CN102453510A - Combined processing method of copyrolysis of heavy oil and coal - Google Patents
Combined processing method of copyrolysis of heavy oil and coal Download PDFInfo
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Abstract
A combined processing method of copyrolysis of heavy oil and coal comprises steps of: (1) introducing coal dust and heavy oil into a cracking reactor, contacting with high temperature coke powder from a gasification reactor for heating, generating a cracking reaction to obtain reacted oil gas and solid products of semicoke and coke powder, etc., carrying out gas-solid separation, introducing the reacted oil gas to a subsequent separating system for further separation and sending the semicoke and coke to the gasification reactor; (2) introducing a gasification medium containing water and oxygen into the gasification reactor, carrying out a gasification reaction on semicoke and coke from a cracker and water and oxygen to generate a synthetic gas and a high temperature coke powder; carrying out gas-solid separation and sending the high temperature coke powder to the cracking reactor to provide heat for the cracking reaction of coal and heavy oil. The method provided by the invention realizes combined production of coal cracking, heavy oil cracking and coal gasification, so as to substantially save energy consumption in coal cracking, heavy oil cracking and coal gasification.
Description
Technical field
The present invention relates to the combine production method of a kind of coal cracking and heavy oit pyrolysis.
Background technology
China is the country of oil-poor rich coal, and crude oil is heaviness, poor qualityization day by day, and heavy component carbon residue in some crude oil and metal content are all very high, is difficult to efficiently it fully utilized with traditional processing method; Simultaneously, 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 can't 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 a kind of more economical method in addition: dry distillation of coal method, and be about to the coal secluding air and add the process that heat-flash makes its decomposition, also cry the coking of coal.Dry distillation of coal process mainly experiences following variation: when the temperature of coal charge is higher than 100 ℃; Moisture evaporation in the coal is come out; When temperature was elevated to more than 200 ℃, combination water was disengaged in the coal, up to more than 350 ℃ the time; Caking coal begins to soften, and further forms heavy-gravity plastic mass (this phenomenon does not take place for mud coal, brown coal etc.); Separate out to 400-500 ℃ of most of coal gas and tar, be called thermal decomposition product one time; At 450-550 ℃, thermolysis is proceeded, residue retrogradation and solidify to form semicoke gradually; Be higher than 550 ℃, semicoke continues to decompose, and separates out remaining volatile matter (staple is a hydrogen) semicoke weightlessness and shrinks simultaneously, forms crackle; Temperature is higher than 800 ℃, and the hardening of semicoke volume-diminished forms porous coke.When destructive distillation was carried out in gas retort, one time thermal decomposition product contacted with red-hot coke and high temperature furnace wall, and the secondary thermolysis takes place, and formed the secondary thermal decomposition product.
The whole temperature of destructive distillation is lower than 700 ℃ and is low-temperature pyrolysis, and the whole temperature of destructive distillation is higher than 900 ℃ and is called coking or high temperature carbonization.Low-temperature pyrolysis can obtain tar, coal gas and semicoke.High temperature carbonization mainly obtains coke.Compare with raw coal, the pollutent that semicoke contains is less than raw coal, and is favourable to environment protection.For units of heat, the 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 fs gained oil plant, and the coal tar repeated hydrogenation is refining can to get oil fuel, compares with liquefaction, and cost is relatively low.
Rich coal resources in China, raw coal is used for coking, transforms the processing except that part, and the overwhelming majority is used for direct burning.Coal directly burnt, and not only thermo-efficiency is low, serious to environment damage, and the hydrogen-rich component that has higher economic worth in the coal can not get reasonable utilization.Therefore, developing coal conversion is that the technological process of 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 with raw coal combustion, make it under relatively mild condition, extract partially liq fuel and fine chemicals has great importance.For example; Disclosing a kind of among the CN 101016482A is the fine coal grading cleaning multiple utilization technology of the first step with the pyrolysis, comprises raw coal processing and preparing, pyrolysis, burning or gasification, and pyrogenic processes is provided with Coal Chemical Industry isolation of purified system; Wherein, Raw coal fine coal entering pyrogenic processes with certain particle size after processing and preparing is carried out pyrolysis, and the gas-phase product after the pyrolysis gets into 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 the pyrolysis is selected as follows: (1) gets into the burning of burning operation, utilizes heat energy power-generating, heat supply; (2) get into the gasification process gasification, produce synthetic raw gas; (3) get into the burning of burning operation, gasification process gasification simultaneously respectively.
