CN111729673A - Application of silica-based sulfonic acid in nitration of toluene - Google Patents
Application of silica-based sulfonic acid in nitration of toluene Download PDFInfo
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- CN111729673A CN111729673A CN202010570492.3A CN202010570492A CN111729673A CN 111729673 A CN111729673 A CN 111729673A CN 202010570492 A CN202010570492 A CN 202010570492A CN 111729673 A CN111729673 A CN 111729673A
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- toluene
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 21
- 238000006396 nitration reaction Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 230000000802 nitrating effect Effects 0.000 claims abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 3
- 239000000047 product Substances 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 12
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- -1 nitroxyl cation Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
一 技术领域a technical field
本发明涉及二氧化硅基磺酸在甲苯硝化反应中的应用的一种方法，属于化学材料制备技术领域。本方法适用于以甲苯为原料、硝酸为硝化剂、二氧化硅基磺酸为选择性催化剂，在常温常压下搅拌合成甲苯的一硝化产物的场合。The invention relates to a method for the application of silica-based sulfonic acid in toluene nitration reaction, and belongs to the technical field of chemical material preparation. The method is suitable for the occasion where toluene is used as raw material, nitric acid is used as nitrating agent, and silica-based sulfonic acid is used as selective catalyst, and the mononitration product of toluene is synthesized by stirring under normal temperature and pressure.
二 背景技术Two background technology
甲苯的硝化物是一类非常重要的化工产品，学术界和工业界都对芳香族化合物的硝化反应的方法和工艺进行了的研究，现有工艺采用一百年前沿用至今的硝-硫混酸硝化法来进行硝化反应，该法存在腐蚀严重，副产物较多以及三废污染严重等缺点(含能材料.2007，15(2)：122-124)。近年来，由于环境污染日益严重以及能源紧缺，节能减排成为人类面临的重要课题，芳香族化合物的清洁硝化成为人们研究的热点之一。Nitrate of toluene is a very important chemical product. Both the academic and industrial circles have carried out research on the method and process of the nitration reaction of aromatic compounds. The nitrification method is used to carry out the nitrification reaction. This method has the disadvantages of serious corrosion, many by-products and serious pollution of the three wastes (Energetic Materials. 2007, 15(2): 122-124). In recent years, due to the increasingly serious environmental pollution and energy shortage, energy conservation and emission reduction have become an important issue faced by mankind, and the clean nitrification of aromatic compounds has become one of the hotspots of research.
市场上对硝基甲苯的需求量远远大于邻、间硝基甲苯，但是，甲苯的硝化产物一般为邻、对、间位三种硝化产物的混合物，其中，邻硝基甲苯约为55～58％，间硝基甲苯为3～5％，对硝基甲苯为35～37％，对位产物和邻位产物的比例(p/o值)约为0.5～0.7，由于对位产物的应用范围、附加值高于邻位产物，因此，提高p/o值具有重要经济价值。The demand for p-nitrotoluene on the market is far greater than that of o- and m-nitrotoluene. However, the nitration product of toluene is generally a mixture of three kinds of nitration products: o-, p-, and m-nitrotoluene. Among them, o-nitrotoluene is about 55~ 58%, m-nitrotoluene is 3-5%, p-nitrotoluene is 35-37%, the ratio of para-product and ortho-product (p/o value) is about 0.5-0.7, due to the application of para-product The range and added value are higher than those of the vicinal products, therefore, improving the p/o value has important economic value.
三 发明内容Three Contents of the Invention
本发明的目的在于提供一种二氧化硅基磺酸在甲苯硝化反应中的应用方法，以可循环使用的二氧化硅基磺酸作为催化剂替代目前普遍使用的浓硫酸，产品与催化剂易分离、产品纯度高、产品的p/o值高的新的硝化反应的工艺。The object of the present invention is to provide a kind of application method of silica-based sulfonic acid in toluene nitration reaction, replace the currently commonly used concentrated sulfuric acid with recyclable silica-based sulfonic acid as catalyst, product and catalyst are easy to separate, A new nitration process with high product purity and high product p/o value.
