CN102382669B - Coal cracking and heavy oil cracking joint production method - Google Patents
Coal cracking and heavy oil cracking joint production method Download PDFInfo
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Abstract
The invention discloses a coal cracking and heavy oil cracking joint production method, which comprises the following steps of: (1) contacting coal with a first heat carrier under the coal cracking condition to obtain a first solid product and a first gas product; (2) contacting heavy oil with a second heat carrier under the heavy oil cracking condition to obtain a second solid product and a second gas product, wherein the second heat carrier comprises the first solid product; and (3) burning the second solid product to obtain a third solid product and a third gas product, wherein the first heat carrier and/or the second heat carrier comprises the third solid product and/or the third gas product. By adopting the method provided by the invention, joint production of coal cracking and heavy oil cracking is realized, and energy consumption in the coal cracking and heavy oil cracking processes is lowered greatly.
Description
Technical field
The present invention relates to the combine production method of a kind of coal cracking and heavy oil cracking.
Background technology
China is the country of oil-poor rich coal, and crude oil is heaviness, in poor quality increasingly, and the heavy component carbon residue in some crude oil and metal content are all very high, is difficult to efficiently it be fully utilized by traditional working method; Meanwhile, the coal resources of China are very abundant, and its workable reserves accounts for 49.6% of the world, and its metabituminous coal output accounts for 75% of national coal ultimate production.76% of China's energy consumption is coal at present, is mainly used in direct burning.Thereby wherein contained chemical resource cannot be utilized effectively.
Gasification and gelatin liquefaction are the important method that is made geseous fuel, synthetic gas and liquid fuel by coal, also have in addition a kind of more economical method: dry distillation of coal method.Destructive distillation final temperature is low-temperature pyrolysis lower than 700 DEG C, and destructive distillation final temperature is called coking or high temperature carbonization higher than 900 DEG C.Low-temperature pyrolysis can obtain tar, coal gas and semicoke.High temperature carbonization mainly obtains coke.Compared with raw coal, the pollutent that semicoke contains is less than raw coal, favourable to environment protection.For units of heat, coal tar oil and gas has higher economic worth than semicoke.Low-temperature pyrolysis coal tar is roughly similar with the character of coal Direct Hydrogenation liquefaction first stage gained oil plant, and coal tar repeated hydrogenation is refining can obtain oil fuel, and compared with liquefaction, cost is relatively low.
Rich coal resources in China, raw coal is except part is for coking, conversion processing, and the overwhelming majority is for directly burning.Coal is directly burnt, and not only thermo-efficiency is low, serious to the destruction of environment, and the hydrogen-rich component in coal with higher economic worth can not get reasonable utilization.Therefore the technological process that, to develop coal conversion be clean fuel and multiple Chemicals has important practical significance.CNPC's shortage of resources, efficient, the comprehensive utilization of coal can reduce the dependence to Imported oil, Sweet natural gas to a certain extent.Therefore,, before by raw coal combustion, make it under relatively mild condition, extract partially liq fuel and fine chemicals has great importance.For example, a kind of powder coal grading cleaning multigang utilization taking pyrolysis as the first step is disclosed in CN 101016482A, comprise raw coal processing preparation, pyrolysis, burning or gasification, pyrogenic processes is provided with Coal Chemical Industry isolation of purified system, wherein, raw coal enters pyrogenic processes with the fine coal of certain particle size and carries out pyrolysis after processing preparation, and the gas-phase product after pyrolysis enters Coal Chemical Industry isolation of purified system, obtains hydro carbons Chemicals, the purified gas of high added value; The subsequent technique of the solid product semi-coke powder after pyrolysis is selected as follows: (1) enters the burning of burning operation, utilizes heat energy power-generating, heat supply; (2) enter gasification process gasification, produce synthetic raw gas; (3) enter respectively the burning of burning operation, gasification process gasification simultaneously.