Handling BO technology commonly used at present is delayed coking, and this technology obtains products such as part coker gasoline, coker gas oil, coking distillate, hydrocarbon gas and coke through making the BO thermally splitting.In this technology, because BO needs at high temperature to generate lighter oil product through the long time through thermally splitting, when the raw material carbon residue was very high, the green coke amount was very big.In order to address this problem, developed the heavy oil cracking technology that temperature of reaction is higher, the residence time is short.For example, CN 1504404A discloses a kind of oil refining and gasification process combined method, and wherein, this method may further comprise the steps: (1) petroleum hydrocarbon contacts in reactor drum, reacts with coke transfer agent; (2) separate reaction oil gas that generates and the coke transfer agent that reacts the back 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 behind stripping; (3) in vapourizing furnace, the coke transfer agent of carbon deposit contacts under gasification condition with oxygen-containing gas with water vapor, to generate synthesis gas, makes the coke transfer agent of carbon deposit obtain regeneration simultaneously; (4) coke transfer agent after step (3) regeneration returns in the described reactor drum of step (1) and recycles.
Yet; The method of disclosed coal cracking and heavy oil cracking all needs outside heat supply in above-mentioned two pieces of patent documentations; And the heat of the solid product that produces in said coal cracking and the heavy oil cracking process can not recycle, thereby causes heat recovery efficiency not high.
Summary of the invention
The present invention is in order to overcome the above-mentioned defective that existing coal cleavage method and heavy oil cracking method exist separately; The combine production method of a kind of coal cracking and heavy oil cracking is provided; Adopt this method can realize coal cracking and heavy oil cracking simultaneously; Make the solid product that produces separately in coal cracking and the heavy oil cracking process to recycle simultaneously, thereby saved energy consumption greatly as thermal barrier.
The invention provides the combine production method of a kind of coal and heavy oil cracking, this method may further comprise the steps:
(1) coal dust and heavy oil are introduced in the cracking reactor; Contact intensification with high temperature coke powder from gasifying reactor; Scission reaction takes place obtain reaction oil gas and solid products such as semicoke, coke powder; After the gas solid separation, reaction oil gas is introduced subsequent separation system and is further separated, and semicoke and coke powder get into gasifying reactor;
(2) introduce the gasifying medium that contains water and oxygen in the gasifying reactor; Semicoke and coke powder and water and oxygen reaction heat release from cracker; Generate synthetic gas and high temperature coke powder; After the gas solid separation, it is coal and heavy oit pyrolysis reaction heat supply that a part of high temperature coke powder returns cracking reactor, discharger after another part fully gasifies.
In the method provided by the invention, the service temperature of cracking reactor is 400-700 ℃ in the step (1), and pressure is 0.1-20Mpa; The service temperature of the gasifying reactor in the step (2) is 800-1200 ℃, and pressure is 0.1-20Mpa.
The beneficial effect of heavy oil provided by the invention and coal cracked combine production method is:
Heavy oit pyrolysis, coal dust cracking and three processes of coke powder gasification are combined, and form round-robin mass transfer system.In cracker, coal dust mixes intensification with thermal barrier-high temperature coke powder from gasifying reactor, contact the generation scission reaction simultaneously with the heavy oil that sprays into cracker.Heavy oil and coal cracking produce solid products such as semicoke, coke powder; Said solid product gets into gasifying reactor and the reaction of gasifying medium generating gasification generates synthetic gas; Contain oxygen in the gasifying medium; Make the fully solid product of gasification burning heat release in the gasifying reactor, obtain the high temperature coke powder and be circulated in the said cracking reactor scission reaction heat supply for coal and heavy oil.Therefore, the combine production method of coal provided by the invention and heavy oit pyrolysis has successfully been realized the combination producing of coal cracking, heavy oil cracking and gasification.Simultaneously, the solid product that produces in coal cracking and the heavy oit pyrolysis process recycles as thermal barrier, thereby has simplified flow process, and has saved the energy consumption in the production process greatly.
Description of drawings
Accompanying drawing is the schematic flow sheet of the combine production method of coal provided by the invention and heavy oit pyrolysis.
Embodiment
Shown in accompanying drawing, heavy oil provided by the invention and coal cracked combine production method are such practical implementations, and this method may further comprise the steps:
(1) coal dust and heavy oil are introduced in the cracking reactor; Contact intensification with high temperature coke powder from gasifying reactor; Scission reaction takes place obtain reaction oil gas and solid products such as semicoke, coke powder, after the gas solid separation, reaction oil gas is introduced subsequent separation system and is further separated; Isolated semicoke and coke powder get into gasifying reactor;
(2) introduce the gasifying medium that contains water and oxygen in the gasifying reactor; Semicoke and coke powder and water and oxygen reaction heat release from cracker; Generate the high temperature coke powder that synthetic gas and carbon (charcoal) content reduce; After the gas solid separation, it is coal and heavy oit pyrolysis reaction heat supply that a part of high temperature coke powder returns cracking reactor, discharger after another part fully gasifies.
