CN104803856A - Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene - Google Patents
Method for synthesizing benzylamine through continuous catalytic hydrogenation of cyanobenzene Download PDFInfo
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 151
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
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- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 229940025084 amphetamine Drugs 0.000 description 2
- -1 amphetamine cephalosporin Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZBBHBTPTTSWHBA-UHFFFAOYSA-N Nicardipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OCCN(C)CC=2C=CC=CC=2)C1C1=CC=CC([N+]([O-])=O)=C1 ZBBHBTPTTSWHBA-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000003939 benzylamines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002327 cardiovascular agent Substances 0.000 description 1
- 229940125692 cardiovascular agent Drugs 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229960001783 nicardipine Drugs 0.000 description 1
- 235000019371 penicillin G benzathine Nutrition 0.000 description 1
- 229940056360 penicillin g Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- GWZBHIYSTKRISW-UHFFFAOYSA-N phenylmethanamine pyrimidine Chemical compound N1=CN=CC=C1.C(C1=CC=CC=C1)N GWZBHIYSTKRISW-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域 technical field
本发明涉及石油化工的工业催化领域，具体地说涉及一种苯甲腈连续催化加氢合成苄胺的方法。 The invention relates to the field of industrial catalysis in petrochemical industry, in particular to a method for synthesizing benzylamine by continuous catalytic hydrogenation of benzonitrile.
技术背景 technical background
苄胺是重要的有机化工原料和精细化工中间体，在医药工业中，苄胺可用于合成广谱抗菌素羟胺苄基青霉素、羟胺苄基头孢霉素、抗菌磺胺增效剂甲氧苄胺嘧啶、心血管药物尼卡地平及外用磺胺药物磺胺米隆等；在农药工业中，苄胺可用于合成新型高效低毒嘧啶水扬苄胺类除草剂；在表面活性剂工业中，苄胺用于合成阳离子表面活性剂 氯化烷基苄基二甲基铵；涂料工业中，苄胺衍生物还用于合成优良的环氧树脂固化剂等。 Benzylamine is an important organic chemical raw material and fine chemical intermediate. In the pharmaceutical industry, benzylamine can be used to synthesize broad-spectrum antibiotics amphetamine benzyl penicillin, amphetamine cephalosporin, antibacterial sulfa synergist trimethoprim, Cardiovascular drug nicardipine and topical sulfonamide drug sulfamepron, etc.; in the pesticide industry, benzylamine can be used to synthesize new high-efficiency and low-toxic pyrimidine benzylamine herbicides; in the surfactant industry, benzylamine is used to synthesize Cationic surfactant Alkylbenzyldimethylammonium chloride; in the coating industry, benzylamine derivatives are also used to synthesize excellent epoxy resin curing agents.
苄胺的主要生产方法包括氯苄加成法、氯苄氨解法、苯甲醛还原氨化法及苯甲腈催化加氢法。氯苄法具有工艺繁琐、设备腐蚀、收率低等缺点，而且由于原料中含氯，产品质量较差，国外已不再采用此工艺。苯甲醛还原氨化法虽然可以避免上述问题，但是反应压力较高，生产成本也高。相比之下，随着芳烃氨氧化技术的不断发展，苯甲腈的生产成本已大幅降低，使苯甲腈催化加氢法在技术、成本和产品质量上都有一定的优势。 The main production methods of benzylamine include benzyl chloride addition method, benzyl chloride ammonolysis method, benzaldehyde reductive amination method and benzonitrile catalytic hydrogenation method. The benzyl chloride method has the disadvantages of cumbersome process, equipment corrosion, low yield, etc., and because the raw material contains chlorine, the product quality is poor, and this process is no longer used abroad. Although the benzaldehyde reductive ammoniation method can avoid the above-mentioned problems, the reaction pressure is higher and the production cost is also high. In contrast, with the continuous development of aromatic hydrocarbon ammoxidation technology, the production cost of benzonitrile has been greatly reduced, so that the catalytic hydrogenation of benzonitrile has certain advantages in technology, cost and product quality.
