CN116004279A - Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) - Google Patents
Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) Download PDFInfo
- Publication number
- CN116004279A CN116004279A CN202111230356.0A CN202111230356A CN116004279A CN 116004279 A CN116004279 A CN 116004279A CN 202111230356 A CN202111230356 A CN 202111230356A CN 116004279 A CN116004279 A CN 116004279A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oil
- hydrogen
- reaction
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
Catalytic hydrogen production from hydrocarbon raw material and CO enrichment 2 The method comprises the steps of feeding petroleum hydrocarbon into a fluidization reactor, contacting the petroleum hydrocarbon with a catalyst containing metal oxide to generate a carbon-hydrogen bond decomposition reaction to generate hydrogen, and separating reaction oil gas obtained by the reaction and the catalyst with carbon; further separating the reacted oil gas into hydrogen, CO and CO 2 Methane and other hydrocarbon productsThe method comprises the steps of carrying out a first treatment on the surface of the Firstly, delivering the catalyst with carbon to a gasifier, and contacting with water vapor to carry out high-temperature gasification reaction to generate hydrogen and carbon dioxide; the gasified deactivated catalyst with small amount of coke is sent to a regenerator to contact with water vapor and oxygen-containing gas to carry out high-temperature gasification and charcoal burning reaction and to be regenerated, the charcoal burned regenerated catalyst is returned to the fluidization reactor for recycling, and the regenerated flue gas is separated to obtain the catalyst containing hydrogen, CO and CO 2 . The invention converts low-value hydrocarbon raw materials into hydrogen, realizes the high-value utilization of petroleum resources, and realizes CO in gasification and regeneration processes 2 Enrichment is beneficial to carbon recovery and trapping.
Description
Technical Field
The invention relates to a method for producing hydrogen and enriching CO 2 Is a method of (2).
Background
Hydrogen is known as the core of future world energy architecture and is also considered the cleanest fuel. However, if the hydrogen is derived from fossil fuels, the process is not "clean". At present, more than 96% of commercial hydrogen is prepared from fossil fuels, and a large amount of carbon dioxide is discharged in the hydrogen production process, and the hydrogen is also called as "gray hydrogen". The production of blue hydrogen is realized by taking fossil energy as a resource, and the blue hydrogen is an effective technical means for solving the problem of hydrogen energy at present. The existing fossil energy hydrogen production mode has a mature technical route of reforming hydrogen production by using fossil energy such as coal, natural gas and the like, and chemical raw materials represented by an alcohol pyrolysis hydrogen production technology are subjected to pyrolysis reforming hydrogen production. At present, domestic natural gas reforming hydrogen production and high-temperature pyrolysis hydrogen production are mainly applied to the large-scale hydrogen production industry. The raw material gas in the hydrogen production process of the natural gas is also fuel gas, and transportation is not needed, but the hydrogen production investment of the natural gas is relatively high, so that the method is suitable for large-scale industrial production. Coal gasification hydrogen production is the first choice for industrial large-scale hydrogen production and is also the mainstream fossil energy hydrogen production method in China. The hydrogen production process converts coal into synthesis gas (CO, CH) through gasification technology 4 、H 2 、CO 2 、N 2 Etc.), and then is subjected to water gas shift separation treatment to extract high-purity hydrogen, which is a raw material for preparing various products such as synthetic ammonia, methanol, liquid fuel, natural gas and the like, and is widely applied to the fields of petrifaction, steel and the like. The coal hydrogen production technology has mature and efficient route and can be stably prepared on a large scale, but the power energy consumption of the coal hydrogen production fuel is higher than that of the natural gas hydrogen production, the requirements on system steam and electric power are high, and enterprises need matched boilers. In addition, the environmental protection problem is outstanding, the environmental requirements of the existing urban refinery are harsh, and the coal transportation is limited by a plurality of factors, so that the application of the technology in modern refineries is also limited.
