CN1400159A - Hydrogen-making method by utilizing catalytic cracked regenerated flue gas - Google Patents
Hydrogen-making method by utilizing catalytic cracked regenerated flue gas Download PDFInfo
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Abstract
The method for making hydrogen by utilizing catalytic cracking regenerated flue gas includes the following steps: (1). contacting hydrocarbon oil raw material with catalytic cracking catalyst and making them produce reaction; (2). separating reaction oil vapour and catalyst of carbon deposit, feeding oil vapour into subsequent separation system, and stripping the catalyst of carbon deposit and feeding it into first regenerator; (3). in first regenerator contacting the catalyst of carbon deposit with oxygen-containing gas for 2-2.5 sec. at 500-660 deg.C and empty bed gas speed of 0.2-0.8 m/s, feeding regenerated flue gas into subsquent hydrogen-making process; (4). separating CO from regenerated flue gas, making CO and water vapour produce conversion reaction and separating hydrogen from the obtained gas product.
Description
Technical Field
The invention relates to a catalytic cracking process and a steam hydrogen production process of petroleum hydrocarbon, in particular to a method for preparing hydrogen by using catalytic cracking regenerated flue gas.
Background
The development trend of crude oil heaviness and deterioration worldwide and the stricter environmental regulations have raised many new problems for the petroleum processing industry. For example, the content of harmful elements such as sulfur, nitrogen, nickel, vanadium and the like in the raw oil is high, and hydrogenation pretreatment is required; the hydrogen-carbon ratio of raw oil is low, and hydrogenation treatment is required to improve the yield of high-value products such as gasoline, diesel oil and the like; the deterioration of the raw material inevitably affects the properties of the product, and therefore, hydrofinishing is indispensable for improving the quality of gasoline and diesel oil. Therefore, the hydrogenation process has become an indispensable secondary processing means, and plays a very important role in the oil refinery. However, "how to obtain a sufficient amount of an inexpensive source of hydrogen? Is a difficult problem which troubles oil refining enterprises. Although the catalytic reforming process can produce high-purity hydrogen as by-product, the amount of hydrogen in the catalytic reforming process is far from meeting the requirement of the hydrogenation process. The prior art also provides various other hydrogen production methods such as methane steam cracking hydrogen production, heavy oil hydrogen production, coal hydrogen production and the like, but the hydrogen produced by the methods has high cost and occupies a considerable proportion of the whole hydrogenation cost (see table 1), which undoubtedly influences the economic benefit of the whole hydrogenation process. Therefore, it is of interest to develop hydrogenation processes while focusing on the source of hydrogen, particularly inexpensive hydrogen.
TABLE 1
| Type of device | Hydrocracking | Steam generatorHydrogenation of oils | Hydrogenation of diesel oil |
| Device size, Mt/a | 0.8 | 0.3 | 0.4 |
| Hydrogen gas accounts for the cost% | 58 | 56 | 40 |
USP5,362,380 discloses a catalytic cracking process for producing hydrogen. The method comprises the steps of enabling a spent catalyst to react with water vapor at 537-649 ℃ for a sufficient time in the absence of oxygen to generate a gas material flow containing hydrogen, carbon dioxide, carbon monoxide and methane, and simultaneously reducing the carbon content on the spent catalyst to 0.3-0.8 wt%; and separating the gas material flow from the catalyst, cooling the gas material flow, further separating the cooled gas material flow into a hydrogen-rich material flow containing 90-97 v% of hydrogen, contacting the catalyst with oxygen-containing gas, regenerating, and recycling the regenerated catalyst. The method for preparing the hydrogen has the advantages that the contact time of the water vapor and the spent catalyst is long, the reaction rate is slow, the economical efficiency of the method is influenced, the hydrothermal aging of the catalyst is accelerated, and the activity and the service life of the catalyst are influenced.
