A method for utilizing gasification ash and a slurry bed residual oil hydrogenation method

Abstract

A method for utilizing gasification ash and a slurry bed residue oil hydrotreating method are disclosed. The method for utilizing gasification ash includes: (1) drying and dehydrating the gasification ash and then pulverizing it; (2) impregnating the obtained gasification ash powder with a soluble salt solution of an active metal component, wherein the active metal component is selected from one or more of Fe, Co, and Ni; (3) drying the impregnated gasification ash powder and then calcining it under a hydrogen or inert gas atmosphere to obtain a residue oil hydrotreating demetallization catalyst. The residue oil hydrotreating demetallization catalyst prepared by the method provided by this invention has high catalytic activity, anti-coking performance, and good demetallization effect. It improves the economic value of gasification ash and realizes the resource recycling of gasification ash. The slurry bed residue oil hydrotreating method provided by this invention has a high residue oil conversion rate and a good demetallization effect.

Description

Technical Field

[0001] This invention relates to a method for heavy oil processing and waste residue utilization in the petrochemical field, and more specifically, to a method for utilizing gasification ash residue. Background Technology

[0002] In recent years, with the continuous growth of oil demand and the shrinking reserves of shallow, easily exploitable light crude oil, the proportion of heavy, inferior crude oil with high sulfur, high metal content, and high carbon residue in global crude oil supply has shown a year-on-year upward trend. At the same time, with increasingly stringent environmental regulations and continuously upgrading product quality standards, it is necessary to deeply process heavy oil resources to improve resource utilization and maximize the production of liquid fuels.

[0003] The solvent deasphalting-de-oil asphalt gasification-deasphalting oil hydrotreating-catalytic cracking combined process is an important approach to solving the deep processing of heavy oil and achieving efficient utilization of petroleum resources. This process uses C3-C5 as the extraction solvent, extracting deasphalted oil from vacuum residue, which is then hydrotreated and used as feedstock for the catalytic cracking unit. The de-oiled asphalt is used as feedstock for the asphalt gasification unit to produce syngas. Asphalt gasification technology uses de-oiled asphalt and oxygen as feedstock, employing a fluidized bed process under pressurized, non-catalytic conditions to carry out a partial oxidation reaction, generating syngas with carbon monoxide and hydrogen as active components. This syngas can be used as fuel for gas turbines to generate electricity through integrated gasification combined cycle (IGCC) systems, or it can be used to produce hydrogen, which is then used as feedstock for hydrogenation in refining units. This integrates refining, hydrogen production, and power generation to maximize the utilization of petroleum resources. Currently, this process has been successfully applied in petrochemical enterprises and has achieved good economic benefits.

[0004] Asphalt gasification units produce a small amount of gasification ash, which is considered industrial waste. Currently, in China, this ash is mainly used as boiler fuel, typically mixed with coal for combustion to generate steam or power, resulting in low utilization value.

[0005] In recent years, several domestic and international companies have conducted extensive research on carbon-supported catalysts for residue hydrotreating, which show broad application prospects. CN102049252A discloses a method for preparing a suspended bed residue hydrotreating catalyst using activated carbon as a support. By chemically modifying the number and distribution of oxygen-containing functional groups on the support surface, the resulting catalyst exhibits high activity and low coking rate. CN103861595B discloses a residue hydrotreating catalyst using graphitized porous activated carbon as a support for metal loading. The porous carbon support can stabilize carbon free radicals, inhibit coking, improve the metal removal rate of the catalyst, and exhibit good catalytic stability.

[0006] The above studies mainly focus on the hydrogenation and demetallization reaction of residue oil after loading metals onto activated carbon, and the metals used are mainly Mo, Co, Ni and W, with high catalyst costs. Summary of the Invention

[0007] One of the technical problems to be solved by this invention is to provide an environmentally friendly method for utilizing gasification ash in the petrochemical field, based on existing technologies.

[0008] The second technical problem to be solved by the present invention is to provide a slurry bed method for hydrogenating residue oil using a residue oil hydrogenation catalyst prepared from gasified ash residue as raw material.

[0009] A method for utilizing gasification ash includes:

[0010] (1) Dry and dehydrate the gasification ash residue and then pulverize it into gasification ash residue powder;

[0011] (2) The gasification ash powder is impregnated with a soluble salt solution of an active metal component, wherein the active metal component is selected from one or more of Fe, Co and Ni.

