酸可以为HCl、硫酸、高氯酸、硝酸和磷酸中的一种或多种，优选为磷酸；所述有机酸可以为C1-C10的有机羧酸，优选为甲酸、乙酸、丙酸、环烷酸过氧乙酸和过氧丙酸中的一种或多种。According to the method of the present invention, the optional range of the kind of described acid is wider, and it can be organic acid and/or inorganic acid, is preferably inorganic acid; Wherein, inorganic acid can be HCl, sulfuric acid, perchloric acid, nitric acid and One or more of phosphoric acid, preferably phosphoric acid; the organic acid can be C1-C10 organic carboxylic acid, preferably one of formic acid, acetic acid, propionic acid, naphthenic acid peracetic acid and peroxypropionic acid one or more species.
根据本发明的方法，所述碱源的种类的可选范围较宽，其可以为有机碱源和/或无机碱源，其中，无机碱源可以为氨、或阳离子为碱金属或碱土金属的碱，如可以为氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、氢氧化钡等，所述有机碱源可以为尿素、脂肪族胺化合物、脂肪族醇胺化合物和季铵碱化合物中的一种或多种。According to the method of the present invention, the optional range of the type of the alkali source is relatively wide, and it can be an organic alkali source and/or an inorganic alkali source, wherein the inorganic alkali source can be ammonia or a cation that is an alkali metal or an alkaline earth metal Alkali, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, etc., the organic alkali source can be urea, aliphatic amine compounds, aliphatic alcohol amine compounds and quaternary ammonium One or more of alkali compounds.
本发明中，所述季铵碱可以为各种有机四级铵碱，所述脂肪族胺可以为各种NH3中的至少一个氢被脂肪族烃基(优选为烷基)取代后形成的化合物，所述脂肪族醇胺可以为各种NH3中的至少一个氢被含羟基的脂肪族烃基(优选为烷基)取代后形成的化合物。In the present invention, the quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be a compound formed after at least one hydrogen in various NH is replaced by an aliphatic hydrocarbon group (preferably an alkyl group) , the aliphatic alcohol amine can be a compound formed after at least one hydrogen in variousNH3 is replaced by a hydroxyl-containing aliphatic hydrocarbon group (preferably an alkyl group).
具体地，所述季铵碱可以为如式II所示的季铵碱，所述脂肪族胺可以为式III表示的脂肪族胺，所述脂肪族醇胺可以为如式IV表示的脂肪族醇胺：Specifically, the quaternary ammonium base may be a quaternary ammonium base as shown in formula II, the aliphatic amine may be an aliphatic amine represented by formula III, and the aliphatic alcohol amine may be an aliphatic amine represented by formula IV Alcoholamine:
式II中，R5、R6、R7和R8各自为C1-C4的烷基，包括C1-C4的直链烷基和C3-C4的支链烷基，例如：R5、R6、R7和R8各自可以为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基。In formula II, each of R5 , R6 , R7 and R8 is a C1 -C4 alkyl group, including a C1 -C4 straight chain alkyl group and a C3 -C4 branched chain alkyl group, for example : each of R5 , R6 , R7 and R8 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R9(NH2)n (式III)R9 (NH2 )n (formula III)
式III中，n为1或2的整数。n为1时，R9为C1～C6的烷基，包括C1～C6的直链烷基和C3-C6的支链烷基，如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、新戊基、异戊基、叔戊基和正己基。n为2时，R9为C1-C6的亚烷基，包括C1～C6的直链亚烷基和C3～C6的支链亚烷基，如亚甲基、亚乙基、亚正丙基、亚正丁基、亚正戊基或亚正己基。更优选脂肪族胺化合物为乙胺、正丁胺、丁二胺和己二胺中的一种或多种In formula III, n is an integer of 1 or 2. When n is 1, R9 is C1 -C6 alkyl, including C1 -C6 straight chain alkyl and C3 -C6 branched chain alkyl, such as methyl, ethyl, n-propyl , isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R9 is C1 -C6 alkylene, including C1 -C6 straight chain alkylene and C3 -C6 branched chain alkylene, such as methylene, ethylene , n-propylene, n-butylene, n-pentylene or n-hexylene. More preferably, the aliphatic amine compound is one or more of ethylamine, n-butylamine, butylenediamine and hexamethylenediamine
(HOR10)mNH(3-m) (式IV)(HOR10 )m NH(3-m) (Formula IV)
式IV中，m个R10相同或不同，各自为C1-C4的亚烷基，包括C1-C4的直链亚烷基和C3-C4的支链亚烷基，如亚甲基、亚乙基、亚正丙基和亚正丁基；m为1、2或3。更优选，所述脂肪族醇胺化合物为单乙醇胺、二乙醇胺和三乙醇胺中的一种或多种。In formula IV, m R10s are the same or different, and each is a C1 -C4 alkylene group, including a C1 -C4 straight chain alkylene group and a C3 -C4 branched chain alkylene group, such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. More preferably, the aliphatic alcohol amine compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
根据本发明的一种优选的实施方式，为了进一步提高合成得到的锡硅分子筛的孔道有序性，优选所述碱源为氢氧化钠、氨水、乙二胺、正丁胺、丁二胺、己二胺、单乙醇胺、二乙醇胺、三乙醇胺、四乙基氢氧化铵和四丙基氢氧化铵中的一种或多种。According to a preferred embodiment of the present invention, in order to further improve the pore order of the synthesized tin-silicon molecular sieve, preferably the alkali source is sodium hydroxide, ammonia water, ethylenediamine, n-butylamine, butylenediamine, One or more of hexamethylene diamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
其中，当所述碱源中含有氨水时，碱源的摩尔比以包括分子形式NH3和离子形式NH4+存在的氨计。Wherein, when the alkali source contains ammonia water, the molar ratio of the alkali source is based on ammonia in molecular form NH3 and ion form NH4+ .
根据本发明的方法，优选所述碱源以碱溶液的形式提供，更优选碱溶液的pH>9。According to the method of the present invention, preferably the alkali source is provided in the form of an alkali solution, more preferably the pH of the alkali solution is >9.