实现本发明目的的技术解决方案为：二氧化硅基磺酸在甲苯硝化反应中的应用，即以无机硅胶和氯磺酸反应，通过硅胶中的羟基与氯磺酸中的氯脱去氯化氢形成氧桥键，得到的二氧化硅基磺酸为对位选择性催化剂，与质子酸催化机理类似，该催化剂可与硝酸作用生产硝酰阳离子，二氧化硅-磺酸根-硝酰阳离子三者之间可以通过氢键、静电引力等相互作用，硝酰阳离子周围的空间位阻不利于甲苯的邻位的进攻，而更多的是甲苯对位的进攻，因此，达到了提高产品的p/o值的目标。The technical solution for realizing the object of the present invention is: the application of silica-based sulfonic acid in the nitration reaction of toluene, that is, the reaction of inorganic silica gel and chlorosulfonic acid is carried out by removing hydrogen chloride from the hydroxyl group in the silica gel and the chlorine in the chlorosulfonic acid to form Oxygen bridge bond, the obtained silica-based sulfonic acid is a para-selective catalyst, similar to the catalytic mechanism of protic acid, the catalyst can react with nitric acid to produce nitroxyl cation, one of the three silica-sulfonate-nitroxyl cations The steric hindrance around the nitroxyl cation is not conducive to the attack of the ortho-position of toluene, but the attack of the para-position of toluene is more, so the p/o of the product can be improved. value of the target.
二氧化硅基磺酸催化剂具有如下的结构：The silica-based sulfonic acid catalyst has the following structure:
本发明所用物料的摩尔比为n(甲苯)∶n(硝酸)＝1∶1～1.5，催化剂用量为甲苯质量的1～10％，所述的物料与催化剂按照比例投料混合搅拌。The molar ratio of the material used in the present invention is n (toluene):n (nitric acid)=1:1～1.5, the catalyst dosage is 1～10% of the toluene quality, and the material and the catalyst are mixed and stirred according to the proportion.
本发明工艺的反应时间为1～2小时。The reaction time of the process of the present invention is 1 to 2 hours.
本发明所用的硝酸的浓度为90～98％。The concentration of nitric acid used in the present invention is 90-98%.
本发明反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，常压或减压精馏后得到精制的邻位、对位的一硝化产物；水相为含有少量水的硝酸，经硝酸镁吸收水分浓缩后，硝酸质量百分比浓度不低于90％，可以回收使用；分离出来的固体催化剂经脱水干燥后可以循环使用，按前一批次的n(甲苯)∶n(硝酸)的比例投料进行下一批合成反应。After the reaction of the present invention is completed, it is left to stand and then suction filtered, and the filtrate is divided into a liquid-liquid two-phase system of an oil phase and an aqueous phase. After distillation, the refined ortho- and para-nitrated products are obtained; the water phase is nitric acid containing a small amount of water, and after absorbing water and concentrating through magnesium nitrate, the mass percentage concentration of nitric acid is not less than 90%, which can be recycled; the separated solid The catalyst can be recycled after being dehydrated and dried, and the next batch of synthesis reaction is carried out according to the ratio of n (toluene):n (nitric acid) of the previous batch.
本发明所依据的化学反应式如下：The chemical reaction formula on which the present invention is based is as follows:
依据本发明提供的一种二氧化硅基磺酸在甲苯硝化反应中提高的应用的新方法，其技术关键是采用二氧化硅基磺酸对位选择性催化甲苯与硝酸进行硝化反应得到甲苯的硝化产物，提高产品的p/o值。本发明与现有技术相比，其优点为：(1)采用二氧化硅基磺酸催化剂，原料来源广泛，制备方便；对水稳定，催化剂不失活，可循环使用；(2)二氧化硅基磺酸催化活性高、用量少，回收方便；(3)甲苯硝化产物的p/o值为1.6，比传统的混酸工艺的p/o值提高了约2～3倍，大大提高了产品的附加值和产值；(4)用二氧化硅基磺酸代替硝/硫混酸工艺中的浓硫酸，反应后的硝酸只含有少量水，回收再利用方便，解决了混酸工艺中硝酸、硫酸无法分离回收使用的难题，安全可靠、环境友好，具有工业化应用前景。According to a new method for improving the application of silica-based sulfonic acid in toluene nitration reaction provided by the present invention, the technical key is to adopt the para-selective catalyst of silica-based sulfonic acid to catalyze the nitration reaction of toluene and nitric acid to obtain toluene. Nitrate the product to increase the p/o value of the product. Compared with the prior art, the present invention has the following advantages: (1) using a silica-based sulfonic acid catalyst, the source of raw materials is wide, and the preparation is convenient; it is stable to water, the catalyst is not deactivated, and can be recycled; (2) dioxide dioxide Silicon-based sulfonic acid has high catalytic activity, less dosage, and is easy to recover; (3) the p/o value of the toluene nitration product is 1.6, which is about 2-3 times higher than that of the traditional mixed acid process, which greatly improves the The added value and output value of the product; (4) use silica-based sulfonic acid to replace the concentrated sulfuric acid in the nitric/sulfur mixed acid process, the nitric acid after the reaction only contains a small amount of water, and it is convenient to recycle and reuse, which solves the problem of nitric acid and sulfuric acid in the mixed acid process. It is safe, reliable, environmentally friendly, and has industrial application prospects.
