改性REY型分子筛性质及裂化性能研究
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摘要
为进一步提高REY分子筛的活性及水热稳定性,降低生产成本,开发研制了一种改性分子筛HAY。该分子筛通过在NaY分子筛上沉淀适量的SiO_2,再经离子交换引入稀土元素,并在焙烧过程中通入定量过热蒸汽进行水热焙烧处理而制成。由该分子筛制备的FCC催化剂用于重油裂解试验,取得良好结果。
本文研究了改性HAY分子筛制备条件并对其物性进行了表征。研究表明,水热焙烧处理提高了分子筛的硅铝比、抑制了大分子(RE-O-RE)~(4+)的形成,使多数RE~(3+)从超笼向方钠石笼迁移,有利于提高分子筛的活性和稳定性;加入适量的活性SiO_2可提高分子筛的结晶度,并可调变分子筛的酸量分布。
本文还研究了改性HAY分子筛催化剂的反应性能。研究表明:改性HAY分子筛制备的FCC催化剂与常规REY分子筛催化剂相比,具有活性高、活性稳定性好、抗积炭能力好的特点。小型固定流化床评价表明,改性HAY分子筛催化剂对产品分布和转化率均有较大幅度的改善,可提高汽油和柴油,减少重油产率。
改性HAY分子筛制备工艺简单,与REY分子筛比较,可将原“二交二焙”工艺简化为一次交换与焙烧过程,因此可以大幅度降低分子筛的制造成本。
In order to increase the activity and hydrothermal stability of REY zeolite and decrease the production cost, a modified REY zeolite(HAY) was developed. During the producing process, HAY zeolite was made by depositing some SiO_2, exchanging rare earth element and injecting superheating stream while calcining. The FCC catalyst which took HAY zeolite as active component got a good result in the heavy oil cracking test.The preparation condition and property of HAY zeolite were investigated. The results showed that the treatment of hydrothermal calcinations controlled the formation of large molecule "(RE-O-RE)~(4+)"and caused the migration of more RE~(3+) from super cage to sodalite cage , which made useful effect on improving the activity and stability of zeolite. The active SiO_2 which was deposited on zeolite could increase the crystallinity of HAY zeolite and adjust the acidity to extent.This article also studied the reacting proverties of HAY zeolite catalyst. The evaluation results showed that compared with conventional REY zeolite catalyst, HAY zeolite catalyst had excellent performances in high activity, good activity stability and good carbon tolerance. The evaluation of fixed fluidizing bed test showed that using improved HAY zeolite catalyst, the product yield distribution with higher gasoline and diesel yield, lower slurry yield was achieved and the conversion was also some increased.The producing process of HAY zeolite catalyst was simplied and one exchanging procedure and one calcining procedure was cut down compared with conventional REY zeolite production thus preparation cost was reduced in large extent.
本文研究了改性HAY分子筛制备条件并对其物性进行了表征。研究表明,水热焙烧处理提高了分子筛的硅铝比、抑制了大分子(RE-O-RE)~(4+)的形成,使多数RE~(3+)从超笼向方钠石笼迁移,有利于提高分子筛的活性和稳定性;加入适量的活性SiO_2可提高分子筛的结晶度,并可调变分子筛的酸量分布。
本文还研究了改性HAY分子筛催化剂的反应性能。研究表明:改性HAY分子筛制备的FCC催化剂与常规REY分子筛催化剂相比,具有活性高、活性稳定性好、抗积炭能力好的特点。小型固定流化床评价表明,改性HAY分子筛催化剂对产品分布和转化率均有较大幅度的改善,可提高汽油和柴油,减少重油产率。
改性HAY分子筛制备工艺简单,与REY分子筛比较,可将原“二交二焙”工艺简化为一次交换与焙烧过程,因此可以大幅度降低分子筛的制造成本。
In order to increase the activity and hydrothermal stability of REY zeolite and decrease the production cost, a modified REY zeolite(HAY) was developed. During the producing process, HAY zeolite was made by depositing some SiO_2, exchanging rare earth element and injecting superheating stream while calcining. The FCC catalyst which took HAY zeolite as active component got a good result in the heavy oil cracking test.The preparation condition and property of HAY zeolite were investigated. The results showed that the treatment of hydrothermal calcinations controlled the formation of large molecule "(RE-O-RE)~(4+)"and caused the migration of more RE~(3+) from super cage to sodalite cage , which made useful effect on improving the activity and stability of zeolite. The active SiO_2 which was deposited on zeolite could increase the crystallinity of HAY zeolite and adjust the acidity to extent.This article also studied the reacting proverties of HAY zeolite catalyst. The evaluation results showed that compared with conventional REY zeolite catalyst, HAY zeolite catalyst had excellent performances in high activity, good activity stability and good carbon tolerance. The evaluation of fixed fluidizing bed test showed that using improved HAY zeolite catalyst, the product yield distribution with higher gasoline and diesel yield, lower slurry yield was achieved and the conversion was also some increased.The producing process of HAY zeolite catalyst was simplied and one exchanging procedure and one calcining procedure was cut down compared with conventional REY zeolite production thus preparation cost was reduced in large extent.
