A method for producing hydrogen from hydrocarbon raw materials and enriching CO2

Abstract

A method for catalytically producing hydrogen from hydrocarbon raw materials and enriching CO2, wherein petroleum hydrocarbons are fed into a fluidized reactor, contacted with a catalyst containing a metal oxide to undergo a carbon-hydrogen bond decomposition reaction to generate hydrogen, and the reaction oil gas and the carbon-bearing catalyst obtained by the reaction are separated; the reaction oil gas is further separated into products containing hydrogen, CO, CO2, methane and other hydrocarbons; the carbon-bearing catalyst is first fed to a gasifier, contacted with water vapor for a high-temperature gasification reaction to generate hydrogen and carbon dioxide; the deactivated catalyst with a small amount of coke after gasification is fed to a regenerator to contact with water vapor and an oxygen-containing gas for a high-temperature gasification and carbonization reaction to be regenerated, the regenerated catalyst with the carbon burned off is returned to the fluidized reactor for recycling, and the regenerated flue gas is separated to obtain products containing hydrogen, CO and CO2. The present invention converts low-value hydrocarbon raw materials into hydrogen, realizes the high-value utilization of petroleum resources, and simultaneously realizes CO2 enrichment in the gasification and regeneration process, which is beneficial to carbon recovery and capture.

Description

Technical Field

[0001] The invention relates to a method for producing hydrogen and enriching CO2. Background Art

[0002] Hydrogen is hailed as the core of the future world energy architecture and is also considered the cleanest fuel. However, if hydrogen comes from fossil fuels, its preparation process is not "clean". At present, more than 96% of commercial hydrogen is produced from fossil fuels, and a large amount of carbon dioxide will be emitted during the hydrogen production process. This type of hydrogen is also called "gray hydrogen". Using fossil energy as a resource to achieve the production of "blue hydrogen" is an effective technical means to solve the current hydrogen energy problem. The more mature technical routes for the existing fossil energy hydrogen production methods include the use of fossil energy such as coal and natural gas to reform hydrogen production, and the high-temperature decomposition reforming of chemical raw materials represented by alcohol cracking hydrogen production technology. At present, domestic natural gas reforming hydrogen production and high-temperature cracking hydrogen production are mainly used in large-scale hydrogen production industry. The raw gas in the natural gas hydrogen production process is also fuel gas, which 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. Coal gasification hydrogen production is the first choice for large-scale industrial hydrogen production, and it is also the mainstream fossil energy hydrogen production method in my country. This hydrogen production process converts coal into synthesis gas (CO, CH4, H2, CO2, N2, etc.) through gasification technology, and then separates and processes it through water-gas shift to extract high-purity hydrogen. It is the raw material for preparing synthetic ammonia, methanol, liquid fuel, natural gas and other products, and is widely used in petrochemical, steel and other fields. The coal-to-hydrogen technology route is mature and efficient, and can be produced stably on a large scale, but the power energy consumption of coal-to-hydrogen fuel is higher than that of natural gas-to-hydrogen, and the system steam and electricity requirements are high, so companies need matching boilers. In addition, environmental protection issues are prominent, the existing urban refineries have stringent environmental requirements, and coal transportation is subject to many constraints, which also limits the application of this technology in modern refineries.

