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Residue Catalytic Cracking Catalysts TMC-06

PRODUCT INTRODUCTION

1. Residual Cracking Catalyst TMC-06

In recent years, with the rapid economic development and substantial raise of people’s living standard in China, domestic sales of automobiles also double increase accordingly, which enables the fuel, especially gasoline requirement to grow with each passing day. China now is the second biggest refining country in the world after USA. No matter from the resource or the economic standpoint, poor quality feedstock will be an inevitable choice for the refineries. At present, the local refineries in Shandong Province use M100 and M180 as feedstock generally for their FCC units. As shown in table 1, M100 has the feature of low content of hydrogen, low content of  saturated hydrocarbon, high carbon residue, high heavy metal (total metal over 60ppm) and high nonmetal impurity such as sulfur and nitrogen. All these factors will poison catalysts, and lead to high yield of slurry, high catalyst consumption and low yield of high value light oil.

To solve the problems mentioned above, large catalyst companies in China or overseas have successively launched new generation heavy oil cracking catalyst.

Although there are several brands of heavy oil catalysts and additives in the market, they do not show the characteristics of high activity and high yield of light oil without solving problems of high catalyst consumption and high yield of slurry. For instance, catalyst consumed over 3.5kg/t in some local refineries with the situation of high vanadium content in equilibrium catalyst, and yield of light oil decreased 2 percentage point in some local refineries by adding Coker Gas Oil (CGO) into the feedstock.

Aiming at FCC with inferior feedstock , Shanxi Tengmao Technology Co., Ltd has designed and developed the residual feed cracking catalyst TMC-06 which is suitable for processing poor quality feedstock such as M100 and so on.

 Shanxi Tengmao Technology Co., Ltd takes the advantage of energy resources in Shanxi Province, and it has developed a manufacturing technology of zeolite NaY with high silica-alumina ratio. That can be produced with silica-alumina ratio from 5.6 to 6.0 which is the highest in China. At the same time, special molecular sieve manufacturing technology (TMZ technology) is applied to improve molecular sieves’ performance of metal resistance, enhance markedly activity and stability of them. By introducing new matrix with large specific surface and pore volume, combining with unique catalyst manufacture technology of Tengmao (TMC technology), commercial catalyst possess abundant mesopore, large specific surface and matrix.with moderate acidity. At present, catalyst TMC-06 whose matrix specific surface over 100 m2/g is one of the largest matrix specific surface of FCC catalyst in China. The combination of several technologies abovementioned ensure TMC-06 to have excellent performance of metal resistance and large molecules cracking of residual oil, making TMC-06 become a perfectly suitable FCC catalyst processing poor quality feedstock such as M100 and so on.


 

 Table 1. The feedstock Properties of a M100

项目 Items

原料M100  feedstock M100

 

密度 g/cm3 20

0.9321

粘度 mm/s 80

18.3

残炭 m%

5.41

元素分析

Element Analysis

C w%

86.15

H w%

11.68

S w%

1.2

N w%

0.38

族组成

Group Composition

饱和烃 w%

52.4

芳烃 w%

32.7

胶质 w%

14.6

沥青质 w%

0.3

重金属  

ppm

Heavy Metal  ppm

Ca

22.7

Fe

9.8

Na

10.6

Ni

10.6

V

24.6

(1). High activity, stability and excellent performance of resistance to basic nitrogen

Increasing activity of the catalyst is in favor of the performance of resistance to basic nitrogen. Higher content of basic nitrogen in Coker Gas Oil(CGO) can neutralize the active site and temporarily inactivate catalyst because of the alkalescence of basic nitrogen. Research shows that when the content of basic nitrogen in catalytic feedstock is more than 400ppm, a 100~150ppm increase in basic nitrogen the activity of the catalyst will decrease 1 point. To a FCC unit of addition 20% CGO to the feedstock, the content of basic nitrogen of feedstock will be more than 1000 ppm. In this case, the equilibrium activity of catalysts will lose 4~6 point, inevitably leading to reduction in the yield of the light oil and increase in the yield of the slurry. To solve the problem, the equilibrium activity of the catalyst must be increased. Table 2 shows the stability of three catalysts by comparing the Microactivity (MA) of catalyst TMC-06 with two widely used domestic residual cracking catalysts in China named as catalyst A and catalyst B respectively. All fresh catalysts had been pre-treated by steam for 17 hours at 800℃ in 100% steam.

