CN113717740A - Coupling method for cracking, coking and coke gasification - Google Patents
Coupling method for cracking, coking and coke gasification Download PDFInfo
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- CN113717740A CN113717740A CN202111032736.3A CN202111032736A CN113717740A CN 113717740 A CN113717740 A CN 113717740A CN 202111032736 A CN202111032736 A CN 202111032736A CN 113717740 A CN113717740 A CN 113717740A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
Abstract
The invention relates to a processing method of hydrocarbon raw materials, in particular to a coupling method of cracking, coking and coke gasification, which comprises the following steps: taking coke particles as coke forming particles to circulate in a cracking reactor, a fluid coking reactor and a coke gasification reactor which are communicated in sequence; coke generated by the cracking reaction and the coking reaction is loaded on coke particles, then the coke particles enter a coke gasification reactor to convert the loaded coke into gasification gas, and the coke particles after the gasification reaction continuously serve as a heat carrier and a carbon carrier to enter the cracking reactor. The method can solve the contradiction that the selectivity of the catalyst or the carrier for generating the olefin and the coke carrying capacity are mutually restricted in the existing olefin preparation process by hydrocarbon cracking; the method couples the technological processes of cracking, coking and coke gasification in the same device, is highly integrated, and can greatly reduce the production cost; and the source of raw materials for preparing the low-carbon olefin is widened, and the economic benefit is further improved.
Description
Technical Field
The invention relates to the technical field of hydrocarbon raw material processing, in particular to a coupling method for cracking, coking and coke gasification.
Background
At present, the process technology for preparing low-carbon olefin adopted in the chemical industry has the following defects:
(1) the technical principle and route of hydrocarbon cracking are generally adopted, and the requirement on the property of raw oil is high.
(2) Wherein, the catalyst or carrier used in the olefin preparation process by hydrocarbon cracking is mainly made of aluminosilicate material, and the specific surface area and acidity thereof are in positive correlation; when the catalyst or the carrier has a larger specific surface area, the catalyst or the carrier has stronger coke carrying capacity but stronger acidity, and the stronger acidity promotes the secondary reaction of the low-carbon olefin in the cracking process of the hydrocarbon more and reduces the selectivity of the low-carbon olefin, so the contradiction that the selectivity of the low-carbon olefin and the coke carrying capacity are mutually restricted exists. In addition, the catalyst or carrier made of aluminosilicate material has fast hydrothermal ageing under the harsh operation condition of hydrocarbon cracking process, needs great agent consumption to ensure the long-period stable operation of the apparatus and has high cost.
Meanwhile, the coking process in the oil refining industry is increasingly lack of competitiveness due to low product value and poor economy.
Disclosure of Invention
Objects of the invention include, for example, providing a coupled process for cracking, coking and gasification of coke, which is intended to ameliorate at least one of the problems mentioned in the background.
Embodiments of the invention may be implemented as follows:
the invention provides a coupling method for cracking, coking and coke gasification, which comprises the following steps:
taking coke particles as coke forming particles to circulate in a cracking reactor, a fluid coking reactor and a coke gasification reactor which are communicated in sequence; in the coke forming particle circulation process, coke generated by cracking reaction and coking reaction is loaded on the coke particles, then the coke particles enter the coke gasification reactor to convert the loaded coke into gasification gas, and the coke particles after gasification reaction continuously serve as a heat carrier and a carbon carrier to enter the cracking reactor.
In an alternative embodiment, the pyrolysis feedstock comprises at least one of crude oil, naphtha, straight-run diesel, wax oil, atmospheric residue, vacuum residue, and liquid products of direct and indirect liquefaction of coal.
In an alternative embodiment, the coker feedstock comprises at least one of crude oil, atmospheric resid, vacuum resid, catalytically cracked slurry oil, and pitch.
In an alternative embodiment, the coke gasification reaction is carried out by using a mixture of air, air and water vapor, oxygen and water vapor, or air, oxygen and water vapor.