In the catalytic cracking process, the regeneration flue gas contains CO gas regardless of single-stage regeneration or two-stage regeneration. The concentration of CO in the regeneration flue gas is typically around 7 v%. This CO gas can form a tail gas, release a large amount of reaction heat, and cause local overheating of the regenerator and aggravate catalyst deactivation. The simplest way to reduce the tail-fire is to control the oxygen content in the flue gas. However, this is done at the expense of the rate or strength of the char. After the tail gas is controlled, the problem of smoke emission needs to be solved. CO is discharged into the atmosphere along with the flue gas, which not only brings adverse effect to the environment, but also causes the loss ofCO chemical energy. For this reason, refinery companies have used CO-fired boilers, which are expensive to manufacture and operate, and Amoco has also invented UltraCat regeneration technology to completely burn CO. In 1974 Mobil began using a platinum CO combustion improver. The combustion improver has satisfactory effect but higher cost. Most manufacturers in China use CO combustion improver until now, which is compelled to meet the requirements of environmental protection and process. Therefore, the problem of CO in the regeneration flue gas has not been properly solved.
Disclosure of Invention
The invention aims to provide a novel method for preparing hydrogen by using catalytic cracking regeneration flue gas, so that CO in the regeneration flue gas can be effectively utilized.
The method for preparing hydrogen by using catalytic cracking regenerated flue gas provided by the invention comprises the following steps:
(1) contacting a hydrocarbon oil raw material with a catalytic cracking catalyst in a reactor, and reacting under catalytic cracking reaction conditions;
(2) separating the reaction oil gas and the catalyst deposited carbon after the reaction, sending the oil gas into a subsequent separation system, and sending the catalyst deposited carbon to a first regenerator after steam stripping;
(3) in the first regenerator, the carbon-deposited catalyst contacts with oxygen-containing gas at the temperature of 500-660 ℃ and the air speed of an empty bed of 0.2-0.8 m/s for 6-25 seconds, and then the regenerated flue gas is sent to the subsequent hydrogen production process;
(4) separating CO from the regeneration flue gas from step (3), subjecting the CO to a shift reaction with steam, and separating hydrogen from the resulting gas product;
(5) the semi-regenerated catalyst from the step (3) enters a second regenerator, contacts with oxygen-containing gas and is regenerated under the conventional catalytic cracking regeneration condition, and the regenerated catalyst is returned to the reactor for recycling.
Compared with the prior art, the beneficial effects of the invention are mainly embodied in the following aspects:
firstly, the regeneration process of the step (3) is carried out at 500-660 ℃, the temperature is obviously lower than the conventional catalytic cracking regeneration temperature, the reaction speed is moderate, the content of CO in the regenerated flue gas is favorably improved, and sufficient raw materials are provided for the subsequent hydrogen production process. The invention makes coke and oxygen-containing gas generate CO as much as possible in the first regenerator, so that the excessive heat in the catalytic cracking process can be stored in a CO stream in the form of chemical energy, thereby reducing the operation load of the catalytic cracking heat remover or operating the catalytic cracking heat remover without arranging heat removing equipment. Therefore, the operation cost of the catalytic cracking device is reduced, the problem that CO in the flue gas pollutes the environment is solved, and simultaneously, a large amount of cheap hydrogen can be provided for a refinery.
Secondly, compared with the prior catalytic cracking hydrogen production technology, the reaction rate of the reaction is higher, and the burning intensity is 52.4kgcoke/(tcatH) and thus the reaction time required for step (3) is short and the volume of the reaction vessel required is comparable to that of a conventional regenerator. These features make the process of the present invention much easier to implement on an industrial setting.
Thirdly, the regeneration operation of the conventional catalytic cracking regeneration process is adjusted, so that the regeneration flue gas generated by the first regenerator is rich in CO and is used as a raw material of the subsequent regeneration process, and the regeneration flue gas and steam are subjected to shift reaction to prepare hydrogen. In the hydrogen production process, the water vapor is not directly contacted with the catalyst, so the process does not cause adverse effect on the hydrothermal stability of the catalyst, and the characteristics are incomparable with the prior art.
Drawings
FIG. 1 is a schematic flow diagram of a method of the present invention.
