CN101643654B - Processing technology of non-caked coal or weakly caking coal - Google Patents
Processing technology of non-caked coal or weakly caking coal Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a processing technology of non-caked coal or weakly caking coal, comprising the following steps: a) performing low medium temperature dry distillation reaction to non-caked coal or weakly caking coal to generate coal gas, semicoke and coal tar; b1) extracting hydrogen from the coal gas by pressure swing adsorption; b2) sending the semicoke into a gas generator, ensuring that semicoke, oxygen and water vapour react to generate synthesis gas and coal ash in the gas generator, wherein, the synthesis gas comprises carbon monoxide and hydrogen, or sending the semicoke into a circulating fluidized bed boiler for generating electricity; b3) performing constant pressure fractionation to the coal tar to obtain light fraction, carbolic oil and tower bottom heavy oil, wherein, the tower bottom heavy oil removes trailing asphalt via vacuum distillation to obtain heavy fraction; obtaining phenols and dephenollized phenol oil by extracting phenol oil; and c) performing hydrogenation to light fraction, dephenollized phenol oil, heavy fraction and hydrogen. The technology can prolong the service life of hydrogenation catalyst, can improve the yield of the final product and brings more products with excellent quality.
Description
Technical field
The present invention relates to the coal complete processing, relate in particular to the complete processing of a kind of dross coal or weak caking coal, belong to coal chemical technology.
Background technology
Dross coal or weak caking coal comprise brown coal, long-flame coal and bottle coal etc.Brown coal are the minimum coals of degree of coalification, its moisture is high, proportion is little, volatile matter is high, non-caked, chemical reactivity strong, poor heat stability, thermal value are low, the humic acid that contains different quantities, the raw material that is used as fuel, gasification more, also can be used to extract montanin wax and humic acid, make sulphonated coal or gac.The volatile content of long-flame coal is also very high, does not have or only have very little cohesiveness, and easy firing has very long flame during burning, therefore the long-flame coal of gaining the name.Long-flame coal can as the raw material of gasification, also can be used as civilian and power fuel.The bottle coal volatile matter is high, and gelatinous layer is thicker, poor heat stability.Separately coking of bottle coal, but the coke of producing is elongated frangible, and shrinking percentage is large, and longitudinal crack is many, and is anti-crushing relatively poor with wear resistance.So bottle coal can only be used as coal-blending coking, also can be used to make coal gas, produce nitrogenous fertilizer or power fuel.
In the incoherences such as brown coal, long-flame coal and bottle coal or the weak caking coal, all contain abundant organic matter, when middle low-temperature pyrolysis, except producing the semicoke, also can generate coal gas and coal tar.
In China, the incoherence such as brown coal, long-flame coal and bottle coal or weak caking coal are that reserves are abundant but almost also not by the resource of fine utilization.Along with the fast development of China's economy, the demand of the energy is also in continuous expansion.Energy strategy more and more becomes the important component part of China's development strategy.China is an oil starvation, weak breath and the relatively abundant country of coal resources, and " oil starvation, weak breath, rich coal " is the fundamental realities of the country of China, and in the fossil energy reserves of verifying, coal accounts for more than 90%.Along with the crude oil demand of the constantly soaring and domestic cumulative year after year of International Crude Oil, domestic petroleum output can not satisfy the needs of national economy high speed development far away.Therefore, for guaranteeing the Sustainable development of Chinese national economy, optimize China's energy structure, reduction is to the interdependency of petroleum import, take full advantage of the coal resources advantage of China's abundant, greatly develop the Coal Chemical Industry new high-tech industry, with Coal Chemical Industry products substitution petrochemicals, oneself is through becoming the inevitable choice of China's energy strategy.
The industrialization technology that has incoherences such as utilizing brown coal, long-flame coal, bottle coal or weak caking coal now has:
1. gasification: gasification is to change coal into can be used as industry or domestic fuel and chemical industry synthesis material coal gas, but gasification is subjected to the restriction of the type of furnace, coal, moisture content, granularity, can not implement in full.