四 具体实施方式Four specific implementations
下面的实施例对本发明做进一步说明，其目的是能够更好理解本发明的内容。但是实施例不以任何方式限制本发明的范围。本专业领域的技术人员在本发明权利要求范围内做出的改进和调整也应属于本发明的权利和保护范围。The following examples further illustrate the present invention, and its purpose is to better understand the content of the present invention. However, the examples do not limit the scope of the invention in any way. Improvements and adjustments made by those skilled in the art within the scope of the claims of the present invention should also belong to the right and protection scope of the present invention.
实施例1Example 1
催化剂二氧化硅基磺酸的制备：在100mL圆底烧瓶中，依次加入0.1mol(6g)无机硅胶，30mL二氯甲烷，常温常压搅拌下，缓慢滴加氯磺酸0.1mol(11.6g)，滴加完毕后继续搅拌0.5小时，过滤分离、乙醚洗涤、真空干燥得到二氧化硅基磺酸催化剂，产率约95％。Preparation of catalyst silica-based sulfonic acid: In a 100 mL round-bottomed flask, 0.1 mol (6 g) of inorganic silica gel and 30 mL of dichloromethane were sequentially added, and 0.1 mol (11.6 g) of chlorosulfonic acid was slowly added dropwise under stirring at normal temperature and pressure. , continue to stir for 0.5 hours after the dropwise addition, filter separation, wash with ether, and vacuum dry to obtain a silica-based sulfonic acid catalyst with a yield of about 95%.
实施例2Example 2
在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.1mol(7g)90％硝酸，0.092g的催化剂，于常温常压条件下混合搅拌2小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约90％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。水相为含有少量水的硝酸，加入硝酸镁吸收水分，浓缩后硝酸质量百分比浓度为90％便可以回收使用；抽滤分离出来的固体催化剂经脱水干燥后可以循环使用。In a 50mL round-bottomed flask, add 0.1mol (9.2g) toluene, 0.1mol (7g) 90% nitric acid, and 0.092g catalyst in sequence, mix and stir for 2 hours under normal temperature and pressure conditions, after the reaction is completed, stand and filter with suction , the filtrate is divided into a liquid-liquid two-phase system of oil phase and water phase, and the oil phase is washed, neutralized and dewatered by vacuum to obtain a mononitrated product with a yield of about 90%. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6. The water phase is nitric acid containing a small amount of water. Magnesium nitrate is added to absorb water. After concentration, the nitric acid can be recycled when the concentration is 90%. The solid catalyst separated by suction filtration can be recycled after being dehydrated and dried.
实施例3Example 3
在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.15mol(10.5g)90％硝酸，0.92g的催化剂，于常温常压条件下混合搅拌1小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约85％。常压精馏，分别收集221～222℃和238～239℃的产物，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。In a 50mL round-bottomed flask, add 0.1mol (9.2g) toluene, 0.15mol (10.5g) 90% nitric acid, and 0.92g catalyst in sequence, mix and stir for 1 hour under normal temperature and pressure conditions, after the reaction is completed, stand and pump Filtration, the filtrate is divided into a liquid-liquid two-phase system of oil phase and water phase, and the oil phase is washed, neutralized and dewatered by vacuum to obtain a mononitrated product with a yield of about 85%. Atmospheric rectification, the products at 221-222°C and 238-239°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o-products was 1.6.