[0003] The country's standards for oil quality requirements have been raised (sulfur content has been reduced) and the market demand for light oil products has increased. These factors have led to the wider application of hydrogenation technology, which has become the main driving force behind the surge in refinery hydrogen demand. According to statistics, the annual growth rate of global refinery hydrogen demand exceeds 4%. The importance of hydrogen production in the refining process has gradually become prominent. A 10Mt / a refinery equipped with a residue oil hydrogenation unit consumes about 1% of the crude oil processing volume, while a refinery without residue oil hydrogenation consumes about 0.7% of the hydrogen. The hydrogen supply from within the refinery will be difficult to meet the future growth in hydrogen demand, so it is necessary to explore a more flexible and feasible hydrogen supply strategy. At present, there is an overcapacity in refining capacity, and the transformation of refining enterprises from "fuel type" to "chemical type" is an inevitable trend. For refining enterprises, it is necessary to significantly reduce the yield of oil products, especially the poor quality gasoline and diesel produced by some secondary processing units. For example, catalytic cracking diesel has always been relatively poor, with high density, high aromatic content, and low cetane number. The existing utilization method is to first perform hydrogenation and quality improvement, and then perform catalytic cracking to produce high-octane gasoline. As the demand for gasoline slows down, the outlet of catalytic cracking diesel has become a difficult problem faced by refineries. If these low-quality and low-value distillates can be converted into hydrogen energy, it will undoubtedly have good economic and social benefits. However, hydrogen production from hydrocarbon raw materials is a decarbonization process. In order to meet the needs of hydrogen production, low-hydrogen coke is not only inevitable, but charcoal burning will also bring about CO2 emissions. Therefore, compared with emission reduction, CO2 capture is the key to the problem. Summary of the invention

[0004] The object of the present invention is to provide a method for catalytically producing hydrogen and enriching CO2 from hydrocarbon raw materials.

[0005] The method for catalytically producing hydrogen from hydrocarbon raw materials and enriching CO2 provided by the present invention comprises the following steps:

[0006] (1) A hydrocarbon feedstock is fed into a fluidized reactor, where it contacts a reduced metal oxide-containing catalyst to generate hydrogen by breaking carbon-hydrogen bonds, thereby obtaining a reaction oil gas containing hydrogen and a deactivated catalyst with deposited coke;

[0007] (2) separating the reaction oil gas containing hydrogen and the deactivated catalyst containing deposited coke;

[0008] (3) The separated reaction oil and gas enters a separation unit and is further separated into products including hydrogen, CO, CO2, methane and other hydrocarbons, and part or all of the separated methane is used as a reducing agent;

[0009] (4) sending the deactivated catalyst of the deposited coke obtained to a gasifier, where it is contacted with water vapor to undergo a high-temperature gasification reaction to generate hydrogen and CO2;

[0010] (5) After gasification, the deactivated catalyst with a small amount of coke enters the regenerator and contacts with oxygen-containing gas to be regenerated by burning. After the coke is burned off, the deactivated catalyst is sent to the reducer as a regenerated catalyst, and the regenerated flue gas is sent to the separation unit to obtain CO and CO2;

[0011] (6) After the regenerated catalyst enters the reducer, it comes into contact with the reducing agent to undergo a reduction reaction. The reduced regenerated catalyst then enters the fluidized bed reactor for a circulation reaction.

[0012] Preferably, the other hydrocarbon products are returned to the reactor as feedstock for further conversion.

[0013] The catalyst comprises the following components by weight percentage: 15% to 65% of natural minerals, 20% to 60% of oxides, and 5% to 30% of metal active components. The metal active components are selected from one or more compounds of transition metal elements.

[0014] The present invention adopts a fluidized reactor to produce hydrogen, and the catalyst circulates between the reactor and the regenerator, which not only realizes the regeneration of the deactivated catalyst, but also transfers a large amount of heat for the reaction, greatly reducing the energy required for the hydrogen production process and achieving process economy.

[0015] The present invention uses high-temperature gasification technology to regenerate the deactivated catalyst with carbon, which not only restores the catalyst activity, but also produces CO and H2, further improving the hydrogen production, and also provides high-quality and cheap raw gas for the water-gas shift process, achieving optimal utilization of resources. At the same time, the concentration of CO2 in the flue gas is greatly increased, CO2 enrichment is achieved, and carbon emissions can be reduced through capture, utilization, and storage technology.

[0016] The present invention performs activation treatment on the catalyst before the hydrogen production reaction, reduces the high-valent metal oxide to a low-valent metal oxide, increases the dehydrogenation activity of the catalyst, and improves the hydrogen selectivity.