2. coking: namely secluding air heats coal, and organic the rising with temperature is decomposed gradually in the coal, and wherein volatile matter is overflowed with gaseous state or vapor state, become coke-oven gas and coal tar, and the non-volatile solids residue is coke.But the incoherences such as brown coal, long-flame coal, bottle coal or weak caking coal can not be separately as the coal of using of coking, and only have bottle coal to can be used as a coal of coke making and coal blending, use range is on the low side.
3. destructive distillation: coal placed destructive distillation can generate tar, coke-oven gas and semicoke under the temperature about 600 ℃.The elementary composition of semicoke mainly is carbon, hydrogen and oxygen, and the nitrogen in the raw coal and element sulphur be almost most of consumption in pyrolytic process, and a small amount of nitrogen, element sulphur are present in the semicoke with the form of heterogeneous ring compound.The carbon proportion reaches 95% in the semicoke, can be used to produce ferrosilicon and calcium carbide etc.
4. Direct Hydrogenation liquefaction: coal, catalysts and solvents oil are mixed, under High Temperature High Pressure, make destruction of organic material in the coal, be converted into low molecule liquid state and gaseous product with the hydrogen effect.But the technology of DCL/Direct coal liquefaction is immature, and investment is quite high, and running cost is also quite large.
The contriver finds, at present, is directed to incoherence or the weak caking coals such as brown coal, long-flame coal, bottle coal, and in the process of carrying out hydrogenation reaction, catalyzer is short work-ing life.
Summary of the invention
For defects, the technical problem that the present invention solves is, the complete processing of a kind of dross coal or weak caking coal is provided, and this complete processing can prolong the work-ing life of the catalyzer in the hydrogenation process.
In order to solve above technical problem, the invention provides following technical scheme:
The complete processing of a kind of dross coal or weak caking coal comprises the steps:
A) dross coal or weak caking coal are carried out middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of described middle low-temperature pyrolysis reaction is 450 ℃～700 ℃;
B1) by pressure-variable adsorption the hydrogen in the described coal gas is proposed;
B2) described semicoke is sent into coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in coal-gas producer, and described synthetic gas comprises carbon monoxide and hydrogen;
Perhaps described semicoke being sent into circular fluid bed generates electricity;
B3) described coal tar is carried out the normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and the tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running at the bottom of the tower;
Carbolic oil carries out the carbolic oil extracting and obtains phenols and dephenolize oil;
C) with step b3) in lighting end, dephenolize oil and last running, carry out hydrogenation reaction with hydrogen.
In above-mentioned complete processing,
At first, at low temperatures dross coal or weak caking coal are carried out low-temperature pyrolysis, generate semicoke, coal gas and coal tar.
Then, respectively these three kinds of destructive distillation products are processed.The first, utilize pressure swing adsorption that the hydrogen in the coal gas is proposed; The second, by being gasificated into synthetic gas, perhaps go circular fluid bed to generate electricity semicoke; The 3rd, coal tar is carried out the normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and the tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running at the bottom of the tower, carbolic oil carries out the carbolic oil extracting and obtains phenols and dephenolize oil, heavy oil removes tail pitch through vacuum fractionation at the bottom of the tower, and with heavies removal, otherwise the restructuring in the coal tar divides the carrying out that is unfavorable for hydrogenation reaction.
At last, with lighting end, dephenolize oil and last running, carry out hydrogenation reaction with hydrogen, the preparation oil product.
The contriver finds, because contain the material of more easy coking in the coal tar, so cause just that catalyzer is also wrapped up by coking in hydrogenation process, so that shorten the work-ing life of catalyzer, and the use activity of catalyzer also decreases, if before hydrogenation, can remove the easy coking composition in the heavy oil at the bottom of the tower that the normal pressure fractionation obtains, in work-ing life that so will extending catalyst, improve its catalytic activity.Complete processing provided by the present invention is before hydrogenation is carried out in last running, heavy oil at the bottom of the tower is carried out vacuum fractionation to be processed, with remove wherein take off tail pitch, reach extending catalyst effect in work-ing life, and heavy oil is processed the last running that obtains at the bottom of the tower through vacuum fractionation, more thorough with hydrogen reaction, can improve the yield of its finished product.
