CN116002614A - Hydrogen production method by using inferior heavy oil - Google Patents
Hydrogen production method by using inferior heavy oil Download PDFInfo
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Abstract
A method for producing hydrogen by using inferior heavy oil, wherein the inferior heavy oil is contacted with a catalyst containing macroporous zeolite and metal oxide and subjected to pre-decomposition reaction to obtain a reactant flow and an inactivated catalyst with carbon; the reactant stream is separated into a reactant gas, light oil and heavy oil; the light oil is sent to a hydrogen production reactor to obtain reaction gas and an inactivated catalyst with carbon; the reaction gas obtained by separating the pre-decomposition reactor and the hydrogen production reactor is sent to a separation unit for further separation into hydrogen, CO and CO 2 And light hydrocarbons; the obtained deactivated catalyst with carbon is sent to a regenerator for regeneration, after the deactivated catalyst is burnt and regenerated, one part of the regenerated catalyst is returned to a pre-decomposition reactor for recycling, and the other part of the regenerated catalyst is returned to a hydrogen production reactor for recycling after reduction, and the regenerated flue gas is separated to obtain CO and CO 2 . The invention pre-decomposes the inferior heavy oil, not only improves the quality of the catalytic cracking raw material, but also simultaneously produces hydrogen to realize the inferior heavy oil resourceEfficient utilization of sources.
Description
Technical Field
The invention relates to a method for pre-decomposing and producing hydrogen by inferior heavy oil, in particular to a method for pre-decomposing and producing hydrogen by inferior heavy oil fluid catalytic cracking.
Background
The crude oil quality shows an inferior trend year by year, and is mainly characterized by higher crude oil density, higher viscosity, higher heavy metal content, sulfur content, nitrogen content, colloid and asphaltene content and acid value. The traditional heavy oil processing is mainly divided into two types, namely a hydrogenation process mainly comprising hydrotreating and hydrofining; and the decarburization process mainly comprises solvent deasphalting, delayed coking and heavy oil catalytic cracking. Inferior heavy oils can be converted to lower boiling point compounds by increasing the hydrogen to carbon ratio by these process techniques. When the inferior heavy oil is treated by adopting a decarburization process, the contents of sulfur, nitrogen and heavy metals and the contents of aromatic hydrocarbon, colloid and asphaltene in the inferior heavy oil have great influence on the decarburization process, the deficiencies of the decarburization process can be made up by a hydrotreating process, the yield of liquid products is high after the inferior heavy oil is hydrotreated, the product properties are good, but the hydrotreating mode tends to have great investment and consume hydrogen sources. Although the catalytic cracking process is difficult to process the inferior heavy oil with high carbon residue and high metal content, the operation flexibility is high, and the process is hopeful to bear the heavy duty of the pre-decomposition of the inferior residual oil.
The hydrogen energy is an ideal novel energy source, and is used as a green energy source with rich reserves, high heat value, large energy density and various sources. The existing main hydrogen production modes are mature in three technical routes, namely reforming hydrogen production by fossil energy sources such as coal, natural gas and the like, high-temperature decomposition reforming hydrogen production by chemical raw materials represented by an alcohol pyrolysis hydrogen production technology and water electrolysis hydrogen production; technical routes such as photolysis water and biomass gasification hydrogen production are still in experimental and development stages, and related technologies are difficult to break through, and the requirement of large-scale hydrogen production is not met. 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. The scale of hydrogen production is 5000m 3 And the natural gas hydrogen production process is more economical when the ratio is higher than/h. In addition, the natural gas raw material accounts for more than 70 percent of the hydrogen production cost, the price of the natural gas is an important factor for determining the price of the hydrogen, and I amThe energy characteristics of rich coal, oil deficiency and less gas restrict the implementation of natural gas hydrogen production in China. 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 technical route of coal hydrogen production is mature and efficient, and the coal hydrogen production can be stably prepared on a large scale, but the power energy consumption of the coal hydrogen production fuel is higher than that of natural gas hydrogen production, the requirements on system steam and electric power are high, the enterprises need matched boilers, and the unified construction of the coal-fired boiler is subject to government requirements. 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.
