A Catalytic Diesel Hydrogenation Conversion Process

A technology of hydrogenation conversion and catalytic diesel oil, which is applied in the fields of hydrotreatment process, petroleum industry, molecular sieve catalyst, etc. It can solve the problem of unfavorable hydrogenation conversion to produce high-octane gasoline, large octane loss of gasoline products, and lower gasoline composition. Hydrogenation saturation and other problems, to meet the high nitrogen tolerance and high reactivity, avoid excessive secondary cracking, reduce the effect of secondary cracking

CN107304373BActive Publication Date: 2019-03-19CHINA PETROLEUM & CHEM CORP +1
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2019-03-19

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Abstract

The invention discloses a hydro-conversion technology for catalytic diesel oil. The technology comprises the following steps: firstly, putting a mixture of catalytic diesel oil and hydrogen into a hydrogenation reactor and performing hydrofining reaction, and then guiding into a cracking reactor and generating contact reaction with hydrocracking catalyst layers, wherein upper and lower catalyst layers are arranged in the hydrocracking reactor; the hydrocracking catalyst in the upper layer has the properties as follows: on the basis of the total weight of the catalyst, 10%-18% of MoO3, 2%-10% of Co, 40%-90% of modified Y-shaped molecular sieve, preferably 50-80%, and the balance of aluminum silicon carrier; the hydrocracking catalyst in the lower layer has the properties as follows: on the basis of the total weight of the catalyst, 15-30% of MoO3 or WO3, 2-15% of NiO, 10%-60% of modified Y-shaped molecular sieve, preferably 20-40%; the filling mass ratio of the hydrocracking catalysts in the upper layer and the lower layer is (1:5)-(5:1). The hydro-conversion technology disclosed by the invention can further increase the device liquid yield, can reduce the hydrogenation saturation of the generated gasoline component and can increase the octane value of the gasoline component under the condition of better meeting the requirement for the conversion rate of catalytic diesel oil.
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Description

technical field

[0001] The invention relates to a hydrocarbon hydrogenation treatment method, in particular to a catalytic diesel hydrogenation conversion process. Background technique

[0002] Since the beginning of the new century, with the increasing awareness of environmental protection, the stricter national environmental protection regulations and the rapid development of the national economy, the demand for clean motor fuels has been increasing all over the world. Catalytic cracking (FCC) technology is one of the main technological means for lightening heavy oil, and it occupies a relatively important position in oil refining enterprises all over the world. The annual processing capacity of catalytic cracking units in my country has exceeded 100 million tons, second only to the United States. In the composition of gasoline and diesel products, catalytic cracking gasoline accounts for about 80%, and catalytic diesel oil accounts for about 30%. In recent years, with t...

Examples

Embodiment 1

[0030] Preparation method and physical and chemical properties of molecular sieve 1:

[0031] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 1.5mol / L according to the liquid-solid ratio of 4:1, exchange at 80°C for 2 hours, repeat this process twice, and the exchanged Y molecular sieve Na content in Na 2 O is calculated as 2.5%;

[0032] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 560°C and 0.1MPa for 2 hours;

[0033] (3) The molecular sieve obtained in step (2) was stirred and mixed with distilled water according to the liquid-solid ratio of 5:1, and then the temperature was raised to 75°C. During the stirring process, 400ml of 0.6mol / L aluminum sulfate solution was added, and the reaction was carried out at constant temperature for 2 hours.

[0034] (4) First dry the molecular sieve obtained in step (3) at 120°C for 3 hours, then soak the molecular sieve obtained i...

Embodiment 2

[0039] Molecular sieve 2 modification process:

[0040] (1) Take 200g of NaY molecular sieve raw powder prepared in the laboratory, mix it with ammonium nitrate with a concentration of 0.6mol / L according to the liquid-solid ratio of 3:1, exchange at 80°C for 3 hours, repeat this process 3 times, and the exchanged Y molecular sieve Na content in Na 2 O is calculated as 2.0%;

[0041] (2) Hydrothermally treat the Y molecular sieve obtained in step (1) at 530°C and 0.1Mpa for 2 hours;

[0042] (3) Step (2) sieve the oxalic acid solution (concentration in H + Total) 400ml mixed, then heated up to 50°C, and reacted at constant temperature for 2 hours;

[0043] (4) The molecular sieve obtained in step (3) was stirred and mixed with distilled water according to the liquid-solid ratio of 5:1, and then the temperature was raised to 80°C. During the stirring process, 400ml of 0.5mol / L aluminum sulfate solution was added, and the reaction was carried out at constant temperature for 2 ...

Embodiment 3

[0051] Preparation method and physical and chemical properties of molecular sieve 3:

[0052] The Y molecular sieve is modified by conventional methods, that is, the NaY molecular sieve is first ammonium-exchanged to Na 2 The O content is 2.0%, and then mixed with 0.10mol / L ammonium fluorosilicate solution according to the liquid-solid ratio of 10:1 and heated to 80°C, then reacted at constant temperature for 2 hours. After being treated with ammonium fluorosilicate, the sample was filtered and washed at 0.1 Molecular sieve 3 was obtained by hydrothermal treatment at Mpa and 540° C. for 2 h. Molecular sieve 3 has a silicon to aluminum ratio of 15.0. XRD analysis results show that its unit cell constant is 2.442 and its relative crystallinity is 92%. The pore volume is 0.36ml / g, and the infrared acid content determined by infrared analysis is 0.93mmol / g.