根据本发明的方法，优选所述贵金属源为贵金属的氧化物、贵金属的卤化物、贵金属的碳酸盐、贵金属的硝酸盐、贵金属的硝酸铵盐、贵金属的氯化氨盐、贵金属的氢氧化物和贵金属的络合物中的一种或多种，所述贵金属为Ru、Rh、Pd、Re、Os、Ir、Pt、Ag和Au中的一种或多种；优选所述贵金属为Pd、Ag、Au和/或Pt，以钯为例，所述贵金属源选自氧化钯、碳酸钯、氯化钯、硝酸钯、硝酸铵钯、氯化氨钯、乙酸钯、氢氧化钯、钯的络合物、醋酸钯和乙酰丙酮钯中的一种或多种。According to the method of the present invention, preferably the noble metal source is an oxide of a noble metal, a halide of a noble metal, a carbonate of a noble metal, a nitrate of a noble metal, an ammonium nitrate salt of a noble metal, an ammonium chloride salt of a noble metal, or a hydroxide of a noble metal One or more in complexes of compounds and noble metals, the noble metal being one or more of Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au; preferably the noble metal is Pd , Ag, Au and/or Pt, taking palladium as an example, the noble metal source is selected from palladium oxide, palladium carbonate, palladium chloride, palladium nitrate, palladium ammonium nitrate, ammonium chloride palladium, palladium acetate, palladium hydroxide, palladium One or more of complexes, palladium acetate and palladium acetylacetonate.
在本发明的一个更优选实施方式中，所述卸出剂与摩尔浓度>0.1mol/L的酸溶液混合打浆处理的过程是在酸溶液回流条件下进行，在此条件下得到的钛硅分子筛具有更明显的特有的物化特征。In a more preferred embodiment of the present invention, the process of mixing the unloading agent and the acid solution with a molar concentration>0.1mol/L for beating is carried out under the condition of reflux of the acid solution, and the titanium-silicon molecular sieve obtained under this condition It has more obvious specific physical and chemical characteristics.
根据本发明，优选本发明的方法还包括从步骤(2)热处理的物料中回收产物的步骤，回收产物的步骤为常规方法，为本领域的技术人员所熟悉，在此并无特别要求，一般是指产物过滤、洗涤、干燥和焙烧的过程。其中，所说的干燥过程可在室温-200℃之间的温度下进行，所说的焙烧过程可在300-800℃之间先在氮气气氛中0.5-6小时后在空气气氛中3-12小时进行。According to the present invention, preferably the method of the present invention also includes the step of recovering the product from the heat-treated material in step (2), the step of recovering the product is a conventional method, familiar to those skilled in the art, and there is no special requirement here, generally Refers to the process of product filtration, washing, drying and roasting. Wherein, said drying process can be carried out at a temperature between room temperature and 200°C, and said roasting process can be performed at 300-800°C in a nitrogen atmosphere for 0.5-6 hours and then in an air atmosphere for 3-12 hours. hours.
根据本发明的方法得到的含贵金属分子筛含有钛元素。优选以含贵金属分子筛的总重计，所述含贵金属分子筛中，钛元素的含量为0.01-5重量％，进一步优选为0.1-3重量％。The noble metal-containing molecular sieve obtained by the method of the present invention contains titanium element. Preferably, based on the total weight of the noble metal-containing molecular sieve, the content of titanium element in the noble metal-containing molecular sieve is 0.01-5 wt%, more preferably 0.1-3 wt%.
由于本发明分子筛材料和本发明方法得到的分子筛材料的苯吸附量较高且具有1.0-1.8nm范围的微孔孔径分布，在催化反应中有利于反应物和产物分子尤其对芳香族烃化合物、环类烃化合物、烯烃化合物等分子参与的催化氧化反应特别有利。Because the molecular sieve material of the present invention and the molecular sieve material obtained by the method of the present invention have a high benzene adsorption capacity and have a micropore pore size distribution in the range of 1.0-1.8nm, it is beneficial to the reactants and product molecules in the catalytic reaction, especially for aromatic hydrocarbon compounds, Catalytic oxidation reactions involving molecules such as cyclic hydrocarbon compounds and olefin compounds are particularly advantageous.
本发明还提供了本发明的含贵金属分子筛以及本发明方法得到的含贵金属分子筛在催化烃直接氧化反应中的应用。在氧化反应中，例如在丙烯环氧化制备环氧丙烷(PO)的反应中，反应产物PO的选择性和催化活性明显提高。The invention also provides the application of the noble metal-containing molecular sieve and the noble metal-containing molecular sieve obtained by the method in the catalytic hydrocarbon direct oxidation reaction. In oxidation reactions, such as the epoxidation of propylene to propylene oxide (PO), the selectivity and catalytic activity of the reaction product PO are significantly improved.
根据本发明的第四方面，本发明提供了一种烯烃直接氧化的方法，该方法包括：以甲醇为溶剂，将烯烃、含氧气体和催化剂接触，所述催化剂含有本发明所述的含贵金属分子筛和本发明所述的制备方法制备得到的含贵金属分子筛。According to the fourth aspect of the present invention, the present invention provides a method for direct oxidation of olefins, the method comprising: using methanol as a solvent, contacting olefins, oxygen-containing gas and a catalyst, the catalyst containing the noble metal-containing compound described in the present invention Molecular sieve and the noble metal-containing molecular sieve prepared by the preparation method of the present invention.
根据本发明的方法，所述接触的条件可以为本领域的常规选择，针对本发明，优选接触的条件包括：温度为0-80℃，压力为0.1-5.0MPa，时间0.1-24h，烯烃空速为0.1-100h-1，烯烃空速也即烯烃气体空速，即单位时间里通过单位催化剂的烯烃的体积的量。According to the method of the present invention, the conditions of the contact can be selected conventionally in this field. For the present invention, the preferred contact conditions include: temperature 0-80°C, pressure 0.1-5.0MPa, time 0.1-24h, olefin air The velocity is 0.1-100h-1 , and the olefin space velocity is also the olefin gas space velocity, that is, the volume of olefin passing through the unit catalyst per unit time.
更优选含氧气体中的氧气与烯烃的摩尔比0.1-10:1。More preferably, the molar ratio of oxygen to olefin in the oxygen-containing gas is 0.1-10:1.
烯烃的种类的可选范围较宽，例如可以为丙烯。The type of olefin can be selected from a wide range, for example, propylene may be used.
根据本发明的方法，所述含氧气体中除了含有氧气外，还可以含有氢气、氮气等气体，优选所述含氧气体中还含有氢气和氮气，优选氧气、氢气与氮气的摩尔比为0.1-10：0.1-10：0.5-100。即，优选烯烃、氧气、氢气与氮气的摩尔比为1:0.1-10：0.1-10：0.5-100。According to the method of the present invention, in addition to oxygen, the oxygen-containing gas may also contain hydrogen, nitrogen and other gases, preferably the oxygen-containing gas also contains hydrogen and nitrogen, preferably the molar ratio of oxygen, hydrogen and nitrogen is 0.1 -10: 0.1-10: 0.5-100. That is, the molar ratio of olefin, oxygen, hydrogen and nitrogen is preferably 1:0.1-10:0.1-10:0.5-100.
