Promotion of LGO production Promotion of LGO production from cellulose pyrolysis over metal salts of heteropoly acid

this study about LGO production from celullose

1. Promotion of LGO production

2. Introduction Less than 3wt% LGO yield is obtained LGO yield can be obtained up to 30wt% Cellulose Non-catalytic pyrolysis Catalytic pyrolysis (metal oxide, H3PO4, H2SO4, ionic liquids etc. Fine chemicals Green solvent Polymer blocks Levoglucosenone (LGO) LGO is a platform molecule that can be used as a feedstock for synthesis of pharmaceuticals, 1,6-hexanediol (a polymer precursor), and Cyrene™ (a solvent).

3. Introduction Heteropoly acids (HPA) and its metal salts such as CSTP, FeTP , AgTP etc., are highly active catalysts for many reactions, for which Bronsted acid sites are supposed to be active centers. Structure of dodecatungstophosphoric acid (H 3 PW 12 O 40 , HTP) Easy to recycle catalyst Thermal stability Environment friendly

4. Catalyst preparation Water solution of metal salts Water solution of HTP Add slowly Precipitating No precipitation Filtration Washing Drying Heating to dryness Calcination Cs2CO3, Co(NO3), Fe(NO3)3, ZrO (NO3)2, AlCl3, SnCl2 , Na2CO3, K2CO3

5. Analytical pyrolysis using Py /GC-MS Samples were made by mechanically mixing cellulose and catalysts in given ratios (generally cat/ cel weight=1/3). In each test, about 0.2-0.4 mg sample was packed and put in the reactor. The heating time is set at 10 seconds. The pyrolysis temperature is range from 255-445 ℃ . Curier point pyrolyzer Temperature controller

6. Effect of different metal salts of HPA Total ion chromatogram of py / gc-ms analysis All tested metal salts of HPA can promote the production of LGO CsTP (Cs2.5H0.5PW12O40) seems to exhibit the best performance among the catalysts Calcination temperature: 350 ℃ Pyrolysis temperature: 358 ℃

7. Effect of different catalyst calcination temperature Total ion chromatogram of py / gc-ms analysis over different calcination temperature CsTP Catalyst: CsTP Pyrolysis temperature: 358 ℃ The increased calcination temperature of catalyst from 350-500 ℃ slightly promote the LGO production.

8. Effect of different pyrolysis temperature Total ion chromatogram of different reaction temperature With the increasing pyrolysis temperature from 255-445 ℃ , the LGO area/cellulose weight increases firstly and then decrease The appropriate pyrolysis temperature is between 350 to 400 ℃ Catalyst: CsTP Calcination temperature: 500 ℃

9. Comparison of HPA and CsTP Performance Compared to metal salts of heteropoly acids, directly using the purchased heteropoly acids is much less effective to promote the LGO formation in cellulose fast pyrolysis. LGO LGA

10. Effect of the catalyst-to cellulose ratio Total ion chromatograms of different catalyst/cellulose ratio samples The increased dosage of CsTP significantly promotes the LGO production. Calcination temperature: 500 ℃ Pyrolysis temperature: 358 ℃

11. Comparison of KTP, NaTP and CsTP Calcination temperature: 350 ℃ Pyrolysis temperature: 358 ℃ Cel /cat ratio: 3:1 Total ion chromatograms of py-gc / ms over different catalyst

12. Conclusion CsTP can effectively catalyze the LGO-formed reaction during cellulose pyrolysis The appropriate pyrolysis temperature is between 350-400 ℃ , and the appropriate calcination temperature is 500 ℃ Heteropoly acids including H 3 PW 12 O 40 and H 4 SiW 12 O 40 can’t promote the LGO production like their metal acids do The ratio of CsTP catalyst and cellulose can dramatically affect the LGO yield in the fast pyrolysis of the samples

13. Future plan Investigate CsTP performance in LGO production from cellulose pyrolysis using a lab-scale vertical flow reactor Characterization of catalysts including XRD, BET surface area, NH 3 temperature programmed desorption The configuration of the pyrolysis reactor