[0017] The present invention uses fluidized bed technology to convert hydrocarbon raw materials into hydrogen and enrich CO2 resources, with a high hydrogen yield. The present invention not only realizes the high-value utilization of low-value hydrocarbon raw materials, but also enriches the CO2 generated in the process, which not only brings hydrogen energy, but also facilitates carbon capture, and can bring greater economic and social benefits to the petrochemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 A process flow chart of a specific implementation method of producing hydrogen and enriching CO2 from hydrocarbon raw materials provided by the present invention. DETAILED DESCRIPTION

[0019] A method for catalytically producing hydrogen from hydrocarbon feedstock while simultaneously enriching CO2, the method comprising the following steps:

[0020] The hydrocarbon feedstock is fed into a fluidized reactor, and is contacted with the reduced metal oxide-containing catalyst to generate hydrogen by breaking the carbon-hydrogen bond, thereby obtaining a reaction oil gas containing hydrogen and a deactivated catalyst with deposited coke;

[0021] Separating the reaction oil gas containing hydrogen and the deactivated catalyst containing deposited coke;

[0022] The separated reaction oil and gas enters a separation unit and is further separated into products including hydrogen, carbon monoxide, carbon dioxide, methane and other hydrocarbons, and part or all of the separated methane is used as a reducing agent;

[0023] The deactivated catalyst of the deposited coke is sent to a gasifier to be contacted with water vapor for high-temperature gasification reaction to generate hydrogen and carbon dioxide;

[0024] After gasification, the deactivated catalyst with a small amount of coke enters the regenerator and contacts with oxygen-containing gas to burn out the coke for regeneration. After the deactivated catalyst burns out the coke, it is sent to the reducer as a regenerated catalyst, and the regenerated flue gas is sent to the separation unit to obtain carbon monoxide and carbon dioxide.

[0025] After the regenerated catalyst enters the reducer, it comes into contact with the reducing agent to undergo a reduction reaction, and the reduced regenerated catalyst enters the fluidized bed reactor for a circulation reaction.

[0026] The hydrocarbon oil is a variety of animal and plant oils rich in hydrocarbons, and the hydrocarbon is selected from one or more mixtures of hydrocarbon raw materials, mineral oils and synthetic oils. Hydrocarbon raw materials are well known to those skilled in the art, for example, can be one or more mixtures of straight-run gasoline, straight-run diesel, vacuum wax oil, atmospheric residue oil, vacuum residue oil or hydrocarbon oils obtained by secondary processing of a primary processing device. The hydrocarbon oil obtained by secondary processing is one or more of coker gasoline, catalytic diesel, hydrogenated diesel, coker diesel, coker wax oil, deasphalted oil, furfural refined raffinate oil. Mineral oil is selected from one or more mixtures of coal liquefaction oil, oil sand oil and shale oil. Synthetic oil is a distillate oil obtained by FT synthesis of coal, natural gas or asphalt.

[0027] The hydrocarbon feedstock meets one or two indicators selected from the group consisting of a hydrogen content of less than 12 wt% and an aromatic hydrocarbon content of greater than 30 wt%.

[0028] The catalyst comprises the following components by weight percentage:

[0029] A) 15% to 65% natural minerals,

[0030] B) 20% to 60% oxide,

[0031] C) 5% to 30% metal active components.

[0032] The method provided by the present invention can be carried out in various existing fluidized reactors, wherein the fluidized reactor is selected from one or a combination of a turbulent bed, a fast bed and a dilute phase transport bed. The fluidized reactor includes a pre-lifting section and at least one reaction zone fluidized reactor from bottom to top. In order to allow the crude oil to react fully and according to different quality requirements of the target product, the reaction zones can be 2-8, preferably 2-3.

[0033] The conditions of the catalytic decomposition reaction include: the reaction temperature of the fluidized reactor is 450-800°C, preferably 550-700°C, the reaction time is 0.1-10 seconds, preferably 1-8 seconds, the weight ratio of the catalyst to the hydrocarbon feedstock is 5-100, preferably 20-50; the weight ratio of water vapor to the hydrocarbon feedstock is 0.1-20, preferably 1-10.