根据本发明的一种优选的实施方式，将0.05-2g(如0.5g)催化剂加入到含有1-500ml(如80ml)甲醇的反应容器中，按照摩尔比为1：0.1-10：0.1-10：0.5-100(如1:1:1:7)通入烯烃、氧气、氢气和氮气等稀释气体，在温度0-80℃(如60℃)，压力0.1-5.0MPa(如1.0MPa)，烯烃空速为0.1-100h-1(如10h-1)的条件下，进行烯烃直接氧化反应，反应时间0.1-24h(如2h)。According to a preferred embodiment of the present invention, 0.05-2g (such as 0.5g) of the catalyst is added to a reaction vessel containing 1-500ml (such as 80ml) of methanol, and the molar ratio is 1:0.1-10:0.1-10 : 0.5-100 (such as 1:1:1:7) into dilute gases such as olefins, oxygen, hydrogen and nitrogen, at a temperature of 0-80°C (such as 60°C), a pressure of 0.1-5.0MPa (such as 1.0MPa), Under the condition that the olefin space velocity is 0.1-100h-1 (such as 10h-1 ), the direct oxidation reaction of olefin is carried out, and the reaction time is 0.1-24h (such as 2h).
下面通过实施例对本发明作进一步说明，但并不因此限制本发明的内容。The present invention will be further described below by embodiment, but content of the present invention is not limited thereby.
对比例和实施例中，所用试剂均为市售的化学纯试剂。In comparative examples and examples, all reagents used are commercially available chemically pure reagents.
以下实施例和对比例的卸出剂按如下步骤得到，且采用以下方法测定钛硅分子筛(包括钛硅分子筛卸出剂，以及钛硅分子筛新鲜剂)的活性。The unloading agents of the following examples and comparative examples were obtained according to the following steps, and the activity of the titanium-silicon molecular sieve (including the unloading agent for the titanium-silicon molecular sieve and the fresh agent for the titanium-silicon molecular sieve) was determined by the following method.
取TS-1分子筛(按“Zeolites，1992，Vol.12：943～950”中所描述的方法制备，TiO2的质量百分含量为2.1％)置于100mL带连续进料和膜分离装置淤浆床反应器内，在搅拌状态下以5.7mL/h的速度加入水和30wt％的过氧化氢的混合物(水与过氧化氢的体积比为10：9)，以10.5mL/h的速度加入环己酮和叔丁醇的混合物(环己酮和叔丁醇的体积比为1：2.5)，以5.7mL/h的速度加入36wt％氨水，上述三股物料流为同时加入，同时以相应的速度连续出料，反应温度维持在80℃，反应稳定后每隔1小时对产物取样用气相色谱法对液相的组成进行分析，采用以下公式计算环己酮的转化率并将其作为钛硅分子筛的活性。环己酮的转化率＝[(加入的环己酮的摩尔量－未反应的环己酮的摩尔量)/加入的环己酮的摩尔量]×100％。Take TS-1 molecular sieve (prepared according to the method described in "Zeolites, 1992, Vol.12: 943～950", the mass percentage ofTiO2 is 2.1%) and place it in a 100mL sludge with continuous feeding and membrane separation device. In the slurry bed reactor, a mixture of water and 30wt% hydrogen peroxide was added at a rate of 5.7mL/h under stirring (the volume ratio of water to hydrogen peroxide was 10:9), and at a rate of 10.5mL/h Add the mixture of cyclohexanone and tert-butanol (the volume ratio of cyclohexanone and tert-butanol is 1:2.5), add 36wt% ammonia water at a speed of 5.7mL/h, the above-mentioned three streams of material flow are added simultaneously, and at the same time The speed of continuous discharge, the reaction temperature is maintained at 80 ° C, after the reaction is stable, the product is sampled every 1 hour to analyze the composition of the liquid phase by gas chromatography, and the conversion rate of cyclohexanone is calculated by the following formula and used as titanium Activity of silica molecular sieves. The conversion rate of cyclohexanone=[(the molar amount of cyclohexanone added−the molar amount of unreacted cyclohexanone)/the molar amount of cyclohexanone added]×100%.
第一次即第1h测定的环己酮转化率为其初始活性，其值为99.5％。经过一段时间约168小时，环己酮转化率由初始的99.5％下降到50％后，分离出催化剂后用焙烧再生方式再生(在570℃下于空气气氛中焙烧4小时)，然后继续用于环己酮氨肟化反应中，反复进行这一步骤，直至再生后的活性低于初始活性的50％，这时失活的氨肟化催化剂样品作为本发明的卸出剂，按照前述方法依次得到卸出剂SH-1(活性为50％)，SH-2(活性为40％)、SH-3(活性为25％)，SH-4(活性为10％)。The conversion rate of cyclohexanone measured for the first time at 1 h was 99.5% of its initial activity. After a period of about 168 hours, the conversion rate of cyclohexanone dropped from the initial 99.5% to 50%. After the catalyst was separated, it was regenerated by roasting regeneration (roasting in air atmosphere at 570 ° C for 4 hours), and then continued to be used for In the ammoximation reaction of cyclohexanone, this step is repeated until the activity after regeneration is lower than 50% of the initial activity. At this time, the deactivated ammoximation catalyst sample is used as the unloading agent of the present invention, followed by the aforementioned method The unloading agents SH-1 (50% active), SH-2 (40% active), SH-3 (25% active) and SH-4 (10% active) were obtained.
在各实施例和对比例中，样品的X-射线衍射(XRD)晶相图在SiemensD5005型X-射线衍射仪上进行测定，以样品与基准样品在2θ为22.5°-25.0°之间五指衍射特征峰的衍射强度(峰高)之和的比值来表示样品相对于基准样品的结晶度，这里以对比例1样品为基准样品，其结晶度计为100％，各样品的相对结晶度数据见表1。样品的苯吸附量、孔容、孔径分布、总比表面积和外比表面积在Micromeritics公司ASAP2405静态氮吸附仪上测定，具体数据见表1。样品的贵金属和硅等元素组成在日本理学电机株式会社3271E型X射线荧光光谱仪上测定，具体数据见表2。In each embodiment and comparative example, the X-ray diffraction (XRD) crystal phase figure of sample is measured on SiemensD5005 type X-ray diffractometer, is 22.5 °-25.0 ° between five-finger diffraction with sample and reference sample at 2θ The ratio of the sum of the diffraction intensities (peak heights) of the characteristic peaks represents the crystallinity of the sample relative to the reference sample. Here, the comparative example 1 sample is the reference sample, and its crystallinity meter is 100%. The relative crystallinity data of each sample is shown in Table 1. The benzene adsorption capacity, pore volume, pore size distribution, total specific surface area and external specific surface area of the samples were measured on the ASAP2405 static nitrogen adsorption instrument of Micromeritics Company, and the specific data are shown in Table 1. The composition of precious metals, silicon and other elements of the samples was measured on a Rigaku Electric Co., Ltd. 3271E X-ray fluorescence spectrometer, and the specific data are shown in Table 2.