专利US4163025公开了一种以骨架镍为主催化剂，锆和铂为助催化剂，在釜式反应器中催化加氢合成苄胺和二苄胺的方法。在反应温度为100 ℃，反应压力为1.1~1.5 MPa的条件下，苄胺的收率达到94.6%；专利US4503251公开了一种用于苯甲腈催化加氢的骨架镍催化剂，以网状结构的骨架镍合金为主催化剂，以钼、钛、钽、钌或铝为助催化剂的体系，在反应温度为175~200 ℃，反应压力为5.5~9.7 MPa的条件下，苄胺的最高收率为66.9%，此方法反应压力高，收率较低；专利CN1467197公开了一种以骨架镍为主催化剂，以硼、稀土金属镧和钨作为助催化剂的体系，在反应温度65 ℃，反应压力为5.0 MPa，乙醇为溶剂、溶剂与苯甲腈体积比为4︰1，反应时间为50 min的条件下，苯甲腈的转化率达到100%，苄胺的选择性为98.1%。 Patent US4163025 discloses a method for synthesizing benzylamine and dibenzylamine by catalytic hydrogenation in a tank reactor with framework nickel as the main catalyst and zirconium and platinum as cocatalysts. Under the condition of reaction temperature of 100 ℃ and reaction pressure of 1.1~1.5 MPa, the yield of benzylamine reaches 94.6%; patent US4503251 discloses a skeleton nickel catalyst for catalytic hydrogenation of benzonitrile, with a network structure The framework nickel alloy is the main catalyst, molybdenum, titanium, tantalum, ruthenium or aluminum as the cocatalyst system, under the conditions of reaction temperature 175~200 ℃, reaction pressure 5.5~9.7 MPa, the highest yield of benzylamine It is 66.9%, the reaction pressure of this method is high, and the yield is low; Patent CN1467197 discloses a kind of system with skeleton nickel as the main catalyst and boron, rare earth metal lanthanum and tungsten as co-catalysts. The conversion rate of benzonitrile reached 100% and the selectivity of benzylamine was 98.1% under the conditions of 5.0 MPa, ethanol as solvent, solvent to benzonitrile volume ratio of 4:1, and reaction time of 50 min.
上述苯甲腈催化加氢合成苄胺的方法均采用间歇釜式反应工艺，增加了后处理过程的复杂性，降低了生产效率。 The above-mentioned methods for synthesizing benzylamine by catalytic hydrogenation of benzonitrile all adopt a batch reaction process, which increases the complexity of the post-treatment process and reduces production efficiency.
有鉴于此，本案发明人特提出一种以苯甲腈为原料，采用固定床连续加氢反应工艺生产苄胺的方法。 In view of this, the inventor of the present case proposes a method for producing benzylamine using benzonitrile as a raw material and adopting a fixed-bed continuous hydrogenation reaction process.
发明内容 Contents of the invention
本发明的目的是公开一种以苯甲腈为原料，采用固定床连续加氢反应工艺生产苄胺的方法，克服了现有间歇釜式反应工艺中的不足。 The purpose of the present invention is to disclose a kind of benzyl nitrile is raw material, adopts the method for the production benzylamine of fixed-bed continuous hydrogenation reaction process, overcomes the deficiency in the existing batch reaction process.
本发明采用的催化剂为可用于固定床加氢工艺的骨架镍催化剂，具体为以铝镍合金（Ni40~50%）为骨架，合金表面经碱液加热处理后制得的骨架镍催化剂。 The catalyst used in the present invention is a skeleton nickel catalyst that can be used in a fixed-bed hydrogenation process, specifically a skeleton nickel catalyst that uses an aluminum-nickel alloy (Ni40-50%) as a skeleton, and the surface of the alloy is heated with lye.
采用固定床连续反应工艺实现苯甲腈的催化加氢合成苄胺的方法，按照下述步骤进行： Adopt the method for the catalytic hydrogenation synthesis benzylamine of benzonitrile that adopts fixed-bed continuous reaction technology to realize, carry out according to the following steps:
将一定量的骨架镍催化剂置于固定床反应器中，通入H2，加热至一定反应温度后，向反应器中通入预热的一定浓度的苯甲腈溶液，反应稳定后，接收产品。 Put a certain amount of skeletal nickel catalyst in a fixed bed reactor, feed H2 , heat to a certain reaction temperature, feed a preheated benzonitrile solution of a certain concentration into the reactor, and receive the product after the reaction is stable .
其中所述的反应温度为80~200 ℃。 Wherein said reaction temperature is 80～200 ℃.
