WO2018053890A1

WO2018053890A1 - Suspended bed hydrocracking catalyst for poor-quality heavy crude oil and preparation method therefor

Info

Publication number: WO2018053890A1
Application number: PCT/CN2016/102409
Authority: WO
Inventors: 岳源源; 李嘉伟; 马永德; 江莉龙; 鲍晓军
Original assignee: 福州大学化肥催化剂国家工程研究中心
Priority date: 2016-09-20
Filing date: 2016-10-18
Publication date: 2018-03-29
Also published as: CN106423142A

Abstract

The present disclosure relates to the preparation of a suspended bed hydrogenation catalyst, and, in particular, to a suspended bed hydrocracking catalyst for a poor-quality heavy crude oil and a preparation method therefor. The catalyst is prepared by using high-temperature hydrothermally-activated bauxite powder as a carrier and then carrying one or more group VIB and/or group VIII transition metals as an active component. The prepared poor-quality heavy crude oil hydrocracking catalyst produces high catalytic activity and a low coke yield for hydrocracking upgrade of poor-quality heavy crude oils. The feedstock used is easily sourced and has a low price and an environmentally-friendly preparation process, greatly reducing preparation costs of the catalyst and operating costs of the hydrocracking process, and thereby having broad application potential.

Description

Inferior heavy oil suspended bed hydrocracking catalyst and preparation method thereof

Technical field

The invention belongs to the field of catalyst preparation for suspension bed hydrogenation, and particularly relates to a poor quality heavy oil suspension bed hydrocracking catalyst and a preparation method thereof.

Background technique

Inferior heavy oil is a general term for a class of difficult-to-volatile, difficult-to-treat high-viscosity materials, including: residual oil, shale oil, oil sand oil, heavy (thick) oil, super heavy oil, deep oil, asphalt, coal tar, and so on. The main characteristics of inferior heavy oil are its high sulfur, high residual carbon, high nitrogen and high metal content, and the output is huge, the processability is high, but the processing is difficult.

In recent years, the heavy and inferior crude oil has become more and more obvious, and the environmental protection regulations have become increasingly strict. This has put forward higher quality requirements for refining products, and it is particularly important to develop inferior and heavy oil lightening and deep processing technology.

The suspended bed hydrogenation process passes the highly dispersed fine particle catalyst or additive through the reactor together with the feedstock oil and hydrogen. It is a low-quality heavy oil deep processing method with low investment and operation cost, and has strong raw material adaptability (especially suitable for treatment). The metal and impurity content is high, the inferior heavy oil which is difficult to be treated by the fixed bed hydrogenation device), the process is simple, the conversion rate and the demetallization rate are high, and the light oil yield is high. Therefore, heavy oil suspension bed hydrogenation technology has attracted extensive attention at home and abroad, and the catalyst as the core of the suspended bed hydrocracking process technology has become the focus of research and development of suspended bed hydrogenation technology.

Catalysts for suspension bed hydrogenation technology are mainly supported catalysts, water-soluble dispersion catalysts and oil-soluble dispersion catalysts. Wherein, the supported catalyst is composed of a carrier and an active component, and the performance of the catalyst depends on the inherent catalytic characteristics of the active component, the nature of the carrier itself, and the interaction between the active component and the carrier, and the catalyst is hydrocracked in the oil. In the process of hydrotreating, etc., it has a wide range of applications. The supported catalyst has the advantages of simple preparation method, easy control of morphology, good coking property and recyclability. The reason for improving the coking ability of the catalyst can be improved to some extent by rational selection of the carrier and modification of the carrier. Dispersibility.

CN102069004A discloses a coal tar special hydrocracking catalyst and a preparation method thereof, wherein the catalyst is a composite of activated alumina, zeolite and BaO. The zeolite is modified with ammonium nitrate and calcined in an air atmosphere containing water vapor; the aluminum hydroxide dry rubber powder is mixed with dichlorobenzene and aqueous hydrochloric acid to obtain a gelatinous mixture, and then calcined to obtain activated alumina; finally, kneaded and extruded. Strips and pretreatment provide a support with a high specific surface area, a suitable pore size and an active center. However, the preparation process of the catalyst carrier is complicated, the steps are cumbersome, and a large amount of acid and organic substances are needed in the preparation process, causing pollution discharge, and the principle of low cost and simple process which does not meet the requirements of industrial applications.