Below in conjunction with concrete steps, complete processing provided by the present invention is described, and the scheme that provides some to be more preferably.
Step a) is carried out middle low-temperature pyrolysis reaction with dross coal or weak caking coal, generates coal gas, semicoke and coal tar, and the temperature of described low-temperature pyrolysis reaction is 450 ℃～700 ℃
The middle low-temperature pyrolysis reaction of this step generation coal is usually also referred to as coal carbonization or coal carbonization reaction etc.The temperature of the middle low-temperature pyrolysis reaction of mentioning among the present invention will be 450 ℃～700 ℃, and dross coal or weak caking coal are carried out generating three kinds of products, i.e. coal gas, semicoke and coal tar after the middle low-temperature pyrolysis.Dry distillation reactor generally occurs in the dry distillation reactor device, and the dry distillation reactor device can adopt fixed-bed type, moving-bed type and fluidized bed type.Preferably, adopt fluidized bed type dry distillation reactor device.Because in the fluidized bed type dry distillation reactor device, coal is sent to after the dry distillation reactor device, can be with dross coal or the abundant fluidisation of weak caking coal, increase reaction contact area, can react well, and, the yield of coal tar is higher, can reach 8%～20% (weight).The more important thing is, raw coal can be cleaned, take off the impurity such as most sulphur, nitrogen, reduce the pollution to environment.After raw coal is processed through destructive distillation, the impurity elements such as the nitrogen in the raw coal and sulphur in pyrolytic process almost most of consumption enter in coal gas and the coal tar, a small amount of nitrogen, element sulphur are present in the semicoke with the form of heterogeneous ring compound.So, semicoke is produced synthetic gas with gasification, also good than raw coal direct gasification, because after semicoke processed through destructive distillation, the impurity such as nitrogen, hydrogen sulfide and ammonia greatly reduced, can greatly reduce the processing cost of synthetic gas.
Preferably, the temperature of middle low-temperature pyrolysis reaction is 450 ℃～700 ℃, and working pressure is 0.05MPa～0.5MPa; More preferably, the temperature of middle low-temperature pyrolysis reaction is 550 ℃～650 ℃, and working pressure is 0.08MPa～0.2MPa.
Step b) three kinds of destructive distillation products is processed
The below is respectively the treating processes of step 3 kind destructive distillation product and sets forth.
B1) by pressure-variable adsorption the hydrogen in the described coal gas is proposed
This step is the treatment step to coal gas.
Coal gas can suitably purify before carrying out pressure-variable adsorption.
Preferably, in the pressure-swing adsorption process, the adsorption bed of utilization comprises aluminum oxide, silica gel, gac, zeolite molecular sieve and absorbent for carbon monooxide, and working pressure is 0.8MPa～2.8MPa.
Preferably, after hydrogen is suggested, what or other that can look the required hydrogen consumption of hydrogenation in the subsequent technique install required amounts of hydrogen judge its whether adopt in the change technology it is generated hydrogen with the water reaction again, the hydrogen that becomes in the carbon monoxide can adopt pressure swing adsorption to propose with the hydrogen that the dry distillation of coal produces, be used for the feed hydrogen of hydrogenation reaction.
The hydrogen that proposes in the coal gas is used for hydrogenation, belongs to Matter Transfer, without exhaust emission, has improved the utilization ratio of dross coal or weak caking coal.
B2) described semicoke is sent into coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in coal-gas producer, and described synthetic gas comprises carbon monoxide and hydrogen;
Perhaps described semicoke being sent into circular fluid bed generates electricity
This step is the treatment step to semicoke.
For the processing of semicoke, it is that in coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash that the first is selected.Synthetic gas comprises carbon monoxide and hydrogen.Coal-gas producer can be fixed-bed type, fluidized bed-type and fluidized bed type, preferably uses the fluidized bed type coal-gas producer, and the advantage step of fluidized-bed is addressed in a), does not repeat them here.Preferably, the reaction pressure of fluidized bed type coal-gas producer is 0.1MPa～4.5MPa, and temperature of reaction is 650 ℃～900 ℃, and the gas-solid volume ratio is 3: 1～8: 1; More preferably, the reaction pressure of fluidized bed type coal-gas producer is 0.1MPa～3.5MPa, and temperature of reaction is 700 ℃～850 ℃, and the gas-solid volume ratio is 4: 1～8: 1.