As shown in figure 1, atomized steam 3 and hydrocarbon oil raw material 2 are injected from the bottom of a riser reactor 27, contact with a regenerant from a pipeline 5 and react, an oil agent mixture enters a separator 28 through the riser reactor, reaction oil gas is separated from a carbon-deposited catalyst, and the oil gas is sent to a subsequent fractionation system through a pipeline 4 and further separated into various products. The carbon-deposited catalyst is stripped by steam 1 and then enters the first regenerator 29 through the delivery pipe 6. An oxygen-containing gas, such as air, is injected from the bottom of the first regenerator via line 7, contacts the carbon-deposited catalyst and partially regenerates it, the CO-rich regeneration flue gas is fed via line 8 to the subsequent hydrogen production process, and the semi-regenerant is fed via line 10 to the second regenerator 30. An oxygen-containing gas, such as air, is injected from the bottom of the second regenerator via line 9, contacts the semi-regenerator and fully regenerates it under conventional catalytic cracking regeneration conditions. The regenerated flue gas is sent to a subsequent heat recovery system through a pipeline 11, and is discharged into the atmosphere after being treated. The regenerant is sent via line 5 to the riser reactor for recycle.
The regeneration flue gas from the first regenerator contains CO and CO2、N2And a small amount of O2SOx, NOx, etc., at a temperature between 500 ℃ and 600 ℃. The regenerated flue gas firstly enters a primary heat exchanger 14 to indirectly exchange heat with low-temperature steam injected from a pipeline 12, and the generated superheated steam is sent out through a pipeline 13. And the regenerated flue gas with the temperature reduced to about 260-350 ℃ enters the secondary heat exchanger 15 through a pipeline 26, and the heat carried by the regenerated flue gas is used for heating the gas material flow 19 mainly containing CO. After passing through the secondary heat exchanger, the temperature of the regeneration gas is reduced to below 100 ℃, and then the temperature of the regeneration flue gas is reduced to below 60 ℃ through the tertiary water-cooling heat exchanger 23, and then the regeneration flue gas is sent to the pressure swing adsorption unit 16 through a pipeline 25. The pressure swing adsorption may be operated intermittently in two or more columns and the resulting waste gas vented via line 17. The desorbed gas is sent to an alkaline washing unit 31 through a pipeline 18, and the desorbed gas is washed by alkaline solution to remove SOx, NOx and a small amount of CO2To make the desorbed gas becomeA gas stream 19 comprising mainly CO.The gas stream is heated to 180-230 ℃ by a secondary heat exchanger, mixed with steam 21 and enters a shift converter 24 together to complete a shift reaction. The resulting gaseous product 22 is decarbonized (CO)2) The final product, hydrogen, is formed.
Detailed Description
The method provided by the invention is implemented as follows:
(1) injecting the preheated hydrocarbon oil raw material into a catalytic cracking reactor, contacting and reacting with a high-temperature regenerated catalyst from a regenerator, wherein the reaction temperature is 460-580 ℃, the reaction time is 0.8-5 seconds, the weight ratio of the catalyst to the hydrocarbon oil raw material is 4-12: 1, the weight ratio of the water vapor to the hydrocarbon oil raw material is 0.02-0.20: 1, and the reaction pressure is 130-450 kPa;
(2) separating the reacted oil gas and the catalyst deposited with carbon, sending the oil gas to a subsequent separation system for further separation into various products, and sending the catalyst deposited with carbon to a first regenerator after steam stripping;
(3) in the first regenerator, the carbon-deposited catalyst is contacted with oxygen-containing gas at 500-660 ℃, 110-450 kPa and the empty bed gas velocity of 0.2-0.8 m/s for incomplete regeneration, and the preferred regeneration conditions are as follows: the temperature is 500-560 ℃, the pressure is 110-350 kPa, the air speed of an empty bed is 0.3-0.6 m/s, the retention time of the regeneration gas is 2-25 seconds, preferably 10-20 seconds, and the generated regeneration flue gas is sent to the subsequent hydrogen production process;
(4) separating CO in the regenerated flue gas from the step (3) by adopting a pressure swing adsorption method, and then obtaining CO with higher purity by utilizing a reduced pressure desorption method or a steam purging desorption method, wherein the purity of the CO can reach more than 70 v%, so that the CO and the steam carry out a shift reaction, and hydrogen is separated from the generated gas product;
(5) and (3) feeding the semi-regenerated catalyst from the step (3) into a second regenerator, contacting with oxygen-containing gas, and regenerating under conventional catalytic cracking regeneration conditions, wherein the regeneration temperature is 650-750 ℃, the regeneration pressure is 130-450 kPa, the regeneration time is 2-5 min, and the regenerated catalyst is returned to the reactor for recycling.
