A method for producing hydrogen from inferior heavy oil

Abstract

A method for producing hydrogen from inferior heavy oil, comprising: contacting the inferior heavy oil with a catalyst containing large-pore zeolite and a metal oxide and undergoing a pre-decomposition reaction to obtain a reaction stream and a deactivated catalyst with carbon; the reaction stream is separated into reaction gas, light oil, and heavy oil; the light oil is sent to a hydrogen production reactor to obtain reaction gas and a deactivated catalyst with carbon; the reaction gas separated from the pre-decomposition reactor and the hydrogen production reactor is sent to a separation unit for further separation into hydrogen, CO, CO2, and light hydrocarbons; the deactivated catalyst with carbon is sent to a regenerator for regeneration; after the deactivated catalyst is regenerated by burning, a portion of the regenerated catalyst is returned to the pre-decomposition reactor for recycling, and the other portion of the regenerated catalyst is returned to the hydrogen production reactor for reduction and recycling, and the regenerated flue gas is separated to obtain CO and CO2. The present invention pre-decomposes the inferior heavy oil, not only improving the quality of the catalytic cracking feedstock, but also producing hydrogen, thereby achieving efficient utilization of inferior heavy oil resources.

Description

Technical Field

[0001] The present invention relates to a method for pre-decomposition and hydrogen production of inferior heavy oil, and more specifically, to a method for pre-decomposition and hydrogen production of inferior heavy oil by fluidized catalytic cracking. Background Art

[0002] Crude oil quality is deteriorating year by year, primarily manifested in increased density, viscosity, heavy metal content, sulfur content, nitrogen content, resin and asphaltenes content, and acid value. Traditional heavy oil processing is divided into two main categories: hydrogenation, which primarily includes hydrotreating and hydrofining; and decarbonization, which primarily includes solvent deasphalting, delayed coking, and heavy oil catalytic cracking. These processes can improve the hydrogen-to-carbon ratio of low-quality heavy oil and convert inferior hydrocarbons into low-boiling-point compounds. When decarbonization is used for low-quality heavy oil, the sulfur, nitrogen, and heavy metal contents, as well as the aromatics, resin, and asphaltenes content, significantly impact the decarbonization process. Hydrotreating can compensate for these deficiencies, resulting in high yields and excellent product properties. However, hydrotreating often requires significant investment and consumes a high hydrogen source. While catalytic cracking struggles with low-quality heavy oils with high carbon residue and high metal content, its operational flexibility makes it a promising candidate for pre-decomposition of low-quality residual oils.

[0003] Hydrogen energy is an ideal new energy source. As a green energy source with abundant reserves, high calorific value, high energy density and diverse sources, there are three relatively mature technical routes for the main hydrogen production methods, namely, the use of fossil energy such as coal and natural gas to produce hydrogen through reforming, the high-temperature decomposition and reforming of chemical raw materials represented by alcohol cracking hydrogen production technology, and the electrolysis of water to produce hydrogen; technical routes such as photolysis of water and biomass gasification to produce hydrogen are still in the experimental and development stage, and it is difficult to make breakthroughs in related technologies, and the demand for large-scale hydrogen production has not yet been met. At present, domestic natural gas reforming and high-temperature cracking hydrogen production are mainly used in large-scale hydrogen production industries. The raw gas in the natural gas hydrogen production process is also fuel gas and does not need to be transported, but the investment in natural gas hydrogen production is relatively high, which is suitable for large-scale industrial production. The general hydrogen production scale is 5000m 3 / h or more, it is more economical to choose the natural gas hydrogen production process. In addition, natural gas raw materials account for more than 70% of the cost of hydrogen production, and the price of natural gas is an important factor in determining the price of hydrogen. The energy characteristics of my country, which is rich in coal, lacking in oil, and less in gas, restrict the implementation of natural gas hydrogen production in my country. Coal gasification hydrogen production is the first choice for industrial large-scale hydrogen production, and it is also the mainstream fossil energy hydrogen production method in my country. The coal-to-hydrogen technology route is mature and efficient, and can be produced stably on a large scale, but the fuel power energy consumption of coal-to-hydrogen is higher than that of natural gas-to-hydrogen, and the requirements for system steam and electricity are high. Enterprises need matching boilers, and the unified construction of coal-fired boilers is subject to government requirements. In addition, environmental protection issues are prominent, the existing urban refineries have stringent environmental requirements, and coal transportation is subject to many factors, which also limits the application of this technology in modern refineries.