In an alternative embodiment, the main operating conditions of the cleavage reactor are: the reaction temperature is 580-780 ℃, the reaction pressure is 0.15-0.35 MPa, the reaction time is 0.5-3.0 s, the mass ratio of the coke particles to the cracking raw material after entering the cracking reactor is 12-50: 1, the mass ratio of the atomized water vapor to the cracking raw material is 0.3-1.0: 1, and the average linear velocity of the gas is 8.0-15.0 m/s.
In an alternative embodiment, the main operating conditions of the fluid coking reactor are: the reaction temperature is 480-560 ℃, the reaction pressure is 0.10-0.30 MPa, the mass ratio of the coke particles to the coking raw material after entering the fluid coking reactor is 4-12: 1, and the average linear speed of gas is 0.5-1.5 m/s.
In an alternative embodiment, the primary operating conditions for the char gasification reactor are: the reaction temperature is 700-900 ℃, and the reaction pressure isThe force is 0.20-0.40 MPa, the reaction time is 5-20 min, the average linear velocity of the gas is 0.5-1.5 m/s, and the oxygen-carbon ratio is 0.04-0.10 m3The steam-carbon ratio is 0-0.05 kg/kg.
In an optional embodiment, in the initial start-up period, the initial coke-forming particles added into the device are catalytic cracking catalyst particles, the particle size of the catalytic cracking catalyst particles is 10-200 microns, and the particle size of the corresponding coke particles after stable operation is 20-2000 microns;
in an optional embodiment, at the initial stage of start-up, the initial coking particles added into the device are semi-coke particles or pulverized coal, the particle size of the initial coking particles is 10-3000 micrometers, and the particle size of the corresponding coking particles after stable operation is 20-5000 micrometers.
In an optional embodiment, the mass ratio of the cracking raw material to the coking raw material is 1: 2-6.
The invention has the following beneficial effects:
(1) coke particles are used as a heat carrier and a carbon carrier for the cracking reaction, and the secondary reaction of an olefin product is effectively inhibited because the coke has no acidity; meanwhile, as the coke is a porous substance continuously generated in the cracking reaction process, the adsorption capacity is strong, the problem of hydrothermal aging does not exist, and the coke generated in the hydrocarbon cracking reaction can be continuously taken away from the reactor in time, the contradiction that the selectivity of the catalyst or carrier for generating the olefin and the capacity of carrying the coke are mutually restricted in the existing process technology for preparing the olefin by cracking the hydrocarbon can be solved, and the defect of high agent consumption caused by quick hydrothermal aging of the catalyst or carrier can be overcome.
(2) The technological processes of hydrocarbon raw material cracking, fluid coking and coke gasification are coupled on the same set of device, high integration and energy complementation are achieved, and therefore construction investment, energy consumption and operation cost are greatly reduced.
(3) If the coal gas obtained by gasification is converted into synthesis gas, the synthesis gas can be further converted into low-carbon olefin, so that the economic benefit of the coking process is greatly improved, the requirements on the properties of the technical raw materials for preparing the low-carbon olefin are effectively reduced, and the raw material sources are widened.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a block diagram of a coupling device according to an embodiment of the present invention.
Icon: 100-a coupling device; 110-a cleavage reactor; 111-feedstock nozzles; 120-a fluid coking reactor; 120 a-a dense phase section of a coking reactor; 124-coking raw material inlet; 140-a char gasification reactor; 140 a-a second gasifying agent distributor; 142-fast bed gasification stage; 143-dense bed gasification section; 190-first gasifying agent distributor.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that if the terms "upper", "lower", "inside", "outside", etc. indicate an orientation or a positional relationship based on that shown in the drawings or that the product of the present invention is used as it is, this is only for convenience of description and simplification of the description, and it does not indicate or imply that the device or the element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
Furthermore, the appearances of the terms "first," "second," and the like, if any, are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
It should be noted that the features of the embodiments of the present invention may be combined with each other without conflict.