[0012] (3) After the impregnated gasified ash powder is dried, it is calcined in a hydrogen or inert gas atmosphere to obtain a hydrogenation demetallization catalyst for residue oil.

[0013] The present invention also provides a residue oil hydrodemetallization catalyst prepared by the above-mentioned method for utilizing gasification ash.

[0014] A slurry bed residue oil hydrotreating method involves mixing the aforementioned residue oil hydrotreating demetallization catalyst with residue oil in a slurry bed reactor and reacting under residue oil hydrotreating operating conditions. After the reaction, the stream is separated into liquid and solid components to obtain hydrotreating residue oil, which is then fractionated into gasoline, diesel, wax oil, and residue oil.

[0015] Compared with existing catalysts, the beneficial effects of the gasification ash utilization method provided by this invention are as follows:

[0016] Gasification ash is an industrial waste, typically disposed of in landfills outside the plant or used as fuel after treatment. The method provided in this invention dries and pulverizes the gasification ash, then uses it as a catalyst carrier, thereby increasing its economic value and achieving resource recycling of the gasification ash.

[0017] Catalysts prepared using gasification ash as raw material can significantly reduce the raw material cost of residue oil hydrotreating catalysts. The residue oil hydrotreating demetallization catalyst prepared by the method provided in this invention exhibits high catalytic activity, anti-coking performance, and good demetallization effect. The method for preparing catalysts using gasification ash provided in this invention has simplified steps, low cost, and reduces emissions of waste gas, wastewater, and solid waste because the support does not require chemical modification to obtain surface groups.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] A method for utilizing gasification ash includes:

[0021] (1) Dry and dehydrate the gasification ash residue and then pulverize it into gasification ash residue powder;

[0022] (2) The gasification ash powder is impregnated with a soluble salt solution of an active metal component, wherein the active metal component is selected from one or more of Fe, Co and Ni.

[0023] (3) After the impregnated gasified ash powder is dried, it is calcined in a hydrogen or inert gas atmosphere to obtain a hydrogenation demetallization catalyst for residue oil.

[0024] In the method provided by this invention, the gasification ash residue mentioned in step 1) is the ash residue generated during the heavy oil gasification process; the heavy oil refers to petroleum fractions with a distillation range greater than 350°C.

[0025] Preferably, the gasification ash is selected from one or a mixture of several of vacuum residue, deoiled bitumen, catalytic slurry, and ethylene tar gasification ash.

[0026] Optionally, the particle size of the gasification ash powder mentioned in step (1) is 10-100 μm; preferably 20-50 μm. The particle size of the gasification ash powder mentioned in this invention is measured by a laser particle size analyzer.

[0027] Preferably, based on the weight of the gasification ash, the gasification ash powder obtained in step (1) contains: 80-85% C, 1-3% H, 1-5% S, 0.1-1% N, 0.5-5% Ni, 1-10% V, and a specific surface area of ​​200-950 m². 2 / g, with a particle size of 20-60μm.

[0028] The high specific surface area of ​​asphalt gasification ash residue, coupled with the naturally occurring oxygen-containing groups on its surface, facilitates the preparation of highly active, coking-resistant residue hydrogenation catalysts. Furthermore, the presence of metals such as Ni, V, and Fe in the ash residue support promotes the residue hydrogenation reaction and enhances catalyst activity.

[0029] Preferably, the active metal component is Fe; the soluble salt of the active metal component is one or more of ferric nitrate, ferric sulfate, and ferrous sulfate; and the concentration of the soluble salt solution of the active metal component, calculated by metal content, is 0.5-5 g Fe / 100 mL.

[0030] Preferably, the impregnation conditions in step (2) are: impregnation temperature of 20-90℃, impregnation time of 30-300 min, and metal loading after impregnation and calcination of 0.5-35% by weight.

[0031] Preferably, the drying conditions in step (3) are: temperature of 90-120℃ and time of 120-360min; the calcination conditions are: temperature of 400-700℃ and time of 90-360min, and the inert gas is nitrogen, argon or helium.

