The Preparation And Catalytic Performance Of Bi-metal Catalysts For The Selective Hydrogenation Of Furfural

The prosective chemicals such as:terahydrogurfuryl alcohol,2-methylfuran and 2-methyltetrahydrofuran,which are regarded as down-stream products of furfural,could be obtained directly by the hydrogenation of cheap and accessible furfural.Terahydrogurfuryl alcohol as an important chemical for excellent and environmental-friendly organic solvent and crude material,which can be produced by the total hydrogenation(HD)of furfural,has a wide application in the drug manufacturing,dyeing and coating industry.2-methylfuran and 2-methyltetrahydrofuran as the main products from the hydrodeoxygenation(HDO)of furfural are widely used in the rubber manufacturing industry and the synthesis of pharmaceutical intermediates.For example,2-methylfuran as raw material can be used to synthetize acetylpropyl alcohol,pentanediol,pentanedione and soon,which also can be employed to produce neuritis resistence chemicals VB1 and dysentery resistence drugs Chloroquine Phosphate and Primaquine Phosphate.Nowsday,Terahydrogurfuryl alcohol is mainly obtained by the hydrogenation of furfural and furfuryl alcohol by using noble metal,Raney Ni and after-modifiction catalysts,however the production of 2-methylfuran is the HDO of furfuryl alcohol and the production of 2-methyltetrahydrofuran is the HD of 2-methylfuran.Given the year production of furfural were huge and most of them were used as cheap export product in our courtry,the effective utilization rate of the chemical is very low,which constrainted the sustainable development of furfural industry.Therefore,the production of the three chemicals through the direct hydrogenation of furfural could have huge potential ecomonic vale,and the decelpoment of efficient?inexpensive and environmental-benign catalysts is the key and difficult points of techonology,which can make dramatic breakthoughs.The paper mainly studied the HDO and HD processing of furfural to the three chemicals.Firstly,to develop a catalyst for the total hydrogenation reation of furfural to terahydrogurfuryl alcohol,there are essentially two tasks in the catalysts filtering tasks.The catalysts are in preparation by screening out the active metal and supports.We choosed noble free metals(Ni,Co,Cu)as active metals and five mesoporous materials as supports(MCM-41,MCM-48,common SBA-15,short-channeled SBA-15 and foam-like MCF-2).And a series of monometal and bimetal loading catalysts are prepared,the internal standard method also is employed to quantitative analysis the target product.Meanwhile,the effect of techenological condition were also studied.Finally,we screened out the optimal catatyst:CAT-Ni/Co(0.67)-10,and lastly we got the most mild and optimum reaction conditions:2h,50bar,90 ? and the conversion of furfural arrived at 100%as well as the molar yiled of 92.1%for terahydrogurfuryl alcohol were achieved.And the catalyst also showed excellent recovery performance.Accoridng to the results of characteriaction,the short channeled SBA-15 had the best performance in the dispersion of metals and could effectively eliminate the negative influence of pore blockage.The syngeristic interaction of Ni0,CoO and NiCo2O4 were also found.Secondly,the study method of the HDO processing for furfural was the same as its HD processing.On the basis of the researching report of the previous chapter,Co was selected as first active metal whem common SBA-15 was used as support.Ni,Fe,Zn,Sn,Mo,Ag were selectively used as the second metal to develop bimtals catalysts.Several mesoporeous SiO2 materials with different microstructure[common SBA-15,foam-like MCF-2,SAl-X(X=10,20,40,60,100.)]were used as supports.The impact of reaction factors including solvent type,reaction temperature and reaction time were also studied.On the basis of the catalytic performance,SAl-00-1.5 could obtain the 83.6%yield of 2-methylfuran at 150?,3h,50bar;meanwhile,the catalyst S-CoAg-0.5 could achieve 2-methyltetrahydrofuran highest yield of 84.6%at 170°C,5h,50bar.The characterization results showed that Ag improved the dispersion of CoO:when the mole ratio number(Ag/Co)was set as 0.5,we noticed that the active metals displayed the zonal distribution.Howbeit,when the molar ratio of Ag/Co was 1.5,the metal particulars almost showed the dot-like distribution.3D and sponge-like SA1-100 was also in favor of the distribution of Ag0 and CoO.Above all,the conceerted catalytic effect of CoO and Ag0 was affirmed obviously.Although the bimetal Co-Ag catalysts showed execllect catalytic performance of the HDO of furfural,but Ag as noble metal increased the cost of the catalysts,which imposed restriction on their wide application.