For the processing of semicoke, it is directly to deliver to circular fluid bed and generate electricity that the second is selected.And preferably selecting is that semicoke is directly sent to generating.Vehicle fuel certainly also in conventional field, is brought into play than the better advantage of raw coal such as generating and gasification aspect.After raw coal is processed through destructive distillation, the impurity elements such as the nitrogen in the raw coal and sulphur in pyrolytic process almost most of consumption enter in coal gas and the coal tar, a small amount of nitrogen, element sulphur are present in the semicoke with the form of heterogeneous ring compound.Adopt CFB boiler (circular fluid bed) generating with semicoke, burning causes the impurity such as the sulphur, nitrogen of topsoil to greatly reduce, and can greatly reduce the environmental protection investments of power generation assembly.Certainly synthetic gas is produced in gasification, and is also good than raw coal direct gasification, because after coke breeze processed through destructive distillation, the impurity such as nitrogen, hydrogen sulfide and ammonia greatly reduced, can greatly reduce the processing cost of synthetic gas.
B3) described coal tar is carried out the normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and the tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running at the bottom of the tower;
Carbolic oil carries out the carbolic oil extracting and obtains phenols and dephenolize oil;
This step is the treatment step to coal tar.
In this step, generally adopt atmospheric fractional tower and vacuum fractionation tower to realize getting final product.At first utilize atmospheric fractional tower to fractionate out lighting end at cat head, side line fractionates out carbolic oil, and heavy oil enters the vacuum fractionation tower at the bottom of the tower.Vacuum fractionation column overhead and side line fractionation obtain last running, are to take off tail pitch at the bottom of the vacuum fractionation tower tower.The final boiling point of lighting end is generally at 180～230 ℃, and the initial boiling point of last running is general＞270 ℃, the amount that VACUUM TOWER BOTTOM coal tar takes off tail pitch according to the coal tar oil properties generally at 10m%～30m% (massfraction).
For atmospheric fractional tower carbolic oil out, can carry out the carbolic oil extraction steps.Further produce phenols and dephenolize oil.
Need to prove, carry out before the processing of this step the pre-treatment step of a coal tar being arranged at coal tar, be mainly used in removing mechanical impurity in the coal tar and water etc., general pretreatment unit comprises centrifugal filter, electrodesalting and electrodehydrating etc.
C) with step b3) in lighting end, dephenolize oil and last running, carry out hydrogenation reaction with hydrogen
This step is the step that hydrogenation reaction prepares oil product.
Usually, described hydrogenation reaction can comprise hydrofining unit and hydrocracking unit.
Preferably, the temperature of reaction in the described hydrofining unit is 180 ℃～427 ℃, and reaction pressure is 10MPa～17MPa, and hydrogen to oil volume ratio is 1000: 1～3500: 1, and volume space velocity is 0.15h during liquid
-1～1h
-1More preferably, the temperature of reaction in the described hydrofining unit is 180 ℃～420 ℃, and reaction pressure is 10MPa～16MPa, and hydrogen to oil volume ratio is 1500: 1～3000: 1, and volume space velocity is 0.2h during liquid
-1～0.8h
-1
Preferably, hydrofining unit oil product out enters the hydrocracking unit, and the temperature of reaction in the described hydrocracking unit is 360 ℃～427 ℃, and reaction pressure is 10MPa～17MPa, and hydrogen to oil volume ratio is 800: 1～2000: 1, and volume space velocity is 0.15h during liquid
-1～1h
-1More preferably, the temperature of reaction in the described hydrocracking unit is 380 ℃～420 ℃, and reaction pressure is 10MPa～16MPa, and hydrogen to oil volume ratio is 1000: 1～1500: 1, and volume space velocity is 0.2h during liquid
-1～0.8h
-1
The complete processing of dross coal provided by the present invention or weak caking coal compared with prior art, before heavy oil at the bottom of the tower carries out hydrogenation, heavy oil at the bottom of the tower is carried out vacuum fractionation to be processed, with remove wherein take off tail pitch, reach and prolong the Useful Time of Hydrogenation Catalyst effect, and through removing the last running that heavy oil obtains at the bottom of the bituminous-treated tower of tail, more thorough with hydrogen reaction, can improve the yield of its finished product.