[0004] With the development of oil refining technology, especially the increasing trend toward heavier / lower-quality crude oil and improved oil product quality, hydrogenation processes have become more widely used, significantly boosting the demand for hydrogen. According to statistics, global refinery hydrogen demand is increasing by more than 4% annually. Hydrogen from refineries primarily comes from process unit byproducts, refinery gas recovery, and existing refinery hydrogen production units. Refinery-generated hydrogen will no longer be able to meet future growth in hydrogen demand. Therefore, it is necessary to explore more flexible and feasible hydrogen supply strategies. The development of a non-hydrogen-based pre-cracking technology for inferior heavy oil that can also produce hydrogen would undoubtedly have significant practical value. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for producing hydrogen from inferior heavy oil.

[0006] The method for producing hydrogen from inferior heavy oil provided by the present invention comprises the following steps:

[0007] (1) introducing inferior heavy oil into a fluidized bed reactor to contact with a catalyst containing large-pore zeolite and metal oxide and perform a pre-decomposition reaction to obtain a reactant stream and a deactivated catalyst with carbon; performing gas-solid separation on the reaction oil gas and the deactivated catalyst with carbon obtained from the pre-decomposition reaction; and introducing the separated reaction oil gas into a fractionating tower to separate it into gas, light oil, and heavy oil;

[0008] (2) sending the separated light oil to a hydrogen production reactor, contacting it with the reduced regenerated catalyst and water vapor to produce a hydrogen production reaction, thereby obtaining a reactant stream and a deactivated catalyst with carbon; and performing gas-solid separation on the reaction oil gas and the deactivated catalyst with carbon obtained from the hydrogen production reaction;

[0009] (3) The reaction oil and gas separated from the fluidized bed reactor and the hydrogen production reactor are sent to the separation unit for further separation into hydrogen, carbon monoxide, carbon dioxide and light hydrocarbons. The separated light hydrocarbons are sent to the reducer for use as a reducing agent.

[0010] (4) The deactivated catalysts of the fluidized bed reactor and the hydrogen production reactor are sent to the regenerator for regeneration. The deactivated catalysts are divided into two parts after being burned and regenerated. One part of the regenerated catalysts is returned to the fluidized bed reactor for recycling, and the other part of the regenerated catalysts is sent to the reducer. After being reduced and stripped, the catalysts are sent to the hydrogen production reactor for recycling. The regenerated flue gas enters the separation unit to separate carbon monoxide and carbon dioxide.

[0011] The inferior heavy oil is selected from the group consisting of oils with a density greater than 940 kg / m 3 , one or more of the following indicators: , carbon residue greater than 8 weight percent, hydrogen content less than 11.8 weight percent, and heavy metal content greater than 50 mg / kg based on the total weight of nickel and vanadium.

[0012] The catalyst comprises the following components by weight: 5% to 65% of natural minerals, 10% to 60% of oxides, 20% to 60% of large-pore zeolite, and 0.1% to 30%, preferably 0.5-20% by weight, of an active metal component. The active metal component is selected from one or more compounds of transition metal elements.

[0013] The carbon monoxide separated by the separation unit can be used as a raw material for water-gas shift to further produce hydrogen and carbon dioxide; it can also be sent to a carbon monoxide boiler to recover flue gas waste heat to generate high-quality steam.

[0014] The present invention subjects inferior heavy oil to a catalytic cracking pre-decomposition reaction under relatively mild conditions. The resulting light oil is used as a hydrogen production feedstock, providing a low-cost feedstock for hydrogen production. The resulting heavy oil is used as a catalytic cracking feedstock, improving the quality of the catalytic cracking feedstock and achieving efficient raw material utilization.

[0015] The present invention couples the inferior heavy oil pre-decomposition reaction and the light oil hydrogen production reaction. During the reaction, metals in the inferior heavy oil are deposited on the catalyst. These metals can act as dehydrogenation active centers in the hydrogen production reaction, thereby strengthening the light oil dehydrogenation reaction and producing more hydrogen.

[0016] The present invention adopts a fluidized bed reactor to produce hydrogen, which can take advantage of the high coke production in the catalytic cracking reaction of inferior heavy oil, transfer a large amount of heat to the hydrogen production reaction, greatly reduce the energy required for the hydrogen production process, and achieve process economy.