The process provided by the present invention is further illustrated below.
The raw material of hydrocarbon oil suitable for the invention is conventional catalytic cracking raw oil which can be selected from: one or more than one of normal pressure wax oil, normal pressure residual oil, vacuum wax oil, vacuum residual oil, coking wax oil, deasphalted oil, hydrocracking tail oil or other secondary processing distillate oil.
The process provided by the present invention can be used in any type of catalytic cracking unit, for example, a riser catalytic cracking unit, a fluid catalytic cracking unit, a catalytic cracking unit employing a downflow reactor, and the like. The method is particularly suitable for a two-stage regeneration catalytic cracking unit, and no specific arrangement mode of the first regenerator and the second regenerator is required. They may be either vertically or horizontally arranged; the two-over-one and two-under or two-over-one and two-under can be adopted. The flue gas of the first and second series is preferably processed by two independent processes, each of which is independent.
The catalyst suitable for the present invention may be any solid acid catalyst suitable for catalytic cracking process, and its active component may be selected from various zeolites commonly used in catalytic cracking catalyst, such as X-type zeolite, Y-type zeolite, mordenite, β zeolite and their modified products obtained by ion exchange or various physicochemical methods, such as USY, REY, REHY, HZSM-5, RE-ZSM-5, etc.
The oxygen-containing gas can be air or a mixed gas containing 20-30 v% of oxygen, for example, a mixed gas of carbon dioxide and oxygen. If the mixed gas of carbon dioxide and oxygen is used as the regeneration medium in the first regenerator of the present invention, the hot potash method, low temperature methanol washing, compression condensation method, etc. can be used to separate the carbon dioxide first, and the residual gas is the gas with high CO content. The gas is heated to about 300 ℃ and mixed with a certain proportion of water vapor to enter a shift converter for reaction, and the target product, namely hydrogen, can be separated from the reaction product.
The reaction temperature in the residual oil catalytic cracking process is generally 480-530 ℃, and the spent catalyst is not greatly reduced after steam stripping, so the spent catalyst can directly contact with oxygen-containing gas for reaction. From the kinetic reaction rates, the rate of reaction of coke with oxygen at 530 ℃ is only 1/28 at 680 ℃ when temperature alone is considered, indicating that the reaction exotherm will be greatly reduced at lower temperatures, which aids in regeneration temperature control and eliminates "flash".
After the spent catalyst passes through the first regenerator, 0-45% of coke can be removed, the semi-regenerated catalyst is directly conveyed into the second regenerator through a conveying pipe, and the catalyst is regenerated under the conventional catalytic cracking regeneration condition, for example, the regeneration temperature is higher than 700 ℃, so that the complete regeneration of the catalyst is realized.
Cooling the regenerated flue gas from the first regenerator to below 60 ℃ through a heat exchanger for pressure swing adsorption, wherein only CO gas with thecontent of 6-14V% in the flue gas is adsorbed by the pressure swing adsorption method, and the rest gas is directly or further subjected to SO removalXAnd NOXAnd then discharged to the atmosphere. China has CO pressure swing adsorption technology (CN86102838B), and if the technology is applied, the separation cost is low.
The shift reaction in step (4) of the present invention can be carried out in two or more fixed catalyst beds, and the shift catalyst used is selected from: one, two or three of Fe-Cr series medium temperature shift catalyst, Cu-Zn series low temperature shift catalyst and Co-Mo series sulfur-resistant shift catalyst. The sulfur tolerant shift catalyst is widely used in China, the catalyst is operated under the condition of low CO content, and the sulfur content is not limited. The desorption gas is mainly CO, the height of each section of bed layer is properly arranged according to the relationship between temperature rise and conversion rate, and the shift reaction is carried out by adopting a multi-section shift mode, so that the influence on the service life of the shift catalyst caused by overhigh temperature rise of the bed layer is avoided.