The complete processing of dross coal provided by the present invention or weak caking coal is specially adapted to the deep processing of the dross coal such as brown coal, long-flame coal, bottle coal or weak caking coal.
Description of drawings
Fig. 1 is the process flow sheet of embodiment 1～3.
Embodiment
For those skilled in the art can understand the present invention better, set forth below in conjunction with specific embodiment.
Embodiment 1
Fig. 1 is the process flow sheet of embodiment 1～3.
The Nanning brown coal are sent in the middle low temperature fluidized-bed dry distillation reactor device carry out dry distillation reactor, pressure 0.1MPa, 500 ℃ of service temperatures generate dry distillation gas, coal tar and semicoke.Destructive distillation coal tar oil properties sees Table 1.After purifying, dry distillation gas enters PSA (pressure-variable adsorption) device, by the adsorption bed by zeolite molecular sieve, working pressure is 2MPa, hydrogen is wherein proposed, and carbon monoxide component wherein, the change technology has generated hydrogen with the water reaction again with it in also adopting, and the hydrogen that produces with the dry distillation of coal adopts the PSA technology to propose to be used for the charging of coal tar hydrocracking device.Pyrolysis Char is then sent into the fluidized bed coal gas generator, and oxygen, water vapour reaction produce synthetic gas and coal ash.During char Gasification, semicoke and oxygen, water vapour (volume ratio of water vapour, oxygen is 5: 1) reaction produce synthetic gas (carbon monoxide and hydrogen) and coal ash; Coal-gas producer reaction pressure 0.13MPa, 900 ℃ of temperature of reaction, gas-solid ratio 5: 1 (v/v), the wherein volume ratio 4: 1 of water vapor, oxygen.Enter atmospheric fractional tower behind destructive distillation coal tar process off line tool impurity and the water, fractionate out heavy oil and carbolic oil (or being called carbolic oil) at the bottom of overhead oil (lighting end), the tower, carbolic oil enters the carbolic oil extraction plant and extracts phenol products and dephenolize oil, and heavy oil enters vacuum distillation tower and fractionates out last running and take off tail coal pitch at the bottom of the atmospheric tower.Enter hydrogenation unit generation hydrofining and hydrocracking reaction production dry gas, liquefied gas, hydrotreated naphtha and hydrogenated diesel oil after wherein last running and atmospheric overhead and dephenolize oil mixes, hydrorefined temperature of reaction is 235 ℃, pressure 15.6MPa, hydrogen to oil volume ratio 1350: 1 and air speed 0.6h
-1380 ℃ of the temperature of reaction of hydrocracking, pressure 14.6MPa, hydrogen to oil volume ratio 1350: 1 and air speed 0.3h
-1Main products character sees Table 4.So far coal tar is that raw material can be produced the products such as phenol, industrial cresols, ortho-cresol, xylenol, liquefied gas, gasoline and diesel oil.