The coupling device 100 for implementing the coupling method of cracking, coking and coke gasification provided by the present application comprises: a cracking reactor 110, a fluid coking reactor 120, and a coke gasification reactor 140;
the cracking reactor 110 and the fluidized coking reactor 120 are coaxially arranged, the cracking reactor 110 is a riser cracking reactor, the fluidized coking reactor 120 is a dense-phase fluidized bed reactor, and the coke gasification reactor 140 is a fast fluidized bed reactor.
The upper part of the cracking reactor 110 is connected with the fluid coking reactor 120 and extends into the fluid coking reactor 120, and the lower part of the wall of the fluid coking reactor 120 and the outer wall of the upper part of the cracking reactor 110 enclose a dense-phase section 120a of the coking reactor;
the coke gasification reactor 140 comprises a fast bed gasification section 142 and a dense bed gasification section 143 which are connected from bottom to top, and the upper part of the fast bed gasification section 142 extends into the dense bed gasification section 143;
the coking reactor dense phase section 120a communicates with the bottom of the fast bed gasification section 142 and the dense bed gasification section 143 communicates with the bottom of the cracking reactor 110.
Specifically, the lower part of the cracking reactor 110 is provided with a raw material nozzle 111, and the lower part of the fluidized coking reactor 120 corresponding to the dense-phase section 120a of the coking reactor is provided with a coking raw material inlet 124; the bottom of the fast bed gasification stage 142 is provided with a first gasification agent distributor 190. A second gasifying agent distributor 140a is arranged in the dense-bed gasifying section 143.
To be noted: the char gasification reactor 140 may actually include an auxiliary combustion chamber (not shown). During the start-up phase of the device, the gasifying agent entering the coke gasification reactor 140 actually passes through the auxiliary combustion chamber and contacts with the supplemented heavy fuel oil to combust to form oxygen-enriched high-temperature flue gas. And entering a stable operation stage, and closing the auxiliary combustion chamber.
For the sake of convenience of distinction, hereinafter, the char particles after participating in the reaction of the char gasification reactor 140 are referred to as high-temperature char particles, the char particles after participating in the reaction of the pyrolysis reactor 110 are referred to as pyrolysis char particles, and the char particles after participating in the reaction of the fluid coking reactor 120 are referred to as coking char particles.
The cracking of the hydrocarbon feedstock, the fluid coking, and the gasification of the char are performed in the same apparatus, and the three reactions are performed in the cracking reactor 110, the fluid coking reactor 120, and the char gasification reactor 140, respectively. The coke gasification is partial gasification, i.e. the coke particles entering the coke gasification reactor 140 are not fully gasified to produce CO or H2. High-temperature coke particles generated by coke gasification are used as a heat carrier and a carbon carrier and enter the bottom of the cracking reactor 110 from the dense-phase bed gasification section 143 through a pipeline, are contacted and mixed with a cracking reaction hydrocarbon raw material entering the lower part of the cracking reactor 110, and move upwards along the cracking reactor 110 under the lifting action of oil gas and participate in cracking reaction. The pyrolysis reaction oil gas and the pyrolysis coke particles are subjected to gas-solid separation at the top outlet of the pyrolysis reactor through a fast separation device, the pyrolysis coke particles enter a dense-phase section 120a of the coking reactor through gravity settling, are in countercurrent contact and mixed with the coking raw material entering the fluidized coking reactor 120 and participate in coking reaction, the pyrolysis coke particles play a role of a heat carrier and a carbon carrier for fluidized coking, and the pyrolysis reaction oil gas enters a gas collection chamber for fast cooling after a small amount of pyrolysis coke particles carried by the pyrolysis reaction oil gas are removed through a cyclone separator. The coking reaction oil gas also enters a gas collection chamber after a small amount of coking coke particles carried by the coking reaction oil gas are removed by a cyclone separator. The coking coke particles generated by the coking reaction enter the bottom of the fast bed gasification section 142 from the dense phase section 120a of the coking reactor through a pipeline, and contact with the gasification agent entering the fast bed gasification section 142 from the first gasification agent distributor 190 under the lifting action of the gasification agentAnd the gas flows upwards in parallel with the oxidant and is subjected to gasification reaction, and coke generated by cracking reaction and coking reaction is converted into gasification gas. The high-temperature coke particles gasified by the fast bed and the gasified gas are subjected to gas-solid separation at the outlet of the fast bed gasification section 142, and the coke particles enter the dense bed gasification section 143 through gravity settling and continue to contact with the gasification agent introduced from the second gasification agent distributor 140a for gasification reaction. Feeding mixed reaction oil gas consisting of cracking reaction oil gas and coking reaction oil gas into a common fractionating tower for fractionating; the gasified gas enters a subsequent purification, energy recovery and conversion device, and the high-temperature coke particles enter the bottom of the cracking reactor 110 through a pipeline for recycling.