Processing the conventional technique of mink cell focus is at present delayed coking, and this technique is by making mink cell focus thermally splitting obtain the products such as part coker gasoline, coker gas oil, coking distillate, hydrocarbon gas and coke.In this technique, because mink cell focus need at high temperature generate lighter oil product through the longer time by thermally splitting, in the time that raw material carbon residue is very high, green coke amount is very large.In order to address this problem, develop the heavy oil cracking technique that temperature of reaction is higher, the residence time is shorter.For example, CN 1504404A discloses the processing method that a kind of oil refining combines with gasification, and wherein, the method comprises the following steps: (1) petroleum hydrocarbon contacts, reacts with coke transfer agent in reactor; (2) separate the reaction oil gas generating and the coke transfer agent that reacts rear carbon deposit, reaction oil gas is sent into follow-up hydrocarbon products separation system, and the coke transfer agent of carbon deposit is delivered to vapourizing furnace after stripping; (3) in vapourizing furnace, the coke transfer agent of carbon deposit contacts with oxygen-containing gas with water vapor under gasification condition, to generate synthesis gas, makes the coke transfer agent of carbon deposit be regenerated simultaneously; (4) coke transfer agent after step (3) regeneration returns in the described reactor of step (1) and recycles.
But, in above-mentioned two sections of patent documentations, the method for disclosed coal cracking and heavy oil cracking all needs outside heat supply, and the heat of the solid product producing in described coal cracking and heavy oil cracking process can not recycle, thereby causes heat recovery efficiency not high.
Summary of the invention
The above-mentioned defect that the present invention exists separately in order to overcome existing coal cleavage method and heavy oil cracking method, the combine production method of a kind of coal cracking and heavy oil cracking is provided, adopt the method can realize coal cracking and heavy oil cracking simultaneously, make the solid product producing separately in coal cracking and heavy oil cracking process to recycle as thermal barrier simultaneously, thereby greatly saved energy consumption.
The combine production method that the invention provides a kind of coal cracking and heavy oil cracking, the method comprises: (1), under the condition of coal cracking, makes coal contact with the first thermal barrier, obtains the first solid product and the first gaseous product; (2) under the condition of heavy oil cracking, mink cell focus is contacted with the second thermal barrier, obtain the second solid product and the second gaseous product, the second thermal barrier comprises the first solid product; (3) make the second solid product burning, obtain the 3rd solid product and the 3rd gaseous product; And the first thermal barrier and/or the second thermal barrier comprise the 3rd solid product and/or the 3rd gaseous product.
The combine production method of coal cracking according to the present invention and heavy oil cracking, by coal cracking, heavy oil cracking and three processes of coke powder burning are combined, and the mass transfer system of formation circulation, the solid product that coal cracking is produced can enter in heavy oil cracking reactor, as the thermal barrier of heavy oil cracking reaction; And the solid product that heavy oil cracking produces can enter in described burner and burns, can produce gaseous product and/or the solid product with high calorie, this gaseous product and/or solid product are circulated in described coal cracking reactor and/or described heavy oil cracking reactor, to provide heat to described coal cracking reactor and/or heavy oil cracking reactor.Therefore, successfully realized the combination producing of coal cracking and heavy oil cracking according to method provided by the invention, meanwhile, the solid product producing in each comfortable coal cracking and heavy oil cracking process can be recycled as thermal barrier, thereby greatly saved production energy consumption.
Brief description of the drawings
Fig. 1 represents according to the schema of the production process of the embodiment of the present invention 1;
Fig. 2 represents according to the schema of the production process of the embodiment of the present invention 2;
Fig. 3 represents according to the schema of the production process of the embodiment of the present invention 3.
Embodiment
Comprise the following steps according to the combine production method of coal cracking of the present invention and heavy oil cracking:
(1) under the condition of coal cracking, coal is contacted with the first thermal barrier, obtain the first solid product and the first gaseous product;
(2) under the condition of heavy oil cracking, mink cell focus is contacted with the second thermal barrier, obtain the second solid product and the second gaseous product, the second thermal barrier comprises the first solid product;
(3) make the second solid product burning, obtain the 3rd solid product and the 3rd gaseous product; And the first thermal barrier and/or the second thermal barrier comprise the 3rd solid product and/or the 3rd gaseous product.
In step (1), coal is under the effect of the first thermal barrier, and the temperature of described coal raises and cracking occurs, and discharges most of volatile wherein, thereby the split product obtaining comprises gaseous product and solid product, be also the first gaseous product and the first solid product.Described the first solid product mainly comprises semicoke and coke powder, and described semicoke is mainly produced by coal scission reaction, and described coke powder is mainly from the thermal barrier entering in described the first reactor.Described the first gaseous product mainly comprises coal tar oil and gas.