引文
1 中国石化总公司炼油处 炼油装置达标简报
2 烃加工出版社,《炼油催化剂制造技术基础》,1989
3 Smith J V. Zeolite Chemistry and Catalyst, Ed by Rabo JA. Am Chem Soc Monograph, 1976(171).
4 Barrier R M. Endeavour, 1964(23): 122
5 Ward J W. J Phys Chem, 1969(73): 2086
6 Venuto P B, Hamilton L A, Landis P S, J Catal, 1966(5): 484
7 Ward J W. J Catal, 1969(13): 321
8 Kerr T. J Phys Chem, 1968(72): 2594
9 USP 3442795, 1969
10 Beyer H K, Belenykaja I. Catalysis by Zeolite, Ed by Imilik B, et al. Elsevier, 1980
11 Skeels G W, Breds D W. Proc of 6th int Zeolite Conf, 1983
12 USP 4503023, 1985
13 Sherzer J. Am Chem Soc Symp Ser. N248. 1984
14 R. E. Ritter, L. Rheaume, W. A. Welsh, J. S. Magee TECHNOLOGY. July 6, 1981 Oil & Gas Journal 103
15 USP 50792021
16 刘希尧等编著,工业催化剂分析测试表征,烃加工出版社,1990
17 Barry T I, Lay L A, Nature, 1965(208): 312
18 石油化工科学研究院内部资料《对分子筛水热过程中化学行为的基础研究》,1996
19 R. Kumar, E. F. Rakiewicz, K. Rajagopalan, Journal of Catalysis 143, 304-307(1993)
20 Olson D H, Kokotailo G Y, Charnell J F. J Colloid Interface Sci, 1968, (28): 305
21 A. stanislaus et al., Applied Catalysis, 39: 239-253(1988)
22 McDaniel C V, Maher P K. Molecular Sieves. Chem Ind, London: Monograph, 1968
23 USP 3449070, 1969
24 苏建明,“超稳Y沸石分子筛的合成研究”,1990
2 烃加工出版社,《炼油催化剂制造技术基础》,1989
3 Smith J V. Zeolite Chemistry and Catalyst, Ed by Rabo JA. Am Chem Soc Monograph, 1976(171).
4 Barrier R M. Endeavour, 1964(23): 122
5 Ward J W. J Phys Chem, 1969(73): 2086
6 Venuto P B, Hamilton L A, Landis P S, J Catal, 1966(5): 484
7 Ward J W. J Catal, 1969(13): 321
8 Kerr T. J Phys Chem, 1968(72): 2594
9 USP 3442795, 1969
10 Beyer H K, Belenykaja I. Catalysis by Zeolite, Ed by Imilik B, et al. Elsevier, 1980
11 Skeels G W, Breds D W. Proc of 6th int Zeolite Conf, 1983
12 USP 4503023, 1985
13 Sherzer J. Am Chem Soc Symp Ser. N248. 1984
14 R. E. Ritter, L. Rheaume, W. A. Welsh, J. S. Magee TECHNOLOGY. July 6, 1981 Oil & Gas Journal 103
15 USP 50792021
16 刘希尧等编著,工业催化剂分析测试表征,烃加工出版社,1990
17 Barry T I, Lay L A, Nature, 1965(208): 312
18 石油化工科学研究院内部资料《对分子筛水热过程中化学行为的基础研究》,1996
19 R. Kumar, E. F. Rakiewicz, K. Rajagopalan, Journal of Catalysis 143, 304-307(1993)
20 Olson D H, Kokotailo G Y, Charnell J F. J Colloid Interface Sci, 1968, (28): 305
21 A. stanislaus et al., Applied Catalysis, 39: 239-253(1988)
22 McDaniel C V, Maher P K. Molecular Sieves. Chem Ind, London: Monograph, 1968
23 USP 3449070, 1969
24 苏建明,“超稳Y沸石分子筛的合成研究”,1990