In the method provided by the invention, in the step (1), be that heavy oit pyrolysis and coal dust scission reaction provide heat in the cracker as thermal barrier from the high temperature coke powder of gasifying reactor.Cracking takes place in said heavy oil and coal dust under cracking condition, generate oil gas and be master's solid product with semicoke, coke powder.
The cracking condition of said heavy oil and coal can suitably be selected in the heavy oil of routine and coal crack reacting condition.Under the preferable case, the service temperature of said cracker is 400-700 ℃, more preferably 450-600 ℃, and pressure is 0.1-20MPa, 0.1-10MPa more preferably.In the present invention, said pressure is meant absolute pressure; Said cracker service temperature is the temperature of heavy oil environment of living in when contacting with thermal barrier with coal, also is heavy oil and coal with after thermal barrier mixes, and temperature heat passage and when reaching balance takes place for the two.
The service temperature of said cracker is come flexible by the amount of the high temperature coke powder of introducing cracker and the temperature of high temperature coke powder.In this case, the temperature of the high temperature coke powder by gasifying reactor is 800-1200 ℃, and the weight ratio of coal and said high temperature coke powder is 1: (1-10), be preferably 1: (2-8).The weight ratio of said BO and coal dust and high-temperature coke powder mixture is 1: (4-50), be preferably 1: (5-20).
In a preferred embodiment, for making the cracking more fully of heavy oil and coal dust, also comprise according to method provided by the invention making coal dust before contacting, be heated to 100-350 ℃ with thermal barrier.BO was heated to 150-500 ℃ before getting into cracking reactor, more preferably be heated to 200-450 ℃.
In the method provided by the invention, said coal dust can be for having the various coals of conventional particle diameter, and under the preferable case, the particle diameter of said coal dust is the 0.05-2 millimeter.Said coal dust is preferably at least a in peat, brown charcoal and the bituminous coal.
In the method provided by the invention; Said heavy oil can be the BO of various routines, for example can be in heavy crude, long residuum, normal pressure wax oil, vacuum residuum, wax tailings, jar end oil, deasphalted oil, viscous crude and the hydrocracking tail oil at least a.
In the method provided by the invention, step (1) can be implemented in the reactor drum of various routines, as long as this reactor drum can be realized the scission reaction of heavy oil and coal, therefore, cracker can be called cracking reactor.Said cracker is preferably the reactor drum of fluidized-bed reactor, riser reactor, down-flow reactor, moving-burden bed reactor or their array configuration.
In the method provided by the invention; In the step (2); Under gasification condition; Contact the generating gasification reaction from solid products such as the semicoke of cracker and coke powders with oxygen with water vapor, generate the coke powder of synthetic gas and carbon content reduction, said synthetic gas mainly contains hydrogen, carbon monoxide, lower carbon number hydrocarbons, carbonic acid gas and water.
Said gasification condition can suitably be selected in the gasification condition of routine.Under the preferable case, be meant that the service temperature of gasifying reactor is 800-1200 ℃, be preferably 800-1000 ℃, pressure is 0.1-20MPa, be preferably 0.1-10MPa.
Said gasifying medium is the gas that contains water vapour and oxygen, wherein, and the volume ratio 1-20 of water vapour and oxygen: 1.The amount that feeds gasifying medium in the gasifying reactor is to guarantee to satisfy the gasification of solid products such as semicoke and coke powder.The weight ratio of the amount of solid product such as semicoke and coke powder, water vapor and oxygen is (2-5): (4-10): 1.
According to method provided by the invention, said water vapor and oxygen can add with the form of the mixed gas that contains water vapor and oxygen, and the temperature of said water vapor and oxygen can be 150-800 ℃, is preferably 200-600 ℃.
In the method provided by the invention; Step (2) can be implemented in the reactor drum of various routines, as long as this reactor drum can be realized the gasification reaction of semicoke and coke powder, therefore; Gasifying reactor also can be called coal gasification reactor, and said coal gasification reactor for example can be fluidized-bed reactor.
Gaseous products such as the oil gas that generates in cracker and the gasifying reactor are with after solid product separates; Method provided by the invention comprises that also the above-mentioned gas product is introduced subsequent separation system further to be separated, and obtains heavy oil fraction, diesel oil distillate, gasoline fraction, water and splitting gas.Said isolating method can adopt conventional method to implement, and for example can adopt separation column or adopt the mode of temperature control condensation to separate according to the difference of the condensing temperature of each different components.