[0034] According to the method provided by the present invention, the deactivated catalyst with carbon is generally first separated from the reaction oil and gas to obtain the deactivated catalyst with carbon and reaction oil and gas, and then the obtained reaction oil and gas are separated by a subsequent separation unit to obtain hydrogen and CO2, CO, methane, other hydrocarbons and other products. The method of separating hydrogen, CO, CO2 and the like from the reaction products is similar to the conventional technical method in the field, and the present invention is not limited to this and is not described in detail herein.

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

[0036] In the method provided by the present invention, the deactivated catalyst with carbon can be gasified and regenerated at high temperature in a conventional regenerator, and a single regenerator or multiple regenerators can be used. During the regeneration process, oxygen-containing gas and water vapor are generally introduced from the bottom of the regenerator. After the oxygen-containing gas and water vapor are introduced into the regenerator, the deactivated catalyst with carbon contacts with oxygen and water vapor to undergo a gasification reaction to generate hydrogen, CO and, and at the same time, the coke on the catalyst is removed to regenerate the catalyst. The flue gas generated after the catalyst is regenerated is separated into gas and solid at the top of the regenerator, and the flue gas enters the separation unit for further separation to obtain hydrogen, CO and CO2.

[0037] In the method provided by the present invention, the CO obtained in the separation unit is sent to the water-gas shift unit to further react with water vapor to obtain hydrogen and CO2. The water-gas shift of the CO and water vapor adopts the existing technology well known to those skilled in the art. The CO2 obtained in the separation unit can be recovered and captured using the existing technology.

[0038] In the method provided by the present invention, the operating conditions of the gasifier are preferably: temperature of 650-1000°C, preferably 700-950°C; gas superficial linear velocity of 0.2-1.0 m / s, preferably 0.3-0.8 m / s, average residence time of the catalyst of 0.5-10 minutes, preferably 1-5 minutes, and weight ratio of water vapor to hydrocarbon feedstock of 0.1-20, preferably 0.5-10.

[0039] In the method provided by the present invention, the oxygen concentration in the oxygen-containing gas at the bottom of the regenerator is 22-100% by volume, preferably 25-80% by volume. The regeneration operation conditions are preferably: temperature of 550-700°C; gas superficial linear velocity of 0.2-1.2 m / s, and average residence time of the deactivated catalyst of 1-10 minutes.

[0040] In the method provided by the present invention, the operating conditions of the reducer for regenerating the catalyst are: temperature of 550-700° C.; gas superficial linear velocity of 0.5-3 m / s.

[0041] In the method provided by the present invention, the reducing agent for regenerating the catalyst is selected from one or more small molecule alkanes, preferably one or more of methane, ethane, propane, n-butane and isobutane.

[0042] In the method provided by the present invention, the natural minerals in the catalyst are selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, and the content of the natural minerals on a dry basis is 15% to 65% by weight, preferably 20% 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 20% to 60% by weight, preferably 20% to 40% by weight, and more preferably 25% to 35% by weight, based on the total amount of the catalyst and in terms of oxide weight percentage.

[0043] Based on the weight of the catalyst, the metal active component content is 5% to 30% by weight, preferably 8-25% by weight. 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.

[0044] In the method provided by the present invention, the catalyst preparation method adopts the preparation method of conventional catalytic cracking catalyst, which is a method well known to those skilled in the art. The metal can be loaded on the catalyst by impregnation method or slurry method, preferably impregnation method, which are well known to those skilled in the art.

[0045] The accompanying drawings are used to provide further understanding of the present disclosure and constitute a part of the specification. They are used to explain the present disclosure together with the following detailed description, but do not constitute a limitation of the present disclosure.