In other embodiments of the present application, the oil gas and the cracked coke particles generated by the cracking reaction may not be subjected to gas-solid separation, and they may be contacted and mixed with the coking raw material together, and the reacted mixed reaction oil gas and the coked coke particles are subjected to gas-solid separation.
The embodiment provides a coupling method for cracking, coking and coke gasification, which comprises the following steps:
the coke particles are used as coke forming particles to circulate in a cracking reactor 110, a fluid coking reactor 120 and a coke gasification reactor 140 which are communicated in sequence; in the coke particle circulation process, coke generated by the cracking reaction and the coking reaction is loaded on the coke particles, and then the coke particles enter the coke gasification reactor 140; the coke particles entering the coke gasification reactor 140 are partially gasified and converted into gasification gas, and then continuously recycled to the cracking reactor 110.
The coupling method for cracking, coking and coke gasification provided by the embodiment of the invention has the following technical effects:
(1) coke particles are used as a heat carrier and a carbon carrier for the cracking reaction, and the secondary reaction of an olefin product is effectively inhibited because the coke has no acidity; meanwhile, as the coke is a porous substance continuously generated in the cracking reaction process, the adsorption capacity is strong, the problem of hydrothermal aging does not exist, and the coke generated in the hydrocarbon cracking reaction can be continuously taken away from the reactor in time, the contradiction that the selectivity of the catalyst or carrier for generating the olefin and the capacity of carrying the coke are mutually restricted in the existing process technology for preparing the olefin by cracking the hydrocarbon can be solved, and the defect of high agent consumption caused by quick hydrothermal aging of the catalyst or carrier can be overcome.
(2) The hydrocarbon raw material cracking, fluid coking and coke gasification operation are coupled on the same set of device, high integration and energy complementation are realized, so that the construction investment, energy consumption and operation cost are greatly reduced.
(3) If the coal gas obtained by gasification is converted into synthesis gas, the synthesis gas can be further converted into low-carbon olefin, so that the economic benefit of the coking process is greatly improved, the requirements on the properties of the technical raw materials for preparing the low-carbon olefin are effectively reduced, and the raw material sources are widened.
Specifically, the cracking raw material comprises at least one of crude oil, naphtha, straight-run diesel oil, wax oil, atmospheric residue, vacuum residue and liquid products directly and indirectly liquefied by coal.
Further, the coking feedstock includes at least one of crude oil, atmospheric resid, vacuum resid, catalytically cracked slurry oil, and pitch.
Preferably, pulverized coal or semi-coke particles can be used as initial coking particles of high-temperature coke particles, cracking coke particles and coking coke particles at the initial start-up stage, the particle size of the initial coking particles is 10-3000 micrometers, and the particle size of the corresponding coke particles after stable operation is 20-5000 micrometers.