According to method provided by the invention, step (1) can be implemented in the reactor of various routines, as long as this reactor can be realized coal scission reaction, therefore, this reactor can be called coal cracking reactor.Described coal cracking reactor can be for example the reactor of fluidized-bed reactor, riser reactor, down-flow reactor, moving-burden bed reactor or their array configuration.In the present invention, described the first solid product refers to the solid product of discharging from coal cracking reactor, and described the first gaseous product refers to expellant gas product from coal cracking reactor.
In step (2), mink cell focus is under the effect of the second thermal barrier, the temperature of described mink cell focus raises rapidly, there is atomization, mink cell focus generation heat scission reaction after atomization simultaneously, thereby the split product obtaining comprises gaseous product and solid product, be also the second gaseous product and the second solid product.Described the second solid product mainly comprises coke powder particle, and described the second gaseous product mainly comprises splitting gas, gasoline fraction, diesel oil distillate and heavy oil fraction.
According to method provided by the invention, step (2) can be implemented in the reactor of various routines, as long as this reactor can be realized heavy oil cracking reaction, therefore, this reactor can be called heavy oil cracking reactor.Described heavy oil cracking reactor can be for example the reactor of fluidized-bed reactor, riser reactor, down-flow reactor or their array configuration.In the present invention, described the second solid product refers to the solid product of discharging from heavy oil cracking reactor, and described the second gaseous product refers to expellant gas product from heavy oil cracking reactor.
In step (3), by the second solid product is burnt, thereby produce high-temperature gas and absorbed the not clean-burning solid of the heat that a large amount of burning produces, also be the 3rd gaseous product and the 3rd solid product, and by the lime-ash producing after burning (solid that fully burning produces) discharge burner.And, by making the first thermal barrier and/or the second thermal barrier comprise the 3rd solid product and/or the 3rd gaseous product, can replenish step (1) and/or the reaction process of step (2) in calorific loss, thereby the temperature of the heavy oil cracking reaction of the temperature of the coal scission reaction of step (1) and/or step (2) can be adjusted in stable scope, make the enforcement that can circulate of described coal cracking and heavy oil cracking process.In the present invention, the temperature of the burning of step (3) can be 800-1500 DEG C, is preferably 800-1200 DEG C.The particle diameter of the 3rd solid product that described burning produces can be 0.01-3 millimeter.According to method provided by the invention, step (3) can be implemented in conventional burner.In the present invention, described the 3rd solid product refers to the not clean-burning solid product of discharging from burner, and described the 3rd gaseous product refers to expellant gas product from burner.
A preferred embodiment of the invention, described the first thermal barrier is the 3rd solid product and/or the 3rd gaseous product, described the second thermal barrier is the first solid product; In preferred situation, described the first thermal barrier is the 3rd solid product, and described the second thermal barrier is the first solid product.
According to method provided by the invention, the condition of described coal cracking can suitably be selected in conventional coal crack reacting condition.Under preferable case, the condition of described coal cracking comprises that the temperature that coal contacts with the first thermal barrier is 450-700 DEG C, more preferably 450-650 DEG C.In this case, the temperature of the first thermal barrier is 600-1500 DEG C, and the weight ratio of coal and this first thermal barrier is 1: 1-10, is preferably 1: 2-8.Under further preferable case, the condition of described coal cracking also comprises that the pressure that coal contacts with the first thermal barrier is 0.1-0.6MPa, more preferably 0.1-0.4MPa.In the present invention, described pressure refers to absolute pressure; The temperature that described coal contacts with the first thermal barrier refers to the temperature of environment of living in when coal contacts with the first thermal barrier, is also after coal mixes with the first thermal barrier, temperature when the two generation heat is transmitted and reaches balance.
In a kind of preferred implementation, for making coal cracking more fully, also comprise and make coal be heated to 100-350 DEG C before contacting with the first thermal barrier according to method provided by the invention.
In the present invention, described coal can be for having the various coals of conventional particle diameter, and under preferable case, the particle diameter of described coal is 0.05-2 millimeter.Described coal can be for example at least one in peat, brown charcoal and bituminous coal.