Embodiment 2
Yilan coal sent in the middle low temperature fluidized-bed dry distillation reactor device carry out dry distillation reactor, pressure 0.12MPa, 600 ℃ of service temperatures generate dry distillation gas, coal tar and semicoke.Destructive distillation coal tar oil properties sees Table 2.Dry distillation gas enters the PSA device after purifying, by the adsorption bed that is consisted of by silica gel, working pressure is 2.45MPa, hydrogen is wherein proposed, and carbon monoxide component wherein, the change technology has generated hydrogen with the water reaction again with it in also adopting, and the hydrogen that produces with the dry distillation of coal adopts the PSA technology to propose to be used for the charging of coal tar hydrogenating unit.Pyrolysis Char is sent into the CFB device and is generated electricity.Destructive distillation coal tar enters atmospheric fractional tower through behind the pretreatment unit, fractionate out heavy oil and carbolic oil at the bottom of overhead oil, the tower, carbolic oil enters the carbolic oil extraction plant and extracts phenol products and dephenolize oil, and heavy oil enters vacuum distillation tower and fractionates out last running and take off tail coal pitch at the bottom of the atmospheric tower.Enter hydrogenation unit generation hydrofining and hydrocracking reaction production dry gas, liquefied gas, hydrotreated naphtha and hydrogenated diesel oil after wherein last running and atmospheric overhead (lighting end) and dephenolize oil mixes, hydrorefined temperature of reaction is 362 ℃, pressure 14.3MPa, hydrogen to oil volume ratio 1550: 1 and air speed 0.23h
-1382 ℃ of the temperature of reaction of hydrocracking, pressure 13.8MPa, hydrogen to oil volume ratio 1000: 1 and air speed 0.48h
-1So far coal tar is that raw material can be produced the products such as phenol, industrial cresols, ortho-cresol, xylenol, liquefied gas, gasoline and diesel oil.
Embodiment 3
The Yilan brown coal are sent in the middle low temperature fluidized-bed dry distillation reactor device carry out dry distillation reactor, pressure 0.18MPa, 650 ℃ of service temperatures generate dry distillation gas, coal tar and semicoke.Destructive distillation coal tar oil properties sees Table 3.Enter PSA (pressure-variable adsorption) device 4 after dry distillation gas purifies, by the adsorption bed that is made of the CO Special adsorbent, working pressure 1.2MPa proposes hydrogen wherein to be used for the charging of coal tar hydrogenating unit.Pyrolysis Char is then sent into the fluidized bed coal gas generator, and oxygen, water vapour reaction produce synthetic gas and coal ash.During char Gasification, semicoke and oxygen, water vapour (volume ratio of water vapour, oxygen is 5: 1) reaction produce synthetic gas (carbon monoxide and hydrogen) and coal ash; Coal-gas producer reaction pressure 1.6MPa, 850 ℃ of temperature of reaction, gas-solid ratio 7: 1 (v/v).Destructive distillation coal tar is through entering atmospheric fractional tower behind the pretreatment unit, fractionates out heavy oil and carbolic oil at the bottom of overhead oil, the tower, and carbolic oil enters the carbolic oil extraction plant and extracts phenol products and dephenolize oil.Heavy oil enters vacuum distillation tower and fractionates out last running and take off tail coal pitch at the bottom of the atmospheric tower.Enter hydrogenation unit generation hydrofining and hydrocracking reaction production dry gas, liquefied gas, hydrotreated naphtha and hydrogenated diesel oil after wherein last running and atmospheric overhead and dephenolize oil mixes, hydrorefined temperature of reaction is 402 ℃, pressure 12.1MPa, hydrogen to oil volume ratio 2200: 1 and air speed 0.46h
-1406 ℃ of the temperature of reaction of hydrocracking, pressure 10.2MPa, hydrogen to oil volume ratio 1450: 1 and air speed 0.58h
-1So far coal tar is that raw material can be produced the products such as phenol, industrial cresols, ortho-cresol, xylenol, liquefied gas, gasoline and diesel oil.