CN102380396A discloses a bimetallic or polymetallic high dispersion composite coal tar hydrogenation catalyst and a preparation method thereof. The catalyst comprises nano-sized low-active component γ-FeOOH particles and metal water-soluble from molybdenum, nickel, tungsten or cobalt. a molecular-level, highly active component of one or more mixtures of a salt compound, the active component being uniformly and highly dispersed on the surface of the micron or even sub-nanometer carrier coal powder, wherein the high active component metal and the low active component metal Fe The mass ratio is between 1:1000 and 1:10, the iron content is 3-15 wt%, the carrier coal content is 50-90 wt% of the catalyst, and the water content is less than 4 wt%, which is in the form of a fine powder. In the invention, in order to obtain a catalyst powder having good dispersibility and to improve the uniform dispersibility of the low active component and the high active component in the catalyst on the carrier coal powder, the mass percentage of the carrier coal is as high as 50-90 wt. %, while the low active component iron content is less, only 3-15wt%, the content of the high active component metal is only one thousandth to one tenth of the mass of the metal Fe, so that the catalyst improves the overall dispersion Simultaneously reduced catalytic activity. In addition, the preparation of the patented catalyst uses a ferrous salt solution to react with a weakly alkaline solution or a strong alkaline solution to form an active component γ-FeOOH, which not only has a low utilization rate of raw materials, but also undergoes subsequent dehydration treatment, and the preparation process A large amount of waste liquid will also be generated, which increases the processing cost and does not comply with industrial and environmental policies.

CN104998693A discloses a carrier, a poor quality oil hydrogenation catalyst based on the carrier and a preparation method thereof. The carrier is a modified bauxite ore, and the modification method comprises immersing the bauxite ore after high temperature baking in an acid solution for acid treatment. The specific surface area and pore volume of the modified bauxite increased significantly, the acid center of the carrier surface was redistributed, and the pore structure was optimized, thereby improving the catalytic hydrogenation performance of the inferior oil. However, the acid treatment method used in the preparation of the catalyst carrier generates a large amount of acidic waste liquid, and at the same time, part of the iron in the bauxite is also immersed in the acid solution by reacting with the acid, so that the utilization rate of the raw material is lowered, and the green chemistry is not met. Concept.

Although the supported catalyst has many advantages, the supported catalyst synthesized by the conventional method still has the disadvantages of low dispersibility, easy coking, short life, and the like, and the novel synthesis method for preparing the highly dispersible catalyst is also subject to factors such as cost and process conditions. Restricted and difficult to industrialize. Therefore, if breakthroughs can be made in reducing catalyst cost, improving catalytic efficiency, and reducing coke yield, supported catalysts are expected to find industrial applications in the field of inferior heavy oil processing.

Summary of the invention

The object of the present invention is to provide a low-quality heavy oil suspension bed hydrocracking catalyst capable of effectively solving the problems of low hydrocracking activity, high coke yield, complicated preparation process and high production cost in view of the above-mentioned deficiencies of the prior art. Its preparation method.

The object of the invention is achieved by the following technical solutions:

A low-quality heavy oil suspension bed hydrocracking catalyst is prepared by using hydrothermally activated bauxite ore powder as a carrier and one or more transition metals of group VIB and/or VIII as an active component; The active component is supported in an amount of from 0.1 to 15% by weight based on the metal oxide.

Further, the transition metal is one or more of molybdenum, nickel, cobalt and tungsten.

The invention provides a preparation method of a poor quality heavy oil suspension bed hydrocracking catalyst, comprising the following steps:

(1) The bauxite ore powder is placed in a hydrothermal activation device for hydrothermal activation, and after cooling, a catalyst carrier is obtained;

(2) The prepared catalyst carrier is impregnated, dried, and calcined with a precursor solution containing a transition metal of Group VIB and/or Group VIII to obtain a spent heavy oil suspension bed hydrocracking catalyst.