In the method provided by the invention, to implement separately separately said cracker and the separating of gaseous product that gasifying reactor produces.
Compared with prior art, the present invention has following advantage:
Coal dust cracking of the present invention and BO oil breaking; Three of coke powder gasifications independently process combine; The semicoke of coal dust and heavy oit pyrolysis and coke powder etc. are introduced gasification production synthetic gas in the gasifying reactor, and the high temperature coke powder that temperature raises, carbon content reduces in the gasifying reactor simultaneously returns cracker as thermal barrier and recycles, and has avoided adding supplementary question and the outer heating carrier and the isolating problem of coke powder of carrier; Make full use of energy, reduced energy consumption.In addition, the common cracking of heavy oil and coal can obtain the transformation efficiency of higher lightweight oil, lower carbon number hydrocarbons, hydrogen and carbon monoxide.
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
Embodiment
Embodiment adopts flow process as shown in Figure 1; With the particle diameter of 100 weight parts is that the coal dust (forming as shown in table 1 below) of 0.3-2 millimeter is heated to 200 ℃; Add in the cracker then; And mix with high temperature coke powder (temperature is 900 ℃) from gasifier, spraying into 300 ℃ of heavy oil of 10 weight parts simultaneously to cracking reactor, heavy oil contacts with thermal barrier to react with coal dust and generates oil gas, semicoke and coke powder.Coal dust is 1: 5 with weight ratio from the high temperature coke powder of gasifying reactor, is 550 ℃ with the temperature regulation of said cracker, and pressure is adjusted to 0.3MPa.
The semicoke of autothermic cracking device, coke powder (temperature is 550 ℃) add in the gasifier in the future; And to wherein injecting the mixed gas (temperature is 200 ℃) that contains water vapor and oxygen; The weight ratio of said semicoke, coke powder and water vapor and oxygen is 3: 5: 1; Semicoke and coke powder at high temperature generate the coke powder of synthetic gas and carbon content reduction with water vapour, oxygen reaction, heat release simultaneously heats up, and the temperature of regulating in the gasifying reactor is 1000 ℃.The high temperature coke powder returns in the cracker and recycles, the lime-ash discharger that gasification produces.
After the cyclonic separator gas solid separation, cracker is introduced separation column with the gaseous product in the gasifying reactor separate.Coal dust (shanxi coal) character is seen table 1, and heavy oil (Liaohe River viscous crude) character is seen table 2, and reaction conditions and product composition are seen table 3, and the gas group prejudice table 4 in the table 3, and the composition of isolated synthetic gas is as shown in table 5 below from the product of coal gasification reaction.
The composition of table 1 coal (wt%)
The character of table 2 heavy oil
| Project | |
| Density (20 ℃)/g.cm -3 | 1.07 |
| Kinematic viscosity (80 ℃)/mm 2·s -1 | 3648 |
| Carbon residue/wt% | 13.9 |
| Carbon content/wt% | 86.5 |
| Hydrogen richness/wt% | 10.9 |
| Sulphur content/wt% | 0.9 |
| Metal content/μ g.g -1 | 180 |
| Boiling range/℃ | |
| Over point | 263 |
| 5％ | 323 |
| 10％ | 361 |
| 30％ | 460 |
| 50％ | 530 |
The product and the yield of table 3 coal and heavy oit pyrolysis reaction
Table 4 splitting gas is formed
| Splitting gas is formed | wt％ |
| Methane | 10.2 |
| Ethane | 2.8 |
| Ethene | 1.9 |
| Propane | 1.8 |
| Propylene | 2.2 |
| C 4+Hydro carbons | 3.9 |
| Hydrogen | 0.9 |
| Carbonic acid gas | 53.6 |
| Carbon monoxide | 21.4 |
| Hydrogen sulfide | 1 |
| Nitrogen | 0.3 |
| Amount to | 100 |
Table 5 synthetic gas is formed
| The composition of synthetic gas | Volume % |
| Methane | 2.1 |
| Hydrogen | 46.8 |
| Carbon monoxide | 32.8 |
| Carbonic acid gas | 18.3 |
| Amount to | 100 |
Can find out according to embodiment, adopt heavy oil provided by the invention and coal cracked combine production method to realize the combination producing of coal cracking, heavy oil cracking and gasification.