[0032] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0033] The deoiled bitumen gasification ash from Fujian United Petrochemical used in this embodiment of the invention, based on the weight of the gasification ash, contains the following components in the dewatered ash: Ni 0.1 wt%, V 0.4 wt%, Fe 0.15 wt%, C 84.44 wt%, H 1.44 wt%, S 1.36 wt%, O 5.60 wt%, and has a specific surface area of ​​200-950 m². 2 / g, with a particle size of 20-60μm.

[0034] Example 1

[0035] (1) The deoiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use;

[0036] (2) Using Fe(NO3)3·9H2O as the active component precursor, prepare an aqueous solution of ferric nitrate with a concentration of 2.5g Fe / 100ml; immerse 10ml of the ferric nitrate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 60℃ for 180min; after immersion, dry at 110℃ for 300min for later use.

[0037] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A1.

[0038] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the iron (calculated as metal) content is 8.44 wt%.

[0039] Example 2

[0040] (1) The deoiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use;

[0041] (2) Using Fe(NO3)3·9H2O as the active component precursor, prepare an aqueous solution of ferric nitrate with a concentration of 2g Fe / 100ml; immerse 20ml of the ferric nitrate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 50℃ for 240min; after immersion, dry at 120℃ for 240min for later use.

[0042] (3) The dried solid powder was placed in a tube furnace and calcined at 550°C for 360 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A2.

[0043] In the catalyst prepared in this embodiment, based on the residue oil hydrodemetallization catalyst, the iron (calculated as metal) content is 11.82 wt%.

[0044] Example 3

[0045] (1) After drying and dehydrating the de-oiled asphalt gasification ash at 120℃, it is crushed to a particle size of 20-60μm for later use.

[0046] (2) Using FeSO4·9H2O as the active component precursor, prepare an aqueous solution of ferrous sulfate with a concentration of 2.5g Fe / 100ml; immerse 30ml of the ferrous sulfate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 70℃ for 180min; after immersion, dry at 110℃ for 240min for later use.

[0047] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A3.

[0048] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the iron (calculated as metal) content is 22.10 wt%.

[0049] Example 4

[0050] (1) The de-oiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use.

[0051] (2) Using FeSO4·9H2O as the active component precursor, prepare an aqueous solution of ferrous sulfate with a concentration of 1.5g Fe / 100ml; immerse 25ml of the ferrous sulfate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at an immersion temperature of 80℃ for 200min; after immersion, dry at 110℃ for 240min for later use.

[0052] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A4.

[0053] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the iron (calculated as metal) content is 13.82 wt%.

[0054] Example 5

[0055] (1) The deoiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use;

[0056] (2) Using Fe2(SO4)3 as the active component precursor, prepare an aqueous solution of ferrous sulfate with a concentration of 3gFe / 100ml; immerse 30ml of the ferrous sulfate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 60℃ for 180min; after immersion, dry at 110℃ for 240min for later use.

[0057] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A5.

[0058] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the iron (calculated as metal) content is 21.71 wt%.

[0059] Example 6

[0060] (1) The deoiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use;

[0061] (2) Using Fe(NO3)3·9H2O and Ni(NO3)2·6H2O as active component precursors, prepare aqueous solutions of ferric nitrate and nickel nitrate with concentrations of 1.5g Fe / 100mL and 0.5g Ni / 100mL, respectively. Immerse 25mL of ferrous sulfate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 60℃ for 180min. After immersion, dry at 120℃ for 300min for later use.

[0062] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A6.

[0063] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the content of iron (calculated as metal) is 8.54 wt% and the content of nickel (calculated as metal) is 5.67 wt%.

[0064] Example 7

[0065] (1) The deoiled asphalt gasification ash residue is dried and dehydrated at 120℃ and then crushed to a particle size of 20-60μm for later use;

[0066] (2) Using Fe(NO3)3·9H2O and Co(NO3)2·6H2O as active component precursors, prepare aqueous solutions of ferric nitrate and nickel nitrate with concentrations of 1.5g Fe / 100mL and 0.5g Co / 100mL, respectively. Immerse 25mL of ferrous sulfate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 60℃ for 180min. After immersion, dry at 120℃ for 300min for later use.

[0067] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst A7.

[0068] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the content of iron (calculated as metal) is 8.73 wt% and the content of cobalt (calculated as metal) is 4.86 wt%.