The national standard for oil quality requirement is improved (sulfur content is reduced), and the market demand for light oil is increased. These factors have led to a wider application of hydrogenation processes, which is the main driving force for the proliferation of hydrogen demand in refineries. The annual increase in global refinery hydrogen demand was statistically more than 4%. The importance of hydrogen production in the process of oil refining is gradually highlighted. A 10Mt/a refinery equipped with resid hydrogenation units consumes about 1% of the crude oil throughput, whereas a refinery without resid hydrogenation consumes about 0.7% of the hydrogen, and the supply of hydrogen from within the refinery will be difficult to meet future hydrogen growth demands, thus a more flexible and viable hydrogen supply strategy needs to be explored. The current oil refining capacity is surplus, the oil refining enterprises are already moving from the fuel type to the chemical type, the oil refining enterprises need to greatly reduce the oil product yield, particularly, the gasoline and diesel oil which are produced by some secondary processing devices and have poor quality, such as catalytic cracking diesel oil, are relatively poor in all times, high in density, high in aromatic hydrocarbon content and low in cetane number, the existing utilization way is to carry out hydrogenation upgrading firstly, then catalytic cracking is carried out to produce high-octane gasoline, and along with the slowing down of the gasoline demand, the problem of the outlet of the catalytic cracking diesel oil becomes a difficult problem faced by refineries, and if the low-quality and low-value distillate oil can be converted into hydrogen energy, the method has good economic benefit and social benefit. However, the hydrocarbon raw material hydrogen production is a decarbonizing process, and in order to meet the hydrogen production requirement, low hydrogen content coke is unavoidable, and CO is brought by the burning of the coke 2 Emissions problems of (2), thus, relative to emission reduction, CO 2 Trapping is the key to the problem.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen and enriching CO by catalyzing hydrocarbon raw materials 2 Is a method of (2).
The hydrocarbon raw material provided by the invention is used for catalyzing hydrogen production and enriching CO 2 The method of (1) comprises the following steps:
(1) Hydrocarbon raw materials are sent into a fluidization reactor to contact with a reduced catalyst containing metal oxide to generate a reaction of breaking carbon-hydrogen bonds to generate hydrogen so as to obtain reaction oil gas containing the hydrogen and an inactivated catalyst of deposited coke;
(2) Separating the reaction oil gas containing hydrogen from the deactivated catalyst with deposited coke;
(3) The separated reaction oil gas enters a separation unit and is further separated into hydrogen, CO and CO 2 Methane and other hydrocarbon products, and part or all of the methane obtained by separation is used as a reducing agent;
(4) The obtained deactivated catalyst of deposited coke is sent to a gasifier to contact with water vapor to carry out high-temperature gasification reaction to generate hydrogen and CO 2 ；
(5) The gasified deactivated catalyst with small amount of coke enters a regenerator, contacts with oxygen-containing gas to perform charcoal burning regeneration, and after the deactivated catalyst burns off the coke, the deactivated catalyst is sent to a reducer as a regenerated catalyst, and the regenerated flue gas is sent to a separation unit to obtain CO and CO 2 ；
(6) After the regenerated catalyst enters the reducer, the regenerated catalyst contacts with the reducer to generate reduction reaction, and the reduced regenerated catalyst enters the fluidization reactor to perform circulation.
Preferably, other hydrocarbon products are returned to the reactor as feed for further conversion.
The catalyst comprises the following components in percentage by weight: 15 to 65 percent of natural mineral, 20 to 60 percent of oxide and 5 to 30 percent of metal active component. The metal active component is selected from one or more of compounds of transition metal elements.
The invention adopts the fluidization reactor to produce hydrogen, and the catalyst circulates between the reactor and the regenerator, thereby not only realizing the regeneration of the deactivated catalyst, but also transferring a large amount of heat for the reaction, greatly reducing the energy required to be consumed in the hydrogen production process and realizing the process economy.
The invention adopts hydrocarbon raw materials as raw materials, which not only reduces the raw material cost of natural gas hydrogen production, but also is beneficial to relieving the situation of shortage of natural gas market supply in China, and has strategic significance for the stable development of energy structures in China.
The invention adopts high temperature gasification technology to regenerate the deactivated catalyst with carbon, not only recovers the catalyst activity, but also produces CO and H 2 Not only further improves the hydrogen yield, but also provides high-quality and low-cost raw gas for the water gas shift process, and realizes the optimal utilization of resources. At the same time, the CO in the flue gas is greatly improved 2 Concentration of CO 2 Enrichment, carbon emission can be reduced by trapping, utilizing and sealing technologies.
The method activates the catalyst before hydrogen production reaction, reduces the high-valence metal oxide into the low-valence metal oxide, improves the dehydrogenation activity of the catalyst, and improves the hydrogen selectivity.