According to method provided by the invention, the condition of described heavy oil cracking can suitably be selected in conventional heavy oil cracking reaction conditions.Under preferable case, the condition of described heavy oil cracking comprises that the temperature that mink cell focus contacts with the second thermal barrier is 450-650 DEG C, more preferably 450-550 DEG C.In this case, the temperature of the second thermal barrier is 450-700 DEG C, and the weight ratio of described mink cell focus and the second thermal barrier is 1: 4-50, is preferably 1: 5-20.Under further preferable case, the condition of described heavy oil cracking also comprises that the pressure that mink cell focus contacts with the second thermal barrier is 0.1-0.6MP, more preferably 0.1-0.4MPa.The temperature that described mink cell focus contacts with the second thermal barrier refers to the temperature of environment of living in when mink cell focus contacts with the second thermal barrier, is also after mink cell focus mixes with the second thermal barrier, temperature when the two generation heat is transmitted and reaches balance.
In a kind of preferred implementation, for making mink cell focus cracking more fully, also comprise and make mink cell focus be heated to 150-500 DEG C before contacting with the second thermal barrier according to method provided by the invention, be more preferably heated to 200-450 DEG C.
In the present invention, described mink cell focus can be the mink cell focus of various routines, for example, can be at least one in oil at the bottom of heavy crude, long residuum, normal pressure wax oil, vacuum residuum, wax tailings, tank, deasphalted oil, viscous crude and hydrocracking tail oil.
According to one embodiment of the present invention, described method can also comprise described the first gaseous product is separated with described the second gaseous product, to be separated into heavy oil fraction, diesel oil distillate, gasoline fraction, water and gas.The method of described separation can adopt conventional method to implement, for example can be according to the difference of the condensing temperature of each different components, and adopt the mode of temperature control condensation to separate.
In the present invention, can implement separately separately described the first gaseous product and separating of described the second gaseous product, after also the two can being converged, implement together again to separate.Consider production cost, after preferably the two being converged, implement together again to separate.
According to one embodiment of the present invention, described method can also comprise discharges described part the second solid product, and the cooling coke powder product to obtain, and makes described second solid product of other parts burn simultaneously.The amount of discharging and carry out cooling described the second solid product can, for the 5-60 % by weight of the gross weight of described the second solid product, be preferably 20-50 % by weight.
The present invention is further detailed explanation by the following examples.
Embodiment 1
The present embodiment is for illustrating the combine production method of described coal cracking provided by the invention and heavy oil cracking.
As shown in Figure 1, the coal dust (shown in table 1 composed as follows) that is 0.05-2 millimeter by the particle diameter of 100 weight parts is heated to 200 DEG C, then add in coal cracking reactor, and with from burner burning produce gas (temperature is 1000 DEG C) mix, making coal dust and the weight ratio of the gas of burning generation is 1: 2, thereby the temperature of described coal cracking reactor is adjusted to 580 DEG C, and pressure is adjusted to 0.3MPa.After processing, coal cracking reactor obtains gaseous product and solid product, i.e. the first gaseous product and the first solid product.
The heavy crude of 10 weight parts (shown in table 2 composed as follows) is heated to 200 DEG C, then add in heavy oil cracking reactor, and mix with the first solid product (temperature is 560 DEG C) from coal cracking reactor, making heavy crude in described heavy oil cracking reactor and the weight ratio of described the first solid product is 1: 8, thereby the temperature of described heavy oil cracking reactor is adjusted to 500 DEG C, and pressure is adjusted to 0.3MPa.After heavy oil cracking reactor for treatment, obtain gaseous product and solid product, i.e. the second gaseous product and the second solid product.Described the second solid product is carried out to stripping, and part is discharged through steam stripped described the second solid product and carry out cooling to obtain coke powder product, remainder is added in burner as fuel through steam stripped described the second solid product, and inject air in described burner, so that burn in described burner, and it is 1100 DEG C by the temperature control in described burner, make the gas (i.e. the 3rd gaseous product) that in described burner, burning produces be circulated in described coal cracking reactor, the lime-ash producing fully burning is discharged burner simultaneously.
For convenience of operation, described the first gaseous product and described the second gaseous product are converged, and adopt the mode of temperature control condensation to separate.Product and yield thereof when table 3 reaches material balance for the reaction of coal scission reaction and heavy oil cracking, and in table 3 from the product of coal scission reaction and heavy oit pyrolysis reaction shown in the table 4 composed as follows of isolated gas.