[0046] like Figure 1 As shown, the regenerated catalyst enters the reducer 22, contacts with the reducing agent 23 to undergo a reduction reaction, and the reduced regenerated catalyst enters the fluidized reactor 1, accelerates upward along the reactor, and the hydrocarbon feedstock is mixed with water vapor from the pipeline 6 through the pipeline 5, and then injected into the fluidized reactor 1 to contact the reduced regenerated catalyst. The hydrocarbon feedstock undergoes a catalytic reaction on the hot regenerated catalyst and accelerates upward. The generated reaction products and the deactivated catalyst with carbon are separated by the cyclone separator 7, and the reaction products enter the separation unit 3 through the gas collection chamber 8 and the pipeline 9 to be separated into hydrogen 10, carbon dioxide 11, carbon monoxide 12, methane 25 and other hydrocarbons 13. The separated other hydrocarbons 13 can be sent back to the fluidized reactor 1 alone, or mixed with the hydrocarbon feedstock 5 and sent to the fluidized reactor 1 together, and the separated methane 25 is partially or completely returned to the reducer 22 for use as a reducing agent.

[0047] The separated catalyst with carbon enters the stripping section 4 to contact with the stripping steam 24 and strip the reaction oil and gas entrained by the catalyst. The catalyst with carbon enters the gasifier 2 through the waiting inclined pipe 19 and contacts with the water vapor 14 entering the bottom of the gasifier to undergo a gasification reaction to generate carbon monoxide, hydrogen and a catalyst with part of the coke. The catalyst with part of the coke enters the regenerator 17 and contacts with the oxygen-rich gas 16 entering through the main air distribution plate 15 to undergo a carbonization reaction to burn off the coke on the deactivated catalyst and regenerate the deactivated catalyst. The gas generated by the gasifier and the regenerator enters the separation unit 3 through the cyclone separator 20 and the flue gas pipeline 21 to separate hydrogen 10, carbon dioxide 11 and carbon monoxide 12. The regenerated catalyst is circulated to the bottom of the reducer 22 through the pipeline 18 for recycling.

[0048] The present invention will be further described in the following examples, but the present invention is not limited thereto.

[0049] The raw materials used in the examples and comparative examples are all catalytic diesel, and the properties are shown in Table 1. The catalyst used in the comparative example is an industrial catalyst, the trade name is DMMC-1, and the properties are shown in Table 2.

[0050] The catalyst preparation method used in the examples is briefly described as follows:

[0051] 1) 75.4 kg of kaolin (solid content 71.6 wt%) was slurried with 250 kg of decationized water, and then 54.8 kg of pseudo-boehmite (solid content 63 wt%) was added, and the pH was adjusted to 2-4 with hydrochloric acid, and stirred evenly. The mixture was allowed to stand and age at 60-70°C for 1 hour, and the pH was maintained at 2-4. The temperature was lowered to below 60°C, and 41.5 kg of aluminum sol (Al2O3 content of 21.7 wt%) was added, and stirred for 40 minutes to obtain a mixed slurry, which was spray-dried and calcined to obtain a matrix sample.

[0052] 2) 3 kg of Ni(NO3)2 was dissolved in 5.5 kg of water to prepare a Ni(NO3)2·6H2O aqueous solution, 10 kg of the molecular sieve catalyst sample was immersed in the Ni(NO3)2·6H2O aqueous solution, and the obtained mixture was dried at 180°C for 4 hours and calcined at 600°C for 2 hours. After repeated immersion, drying and calcination, the content of Ni loaded on the catalyst sample reached 15%, and the catalyst A of the embodiment was obtained.

[0053] Example 1

[0054] according to Figure 1 The process is tested, and the catalytic decomposition reaction test of catalytic diesel is carried out on the riser reactor. Methane as a reducing gas first contacts the catalyst to cause a reduction reaction of the metal catalyst. The catalytic diesel is injected into the lower part of the riser reactor, contacts the hot regenerated catalyst and undergoes a catalytic decomposition reaction. The reaction products and the deactivated catalyst with coke enter the closed cyclone separator from the reactor outlet, and the reaction products and the deactivated catalyst are separated at a high speed. The reaction products are separated into cracked gas and liquid products in the separation system.