其中所述的溶解苯甲腈的溶剂为C原子数为1~3的醇类化合物或醚类物质或它们的混合物，如甲醇、乙醇、四氢呋喃等； Wherein the solvent for dissolving benzonitrile is an alcohol compound or an ether substance or a mixture thereof, such as methanol, ethanol, tetrahydrofuran, etc., with 1 to 3 C atoms;
其中所述苯甲腈与溶剂的体积比为1∶1~10； Wherein the volume ratio of benzonitrile and solvent is 1: 1～10;
其中所述的反应压力为2.0~8.0 MPa； Wherein said reaction pressure is 2.0~8.0 MPa;
其中所述的液时空速为0.2~1.0 h-1； The liquid hourly space velocity mentioned therein is 0.2~1.0 h -1 ;
其中所述的氢气与苯甲腈的摩尔比为1~6∶1。 Wherein the molar ratio of hydrogen to benzonitrile is 1-6:1.
其特征在于其中所述的骨架镍催化剂，其制备方法参考专利CN101058526，催化剂粒径分布为1~3 mm，铝含量为23%。 It is characterized in that the skeleton nickel catalyst described therein, its preparation method refers to the patent CN101058526, the particle size distribution of the catalyst is 1-3 mm, and the aluminum content is 23%.
本发明以可用于固定床加氢工艺的骨架镍为催化剂，采用固定床连续催化加氢工艺实现苯甲腈的连续加氢反应合成苄胺，具有工艺流程简单，后处理方便等特点，有望在相关领域得到应用。 The present invention uses the skeleton nickel that can be used in the fixed bed hydrogenation process as a catalyst, adopts the fixed bed continuous catalytic hydrogenation process to realize the continuous hydrogenation reaction of benzonitrile to synthesize benzylamine, has the characteristics of simple process flow and convenient post-treatment, and is expected to be used in related fields have been applied.
附图说明 Description of drawings
图1是本发明的苯甲腈固定床连续催化加氢合成苄胺工艺的工艺流程示意图。 Fig. 1 is the process schematic diagram of the benzonitrile fixed-bed continuous catalytic hydrogenation synthesis benzylamine process of the present invention.
具体实施方式 Detailed ways
结合本发明具体工艺流程图1，下面通过实施例详细叙述本发明。 In conjunction with the specific process flow diagram 1 of the present invention, the present invention will be described in detail below through examples.
实施例1：在固定床反应器中装填20 mL骨架镍催化剂，通入氢气，流量为60 mL/min（氢气与苯甲腈的摩尔比为3︰1），压力为6.0 MPa，加热反应温度至160 ℃后，通入苯甲腈的乙醇溶液（苯甲腈与乙醇的体积比为1︰6），液时空速为0.6 h-1，反应稳定后，接收产品。产物分析采用内标法在科晓GC-1690气相色谱仪上完成。苯甲腈的转化率95.2%，苄胺的选择性为96.6%。 Example 1: Fill 20 mL of skeletal nickel catalyst in a fixed bed reactor, feed hydrogen, the flow rate is 60 mL/min (the molar ratio of hydrogen to benzonitrile is 3:1), the pressure is 6.0 MPa, and the reaction temperature is heated After reaching 160 ℃, pass through ethanol solution of benzonitrile (the volume ratio of benzonitrile to ethanol is 1:6), the liquid hourly space velocity is 0.6 h -1 , and the product is received after the reaction is stable. Product analysis was completed on a Kexiao GC-1690 gas chromatograph using the internal standard method. The conversion rate of benzonitrile is 95.2%, and the selectivity of benzylamine is 96.6%.
实施例2：按照实施例1中的步骤，只是反应条件中，反应温度为80 ℃，苯甲腈的转化率45.2%，苄胺的选择性为81.2%。 Embodiment 2: according to the step in embodiment 1, just in reaction condition, reaction temperature is 80 ℃, the conversion rate of benzonitrile is 45.2%, and the selectivity of benzylamine is 81.2%.
实施例3：按照实施例1中的步骤，只是反应条件中，反应温度为200 ℃，苯甲腈的转化率98.2%，苄胺的选择性为91.1%。 Embodiment 3: according to the step in embodiment 1, just in the reaction condition, reaction temperature is 200 ℃, the conversion rate of benzonitrile is 98.2%, and the selectivity of benzylamine is 91.1%.