Table 1 coal tar main character
Table 2 destructive distillation coal tar main character
Table 3 destructive distillation coal tar main character
Table 4 gasoline fraction main character
| Density (20 ℃)/gcm -3 | 0.7329 |
| Boiling range/℃ | |
| IBP/10％ | 84/101 |
| 30％/50％ | 111/113 |
| 70％/90％ | 136/157 |
| EBP | 180 |
| S/μg·g -1(microgram/gram) | ＜0.5 |
| N/μg·g -1 | ＜0.5 |
| Compositional analysis, quality % | |
| Alkane | 6.2 |
| C 4/C 5 | 0.2/0.9 |
| C 6/C 7 | 1.9/1.7 |
| C 8/C 9 | 0.9/0.5 |
| C 10 | 0.1 |
| Naphthenic hydrocarbon | 88.6 |
| C 5/C 6 | 0.2/19.0 |
| C 7/C 8 | 23.4/17.6 |
| C 9/C 10 | 14.2/13.3 |
| C 11 | 1.9 |
| Aromatic hydrocarbons | 4.2 |
| C 6/C 7 | 1.5/0.9 |
| C 8/C 9 | 0.8/0.9 |
| C 10 | 0.11 |
| Virtue is dived, % | 89.1 |
Continued 4 diesel oil distillate character
| Density (20 ℃)/gcm -3 | 0.8623 |
| Boiling range/℃ | |
| IBP/10％ | 173/211 |
| 30％/50％ | 226/235 |
| 70％/90％ | 260/293 |
| 95％/EBP | 308/341 |
| Viscosity (20 ℃)/mm 2·s -1 | |
| Acidity/mgKOH (100mL) -1 | 1.57 |
| 10% steams excess carbon residue, % | ＜0.01 |
| Refractive power (20 ℃) | |
| Flash-point/℃ | 56 |
| Condensation point/℃ | ＜-50 |
| Cold filter clogging temperature/℃ | ＜-41 |
| Cetane value | 39.6 |
| S/μg·g -1 | ＜5 |
| N/μg·g -1 | ＜1.0 |
The physical properties of continued 4 several main lower boiling phenol
In the phenol products of the present invention (quality percentage composition):
Industry phenol ctystallizing point is no less than 31 ℃ of neutral oils and is not more than 0.5% moisture and is not more than 1.5% pyridine base 0.3%;
Ortho position cresols is not less than 96% phenol content and is not more than 2% xylenol and is not more than 2% moisture and is not more than 0.5%;
Flow out before discharge is not more than 3%210 ℃ before 190 ℃ of the 3 mixed cresols and be not less than 96%; Between position cresols be not less than 41% neutral oil content and be not more than 1% moisture and be not more than 0.5%;
Discharge is not less than 90% before being not more than 0.5% 225 ℃ before 205 ℃ of the technical xylenols, and neutral oil is not more than 1.8% moisture and is not more than 1.2%.
As can be seen from the table above, the present invention is by to the optimization design of flow process, realized the deep processing to the incoherence such as brown coal, long-flame coal, bottle coal or weak caking coal, Effective Raise the utilization ratio of raw material.
The complete processing of dross coal provided by the present invention or weak caking coal compared with prior art, before hydrogenation is carried out in last running, vacuum fractionation is carried out in last running to be processed, with remove wherein take off tail pitch, reach and prolong the Useful Time of Hydrogenation Catalyst effect, and process removes the bituminous-treated last running of tail, and is more thorough with hydrogen reaction, can improve the yield of its finished product.
The complete processing of dross coal provided by the present invention or weak caking coal is specially adapted to the deep processing of the dross coal such as brown coal, long-flame coal, bottle coal or weak caking coal.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (14)
1. the complete processing of a dross coal or weak caking coal comprises the steps:
A) dross coal or weak caking coal are carried out middle low-temperature pyrolysis reaction, generate coal gas, semicoke and coal tar, the temperature of described middle low-temperature pyrolysis reaction is 450 ℃～700 ℃;
B1) by pressure-variable adsorption the hydrogen in the described coal gas is proposed;
B2) described semicoke is sent into coal-gas producer, semicoke, oxygen and water vapour reaction generate synthetic gas and coal ash in coal-gas producer, and described synthetic gas comprises carbon monoxide and hydrogen;
Perhaps described semicoke being sent into circular fluid bed generates electricity;
B3) described coal tar is carried out the normal pressure fractionation, obtain heavy oil at the bottom of lighting end, carbolic oil and the tower, heavy oil removes hangover pitch through vacuum fractionation and obtains last running at the bottom of the tower;
Carbolic oil carries out the carbolic oil extracting and obtains phenols and dephenolize oil;
C) with step b3) in lighting end, dephenolize oil and last running, carry out hydrogenation reaction with hydrogen.