对比例1Comparative example 1
本对比例说明常规利用硅酯为硅源水热晶化制备不含有贵金属的钛硅分子筛样品的过程。This comparative example illustrates the process of conventionally using silicon ester as a silicon source for hydrothermal crystallization to prepare a titanium-silicon molecular sieve sample that does not contain noble metals.
将正硅酸四乙酯、异丙醇钛与四丙基氢氧化铵混合，并加入适量蒸馏水搅拌混合，反应体系之中摩尔组成为正硅酸四乙酯：异丙醇钛：四丙基氢氧化铵：水＝100：5：10：200，其中正硅酸四乙酯以SiO2计；于常压及60℃下水解1.0h，再在75℃下搅拌3h，然后将混合液放入不锈钢密封反应釜，在170℃的温度下恒温放置3d，得到晶化产物的混合物；将此混合物过滤、用水洗涤，并于110℃干燥60min，得到分子筛原粉，并于550℃温度下焙烧3h，得水热直接晶化的钛硅分子筛，其XRD晶相为MFI结构。Mix tetraethyl orthosilicate, titanium isopropoxide and tetrapropyl ammonium hydroxide, and add an appropriate amount of distilled water to stir and mix. The molar composition of the reaction system is tetraethyl orthosilicate: titanium isopropoxide: tetrapropyl Ammonium hydroxide: water = 100: 5: 10: 200, of which tetraethyl orthosilicate is calculated as SiO2 ; hydrolyze at normal pressure and 60°C for 1.0h, then stir at 75°C for 3h, and then put the mixture Put it into a stainless steel sealed reaction kettle, and place it at a constant temperature at 170°C for 3 days to obtain a mixture of crystallized products; filter the mixture, wash with water, and dry at 110°C for 60 minutes to obtain molecular sieve powder, which is then roasted at 550°C After 3 hours, a hydrothermally directly crystallized titanium-silicon molecular sieve was obtained, and its XRD crystal phase was MFI structure.
对比例2Comparative example 2
本对比例说明常规利用硅酯为硅源水热晶化制备含有贵金属的钛硅分子筛样品的过程。This comparative example illustrates the process of conventionally using silicon ester as a silicon source for hydrothermal crystallization to prepare a titanium-silicon molecular sieve sample containing noble metals.
将正硅酸四乙酯、氯化钯、异丙醇钛与四丙基氢氧化铵混合，并加入适量蒸馏水搅拌混合，反应体系之中摩尔组成为正硅酸四乙酯：异丙醇钛：氯化钯：四丙基氢氧化铵：水＝100：5：2：10：200，其中正硅酸四乙酯以SiO2计；于常压及60℃下水解1.0h，再在75℃下搅拌3h，然后将混合液放入不锈钢密封反应釜，在170℃的温度下恒温放置3d，得到晶化产物的混合物；将此混合物过滤、用水洗涤，并于110℃干燥60min，得到分子筛原粉，并于550℃温度下焙烧3h，得水热直接晶化的钛硅分子筛，其XRD晶相图与对比例1一致为MFI结构。Mix tetraethyl orthosilicate, palladium chloride, titanium isopropoxide and tetrapropylammonium hydroxide, and add an appropriate amount of distilled water to stir and mix. The molar composition of the reaction system is tetraethyl orthosilicate: titanium isopropoxide : Palladium Chloride: Tetrapropylammonium Hydroxide: Water = 100:5:2:10:200, wherein Tetraethyl Orthosilicate is calculated as SiO2 ; Hydrolyze at normal pressure and 60°C for 1.0h, then at 75 Stir at ℃ for 3 hours, then put the mixture into a sealed stainless steel reaction vessel, and place it at a constant temperature at 170℃ for 3d to obtain a mixture of crystallized products; filter the mixture, wash with water, and dry at 110℃ for 60min to obtain molecular sieves raw powder, and calcined at 550° C. for 3 hours to obtain a hydrothermally directly crystallized titanium-silicon molecular sieve, whose XRD crystal phase diagram is consistent with that of Comparative Example 1, with an MFI structure.
对比例3Comparative example 3
本对比例说明利用对比例1制备的钛硅分子筛样品浸渍负载贵金属的过程。This comparative example illustrates the process of impregnating the loaded noble metal with the titanium-silicon molecular sieve sample prepared in Comparative Example 1.
将对比例1制备的钛硅分子筛与氯化钯水溶液混合，其中钛硅分子筛与氯化钯以及水的质量比例为10:2:25，于常压及60℃下搅拌6h，然后将此混合物过滤、用水洗涤，并于110℃干燥60min，并于550℃温度下焙烧3h，得负载有贵金属的钛硅分子筛，其XRD晶相为MFI结构。Mix the titanium-silicon molecular sieve prepared in Comparative Example 1 with an aqueous solution of palladium chloride, wherein the mass ratio of titanium-silicon molecular sieve to palladium chloride and water is 10:2:25, stir at normal pressure and 60°C for 6h, and then mix the mixture Filtrate, wash with water, dry at 110°C for 60 minutes, and bake at 550°C for 3 hours to obtain a titanium-silicon molecular sieve loaded with noble metals, whose XRD crystal phase is MFI structure.
对比例4Comparative example 4
本对比例说明利用卸出剂SH-2样品浸渍负载贵金属的过程。This comparative example illustrates the process of impregnating loaded precious metals with the unloading agent SH-2 sample.
将卸出剂SH-2与氯化钯水溶液混合，其中钛硅分子筛与氯化钯以及水的质量比例为10:0.5:10，于常压及40℃下搅拌12h，然后将此混合物过滤、用水洗涤，并于110℃干燥60min，并于550℃温度下焙烧3h，得负载有贵金属的钛硅分子筛，其XRD晶相为MFI结构。Mix the unloading agent SH-2 with palladium chloride aqueous solution, wherein the mass ratio of titanium silicon molecular sieve to palladium chloride and water is 10:0.5:10, stir at normal pressure and 40°C for 12h, then filter the mixture, Washing with water, drying at 110°C for 60 minutes, and calcining at 550°C for 3 hours to obtain a titanium-silicon molecular sieve loaded with precious metals, whose XRD crystal phase is MFI structure.
