通过Hβ分子筛上的烯烃水合反应提高FCC汽油品质

第26卷第6期催化学报2005年6月Vol. 26 No. 6Chinese Journal of CatalysisJune 2005Article ID :0253-983X 2005 )6-0451-02Connmunication :451 -~452Up-Grading of FCC Gasoline by Olefin Hydration over耶ZeoliteWANG Hua , HUANG Tao ,DU Juan , LIU Zhongmin( Natural Gas Utilization and Applied Catalysis Laboratory , Dalian Institute of Chemical Physics ,The Chinese Academy of 'Sciences , Dalian 116023 , Liaoning , China )Key words : olefin , hydration , FCC gasoline , up grading , H zeoliteCLC number :O643/TQ53Document code :AThe large increase in automobiles and the greatlyformed under 5.0 MPa , WHSV=1 h-1 and 100 ~increased consumption of fuel has caused very serious170 C conditions for 10 h. The effluent was collectedair pollution from the emissionof tail gas 11. Govern-in a chilled flask containing 5 g acetone to dissolvements all over the world have regulated new standardsboth the aqueous and organic phase products , and thefor the components of gasoline. Decreasing themixtures were analyzed by a Varian CP 3800 gasolefins, limiting the aromatics , and increasing thechromatograph equipped with an FFAP capillary col-oxygenates in gasoline are the general requirements.umn( 25 m ) and an FID detector. Benzene , which isApproximately 80% of the gasoline used in our coun-inert in the hydration reaction , was used as the inter-try comes from fluidized catalytic cracking( FCC ).nal standard. To simplify the calculation , the re-The gasoline produced by a conventional FCC processsponse factor of tert -pentyl alcohol , the major hydra-contains more than 45% olefins , which is greatly intion product , was taken as the response factor of allexcess of the standard that will become effective( thethe oxygenate products. The conversion was calculat-permitted content of olefins in the new standard ised based on the olefins in the gasoline.35%[2]). To meet the requirements of the new stan-Table 1 Composition of light FCC gasoline( ≤80 C )dard , several technologies have been developed , suchCompositionw/%φ/%as the optimization of the FCC process by using newOlefin43.643.445.4FCC catalysts 3] , hydrogenatiorf 3] , isomerization and1.3aromatizatiortThese methods focus on decreas-Cycloparaffin42.143.140.8ing the olefins. The hydration of the light fraction ofn-Prffin5.75.3FCC gasoline can provide a way to increase oxygenatei-Paraffin4.84. 9content and reduce olefin content at the same time.Others2.52.4Moreover , the process of olefin hydration possesses aThe gasoline was analyzed with DHA software on a Varanhigh atom economy. The aim of this work is to up-CP-3800 gas chromatograph equipped with a PONA cpillarycolumn( 100 mx0.25 mm ).grade FCC gasoline by hydration of olefins over Hβzeolite.Fig 1 shows the effect of the water/oil ratio onThe composition of the light FCC gasolin( ≤80olefin hydration over Hβ zeolite. It can be seen thatC )is listed in Table 1. β zeolite with n( si)n( Al)=Hβ is an effective catalyst for hydration of olefin in46.2 was obtained from Fushun Petrochemical Com-FCC gasoline and gave a dramatic decrease of thepany. The zeolite was first ion. exchanged to the am-olefins. In all the cases investigated , the concentra-monium form by treatment with 0.1 mol/L NHNO3tion of polymerization products in the bulk liquid re-solution and then calcined at 550 C for 3 h to obtainaction medium was below the detection limit. ThusHβ zeolite. The catalyst( 20 ~ 40 mesh,6 g) wasthe small amount of oligomers that might have formedcharged into a stainless steel reactor with 12 mm in-could hardly affect the conversion and carbon balance ,ner diameter , and the hydration reaction was per-and the selectivity for hydration was taken as 100% .Received date : 2005-03-01. First author : WANG Hua , male , borm in 1973 , PhD , asociate professor.Corresponding author :LIU Zhongmin. Tel :( 0411 84685510 ;E mail : liuzm@ dicp. ac. cn.Foundation item : Supported by the Key Scientific Research and Technology Exploitation Foundation of PetroChina Company Limited( 200804-05 ).452催化学报第26卷Increasing the ratio of water/ oil gave a sharp increase3-hexanol , 2-methyl-2- butanol , 3-methyl-2-butanol ,of olefin conversion that went through a maximum at2 3-dimethyl-2-butanol and 4 A-dimethyl-3-pen-V( H2OV V(oil)= 0.6 and then decreased.tanol.8-20 C6F15 F40F2F510610123014015060170VH2O)/ Voil)Temperature (C)Fig 1 Effect of water/ oil ratio on olefin hydration over H zeoliteFig 2 Effect of reaction temperature on olefin hydrationover邯zeolite at V( H2OV V( oil)=0.6The reaction temperature is an important param-eter in the hydration process as it both influences theIn conclusion , the hydration of olefins over Hβreaction rate and has a major impact on the distribu-zeolite is a promising way for reducing olefins and in-tion of the alcohols in the organic and aqueous phases ,creasing oxygenates in FCC gasoline. An olefin con-which affects the balance of the forward reaction( hy-version of 16.7% and 9.5% oxygenates can be ob-dration of olefins ) and the reverse reaction ( dehydra-tained under the given conditions.tion of alcohols). The effect of the reaction tempera-Referencesture on hydration of olefin is shown in Fig 2. Theconversion of olefins increased with the reaction tem-1 Sanche-DelgadoR A. J Mol Catal , 1994 ,86( 1-3):287perature and reached 16.7% at 140 C , and it re2 China Nat Environ Protect Bureau. GB 17930- 999.1999mained unchanged at 140 ~ 170 C , which indicated3 StikkersD E. Sci Total Environ ,2002 , 299( 1-3):37that the forward and reverse reactions were balanced4 YangF , Wang X Sh. Cuihua Xuebao( Chin J Catal ),in this temperature range. The content of oxygenated .2002 , 23(3):195products was about 9.5% at the highest olefin con-5 Zhang P Q, Wang X Sh, Guo H Ch. Cuihua Xuebaoversion. GC-MS results showed that besides the ma-( Chin J Catal ),2003 ,24( 3):159jor hydration product ( tert -pentyl alcohol )，there) ZhangP Q , WangX Sh ,Guo HCh ,Zhu W L ,ZhaoLP ,were several oxygenates in the effluent such as tert -Hu Y K. Cuihua Xuebao( ChinJ Catal ),2003 , 24( 8):butyl alcohol ，2-butanol ，2-pentanol ，2-hexanol ,585通过H分子筛上的烯烃水合反应提高FCC汽油品质王华，黄韬，杜娟，刘中民(中国科学院大连化学物理研究所天然气化工与应用催化研究室,辽宁大连116023)摘要:以Hβ分子筛为催化剂通过烯烃水合反应可以降低FCC轻汽油(≤80C)中烯烃含量并提高含氧化合物含量，从而提高汽油的品质.在V( H2OVV(oil)=0.6 ,WHSV=1h-1中=5.0 MPa ,0= 140 C和t= 10 h的条件下,FCC轻汽油中烯烃的转化率为16.7%产物中含氧化合物的含量为9.5%.关键词:烯烃,水合,FCC汽油,改质,Hβ分子筛( Ed YHM)