Table 1
Table 2
Table 3
Table 4
| The composition of gas | % by weight |
| Methane | 6.9 |
| Ethane | 1.6 |
| Ethene | 1.1 |
| Propane | 0.9 |
| Propylene | 1.3 |
| C 4+Hydro carbons | 1.5 |
| Hydrogen | 1.0 |
| Carbonic acid gas | 32.0 |
| Carbon monoxide | 15.6 |
| Hydrogen sulfide | 0.1 |
| Nitrogen | 38.0 |
| Amount to | 100 |
Embodiment 2
The present embodiment is for illustrating the combine production method of described coal cracking provided by the invention and heavy oil cracking.
As shown in Figure 2, the coal dust (composition as shown in Table 1) that is 0.05-2 millimeter by the particle diameter of 100 weight parts is heated to 100 DEG C, then add in coal cracking reactor, and with from not clean-burning solid product in burner, (temperature is 850 DEG C, particle diameter is 0.01-3 millimeter) mix, the weight ratio that makes coal dust and described not clean-burning solid product is 1: 4, thereby the temperature of described coal cracking reactor is adjusted to 590 DEG C, and pressure is adjusted to 0.2MPa.After processing, coal cracking reactor obtains gaseous product and solid product, i.e. the first gaseous product and the first solid product.
The heavy crude of 10 weight parts (forming as above shown in table 2) is heated to 300 DEG C, then add in heavy oil cracking reactor, and mix with the first solid product (temperature is 575 DEG C) from coal cracking reactor, making heavy crude in described heavy oil cracking reactor and the weight ratio of described the first solid product is 1: 5, thereby the temperature of described heavy oil cracking reactor is adjusted to 550 DEG C, and pressure is adjusted to 0.2MPa.After heavy oil cracking reactor for treatment, obtain gaseous product and solid product, i.e. the second gaseous product and the second solid product.Described the second solid product is carried out to stripping, and part is discharged through steam stripped described the second solid product and carry out cooling to obtain coke powder product, remainder is added in burner as fuel through steam stripped described the second solid product, and inject air in described burner, so that burn in described burner, and it is 950 DEG C by the temperature control in described burner, make not clean-burning solid product in described burner (i.e. the 3rd solid product) be circulated in described coal cracking reactor simultaneously, the lime-ash producing fully burning is discharged burner.
For convenience of operation, described the first gaseous product and described the second gaseous product are converged, and adopt the mode of temperature control condensation to separate.Product and yield thereof when table 5 reaches material balance for the reaction of coal scission reaction and heavy oil cracking, and in table 5 from the product of coal scission reaction and heavy oit pyrolysis reaction shown in the table 6 composed as follows of isolated gas.
Table 5
Table 6
| The composition of gas | % by weight |
| Methane | 12.9 |
| Ethane | 4.6 |
| Ethene | 2.7 |
| Propane | 1.7 |
| Propylene | 4.2 |
| C 4+Hydro carbons | 4.0 |
| Hydrogen | 1.3 |
| Carbonic acid gas | 47.3 |
| Carbon monoxide | 20.8 |
| Hydrogen sulfide | 0.2 |
| Nitrogen | 0.3 |
| Amount to | 100 |
Embodiment 3
The present embodiment is for illustrating the combine production method of described coal cracking provided by the invention and heavy oil cracking.
As shown in Figure 3, the coal dust (composition as shown in Table 1) that is 0.05-2 millimeter by the particle diameter of 100 weight parts is heated to 250 DEG C, then add in coal cracking reactor, and with from burner burning produce gas and not clean-burning solid product (temperature is 950 DEG C, particle diameter is 0.01-3 millimeter) mix, making coal dust, the gas of described burning generation and the weight ratio of described not clean-burning solid product is 1: 1: 2, thereby the temperature of described coal cracking reactor is adjusted to 550 DEG C, and pressure is adjusted to 0.15MPa.After processing, coal cracking reactor obtains gaseous product and solid product, i.e. the first gaseous product and the first solid product.