对比例5Comparative example 5
本对比例说明利用卸出剂SH-3浸渍负载贵金属的过程。This comparative example illustrates the process of impregnating loaded precious metals with the unloading agent SH-3.
将SH-3与氯化钯水溶液混合，其中钛硅分子筛与氯化钯以及水的质量比例为10:1:50，于常压及40℃下搅拌12h，然后将此混合物过滤、用水洗涤，并于110℃干燥60min，并于550℃温度下焙烧3h，得负载有贵金属的钛硅分子筛，其XRD晶相为MFI结构。Mix SH-3 with palladium chloride aqueous solution, wherein the mass ratio of titanium silicon molecular sieve to palladium chloride and water is 10:1:50, stir at normal pressure and 40°C for 12h, then filter the mixture and wash with water, And drying at 110°C for 60 minutes, and calcining at 550°C for 3 hours to obtain a titanium-silicon molecular sieve loaded with precious metals, whose XRD crystal phase is MFI structure.
对比例6Comparative example 6
本对比例说明利用卸出剂SH-4浸渍负载贵金属的过程。This comparative example illustrates the process of impregnating loaded precious metals with the unloading agent SH-4.
将SH-4与氯化钯水溶液混合，其中钛硅分子筛与氯化钯以及水的质量比例为10:2:20，于常压及50℃下搅拌3h，然后将此混合物过滤、用水洗涤，并于110℃干燥60min，并于550℃温度下焙烧3h，得负载有贵金属的钛硅材料，其XRD晶相为MFI结构。Mix SH-4 with palladium chloride aqueous solution, wherein the mass ratio of titanium silicon molecular sieve to palladium chloride and water is 10:2:20, stir at normal pressure and 50°C for 3h, then filter the mixture and wash with water, It was dried at 110°C for 60 minutes, and calcined at 550°C for 3 hours to obtain a titanium-silicon material loaded with noble metals, whose XRD crystal phase was MFI structure.
实施例1Example 1
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温(20℃，其余对比例和实施例相同)常压(0.1MPa，其余对比例和实施例相同)下，先将失活的环己酮肟化催化剂SH-2与1mol/L的盐酸水溶液混合打浆，接着将混合浆液在80℃下混合搅拌处理12h；固液分离后将固体、贵金属源氯化钯与氢氧化钠水溶液(pH为12)混合后将混合液放入不锈钢密封反应釜，在170℃下处理12h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：1：10：5：250，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以OH-计。将所得产物过滤、用水洗涤，并于110℃烘干120min，然后在550℃温度下焙烧3h，获得分子筛，其XRD晶相图与对比例1一致，说明得到的是具有MFI结构的钛硅分子筛。At normal temperature (20°C, the rest of the comparative examples are the same as the examples) and normal pressure (0.1MPa, the rest of the comparative examples are the same as the examples), the deactivated cyclohexanone oximation catalyst SH-2 and 1mol/L hydrochloric acid The aqueous solution is mixed and beaten, and then the mixed slurry is mixed and stirred at 80°C for 12 hours; after solid-liquid separation, the solid, precious metal source palladium chloride and sodium hydroxide aqueous solution (pH 12) are mixed, and the mixed solution is put into a stainless steel sealed reaction kettle , treated at 170°C for 12 hours, wherein, the mass composition of the material is deactivated cyclohexanone oxime catalyst: noble metal source: acid: alkali: water = 100:1:10:5:250, deactivated cyclohexanone oxime Catalysts are counted asSiO2 , acids are counted as H+ , and bases are counted asOH- . The obtained product was filtered, washed with water, dried at 110°C for 120 minutes, and then calcined at 550°C for 3 hours to obtain a molecular sieve, whose XRD crystal phase diagram was consistent with Comparative Example 1, indicating that the obtained was a titanium-silicon molecular sieve with an MFI structure .
对比例7Comparative example 7
本对比例说明利用卸出剂SH-2酸处理后浸渍负载贵金属的过程。This comparative example illustrates the process of impregnating loaded precious metals after treatment with the unloading agent SH-2 acid.
在常温常压下，先将失活的环己酮肟化催化剂SH-2与1mol/L的盐酸水溶液混合打浆，接着将混合浆液在80℃下混合搅拌处理12h；固液分离后得到酸处理的SH-2，然后将其与氯化钯水溶液混合，其中钛硅分子筛与氯化钯以及水的质量比例为10:2:20，于常压及50℃下搅拌3h，然后将此混合物过滤、用水洗涤，并于110℃干燥60min，并于550℃温度下焙烧3h，得负载有贵金属的钛硅材料，其XRD晶相为MFI结构。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-2 with 1mol/L hydrochloric acid aqueous solution for beating, and then mix and stir the mixed slurry at 80°C for 12 hours; after solid-liquid separation, acid treatment SH-2, and then mix it with palladium chloride aqueous solution, wherein the mass ratio of titanium silicon molecular sieve to palladium chloride and water is 10:2:20, stir at normal pressure and 50°C for 3h, and then filter the mixture 1. Washing with water, drying at 110°C for 60 minutes, and calcining at 550°C for 3 hours to obtain a titanium-silicon material loaded with noble metals, whose XRD crystal phase is MFI structure.