In the invention, the hydrocarbon raw material is converted into hydrogen and enriched with CO by adopting the fluidized bed technology 2 The resource and the hydrogen yield are high. The invention not only realizes the high-value utilization of low-value hydrocarbon raw materials, but also leads CO generated in the process to be utilized 2 The enrichment is carried out, so that not only is the hydrogen energy source brought, but also the carbon capture is facilitated, and the method can bring greater economic benefit and social benefit to the petrochemical industry.
Drawings
FIG. 1 shows the hydrogen production and CO enrichment of a hydrocarbon feedstock in accordance with the present invention 2 A process flow diagram of a specific embodiment of (a).
Detailed Description
Hydrogen production by hydrocarbon raw material catalysis and CO enrichment 2 The method comprising the steps of:
feeding hydrocarbon raw materials into a fluidization reactor, and connecting the hydrocarbon raw materials with the reduced catalyst containing metal oxide to trigger the reaction of generating carbon hydrogen bonds to break to generate hydrogen so as to obtain reaction oil gas containing the hydrogen and an inactivated catalyst for depositing coke;
separating the reaction oil gas containing hydrogen from the deactivated catalyst with deposited coke;
the separated reaction oil gas enters a separation unit and is further separated into products containing hydrogen, carbon monoxide, carbon dioxide, methane and other hydrocarbons, and part or all of the methane obtained by separation is used as a reducing agent;
sending the obtained deactivated catalyst with deposited coke to a gasifier, and contacting with water vapor to carry out high-temperature gasification reaction to generate hydrogen and carbon dioxide;
the gasified deactivated catalyst with a small amount of coke enters a regenerator to contact with oxygen-containing gas for charcoal burning regeneration, the deactivated catalyst is sent to a reducer as a regenerated catalyst after the coke is burned off, and the regenerated flue gas is sent to a separation unit to obtain carbon monoxide and carbon dioxide;
after the regenerated catalyst enters the reducer, the regenerated catalyst contacts with the reducer to generate reduction reaction, and the reduced regenerated catalyst enters the fluidization reactor to perform circulation.
The hydrocarbon oil is various animal and vegetable oils rich in hydrocarbon, and the hydrocarbon is one or more selected from hydrocarbon raw materials, mineral oil and synthetic oil. The hydrocarbon feedstock is well known to those skilled in the art and may be, for example, straight run gasoline, straight run diesel oil, reduced pressure wax oil, atmospheric residue, vacuum residue, or a mixture of one or more hydrocarbon oils obtained by secondary processing in a primary processing unit. And hydrocarbon oil obtained by secondary processing, such as one or more of coker gasoline, catalytic diesel, hydrogenated diesel, coker wax oil, deasphalted oil and furfural refined raffinate oil. The mineral oil is selected from one or more of coal liquefied oil, oil sand oil and shale oil. The synthetic oil is distillate oil obtained by F-T synthesis of coal, natural gas or asphalt.
The hydrocarbon feedstock meets one or both criteria selected from the group consisting of a hydrogen content of less than 12 wt% and an aromatic hydrocarbon content of greater than 30 wt%.
The catalyst comprises the following components in percentage by weight:
a) 15 to 65 percent of natural mineral substances,
b) 20 to 60 percent of oxide,
c) 5% -30% of metal active component.
The method provided by the invention can be carried out in various existing fluidization reactors, wherein the fluidization reactors are selected from one or a combination of a plurality of turbulent flow beds, rapid beds and dilute phase conveying beds. The fluidization reactor comprises a pre-lifting section and at least one reaction zone fluidization reactor from bottom to top in sequence, and in order to enable the raw oil to fully react, and according to different quality requirements of target products, the number of the reaction zones can be 2-8, preferably 2-3.
The conditions of the catalytic decomposition reaction include: the fluidization reactor has a reaction temperature of 450-800 ℃, preferably 550-700 ℃, a reaction time of 0.1-10 seconds, preferably 1-8 seconds, and a weight ratio of catalyst to hydrocarbon feedstock of 5-100, preferably 20-50; the weight ratio of water vapor to hydrocarbon feedstock is 0.1-20, preferably 1-10.