More specifically, in the hydrothermal activation in the step (1), the mass ratio of the bauxite ore powder to the water vapor in the hourly inlet device is 1:0.2 to 2, the activation temperature is 400 to 1000 ° C, and the activation time is 2 ~ 10h.

More specifically, the precursor of the transition metal of Group VIB and/or Group VIII described in the step (2) is one or more of ammonium molybdate, nickel nitrate, cobalt nitrate and ammonium metatungstate; For equal volume impregnation.

More specifically, the drying temperature in the step (2) is 90 to 150 ° C, the drying time is 2 to 12 hours, the baking temperature is 400 to 800 ° C, and the baking time is 2 to 8 hours.

The inferior heavy oil hydrocracking catalyst prepared by the method of the invention exhibits high catalytic activity and low growth for hydrocracking of inferior heavy oil (normal pressure residual oil, vacuum residue, coal tar, shale oil, etc.). The coke rate effectively solves the problems of low hydrocracking activity, high coke yield, complicated preparation process and high production cost of the existing inferior heavy oil hydrocracking catalyst.

The invention provides a poor quality heavy oil suspension bed hydrocracking catalyst and a preparation method thereof, which have the following advantages compared with the prior art:

(1) The carrier of the invention directly uses natural bauxite which is abundant in reserves and low in price as raw material, can effectively reduce the preparation cost of the catalyst, and the hydrothermal activation process is simple, easy to operate, green and environmentally friendly, and has good performance. Industrial application prospects;

(2) The specific surface area of the hydrothermally activated bauxite carrier according to the present invention is significantly increased compared with that before the hydrothermal treatment, and has a large pore diameter, which can improve the catalyst on asphalt, colloidal and condensed aromatic hydrocarbons. The hydrogenation activity of the molecule, thus having a higher hydrocracking activity and a lower coke yield when used in a catalytic reaction of a low-quality heavy oil suspension bed hydrocracking.

detailed description

The embodiments of the present invention and the beneficial effects thereof are described in detail below by way of specific examples, which are intended to provide a better understanding of the nature and features of the present invention. Examples 1 to 4 illustrate the preparation of the support and the catalyst, and Comparative Examples 1 to 2 illustrate the preparation of the catalyst carrier and the catalyst as a comparison, and Examples 5 to 9 illustrate the application of the catalyst in the hydrocracking reformation of the inferior heavy oil suspension bed. Effect.

The specific surface area and average pore diameter described in the respective examples were measured by an N ₂ adsorption-desorption experiment; the analysis items for evaluating the catalytic performance of the catalyst were mainly simulated distillation of the liquid product and toluene insoluble content. The distillate yield, the inferior heavy oil conversion rate and the coke yield were the main evaluation indexes of the catalyst performance. The calculation method is as follows:

Inferior heavy oil conversion rate = 524 ° C or less component quality (including gas) / feedstock oil quality × 100%;

Distillate yield = 524 ° C or less liquid component mass / feedstock oil mass × 100%;

Biofocus rate = toluene insoluble mass / raw material oil quality × 100%;

Liquid yield = liquid product quality / feedstock quality × 100%;

Gas yield = (feedstock amount - solid, total liquid product) / feedstock quality x 100%.

Example 1

A preparation method of a low-quality heavy oil suspension bed hydrocracking catalyst, the specific steps are as follows:

1) Weigh 40.00g of natural bauxite ore raw powder and put it into a hydrothermal device for activation treatment. The activation temperature is 700 ° C, the activation time is 8 h, the mass of water vapor in the device and the quality of bauxite powder per hour. The ratio is 1:1, the activation is completed to obtain a catalyst carrier, the specific surface area is 110 m ² /g, and the average pore diameter is 7.7 nm;

2) 20.00 g of the above-obtained carrier was weighed and immersed in an aqueous solution of (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O containing 0.70 g of active metal Mo (calculated as Mo ₂ O ₃ ) in an equal volume. The impregnation method is impregnated with (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O on the support, the immersion temperature is room temperature, the immersion time is 10 h, and then dried at 110 ° C for 8 h and 650 ° C for 6 h to obtain the inferior quality. Heavy oil hydrocracking catalyst A.