With the development of oil refining technology, particularly the heavy/inferior trend of crude oil is aggravated, and the quality of oil is improved, so that the hydrogenation technology is widely applied, and the hydrogen demand is greatly promoted. The annual increase in global refinery hydrogen demand was statistically more than 4%. Hydrogen from refineries comes mainly from process plant byproducts, refinery gas recovery, existing refinery hydrogen production facilities, and the hydrogen production from refineries will have difficulty meeting future hydrogen growth demands, thus, more flexible and feasible hydrogen supply strategies need to be explored. If a non-critical inferior heavy oil pre-decomposition technology can be developed, hydrogen can be produced at the same time, and the method has definitely great practical value.
Disclosure of Invention
The invention aims to provide a method for producing hydrogen by inferior heavy oil.
The method for producing hydrogen by inferior heavy oil provided by the invention comprises the following steps:
(1) Introducing inferior heavy oil into a fluidization reactor, contacting with a catalyst containing large-pore zeolite and metal oxide, and performing pre-decomposition reaction to obtain a reactant stream and a deactivated catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pre-decomposition reaction and the deactivated catalyst with carbon; the separated reaction oil gas enters a fractionating tower and is separated into gas, light oil and heavy oil;
(2) The separated light oil is sent to a hydrogen production reactor, contacts with the reduced regenerated catalyst and steam and generates hydrogen production reaction to obtain a reactant flow and an inactivated catalyst with carbon; carrying out gas-solid separation on reaction oil gas obtained by hydrogen production reaction and deactivated catalyst with carbon;
(3) And (3) sending the reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor into a separation unit, further separating the reaction oil gas into hydrogen, carbon monoxide, carbon dioxide and light hydrocarbon, and sending the light hydrocarbon obtained by separation into a reducer to be used as a reducing agent.
(4) And (3) sending the obtained fluidized reactor and the deactivated catalyst of the hydrogen production reactor to a regenerator for regeneration, wherein the deactivated catalyst is separated into two parts after being burnt and regenerated, one part of the regenerated catalyst is returned to the fluidized reactor for recycling, the other part of the regenerated catalyst is sent to a reducer, and enters the hydrogen production reactor for recycling after reduction and steam stripping, and the regenerated flue gas enters a separation unit for separation to obtain carbon monoxide and carbon dioxide.
The inferior heavy oil is selected from the group consisting of oils having a density greater than 940 kg/m 3 One or more of carbon residue greater than 8 wt%, hydrogen content less than 11.8 wt%, and heavy metal content greater than 50 mg/kg based on the total weight of nickel and vanadium.
The catalyst comprises the following components in percentage by weight: 5 to 65 percent of natural mineral, 10 to 60 percent of oxide, 20 to 60 percent of macroporous zeolite, and 0.1 to 30 percent, preferably 0.5 to 20 percent of metal active component by weight. The metal active component is selected from one or more compounds of transition metal elements.
The carbon monoxide obtained by the separation unit can be used as a raw material for water gas shift to further produce hydrogen and carbon dioxide; and the waste heat of the flue gas can be recycled by the carbon monoxide boiler so as to generate high-quality steam.
The invention carries out catalytic cracking pre-decomposition reaction on the inferior heavy oil under a relatively mild condition, and the generated light oil is used as a raw material for hydrogen production, thereby providing a cheap raw material for hydrogen production. The generated heavy oil is used as a catalytic cracking raw material, so that the quality of the catalytic cracking raw material is improved, and the efficient utilization of the raw material is realized.