实施例2Example 2
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-3与5mol/L的盐酸溶液混合打浆，接着将混合浆液在60℃下混合搅拌处理1h；固液分离后将固体、贵金属源乙酰丙酮钯与四丙基氢氧化铵水溶液(pH为10)混合后将混合液放入不锈钢密封反应釜，在150℃下处理12h，其中物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：0.5：15：15：200，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以OH-计。然后按照实施例1的方法回收产物，获得含贵金属分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-3 with 5mol/L hydrochloric acid solution for beating, then mix and stir the mixed slurry at 60°C for 1 hour; after solid-liquid separation, separate the solid, The precious metal source palladium acetylacetonate and tetrapropyl ammonium hydroxide aqueous solution (pH 10) are mixed, and the mixture is put into a stainless steel sealed reaction kettle, and treated at 150°C for 12 hours, wherein the mass composition of the material is deactivated cyclohexanone oximation Catalyst: Noble metal source: acid: base: water = 100:0.5:15:15:200, deactivated cyclohexanone oximation catalyst is calculated asSiO2 , acid is calculated as H+ , base is calculated asOH- . Then the product was recovered according to the method of Example 1 to obtain a noble metal-containing molecular sieve, whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
实施例3Example 3
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，将失活的环己酮肟化催化剂SH-4与8mol/L的硝酸水溶液混合打浆，接着将混合浆液在100℃下混合搅拌处理2h；固液分离后将固体、贵金属源乙酸钯与乙二胺水溶液(pH为11)混合后将混合液放入不锈钢密封反应釜，在140℃下水热处理18h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：2：10：5：150，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以N计。然后按照实施例1的方法回收产物，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, mix the deactivated cyclohexanone oximation catalyst SH-4 with 8mol/L nitric acid aqueous solution for beating, then mix and stir the mixed slurry at 100°C for 2 hours; Source palladium acetate and ethylenediamine aqueous solution (pH 11) are mixed, and the mixed solution is put into a stainless steel sealed reactor, and hydrothermally treated at 140°C for 18 hours, wherein, the mass composition of the material is deactivated cyclohexanone oximation catalyst: precious metal source :acid:base:water=100:2:10:5:150, deactivated cyclohexanone oximation catalyst inSiO2 , acid in H+ , base in N. Then the product was recovered according to the method of Example 1 to obtain a molecular sieve whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
实施例4Example 4
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-1与5mol/L的硫酸水溶液混合打浆，接着将混合浆液在120℃下混合搅拌处理1h；固液分离后将固体、贵金属源氯化铂与正丁胺水溶液(pH为12.0)混合后将混合液放入不锈钢密封反应釜，在170℃下处理12h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：1：2：2：50，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以N计。将所得产物过滤、用水洗涤，并于110℃烘干120min，然后在550℃温度下焙烧3h，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-1 with 5mol/L sulfuric acid aqueous solution for beating, then mix and stir the mixed slurry at 120°C for 1 hour; after solid-liquid separation, separate the solid, The precious metal source platinum chloride is mixed with n-butylamine aqueous solution (pH is 12.0), and the mixed solution is put into a stainless steel sealed reactor, and treated at 170°C for 12 hours, wherein, the mass composition of the material is an inactivated cyclohexanone oximation catalyst: Noble metal source: acid: base: water = 100:1:2:2:50, the deactivated cyclohexanone oximation catalyst is calculated asSiO2 , the acid is calculated as H+ , and the base is calculated as N. The obtained product was filtered, washed with water, dried at 110° C. for 120 minutes, and then calcined at 550° C. for 3 hours to obtain a molecular sieve whose XRD crystal phase pattern was consistent with Comparative Example 1.
实施例5Example 5
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-2与2mol/L的高氯酸水溶液混合打浆，接着将混合浆液在70℃下混合搅拌处理5h；固液分离后将固体、贵金属源硝酸银与氨水(pH为11)混合后将混合液放入不锈钢密封反应釜，在170℃下处理12h，其中物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：1：5：20：100，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以N计。将所得产物过滤、用水洗涤，并于110℃烘干120min，然后在550℃温度下焙烧3h，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-2 with 2mol/L perchloric acid aqueous solution for beating, then mix and stir the mixed slurry at 70°C for 5 hours; after solid-liquid separation, Solid, precious metal source Silver nitrate and ammonia water (pH 11) are mixed, and the mixed solution is put into a stainless steel sealed reactor, and treated at 170°C for 12 hours, wherein the mass composition of the material is deactivated cyclohexanone oximation catalyst: precious metal source: Acid:base:water=100:1:5:20:100, the deactivated cyclohexanone oximation catalyst is calculated asSiO2 , the acid is calculated as H+ , and the base is calculated as N. The obtained product was filtered, washed with water, dried at 110° C. for 120 minutes, and then calcined at 550° C. for 3 hours to obtain a molecular sieve whose XRD crystal phase pattern was consistent with Comparative Example 1.
实施例6Example 6
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-2与12mol/L的乙酸水溶液混合打浆，接着将混合浆液在160℃下混合搅拌处理6h；固液分离后将固体、贵金属源氯化钯与二乙醇胺水溶液(pH为11)混合后将混合液放入不锈钢密封反应釜，在170℃下处理24h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：0.2：12：18：500，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以N计。然后按照实施例1的方法回收产物，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-2 with 12mol/L acetic acid aqueous solution for beating, then mix and stir the mixed slurry at 160°C for 6 hours; after solid-liquid separation, separate the solid, The precious metal source palladium chloride and diethanolamine aqueous solution (pH 11) are mixed, and the mixed solution is put into a stainless steel sealed reactor, and treated at 170°C for 24 hours, wherein, the mass composition of the material is deactivated cyclohexanone oximation catalyst: noble metal Source: acid: base: water = 100:0.2:12:18:500, deactivated cyclohexanone oximation catalyst inSiO2 , acid in H+ , base in N. Then the product was recovered according to the method of Example 1 to obtain a molecular sieve whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
实施例7Example 7
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-2与0.5mol/L的硫酸水溶液混合打浆，接着将混合浆液在130℃下混合搅拌处理4h；固液分离后将固体、贵金属源氯金酸与四乙基氢氧化铵水溶液(pH为11)混合后将混合液放入不锈钢密封反应釜，在170℃下处理12h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：1：1：1：800，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以OH-计。然后按照实施例1的方法回收产物，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-2 with 0.5mol/L sulfuric acid aqueous solution for beating, and then mix and stir the mixed slurry at 130°C for 4 hours; after solid-liquid separation, the solid 1. After mixing the precious metal source chloroauric acid and tetraethylammonium hydroxide aqueous solution (pH is 11), the mixed solution is put into a stainless steel sealed reaction kettle, and treated at 170° C. for 12 hours, wherein the quality of the material consists of deactivated cyclohexanone Oximation catalyst: noble metal source: acid: base: water = 100:1:1:1:800, deactivated cyclohexanone oximation catalyst is calculated asSiO2 , acid is calculated as H+ , and base is calculated asOH- . Then the product was recovered according to the method of Example 1 to obtain a molecular sieve whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
实施例8Example 8
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
在常温常压下，先将失活的环己酮肟化催化剂SH-2与15mol/L的磷酸水溶液混合打浆，接着将混合浆液在180℃下混合搅拌处理3h；固液分离后将固体、贵金属源乙酸铂与氢氧化钠水溶液(pH为14)混合后将混合液放入不锈钢密封反应釜，在150℃下处理6h，其中，物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：2：10：15：600，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以OH-计。然后按照实施例1的方法回收产物，获得分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-2 with 15mol/L phosphoric acid aqueous solution for beating, then mix and stir the mixed slurry at 180°C for 3 hours; after solid-liquid separation, separate the solid, The precious metal source platinum acetate is mixed with sodium hydroxide aqueous solution (pH 14), and the mixed solution is put into a stainless steel sealed reactor, and treated at 150°C for 6 hours, wherein, the mass composition of the material is deactivated cyclohexanone oximation catalyst: noble metal Source: acid: base: water = 100:2:10:15:600, deactivated cyclohexanone oximation catalyst inSiO2 , acid in H+ , base inOH- . Then the product was recovered according to the method of Example 1 to obtain a molecular sieve whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
实施例9Example 9
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例8的方法制备分子筛，不同的是物料质量组成中，失活的环己酮肟化催化剂：酸＝100：5，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 8, except that in the mass composition of materials, deactivated cyclohexanone oximation catalyst:acid=100:5, and the XRD crystal phase diagram of the obtained sample was consistent with Comparative Example 1.