实施例4：按照实施例1中的步骤，只是反应条件中，苯甲腈采用四氢呋喃稀释（苯甲腈与四氢呋喃的体积比为1︰6），苯甲腈的转化率92.3%，苄胺的选择性为93.6%。 Example 4: According to the steps in Example 1, except that in the reaction conditions, benzonitrile is diluted with tetrahydrofuran (the volume ratio of benzonitrile and tetrahydrofuran is 1:6), the conversion rate of benzonitrile is 92.3%, and that of benzylamine The selectivity is 93.6%.
实施例5：按照实施例1中的步骤，只是反应条件中，苯甲腈与乙醇的体积比为1∶1，苯甲腈的转化率52.6%，苄胺的选择性为73.5%。 Example 5: According to the steps in Example 1, only in the reaction conditions, the volume ratio of benzonitrile and ethanol is 1:1, the conversion rate of benzonitrile is 52.6%, and the selectivity of benzylamine is 73.5%.
实施例6：按照实施例1中的步骤，只是反应条件中，苯甲腈与溶剂乙醇的体积比为1∶10，苯甲腈的转化率94.3%，苄胺的选择性为93.5%。 Example 6: According to the steps in Example 1, only in the reaction conditions, the volume ratio of benzonitrile and solvent ethanol is 1: 10, the conversion rate of benzonitrile is 94.3%, and the selectivity of benzylamine is 93.5%.
实施例7：按照实施例1中的步骤，只是反应条件中，反应压力为2.0MPa，苯甲腈的转化率25.2%，苄胺的选择性为66.7%。 Example 7: According to the steps in Example 1, except that in the reaction conditions, the reaction pressure is 2.0 MPa, the conversion rate of benzonitrile is 25.2%, and the selectivity of benzylamine is 66.7%.
实施例8：按照实施例1中的步骤，只是反应条件中，反应压力为8.0MPa，苯甲腈的转化率95.6%，苄胺的选择性为96.9%。 Example 8: According to the steps in Example 1, except that in the reaction conditions, the reaction pressure is 8.0 MPa, the conversion rate of benzonitrile is 95.6%, and the selectivity of benzylamine is 96.9%.
实施例9：按照实施例1中的步骤，只是反应条件中，液时空速为0.2 h-1，苯甲腈的转化率97.2%，苄胺的选择性为96.7%。 Example 9: The steps in Example 1 were followed, except that in the reaction conditions, the liquid hourly space velocity was 0.2 h -1 , the conversion rate of benzonitrile was 97.2%, and the selectivity of benzylamine was 96.7%.
实施例10：按照实施例1中的步骤，只是反应条件中，液时空速为1.0 h-1，苯甲腈的转化率77.5%，苄胺的选择性为86.7%。 Example 10: The steps in Example 1 were followed, except that in the reaction conditions, the liquid hourly space velocity was 1.0 h -1 , the conversion rate of benzonitrile was 77.5%, and the selectivity of benzylamine was 86.7%.
实施例11：按照实施例1中的步骤，只是反应条件中，氢气流量为20 mL/min（氢气与苯甲腈的摩尔比为1︰1），苯甲腈的转化率57.0%，苄胺的选择性为76.8%。 Example 11: Follow the steps in Example 1, except that in the reaction conditions, the hydrogen flow rate is 20 mL/min (the molar ratio of hydrogen to benzonitrile is 1:1), the conversion rate of benzonitrile is 57.0%, and benzylamine The selectivity is 76.8%.
实施例12：按照实施例1中的步骤，只是反应条件中，氢气流量为120 mL/min（氢气与苯甲腈的摩尔比为6︰1），苯甲腈的转化率95.5%，苄胺的选择性为86.9%。 Example 12: According to the steps in Example 1, except that in the reaction conditions, the hydrogen flow rate is 120 mL/min (the molar ratio of hydrogen to benzonitrile is 6:1), the conversion rate of benzonitrile is 95.5%, and benzylamine The selectivity is 86.9%.
以上实例仅用于说明本发明的内容，除此之外，本发明还有其它实施方式。但是凡采用等同替换或等效变形方式形成的技术方案均落在本发明的保护范围内。 The above examples are only used to illustrate the content of the present invention, in addition, the present invention also has other implementations. However, all technical solutions formed by equivalent replacement or equivalent deformation fall within the protection scope of the present invention.
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