Further preferably, when pulverized coal or semi-coke particles are used as the starting char-forming particles, the amount of char that undergoes gasification reactions within the char gasification reactor 140 is equal to (herein "equal to" is understood to be about equal to) the loading of the char particles; i.e., the sum of the coke formation per unit time for the cracking reaction and the coking reaction is approximately equal to the amount of coke undergoing the gasification reaction in the coke gasification reactor 140.
In the above operation process, large particles exceeding the particle size range appear in the coke particles as the reaction proceeds, which adversely affects the fluidization of the coke particles, and in order to maintain the particle size of the coke particles within the allowable range, the coke particles having a particle size of > 5000 μm can be separated and discharged outside by a dedicated device provided in the coke gasification reactor.
Preferably, catalytic cracking catalyst particles can be used as initial coking particles of high-temperature coke particles, cracking coke particles and coking coke particles at the initial startup, the particle size of the initial coking particles is 10-200 microns, and the particle size of the corresponding coke particles after stable operation is 20-2000 microns.
Further preferably, when the catalytic cracking catalyst particles are used as the initial coke-forming particles, the amount of the coke undergoing gasification reaction in the coke gasification reactor 140 at the initial startup is less than the loading amount of the coke particles, i.e., the sum of the coke formation amounts of the cracking reaction and the coking reaction per unit time is greater than the amount of the coke undergoing gasification reaction in the coke gasification reactor 140; during the stationary phase, the amount of char undergoing gasification reactions within the char gasification reactor 140 is equal to (herein "equal to" is understood to be about equal to) the amount of coke shot, i.e., the sum of the coke yields of cracking reactions and coking reactions per unit time is about equal to the amount of char undergoing gasification reactions within the char gasification reactor 140.
It is recommended to use the equilibrium catalyst discharged from the catalytic cracking unit; in the initial stage of the start-up of the device, in order to deposit a certain amount of coke on the catalyst particles and form coke particles under the condition of ensuring the heat balance of the device, a certain amount of heavy fuel oil needs to be injected into the coke gasification reactor for afterburning, and the afterburning is stopped until the device enters a stable operation period.
It should be noted that the starting coke-forming particles mentioned in the above description are different from the coke-forming particles, and the starting coke-forming particles refer to the coke-forming particles added to the apparatus at the time of the apparatus being started. And the coke particles are coke forming particles which circulate in the device when the device is in stable operation. In the above operation process, after initial coke-forming particles and coke-forming particles are circulated for a long time, small particles are generated due to chipping and abrasion, and the small particles are carried out of the device by mixed reaction oil gas or gasification gas. Because the coke particles are used as coke forming particles, coke generated by cracking and coking reaction is loaded on the initial coke forming particles and the generated coke particles to continuously form new coke particles meeting the requirement of fluidized particle size, and the new coke particles are continuously circulated as the coke forming particles after the device stably operates, the initial coke forming particles and the coke forming particles do not need to be supplemented.
Further, the gasifying agent participating in the coke gasification reaction is air, a mixed gas of air and water vapor, oxygen, a mixed gas of oxygen and water vapor or a mixed gas of air, oxygen and water vapor.
Specifically, the main operating conditions of the cleavage reactor 110 are: the reaction temperature is 580-780 ℃, preferably 600-750 ℃, and most preferably 620-700 ℃; the reaction pressure is 0.15-0.35 MPa (absolute atmospheric pressure), the reaction time is 0.5-3.0 s, preferably 0.6-2.5 s, more preferably 0.8-2.0 s, and the mass ratio of the coke particles to the cracking raw material after entering the cracking reactor 110 is 12-50: 1, preferably 15-35: 1, preferably 20-30: 1, the mass ratio of the atomized water vapor to the cracking raw material is 0.3-1.0: 1, preferably 0.4-0.9, preferably 0.5-0.8, and the average linear velocity of the gas is 8.0-15.0 m/s.