实施例10Example 10
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例8的方法制备分子筛，不同的是物料质量组成中，失活的环己酮肟化催化剂：酸＝100：100，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 8, except that in the mass composition of materials, deactivated cyclohexanone oximation catalyst:acid=100:100, and the XRD crystal phase diagram of the obtained sample was consistent with Comparative Example 1.
实施例11Example 11
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例8的方法制备分子筛，不同的是磷酸水溶液的浓度为0.2mol/L，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 8, except that the concentration of the phosphoric acid aqueous solution was 0.2 mol/L, and the XRD crystal phase diagram of the obtained sample was consistent with Comparative Example 1.
实施例12Example 12
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例8的方法制备分子筛，不同的是，将卸出剂SH-2进行焙烧然后进行后续的打浆、热处理过程，其中，焙烧的条件包括：570℃下于空气气氛中焙烧4h，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 8, the difference was that the unloading agent SH-2 was roasted and then subjected to subsequent beating and heat treatment processes, wherein the roasting conditions included: roasting at 570°C for 4 hours in an air atmosphere, and the obtained sample The XRD crystal phase diagram is consistent with Comparative Example 1.
实施例13Example 13
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例8的方法制备分子筛，不同的是将失活的环己酮肟化催化剂SH-2与15mol/L的磷酸水溶液混合打浆得到的混合浆液在180℃下密闭静止处理3小时，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 8, except that the mixed slurry obtained by mixing the deactivated cyclohexanone oximation catalyst SH-2 and 15 mol/L phosphoric acid aqueous solution for beating was closed and statically treated at 180° C. for 3 hours, and the obtained sample The XRD crystal phase diagram is consistent with Comparative Example 1.
实施例14Example 14
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例2的方法制备分子筛，不同的是用磷酸替代HCl。所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 2, except that HCl was replaced by phosphoric acid. The XRD crystal phase diagram of the obtained sample is consistent with Comparative Example 1.
实施例15Example 15
本实施例说明本发明提供的方法和产品。This example illustrates the methods and products provided by the invention.
按照实施例2的方法制备分子筛，不同的是，将卸出剂SH-3进行焙烧然后进行后续的打浆、热处理过程，其中，焙烧的条件包括：570℃下于空气气氛中焙烧4h，所得样品的XRD晶相图与对比例1一致，所得样品的XRD晶相图与对比例1一致。Molecular sieves were prepared according to the method of Example 2, the difference was that the unloading agent SH-3 was roasted and then subjected to subsequent beating and heat treatment processes, wherein the roasting conditions included: roasting at 570°C for 4 hours in an air atmosphere, and the obtained sample The XRD crystal phase diagram of the obtained sample is consistent with Comparative Example 1, and the XRD crystal phase diagram of the obtained sample is consistent with Comparative Example 1.
实施例16Example 16
按照实施例2的方法制备分子筛，不同的是，使用的卸出剂为SH-1，其余条件均相同，所得样品的XRD晶相图与对比例1一致。The molecular sieve was prepared according to the method of Example 2, except that the unloading agent used was SH-1, and the rest of the conditions were the same, and the XRD crystal phase diagram of the obtained sample was consistent with Comparative Example 1.
实施例17Example 17
按照实施例2的方法制备分子筛，不同的是，原料加入顺序改变：Molecular sieves are prepared according to the method of Example 2, the difference is that the order of adding raw materials is changed:
在常温常压下，先将失活的环己酮肟化催化剂SH-3与5mol/L的盐酸溶液混合打浆，接着将混合浆液在60℃下混合搅拌处理1h，固液分离后得到固体，将贵金属源乙酰丙酮钯与四丙基氢氧化铵水溶液(pH为10)混合得到混合液，将固体、混合液混合后放入不锈钢密封反应釜，在150℃下处理12h，其中物料质量组成为失活的环己酮肟化催化剂：贵金属源：酸：碱：水＝100：0.5：15：15：200，失活的环己酮肟化催化剂以SiO2计，酸以H+计，碱以OH-计。然后按照实施例1的方法回收产物，获得含贵金属分子筛，其XRD晶相图与对比例1一致。At normal temperature and pressure, first mix the deactivated cyclohexanone oximation catalyst SH-3 with 5mol/L hydrochloric acid solution for beating, then mix and stir the mixed slurry at 60°C for 1 hour, and obtain a solid after solid-liquid separation. Mix the precious metal source palladium acetylacetonate and tetrapropylammonium hydroxide aqueous solution (pH 10) to obtain a mixed solution, mix the solid and the mixed solution and put them into a stainless steel sealed reaction kettle, and treat them at 150°C for 12 hours, wherein the mass composition of the materials is Deactivated cyclohexanone oximation catalyst: noble metal source: acid: base: water = 100:0.5:15:15:200, deactivated cyclohexanone oximation catalyst asSiO2 , acid as H+ , base Measured inOH- . Then the product was recovered according to the method of Example 1 to obtain a noble metal-containing molecular sieve, whose XRD crystal phase diagram was consistent with that of Comparative Example 1.
表1Table 1
从表1的结果可以看出：It can be seen from the results in Table 1 that:
本发明优选方法制备的含贵金属分子筛其孔容大于0.3cm3/g，苯吸附量大于65mg/g，总比表面积为200-450m2/g，其中，外表面积为30-150m2/g，且外表面积占总比表面积的比例在10％-35％之间；本发明优选方法制备的含贵金属分子筛其在1.0-1.8nm范围的微孔孔径占总微孔孔径分布量的比例为>5％。The precious metal-containing molecular sieve prepared by the preferred method of the present invention has a pore volume greater than 0.3 cm3 /g, a benzene adsorption capacity greater than 65 mg/g, and a total specific surface area of 200-450 m2 /g, wherein the outer surface area is 30-150 m2 /g, And the ratio of the outer surface area to the total specific surface area is between 10% and 35%; the ratio of the micropore diameter in the range of 1.0-1.8nm to the total micropore diameter distribution of the precious metal-containing molecular sieve prepared by the preferred method of the present invention is>5 %.