[0017] The present invention performs reduction treatment on the catalyst before the hydrogen production reaction to reduce the high-valent metal oxide to a low-valent metal oxide, thereby increasing the dehydrogenation activity of the catalyst and improving the hydrogen selectivity.

[0018] The present invention preferably adopts low-temperature incomplete regeneration technology to increase the CO / CO2 ratio in the regenerated flue gas, providing a cheap feed gas for the water-gas shift process and optimizing resource utilization. At the same time, the oxygen-containing gas used in the regeneration process preferably adopts oxygen-enriched gas, which greatly increases the concentration of CO2 in the flue gas, enabling large-scale production of CO2. Then, carbon emissions are reduced through capture, utilization, and storage technologies, realizing the production of blue hydrogen. Therefore, the present invention not only provides hydrogen energy, but also facilitates carbon capture, and can bring greater economic and social benefits to the petrochemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The present invention provides a process flow chart of a specific embodiment of the method for pre-decomposition of inferior heavy oil and production of hydrogen. DETAILED DESCRIPTION

[0020] A method for producing hydrogen from inferior heavy oil, the method comprising the following steps:

[0021] Inferior heavy oil is introduced into a fluidized bed reactor and contacted with a catalyst containing large-pore zeolite and metal oxides to undergo a pre-decomposition reaction, thereby obtaining a reactant stream and a deactivated catalyst with carbon. The reaction oil gas and the deactivated catalyst with carbon obtained from the pre-decomposition reaction are subjected to gas-solid separation. The separated reaction oil gas enters a fractionation tower and is further separated into gas, light oil, and heavy oil according to the distillation range. The separated heavy oil is used as a feedstock for a conventional catalytic cracking unit.

[0022] The separated light oil is sent to a hydrogen production reactor, where it contacts the reduced regenerated catalyst and undergoes a hydrogen production reaction, thereby obtaining a reactant stream and a deactivated catalyst with carbon. The reaction oil gas obtained from the hydrogen production reaction and the deactivated catalyst with carbon are subjected to gas-solid separation.

[0023] The reaction oil and gas separated from the fluidized bed reactor and the hydrogen production reactor are sent to the separation unit for further separation into H2, CO, CO2 and light hydrocarbons. The separated light hydrocarbons are sent to the reducer for use as reducing agents.

[0024] The deactivated catalysts from the fluidized bed reactor and hydrogen production reactor are sent to the regenerator for regeneration. After charring and regeneration, the deactivated catalysts are divided into two parts. One part of the regenerated catalysts is returned to the fluidized bed reactor for recycling, and the other part of the regenerated catalysts is sent to the reducer, and after reduction and stripping, it enters the hydrogen production reactor for recycling. The regenerated flue gas enters the separation unit to separate CO and CO2.

[0025] The inferior heavy oil is selected from the group consisting of oils with a density greater than 940 kg / m 3 , one or more of the following indicators: , carbon residue greater than 8 weight percent, hydrogen content less than 11.8 weight percent, and heavy metal content greater than 50 mg / kg based on the total weight of nickel and vanadium.

[0026] The catalyst comprises the following components by weight percentage:

[0027] A) 5% to 65% natural minerals,

[0028] B) 10% to 60% oxides,

[0029] C) 20% to 60% of large pore zeolite, and

[0030] D) 0.1% to 30% metal active component.

[0031] According to the method provided by the present invention, the low-quality heavy oil catalytic cracking pre-decomposition reactor and the hydrogen production reactor are selected from fluidized bed reactors. The fluidized bed reactor is selected from one or a combination of a turbulent bed, a fast bed, and a dilute phase transport bed. The fluidized bed reactor comprises, from bottom to top, a pre-elevation section and at least one reaction zone fluidized bed reactor. To ensure sufficient reaction of the feedstock oil and based on different target product quality requirements, the number of reaction zones can be 2-8, preferably 2-3.

[0032] According to the method provided by the present invention, the conditions for pre-decomposition of the inferior heavy oil include: a reaction temperature of the fluidized bed reactor of 450-600°C, preferably 480-550°C, a reaction time of 0.5-8 seconds, preferably 1-6 seconds, a weight ratio of the catalyst to the inferior heavy oil of 1-30, preferably 5-20; and a weight ratio of water vapor to the inferior heavy oil of 0.01-1, preferably 0.05-0.3.