The heavy crude of 10 weight parts (forming as above shown in table 2) is heated to 200 DEG C, then add in heavy oil cracking reactor, and mix with the first solid product (temperature is 540 DEG C) from coal cracking reactor, making heavy crude in described heavy oil cracking reactor and the weight ratio of described the first solid product is 1: 10, thereby the temperature of described heavy oil cracking reactor is adjusted to 500 DEG C, and pressure is adjusted to 0.25MPa.After heavy oil cracking reactor for treatment, obtain gaseous product and solid product, i.e. the second gaseous product and the second solid product.Described the second solid product is carried out to stripping, and part is discharged through steam stripped described the second solid product and carry out cooling to obtain coke powder product, remainder is added in burner as fuel through steam stripped described the second solid product, and inject air in described burner, so that burn in described burner, and it is 1000 DEG C by the temperature control in described burner, make gas (i.e. the 3rd gaseous product) and not clean-burning solid product (i.e. the 3rd solid product) that in described burner, burning produces be circulated in described coal cracking reactor simultaneously, the lime-ash producing fully burning is discharged burner.
For convenience of operation, described the first gaseous product and described the second gaseous product are converged, and adopt the mode of temperature control condensation to separate.Product and yield thereof when table 7 reaches material balance for the reaction of coal scission reaction and heavy oil cracking, and in table 7 from the product of coal scission reaction and heavy oit pyrolysis reaction shown in the table 8 composed as follows of isolated gas.
Table 7
Table 8
| The composition of gas | % by weight |
| Methane | 8.5 |
| Ethane | 2.3 |
| Ethene | 1.5 |
| Propane | 1.4 |
| Propylene | 1.8 |
| C 4+Hydro carbons | 3.0 |
| Hydrogen | 0.7 |
| Carbonic acid gas | 43.7 |
| Carbon monoxide | 17.3 |
| Hydrogen sulfide | 0.8 |
| Nitrogen | 19.0 |
| Amount to | 100 |
Can find out according to above embodiment 1-3, adopt the combine production method of coal cracking provided by the invention and heavy oil cracking to realize the combination producing of coal cracking and heavy oil cracking.
Claims (9)
1. a combine production method for coal cracking and heavy oil cracking, is characterized in that, the method comprises the following steps:
(1) under the condition of coal cracking, coal is contacted with the first thermal barrier, obtain the first solid product and the first gaseous product;
(2) under the condition of heavy oil cracking, mink cell focus is contacted with the second thermal barrier, obtain the second solid product and the second gaseous product, the second thermal barrier comprises the first solid product;
(3) make the second solid product burning, obtain the 3rd solid product and the 3rd gaseous product; And the first thermal barrier and/or the second thermal barrier comprise the 3rd solid product and/or the 3rd gaseous product;
Wherein, the condition of described coal cracking comprises that the temperature that coal contacts with the first thermal barrier is 450-700 DEG C;
Wherein, in step (3), the temperature of described burning is 800-1500 DEG C.
2. method according to claim 1, wherein, described the first thermal barrier is the 3rd solid product and/or the 3rd gaseous product, described the second thermal barrier is the first solid product.
3. method according to claim 1, wherein, the temperature of the first thermal barrier is 600-1500 DEG C, and the weight ratio of coal and this first thermal barrier is 1:1-10.
4. method according to claim 1, wherein, the condition of described coal cracking also comprises that the pressure that coal contacts with the first thermal barrier is 0.1-0.6MPa.
5. method according to claim 1 and 2, wherein, the particle diameter of described coal is 0.05-2 millimeter, the particle diameter of the 3rd solid product is 0.01-3 millimeter.
6. method according to claim 1 and 2, wherein, the condition of described heavy oil cracking comprises that the temperature that mink cell focus contacts with the second thermal barrier is 450-650 DEG C.
7. method according to claim 6, wherein, the temperature of the second thermal barrier is 450-700 DEG C, the weight ratio of described mink cell focus and the second thermal barrier is 1:4-50.
8. method according to claim 7, wherein, the condition of described heavy oil cracking also comprises that the pressure that mink cell focus contacts with the second thermal barrier is 0.1-0.6MPa.
9. method according to claim 1, wherein, described mink cell focus is at least one in oil at the bottom of heavy crude, long residuum, normal pressure wax oil, vacuum residuum, wax tailings, tank, deasphalted oil, viscous crude and hydrocracking tail oil.
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