Table 2. Stability comparison of Catalyst TMC-06 and two other residual cracking catalysts

催化剂

Catalyst

TMC-06

国内重油剂A

 Residual cracking cat A

国内重油剂B

Residual cracking cat B

800, 17h

100% 水蒸气微活

 800, 17h

100% Steam MA

65

62

58

Equilibrium activity in industrial units can be simulated by steaming fresh catalysts for 17 hours, at 800℃ in 100% steam. Table 2 shows that the stability of catalyst TMC-06 is higher above 3 points than that of two other domestic residual cracking catalysts, so it still can maintain good activity after contaminated by basic nitrogen. Table 3 shows the evaluation data of catalyst TMC-06 and two widely used domestic residual cracking catalysts in China named as catalyst A and catalyst B respectively. They are evaluated in the lab on the Fixed Fluidized Bed (FFB) reactor with the feedstock blending 20 w% CGO.

Table 3. the evaluation data of catalyst TMC-06 and two other domestic residual cracking catalysts A and B

催化剂

Catalyst

TMC-06

国内重油剂A

 Residual cracking cat A

国内重油剂B

Residual cracking cat B

产品分布

w%

Product Distribution

干气 Dry Gas

2.1

2.0

2.1

液化气 LPG

13.7

13.4

13.5

汽油 Gasoline

48.6

47.3

45.9

柴油 Diesel

22.1

21.7

21.2

油浆 Slurry

5.1

7.2

9.0

焦碳Coke

8.4

8.4

8.3

总轻油收率

Yield of light oil

84.4

82.4

80.6

According to the evaluation data of table 3, when adding CGO with higher content of basic nitrogen to FCC feedstock, the yield of light oil and total liquid of catalyst TMC-06 increase 2%~4% compared to that of current domestic residual cracking catalysts, the yield of slurry decreases more than 2%.

 (2). Excellent performance of Residue cracking and resistance to Heavy metals

During the manufacture of catalysts, catalysts with larger pore volume can be made by choosing mecropore materials and controlling strictly the operation condition of gel forming. Research indicates that the heavy metals Fe, Ca, Ni in the FCC feedstock deposit on the surface of FCC catalyst, plugging the pores of catalyst after the feedstock first cracking, blocking Large resid molecules approaching the pores of the catalyst, making large resid molecules adsorb on the surface of the catalyst instead of cracking. They either change into slurry in the stripping section after being stripped or adhere to the catalyst turning into coke. To solve the problem, the pore volume of catalyst should be increased, especially in 40100Å mesopore and over 100Å macropore of the catalyst, avoiding heavy metals such as Fe, Ca, Ni and so on plugging the pores of catalyst. Catalyst TMC-06 has abundant mesopore and macropore, which can achieve it’s aims of resistance to contamination by heavy metals and accelerating the large resid molecules cracking, thus has excellent performance of high yield of light oil and low yield of slurry.

Table 4 is the evaluation data of catalyst TMC-06 and two widely used residual cracking catalysts in local refineries of Shandong Province named as catalyst A and catalyst B respectively on FFB. It shows that the conversion rate of catalyst TMC-06 is higher 2%~3% than that of residual catalyst A and B, the yield of coke is approximately equal, the yield of gasoline is higher 1.5%, the yield of light oil is higher 1%~2%, and the yield of slurry is lower 1%~2%, which fully indicate catalyst TMC-06 excellent performance of residue cracking and resistance to deactivation by heavy metals.

Table 4.  the evaluation data of catalyst TMC-06 and two other residual cracking catalysts (M100 as the feedstock )

催化剂

Catalyst

TMC-06

国内重油剂A

 Residual cracking cat A

国内重油剂B

Residual cracking cat B

产品分布

w%

Product Distribution

干气 Dry Gas

2.5

2.5

2.4

液化气 LPG

14.1

13.9

14.0

汽油 Gasoline

47.2

45.7

44.2

柴油 Diesel

21.1

21.6

21.8

油浆 Slurry

5.9

7.0

8.2

焦碳Coke

9.2

9.3

9.4

总轻油收率

Yield of light oil

82.4

81.2

80.0

化率 Conversion rate m%

73.0

71.4

70.0

TMC-06催化剂具有强度好、球形度好和细粉少的特点。表5TMC-06催化剂典型数据。

(3). Excellent physical and chemical properties

TMC-06 has the characteristics of high strength, good sphericity  and less fine power. Table 5 shows the typical data of catalyst TMC-06.