Example 2

1) Weigh 40.00g of natural bauxite ore raw powder and put it into a hydrothermal device for activation treatment. The activation temperature is 600 ° C, the activation time is 6 h, and the mass of water vapor and the quality of bauxite powder are introduced into the device per hour. a ratio of 0.5:1, the end of the activation to obtain a catalyst carrier, a specific surface area of 114 m ² /g, an average pore diameter of 6.5 nm;

2) 20.00 g of the above-obtained carrier was weighed and immersed in an aqueous solution of Co(NO ₃ ) ₂ ·6H ₂ O containing 1.40 g of active metal Co (as Co ₂ O ₃ ), using an equal volume impregnation method The carrier is impregnated with Co(NO ₃ ) ₂ ·6H ₂ O, the immersion temperature is room temperature, the immersion time is 12 h, and then dried at 110 ° C for 12 h and 600 ° C for 4 h to obtain the inferior heavy oil hydrocracking catalyst. B.

Example 3

1) Weigh 40.00g of natural bauxite ore powder and place it in a hydrothermal activation device for activation treatment. The activation temperature is 500 ° C, the activation time is 4 h, and the mass of water vapor and the bauxite powder are introduced into the device every hour. The mass ratio is 2:1, and the catalyst carrier is obtained after the activation, the specific surface area is 120 m ² /g, and the average pore diameter is 7.8 nm;

2) 20.00 g of the above-obtained support was weighed and immersed in Ni (NO ₃ ) containing 0.20 g of active metal Ni (as Ni ₂ O ₃ ) and 0.40 g of active metal Mo (calculated as Mo ₂ O ₃ ) In a mixed aqueous solution of ₂ ·6H ₂ O and (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O, the carrier is impregnated with Ni(NO ₃ ) ₂ ·6H ₂ O and (NH ₄ ) by an equal volume impregnation method. ₆ Mo ₇ O ₂₄ · 4H ₂ O, the impregnation temperature is room temperature, the immersion time is 12 h, and then dried at 110 ° C for 6 h and calcined at 500 ° C for 8 h to obtain the inferior heavy oil hydrocracking catalyst C.

Example 4

1) Weigh 40.00g of natural bauxite ore powder and place it in a hydrothermal activation device for activation treatment. The activation temperature is 500 ° C, the activation time is 4 h, and the mass of water vapor and the bauxite powder are introduced into the device every hour. The mass ratio is 2:1, and the catalyst carrier is obtained after the activation, the specific surface area is 117 m ² /g, and the average pore diameter is 7.5 nm;

2) 20.00 g of the above-obtained support was weighed and immersed in an aqueous solution of (NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ ·nH ₂ O containing 0.70 g of active metal W (as WO ₃ ), using an equal volume The impregnation method is performed by impregnating (NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ ·nH ₂ O on the support, the immersion temperature is room temperature, the immersion time is 12 h, and then drying at 110 ° C for 6 h, 500 ° C for 8 h, the obtained Inferior heavy oil hydrocracking catalyst D.

Comparative example 1

20.00 g of unactivated natural bauxite ore powder (having a specific surface area of 94 m ² /g, an average pore diameter of 5.9 nm) was weighed and immersed in 0.70 g of active metal Mo (calculated as Mo ₂ O ₃ ) of _{_{_{(NH 4) 7 O 24 ·}}} 4H 2 O aqueous solution ₆ Mo, the use of incipient wetness impregnation on the carrier is impregnated _{_{_{(NH 4) 6 Mo 7 O}}} 24 · 4H 2 O, the immersion temperature is room temperature, dipping time After 10 h, it is dried at 110 ° C for 8 h and calcined at 650 ° C for 6 h to obtain the inferior heavy oil hydrocracking catalyst E.