Preferably, the main operating conditions of the fluid coking reactor 120 are: the reaction temperature is 480-560 ℃, preferably 490-550 ℃, most preferably 500-540 ℃, the reaction pressure is 0.10-0.30 MPa (absolute atmospheric pressure), and the mass ratio of the coke particles to the coking raw material after entering the fluid coking reactor 120 is 4-12: 1, preferably 5-10: 1, preferably 6 to 8:1, and an average linear velocity of gas of 0.5 to 1.5 m/s.
Preferably, the primary operating conditions of the char gasification reactor 140 are: the reaction temperature is 700-900 ℃, preferably 730-870 ℃, most preferably 750-850 ℃, the reaction pressure is 0.20-0.40 MPa, the reaction time is 5-20 min, preferably 6-15 min, most preferably 8-10 min, the average linear velocity of gas is 0.5-1.5 m/s, the oxygen-carbon ratio is 0.04-0.10 m3/kg, and the steam-carbon ratio is 0-0.05 kg/kg. The specific amount of gasification gas entering the fast bed section and the dense phase section of the coke gasification reactor 140 is determined by process calculations as required by the operating conditions and can be determined by one skilled in the art.
Further, the mass ratio of the cracking raw material to the coking raw material is 1: 2-6.
Comparative example and example
Comparative example
Comparative examples 1-3 tests were conducted on riser hydrocarbon cracking pilot plant. The riser design throughput of the pilot plant was 60kg/d (kg/day).
In comparative examples 1 to 3, the heavy oil raw material processed by the riser was Arabian light wax oil, and a self-developed R2D cracking catalyst subjected to hydrothermal aging at 800 ℃ for 4 hours was used for single-pass operation. The carbon content of the regenerated catalyst was 0.02%. The cracking feedstock properties are shown in Table 1, and the main operating conditions and product distribution of comparative examples 1-3 are shown in Table 3.
Examples
Examples 1-3 experiments were conducted on the hydrocarbon-coupled processing apparatus of the present invention as shown in fig. 1, using pulverized coal particles as the initial char-forming core, wherein the hydrocarbon feedstock processed by the cracking reactor was the same arabic light wax as in comparative examples 1-3, and high-temperature char particles were used as the heat carrier and carbon carrier; the hydrocarbon raw material processed by the fluid coking reactor 120 is Arabic light vacuum residue, and cracking coke particles are used as a heat carrier and a carbon carrier. The coke gasification reactor uses oxygen and water vapor as raw materials in a mass ratio of 1:4 between the cracking reactor and the fluid coking reactor 120. The main operating conditions and product distribution of the cleavage reactors of examples 1 to 3 are shown in Table 4. The properties of the fluid coking raw materials of examples 1 to 3 are shown in Table 2, the main operating conditions and the product distribution of the fluid coking reactors 120 of examples 1 to 3 are shown in Table 5, and the main operating conditions and the gasified gas composition of the coke gasification reactors of examples 1 to 3 are shown in Table 6.