[0069] Comparative Example 1

[0070] (1) Dry the activated carbon at 120℃ to remove water and then pulverize it to a particle size of 20-60μm for later use;

[0071] (2) Using Fe(NO3)3·9H2O as the active component precursor, prepare an aqueous solution of ferric nitrate with a concentration of 2.5g Fe / 100mL; immerse 10mL of the ferric nitrate aqueous solution into 2.5g of the above-mentioned dried gasification ash residue at a temperature of 60℃ for 180min; after immersion, dry at 110℃ for 240min for later use.

[0072] (3) The dried solid powder was placed in a tube furnace and calcined at 600°C for 300 min under N2 gas protection to prepare residue oil hydrodemetallization catalyst B1.

[0073] In the catalyst prepared in this embodiment, based on the residue hydrodemetallization catalyst, the iron (calculated as metal) content is 8.79 wt%.

[0074] Examples 8-15 and Comparative Example 2 are examples for catalyst evaluation.

[0075] Example 8

[0076] Using vacuum residue as the reaction feedstock, the specific properties of which are shown in Table 3, 200g of feedstock oil and 1.896g of residue hydrodemetallization catalyst A1 (metal addition amount of 800μg·g) were added to a 1.8L high-pressure reactor. –1 The vulcanizing agent was sublimed sulfur, added at a mass of 0.112 g. At room temperature, the air inside the reactor was first replaced with nitrogen, then the nitrogen was replaced with hydrogen and pressurized to 6.0 MPa. The reaction temperature was 430℃, and the reaction was continued for 120 min after reaching the reaction temperature. After the reaction was completed, the temperature was allowed to drop to room temperature, and the gas was collected using a gas bag for analysis. The solid residue and liquid product were separated and weighed, and the residue-oil conversion rate, liquid yield, and coking rate were calculated. The operating conditions and reaction results are shown in Table 4.

[0077] The following formulas are used to calculate the residue oil conversion rate, distillate oil yield, metal removal rate, and coking rate, which serve as evaluation indicators of the reaction effect:

[0078] Residue oil conversion rate = (Mass of components below 524℃ / Mass of feedstock oil) × 100%

[0079] Distillate oil yield = (Mass of liquid component below 524℃ / Mass of feedstock oil) × 100%

[0080] Metal removal rate = (1 - Metal content in liquid product × Liquid product yield / Metal content in raw material) × 100%

[0081] Example 9

[0082] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A1 was evaluated, except that the amount of catalyst A1 added for the hydrodemetallization of residue oil was 0.948 g (the amount of metal added was 400 μg·g). –1 The vulcanizing agent was sublimed sulfur, with an addition mass of 0.056 g. The reaction temperature was 435℃, the initial hydrogen pressure was 7.0 MPa, and the reaction time was 90 min. The operating conditions and reaction results are shown in Table 4.

[0083] Example 10

[0084] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A2 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A2 added was 1.354 g (the amount of metal added was 800 μg·g). –1 The vulcanizing agent was sublimed sulfur, with an addition mass of 0.112 g. The reaction temperature was 420℃, the initial hydrogen pressure was 9.0 MPa, and the reaction time was 300 min. The operating conditions and reaction results are shown in Table 4.

[0085] Example 11

[0086] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A3 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A3 added was 0.724 g (the amount of metal added was 800 μg·g). –1 The vulcanizing agent was sublimed sulfur, with an addition mass of 0.112 g. The reaction temperature was 420℃, the initial hydrogen pressure was 8.0 MPa, and the reaction time was 240 min. The operating conditions and reaction results are shown in Table 4.

[0087] Example 12

[0088] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A4 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A4 added was 0.724 g (the amount of metal added was 800 μg·g). –1 The sulfiding agent was carbon disulfide, with an addition mass of 0.134 g. The reaction temperature was 430℃, the initial hydrogen pressure was 6.0 MPa, and the reaction time was 120 min. The operating conditions and reaction results are shown in Table 5.

[0089] Example 13

[0090] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A5 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A5 added was 0.724 g (the amount of metal added was 800 μg·g). –1 The vulcanizing agent was dimethyl disulfide, with an addition mass of 0.165 g. The reaction temperature was 430℃, the initial hydrogen pressure was 6.0 MPa, and the reaction time was 120 min. The operating conditions and reaction results are shown in Table 5.