According to the method provided by the invention, generally, firstly, the deactivated catalyst with carbon and the reaction oil gas are separated to obtain the deactivated catalyst with carbon and the reaction oil gas, and then, the obtained reaction oil gas is separated by a subsequent separation unit to obtain hydrogen and CO 2 Separating hydrogen, CO and other hydrocarbon products from the reaction products 2 The methods of the present invention are similar to those of the conventional art, and the present invention is not limited thereto and will not be described in detail herein.
In the method provided by the invention, preferably, the deactivated catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the deactivated catalyst are stripped by steam, and the stripped deactivated catalyst enters a regenerator.
In the method provided by the invention, the deactivated catalyst with carbon can be gasified and regenerated at high temperature in a conventional regenerator, and a single regenerator or a plurality of regenerators can be used. In the regeneration process, oxygen-containing gas and water vapor are generally introduced from the bottom of the regenerator, and after the oxygen-containing gas and the water vapor are introduced into the regenerator, the deactivated catalyst with carbon contacts with the oxygen and the water vapor to generate gasification reaction to generate hydrogen, CO and CO, and simultaneously, coke on the catalyst is removed, so that the catalyst is regenerated. Gas-solid separation is carried out on the flue gas generated after the catalyst regeneration at the upper part of the regenerator, and the flue gas enters a separation unit for further separation to obtain hydrogen, CO and CO 2 。
The invention providesIn the method, CO obtained in the separation unit is sent to a water gas shift unit to react with water vapor to further react to obtain hydrogen and CO 2 . The CO and steam are converted into water and gas using prior art techniques well known to those skilled in the art. CO from the separation unit 2 Recovery and trapping can be performed using existing techniques.
In the method provided by the invention, the operating conditions of the gasifier are preferably as follows: the temperature is 650-1000 ℃, preferably 700-950 ℃; the gas superficial linear velocity is 0.2 to 1.0 m/s, preferably 0.3 to 0.8 m/s, the average residence time of the catalyst is 0.5 to 10 minutes, preferably 1 to 5 minutes, and the weight ratio of the water vapor to the hydrocarbon feedstock is 0.1 to 20, preferably 0.5 to 10.
In the method provided by the invention, the concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 22-100 vol%, preferably 25-80 vol%. The regeneration operating conditions are preferably: the temperature is 550-700 ℃; the apparent linear velocity of the gas is 0.2-1.2 m/s, and the average residence time of the deactivated catalyst is 1-10 minutes.
In the method provided by the invention, the operating conditions of the reducer for regenerating the catalyst are as follows: the temperature is 550-700 ℃; the apparent linear velocity of the gas is 0.5-3 m/s.
In the method provided by the invention, the reducing agent of the regenerated catalyst is selected from one or more of small-molecule alkane, preferably one or more of methane, ethane, propane, n-butane and isobutane.
In the method provided by the invention, the natural mineral substances in the catalyst are selected from one or more of kaolin, halloysite, montmorillonite, kieselguhr, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, wherein the content of the natural mineral substances in a dry basis is 15-65 wt%, preferably 20-60 wt%; the oxide is one or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and amorphous silicon aluminum, and the content of the oxide is 20-60 wt%, preferably 20-40 wt%, more preferably 25-35 wt% based on the total catalyst weight.
The metal active component content is 5 to 30 wt%, preferably 8 to 25 wt%, based on the weight of the catalyst. The metal active component is selected from one or more of compounds of transition metal elements, preferably one or more of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium and chromium.
In the method provided by the invention, the catalyst preparation method adopts a preparation method of a conventional catalytic cracking catalyst, which is a method known to a person skilled in the art. The metal supported on the catalyst may be impregnated or slurry mixed, preferably impregnated, as is well known to those skilled in the art.
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and, together with the description, do not limit the disclosure.
As shown in fig. 1, the regenerated catalyst enters a reducer 22, contacts with a reducer 23 to perform a reduction reaction, the reduced regenerated catalyst enters a fluidized reactor 1, moves upward along the reactor at an accelerated speed, hydrocarbon raw materials are mixed with steam from a pipeline 6 through a pipeline 5, then are injected into the fluidized reactor 1 to contact with the reduced regenerated catalyst, and the hydrocarbon raw materials are subjected to a catalytic reaction on the hot regenerated catalyst and move upward at an accelerated speed. After the generated reaction product and the deactivated catalyst with carbon are separated by the cyclone separator 7, the reaction product enters 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 may be fed to the fluidized-bed reactor 1 alone or mixed with the hydrocarbon raw material 5 and fed to the fluidized-bed reactor 1, and part or all of the separated methane 25 may be returned to the reducer 22 to be used as a reducing agent.