Table 5. the typical data of catalyst TMC-06

序号 No.

项目 Items

TMC-06

1

Al2O3  m%

50

2

Na2O  m%

0.13

3

Re2O3  m%

5.0~5.5

4

总比表面积 , /g  Total specific surface area

262

5

孔体积(水滴法)PV , ml/g  Pore volume

0.40

6

表观堆密度 , g/ml Apparent bulk density

0.72

7

筛分 Particle Size Distribution , 0 ~ 20μm , w%

1.7

0 ~ 40μm ,w %

16.9

0 ~ 149μm , w%

94.1

8

磨损指数, % 1/h   Attrition Index

2.0

9

活性 , 800/4h , %   MA

81

10

活性 , 800/17h , %   MA

65

2. Residual Cracking Catalyst TMC-08

Residual Cracking Catalyst TMC-08 has some excellent features in cracking resid macromolecule, in the resistance to contamination by heavy metal and salt from residual oil as well as another residual Cracking Catalyst TMC-06. TMC-08 is more suitable for processing paraffinic feed than TMC-06. Because of TMC-08’s moderate cracking activity, overcracking is inhibited effectivelyusing TMC-08 can be obtain more light oil, especially more gasoline as well as less heavy oil and coke.

 (1) Two sets of evaluation data about the performance of TMC-08 being given on table 6 and table 7

The feedstock for evaluation which came from a FCC unit of a refinery in China sampling from the pipe access to the unit. Contrast catalyst A was used in the third FCC unit in a refinery while contrast catalyst B was used in the second FCC unit of the same refinery. Contrast A and B were produced by two famous catalyst factories in China respectively.

Table 6. evaluation data which Feedstock was composed of  75% Shanbei Atmospheric residue and 25% Yulin Atmospheric residue

催化剂

Catalysts

TMC-08

对比剂A

Contrast Cat A

对比剂B

Contrast Cat B

剂油比 w/w  Cat/Oil

5.92

5.92

5.92

反应温度 

Reaction Temperature

500

500

500

产率m%

 

Yields

m%

干气 Dry Gas

1.04

0.92

1.04

液化气 LPG

13.88

10.76

15.21

汽油 Gasoline

55.86

46.86

53.03

柴油 Diesel

14.21

16.69

14.43

重油 Heavy Oil

8.17

19.02

9.69

焦碳+损失 Coke+Loss

6.83

5.75

6.60

汽油+柴油+液化气 Gasoline+Diesel+LPG

83.95

74.31

82.67

转化率 Conversion rate m%

77.61

64.29

75.88

 


 

 

Table 7. evaluation data which Feedstock was 100% Shanbei Atmospheric residue

,

催化剂

Catalysts

TMC-08

对比剂A

Contrast Cat A

对比剂B

Contrast Cat B

剂油比 w/w Cat/Oil

5.92

5.92

5.92

反应温度

Reaction Temperature

500

500

500

产率

m%

 

Yields

m%

干气 Dry Gas

1.07

0.89

1.09

液化气 LPG

15.57

12.98

17.37

汽油 Gasoline

55.83

50.33

53.54

柴油 Diesel

13.40

15.43

13.14

重油 Heavy Oil

7.62

15.06

8.44

焦碳+损失 Coke+Loss

6.49

5.30

6.41

汽油+柴油+液化气 Gasoline+Diesel+LPG

84.80

78.74

84.05

转化率 Conversion rate m%

79.07

69.51

78.42

(2) The main specifications of Catalyst TMC-08 listed on the table 8

Table 8. The main specifications of Catalyst TMC-08 

序号 No.

项目 Items

TMC-08

1

Al2O3 , m%

≥ 48

2

Na2O , m%

≤ 2.0

3

Re2O3 , m%

5.0 ~ 5.5

4

总比表面积 , /g  Total specific surface area

≥ 230

5

孔体积(水滴法)PV , ml/g  Pore volume 

≥ 0.35

6

表观堆密度 , g/ml Apparent bulk density

0.70 ~ 0.80

7

筛分 Particle Distribution , 0 ~ 20μm , m%

≤ 5

0 ~ 40μm ,m %

≤ 20

0 ~ 149μm , m%

≥ 90

8

平均粒径 DV , 0.5 , μm Average particle size

65 ~ 80

9

磨损指数, % 1/h   Attrition index

≤ 3.0

10

活性 MA ,  800/4h , % 

≥ 75

3. Gas oil FCC catalyst TMC-09

In recent years, some FCC units process straight run gas oil, poor quality gas oil (such as coker gas oil and so on), or hydro-treating gas oil treating by hydro-upgrading in order to improve the qualities of FCC products, increase the yields of the products, reduce the energy consumption of the unit, decrease the loss of catalyst and lessen the pollution to the circumstance. Catalyst TMC-09 has been developed for gas oil processing. The product selectivity is significantly optimized  by ensuring the extent of cracking. Then high yield of light oil, especially high yield of gasoline and high octane number are achieved meanwhile the yield of coke decrease.

(1) Evaluation results of the catalyst TMC-09

The evaluation feedstock supplied by a refinery in China is a kind of poor quality gas oil such as coker gas oil CGOtreated by mid-pressure mild hydro-upgrading.

 Except TMC-09 other four catalysts were supplied by the same refinery but manufactured by different catalyst factories, which are assigned the number of 1#2#3#4#. All five fresh catalysts are steamed at 800℃, in the presence of 100% steam for 17 hours. The evaluation condition is at reaction temperature 500℃, feed injection time 90s, catalyst 9.0g, cat/oil ration 5.0. FCC product distributions of five catalysts are given in the table 9.


 

 Table 9.  evaluation results of the catalyst TMC-09

催化剂

Catalyst

1

2

3

4

TMC-09

产率

m%

 

Yields

m%

干气 Dry Gas

1.50

1.41

1.51

1.28

1.49

液化气 LPG

12.11

8.60

13.32

5.31

13.70

汽油 Gasoline

40.42

36.31

37.65

25.77

39.90

柴油 Diesel

25.39

26.95

26.01

26.69

25.05

重油 Heavy Oil

13.30

19.90

14.30

34.34

13.01

焦碳+损失 Coke+Loss

7.28

6.83

7.21

6.61

6.85

汽油+柴油+液化气  Gasoline+Diesel+LPG

77.92

71.86

76.98

57.77

78.65

转化率   m%

Conversion rate  m%

61.31

53.15

59.69

38.97

61.94

2The main specifications of Catalyst TMC-09 list on the table 10

Table 10.  The main specifications of Catalyst TMC-09

序号 No.

项目 Items

TMC-09

1

Al2O3 , m%

≥ 48

2

Na2O , m%

≤ 0.2

3

Re2O3 , m%

2.0 ~ 2.5

4

总比表面积 , /g Total specific surface area

≥200

5

孔体积(水滴法) PV , ml/g Pore volume

≥ 0.35

6

表观堆密度 , g/ml Apparent bulk density

0.70 ~ 0.80

7

筛分 Particle Distribution , 0 ~ 20μm ,  m%

≤2

0 ~ 40μm ,  m%

≤ 20

0 ~149μm ,  m%

≥ 90

8

平均粒径 DV , 0.5 , μm  Average particle size

65 ~ 80

9

磨损指数 , % 1/h  Attrition index

≤ 3.0

10

活性 MA, 750/13h , %

≥70

4. catalyst TMC-10 specially for DCC Process

Catalyst TMC-10 is a catalyst specially designed for DCC Process aiming at maximizing as much as possible the light olefins yield.

DCC is a proprietary process, which requires higher H/C ratio of feedstock, suitable reaction temperature and reaction time, as well as higher steam partial pressure and lower oil partial pressure.

Catalyst TMC-10 can produce above 20% propylene based on feedstock under the right condition with more butylenes and ethylene. At the same time, high octane number gasoline is produced using as the high grade gasoline blending agent.

5. More light olefins & higher octane number additive TMZ-01

TMZ-01 is an additive using for increasing light olefins in FCC products and enhancing the gasoline octane number. Shape selectivity zeolite is adopted to crack selectively straight chain molecule to LPG components, mainly light olefins. Thus the gaseous olefin yield is increased primarily propylene and butylenes.

TMZ-01 not only contributes to increasing light olefin yield, bus also increases gasoline octane number, which is attributable to TMZ-01’s olefin isomerization ability and hydrogen transfer activity. So the content of iso-paraffin with higher octane number in gasoline is increased. On the other hand, because some gasoline is converted into gas, the content of aromatic in the gasoline increases relatively.

In ordinary operation, only above 5% TMZ-01 of total catalyst inventory being added in the system will significantly increase gaseous olefin 10%-20% yield as well as increasing 1-2 gasoline octane number basically maintaining invariable to the operation condition of the unit and light oil yields.

1The evaluation data of additive TMZ-01 list on the table 11

The evaluation feedstock was 70%VGO+30%VR. All FCC catalysts and additives were steamed at 800℃ and in the presence of 100% steam for 17 hours. FCC catalyst A was TMC-06 and FCC catalyst B was TMC-09. The additive TMZ-01 was mixed by 5% with these two catalysts.

 

Table 11. The evaluation data of additive TMZ-01

催化剂

Catalyst

主剂A

FCC Catalyst A

主剂A + 5%助剂

FCC Catalyst A+5% Additive

主剂B

FCC Catalyst B

主剂B + 5%助剂

FCC Catalyst B+5% Additive

反应条件

Reaction condition

反应温度

Reaction Temperature

510

510

510

510

剂油比w/w

Cat/Oil

6.08

6.08

6.08

6.08

产品分布m%

 

Product distribution

干气

Dry Gas

1.56

1.60

1.375

1.427

液化气

LPG

19.25

25.78

19.888

23.656

汽油

Gasoline

44.79

40.74

40.866

38.338

柴油

Diesel

16.99

15.68

19.226

18.747

重油

Heavy Oil

9.25

8.00

12.438

11.676

焦碳+损失

Coke+Loss

8.17

8.20

6.208

6.155

汽油+柴油+液化气 Gasoline+Diesel+LPG

81.03

82.20

79.98

80.741

转化率  m%

Conversion rate m%

73.76

76.35

68.34

76.35

辛烷值RON

87.80

89.70

89.50

91.20

辛烷值MON

72.80

74.20

74.20

75.80

 


 

(2)The main specifications of additive TMZ-01 list on the table 12

Table 12. The main specifications of additive TMZ-01

序号No.

项目

Items

TMZ-01

1

Al2O3 , m%

≥ 45

2

Na2O , m%

≤ 0.12

3

总比表面积 , /g Total specific surface area

≥150

4

孔体积(水滴法) PV , ml/g Pore volume

≥ 0.30

5

表观堆密度 , g/ml Apparent bulk density

0.65 ~ 0.85

6

筛分 Particle Distribution , 0 ~ 20μm , m%

≤5

0 ~ 40μm ,  m%

≤ 20

0 ~ 149μm ,  m%

≥ 90

7

平均粒径 DV , 0.5 , μm Average particle size

65 ~ 80

8

磨损指数 , %1/h Attrition index

≤ 3.5

6. reducing coke additive TMZ-02

Additive TMZ-02 can reduce coke yield as well as ensuring heavy oil cracking. When TMZ-2 content in inventory reached a level of 10 m%-20 m %, the yield of coke based on feedstock can reduce 0.5%-1.0%. Table 13 shows the main specifications of additive TMZ-02. 


 

 Table13. The main specifications of additive TMZ-02 

序号No.

项目Items

TMZ-02

1

Al2O3 , m%

≥ 65

2

Na2O , m%

≤ 0.10

3

总比表面积 , /g Total specific surface area

≥ 150

4

孔体积(水滴法) PV , ml/g Pore volume

≥ 0.35

5

表观堆密度 , g/ml Apparent bulk density

0.65 ~ 0.85

6

筛分Particle Distribution, 0 ~ 20μm ,  m%

≤ 5

0 ~ 40μm ,  m%

≤ 20

0 ~ 149μm ,  m%

≥ 90

7

平均粒径 DV , 0.5 , μm  Average particle size

65 ~ 80

8

磨损指数 , %1/h  Attrition index

≤ 5.0

 

 

Shanxi Tengmao Technology Co., Ltd has dozens of domestic and international clients. The company provides high-quality products and excellent services to refineries. We can develop and manufacture exclusive use catalyst according to the equipment and technological characteristics, the feedstock property and expecting product distribution of refinery FCC units for creating greater economic benefits and social benefits.

We provide after-sale services helping our customers to handle all kinds of issues during the period of product application,

We are looking forward to providing high-quality products and excellent services to more clients around the world.

 
 

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