从表1的结果还可以看出：It can also be seen from the results in Table 1 that:
本发明优选方法制备的含贵金属分子筛其相对结晶度、孔容、总比表面积、外比表面积、1.0-1.8nm孔径分布、苯吸附量等数据完全满足本发明产品的全部特征。相对的，无论是对比例1利用硅酯为硅源制备的不含有贵金属的钛硅分子筛、对比例2利用硅酯为硅源制备的含有贵金属的钛硅分子筛、对比例3利用如对比例1制备的钛硅分子筛负载贵金属而制备的含有贵金属的钛硅分子筛，还是对比例4-6利用卸出剂负载贵金属得到的钛硅材料和对比例7卸出剂经酸处理后负载贵金属得到的钛硅材料，其相对结晶度、孔容、总比表面积、外比表面积、1.0-1.8nm孔径分布、苯吸附量等数据无法满足本发明产品的全部特征。如对比例1的分子筛其孔容只有0.264cm3/g，外表面积24m2/g，且外表面积占总比表面积的比例在5％左右。The relative crystallinity, pore volume, total specific surface area, external specific surface area, 1.0-1.8nm pore size distribution, benzene adsorption capacity and other data of the precious metal-containing molecular sieve prepared by the preferred method of the present invention fully meet all the characteristics of the product of the present invention. In contrast, whether it is the titanium-silicon molecular sieve that does not contain noble metals prepared by using silicon esters as the silicon source in Comparative Example 1, the titanium-silicon molecular sieves containing noble metals prepared by using silicon esters as the silicon source in Comparative Example 2, and Comparative Example 3 uses The prepared titanium-silicon molecular sieve loaded with noble metals is the titanium-silicon molecular sieve containing noble metals prepared, or the titanium-silicon material obtained by using the unloading agent to load noble metals in Comparative Example 4-6 and the titanium obtained by loading the unloading agent with noble metals after acid treatment in Comparative Example 7. Silicon material, its relative crystallinity, pore volume, total specific surface area, external specific surface area, 1.0-1.8nm pore size distribution, benzene adsorption and other data cannot meet all the characteristics of the product of the present invention. For example, the molecular sieve of Comparative Example 1 has a pore volume of only 0.264 cm3 /g, an external area of 24 m2 /g, and the ratio of the external area to the total specific surface area is about 5%.
测试实施例Test Example
将0.5g催化剂加入到含有50ml甲醇的密闭釜式反应器中，接着按照摩尔比为1:1:1:7的比例通入丙烯、氧气、氢气和氮气(稀释气体)，在温度50℃，压力1.5MPa，烯烃空速为10h-1的条件下，进行烯烃直接氧化反应。反应时间4h的丙烯转化率和PO选择性等结果见表2。其中，丙烯转化率和PO选择性按照如下公式计算：0.5g of catalyst was added into a closed tank reactor containing 50ml of methanol, followed by feeding propylene, oxygen, hydrogen and nitrogen (diluent gas) in a molar ratio of 1:1:1:7, at a temperature of 50°C, Under the conditions of pressure 1.5MPa and olefin space velocity of 10h-1 , the direct oxidation reaction of olefins is carried out. Table 2 shows the results of propylene conversion and PO selectivity at a reaction time of 4 hours. Wherein, propylene conversion rate and PO selectivity are calculated according to the following formula:
丙烯转化率＝(参与反应的丙烯的物质的量/总加入的丙烯的物质的量)*100％；Propylene conversion = (the amount of propylene involved in the reaction/the total amount of propylene added) * 100%;
PO选择性＝(反应生成的PO的物质的量/总产物的物质的量)*100％。PO selectivity=(substance amount of PO produced by reaction/substance amount of total product)*100%.
表2Table 2
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205639A (en)* | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | Modified with noble metals si molecular sieves and its preparation method and application and the method for producing hydrogen peroxide |
| CN110759358A (en)* | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Precious metal silicon molecular sieve and preparation method and application thereof |
| CN110872125A (en)* | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Iron-silicon molecular sieve, preparation method thereof and thioether oxidation method |
| CN111346664A (en)* | 2018-12-24 | 2020-06-30 | 中国石油化工股份有限公司 | Modified vanadium silicon molecular sieve and its preparation method and sulfide oxidation method |
| CN111482197A (en)* | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Iron vanadium molecular sieve and preparation method and application thereof, and method for preparing diphenol |
| CN112916039A (en)* | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and preparation and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4061724A (en)* | 1975-09-22 | 1977-12-06 | Union Carbide Corporation | Crystalline silica |
| CN103183355A (en)* | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN103183356A (en)* | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103896302A (en)* | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Silicon molecular sieve and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4061724A (en)* | 1975-09-22 | 1977-12-06 | Union Carbide Corporation | Crystalline silica |
| CN103183355A (en)* | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Precious metal modification method of titanium silicalite molecular sieve |
| CN103183356A (en)* | 2011-12-30 | 2013-07-03 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite molecular sieve by precious metal source |
| CN103896302A (en)* | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Silicon molecular sieve and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205639A (en)* | 2017-06-29 | 2019-01-15 | 中国石油化工股份有限公司 | Modified with noble metals si molecular sieves and its preparation method and application and the method for producing hydrogen peroxide |
| CN109205639B (en)* | 2017-06-29 | 2020-08-18 | 中国石油化工股份有限公司 | Noble metal modified silicon molecular sieve, preparation method and application thereof, and method for producing hydrogen peroxide |
| CN110759358A (en)* | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Precious metal silicon molecular sieve and preparation method and application thereof |
| CN110872125A (en)* | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Iron-silicon molecular sieve, preparation method thereof and thioether oxidation method |
| CN110872125B (en)* | 2018-08-29 | 2021-09-07 | 中国石油化工股份有限公司 | Iron-silicon molecular sieve and preparation method thereof and sulfide oxidation method |
| CN111346664A (en)* | 2018-12-24 | 2020-06-30 | 中国石油化工股份有限公司 | Modified vanadium silicon molecular sieve and its preparation method and sulfide oxidation method |
| CN111346664B (en)* | 2018-12-24 | 2022-11-15 | 中国石油化工股份有限公司 | Modified vanadium silicon molecular sieve, preparation method thereof, and sulfide oxidation method |
| CN111482197A (en)* | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Iron vanadium molecular sieve and preparation method and application thereof, and method for preparing diphenol |
| CN112916039A (en)* | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and preparation and application thereof |
| CN112916039B (en)* | 2019-12-06 | 2022-02-01 | 中国科学院大连化学物理研究所 | Gaseous hydrocarbon catalytic oxidation deoxidation Pt/Beta catalyst and preparation and application thereof |
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