Reporter: Sun Rui Supervisor: Xin Feng 2013-4-24

1. Study of deactivation and regeneration of titanium silicalite-1 catalyst in cyclohexanone ammoximation Reporter: Sun Rui Supervisor: Xin Feng 2013-4-24

2. Study of deactivation and regeneration of titanium silicalite-1 catalyst in cyclohexanone ammoximation • Introduction • Reasons for titanium silicalite-1 catalyst deactivation in cyclohexanone ammoximation • Regeneration of titanium silicalite-1 catalyst in cyclohexanone ammoximation • Ideas and expectations Tianjin University

3. 1. Introduction 1.1 TS-1 is a ZSM-5 like zeolite, not containing aluminium, where a part of silicon is statistically substituted with titanium. The use of this catalyst allows to obtain an high selectivity and conversion. Fig.1-1 (ring)oxidation reaction on titanium silicalite-1 Tianjin University

4. 1. Introduction The advantages of TS-1: 1. Reaction conditions can be carried out under low temperature and pressure; 2. Good product yield and selectivity; 3. Simple process; 4. Low concentration of hydrogen peroxide as the oxidant; 5. Without pollution 1.2 Cyclohexanone oxime is an important intermediate in chemical industry, particularly as a key precursor of ε -caprolactam for nylon production. In 1988, Enichem developed a new process for producing cyclohexanone oxime from ammoximation of cyclohexanone catalyzed by TS-1. Ammonia and hydrogen peroxide were used as the raw materials. Tianjin University

5. 1. Introduction Fig. 1-2 Enichem’s ammoximation process of cyclohexanone oxime Tianjin University

6. 2. TS-1 catalyst deactivation in cyclohexanoneammoximation Fig.2-1 （l ）a，（Z ）X（CHN），（3 ）X（H2O2）,（4 ）S（H2O2） （Reaction conditions ：n（CHN）: n（NH3）: n（H2O2）= 1: 1.5: 1.2. a- TS-l activity X - Conversion ，S -Selectivity ，CHN -cyclohexanone ） Tianjin University

7. 2. TS-1 catalyst deactivation in cyclohexanoneammoximation Three main deactivation processes are identified: (i) Slow dissolution of the framework with accumulation of Ti on the external of the remaining solid; (ii) Direct removal of Ti from the framework; (iii) Pore filling by by-products 2.1 The dissolution erosion of TS-1 in cyclohexanoneammoximation 2.1.1 The effect of ammonia Table. 2-1 Dissolution effect of ammonia on TS-1 Tianjin University

8. 2.1 The dissolution erosion of TS-1 Fig. 2-3 Raman spectra of fresh catalyst and samples after 350h Fig. 2-2 Raman spectra of fresh and ammonia treatment catalyst samples Tianjin University

9. 2.1 The dissolution erosion of TS-1 2.1.2 Inhibition of silicon in the TS-1 dissolved Table 2-4. Effect of additives on the TS-1 catalyst 2.1.3 Conclusions (i) Ammonia was the primary factor leading to deactivation of the catalyst. (ii) The study proved that the dissolution erosion of silicon in the basic solution was connected with the solution polarity and ammonia concentration. Adding an additive into the solution could inhibit the dissolution erosion of silicon from the catalyst , and the stable running period of the catalyst was prolonged. Tianjin University

10. 2. 2 Coke deposition on TS-1 catalyst in cyclohexanone ammoximation 2.2 Coke deposition on TS-1 catalyst in cyclohexanoneammoximation (The main reason) 2.2.1 Characterization of TS-1 catalyst deactivation Fig.2-4 TG-DTA chart of deactivated TS-1 Tianjin University

11. 2. 2 Coke deposition on TS-1 catalyst in cyclohexanone ammoximation 2.2 Coke deposition on TS-1 catalyst in cyclohexanoneammoximation 2.2.1 Characterization of TS-1 catalyst deactivation Fig.2-5 In situ IR spectra of TPO coke combustion of deactivated TS-1 a 40℃; b 60℃; c 80℃; d 100℃; e 120℃; f 150℃; g 200℃; h 300℃; i 400℃; j 500℃; k 600℃; m 700℃ Tianjin University

12. 2. 2 Coke deposition on TS-1 catalyst in cyclohexanone ammoximation 2.2 Coke deposition on TS-1 catalyst in cyclohexanoneammoximation 2.2.1 Characterization of TS-1 catalyst deactivation Fig.2-7 XRD patterns of TS-1 before and after deavtivation a fresh; b deactivation c regeneratation at 350℃;d regeneration at 700℃ Fig.2-6 IR spectra of framework stretching region of TS-1 before and after deavtivation a fresh; b deactivation c regeneratation at 350℃;d regeneration at 700℃ Tianjin University

13. 2. 2 Coke deposition on TS-1 catalyst in cyclohexanone ammoximation 2.2 Coke deposition on TS-1 catalyst in cyclohexanoneammoximation 2.2.2 GC-MS analysis Fig.2-8 GC-MS total ion current spectrum of dissoluble deposit Tianjin University

14. 3. Regeneration of TS-1 catalyst in cyclohexanone ammoximation Regeneration methods of TS-1 (i) Oxidation of catalyst by in situ hydrogen peroxide (ii) Solvent extraction (iii) Calcination The main regenieration method of TS-1 A deactivated catalyst is treated in an acidic solution having a pH value of <=3, and then dried and calcined. The process is simple in procedure and can make the catalytic activity, selectivity and stability of the regenerated catalyst be recovered to the level of its fresh catalyst. Tianjin University

15. 4. Ideas and expectations (i) Have a deeper understanding of the continuous cyclohexanone ammoximation reaction and the TS-1 monolithic catalyst. (ii) Look for the properties of substances in the reaction systems, respectively. Try to find new ways to separate more cyclohexanone-oxime from the reaction system. Electro-deposition for example. (iii) Think about the method of regenerating TS-1 catalyst by using hydrogen peroxide or solvent washing combined with the technology (iiii)Try to prove the main reason that causes the TS-1 catalyst to deactivate is cyclohexanone-oxime Tianjin University

16. Thank You !