After the catalyst with carbon obtained by separation enters a stripping section 4 to be contacted with stripping steam 24 and the reaction oil gas carried by the catalyst is stripped, the catalyst with carbon enters a gasifier 2 through a waiting inclined tube 19 and contacts with steam 14 entering from the bottom of the gasifier to carry out gasification reaction, so as to generate carbon monoxide, hydrogen and the catalyst with partial coke; the catalyst with part of coke enters a regenerator 17, contacts oxygen-enriched gas 16 entering through a main wind distribution plate 15 to generate a charcoal burning reaction, burns coke on the deactivated catalyst, regenerates the deactivated catalyst, and gas generated by the gasifier and the regenerator enters a separation unit 3 through a cyclone separator 20 and a flue gas pipeline 21 to separate hydrogen 10, carbon dioxide 11 and carbon monoxide 12. Regenerated catalyst after regeneration is recycled to the bottom of reducer 22 via line 18 for reuse.
The following examples further illustrate the invention but are not intended to limit it.
The starting materials used in the examples and comparative examples were catalytic diesel, and the properties are shown in table 1. The commercial catalyst used in the comparative example, commercially available under the trade designation DMMC-1, has the properties shown in Table 2.
The catalyst preparation used in the examples is briefly described as follows:
1) Pulping 75.4 kg of kaolin (solid content 71.6 wt%) with 250 kg of decationizing water, adding 54.8 kg of pseudo-boehmite (solid content 63 wt%) and regulating pH to 2-4 with hydrochloric acid, stirring, standing at 60-70deg.C for aging for 1 hr, maintaining pH at 2-4, cooling to below 60deg.C, adding 41.5 kg of aluminum sol (Al) 2 O 3 The content of the matrix is 21.7 weight percent), stirring for 40 minutes to obtain mixed slurry, spray drying and forming, and roasting to obtain the matrix sample.
2) 3 kg of Ni (NO) 3 ) 2 Dissolving in 5.5 kg water to obtain Ni (NO) 3 ) 2 ·6H 2 O aqueous solution, 10 kg of a molecular sieve catalyst sample was impregnated with Ni (NO 3 ) 2 ·6H 2 The resulting mixture was dried in O aqueous solution at 180℃for 4 hours and calcined at 600℃for 2 hours. And (3) repeatedly soaking, drying and baking to ensure that the Ni content loaded on the catalyst sample reaches 15%, thus obtaining the catalyst A of the embodiment.
Example 1
According to the flow of FIG. 1, the catalytic decomposition reaction test of catalytic diesel oil is carried out on a riser reactor, methane is firstly contacted with a catalyst as reducing gas to carry out the reduction reaction of a metal catalyst, the catalytic diesel oil is injected into the lower part of the riser reactor, is contacted with a hot regenerated catalyst to carry out the catalytic decomposition reaction, a reaction product and an inactivated catalyst with coke enter a closed cyclone separator from the outlet of the reactor, the reaction product and the inactivated catalyst are rapidly separated, and the cracking gas and the liquid product are separated from the reaction product in a separation system.
The deactivated catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the deactivated catalyst are stripped by steam, and the stripped deactivated catalyst sequentially enters a gasifier and a regenerator to contact with steam and air rich in oxygen for gasification and regeneration reaction; the regenerated catalyst is 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.
As can be seen from the results in Table 4, the hydrogen yield was as high as 22.20%, and the CO yield in the reaction product was 27.66%, CO 2 The yield was 24.09%. The concentration of CO in the regenerated flue gas is 51.24 volume percent, CO 2 The concentration was 4.96% by volume and the hydrogen concentration in the flue gas was 10.86% by volume.
Comparative example 1
The test was carried out on a medium-sized apparatus for a riser, the catalytic diesel feed was the same as in example 1, and the catalyst was DMMC-1.
The catalytic diesel oil enters a hot DMMC-1 catalyst under a riser reactor to contact and carry out catalytic decomposition reaction, a reaction product and a spent catalyst enter a closed cyclone separator from an outlet of the reactor, the reaction product and the spent catalyst are rapidly separated, and the reaction product is separated into products such as gas, liquid and the like according to a distillation range in a separation system.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be in contact with air for regeneration; the regenerated catalyst is returned to the riser reactor for recycling; the operating conditions and product distribution are listed in tables 3 and 4.