[0091] Example 14

[0092] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A6 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A6 added was 1.176 g (the amount of metal added was 800 μg·g). –1 The vulcanizing agent was sublimed sulfur, with an addition mass of 0.12 g. The reaction temperature was 430℃, the initial hydrogen pressure was 6.0 MPa, and the reaction time was 120 min. The operating conditions and reaction results are shown in Table 5.

[0093] Example 15

[0094] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst A7 for hydrodemetallization of residue oil was evaluated. The difference from Example 8 was that the amount of catalyst A7 added was 1.178 g (the amount of metal added was 800 μg·g). –1The vulcanizing agent was sublimed sulfur, with an addition mass of 0.12 g. The reaction temperature was 430℃, the initial hydrogen pressure was 6.0 MPa, and the reaction time was 120 min. The operating conditions and reaction results are shown in Table 5.

[0095] Comparative Example 2

[0096] The reaction apparatus and experimental methods were the same as in Example 8. The reaction performance of catalyst B1 for residue hydrodemetallization was evaluated by conducting experiments on catalyst B1 in a slurry bed residue hydrotreating system. The operating conditions and reaction results are shown in Table 5.

[0097] As shown in Tables 4 and 5, compared with Example 8 and Comparative Example 2, the iron catalyst supported on gasified ash is superior to the catalyst supported on activated carbon in terms of residue oil conversion rate, liquid yield, coking rate, and demetallization rate. This indicates that the slurry-bed residue oil hydrodemetallization catalyst prepared by this invention has a high demetallization rate, high liquid yield, and low coking rate. Furthermore, comparing Examples 8, 14, and 15, it can be seen that the FeNi and FeCo bimetallic supported catalysts are slightly superior to the Fe catalyst in terms of coking rate, while other reaction performances are comparable. However, considering that nickel is 30 times more expensive than iron, and cobalt is 70 times more expensive than iron, iron is preferred as the metal component of this catalyst for economic reasons. This catalyst also has the advantages of low cost, simple preparation, and the ability to utilize hazardous waste resources.

[0098] Table 1. Composition and physical properties of catalysts

[0099] Instance number Example 1 Example 2 Example 3 Example 4 catalyst A1 A2 A3 A4 Composition / wt% Fe 8.44 11.82 22.10 13.82 Ni 0.12 0.09 0.11 0.13 Co - - - - <![CDATA[Specific surface area / m 2 / g]]> 621 580 556 612 Particle size / μm 35.4 28.9 40.6 27.3

[0100] Table 2 Composition and physical properties of catalysts

[0101] Instance number Example 5 Example 6 Example 7 Comparative Example 1 catalyst A5 A6 A7 B1 Composition / wt% Fe 21.71 8.54 8.63 8.79 Ni 0.08 5.07 0.09 - Co - - 4.86 - <![CDATA[Specific surface area / m 2 / g]]> 573 605 595 643 Particle size / μm 34.2 26.8 32.1 27.2

[0102] Table 3 Properties of vacuum residue

[0103] Elemental composition / wt% vacuum residue C 84.41 H 11.03 S 4.02 N 0.27 Residual carbon / wt% 12.6 Asphalt / wt% 4.0 <![CDATA[Metal / (μg·g –1 )]]> Ni 29.5 V 81.1 Fe 5.9 Ni+V 110.6

[0104] Table 4. Reaction conditions and evaluation results of iron-based monometallic catalysts

[0105] Example 8 Example 9 Example 10 Example 11 catalyst A1 A1 A2 A3 <![CDATA[Metal / (μg·g –1 )]]> 800 400 800 800 Temperature / °C 430 435 420 420 Pressure / MPa 6 7 9 8 Time / min 120 90 300 240 Residue oil conversion rate / % 78.46 83.11 79.99 74.82 Liquid yield / % 89.47 86.42 89.24 91.14 Coking rate / % 1.82 5.31 1.87 2.37 Nickel removal rate / % 90.29 85.06 83.97 78.99 Vanadium removal rate / % 91.17 90.41 82.39 83.14

[0106] Table 5. Reaction conditions and evaluation results for iron-based monometallic and bimetallic catalysts.