[0033] According to the method provided by the present invention, the conditions of the light oil hydrogen production reactor include: reaction temperature of 600-1000°C, preferably 650-900°C, reaction time of 1-10, preferably 2-8 seconds, weight ratio of catalyst to light oil of 5-100, preferably 20-50; weight ratio of water vapor to light oil of 0.1-50, preferably 1-20.

[0034] According to the method provided by the present invention, the deactivated catalyst with carbon is separated from the reaction oil and gas in the inferior heavy oil pre-cracking reactor and the hydrogen production reactor to obtain the deactivated catalyst with carbon and the reaction oil and gas. The obtained reaction oil and gas are then separated into hydrogen, CO2, CO, light hydrocarbons, and other fractions through a subsequent separation unit. The separation of hydrogen, CO2, CO, light hydrocarbons, etc. from the reaction products is similar to conventional methods in the art and is not limited by the present invention and is not described in detail here. The CO obtained in the separation unit can be used as a feedstock for the water-gas shift reaction.

[0035] In the method provided by the present invention, the deactivated catalyst with carbon preferably enters the stripping section under the action of gravity, and the hydrocarbon products adsorbed on the deactivated catalyst with carbon are stripped by water vapor. The deactivated catalyst with carbon after stripping enters the regenerator.

[0036] In the method provided by the present invention, the deactivated catalyst with carbon can be regenerated in a conventional regenerator, and a single regenerator or multiple regenerators can be used. During the regeneration process, an oxygen-containing gas is generally introduced from the bottom of the regenerator. After the oxygen-containing gas is introduced into the regenerator, the deactivated catalyst with carbon contacts with oxygen and is burned and regenerated. The flue gas generated after the catalyst is burned and regenerated is separated into gas and solid at the top of the regenerator, and the flue gas enters the water-gas shift unit. The method for regenerating the deactivated catalyst with carbon adopts oxygen-enriched regeneration. The concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 22-100% by volume, preferably 25-80% by volume.

[0037] In the method provided by the present invention, low-temperature incomplete regeneration is preferred, and the operating conditions are: temperature of 550-700°C, preferably 600-650°C; gas superficial linear velocity of 0.2-1.2 m / s, preferably 0.4-0.8 m / s, and the average residence time of the deactivated catalyst with carbon is 1-10 minutes, preferably 2-6 minutes.

[0038] In the method provided by the present invention, the operating conditions of the reducer for regenerating the catalyst are: temperature of 550-700° C.; and gas superficial linear velocity of 0.5-3 m / s.

[0039] In the method provided by the present invention, the natural minerals in the catalyst are selected from one or more of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite, and the content of the natural minerals on a dry basis is 5% to 65% by weight, preferably 15% to 60% by weight; the oxides are one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and amorphous silicon aluminum, and the content of the oxides is 10% to 60% by weight, preferably 10% to 30% by weight, and more preferably 12% to 28% by weight, based on the total amount of the catalyst. The zeolite includes a large-pore zeolite, and the large-pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y, and high-silicon Y.

[0040] The content of the metal active component is 0.1% to 30% by weight, preferably 0.5% to 20% by weight, based on the weight of the catalyst. The metal active component is selected from one or more compounds of transition metal elements, preferably one or more of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium.

[0041] In the method provided by the present invention, the catalyst is prepared using conventional methods for preparing catalytic cracking catalysts, which are well known to those skilled in the art. The metal can be loaded onto the catalyst by impregnation or slurry mixing, with impregnation being preferred, and these methods are well known to those skilled in the art.

[0042] The accompanying drawings are used to provide further understanding of the present disclosure and constitute a part of the specification. Together with the following detailed description, they are used to explain the present disclosure, but do not constitute a limitation of the present disclosure.

[0043] like Figure 1As shown, regenerated catalyst from line 7 enters pre-cracking reactor 1, accelerating upward along the reactor. Degraded heavy oil, after mixing with steam from line 6 via line 5, is then injected into pre-cracking reactor 1, where it comes into contact with the regenerated catalyst. Pre-cracking of the degraded heavy oil occurs on the hot catalyst, accelerating upward. The resulting reaction products and deactivated catalyst with carbon are separated, and the reaction products enter fractionation tower 3 via line 8. The reaction products are separated into reaction gas, light oil, and heavy oil according to the distillation range. The heavy oil exits the reactor via line 14 and can be used as feed for a conventional catalytic cracking unit.

[0044] The light oil is mixed with water vapor from pipeline 21 through pipeline 13 and sent to the hydrogen production reactor 4, where it comes into contact with the reduced regenerated catalyst from the reducer 24 to produce hydrogen. The generated reaction gas 16 is mixed with the reaction gas 12 coming out of the distillation tower 3 and sent to the separation unit 23 to be separated into hydrogen 17, carbon dioxide 18, carbon monoxide 19 and light hydrocarbons 20.

[0045] The deactivated catalyst 9 with carbon in the pre-decomposition reactor and the deactivated catalyst 15 with carbon in the hydrogen production reactor enter the regenerator 2, contact with the oxygen-rich gas from the pipeline 10, burn off the coke on the deactivated catalyst, and regenerate the deactivated catalyst with carbon. The regenerated flue gas enters the separation unit 23 through the flue gas pipe 11. The separation unit separates carbon dioxide 18 and carbon monoxide 19. The regenerated regenerated catalyst is divided into two parts, one part of the regenerated catalyst is circulated to the bottom of the pre-decomposition reactor 1 through the regeneration pipeline 7 for recycling, and the other part of the regenerated catalyst is circulated to the reducer 24 through the pipeline 22 to contact the light hydrocarbons 20 separated by the separation unit for reduction reaction. The reduced regenerated catalyst goes upward and contacts with the water vapor injected through the pipeline 25, and the carbon oxides entrained in the regenerated catalyst are stripped. The reduced and stripped regenerated catalyst enters the bottom of the hydrogen production reactor 4 for recycling.

[0046] The present invention will be further described in the following examples, but are not intended to limit the present invention.

[0047] The raw materials used in the examples and comparative examples were all vacuum residue oils, and their properties are shown in Table 1. The properties of catalyst A are shown in Table 2.

[0048] The preparation method of catalyst A used in the examples is briefly described as follows:

[0049] 1) 75.4 kg of kaolin (solid content 71.6 wt%) was slurried with 250 kg of decationized water, and 54.8 kg of pseudo-boehmite (solid content 63 wt%) was added. The pH was adjusted to 2-4 with hydrochloric acid and stirred uniformly. The mixture was allowed to stand and age at 60-70°C for 1 hour, maintaining the pH at 2-4. The temperature was lowered to below 60°C, and 41.5 kg of aluminum sol (Al2O3 content 21.7 wt%) was added. The mixture was stirred for 40 minutes to obtain a mixed slurry.

[0050] 2) ZRP-1 (2 kg on dry basis) and DASY zeolite (22.5 kg on dry basis) were added to the obtained mixed slurry, stirred evenly, spray-dried into a slurry, and washed with ammonium dihydrogen phosphate solution (phosphorus content 1 wt%) to remove free Na + , and the molecular sieve catalyst sample is obtained after calcination.

[0051] 3. A Ni(NO₃)₂·6H₂O aqueous solution was prepared by dissolving 3 kg of Ni(NO₃)₂ in 5.5 kg of water. A 10 kg sample of the molecular sieve catalyst was then immersed in the Ni(NO₃)₂·6H₂O aqueous solution. The resulting mixture was dried at 180°C for 4 hours and calcined at 600°C for 2 hours. Repeated impregnation, drying, and calcination resulted in a Ni loading of 2 wt% on the catalyst sample, yielding Catalyst A of Example 1.

[0052] Example 1

[0053] according to Figure 1 The process was tested, and a pre-decomposition reaction test of atmospheric residue was carried out on the riser reactor. The atmospheric residue entered the lower part of the riser reactor, came into contact with the hot regenerated catalyst and underwent a pre-decomposition reaction. The reaction products and the deactivated catalyst entered the closed cyclone separator from the reactor outlet. The reaction products and the deactivated catalyst were quickly separated. The reaction products were separated into gas, light oil and heavy oil according to the distillation range in the separation system.

[0054] The light oil enters the lower part of another hydrogen riser, contacts the regenerated catalyst after methane reduction, and undergoes hydrogen production reaction. The reaction products and deactivated catalyst enter the closed cyclone separator from the reactor outlet, and the reaction products and deactivated catalyst are quickly separated.

[0055] The deactivated catalyst enters the stripping section under gravity, where steam strips the hydrocarbon products adsorbed on the deactivated catalyst. The stripped deactivated catalyst then enters the regenerator, where it is regenerated by contact with oxygen-rich air. The regenerated catalyst is then returned to the riser reactor for recycling. The operating conditions and product distribution are listed in Tables 3 and 4.

[0056] From the results in Table 4, it can be seen that the hydrogen yield is as high as 6.16%, the heavy oil yield is 77.93%, and the properties of the heavy oil are significantly improved, with a density of 928.3 kg / m3 The hydrogen content was increased to 12.08% by weight, meeting the requirements of conventional catalytic cracking feedstock. The CO2 concentration in the regeneration flue gas was 32.77% by volume.

[0057] Comparative Example 1

[0058] The test was conducted on a medium-sized device in a riser. The atmospheric residue feedstock was the same as that in Example 1, and the catalyst was Catalyst A.

[0059] Atmospheric residue oil enters the riser reactor and contacts the hot re-heavy catalyst to undergo a pre-decomposition reaction. The reaction products and deactivated catalyst enter the closed cyclone separator from the reactor outlet. The reaction products and deactivated catalyst are quickly separated. The reaction products are separated into gas and liquid products according to the distillation range in the separation system.

[0060] The deactivated catalyst enters the stripping section under the action of gravity, where the hydrocarbon products adsorbed on the deactivated catalyst are stripped by steam. The stripped deactivated catalyst enters the regenerator and is regenerated by contact with air. The regenerated catalyst is then returned to the riser reactor for recycling. The operating conditions and product distribution are listed in Tables 3 and 4.

[0061] From the results in Table 4, it can be seen that the hydrogen yield is 1.74%, the heavy oil yield is 77.51%, and the properties of the heavy oil are significantly improved, with a density of 928.7 kg / m 3 , the hydrogen content increased to 12.0 wt %. The CO2 concentration in the regeneration flue gas was 31.79 vol %.

[0062] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0063] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0064] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the spirit of the present invention, they should also be regarded as the content of the present invention.

[0065] Table 1

[0066] name atmospheric residue <![CDATA[Density (20 °C) / (kg / m 3 )]]> 974.7 <![CDATA[Viscosity (100 °C) / (mm 2 / s)]]> 62.75 Carbon residue value / weight% 10.34 Element content / weight% carbon 84.30 hydrogen 11.06 sulfur 4.18 nitrogen 0.24 Four components composition / weight% Saturation 31.0 Aroma 46.8 colloid 18.8 Asphaltene 3.4 Metal content / (μg / g) Ca 1.7 Fe 2.9 Ni 21.1 V 60.5

[0067] Table 2

[0068] Catalyst A Physical properties <![CDATA[Specific surface area, m 2 / g]]> 128 <![CDATA[Specific surface area of molecular sieve, m 2 / g]]> 47 <![CDATA[Pore volume, cm 3 / g]]> 0.137 Sieve composition, weight % 0~40 microns 22.7 0~80 microns 64.4 0~105 microns 87.1 0~149 microns 97.9 Average particle size / micron 55.0 Micro-antibody activity, % 50 Metal content, weight % Ni 2.0

[0069] Table 3

[0070]

[0071] Table 4

[0072] Example 1 Comparative Example 1 Product distribution, weight % CO 2.27 0.06 <![CDATA[CO2]]> 4.11 0.33 <![CDATA[H2]]> 6.16 1.74 gaseous hydrocarbons / 1.02 Light oil / 7.23 heavy oil 77.93 77.51 coke 9.53 12.11 total 100 100 Flue gas composition, volume % CO 8.15 7.94 <![CDATA[CO2]]> 32.77 31.79 <![CDATA[N2]]> 59.08 59.95 Properties of heavy oil obtained by pre-decomposition <![CDATA[Density (20 °C) / (kg / m 3 )]]> 928.3 928.7 <![CDATA[Viscosity (100 °C) / (mm 2 / s)]]> 22.84 22.8 Hydrogen content, weight % 12.08 12.0 Carbon residue, weight % 5.5 5.5

Claims

1. A method for producing hydrogen from inferior heavy oil, the method comprising the following steps: (1) Inferior heavy oil is introduced into a fluidized bed reactor and brought into contact with a catalyst containing large-pore zeolite and metal active components to undergo a pre-decomposition reaction, thereby obtaining a reactant stream and a deactivated catalyst with carbon; the reaction oil and gas obtained from the pre-decomposition reaction and the deactivated catalyst with carbon are subjected to gas-solid separation; the separated reaction oil and gas enter a fractionation tower and are separated into gas, light oil, and heavy oil; The inferior heavy oil meets at least one of the following indicators: density greater than 940 kg / m 3 , the carbon residue is greater than 8% by weight, the hydrogen content is less than 11.8% by weight, and the heavy metal content, calculated on the total weight of nickel and vanadium, is greater than 50 mg / kg; The catalyst comprises, based on the dry weight of the catalyst, 5% to 65% of natural minerals, 10% to 60% of oxides, 20% to 60% of zeolites and 0.1% to 30% of metal active components; (2) The separated light oil is sent to a hydrogen production reactor, where it contacts the reduced regenerated catalyst and water vapor and undergoes a hydrogen production reaction to obtain a reactant stream and a deactivated catalyst with carbon; the reaction oil gas and the deactivated catalyst with carbon obtained from the hydrogen production reaction are subjected to gas-solid separation; (3) The gas separated by the fractionation tower and the reaction oil gas obtained by gas-solid separation in the hydrogen production reactor are sent to the separation unit for further separation into hydrogen, carbon monoxide, carbon dioxide and light hydrocarbons. The separated light hydrocarbons are sent to the reducer for use as a reducing agent; (4) The deactivated catalysts of the fluidized bed reactor and the hydrogen production reactor are sent to the regenerator for regeneration. After the deactivated catalysts are charred and regenerated, they are divided into two parts. One part of the regenerated catalysts is returned to the fluidized bed reactor for recycling, and the other part of the regenerated catalysts is sent to the reducer, reduced, and stripped before being recycled into the hydrogen production reactor. The regenerated flue gas enters the separation unit to separate carbon monoxide and carbon dioxide. The conditions for pre-cracking of inferior heavy oil include: The reaction temperature is 450-600°C, the reaction time is 0.5-8 seconds, the weight ratio of the catalyst to the inferior heavy oil is 1-30, and the weight ratio of water vapor to the inferior heavy oil is 0.01-1; The conditions of the light oil hydrogen production reactor include: reaction temperature of 600-1000°C, reaction time of 1-10 seconds, weight ratio of catalyst to light oil of 5-100; weight ratio of water vapor to light oil of 0.1-50; The regeneration operating conditions are: temperature of 550-700°C; gas superficial velocity of 0.2-1.2 m / s; average residence time of deactivated catalyst of 1-10 minutes; The operating conditions of the reducer are: temperature of 550-700°C and gas superficial velocity of 0.5-3 m / s.

2. The method according to claim 1, characterized in that The fluidized bed reactor is selected from one or a combination of turbulent bed, fast bed and dilute phase transport bed.

3. The method according to claim 2, characterized in that The pre-decomposition reactor comprises at least one reaction zone connected in series.

4. The method according to claim 1, wherein The hydrogen production reactor is selected from a fluidized bed reactor, and the fluidized bed reactor is selected from one or a combination of turbulent bed, fast bed and dilute phase transport bed.

5. The method according to claim 1, wherein The conditions for pre-decomposition of the inferior heavy oil include: reaction temperature of 480-550° C., reaction time of 1-6 seconds, weight ratio of catalyst to inferior heavy oil of 5-20; and weight ratio of water vapor to inferior heavy oil of 0.05-0.

3.

6. The method according to claim 1, characterized in that The conditions of the light oil hydrogen production reactor include: reaction temperature of 650-900°C, reaction time of 2-8 seconds, weight ratio of catalyst to light oil of 20-50; weight ratio of water vapor to light oil of 1-20.

7. The method according to claim 1, characterized in that The oxygen concentration in the oxygen-containing gas at the bottom of the regenerator is 22-100% by volume.

8. The method according to claim 1, characterized in that The oxygen concentration in the oxygen-containing gas at the bottom of the regenerator is 25-80% by volume.

9. The method according to claim 1, characterized in that The regeneration operating conditions are: temperature of 600-650° C.; gas superficial linear velocity of 0.4-0.8 m / s; and average residence time of the deactivated catalyst of 2-6 minutes.

10. The method according to claim 1, characterized in that The zeolite includes large-pore zeolite, and the large-pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high-silicon Y.

11. The method according to claim 1, wherein The content of the metal active component is 0.5-20% by weight.

12. The method according to claim 1, characterized in that The metal active component is selected from one or more compounds of transition metal elements.

13. The method according to claim 1, wherein The metal active component is selected from one or more of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium.

14. The method according to claim 1, wherein The oxide is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and amorphous silicon aluminum.

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