As can be seen from the results in Table 4, the hydrogen yield was 1.62%, and the reaction product wasNeutralizing CO and CO 2 The yield is lower. CO is not detected in the regenerated flue gas, and CO 2 Concentration of 15.78 vol%, O 2 The concentration was 3.91% by volume.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the present invention can be made, as long as it does not depart from the gist of the present invention, which is also regarded as the content of the present invention.
TABLE 1
| Project | Catalytic diesel |
| Density (20 ℃ C.)/(kg/m) 3 ) | 948.9 |
| Kinematic viscosity (20 ℃ C.)/(mm 2 Second | 3.754 |
| Total acid number/(mg KOH/g) | <0.05 |
| Freezing point/°c | -27 |
| Closed flash point/°c | 66 |
| Distillation range/. Degree.C | |
| Initial point of distillation | 197.9 |
| 5％ | 220.4 |
| 10％ | 228.4 |
| 50％ | 262.5 |
| 70％ | 283.1 |
| 90％ | 308.6 |
| 95％ | 319.5 |
| End point of distillation | 329.9 |
TABLE 2
| Comparative example 1 | Example 1 | |
| DMMC-1 | Catalyst A | |
| Physical Properties | ||
| Specific surface area, rice 2 Gram/gram | 106 | 118 |
| Specific surface area of matrix, rice 2 Gram/gram | 64 | 95 |
| Pore volume, cm 3 Gram/gram | 0.13 | 0.106 |
| Sieving composition, weight percent | ||
| 0-40 micrometers | 30.9 | 20.7 |
| 0-80 micrometers | 75.0 | 76.1 |
| 0-105 micrometers | 89.1 | 84.3 |
| 0-149 micrometers | 98.4 | 97.5 |
| Average particle size/micron | 55.6 | 54.9 |
| Micro-inverse Activity,% | 65 | 40 |
| Metal content, weight percent | ||
| Ni | 0.06 | 15.0 |
TABLE 3 Table 3
| Example 1 | Comparative example 1 | |
| Riser reaction conditions | ||
| Reaction temperature, DEG C | 675 | 675 |
| Reaction time, seconds | 1.8 | 1.8 |
| Catalyst to catalytic |
20 | 20 |
| Water-oil weight ratio | 0.25 | 0.25 |
| Gasifier conditions | ||
| Gasification temperature, DEG C | 700 | / |
| Weight ratio of water vapor to catalytic diesel | 0.5 | / |
| Apparent linear velocity of gas, meter/second | 0.8 | / |
| Average residence time, min | 4.5 | / |
| Regenerator conditions | ||
| Regeneration temperature, DEG C | 680 | 680 |
| Oxygen concentration in the regenerated air, volume% | 50 | 21 |
| Apparent linear velocity of gas, meter/second | 0.8 | 0.8 |
| Average residence time, min | 4.5 | 4.5 |
| Conditions of the reducer | ||
| Reduction temperature, DEG C | 650 | / |
| Apparent linear velocity of gas, meter/second | 1.0 | / |
TABLE 4 Table 4
| Example 1 | Comparative example 1 | |
| Distribution of the product, weight percent | ||
| CO | 27.66 | 0.24 |
| CO 2 | 24.09 | 0.95 |
| H 2 | 22.20 | 1.62 |
| Methane | 4.83 | 3.70 |
| Other hydrocarbons | 9.35 | 83.08 |
| Coke | 11.87 | 10.41 |
| Totalizing | 100.00 | 100.00 |
| The regenerated flue gas composition is in volume percent | ||
| CO | 51.24 | 0 |
| CO 2 | 4.96 | 15.78 |
| N 2 | 32.92 | 80.31 |
| O 2 | 0.02 | 3.91 |
| H 2 | 10.86 | 0 |
Claims (16)
1. Catalytic hydrogen production from hydrocarbon raw material and CO enrichment 2 The method comprising the steps of:
(1) Hydrocarbon raw materials are sent into a fluidization reactor to contact with the reduced catalyst containing metal oxide to generate a reaction of hydrocarbon bond breakage to generate hydrogen, so as to obtain reaction oil gas containing hydrogen and an inactivated catalyst for depositing coke;
(2) Separating the reaction oil gas containing hydrogen from the deactivated catalyst with deposited coke;
(3) The separated reaction oil gas enters a separation unit and is further separated into hydrogen, CO and CO 2 Methane and other hydrocarbon products, and part or all of the methane obtained by separation is used as a reducing agent;
(4) The obtained deactivated catalyst of deposited coke is sent to a gasifier to contact with water vapor to carry out high-temperature gasification reaction to generate hydrogen and CO 2 ；
(5) The gasified deactivated catalyst with carbon enters a regenerator to contact with oxygen-containing gas for carbon burning regeneration, the deactivated catalyst burns off coke and is sent to a reducer as a regenerated catalyst, and the regenerated flue gas is sent to a separation unit to obtain CO and CO 2 ；
(6) After the regenerated catalyst enters the reducer, the regenerated catalyst contacts with the reducer to generate reduction reaction, and the reduced regenerated catalyst enters the fluidization reactor to perform circulation.