Claims (12)
1. the combined processing method of heavy oil and coal copyrolysis is characterized in that, may further comprise the steps:
(1) coal dust and heavy oil are introduced in the cracking reactor; Contact intensification with high temperature coke powder from gasifying reactor; And the generation scission reaction obtains reaction oil gas and solid products such as semicoke, coke powder; After the gas solid separation, reaction oil gas is introduced subsequent separation system and is further separated, and semicoke and coke powder get into gasifying reactor;
(2) introduce the gasifying medium that contains water and oxygen in the gasifying reactor; From the semicoke of cracker and coke powder and water, the reaction of oxygen generating gasification; Generate synthetic gas and high temperature coke powder, after the gas solid separation, it is coal and heavy oit pyrolysis reaction heat supply that the high temperature coke powder gets into cracking reactor.
2. according to the method for claim 1, the service temperature that it is characterized in that cracking reactor described in the step (1) is 400-700 ℃, and pressure is 0.1-20MPa.
3. according to the method for claim 2, the service temperature that it is characterized in that the cracking reactor described in the step (1) is 450-600 ℃, and pressure is 0.1-10MPa.
4. according to claim 1,2 or 3 method, the weight ratio that it is characterized in that coal dust described in the step (1) and said high temperature coke powder is 1: (1-10), the weight ratio of said heavy oil and coal dust and high-temperature coke powder mixture is 1: (4-50).
5. according to the method for claim 4, the weight ratio that it is characterized in that coal dust described in the step (1) and said high temperature coke powder is 1: (2-8), the weight ratio of said heavy oil and coal dust and high-temperature coke powder mixture is 1: (5-20).
6. according to the method for claim 1, it is characterized in that the cracking reactor described in the step (1) is selected from: the reactor drum of fluidized-bed reactor, riser reactor, down-flow reactor, moving-burden bed reactor and above-mentioned reaction one or more combination form.
7. according to the method for claim 1, the operational condition that it is characterized in that gasifying reactor described in the step (2) is that temperature is 800-1200 ℃, and pressure is 0.1-20MPa.
8. according to the method for claim 7, the operational condition that it is characterized in that gasifying reactor described in the step (2) is 800-1000 ℃, and pressure is 0.1-10MPa.
9. according to the method for claim 1, it is characterized in that said BO is selected from least a in heavy crude, long residuum, normal pressure wax oil, vacuum residuum, wax tailings, jar end oil, deasphalted oil, viscous crude and the hydrocracking tail oil.
10. according to the method for claim 1, it is characterized in that said coal dust is selected from: a kind of in peat, brown coal, the bituminous coal or more than one mixture.
11., it is characterized in that described in the step (2) that the volume ratio of water vapour and oxygen is (1-20) in the gasifying medium: 1 according to the method for claim 1.
12., it is characterized in that the weight ratio of solid product, water vapour and oxygen such as the semicoke in the introducing gasifying reactor, coke powder in the step (2) is (2-5): (4-10): 1 according to the method for claim 1.
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Cited By (6)
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| CN103497786A (en) * | 2013-09-11 | 2014-01-08 | 李大鹏 | Method for preparing synthesis gas from dust coke |
| CN104046373A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Method for preparing bio-oil and synthesis gas from biomass |
| CN104046372A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Method for preparing bio-oil and synthesis gas from biomass |
| CN104312605A (en) * | 2014-09-23 | 2015-01-28 | 赵建勋 | Method for preparing combustible gas and active coke powder through pyrolysis |
| CN105586095A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Biomass microwave pyrolysis gasification reaction apparatus |
| CN113046129A (en) * | 2021-03-22 | 2021-06-29 | 邢彩虹 | Energy-saving kerosene co-refining method and device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104046373A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Method for preparing bio-oil and synthesis gas from biomass |
| CN104046372A (en) * | 2013-03-15 | 2014-09-17 | 中国石油化工股份有限公司 | Method for preparing bio-oil and synthesis gas from biomass |
| CN104046373B (en) * | 2013-03-15 | 2016-12-28 | 中国石油化工股份有限公司 | The method being prepared bio-oil and synthesis gas by biomass |
| CN103497786A (en) * | 2013-09-11 | 2014-01-08 | 李大鹏 | Method for preparing synthesis gas from dust coke |
| CN104312605A (en) * | 2014-09-23 | 2015-01-28 | 赵建勋 | Method for preparing combustible gas and active coke powder through pyrolysis |
| CN105586095A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Biomass microwave pyrolysis gasification reaction apparatus |
| CN105586095B (en) * | 2014-10-22 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of biomass microwave pyrolytic gasification reaction unit |
| CN113046129A (en) * | 2021-03-22 | 2021-06-29 | 邢彩虹 | Energy-saving kerosene co-refining method and device |
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| CN102453510B (en) | 2013-11-27 |
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