The method couples the pre-decomposition reaction of the inferior heavy oil and the hydrogen production reaction of the light oil, and in the reaction process, metals in the inferior heavy oil are deposited on the catalyst and can play a role of a dehydrogenation active center in the hydrogen production reaction process, so that the dehydrogenation reaction of the light oil is enhanced, and more hydrogen is produced.
The invention adopts the fluidization reactor to produce hydrogen, can utilize the characteristic of high coke formation of the catalytic cracking reaction of inferior heavy oil, transfers a large amount of heat for the hydrogen production reaction, greatly reduces the energy required to be consumed in the hydrogen production process, and realizes the process economy.
The method reduces the catalyst before hydrogen preparation 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.
The invention preferably adopts a low-temperature incomplete regeneration technology to ensure that CO/CO in the regenerated flue gas 2 The ratio is high, and the low-cost raw gas can be provided for the water gas shift process, so that the optimal utilization of resources is realized. Meanwhile, the oxygen-containing gas used in the regeneration process preferably adopts oxygen-enriched gas, so that CO in the flue gas is greatly improved 2 Can realize the concentration of CO 2 And the large-scale production is carried out, and then the carbon emission is reduced by the technologies of trapping, utilizing and sealing, so that the production of blue hydrogen is realized. Therefore, the invention not only brings hydrogen energy, but also is beneficial to carbon capture, and can bring great economic and social benefits for petrochemical industry.
Drawings
FIG. 1 is a process flow diagram of an embodiment of a method for pre-decomposing and producing hydrogen from a poor heavy oil provided by the present invention.
Detailed Description
A method for producing hydrogen from a poor heavy oil, the method comprising the steps of:
introducing inferior heavy oil into a fluidization reactor, contacting with a catalyst containing large-pore zeolite and metal oxide, and performing pre-decomposition reaction to obtain a reactant stream and a deactivated catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pre-decomposition reaction and the deactivated catalyst with carbon; the separated reaction oil gas enters a fractionating tower and is further separated into gas, light oil and heavy oil according to a distillation range, and the separated heavy oil is used as a raw material of a conventional catalytic cracking device;
the separated light oil is sent to a hydrogen production reactor to contact with a reduced regenerated catalyst and produce hydrogen production reaction, so as to obtain a reactant flow and an inactivated catalyst with carbon; carrying out gas-solid separation on reaction oil gas obtained by hydrogen production reaction and deactivated catalyst with carbon;
the reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor is sent to a separation unit for further separation into H 2 、CO、CO 2 And light hydrocarbon, the light hydrocarbon obtained by separation is sent into a reducer to be used as a reducer.
The obtained fluidized reactor and the deactivated catalyst of the hydrogen production reactor are sent to a regenerator for regeneration, the deactivated catalyst is divided into two parts after being burnt and regenerated, one part of the regenerated catalyst is returned to the fluidized reactor for recycling, the other part of the regenerated catalyst is sent to a reducer, is reduced and stripped and then enters the hydrogen production reactor for recycling, and the regenerated flue gas enters a separation unit for separation to obtain CO and CO 2 。
The inferior heavy oil is selected from the group consisting of oils having a density greater than 940 kg/m 3 One or more of carbon residue greater than 8 wt%, hydrogen content less than 11.8 wt%, and heavy metal content greater than 50 mg/kg based on the total weight of nickel and vanadium.
The catalyst comprises the following components in percentage by weight:
a) 5 to 65 percent of natural mineral substances,
b) 10 to 60 percent of oxide,
c) 20 to 60 percent of macroporous zeolite, and
d) 0.1 to 30 percent of metal active component.
According to the method provided by the invention, the catalytic cracking pre-decomposition reactor and the hydrogen production reactor of the inferior heavy oil are selected from fluidization reactors. The fluidized reactor is selected from one or a combination of a plurality of turbulent bed, fast bed and dilute phase conveying bed. 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 target product quality requirements, the number of the reaction zones can be 2-8, preferably 2-3.
According to the method provided by the invention, the conditions for pre-decomposing the inferior heavy oil comprise: the fluidization reactor has a reaction temperature of 450-600 ℃, preferably 480-550 ℃, a reaction time of 0.5-8 seconds, preferably 1-6 seconds, and a weight ratio of catalyst to inferior heavy oil of 1-30, preferably 5-20; the weight ratio of water vapor to inferior heavy oil is 0.01-1, preferably 0.05-0.3.
According to the method provided by the invention, the conditions of the light oil hydrogen production reactor comprise: the reaction temperature is 600-1000 ℃, preferably 650-900 ℃, the reaction time is 1-10, preferably 2-8 seconds, and the weight ratio of the catalyst to the light oil is 5-100, preferably 20-50; the weight ratio of water vapor to light oil is 0.1-50, preferably 1-20.
According to the method provided by the invention, the deactivated catalyst with carbon is separated from the reaction oil gas in the inferior heavy oil pre-decomposition reactor and the hydrogen production reactor to obtain the deactivated catalyst with carbon and the reaction oil gas, and then the obtained reaction oil gas is separated into hydrogen and CO by a subsequent separation unit 2 Fractions such as CO and light hydrocarbon, and the like, and separating hydrogen and CO from reaction products 2 The methods of CO, light hydrocarbons, etc. are similar to those of the conventional art, and the present invention is not limited thereto and will not be described in detail herein. The CO obtained in the separation unit may be used as feed for water gas shift.
In the method provided by the invention, preferably, the deactivated catalyst with carbon enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the deactivated catalyst with carbon are stripped by steam, and the deactivated catalyst with carbon after stripping enters a regenerator.
In the process provided by the invention, the deactivated catalyst with char may be regenerated in a conventional regenerator, either a single regenerator or multiple regenerators may be used. In the regeneration process, 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 for burning regeneration, the flue gas generated after the burning regeneration of the catalyst is subjected to gas-solid separation at the upper part of the regenerator, and the flue gas enters a water gas conversion 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 to 100% by volume, preferably 25 to 80% by volume.
In the method provided by the invention, low-temperature incomplete regeneration is preferable, and the operation conditions are as follows: the temperature is 550-700 ℃, preferably 600-650 ℃; the gas superficial linear velocity is 0.2 to 1.2 m/s, preferably 0.4 to 0.8 m/s, and the average residence time of the deactivated catalyst with carbon is 1 to 10 minutes, preferably 2 to 6 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 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 is 5-65 wt%, preferably 15-60 wt% on a dry basis; 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 10-60 wt%, preferably 10-30 wt%, more preferably 12-28 wt% based on the total catalyst weight. The zeolite comprises 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.
The metal active component content is 0.1 to 30 wt%, preferably 0.5 to 20 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 preparation method well known to a person skilled in the art. The metal supported on the catalyst may be impregnated or slurry mixed, preferably impregnated, as 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 serve to explain, but do not limit the disclosure.
As shown in fig. 1, the regenerated catalyst from line 7 enters the pre-decomposition reactor 1, moves up the reactor with acceleration, and after being mixed with steam from line 6 via line 5, the inferior heavy oil is injected into the pre-decomposition reactor 1 to contact the regenerated catalyst, and the inferior heavy oil undergoes a pre-decomposition reaction on the hot catalyst and moves up with acceleration. After the generated reaction product and the deactivated catalyst with carbon are separated, the reaction product enters the fractionating tower 3 through a pipeline 8, and the reaction product is separated into reaction gas, light oil and heavy oil according to the distillation range. Heavy oil is fed out of the unit via line 14 and can be fed to a conventional catalytic cracker.
The light oil is mixed with steam from a pipeline 21 through a pipeline 13 and then sent to a hydrogen production reactor 4, and is contacted with a regenerated catalyst after reduction from a reducer 24 to produce hydrogen production reaction, and the produced reaction gas 16 is mixed with the reaction gas 12 from the fractionating tower 3 and then sent to a separation unit 23 to be separated into hydrogen 17, carbon dioxide 18, carbon monoxide 19 and light hydrocarbon 20.
The method comprises the steps that a carbon-carrying deactivated catalyst 9 of a pre-decomposition reactor and a carbon-carrying deactivated catalyst 15 of a hydrogen production reactor enter a regenerator 2, contact oxygen-enriched gas from a pipeline 10, burn coke on the deactivated catalyst, regenerate the carbon-carrying deactivated catalyst, regenerated flue gas enters a separation unit 23 through a flue gas pipeline 11, carbon dioxide 18 and carbon monoxide 19 are separated by the separation unit, the regenerated catalyst is divided into two parts, one part of the regenerated catalyst is recycled to the bottom of the pre-decomposition reactor 1 through a regeneration pipeline 7 and is subjected to reduction reaction by contacting light hydrocarbon 20 separated by the separation unit through a pipeline 22, the regenerated catalyst after reduction is in uplink contact with water vapor injected through a pipeline 25, the carbon oxide carried by the regenerated catalyst after reduction is stripped, and the regenerated catalyst after reduction and stripping enters the bottom of the hydrogen production reactor 4 for recycling.
The following examples further illustrate the invention, but are not intended to limit it.
The feeds used in the examples and comparative examples were vacuum residuum, the properties of which are shown in Table 1. Catalyst a properties are shown in table 2.
The preparation of catalyst A used in the examples is briefly described below:
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 was 21.7% by weight), and stirred for 40 minutes to obtain a mixed slurry.
2) ZRP-1 (dry basis: 2 kg) and DASY zeolite (dry basis: 22.5 kg) were added to the resulting mixed slurry, stirred uniformly, spray-dried to form, washed with a monoammonium phosphate solution (phosphorus content: 1 wt%) to remove free Na + Roasting to obtain the molecular sieve catalyst sample.
3) 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 roasting to ensure that the Ni content loaded on the catalyst sample reaches 2 wt%, thus obtaining the catalyst A of the embodiment.
Example 1
The test was carried out according to the flow of FIG. 1, in which the atmospheric residuum was subjected to a pre-decomposition reaction on a riser reactor, the atmospheric residuum was introduced into the lower portion of the riser reactor, contacted with a hot regenerated catalyst and subjected to a pre-decomposition reaction, and the reaction product and the deactivated catalyst were introduced into a closed cyclone from the outlet of the reactor, and the reaction product and the deactivated catalyst were rapidly separated, and the reaction product was separated into gas, light oil and heavy oil in a separation system according to the distillation range.
The light oil enters the lower part of another riser hydrogen production reactor, contacts with the regenerated catalyst after methane reduction and carries out hydrogen production reaction, and the reaction product and the deactivated catalyst enter a closed cyclone separator from the outlet of the reactor, so that the reaction product and the deactivated catalyst are rapidly separated.
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 to be contacted with air rich in oxygen 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 of Table 4, the hydrogen yield was as high as 6.16%, the heavy oil yield was 77.93%, and the heavy oil properties were significantly improved with a density of 928.3 kg/m 3 The hydrogen content is improved to 12.08 weight percent, and the requirement of the conventional catalytic cracking raw material is met. CO in regenerated flue gas 2 The concentration was 32.77% by volume.
Comparative example 1
The test was carried out on a medium-sized riser unit with the same atmospheric residuum feed as in example 1 with catalyst a.
The atmospheric residuum enters a thermal re-heavy catalyst under a riser reactor to contact and carry out pre-decomposition reaction, reaction products and deactivated catalyst enter a closed cyclone separator from an outlet of the reactor, the reaction products and the deactivated catalyst are rapidly separated, and the reaction products are separated into products such as gas, liquid and the like according to distillation ranges 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 enters a regenerator to be contacted 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 1.74%, the heavy oil yield was 77.51%, and the heavy oil properties were significantly improved with a density of 928.7 kg/m 3 The hydrogen content was raised to 12.0 wt%. CO in regenerated flue gas 2 The concentration was 31.79% 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
| Name of the name | Atmospheric residuum |
| Density (20 ℃ C.)/(kg/m) 3 ) | 974.7 |
| Viscosity (100 ℃ C.)/(mm) 2 Second | 62.75 |
| Carbon residue value/wt% | 10.34 |
| Element content/wt% | |
| Carbon (C) | 84.30 |
| Hydrogen gas | 11.06 |
| Sulfur (S) | 4.18 |
| Nitrogen and nitrogen | 0.24 |
| Four component composition/wt% | |
| Saturation fraction | 31.0 |
| Aromatic components | 46.8 |
| Colloid | 18.8 |
| Asphaltenes | 3.4 |
| Metal content/(micrograms/gram) | |
| Ca | 1.7 |
| Fe | 2.9 |
| Ni | 21.1 |
| V | 60.5 |
TABLE 2
| Catalyst A | |
| Physical Properties | |
| Specific surface area, rice 2 Gram/gram | 128 |
| Molecular sieve specific surface area, rice 2 Gram/gram | 47 |
| Pore volume, cm 3 Gram/gram | 0.137 |
| Sieving composition, weight percent | |
| 0-40 micrometers | 22.7 |
| 0-80 micrometers | 64.4 |
| 0-105 micrometers | 87.1 |
| 0-149 micrometers | 97.9 |
| Average particle size/micron | 55.0 |
| Micro-inverse Activity,% | 50 |
| Metal content, weight percent | |
| Ni | 2.0 |
TABLE 3 Table 3
TABLE 4 Table 4
| Example 1 | Comparative example 1 | |
| Distribution of the product, weight percent | ||
| CO | 2.27 | 0.06 |
| CO 2 | 4.11 | 0.33 |
| H 2 | 6.16 | 1.74 |
| Gaseous hydrocarbons | / | 1.02 |
| Light oil | / | 7.23 |
| Heavy oil | 77.93 | 77.51 |
| Coke | 9.53 | 12.11 |
| Totalizing | 100 | 100 |
| Smoke composition, volume% | ||
| CO | 8.15 | 7.94 |
| CO 2 | 32.77 | 31.79 |
| N 2 | 59.08 | 59.95 |
| Properties of heavy oil obtained by pre-decomposition | ||
| Density (20 ℃ C.)/(kg/m) 3 ) | 928.3 | 928.7 |
| Viscosity (100 ℃ C.)/(mm) 2 Second | 22.84 | 22.8 |
| Hydrogen content, wt% | 12.08 | 12.0 |
| Residual carbon, weight percent | 5.5 | 5.5 |
Claims (16)
1. A method for producing hydrogen from a poor heavy oil, the method comprising the steps of:
(1) Introducing inferior heavy oil into a fluidization reactor, contacting with a catalyst containing large-pore zeolite and metal oxide, and performing pre-decomposition reaction to obtain a reactant stream and a deactivated catalyst with carbon; carrying out gas-solid separation on the reaction oil gas obtained by the pre-decomposition reaction and the deactivated catalyst with carbon; the separated reaction oil gas enters a fractionating tower and is separated into gas, light oil and heavy oil;
(2) The separated light oil is sent to a hydrogen production reactor, contacts with the reduced regenerated catalyst and steam and generates hydrogen production reaction to obtain a reactant flow and an inactivated catalyst with carbon; carrying out gas-solid separation on reaction oil gas obtained by hydrogen production reaction and deactivated catalyst with carbon;
(3) And (3) sending the reaction oil gas obtained by separating the fluidization reactor and the hydrogen production reactor into a separation unit, further separating the reaction oil gas into hydrogen, carbon monoxide, carbon dioxide and light hydrocarbon, and sending the light hydrocarbon obtained by separation into a reducer to be used as a reducing agent.