2. The process of claim 1 wherein the fluidization reactor has a reaction temperature of 450 to 800 ℃, a reaction time of 0.1 to 10 seconds, a weight ratio of catalyst to hydrocarbon feedstock of 5 to 100, and a weight ratio of water vapor to hydrocarbon feedstock of 0.1 to 20.
3. The process of claim 1 wherein the fluidization reactor has a reaction temperature of 550 to 700 ℃ and a reaction time of 1 to 8 seconds, the weight ratio of catalyst to hydrocarbon feedstock being 20 to 50; the weight ratio of the water vapor to the hydrocarbon raw material is 1-10.
4. The method of claim 1, wherein the fluidization reactor is selected from one or a combination of several of a riser reactor, a fast bed, and a dense-phase fluidized bed.
5. The process according to claim 4, wherein the fluidization reactor comprises, in order from bottom to top, a pre-lift section and at least one reaction zone, which may be 2-8, preferably 2-3.
6. The method according to claim 1, wherein the gasifier is operated at a temperature of 650-1000 ℃, a gas superficial linear velocity of 0.2-1.0 m/s and an average residence time of the catalyst of 0.5-10 minutes.
7. The method according to claim 1, wherein the operating conditions of the gasifier are preferably a temperature of 750-950 ℃; the apparent linear velocity of the gas is 0.3-0.8 m/s, and the average residence time of the catalyst is 1-5 minutes.
8. The method of claim 1, wherein the concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 22-100% by volume and the volume ratio of water vapor to oxygen-containing gas is 1-10.
9. The method of claim 1, wherein the concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 25% to 80% by weight, and the volume ratio of the water vapor to the oxygen-containing gas is 1 to 5.
10. The method according to claim 1, characterized in that the regeneration operating conditions are preferably: the temperature is 550-700 ℃; the apparent linear velocity of the gas is 0.2-1.2 m/s, and the average residence time of the deactivated catalyst is 1-10 minutes.
11. The method of claim 1, wherein the reducer operating conditions are: the temperature is 550-700 ℃; the apparent linear velocity of the gas is 0.5-3 m/s.
12. The method according to claim 1, wherein the reducing agent is selected from one or more of small-molecule alkanes, preferably one or more of methane, ethane, propane, n-butane and isobutane.
13. The method according to claim 1, wherein the hydrocarbon is selected from one or more of petroleum hydrocarbon, petroleum oil, diesel oil, vacuum wax oil, atmospheric residuum, vacuum wax oil blended portion vacuum residuum or hydrocarbon oil obtained by secondary processing; the mineral oil is selected from one or more of coal liquefied oil, oil sand oil and shale oil; the synthetic oil is distillate oil obtained by F-T synthesis of coal, natural gas or asphalt.
14. The method of claim 13, wherein the hydrocarbon oil obtained by secondary processing is one or more of coker gasoline, catalytic diesel, hydrogenated diesel, coker wax oil, deasphalted oil, and furfural refined raffinate.
15. The method of claim 1, wherein the catalyst comprises 15% to 65% natural minerals, 20% to 60% oxides, and 5% to 30% metal active component on a dry weight basis of the catalyst.
