Page 107 - 201811
P. 107

第 35 卷第 11 期                            精   细   化   工                                 Vol.35, No.11
             2018 年 11 月                             FINE CHEMICALS                                Nov.   2018


              催化与分离提纯技术
                      磷化镍的制备及其催化糠醛加氢制备环戊酮



                                                   1*
                                       1
                                                                              1
                                                                                           1
                                                                 2
                             王明远 ,冷一欣 ,黄春香 ,王   俊 ,韶   晖
                 (1.常州大学  石油化工学院,江苏  常州   213164;2.  江苏省先进催化与绿色制造协同创新中心  常州大
                 学,江苏  常州  213164)
                 摘要:以 NiCl 2 •6H 2 O 为镍源、NaH 2 PO 2 •H 2 O 为磷源、乙二醇为溶剂、n(P)∶n(Ni)=3∶1,采用溶剂热法制备得
                 到磷化镍(Ni-P)催化剂,并采用 XRD、SEM、TEM、H 2 -TPR、H 2 -TPD、N 2 吸附-脱附、XPS 对其进行了表征。
                 催化剂应用于糠醛加氢制备环戊酮的反应中效果良好,并考察了催化剂用量、氢气压力、反应温度、反应时间
                 对反应的影响。结果表明,较优的工艺条件为:以水作为溶剂,原料与催化剂质量比为 12,在反应温度 150 ℃、
                 氢气压力 2.0 MPa、反应时间 4 h 时,糠醛转化率达到 98.87%,环戊酮收率为 68.65%。对催化剂进行稳定性测
                 试,4 次重复使用后环戊酮收率仅下降 3.25%。
                 关键词:糠醛;加氢;环戊酮;Ni-P;催化技术
                 中图分类号:O643.3      文献标识码:A     文章编号:1003-5214 (2018) 11-1893-07


                    Preparation of Nickel Phosphide and Its Catalytic Hydrogenation of
                                            Furfural to Cyclopentanone


                                       1
                                                                                                  1
                                                     1*
                                                                          2
                                                                                      1
                      WANG Ming-yuan , LENG Yi-xin , HUANG Chun-xiang , WANG Jun , SHAO Hui
                 (1.  School of  Petrochemical Engineering, Changzhou University, Changzhou 213614, Jiangsu, China; 2.  Advanced
                 Catalysis and  Green Manufacturing Collaborative Innovation Center, Changzhou University, Changzhou  213164,
                 Jiangsu, China)
                 Abstract: Nickel phosphide (Ni-P) catalyst was prepared by a solvothermal method using ethylene glycol
                 as solvent, NiCl 2·6H 2O and NaH 2PO 2·H 2O as nickel source and phosphorous source respectively, where the
                 molar ratio of phosphorus to nickel was 3 : 1. The sample was characterized by XRD, SEM, TEM, H 2-TPR,
                 H 2-TPD, N 2 adsorption-desorption and XPS. The effects of dosage of catalyst, hydrogen pressure, reaction
                 temperature and  reaction time on the  hydrogenation of furfural to cyclopentanone  were evaluated. The
                 results showed that the optimal process conditions were: water as solvent, mass ratio of raw material to
                 catalyst 12, reaction temperature 150 ℃, hydrogen pressure 2.0 MPa and reaction time 4 h. Under these
                 conditions, the conversion  of  furfural and the yield  of cyclopentanone reached  98.87% and  68.65%,
                 respectively. In addition, the stability test of Ni-P was carried out. It was found that there was no obvious
                 decrease in the catalytic activity of the reused catalyst even after being recycled four times. The yield of
                 cyclopentanone decreased by only 3.25%.
                 Key words: furfural; hydrogenation; cyclopentanone; Ni-P; catalysis technology


                                                                               [6]
                 环戊酮具备很好的物理和化学性质,可用于农                          代替传统的己二酸 和环戊烯             [7-8] 等化石能源生产环
            药、医药、香料、电子           [1-3] 等行业,因而市场需求量             戊酮,不仅解决了化石能源的消耗问题,还可以有
                [4]
                                   [5]
            较大 。2012 年,Hronec 等在用 Pt/C 催化剂对糠                   效提高生物质能源的利用率。
                                                                                                         [9]
            醛催化加氢时发现了少量的环戊酮和环戊醇,通过                                 目前,对该工艺的报道相对较少,Hronec 等
            深入的研究后提出了利用糠醛为原料生产环戊酮的                             采用 Pd-Cu 负载于碳载体上作为催化剂,在氢气压
            工艺。该工艺采用生物质平台化合物糠醛作为原料                             力 3.0 MPa,转速 1500 r/min 下得到 92%的环戊酮


                 收稿日期:2017-11-02;  定用日期:2018-03-19; DOI: 10.13550/j.jxhg.20170896
                 作者简介:王明远(1993—),男,硕士生。联系人:冷一欣(1961—),女,教授,电话:0519-86330356,E-mail:lengyixin61@163.cm。
   102   103   104   105   106   107   108   109   110   111   112