TABLE 1 cracking feedstock Properties (comparative example, examples)
| Cracking feedstock | Arab light wax oil |
| Density (20 ℃), kg/m3 | 914.1 |
| Residual carbon content% | 0.12 |
| Group composition of% | |
| Saturated hydrocarbons | 65.8 |
| Aromatic hydrocarbons | 31.6 |
| Colloid plus asphaltene | 2.6 |
| Hydrogen content% | 11.69 |
| Sulfur content% | 2.61 |
| Nitrogen content% | 0.08 |
| Characteristic factor | 11.85 |
TABLE 2 fluid coking feedstock Properties (examples)
| Fluidized coking feedstock | Arab light vacuum residuum |
| Density (20 ℃), kg/m3 | 1003.1 |
| Residual carbon content% | 18.2 |
| Group composition of% | |
| Saturated hydrocarbons | 21.0 |
| Aromatic hydrocarbons | 54.7 |
| Colloid plus asphaltene | 13.2 |
| Hydrogen content% | 10.30 |
| Sulfur content% | 3.93 |
| Nitrogen content% | 0.22 |
| Characteristic factor | 11.50 |
| Ni，μg/g | 16.4 |
| V，μg/g | 62.2 |
TABLE 3 Main operating conditions and product distribution for the comparative example cracking reactor
TABLE 4 example Main operating conditions and product distribution of the cleavage reactor
TABLE 5 examples main operating conditions and product distribution of the fluid coking reactor
| Main operating conditions | Example 1 | Example 2 | Example 3 |
| Reaction temperature of | 510 | 530 | 550 |
| Mass ratio of cracked coke particles to hydrocarbon feedstock | 6 | 6 | 6 |
| Reaction pressure, MPa (gauge) | 0.12 | 0.12 | 0.12 |
| Product distribution (yield)% | |||
| H2S | 1.82 | 1.85 | 1.89 |
| Dry gas | 4.85 | 5.25 | 6.16 |
| H2 | 0.05 | 0.06 | 0.08 |
| CH4 | 2.32 | 2.48 | 2.93 |
| C2H4 | 0.30 | 0.37 | 0.49 |
| C2H6 | 2.18 | 2.34 | 2.66 |
| Liquefied gas | 4.20 | 4.92 | 6.78 |
| C3H6 | 0.68 | 0.83 | 1.14 |
| C3H8 | 1.57 | 1.84 | 2.45 |
| C4H8 | 0.82 | 0.97 | 1.57 |
| C4H10 | 1.13 | 1.28 | 1.62 |
| Gasoline (IBP-180 degree) | 15.54 | 16.30 | 17.99 |
| Diesel oil (180-350 deg.C) | 18.06 | 18.16 | 17.24 |
| Wax oil | 28.97 | 26.40 | 21.82 |
| Coke | 26.35 | 26.92 | 27.90 |
| Loss of power | 0.21 | 0.20 | 0.22 |
| Total up to | 100 | 100 | 100 |
Table 6 examples main operating conditions and gasification gas composition of coke gasification reactor
As can be seen from the comparison of the experimental results in the tables, the cracking reactor has no coke retention and the olefin yield is obviously higher than that of the comparative example by adopting the coupling method provided by the embodiment of the invention. The coupling method provided by the embodiment of the invention has the advantages that the selectivity of the olefin generated by cracking the hydrocarbon is better than that of a comparative example, and the coke generated by the cracking reaction can be taken away in time. At the same time, cracking, coking and coke gasification are coupled in one plant, the product types are significantly more than in the comparative example, and contain gaseous components which can be further converted into synthesis gas. The coupling method provided by the embodiment of the invention can improve economic benefits and broaden the source of raw materials for preparing olefin.
In summary, the coupling method for cracking, coking and coke gasification provided by the embodiment of the invention adopts the coke particles as the heat carrier and the carbon carrier of the cracking reaction, and the secondary reaction of the olefin product is effectively inhibited because the coke has no acidity; meanwhile, as the coke is a porous substance continuously generated in the cracking reaction process, the adsorption capacity is strong, the problem of hydrothermal aging does not exist, and the coke generated in the hydrocarbon cracking reaction can be continuously taken away from the reactor in time, so that the contradiction that the selectivity of the catalyst or carrier for generating olefin and the capacity of carrying the coke are mutually restricted in the existing process technology for preparing olefin by cracking hydrocarbons can be solved, and the defect of high agent consumption caused by quick hydrothermal aging of the catalyst or carrier is overcome; the hydrocarbon raw material cracking, fluid coking and coke gasification operation are coupled on the same set of device, high integration and energy complementation are realized, so that the construction investment, energy consumption and operation cost are greatly reduced; if the coal gas obtained by gasification is converted into synthesis gas, the synthesis gas can be further converted into low-carbon olefin, so that the economic benefit of the coking process is greatly improved, the requirements on the properties of the technical raw materials for preparing the low-carbon olefin are effectively reduced, and the raw material sources are widened.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method of coupling cracking, coking and coke gasification, comprising:
taking coke particles as coke forming particles to circulate in a cracking reactor, a fluid coking reactor and a coke gasification reactor which are communicated in sequence; in the coke forming particle circulation process, coke generated by cracking reaction and coking reaction is loaded on the coke particles, then the coke particles enter the coke gasification reactor to convert the loaded coke into gasification gas, and the coke particles after gasification reaction continuously serve as a heat carrier and a carbon carrier to enter the cracking reactor.