Comparative example 2

20.00 g of unactivated natural bauxite ore raw powder is weighed, and the inferior heavy oil hydrocracking catalyst F is obtained without any active metal.

Examples 5-9

In order to demonstrate the application effect of the catalyst of the present invention in the inferior heavy oil suspension bed hydrocracking reaction, the present invention tested the suspension bed hydrocracking catalytic performance of the catalysts in the examples and comparative examples. The specific steps are as follows: high temperature coal tar (the nature of which is shown in Table 1) is used as a reaction raw material, and 100-2000 ppm of the catalysts obtained in the above Examples 1-3 and Comparative Examples 1-2 and 100-2000 ppm of sublimed sulfur are added to the autoclave. At room temperature, the air in the kettle is fully replaced with hydrogen, and then pressurized to 5 to 24 MPa, the reaction temperature is 350 to 450 ° C, and the reaction time is 0.5 to 4 hours. The specific reaction conditions are shown in Table 2. After the reaction was completed, the liquid oil to be taken out was weighed until the temperature was lowered to room temperature. The activity test results obtained in the experiment are shown in Table 3.

Table 1 high temperature coal tar properties

Table 2 Activity test conditions of different suspension bed hydrogenation catalysts

Table 3 Evaluation Index of Inferior Heavy Oil Suspension Bed Hydrocracking Catalyst

It can be seen from the data in Table 3 that the inferior heavy oil suspension bed hydrocracking catalyst (sample AC) of the present invention has a poor quality heavy oil conversion rate of more than 90% by weight, a distillate oil yield of more than 80% by weight, and a liquid yield of light oil. The yield of the component can reach 95.0wt%, and the coke yield is lower than 0.5wt%; and the inferior heavy oil conversion rate and fraction of the catalyst prepared by using the unactivated bauxite raw powder as the carrier (samples D and E) Both the oil yield and the liquid yield were significantly lower, and the coke yield was higher than 3.0 wt%.

It can be seen from the above results that the catalyst of the present invention has higher catalytic activity and lower coke yield for hydrocracking modification of inferior heavy oil.

Claims

An inferior heavy oil suspension bed hydrocracking catalyst characterized in that the catalyst is a hydrothermally activated bauxite ore powder as a carrier, and one or more transition metals of group VIB and/or VIII It is prepared as an active component; wherein the active component is supported in an amount of from 0.1 to 15% by weight based on the metal oxide.
The inferior heavy oil suspension bed hydrocracking catalyst according to claim 1, wherein the transition metal is one or more of molybdenum, nickel, cobalt and tungsten.
A method for preparing a poor quality heavy oil suspension bed hydrocracking catalyst according to claim 1 or 2, comprising the steps of:

(1) The bauxite ore powder is placed in a hydrothermal activation device for hydrothermal activation, and after cooling, a catalyst carrier is obtained;

(2) The prepared catalyst carrier is impregnated, dried, and calcined with a precursor solution containing a transition metal of Group VIB and/or VIII to obtain a spent heavy oil suspension bed hydrocracking catalyst.
The method for preparing a low-quality heavy oil suspension bed hydrocracking catalyst according to claim 3, wherein the specific parameters of the hydrothermal activation in the step (1) are: bauxite ore powder and an hourly inlet device. The mass ratio of water vapor is 1:0.2 to 2, the activation temperature is 400 to 1000 ° C, and the activation time is 2 to 10 h.
The method for preparing a low-quality heavy oil suspension bed hydrocracking catalyst according to claim 3, wherein the precursor of the group VIB and/or VIII transition metal according to the step (2) is ammonium molybdate, nickel nitrate and nitric acid. One or more of cobalt and ammonium metatungstate; the impregnation is an equal volume impregnation.
The method for preparing a low-quality heavy oil suspension bed hydrocracking catalyst according to claim 3, wherein the drying temperature in the step (2) is 90 to 150 ° C, the drying time is 2 to 12 hours, and the baking temperature is 400 to 800. °C, roasting time is 2 ~ 8h.