[0055] The deactivated catalyst enters the stripping section under the action of gravity, and the hydrocarbon products adsorbed on the deactivated catalyst are stripped by water vapor. The deactivated catalyst after stripping enters the gasifier and regenerator in turn, and contacts with water vapor and oxygen-rich air for gasification and regeneration reaction; the regenerated catalyst is then returned to the riser reactor for recycling, and the regenerated flue gas enters the separation system. 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 22.20%, the CO yield in the reaction product is 27.66%, and the CO2 yield is 24.09%. The CO concentration in the regenerated flue gas is 51.24% by volume, the CO2 concentration is 4.96% by volume, and the hydrogen concentration in the flue gas is 10.86% by volume.

[0057] Comparative Example 1

[0058] The test was carried out on a medium-sized device of a riser, the catalytic diesel feedstock was the same as in Example 1, and the catalyst was DMMC-1.

[0059] The catalytic diesel enters the riser reactor and contacts the hot DMMC-1 catalyst to undergo a catalytic decomposition reaction. The reaction products and the regenerated catalyst enter the closed cyclone separator from the reactor outlet. The reaction products and the regenerated 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 spent catalyst enters the stripping section under the action of gravity, and the hydrocarbon products adsorbed on the spent catalyst are stripped by water vapor. The spent catalyst after stripping 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 1.62%, and the CO and CO2 yields in the reaction products are low. No CO was detected in the regeneration flue gas, the CO2 concentration was 15.78% by volume, and the O2 concentration was 3.91% by volume.

[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, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope 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 suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

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

[0065] Table 1

[0066] project Catalytic diesel <![CDATA[Density (20 °C) / (kg / m 3 )]]> 948.9 <![CDATA[Kinematic viscosity (20 °C) / (mm 2 / s)]]> 3.754 Total acid value / (mg KOH / g) <0.05 Freezing point / ℃ -27 Closed cup flash point / ℃ 66 Distillation range / ℃ Initial distillation point 197.9 5％ 220.4 10％ 228.4 50％ 262.5 70％ 283.1 90％ 308.6 95％ 319.5 Final distillation point 329.9

[0067] Table 2

[0068] Comparative Example 1 Example 1 DMMC-1 Catalyst A Physical properties <![CDATA[Specific surface area, m 2 / g]]> 106 118 <![CDATA[Matrix specific surface area, m 2 / g]]> 64 95 <![CDATA[Pore volume, cm 3 / g]]> 0.13 0.106 Sieve composition, weight % 0~40 microns 30.9 20.7 0~80 microns 75.0 76.1 0~105 microns 89.1 84.3 0~149 microns 98.4 97.5 Average particle size / micron 55.6 54.9 Micro-anti-activity, % 65 40 Metal content, weight % Ni 0.06 15.0

[0069] Table 3

[0070] Example 1 Comparative Example 1 Riser reaction conditions Reaction temperature, °C 675 675 Reaction time, seconds 1.8 1.8 Weight ratio of catalyst to catalytic diesel 20 20 Water to oil weight ratio 0.25 0.25 Gasifier conditions Vaporization temperature, °C 700 / Water vapor to catalytic diesel weight ratio 0.5 / Gas superficial velocity, m / s 0.8 / Average stay time, minutes 4.5 / Regenerator conditions Regeneration temperature, °C 680 680 Oxygen concentration in regeneration air, volume % 50 21 Gas superficial velocity, m / s 0.8 0.8 Average stay time, minutes 4.5 4.5 Reducer conditions Reduction temperature, °C 650 / Gas superficial velocity, m / s 1.0 /