[0107] Example 12 Example 13 Example 14 Example 15 Comparative Example 2 catalyst A4 A5 A6 A7 B1 <![CDATA[Metal / (μg·g –1 )]]> 800 800 800 800 800 Temperature / °C 430 430 430 430 430 Pressure / MPa 6 6 6 6 6 Time / min 120 120 120 120 120 Residue oil conversion rate / % 76.95 78.21 77.81 79.32 73.70 Liquid yield / % 89.47 88.65 90.02 89.43 86.54 Coking rate / % 1.92 1.74 1.32 1.26 5.97 Nickel removal rate / % 89.91 90.71 93.67 92.83 73.60 Vanadium removal rate / % 90.14 91.03 92.25 93.05 74.39

Claims

1. A method for utilizing gasification ash, characterized in that, include: (1) The gasification ash residue is dried and dehydrated and then pulverized into gasification ash residue powder; (2) The gasification ash powder is impregnated with a soluble salt solution of an active metal component, wherein the active metal component is selected from one or more of Fe, Co and Ni; (3) After the impregnated gasification ash powder is dried, it is calcined under hydrogen or an inert atmosphere to obtain a hydrogenation demetallization catalyst for residue oil. Based on the weight of the gasification ash, the carbon content in the gasification ash powder is 80-85%. wt The H content is 1-3%. wt The content of S is 1-5%. wt The content of N is 0.1-1%. wt The Ni content is 0.05-5%. wt The content of V is 0.1-10%. wt %.

2. The method for utilizing gasification ash as described in claim 1, characterized in that, The gasification ash slag mentioned in step (1) is the ash slag produced during the heavy oil gasification process.

3. The method for utilizing gasification ash according to claim 2, characterized in that, The gasification ash is selected from one or a mixture of several of vacuum residue, deoiled bitumen, catalytic slurry, and ethylene tar gasification ash.

4. The method for utilizing gasification ash as described in claim 1, characterized in that, The gasification ash powder mentioned in step (1) has a particle size of 10-100 μm and a specific surface area of ​​100-1000 m². 2 / g.

5. The method for utilizing gasification ash according to claim 4, characterized in that, The gasification ash powder has a particle size of 20-50 μm and a specific surface area of ​​400-1000 m². 2 / g.

6. The method for utilizing gasification ash according to claim 5, characterized in that, The specific surface area of ​​the gasified ash powder is 450-950 m². 2 / g.

7. The method for utilizing gasification ash according to any one of claims 1-6, characterized in that, The active metal component is Fe; the soluble salt of the active metal component is one or more of ferric nitrate, ferric sulfate and ferrous sulfate; the concentration of the soluble salt solution of the active metal component is 0.5-5 g Fe / 100 mL, calculated by metal content.

8. The method for utilizing gasification ash slag according to any one of claims 1-6, characterized in that, The impregnation conditions in step (2) are: impregnation temperature of 20-90℃, impregnation time of 30-300min, and metal loading after impregnation and calcination of 0.5-35% by weight.

9. The method for utilizing gasification ash slag according to any one of claims 1-6, characterized in that, The drying conditions in step (3) are: temperature of 90-120℃ and time of 120-360min; the calcination conditions are: temperature of 400-700℃ and time of 90-360min; and the inert atmosphere is nitrogen, argon or helium.

10. The residue oil hydrodemetallization catalyst prepared by the method of utilizing the gasification ash residue according to any one of claims 1-9.

11. A slurry bed residue oil hydrogenation method, characterized in that, In a slurry bed reactor, the residue oil hydrodemetallization catalyst of claim 10 is mixed with residue oil feedstock, a sulfiding agent is added, and the reaction is carried out under residue oil hydrotreating conditions. After the reaction, the stream is separated by liquid-solid separation to obtain hydrotreated residue oil, which is then fractionated into gasoline, diesel, wax oil and residue oil.

12. The slurry bed residue hydrotreating method according to claim 11, characterized in that, The operating conditions for the hydrotreating of the residue oil are as follows: the reaction temperature is 400-440℃, the reaction time is 90-360 min, the initial hydrogen pressure is 5-9 MPa, the ratio of the hydrotreating demetallization catalyst to the feed oil is 300-1200 μg / g (calculated as metal), and the molar ratio of the sulfiding agent to the hydrotreating demetallization catalyst (calculated as metal) is (1-2):1 (calculated as sulfur).