Taking RFCCU with annual processing capacity of 140 ten thousand tons as an example, if the CO content in the flue gas is 6.15 percent during regeneration, the CO content is2When the/CO is 1.2, the excess heat energy is maintained with the solvent-to-oil ratio unchanged (3697.9 × 10)4Kcal/h) is stored in the CO stream in the form of chemical energy, and the CO is separated and then converted by the steam shift technology: the hydrogen can be produced at equal molar ratio of about 9367.5 tons/year, and this hydrogen flow can ensure the hydrogen supply of gasoline hydrofining unit with 180 ten thousand tons of annual processing amount (0.5% hydrogen consumption) or the hydrogenfor the process of hydrocracking unit with 30 ten thousand tons of annual processing amount (3% hydrogen consumption).
The following examples further illustrate the process of the present invention but are not intended to limit the invention thereto.
Example 1
This example illustrates: the catalyst to be regenerated is incompletely regenerated under the condition of the step (3) of the invention, so that the concentration of CO in the regenerated flue gas can be greatly improved.
At phi Inner part22, GVR-1 industrial spent agent (made from Qilu petrochemical plant)Company catalyst plant industries) was tested, and the carbon content of the agent was 1.2 wt%. The test procedure is as follows: 80 g of the spent agent is put into a small-sized fixed fluidized bed reactor, and the spent agent is incompletely regenerated under the conditions of 530 ℃, 0.12MPa, 0.2m/s of bed space velocity and 2.8 seconds of regeneration gas residence time; the regeneration flue gas was collected and analyzed for composition. The test results are shown in Table 2.
Comparative example 1
The GVR-1 industrial regenerant was regenerated on a small fixed fluidized bed unit under conventional catalytic cracking regeneration conditions using the same catalyst as in example 1. The test procedure is as follows: 80 g of the spent agent is put into a small-sized fixed fluidized bed reactor, and the spent agent is incompletely regenerated under the conditions of 700 ℃, 0.12Mpa, 0.2m/s of bed space velocity and 2.8 seconds of regeneration gas residence time; the regeneration flue gas was collected and analyzed for composition. The test results are shown in Table 2.
As can be seen from Table 2, the CO concentration of example 1 was 5.15 v%, while that of comparative example 1 was3.56 v%. Therefore, the regeneration condition in the step (3) of the invention can greatly improve the concentration of CO in the regenerated flue gas, and a large amount of raw material gas is provided for the subsequent hydrogen production process.
In addition, specific mention is made of: due to the limitation of the test conditions, the residence time of the regeneration gas in the reactor is relatively short in the example 1 and the comparative example 1, and the concentration of CO in the regeneration flue gas is relatively low. When the method provided by the invention is applied to an industrial device, the retention time of the regenerated flue gas is about 10 seconds, and the CO content can reach about 14 v%.
TABLE 2
| Item | Example 1 | Comparative example 1 |
| The main operating conditions are as follows: | ||
| regeneration temperature of | 530 | 700 |
| Regeneration pressure, Mpa | 0.12 | 0.12 |
| Space velocity in bed, m/s | 0.2 | 0.2 |
| Residence time of regeneration gas, s | 2.8 | 2.8 |
| Composition of regeneration flue gas, v% | ||
| CO2 | 13.82 | 17.08 |
| O2 | 1.83 | 0.97 |
| N2 | 79.2 | 78.39 |
| CO | 5.15 | 3.56 |
Example 2
This example illustrates: the catalyst to be regenerated is incompletely regenerated under the condition of the step (3) of the invention, so that the concentration of CO in the regenerated flue gas can be greatly improved.
At phiInner partOn a 50 small fixed fluidized bed unit, a GVR-1 industrial spent catalyst (commercially produced by catalyst works of the qilu petrochemical company) was used for the test, the carbon content of the agent being 1.2 wt%. The test procedure is as follows: 1500 g of the spent agent is put into a small-sized fixed fluidized bed reactor, and the spent agent is incompletely regenerated under the conditions of 660 ℃, 0.12Mpa, 0.3m/s of bed space velocity and 5 seconds of regeneration gas residence time; the regeneration flue gas was collected and analyzed for composition. The test results are shown in Table 3.