16. The method according to claim 15, wherein the metal active component is present in an amount of 5 to 30 wt%, preferably 8 to 25 wt%, and 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111230356.0A CN116004279A (en) | 2021-10-22 | 2021-10-22 | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111230356.0A CN116004279A (en) | 2021-10-22 | 2021-10-22 | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116004279A true CN116004279A (en) | 2023-04-25 |
Family
ID=86032270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111230356.0A Pending CN116004279A (en) | 2021-10-22 | 2021-10-22 | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116004279A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116712947A (en) * | 2023-08-02 | 2023-09-08 | 罗托布斯特(上海)氢能科技有限公司 | Offshore facility and marine flowable raw material gas catalytic pyrolysis system and process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0101878A2 (en) * | 1982-07-29 | 1984-03-07 | Ashland Oil, Inc. | Combination process for upgrading reduced crude |
| CN101210197A (en) * | 2006-12-29 | 2008-07-02 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN109705903A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Inferior heavy oil processing-coke gasification combined method |
| CN109705899A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Inferior heavy oil processing-coke gasification combined method |
-
2021
- 2021-10-22 CN CN202111230356.0A patent/CN116004279A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0101878A2 (en) * | 1982-07-29 | 1984-03-07 | Ashland Oil, Inc. | Combination process for upgrading reduced crude |
| CN101210197A (en) * | 2006-12-29 | 2008-07-02 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN109705903A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Inferior heavy oil processing-coke gasification combined method |
| CN109705899A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Inferior heavy oil processing-coke gasification combined method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116712947A (en) * | 2023-08-02 | 2023-09-08 | 罗托布斯特(上海)氢能科技有限公司 | Offshore facility and marine flowable raw material gas catalytic pyrolysis system and process |
| CN116712947B (en) * | 2023-08-02 | 2024-02-06 | 罗托布斯特(上海)氢能科技有限公司 | Offshore facility and marine flowable raw material gas catalytic pyrolysis system and process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100586909C (en) | Catalytic conversion method for increasing propylene yield | |
| CN108017496B (en) | Apparatus for producing olefins and aromatic hydrocarbons and method thereof | |
| CN101029248B (en) | Method for increasing light olefin yield | |
| CN102234534B (en) | Method for processing inferior heavy oil | |
| CN102746880A (en) | Method for preparing gasoline, diesel oil, ethylene and propylene through coupled catalytic cracking of light hydrocarbons and heavy oil | |
| CN1069016A (en) | The method of preparing ethene by direct conversion of heavy hydrocarbon | |
| CN110499182A (en) | A kind of catalyst cracking method of hydro carbons and its derivative | |
| CN102234535B (en) | Method for processing low-quality heavy oil and simultaneously producing synthetic gas | |
| CN101205475B (en) | Hydrocarbons catalytic conversion method for preparing low olefin-content gasoline | |
| CN102250641B (en) | Method and apparatus for preparing ethylene and propylene with maximized yield | |
| CN108485704B (en) | Process for preparing chemical raw materials in maximized mode by combining millisecond-graded gas-phase catalytic cracking and hydrogenation of crude oil | |
| CN116004279A (en) | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) | |
| CN101210197B (en) | Conversion method for hydrocarbon oil | |
| CN101457152A (en) | Hydrocarbon oil conversion method | |
| CN102746873A (en) | Method for preparing ethylene and propylene through catalytic cracking of light hydrocarbons | |
| CN112538372B (en) | Integrated method and device for co-producing synthesis gas by catalytic cracking of heavy oil | |
| EP3165588A1 (en) | Process for production of syngas through regeneration of coked cracking agent | |
| CN116002614A (en) | Hydrogen production method by using inferior heavy oil | |
| CN103055959A (en) | Catalyst regeneration method | |
| CN101210196B (en) | Conversion method for hydrocarbon oil | |
| CN106609151B (en) | A kind of method for producing low-carbon alkene | |
| CN116004275A (en) | Method for preparing hydrogen and enriching carbon dioxide by catalysis | |
| US20110297585A1 (en) | Process For Reducing The Quantity Of Carbon Dioxide Produced In A Fluid Catalytic Cracking Regeneration Off Gas | |
| CN116004277A (en) | Method for simultaneously preparing hydrogen and low-carbon olefin by using hydrocarbon raw material | |
| CN116004274A (en) | Method for producing hydrogen and low-carbon olefin by catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |