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Heavy metal-resistant new matrix-type cracking catalyst and its preparing process

A technology for anti-heavy metals and catalysts, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, molecular sieve catalysts, etc. The anti-vanadium effect is not obvious, etc., to achieve the effect of reducing the preparation cost, simplifying the preparation process, and high activity

Inactive Publication Date: 2005-10-19
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Most of the above-mentioned patents add one or several components that act as anti-heavy metals to the catalyst to improve the anti-heavy metal performance of the catalyst, but there are various deficiencies in the current technology: due to the strong basic center of alkaline earth metals, they can neutralize and zeolite acid sites, leading to a decrease in cracking activity; and exchangeable rare earth oxides also have a certain vanadium passivation effect, but increase the acid site density of the catalyst, thus making the coke selectivity worse
Although other anti-vanadium additives have a certain anti-vanadium effect, they reduce the catalyst activity and selectivity, or the anti-vanadium effect is not significant

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] 1.2 kg of kaolin (dry basis), 0.3 kg of activated alumina (Al 2 o 3 ), 1.0 kg of zeolite containing rare earth oxalate through a chemical treatment (simultaneously carrying out chemical dealumination and ammonium salt exchange of zeolite) and a hydrothermal treatment, 1.6 kg of aluminum sol and 3.0 kg of chemical water are mixed and beaten, stirred for 1 hour, homogeneous After spray drying molding. The resulting microspheres were calcined at 450°C for 0.5 hours. Get 2 kilograms of calcined microspheres, add 20 kilograms of chemical water and 0.45 kilogram of ammonium chloride and stir evenly, wash at 75 ℃ for 20 minutes, add ammonium phosphate after filtering (making the catalyst phosphorus content be 1.0m%) and 20 kilograms of chemical water, stir Evenly, wash at 75°C for 10 minutes, filter and dry to obtain Catalyst A.

Embodiment 2

[0047] Catalysts A, B, C, and D were polluted with 5000 ppm V by dipping vanadyl oxalate method, and the micro-reaction activity of the cracking catalyst was measured by micro-reaction experiment. Experimental conditions: 800°C, 100% steam for 4 hours, then react at 460°C for 70 seconds. The catalyst load is 5.0 grams, the agent-to-oil ratio is 3.2, the raw material oil is straight-run light diesel oil, and the oil intake is 1.56 grams. The results of the micro-reverse experiment are shown in Table 2.

[0048] catalyst

Zeolite

Types of

Rare earth introduction

Way

Vanadium pollution

ppm

Micro-reactive activity% (800℃ / 4h)

microreactivity

Retention%

Before pollution

After pollution

A

hand in a bake

precipitation

5000

72

67

93

B

hand in a bake

Pay later

5000

76

63

83

C

Two cross two bake

Pay later

5000

72

...

Embodiment 3

[0052] A small fixed fluidized bed was used to evaluate the reactivity and selectivity of the cracking catalyst prepared by the present invention. Experimental conditions: The catalyst was aged at 800°C with 100% steam for 10 hours, the reaction temperature was 500°C, the ratio of agent to oil was 3.0, and the raw oil was 70% Xinjiang distillate oil mixed with 30% Xinjiang vacuum residue. The experimental results are shown in Table 3.

[0053] project

A

B

D

Product distribution m, %

h 2 ~C 2

C 3 ~C 4

gasoline

diesel fuel

heavy oil

coke

1.6

22.0

48.5

15.0

7.4

3.6

1.4

21.6

47.2

15.5

9.2

3.2

2.3

23.0

46.2

14.1

7.1

5.2

Conversion rate m, %

Light oil yield m,%

gasoline / conversion

coke / conversion

75.6

63.4

0.640

0.048

73.4

62.7

0.643

0.044

76.7

60.3

0.600

...

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PUM

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Abstract

A heavy metal-resistant cracking catalyst (FCC) with novel matrix for cracking the heavy oil with high content of Ni or V contains clay (20-80 m%), binder (5-40m%), metal capture (such as rare-earth oxalate) (1-25m%), other oxides (such as activated alumina) (0-30m%), and faujasite or ZSM-5 zeolite or beta-zeolite or their mixture (5-40m%). It has excellent heavy metal resistance.

Description

technical field [0001] The invention relates to a cracking catalyst, in particular to a heavy metal-resistant FCC catalyst. Background technique [0002] With the continuous heavy and inferior quality of catalytic cracking raw oil, the FCC feed may contain a large amount of heavy metal compounds, which can damage the FCC catalyst and affect the distribution of cracked products. The metal vanadium and nickel in the FCC feed have the greatest impact. Vanadium can form vanadic acid, destroy the zeolite framework structure, reduce its surface area, decrease its activity, and increase the yield of non-target products hydrogen and coke; nickel in the catalyst will not destroy Crystal structure of zeolite, but produces a lot of hydrogen and coke. Due to the deposition of heavy metals such as nickel and vanadium on the catalyst, the catalyst must be continuously unloaded from the FCC unit and replenished with new agents, which will inevitably lead to a waste of resources and manpow...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J21/00B01J23/10B01J29/00C10G11/02
Inventor 孙书红庞新梅马燕青赵连鸿丁伟
Owner PETROCHINA CO LTD
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