实施例4Example 4
在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.1mol(6.7g)95％硝酸，0.45g的催化剂，于常温常压条件下混合搅拌1.5小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约88％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。In a 50mL round-bottomed flask, add 0.1mol (9.2g) toluene, 0.1mol (6.7g) 95% nitric acid, and 0.45g catalyst in sequence, mix and stir at normal temperature and pressure for 1.5 hours, after the reaction is completed, stand and pump Filtration, the filtrate is divided into a liquid-liquid two-phase system of oil phase and water phase, and the oil phase is washed, neutralized and dewatered by vacuum to obtain a mononitrated product with a yield of about 88%. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6.
实施例5Example 5
在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.12mol(8.4g)90％硝酸，0.35g的催化剂，于常温常压条件下混合搅拌1.5小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约90％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。In a 50mL round-bottomed flask, add 0.1mol (9.2g) toluene, 0.12mol (8.4g) 90% nitric acid, and 0.35g catalyst in sequence, mix and stir for 1.5 hours under normal temperature and pressure conditions, after the reaction is completed, stand and pump Filtration, the filtrate is divided into a liquid-liquid two-phase system of oil phase and water phase, and the oil phase is washed, neutralized and dewatered by vacuum to obtain a mononitrated product with a yield of about 90%. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6.
实施例6Example 6
在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.1mol(6.8g)98％硝酸，0.092g的催化剂，于常温常压条件下混合搅拌1小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约87％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。In a 50mL round-bottomed flask, add 0.1mol (9.2g) toluene, 0.1mol (6.8g) 98% nitric acid, and 0.092g catalyst in sequence, mix and stir for 1 hour under normal temperature and pressure conditions, after the reaction is completed, stand and pump Filtration, the filtrate is divided into a liquid-liquid two-phase system of oil phase and water phase, and the oil phase is washed, neutralized and dewatered by vacuum to obtain a mononitrated product with a yield of about 87%. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6.
实施例7Example 7
在250mL圆底烧瓶中，依次加入1mol(92g)甲苯，1mol(70g)90％硝酸，2.8g的催化剂，于常温常压条件下混合搅拌1小时，反应完毕后静置后抽滤，滤液分为油相、水相的液-液两相体系，油相经过洗涤、中和、真空除水后得到一硝化产物，产率约89％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。In a 250mL round-bottomed flask, add 1mol (92g) toluene, 1mol (70g) 90% nitric acid, and 2.8g catalyst in sequence, mix and stir for 1 hour under normal temperature and pressure conditions, after the reaction is completed, stand and filter with suction. It is a liquid-liquid two-phase system of oil phase and water phase. After the oil phase is washed, neutralized and dewatered by vacuum, a mononitrated product is obtained, and the yield is about 89%. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6.
实施例8Example 8
在实施例2反应结束后，过滤分离回收得到的催化剂经二氯甲烷洗涤、负压(4kPa)50℃干燥2小时后可以再生利用：在50mL圆底烧瓶中，依次加入0.1mol(9.2g)甲苯，0.1mol(7g)90％回收的硝酸，0.092g回收的催化剂，于常温常压条件下混合搅拌1小时，反应完毕后静置后抽滤，滤液经过洗涤、中和、真空除水后得到一硝化产物，产率约90％。减压精馏(4kPa)，分别收集124.5～125.5℃和139.5～140.4℃的馏分，得到邻硝基甲苯和对硝基甲苯，对/邻产物的p/o值为1.6。After the reaction in Example 2, the catalyst obtained by filtration, separation and recovery was washed with dichloromethane, dried at 50°C under negative pressure (4kPa) for 2 hours and then regenerated: in a 50mL round-bottomed flask, 0.1mol (9.2g) was added in turn. Toluene, 0.1mol (7g) of 90% recovered nitric acid, and 0.092g of recovered catalyst were mixed and stirred for 1 hour under normal temperature and pressure conditions. After the reaction was completed, it was allowed to stand for suction filtration. The filtrate was washed, neutralized, and dewatered by vacuum. The mononitrated product was obtained in about 90% yield. Under vacuum distillation (4kPa), the fractions at 124.5-125.5°C and 139.5-140.4°C were collected respectively to obtain o-nitrotoluene and p-nitrotoluene, and the p/o value of p/o products was 1.6.
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