2. The coupling process of claim 1, wherein the pyrolysis feedstock comprises at least one of crude oil, naphtha, straight-run diesel, wax oil, atmospheric residue, vacuum residue, and liquid products of direct and indirect liquefaction of coal.
3. The coupling process of claim 1, wherein the coker feedstock comprises at least one of crude oil, atmospheric resid, vacuum resid, catalytically cracked slurry oil, and pitch.
4. The coupling method according to claim 1, wherein the coke gasification reaction is carried out by using a mixture of air, air and water vapor, oxygen and water vapor, or a mixture of air, oxygen and water vapor.
5. The coupling process according to claim 1, characterized in that the main operating conditions of the cracking reactor are: the reaction temperature is 580-780 ℃, the reaction pressure is 0.15-0.35 MPa, the reaction time is 0.5-3.0 s, the mass ratio of the coke particles to the cracking raw material after entering the cracking reactor is 12-50: 1, the mass ratio of the atomized water vapor to the cracking raw material is 0.3-1.0: 1, and the average linear velocity of the gas is 8.0-15.0 m/s.
6. The coupling process of claim 1, wherein the main operating conditions of the fluid coking reactor are: the reaction temperature is 480-560 ℃, the reaction pressure is 0.10-0.30 MPa, the mass ratio of the coke particles to the coking raw material after entering the fluid coking reactor is 4-12: 1, and the average linear speed of gas is 0.5-1.5 m/s.
7. The coupling method according to claim 1, wherein the main operating conditions of the char gasification reactor are: the reaction temperature is 700-900 ℃, the reaction pressure is 0.20-0.40 MPa, the reaction time is 5-20 min, the average linear velocity of the gas is 0.5-1.5 m/s, and the oxygen-carbon ratio is 0.04-0.10 m3The steam-carbon ratio is 0-0.05 kg/kg.
8. The coupling method according to claim 1, wherein the initial coke-forming particles added to the apparatus at the initial start-up stage are catalytic cracking catalyst particles having a particle size of 10 to 200 μm, and the corresponding coke particles after stable operation have a particle size of 20 to 2000 μm.
9. The coupling method according to claim 1, wherein at the initial start-up stage, the initial coke-forming particles added into the device are semi-coke particles or pulverized coal, the particle size of the semi-coke particles or the pulverized coal is 10-3000 microns, and the particle size of the corresponding coke particles after stable operation is 20-5000 microns.
10. The coupling method of claim 1, wherein the mass ratio of the cracking feedstock to the coking feedstock is 1: 2-6.
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| CN114540069A (en) * | 2022-01-04 | 2022-05-27 | 中国石油化工股份有限公司 | Method and device for preparing olefin by cracking petroleum hydrocarbon and application |
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| CN106635124A (en) * | 2015-11-04 | 2017-05-10 | 中国石油天然气股份有限公司 | Flexible coking process method and device for processing inferior heavy oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106635124A (en) * | 2015-11-04 | 2017-05-10 | 中国石油天然气股份有限公司 | Flexible coking process method and device for processing inferior heavy oil |
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| CN114540069A (en) * | 2022-01-04 | 2022-05-27 | 中国石油化工股份有限公司 | Method and device for preparing olefin by cracking petroleum hydrocarbon and application |
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