Comparative example 2
At phiInner part50 on a small fixed fluidized bed unit, the GVR-1 industrial spent catalyst was regenerated under conventional catalytic cracking regeneration conditions using the same catalyst as in example 1. The test procedure is as follows: 1500 g of the spent agent is put into a small-sized fixed fluidized bed reactor, and the spent agent is incompletely regenerated under the conditions of 660 ℃, 0.12Mpa, 0.3m/s of bed space velocity and 2.8 seconds of regeneration gas residence time; the regeneration flue gas was collected and analyzed for composition. The test results are shown in Table 3.
TABLE 3
| Item | Example 2 | Comparative example 2 |
| The main operating conditions are as follows: | ||
| regeneration temperature of | 660 | 660 |
| Regeneration pressure, Mpa | 0.12 | 0.12 |
| Space velocity in bed, m/s | 0.3 | 0.3 |
| Residence time of regeneration gas, | 5 | 2.8 |
| Composition of regeneration flue gas, v% | ||
| CO2 | 16.01 | 16.87 |
| O2 | 1.60 | 2.78 |
| N2 | 77.22 | 77.51 |
| CO | 5.17 | 2.84 |
Example 3
This example illustrates: the method provided by the invention is implemented on an industrial device.
The tests were carried out on a catalytic cracking unit having a throughput of 80 ten thousand t/a. The main physicochemical properties of the GVR-1 catalyst used in the test are shown in Table 4, and theproperties of the raw oil, which is Daqing atmospheric residue, are shown in Table 5. As shown in figure 1, atomized steam 3 and raw material 2 are injected from the bottom of a riser reactor 27, contact with a regenerant from a pipeline 5 and react, an oil agent mixture enters a separator 28 through the riser reactor, reaction oil gas is separated from a carbon-deposited catalyst, and the oil gas is sent to a subsequent fractionation system through a pipeline 4 and further separated into various products. The carbon-deposited catalyst is stripped by steam 1 and then enters the first regenerator 29 through the delivery pipe 6. Compressed air is injected from the bottom of the first regenerator via line 7, contacts the coked catalyst and partially regenerates it under the following conditions: 530 ℃, 0.12Mpa, 0.4m/s of bed space velocity and 10 seconds of regeneration gas residence time. The regenerated flue gas containing 12 v% of CO is sent to the subsequent hydrogen production process through a pipeline 8, and the semi-regenerant enters a second regenerator 30 through a pipeline 10. Compressed air is injected from the bottom of the second regenerator via line 9, is in contact with the semi-regenerant and fully regenerates it under the following conditions: 720 ℃, 0.12Mpa, 0.8m/s of bed space velocity and 9 seconds of regeneration gas retention time. The regenerated flue gas is sent to a subsequent heat recovery system through a pipeline 11, and is discharged into the atmosphere after being treated. The regenerant is sent via line 5 to the riser reactor for recycle.
The regeneration flue gas from the first regenerator contains CO and CO2、N2And a small amount of O2SOx, NOx, etc., at a temperature of about 550 ℃. The regenerated flue gas firstly enters a primary heat exchanger 14 to indirectly exchange heat with low-temperature steam injected from a pipeline 12, and the generated superheated steam is sent out through a pipeline 13. The regenerated flue gas with the temperature reduced to about 300 ℃ enters the secondary heat exchanger 15 through a pipeline 26, and the heat carried by the regenerated flue gas is used for heating the gas stream 19 mainly containing CO. After passing through the secondary heat exchanger, the temperature of the regeneration gas is reduced to below 100 ℃, and then the temperature of the regeneration flue gas is reduced to below 60 ℃ through the tertiary water-cooling heat exchanger 23, and then the regeneration flue gas is sent to the pressure swing adsorption unit 16 through a pipeline 25. The pressure swing adsorption is operated intermittently in double or multiple columns and the resulting waste gas is vented via line 17. The desorbed gas is sent to the alkaline washing process via line 18, and the desorbed gas is washed with alkaline solution to remove SOx, NOx and a small amount of CO2The desorption gas is brought to a gas stream 19 comprising mainly CO (above 70 v%). The gas flow is heated to about 200 ℃ by a secondary heat exchanger, mixed with steam 21 and enters a shift converterThe shift reaction is completed 24. The resulting gaseous product 22 is decarbonized (CO)2) The final product, hydrogen, is formed. The hydrogen flow rate can reach 0.345 ton/h or 2480 ton/year.