2. complete processing according to claim 1 is characterized in that, in the step a), described middle low-temperature pyrolysis reaction is carried out in the dry distillation reactor device, and described dry distillation reactor device is fluidized bed type dry distillation reactor device.
3. complete processing according to claim 1 is characterized in that, in the step a), the temperature of described middle low-temperature pyrolysis reaction is 450 ℃～700 ℃, and working pressure is 0.05MPa～0.5MPa.
4. complete processing according to claim 3 is characterized in that, in the step a), the temperature of described middle low-temperature pyrolysis reaction is 550 ℃～650 ℃, and working pressure is 0.08MPa～0.2MPa.
5. complete processing according to claim 1, it is characterized in that step b1) in, in the described pressure-swing adsorption process, the adsorption bed of utilizing comprises aluminum oxide, silica gel, gac, zeolite molecular sieve and absorbent for carbon monooxide, and working pressure is 0.8MPa～2.8MPa.
6. complete processing according to claim 1, it is characterized in that, step b1) in, after hydrogen is suggested, carbon monoxide in the products therefrom, the change technology generates hydrogen with the water reaction again with it in alternative the employing, and the hydrogen that becomes in the carbon monoxide can adopt pressure swing adsorption to propose with the hydrogen that the dry distillation of coal produces, be used for the feed hydrogen of hydrogenation reaction.
7. complete processing according to claim 1 is characterized in that, step b2) in, described coal-gas producer is the fluidized bed type coal-gas producer.
8. complete processing according to claim 7 is characterized in that, step b2) in, the reaction pressure of described fluidized bed type coal-gas producer is 0.1MPa～4.5MPa, and temperature of reaction is 650 ℃～900 ℃, and the gas-solid volume ratio is 3:1～8:1.
9. complete processing according to claim 8 is characterized in that, step b2) in, the reaction pressure of described fluidized bed type coal-gas producer is 0.1MPa～3.5MPa, and temperature of reaction is 700 ℃～850 ℃, and the gas-solid volume ratio is 4:1～8:1.
10. complete processing according to claim 1 is characterized in that, in the step c), described hydrogenation reaction comprises hydrofining unit and hydrocracking unit.
11. complete processing according to claim 10 is characterized in that, the temperature of reaction in the described hydrofining unit is 180 ℃～427 ℃, and reaction pressure is 10MPa～17MPa, and hydrogen to oil volume ratio is 1000:1～3500:1, and volume space velocity is 0.15h during liquid
-1～1h
-1
12. complete processing according to claim 11 is characterized in that, the temperature of reaction in the described hydrofining unit is 180 ℃～420 ℃, and reaction pressure is 10MPa～16MPa, and hydrogen to oil volume ratio is 1500:1～3000:1, and volume space velocity is 0.2h during liquid
-1～0.8h
-1
13. complete processing according to claim 10, it is characterized in that, hydrofining unit oil product out enters the hydrocracking unit, temperature of reaction in the described hydrocracking unit is 360 ℃～427 ℃, reaction pressure is 10MPa～17MPa, hydrogen to oil volume ratio is 800:1～2000:1, and volume space velocity is 0.15h during liquid
-1～1h
-1
14. complete processing according to claim 13 is characterized in that, the temperature of reaction in the described hydrocracking unit is 380 ℃～420 ℃, and reaction pressure is 10MPa～16MPa, and hydrogen to oil volume ratio is 1000:1～1500:1, and volume space velocity is 0.2h during liquid
-1～0.8h
-1
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| WO2015076992A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for pyrolysis of coal |
| WO2015076973A1 (en) * | 2013-11-19 | 2015-05-28 | Uop Llc | Process for pyrolysis of a coal feed |
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| CN102816596B (en) * | 2012-09-07 | 2014-08-13 | 中铝能源有限公司 | Deep processing method of non-caking coal or feebly caking coal |
| CN103468285B (en) * | 2013-09-13 | 2015-12-09 | 神木富油能源科技有限公司 | In pulverized coal pyrolysis, coalite tar produces the method for oil fuel |
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