(4) And (3) sending the obtained fluidized reactor and the deactivated catalyst of the hydrogen production reactor to a regenerator for regeneration, wherein the deactivated catalyst is separated into two parts after being burnt and regenerated, one part of the regenerated catalyst is returned to the fluidized reactor for recycling, the other part of the regenerated catalyst is sent to a reducer, and enters the hydrogen production reactor for recycling after reduction and steam stripping, and the regenerated flue gas enters a separation unit for separation to obtain carbon monoxide and carbon dioxide.
2. The method of claim 1, wherein the inferior heavy oil catalytic cracking pre-decomposition reactor is selected from a fluidized reactor selected from one or a combination of a turbulent bed, a fast bed and a dilute phase transport bed.
3. The method of claim 2, wherein the pre-decomposition reactor comprises at least one or more reaction zones in series.
4. The method of claim 1, wherein the hydrogen production reactor is selected from the group consisting of a fluidized reactor selected from the group consisting of a turbulent bed, a fast bed, and a dilute phase transport bed.
5. The method of claim 1, wherein the conditions for pre-decomposing the inferior heavy oil include: the reaction temperature is 450-600 ℃, 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 the water vapor to the inferior heavy oil is 0.01-1.
6. The method of claim 1, wherein the conditions for pre-decomposing the inferior heavy oil include: the reaction temperature is 480-550 ℃, the reaction time is 1-6 seconds, and the weight ratio of the catalyst to the inferior heavy oil is 5-20; the weight ratio of water vapor to inferior heavy oil is 0.05-0.3.
7. The method of claim 1, wherein the conditions of the light oil hydrogen production reactor comprise: the reaction temperature is 600-1000 ℃, the reaction time is 1-10 seconds, and the weight ratio of the catalyst to the light oil is 5-100; the weight ratio of the water vapor to the light oil is 0.1-50.
8. The method of claim 1, wherein the conditions of the light oil hydrogen production reactor comprise: the reaction temperature is 650-900 ℃, the reaction time is 2-8 seconds, and the weight ratio of the catalyst to the light oil is 20-50; the weight ratio of the water vapor to the light oil is 1-20.
9. 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.
10. The method of claim 1, wherein the concentration of oxygen in the oxygen-containing gas at the bottom of the regenerator is 25-80% by volume.
11. The method of claim 1, wherein the regeneration operating conditions are: 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.
12. The method of claim 1, wherein the regeneration operating conditions are: the temperature is 600-650 ℃; the apparent linear velocity of the gas is 0.4-0.8 m/s, and the average residence time of the deactivated catalyst is 2-6 minutes.
13. 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.
14. The method of claim 1, wherein the inferior heavy oil is selected from the group consisting of oils having a density greater than 940 kg/m 3 One or more of carbon residue greater than 8 wt%, hydrogen content less than 11.8 wt%, and heavy metal content greater than 50 mg/kg based on the total weight of nickel and vanadium.
15. The method of claim 1, wherein the catalyst comprises 5% to 65% natural minerals, 10% to 60% oxides, 20% to 60% zeolite comprising a large pore zeolite selected from one or more of rare earth Y, rare earth hydrogen Y, ultrastable Y, and high silicon Y, and 0.1% to 30% metal active component based on the dry weight of the catalyst.
16. The method according to claim 15, wherein the metal active component is contained in an amount of 0.1 to 30 wt%, preferably 0.5 to 20 wt%, and the metal active component is selected from one or more of compounds of transition metal elements, preferably one or more of metals of nickel, cobalt, iron, tungsten, molybdenum, manganese, copper, zirconium, chromium, etc.
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| CN116855971A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Gas preparation method and control device thereof, gas preparation equipment and electronic equipment |
| CN116855971B (en) * | 2023-09-04 | 2023-11-24 | 中石油深圳新能源研究院有限公司 | Gas preparation method and control device thereof, gas preparation equipment and electronic equipment |
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