TABLE 4
| Commodity brand | GVR-1 |
| Chemical composition, weight% | |
| Alumina oxide | 34.4 |
| Sodium oxide | 0.39 |
| Iron oxide | 0.46 |
| Apparent density in kg/m3 | 780 |
| Pore volume, ml/g | 0.34 |
| Specific surface area, rice2Per gram | 249 |
| Abrasion index in% by weight-1 | 1.2 |
| Sieving to obtain fine powder | |
| 0 to 40 μm | 17.4 |
| 40 to 80 μm | 36.6 |
| Greater than 80 microns | 46.0 |
| Micro-reverse activity MA | 70 |
TABLE 5
| Raw oil name | Daqing atmospheric residue |
| Density of(20℃)g/cm3 | 0.8951 |
| Carbon residue, by weight% | 4.6 |
| Freezing point, deg.C | 37 |
| Viscosity (80 ℃ C.), mm2/s | 54.9 |
| The element composition is weight percent | |
| C | 86.68 |
| H | 12.94 |
| S | 0.18 |
| N | 0.12 |
| Group composition, weight% | |
| Saturated hydrocarbons | 49.5 |
| Aromatic hydrocarbons | 30.3 |
| Glue | 20 |
| Asphaltenes | 0.2 |
Claims (10)
1. A method for producing hydrogen by using catalytic cracking regenerated flue gas comprises thefollowing steps:
(1) contacting a hydrocarbon oil raw material with a catalytic cracking catalyst in a reactor, and reacting under catalytic cracking reaction conditions;
(2) separating the reaction oil gas and the catalyst deposited carbon after the reaction, sending the oil gas into a subsequent separation system, and sending the catalyst deposited carbon to a first regenerator after steam stripping;
(3) in the first regenerator, the carbon-deposited catalyst contacts with oxygen-containing gas at the temperature of 500-660 ℃ and the air speed of an empty bed of 0.2-0.8 m/s for 2-25 seconds, and then the regenerated flue gas is sent to the subsequent hydrogen production process;
(4) separating CO from the regeneration flue gas from step (3), subjecting the CO to a shift reaction with steam, and separating hydrogen from the resulting gas product;
(5) the semi-regenerated catalyst from the step (3) enters a second regenerator, contacts with oxygen-containing gas and is regenerated under the conventional catalytic cracking regeneration condition, and the regenerated catalyst is returned to the reactor for recycling.
2. The process according to claim 1, characterized in that the reaction conditions of the hydrocarbon oil feedstock in said step (1) are: the reaction temperature is 460-580 ℃, the reaction time is 0.8-5 seconds, the weight ratio of the catalyst to the hydrocarbon oil raw material is 4-12: 1, the weight ratio of the water vapor to the hydrocarbon oil raw material is 0.02-0.20: 1, and the reaction pressure is 130-450 kPa.
3. The method according to claim 1, wherein the catalyst deposited on carbon in the step (3) is subjected to incomplete regeneration by contacting with an oxygen-containing gas at 500 to 560 ℃ at an air bed gas velocity of 0.3 to 0.6m/s and a bed pressure of 110 to 450kPa, and the residence time of the regeneration gas is 10 to 20 seconds.
4. The process according to claim 1, characterized in that said hydrocarbon oil feedstock is selected from the group consisting of: one or more than one of normal pressure wax oil, normal pressure residual oil, vacuum wax oil, vacuum residual oil, coking wax oil, deasphalted oil, hydrocracking tail oil or other secondary processing distillate oil.
5. The process of claim 1, wherein the active component of the catalyst is selected from the group consisting of X-type zeolite, Y-type zeolite, mordenite, β zeolite, and modified products thereof obtained by ion-exchange or by various physical and chemical methods.
6. The process according to claim 1, wherein the process is applied to a two-stage regenerative catalytic cracking unit.
7. The process of claim 6 wherein in said two stage regenerative catalytic cracking unit the first regenerator and the second regenerator are either vertically or horizontally disposed with respect to each other.