[0071] Table 4

[0072] Example 1 Comparative Example 1 Product distribution, weight % CO 27.66 0.24 <![CDATA[CO2]]> 24.09 0.95 <![CDATA[H2]]> 22.20 1.62 Methane 4.83 3.70 Other hydrocarbons 9.35 83.08 Coke 11.87 10.41 total 100.00 100.00 Regeneration flue gas composition, volume % CO 51.24 0 <![CDATA[CO2]]> 4.96 15.78 <![CDATA[N2]]> 32.92 80.31 <![CDATA[O2]]> 0.02 3.91 <![CDATA[H2]]> 10.86 0

Claims

1. A method for catalytically producing hydrogen from hydrocarbon feedstock and enriching CO2, the method comprising the following steps: (1) A hydrocarbon feedstock is fed into a fluidized reactor and brought into contact with a reduced catalyst containing metal oxides to generate hydrogen by breaking carbon-hydrogen bonds. The reaction temperature of the fluidized reactor is 450-800° C., the reaction time is 0.1-10 seconds, the weight ratio of the catalyst to the hydrocarbon feedstock is 5-100, and the weight ratio of water vapor to the hydrocarbon feedstock is 0.1-20, to obtain a deactivated catalyst containing hydrogen-containing reaction oil gas and deposited coke. The catalyst containing metal oxides, based on the dry weight of the catalyst, comprises 15 %-65% of natural minerals, 20%-60% of oxides, and 5%-30% of metal active components, the natural minerals are selected from one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, the oxides are one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, amorphous silicon aluminum, the metal active components are selected from one or more of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium, and the hydrocarbon feedstock is catalytic diesel; (2) Separating the reaction oil gas containing hydrogen and the deactivated catalyst containing deposited coke; (3) The separated reaction oil and gas enters the separation unit and is further separated into products including hydrogen, CO, CO2, methane and other hydrocarbons, and part or all of the separated methane is used as a reducing agent; (4) sending the deactivated catalyst of the deposited coke obtained to a gasifier, where it is contacted with water vapor for high-temperature gasification reaction to generate hydrogen and CO2, and the average residence time of the catalyst is 0.5-5 minutes; (5) After gasification, the deactivated catalyst with char enters the regenerator and contacts with oxygen-containing gas to perform charring regeneration. The regeneration operating conditions are as follows: temperature of 550-700°C; gas superficial linear velocity of 0.2-1.2 m / s; average residence time of the deactivated catalyst of 1-10 minutes; after the deactivated catalyst burns off the coke, it is sent to the reducer as a regenerated catalyst; the gas generated by the gasifier and the regenerator enters the separation unit of step (3) through the cyclone separator and the flue gas pipeline; the oxygen concentration in the oxygen-containing gas is 25 wt%-80 wt%; (6) After the regenerated catalyst enters the reducer, it contacts with the reducing agent to undergo a reduction reaction. The operating conditions of the reducer are: a temperature of 550-700°C; a gas superficial velocity of 0.5-3 m / s. The reduced regenerated catalyst enters the fluidized bed reactor for a circulation reaction.

2. The method according to claim 1, characterized in that The reaction temperature of the fluidized bed reactor is 550-700°C, the reaction time is 1-8 seconds, the weight ratio of the catalyst to the hydrocarbon raw material is 20-50; the weight ratio of water vapor to the hydrocarbon raw material is 1-10.

3. The method according to claim 1, characterized in that The fluidized reactor is selected from one or a combination of a riser reactor, a fast bed and a dense phase fluidized bed.

4. The method according to claim 3, characterized in that The fluidized reactor comprises, from bottom to top, a pre-lifting section and at least one reaction zone.

5. The method according to claim 4, characterized in that The number of the reaction zones is 2-8.

6. The method according to claim 4, characterized in that The number of the reaction zones is 2-3.

7. The method according to claim 1, characterized in that The operating conditions of the gasifier are a temperature of 650-1000° C. and a gas superficial velocity of 0.2-1.0 m / s.

8. The method according to claim 1, characterized in that: The operating conditions of the gasifier are a temperature of 750-950° C. and a gas superficial velocity of 0.3-0.8 m / s.

9. The method according to claim 1, characterized in that: The content of the metal active component is 8% to 25% by weight.

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