8. A method according to claim 6 or 7, characterized in that in said two-stage regenerative catalytic cracking unit, the flue gases of the first and second regenerator are treated separately in two passes.
9. The method according to claim 1, wherein the oxygen-containing gas is air or a mixed gas of carbon dioxide and oxygen having an oxygen content of 20 to 30% by volume.
10. The process according to claim 1, characterized in that the shift reaction in step (4) is carried out in two or more fixed catalyst beds and the shift catalyst used is selected from the group consisting of: one, two or three of Fe-Cr series medium temperature shift catalyst, Cu-Zn series low temperature shift catalyst and Co-Mo series sulfur-resistant shift catalyst.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453181C (en) * | 2004-03-17 | 2009-01-21 | 本田技研工业株式会社 | Control method of catalyst activity |
| CN101875858A (en) * | 2009-04-30 | 2010-11-03 | 中国石油化工股份有限公司 | Method for treating solid particles of deposited carbon-containing compound |
| CN101210197B (en) * | 2006-12-29 | 2011-08-10 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN102260529A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Combined method for processing inferior heavy oil |
| CN101457153B (en) * | 2007-12-14 | 2012-07-18 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN101463269B (en) * | 2007-12-17 | 2012-09-12 | 中国石油化工股份有限公司 | Hydrocarbon oil transforming method |
| CN102698817A (en) * | 2012-05-28 | 2012-10-03 | 清华大学 | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method |
| TWI498162B (en) * | 2010-03-25 | 2015-09-01 | China Petrochemical Technology Co Ltd | A catalyst regeneration method for improving catalyst selectivity |
| CN107126976A (en) * | 2017-04-25 | 2017-09-05 | 广东新华粤树脂科技有限公司 | Crack the hydrogenation catalyst steam blowing hydrogen heat air lift combining and regenerating method of carbon nine |
| CN109382116A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN116004274A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Method for producing hydrogen and low-carbon olefin by catalysis |
-
2001
- 2001-07-31 CN CNB011237708A patent/CN1169707C/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453181C (en) * | 2004-03-17 | 2009-01-21 | 本田技研工业株式会社 | Control method of catalyst activity |
| CN101210197B (en) * | 2006-12-29 | 2011-08-10 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN101457153B (en) * | 2007-12-14 | 2012-07-18 | 中国石油化工股份有限公司 | Hydrocarbon oil conversion method |
| CN101463269B (en) * | 2007-12-17 | 2012-09-12 | 中国石油化工股份有限公司 | Hydrocarbon oil transforming method |
| CN101875858A (en) * | 2009-04-30 | 2010-11-03 | 中国石油化工股份有限公司 | Method for treating solid particles of deposited carbon-containing compound |
| CN101875858B (en) * | 2009-04-30 | 2014-03-26 | 中国石油化工股份有限公司 | Method for treating solid particles of deposited carbon-containing compound |
| TWI498162B (en) * | 2010-03-25 | 2015-09-01 | China Petrochemical Technology Co Ltd | A catalyst regeneration method for improving catalyst selectivity |
| CN102260529B (en) * | 2010-05-27 | 2014-07-30 | 中国石油化工股份有限公司 | Combined method for processing inferior heavy oil |
| CN102260529A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Combined method for processing inferior heavy oil |
| CN102698817B (en) * | 2012-05-28 | 2014-06-18 | 清华大学 | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method |
| CN102698817A (en) * | 2012-05-28 | 2012-10-03 | 清华大学 | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method |
| CN107126976A (en) * | 2017-04-25 | 2017-09-05 | 广东新华粤树脂科技有限公司 | Crack the hydrogenation catalyst steam blowing hydrogen heat air lift combining and regenerating method of carbon nine |
| CN107126976B (en) * | 2017-04-25 | 2021-11-16 | 广东新华粤树脂科技有限公司 | Steam purging-hydrogen hot gas stripping combined regeneration method for cracking carbon nine hydrogenation catalyst |
| CN109382116A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN109382116B (en) * | 2017-08-02 | 2021-08-10 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN116004274A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Method for producing hydrogen and low-carbon olefin by catalysis |
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